Silane compounds and their uses

Abstract

An object of the present invention is to provide a novel silane compound and its uses. Specifically, the object is to provide a novel silane compound, a surface treatment agent containing the silane compound and an adhesion method therefor, a resin composition containing the silane compound and a cured product thereof. SOLUTION: A silane compound represented by chemical formula (I). [Formula 1] TIFF0007746515000013.tif22136 (in the formula, R 1 are the same or different and represent a hydrogen atom or an alkyl group having 1 to 3 carbon atoms; R 2 represents an alkyl group having 1 to 3 carbon atoms or a phenyl group, and R 3 represents a hydrogen atom, an alkyl group having 1 to 3 carbon atoms or a phenyl group, and X represents an iodine atom. n represents an integer of 1 to 5, m represents an integer of 2 to 5, and p represents an integer of 1 to 3.

Description

[Technical Field]

[0001] The present invention relates to a novel silane compound and the use of said compound. [Background technology]

[0002] In recent years, printed wiring boards have become increasingly multilayered in response to the miniaturization and thinning of electronic devices and electronic components, and so-called multilayer printed wiring boards are manufactured by stacking an outer layer circuit board or copper foil via a prepreg on an inner layer circuit board having a circuit made of copper foil or the like on one or both sides, and integrating them. In such multilayer printed wiring boards, however, ensuring adhesion between the copper circuit formed on the inner layer circuit board and the insulating adhesive resin of the prepreg that laminates the outer layer circuit board or copper foil is an important issue.

[0003] Patent Document 1 describes an invention relating to a copper foil surface treatment agent that improves the adhesiveness between copper foil and prepreg and the solder heat resistance of a copper-clad laminate obtained by bonding copper foil and prepreg. This document discloses the combined use of a trialkoxysilane compound and a tetraalkoxysilane compound having an imidazole ring as components of the surface treatment agent. However, surface treatment agents containing these silane compounds still have room for improvement in terms of adhesiveness.

[0004] Patent Document 2 describes an invention relating to a silane coupling agent and a polymer composition. This document discloses various substances as components of silane coupling agents used in primers for bonding glass or metal to rubber, each having a structure in which a nitrogen-containing heterocycle such as triazole or thiadiazole is bonded to a silyl group such as a trimethoxysilyl group or a triethoxysilyl group via an organic group. However, polymer compositions containing these silane compounds still have room for improvement in terms of adhesiveness. [Prior art documents] [Patent documents]

[0005] [Patent Document 1] Japanese Patent Application Publication No. 7-286160 [Patent Document 2] Japanese Patent Application Laid-Open No. 2002-363189 Summary of the Invention [Problem to be solved by the invention]

[0006] An object of the present invention is to provide a novel silane compound and its uses. Specifically, the object is to provide a novel silane compound, a surface treatment agent containing the silane compound and an adhesion method therefor, a resin composition containing the silane compound and a cured product thereof. [Means for solving the problem]

[0007] As a result of extensive research to solve the above-mentioned problems, the inventors have discovered that a silane compound having two or more iodine atoms in the molecule is a novel compound, and that treating the surface of a workpiece with a surface treatment agent containing this compound increases the surface free energy of the surface (for example, reduces the contact angle), thereby completing the present invention. That is, the first invention is a silane compound represented by chemical formula (I).

[0008] [ka] (In the formula, R 1 are the same or different and represent a hydrogen atom or an alkyl group having 1 to 3 carbon atoms; R 2 represents an alkyl group having 1 to 3 carbon atoms or a phenyl group, and R 3 represents a hydrogen atom, an alkyl group having 1 to 3 carbon atoms or a phenyl group, and X represents an iodine atom. n represents an integer of 1 to 5, m represents an integer of 2 to 5, and p represents an integer of 1 to 3.

[0009] The second invention is a surface treatment agent containing the compound of the first invention. A third invention is the surface treatment agent of the second invention, characterized in that it is used to treat the surface of at least one material selected from the group consisting of metals, inorganic materials, and resin materials. A fourth invention is a bonding method comprising contacting the surface treatment agent of the second invention with at least one material selected from the group consisting of metals, inorganic materials, and resin materials to form a chemical conversion coating on at least one of the materials, and bonding the materials to each other via the chemical conversion coating. A fifth invention is a printed wiring board characterized in that two materials selected from the group consisting of metals, inorganic materials, and resin materials are bonded via a chemical conversion coating formed by the surface treatment agent of the second invention. A sixth invention is a resin composition containing the compound of the first invention and a resin or a curable compound. A seventh aspect of the present invention is a cured product obtained by curing the resin composition of the sixth aspect of the present invention. [Effects of the Invention]

[0010] The silane compound of the present invention has a silyl group (-Si(OR 1 ) p (R 2 ) 3-p / In the formula, R 1 , R 2 and p is the same as above.) and is therefore expected to be used as a component of a surface treatment agent or a raw material for a resin composition. Furthermore, since the silane compound of the present invention has two or more iodine atoms in the molecule, when used as a component of a surface treatment agent, it is possible to increase the surface free energy of the treated surface of the treated material compared to when a conventional silane compound (silane coupling agent) is used, and it is expected that the adhesion between the treated material and resin will be improved. Furthermore, when the silane compound of the present invention is used as a raw material for a resin composition, the intermolecular interaction between the resin or curable compound and the silane compound of the present invention is enhanced, which is expected to increase the surface free energy of the resin composition itself and result in a uniform cured product. DETAILED DESCRIPTION OF THE INVENTION

[0011] The present invention will be described in detail below. 1. Silane compounds The present invention relates to a silane compound represented by chemical formula (I) (hereinafter, sometimes referred to as "the compound of the present invention"). Examples of the compound of the present invention include compounds represented by chemical formulas (I-1) to (I-47).

