Silane compounds and their uses

Abstract

The present invention aims to provide novel silane compounds and their applications. Specifically, it aims to provide novel silane compounds, surface treatment agents containing the silane compounds and methods for bonding them, resin compositions containing the silane compounds and their cured products. [Solution] A silane compound represented by chemical formula (I). [Formula 1] TIFF2026103006000013.tif22136 (in the formula, R 1 R represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, either identical or different. 2 R represents an alkyl group or phenyl group having 1 to 3 carbon atoms. 3 (where 'n' represents a hydrogen atom, an alkyl group with 1 to 3 carbon atoms, or a phenyl group; 'X' represents an iodine atom; 'n' represents an integer from 1 to 5; 'm' represents an integer from 2 to 5; and 'p' represents an integer from 1 to 3.)

Description

[Technical Field]

[0001] This invention relates to novel silane compounds and the use of said compounds. [Background technology]

[0002] In recent years, printed circuit boards (PCBs) have been increasingly multilayered to accommodate the miniaturization and thinning of electronic devices and components. So-called multilayer PCBs are manufactured by layering an outer circuit board or copper foil onto an inner circuit board, which has circuits made of copper foil on one or both sides, via a prepreg, and then integrating them. However, in such multilayer PCBs, ensuring adhesion between the copper circuits formed on the inner circuit board and the insulating adhesive resin of the prepreg that laminates the outer circuit board or copper foil is a crucial challenge.

[0003] Patent Document 1 describes an invention relating to a copper foil surface treatment agent that improves the adhesion 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 that the surface treatment agent uses a combination of a trialkoxysilane compound having an imidazole ring and a tetraalkoxysilane compound as components. However, surface treatment agents containing these silane compounds still had room for improvement in terms of adhesion.

[0004] Patent Document 2 describes an invention relating to a silane coupling agent and a polymer composition. This document discloses various substances used as components of silane coupling agents for bonding glass or metal to rubber, in which nitrogen-containing heterocycles such as triazole and thiadiazole are bonded to silyl groups such as trimethoxysilyl and triethoxysilyl groups via organic groups. However, polymer compositions containing these silane compounds still had room for improvement in terms of adhesive properties. [Prior art documents] [Patent Documents]

[0005] [Patent Document 1] Japanese Patent Application Publication No. 7-286160 [Patent Document 2] Japanese Patent Publication No. 2002-363189 [Overview of the project] [Problems that the invention aims to solve]

[0006] The present invention aims to provide novel silane compounds and their applications. Specifically, it aims to provide novel silane compounds, surface treatment agents containing the silane compounds and methods for bonding them, resin compositions containing the silane compounds and their cured products. [Means for solving the problem]

[0007] The present inventors conducted extensive research to solve the aforementioned problems and discovered that a silane compound having two or more iodine atoms in its molecule is a novel compound, and that treating the surface of a material with a surface treatment agent containing this compound increases the surface free energy of the surface (for example, the contact angle decreases), thus completing the present invention. In other words, the first invention is a silane compound represented by chemical formula (I).

[0008] [ka] (In the formula, R 1 R represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, either identical or different. 2 R represents an alkyl group or phenyl group having 1 to 3 carbon atoms. 3 (where 'n' represents a hydrogen atom, an alkyl group with 1 to 3 carbon atoms, or a phenyl group; 'X' represents an iodine atom; 'n' represents an integer from 1 to 5; 'm' represents an integer from 2 to 5; and 'p' represents an integer from 1 to 3.)

[0009] The second invention is a surface treatment agent containing the compound of the first invention. The third invention is a surface treatment agent of the second invention, which is characterized by being used for treating at least one surface selected from the group consisting of metals, inorganic materials, and resin materials. The fourth invention is an adhesion method characterized by bringing the surface treatment agent of the second invention into contact with at least one selected from the group consisting of metals, inorganic materials, and resin materials to form a chemical conversion film on the at least one surface, and bonding them to each other through the chemical conversion film. The 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 through a chemical conversion film formed by the surface treatment agent of the second invention. The sixth invention is a resin composition containing the compound of the first invention and a resin or a curable compound. The seventh invention is a cured product obtained by curing the resin composition of the sixth invention.

Advantages of the Invention

[0010] Since the silane compound of the present invention has a silyl group (-Si(OR 1 ) p (R 2 ) 3-p / wherein R 1 , R 2 and p are the same as described above.) in the molecule, it is expected to be used as a component of a surface treatment agent or a raw material of a resin composition. And, 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 can increase the surface free energy of the surface of the treated material to be treated compared with the case of using a conventional silane compound (silane coupling agent), and it is expected to improve the adhesion between the material to be treated and the resin. Further, when the silane compound of the present invention is used as a raw material of a resin composition, the intermolecular interaction between the resin or the curable compound and the silane compound of the present invention is enhanced, so that the surface free energy of the resin composition itself