[0012] [ka]

[0013] [ka]

[0014] [ka]

[0015] [ka]

[0016] In the compounds of the present invention, preferred substituents are as follows. R 1 are the same or different and are preferably alkyl groups having 1 to 3 carbon atoms, and more preferably alkyl groups having 1 to 2 carbon atoms. R 2 However, it is preferably an alkyl group having 1 to 3 carbon atoms, and more preferably an alkyl group having 1 to 2 carbon atoms. R 3 is preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and more preferably a hydrogen atom or an alkyl group having 1 to 2 carbon atoms. It is preferable that n is an integer of 2 to 4. Preferably, m is an integer of 3 to 5, and more preferably an integer of 3 to 4. It is preferable that p is an integer of 2 to 3.

[0017] 2.Synthesis method The compound of the present invention can be synthesized by reacting an aromatic carboxylic acid represented by chemical formula (II) with an aminoalkylsilane represented by chemical formula (III) in the presence of a condensing agent (i) (see reaction scheme (A)).

[0018] [ka] (In the formula, R 1 ~R 3 , X, m, n, and p are the same as above.

[0019] Examples of the aromatic carboxylic acid represented by the chemical formula (II) include aromatic carboxylic acids represented by the chemical formulas (II-1) to (II-16).

[0020] [ka]

[0021] These aromatic carboxylic acids can be purchased as commercially available reagents.

[0022] The aminoalkylsilane represented by the chemical formula (III) includes aminoalkylsilanes represented by the chemical formulas (III-1) to (III-32).

[0023] [ka]

[0024] [ka]

[0025] These aminoalkylsilanes can be purchased as commercially available reagents.

[0026] The amount of the aminoalkylsilane represented by the chemical formula (III) used is preferably an appropriate ratio in the range of 0.1 to 10 times the amount (charge amount) of the aromatic carboxylic acid represented by the chemical formula (II) used.

[0027] Examples of the condensing agent (i) include 1,3-dicyclohexylcarbodiimide, 1,3-diisopropylcarbodiimide, 1,3-di-tert-butylcarbodiimide, 1,3-di-p-tolylcarbodiimide, 1-tert-butyl-3-ethylcarbodiimide, 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide, 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride, 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide methiodide, 1-cyclohexyl-3-(2-morpholinoethyl)carbodiimide metho-p-toluenesulfonate, and 1-hydroxybenzotriazole. , diphenylphosphoric acid azide, (benzotriazol-1-yloxy)tripyrrolidinophosphonium hexafluorophosphate (PyBOP), (7-azabenzotriazol-1-yloxy)tripyrrolidinophosphonium hexafluorophosphate (PyAOP), bromotris(dimethylamino)phosphonium hexafluorophosphate (BroP), chlorotrispyrrolidinophosphonium hexafluorophosphate (PyCloP), bromotrispyrrolidinophosphonium hexafluorophosphate (PyBroP), 3-(diethoxyphosphoryloxy)-1,2,3-benzotriazin-4(3H)-one (BEPBT), etc. These may be used alone or in combination of two or more. The amount of the condensing agent (i) used (charged amount) is preferably an appropriate ratio in the range of 0.1 to 10 times the amount of the aromatic carboxylic acid represented by the chemical formula (II) used (charged amount).

[0028] In carrying out this reaction, a base (ii) may be used to promote the reaction, and a reaction solvent (iii) may be used appropriately, if necessary.

[0029] Examples of the base (ii) include trimethylamine, triethylamine, tributylamine, N,N-diisopropylethylamine, N-methylmorpholine, 1,5-diazabicyclo[4.3.0]non-5-ene (DBN), 1,4-diazabicyclo[2.2.2]octane (DABCO), 1,8-diazabicyclo[5.4.0]-7-undecene (DBU), pyridine, 4-(N,N-dimethylamino)pyridine, picoline, N,N-dimethylaniline, N,N-diethylaniline, imidazole, lithium hydride, sodium hydride, potassium hydride, lithium hydroxide, sodium hydroxide, potassium hydroxide, cesium hydroxide, lithium carbonate, and sodium carbonate. Examples of suitable alkoxides include lithium carbonate, potassium carbonate, cesium carbonate, lithium hydrogen carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, cesium hydrogen carbonate, trilithium phosphate, trisodium phosphate, tripotassium phosphate, tricesium phosphate, dilithium hydrogen phosphate, disodium hydrogen phosphate, dipotassium hydrogen phosphate, disodium hydrogen phosphate, disodium hydrogen phosphate, lithium dihydrogen phosphate, sodium dihydrogen phosphate, potassium dihydrogen phosphate, cesium dihydrogen phosphate, lithium acetate, sodium acetate, potassium acetate, cesium acetate, lithium alkoxides (lithium methoxide, etc.), sodium alkoxides (sodium methoxide, sodium ethoxide, etc.), potassium alkoxides (potassium t-butoxide, etc.), etc. These may be used alone or in combination of two or more. The amount of base (ii) used (charged amount) is preferably an appropriate ratio in the range of 0.1 to 10 times the amount of aromatic carboxylic acid represented by chemical formula (II) used (charged amount).

[0030] The reaction solvent (iii) is not particularly limited as long as it does not inhibit the reaction, and examples thereof include methanol, ethanol, propanol, tetrahydrofuran, dioxane, ethyl acetate, acetone, acetonitrile, benzene, toluene, xylene, dichloromethane, chloroform, carbon tetrachloride, tetrachloroethane, dichlorobenzene, dimethylformamide, dimethylacetamide, dimethyl sulfoxide, hexamethylphosphoric triamide, and the like. These can be combined as necessary and used in appropriate amounts.

[0031] In this reaction, the reaction temperature is preferably set in the range of 20 to 80° C. The reaction time is appropriately set depending on the set reaction temperature, but is preferably set in the range of 1 to 96 hours.

[0032] After completion of the reaction, the target compound of the present invention can be isolated from the resulting reaction mixture by, for example, concentrating the reaction mixture by distilling off the reaction solvent or by solvent extraction. If necessary, the product can be further purified by washing with water or the like, treatment with activated carbon, silica gel chromatography, recrystallization, or the like.

[0033] 3. Surface treatment agents The surface treatment agent of the present invention contains the compound of the present invention, and may contain one or more compounds of the present invention. The surface treatment agent of the present invention may contain a solvent together with the compound of the present invention. Examples of the solvent include water, an organic solvent, and a mixture of water and an organic solvent. In addition, a solubilizer (acid, alkali) can be used to promote dissolution (formation of an aqueous solution) of the compound of the present invention. The surface treatment agent of the present invention can be prepared by mixing the compound of the present invention, a solvent, and a solubilizing agent by any suitable means.

[0034] Examples of the organic solvent include methanol, ethanol, 1-propanol, 2-propanol, butanol, tert-butyl alcohol, ethylene glycol, propylene glycol, 1,4-butanediol, glycerin, diethylene glycol, triethylene glycol, ethylene glycol monomethyl ether, ethylene glycol dimethyl ether, ethylene glycol monoethyl ether, ethylene glycol diethyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monobutyl ether, and diethylene glycol monomethyl ether. Examples of the organic solvent include tetrahydrofurfuryl alcohol, diethylene glycol dimethyl ether, diethylene glycol monoethyl ether, diethylene glycol diethyl ether, diethylene glycol monobutyl ether, triethylene glycol dimethyl ether, triethylene glycol diethyl ether, tetrahydrofurfuryl alcohol, furfuryl alcohol, acetone, tetrahydrofuran, dioxane, acetonitrile, 2-pyrrolidone, formamide, dimethylformamide, dimethylacetamide, dimethyl sulfoxide, sulfolane, dimethyl carbonate, ethylene carbonate, N-methylpyrrolidone, γ-butyrolactone, 1,3-dimethyl-2-imidazolidinone, etc. These organic solvents may be used alone or in combination of two or more.

[0035] Examples of the acid include inorganic acids such as hydrochloric acid, sulfuric acid, nitric acid, and phosphoric acid, and organic acids such as formic acid, acetic acid, propionic acid, butyric acid, 2-ethylbutyric acid, valeric acid, caproic acid, enanthic acid, caprylic acid, pelargonic acid, capric acid, lauric acid, myristic acid, palmitic acid, margaric acid, oleic acid, stearic acid, glycolic acid, lactic acid, gluconic acid, glyceric acid, malonic acid, succinic acid, levulinic acid, benzoic acid, oxalic acid, tartaric acid, malic acid, benzenesulfonic acid, tosylic acid, methanesulfonic acid, 5-sulfosalicylic acid, 4-hydroxybenzenesulfonic acid, 3-methyl-4-hydroxybenzenesulfonic acid, 4-aminobenzenesulfonic acid, camphorsulfonic acid, benzenedisulfonic acid, benzenetrisulfonic acid, sulfamic acid, and amino acids. These acids may be used alone or in combination of two or more.

[0036] Examples of the alkali include alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, and amines such as ammonia, methylamine, dimethylamine, trimethylamine, ethylamine, diethylamine, triethylamine, propylamine, isopropylamine, butylamine, pentylamine, hexylamine, heptylamine, octylamine, nonylamine, allylamine, ethylenediamine, diethylenetriamine, triethylenetetramine, monoethanolamine, diethanolamine, triethanolamine, monopropanolamine, dipropanolamine, tripropanolamine, monoisopropanolamine, diisopropanolamine, triisopropanolamine, 2-amino-1-propanol, N,N-dimethylethanolamine, cyclohexylamine, aniline, pyrrolidine, piperidine, piperazine, and pyridine. These alkalis may be used alone or in combination of two or more.

[0037] When a mixture of water and an organic solvent is used as the solvent, the surface treatment agent may be prepared by mixing the compound of the present invention with water and then adding the organic solvent, by mixing the compound of the present invention with a mixture of water and an organic solvent, or by mixing the compound of the present invention with an organic solvent and then adding water. Furthermore, the water used in preparing the surface treatment agent is preferably pure water such as ion-exchanged water or distilled water.

[0038] The concentration of the compound of the present invention in the surface treatment agent of the present invention is preferably in the range of 0.001 to 20% by weight. If the concentration of the compound of the present invention is less than 0.001% by weight, there is a risk that the adhesiveness improving effect will not be sufficient, and if it exceeds 20% by weight, the adhesiveness improving effect will almost plateau, and the amount of the compound of the present invention used will simply increase, which is not economical.

[0039] In order to improve the stability of the surface treatment agent and the uniformity of the chemical conversion coating, it is also possible to use a substance that generates halide ions such as fluoride ions, chloride ions, bromide ions, and iodide ions, or metal ions such as copper ions, iron ions, and zinc ions.

[0040] Halide ions are effective in forming uniform flat portions of the chemical conversion coating. Examples of substances that generate halide ions include lithium fluoride, sodium fluoride, potassium fluoride, magnesium fluoride, calcium fluoride, lithium chloride, sodium chloride, potassium chloride, magnesium chloride, calcium chloride, lithium bromide, sodium bromide, potassium bromide, magnesium bromide, calcium bromide, lithium iodide, sodium iodide, potassium iodide, magnesium iodide, calcium iodide, ammonium fluoride, ammonium chloride, ammonium bromide, ammonium iodide, cuprous chloride, cupric chloride, cuprous bromide, and cupric bromide. Halogen compounds may be contained as impurities in other components.

[0041] The content of halide ions in the surface treatment agent is not particularly limited, and is, for example, preferably 0.1 mol / L or less (particularly 0 to 0.1 mol / L), more preferably 0.05 mol / L or less (particularly 0 to 0.05 mol / L), even more preferably 0.02 mol / L or less (particularly 0 to 0.02 mol / L), and particularly preferably 0.01 mol / L or less (particularly 0 to 0.01 mol / L).

[0042] Copper ions can increase the strength of chemical conversion coatings and the adhesive strength between metals and resins. The valence of copper ions can be monovalent or divalent. Examples of substances that generate copper ions include metallic copper, copper sulfate (and its hydrates (particularly the pentahydrate)), copper formate (and its hydrates (particularly the tetrahydrate)), copper nitrate, cuprous chloride, cupric chloride, copper acetate (and its hydrates (particularly the monohydrate)), copper hydroxide, copper oxide, copper sulfide, copper carbonate, cuprous bromide, cupric bromide, copper phosphate, and copper benzoate. The copper ions in the surface treatment agent may also include copper ions eluted from metallic copper or copper oxide contained in the copper circuit during treatment of the copper circuit with the surface treatment agent.

[0043] The content of copper ions in the surface treatment agent is not particularly limited, and is, for example, preferably 1 mol / L or less (particularly 0 mol / L or more and 1 mol / L or less), more preferably 0.5 mol / L or less (particularly 0 mol / L or more and 0.5 mol / L or less), even more preferably 0.1 mol / L or less (particularly 0 mol / L or more and 0.1 mol / L or less), and particularly preferably 0.01 mol / L or less (particularly 0 mol / L or more and 0.01 mol / L or less).

[0044] A known coupling agent may be used in combination as long as it does not impair the effects of the present invention. Examples of known coupling agents include silane-based coupling agents having a thiol group (mercapto group), a vinyl group, an epoxy group, a (meth)acrylic group, an amino group, a chloropropyl group, etc., aluminum-based coupling agents, titanium-based coupling agents, and zirconium-based coupling agents.

[0045] Examples of the silane coupling agent include: 3-mercaptopropyltrimethoxysilane, mercaptosilane compounds such as 3-mercaptopropylmethyldimethoxysilane; vinyltrichlorosilane, vinyltrimethoxysilane, vinylsilane compounds such as vinyltriethoxysilane; styrylsilane compounds such as p-styryltrimethoxysilane; 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, epoxysilane compounds such as 3-glycidoxypropyltriethoxysilane; acryloxysilane compounds such as 3-acryloxypropyltrimethoxysilane; 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, methacryloxysilane compounds such as 3-methacryloxypropyltriethoxysilane; N-2-(aminoethyl)-3-aminopropylmethyldimethoxysilane, N-2-(aminoethyl)-3-aminopropyltrimethoxysilane, N-2-(aminoethyl)-3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N-(1,3-dimethyl-butylidene)propylamine, N-phenyl-3-aminopropyltrimethoxysilane, aminosilane compounds such as N-(vinylbenzyl)-2-aminoethyl-3-aminopropyltrimethoxysilane; ureidosilane compounds such as 3-ureidopropyltriethoxysilane; chloropropylsilane compounds such as 3-chloropropyltrimethoxysilane; Sulfide silane compounds such as bis(triethoxysilylpropyl)tetrasulfide, and Examples include isocyanatosilane compounds such as 3-isocyanatopropyltriethoxysilane.

[0046] The surface treatment agent of the present invention can usually be adjusted to a pH of -1 to 12. The surface treatment agent of the present invention preferably has a pH of 3 to 11.5. If it is in the acidic range, it more preferably has a pH of 3 to 7, and if it is in the basic range, it more preferably has a pH of 8 to 11.5, and even more preferably has a pH of 8.5 to 9.5.

[0047] In addition to the above, the surface treatment agent of the present invention may contain appropriate additives depending on the type of material to be treated (described later) to be treated, the intended use, etc.

[0048] (Material to be treated) Materials to be treated to which the surface treatment agent of the present invention is applied include, for example, granular, needle-like, fibrous, thin film, plate-like, and amorphous materials formed from metals, inorganic materials, resin materials, etc.

[0049] Examples of the metal include copper, aluminum, titanium, nickel, tin, iron, silver, gold, and alloys thereof. Specific examples of the alloy include copper alloys, but are not limited to those containing copper. Examples include Cu-Ag, Cu-Te, Cu-Mg, Cu-Sn, Cu-Si, Cu-Mn, Cu-Be-Co, Cu-Ti, Cu-Ni-Si, Cu-Zn-Ni, Cu-Cr, Cu-Zr, Cu-Fe, Cu-Al, Cu-Zn, and Cu-Co alloys. Other alloys include aluminum alloys (Al-Si alloys), nickel alloys (Ni-Cr alloys), and iron alloys (Fe-Ni alloys, stainless steel). Among these metals, copper and copper alloys are preferred. Examples of metal forms include foils (e.g., electrolytic copper foils and rolled copper foils) used in electronic devices such as printed wiring boards and lead frames, decorative items, and building materials; plated films (e.g., electroless copper plating films and electrolytic copper plating films); thin films formed by vapor deposition, sputtering, damascene, etc.; and metals used in applications and forms such as granular, needle-like, fibrous, wire-like, rod-like, tubular, and plate-like. In the case of copper wiring through which recent high-frequency electrical signals flow, it is preferable that the copper surface be smooth with an average roughness of 0.1 μm or less. The copper surface may be plated with nickel, zinc, chromium, tin, etc. as a pretreatment.

[0050] Examples of the inorganic materials include silicon, ceramics, carbon used as fillers, inorganic salts, and glass. Specific examples include silicon compounds such as silicon, silicon carbide, silica, glass, diatomaceous earth, calcium silicate, talc, glass beads, sericite activated clay, and bentonite; oxides such as alumina, zinc oxide, iron oxide, magnesium oxide, tin oxide, and titanium oxide; hydroxides such as magnesium hydroxide, aluminum hydroxide, and basic magnesium carbonate; carbonates such as calcium carbonate, zinc carbonate, hydrotalcite, and magnesium carbonate; sulfates such as barium sulfate and gypsum; titanates such as barium titanate; nitrides such as aluminum nitride and silicon nitride; graphites such as flake graphite (natural graphite), expanded graphite, and expanded graphite (synthetic graphite); activated carbons; carbon fibers; and carbon black. Among these inorganic materials, silicon, ceramics (alumina, silicon carbide, aluminum nitride, silicon nitride, and barium titanate), glass, and inorganic salts are preferred.

[0051] The resin material may be either a thermoplastic resin or a thermosetting resin. Specific examples include acrylate resins, epoxy resins, polyimide resins, bismaleimide resins, maleimide resins, cyanate resins, polyphenylene ether resins, polyphenylene oxide resins, olefin resins, fluorine-containing resins, polyetherimide resins, polyether ether ketone resins, and liquid crystal resins, all of which have excellent heat resistance and insulating properties. These resins may be mixed or modified to form a combination. Furthermore, the degree of polymerization of these resins is not particularly limited, and they may be appropriately polymerized (cured) after surface treatment. Among these resin materials, acrylate resins, epoxy resins, and polyimide resins are preferred.

[0052] (Surface treatment method) The method for contacting the surface treatment agent of the present invention with the surface of the workpiece is not particularly limited, and methods such as immersion, coating, and spraying can be used. The time for which the surface treatment agent is in contact with the workpiece (treatment time) is preferably 1 second to 10 minutes, and more preferably 5 seconds to 3 minutes. If the treatment time is less than 1 second, the film formed on the surface of the workpiece will be thin, and sufficient adhesive strength between different materials will not be obtained. On the other hand, if the treatment time is longer than 10 minutes, there will be no significant difference in the film thickness, and no improvement in adhesiveness can be expected. In addition, the temperature of the surface treatment agent when contacting it with the surface of the workpiece is preferably 5 to 50°C, but this may be set appropriately in relation to the treatment time.

[0053] After contacting the material to be treated with the surface treatment agent of the present invention, the material may be washed with water and then dried, or may be dried without being washed with water. The drying temperature is preferably in the range of room temperature to 150°C. The water used for washing is preferably pure water such as ion-exchanged water or distilled water, but there are no particular restrictions on the method or time of washing, and it may be sprayed, immersed, or other means for an appropriate time.

[0054] When the surface treatment agent of the present invention is brought into contact with a metal surface, an aqueous solution containing copper ions may be brought into contact with the metal surface beforehand. This aqueous solution containing copper ions serves to uniformize the thickness (film thickness) of the coating formed on the metal surface. The copper ion source for the aqueous solution containing copper ions is not particularly limited as long as it is a copper salt that dissolves in water, and examples thereof include copper salts such as copper sulfate, copper nitrate, copper chloride, copper formate, and copper acetate. Ammonia or hydrochloric acid may be added to solubilize the copper salt in water. Furthermore, after the surface treatment agent of the present invention has been brought into contact with the metal surface, an acidic or alkaline aqueous solution may be brought into contact with the metal surface. This acidic or alkaline aqueous solution also serves to uniformize the thickness of the coating formed on the metal surface, similar to the aqueous solution containing copper ions. The acidic and alkaline aqueous solutions are not particularly limited, but examples of acidic aqueous solutions include aqueous solutions containing mineral acids such as sulfuric acid, nitric acid, and hydrochloric acid, and aqueous solutions containing organic acids such as formic acid, acetic acid, lactic acid, glycolic acid, and amino acids. Examples of alkaline aqueous solutions include aqueous solutions containing alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, and amines such as ammonia, ethanolamine, and monopropanolamine.

[0055] The surface treatment agent of the present invention can be used to treat the surface of at least one workpiece selected from the group consisting of metals, inorganic materials, and resin materials. By treating the surface of a workpiece using the surface treatment agent of the present invention, a film is formed on the surface of the workpiece, improving adhesion to other materials. This film has high heat resistance, and maintains its adhesive strength even after solder reflow heating (approximately 260°C). To enhance the effects of this treatment, the surface-treated workpiece may be heat-treated.

[0056] (Adhesion method) Two materials selected from the metals, inorganic materials, and resin materials described above can be bonded using the surface treatment agent of the present invention. By bonding the two materials via a film formed by the surface treatment agent of the present invention, their mutual affinity can be improved, allowing for stronger bonding even between materials of different properties. The thickness of the film is preferably 0.0001 to 1 μm, and more preferably 0.001 to 0.5 μm.

[0057] As the adhesion method, known methods can be adopted, including, for example, a method in which the surface treatment agent of the present invention is brought into contact with the surface of a material to be treated selected from metals, inorganic materials, and resin materials to form a film, and then another material to be treated is applied to part or all of the formed film, pressed, mixed, or the like, or an adhesive, an adhesive sheet (film), or a combination of these methods is used for adhesion.

[0058] Another example is a method in which the surface treatment agent of the present invention is brought into contact with the surfaces of two treated materials selected from metals, inorganic materials, and resin materials to form a film on each surface of the two treated materials, and the two treated materials are then bonded together by means of pressing or mixing, or by using an adhesive or an adhesive sheet (film), or by a combination of these means.

[0059] (Use of surface treatment agents) As described above, the surface treatment agent of the present invention can be used to bond two materials, particularly two materials of different properties, and can therefore be suitably used in the production of materials for electrical and electronic applications (electronic devices such as various electrical and electronic components and printed wiring boards), construction, civil engineering, automotive, medical, and other applications.

[0060] The surface treatment agent of the present invention can be suitably used for a treated material formed of a metal, particularly copper or a copper alloy. For example, it is suitable for the purpose of improving the adhesion (adhesion) between a copper circuit (copper wiring layer) and a semi-cured or cured prepreg, solder resist, or semi-cured or cured dry film (insulating resin layer), and can improve the adhesion between the copper wiring layer and the insulating resin layer in a printed wiring board having an insulating resin layer in contact with the copper wiring layer.

[0061] Examples of applications of the surface treatment agent of the present invention include copper foil, prepreg, copper-clad laminate, and sheet-like members treated with the surface treatment agent; resin-coated copper foil in which copper foil and a resin layer are laminated via a film made of the surface treatment agent; and printed wiring boards equipped with these members.

[0062] The printed wiring board can be produced, for example, by contacting the surface of a copper wiring layer formed on a copper-clad laminate with the surface treatment agent of the present invention, followed by rinsing with water and drying, and then forming an insulating resin layer on the surface of the copper wiring layer. The contacting method is as described above, and immersing the copper wiring layer in the surface treatment agent or spraying the surface of the copper wiring layer with the surface treatment agent is simple, reliable, and preferable.

[0063] The water washing method is not particularly limited, but immersing the copper wiring layer in washing water or spraying the surface of the copper wiring layer with washing water is simple, reliable, and preferred. The insulating resin layer can be formed by known methods, such as applying a semi-cured resin material or applying a liquid resin material containing a solvent. Next, via holes are formed to connect the upper and lower wiring. By repeating this process, a multilayer printed wiring board can be manufactured.

[0064] The copper wiring layer may be produced by any method such as electroless plating, electrolytic plating, vapor deposition, sputtering, or damascene, and may include inner via holes, through holes, connection terminals, etc.

[0065] Japanese Patent Application Laid-Open Publication No. 2009-19266 describes a method for forming a silane coupling agent film, which comprises the steps of applying a liquid containing a silane coupling agent to a metal surface, drying the applied metal surface at a temperature of 25 to 150°C for 5 minutes or less, and rinsing the dried metal surface with water. It also states that the metal surface may be pre-treated by forming an adhesive metal layer such as tin using an immersion plating solution. The surface treatment agent of the present invention can be used as the liquid containing the silane coupling agent. The disclosure of this patent publication is incorporated herein by reference.

[0066] 4.Resin composition The resin composition of the present invention contains the compound of the present invention and a resin or a curable compound. The resin composition of the present invention may contain one or more compounds of the present invention.

[0067] The "resin or curable compound" includes a thermoplastic resin, a thermo- or actinic ray-curable resin monomer, and a partially polymerized or semi-cured product of the monomer. In the case of a thermo- or actinic ray-curable resin, the resin may be in any of the A-stage, B-stage, and C-stage states.

[0068] Examples of such "resins or curable compounds" include acrylate resins, epoxy resins, polyimide resins, bismaleimide resins, maleimide resins, cyanate resins, polyphenylene ether resins, polyphenylene oxide resins, olefin resins, fluorine-containing resins, polyetherimide resins, polyether ether ketone resins, and liquid crystal resins, all of which have excellent heat resistance and insulating properties. These may also be mixed or modified and combined. Of these, acrylate resins, epoxy resins, and polyimide resins are preferred.

[0069] The content of the compound of the present invention in the resin composition of the present invention is preferably in the range of 0.001 to 10% by weight, more preferably in the range of 0.01 to 5% by weight. If the content of the compound of the present invention is less than 0.001% by weight, the effect of improving adhesion is insufficient, and if the content exceeds 10% by weight, the effect of improving adhesion almost levels off, and the amount of triazine compound used simply increases, which is uneconomical.

[0070] In addition to the compound of the present invention and the resin or curable compound, the resin composition of the present invention may contain appropriate amounts of solvents (water, organic solvents, mixtures of water and organic solvents), additives (curing agents, curing accelerators, flame retardants, dyes, pigments, UV absorbers, lubricants, fillers, etc.) depending on the intended use, etc. The organic solvents that can be used are those described in the section 3. Surface Treatment Agent above.

[0071] The resin composition of the present invention can be prepared by a known method. For example, the compound of the present invention can be dissolved in an organic solvent and mixed with a solid or liquid resin or curable compound. Alternatively, the compound of the present invention may be directly added to a resin or curable compound and mixed to prepare the resin composition.

[0072] (Use of resin composition) Since the resin composition of the present invention contains the compound of the present invention, the cured resin layer adheres (bonds) with high strength to adjacent (contacting) layers or members, such as layers or members of metal or inorganic materials, and can therefore be suitably used in the production of materials for various electrical and electronic applications (electrical and electronic components, electronic devices such as printed wiring boards), construction, civil engineering, automotive, medical, and other applications.

[0073] Specific examples of the use of the resin composition of the present invention include a solder resist ink containing the resin composition of the present invention as a component, a printed wiring board comprising a solder resist layer formed from the solder resist ink, a prepreg composed of a substrate (paper, glass cloth, glass nonwoven fabric, etc.) and the resin composition of the present invention, a copper-clad laminate composed of the prepreg and copper foil, a resin-coated copper foil composed of copper foil and a resin layer formed from the resin composition of the present invention, a printed wiring board comprising a resin layer formed from the resin composition of the present invention, and a semiconductor encapsulating material containing the resin composition of the present invention as a component.

[0074] The solder resist layer can be obtained by applying the solder resist ink onto a suitable substrate, drying the ink to form a resin layer, and curing the resin layer with heat or active energy rays. The printed wiring board can be produced by a known method using the solder resist ink. The prepreg can be produced, for example, by applying the resin composition of the present invention to a substrate (paper, glass cloth, glass nonwoven fabric, etc.) or by immersing the substrate in the resin composition of the present invention to impregnate it. The copper-clad laminate can be produced by laminating the prepreg and copper foil. The resin-coated copper foil can be produced by applying the resin composition of the present invention onto a copper foil, followed by drying, semi-curing or curing. In the printed wiring board, examples of the "resin layer formed from the resin composition of the present invention" include the resins in the solder resist, prepreg, resin-coated copper foil, etc. The resin composition of the present invention can also be used as a semiconductor encapsulating material.

[0075] Furthermore, since excellent adhesive properties, heat resistance, insulating properties, and the like can be imparted to members to which the surface treatment agent or resin composition of the present invention is applied, by adding an appropriate auxiliary as necessary, the resulting products can be used as conductive pastes, underfills, die attach materials, semiconductor chip mounting materials, non-conductive adhesives, liquid crystal sealants, display materials, reflectors, paints, adhesives, varnishes, elastomers, inks, waxes, sealants, and the like. [Example]

[0076] The present invention will be specifically described below with reference to examples and comparative examples, but the present invention is not limited to these. The main raw materials used in the examples are as follows.

[0077] [Main raw materials] 2,3,5-Triiodobenzoic acid (see chemical formula (II-8), manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) 3-Aminopropyltriethoxysilane (see chemical formula (III-3), manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) 4-(N,N-dimethylamino)pyridine (Fujifilm Wako Pure Chemical Industries, Ltd.) 1,3-Diisopropylcarbodiimide (Fujifilm Wako Pure Chemical Industries, Ltd.)

[0078] The silane compounds used in the comparative examples (evaluation tests) are as follows: N-[3-(triethoxysilyl)propyl]benzamide (see chemical formula (1), synthesized according to the method described in Catalysis Letters (2016), 146(9), 1718-1728; hereinafter referred to as "silane compound 1") 4-Iodo-N-[3-(triethoxysilyl)propyl]benzamide (see chemical formula (2), synthesized according to the method described in Advanced Synthesis & Catalysis (2012), 354(2-3), 313-320; hereinafter referred to as "silane compound 2")

[0079] [ka]

[0080] The evaluation test methods (surface free energy measurement) employed in the examples and comparative examples are as follows.

[0081] [Surface free energy measurement] The M side of a 4 cm x 4 cm electrolytic copper foil (thickness: 33 μm) was plated with brass, and then plated with a mixture of zinc and chromium oxide to prepare a test specimen. The test specimen was then immersed in a surface treatment agent (room temperature x 5 minutes), removed and drained, then immersed in THF to remove excess surface treatment agent, and dried at room temperature for 24 hours. The surface free energy dispersion force component γ was measured for the S side of the test specimen treated with the surface treatment agent using a contact angle meter (DropMaster 500, manufactured by Kyowa Interface Science). d and polar force component γ p The contact angles of the test piece surfaces were measured using water and diiodomethane, the contact angles of which were known. From the contact angle results, the γ value of the solid surface was calculated using Owen's approximation formula. S d and γ S p Calculate the surface free energy γ S was calculated. gamma S =γ S d +γ S p

[0082] Example 1 Synthesis of 2,3,5-triiodo-N-[3-(triethoxysilyl)propyl]benzamide A 500 mL flask was charged with 14.99 g (30 mmol) of 2,3,5-triiodobenzoic acid, 0.37 g (3 mmol) of 4-(N,N-dimethylamino)pyridine, 7.97 g (36 mmol) of 3-aminopropyltriethoxysilane, 4.54 g (36 mmol) of 1,3-diisopropylcarbodiimide, and 300 g of chloroform, and the resulting mixture was stirred for 20 hours at 40° C. The resulting reaction solution was concentrated and purified by silica gel column chromatography (chloroform / ethanol = 10 / 1 (wt / wt)), yielding 6.75 g of a pale yellow solid (yield: 32%).

[0083] The resulting pale yellow solid 1 The H-NMR spectrum data was as follows: · 1 H-NMR(DMSO-d6) δ: 8.43(t, 1H), 8.26(d, 1H), 7.49(d, 1H), 3.75(q, 6H), 3.15(dt, 2H), 1.56(quin., 2H), 1.15(t, 9H), 0.62(t, 2H). From these spectral data, the obtained pale yellow solid was identified as the title compound represented by chemical formula (I-8).

[0084] Example 2 THF and ion-exchanged water were mixed in a ratio of 95:5, and the pH was adjusted to 4.5 using acetic acid. To this solution, 2,3,5-triiodo-N-[3-(triethoxysilyl)propyl]benzamide synthesized in Example 1 was added so as to give a concentration of 2% by weight, and the mixture was stirred at room temperature for 5 minutes to prepare a surface treatment agent. This surface treatment agent was used to carry out an evaluation test (measurement of surface free energy), and the test results obtained are shown in Table 1.

[0085] Comparative Example 1 An evaluation test (surface free energy measurement) was carried out using a test piece that had not been treated with a surface treatment agent, and the test results obtained are as shown in Table 1.

[0086] Comparative Examples 2 and 3 Surface treatment agents were prepared in the same manner as in Example 2, except that the silane compounds shown in Table 1 were used instead of 2,3,5-triiodo-N-[3-(triethoxysilyl)propyl]benzamide. Evaluation tests (surface free energy measurements) were carried out using these surface treatment agents, and the test results obtained are shown in Table 1.

[0087] [Table 1]

[0088] The test results shown in Table 1 indicate that the use of the compound of the present invention as a surface treatment agent can increase the surface free energy of the substrate surface. Therefore, the use of the compound of the present invention as a component of the surface treatment agent can improve the adhesion between the treated material and resin. [Industrial Applicability]

[0089] The silane compound of the present invention has two or more iodine atoms in the molecule, and when used as a component of a surface treatment agent, it is expected to increase the surface free energy of the treated surface of the treated material and improve the adhesion between the treated material and resin. Therefore, it is possible to sufficiently ensure adhesion with resin while maintaining a smooth surface of the treated material without roughening the surface. Therefore, the present invention can greatly contribute to the realization of smaller, thinner, higher frequency, higher density, etc., electronic components and devices, and is therefore highly applicable in industry.

Claims

1. A silane compound represented by chemical formula (I): 【Chemical 1】 (In the formula, R １ are the same or different and represent a hydrogen atom or an alkyl group having 1 to 3 carbon atoms; R ２ represents an alkyl group having 1 to 3 carbon atoms or a phenyl group, and R ３ represents a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, or a phenyl group, and X represents an iodine atom. n represents an integer of 1 to 5, m represents an integer of 2 to 5, and p represents an integer of 1 to 3.

2. A surface treatment agent containing the compound according to claim 1.

3. The surface treatment agent according to claim 2, which is used to treat the surface of at least one material selected from the group consisting of metals, inorganic materials, and resin materials.

4. A bonding method comprising contacting the surface treatment agent according to claim 2 with at least one material selected from the group consisting of metals, inorganic materials, and resin materials to form a chemical conversion coating on at least one of the materials, and bonding the materials together via the chemical conversion coating.

5. A printed wiring board, characterized in that two materials selected from the group consisting of metals, inorganic materials, and resin materials are bonded via a chemical conversion coating formed by the surface treatment agent according to claim 2.

6. A resin composition comprising the compound according to claim 1 and a resin or a curable compound.

7. A cured product obtained by curing the resin composition according to claim 6.

Images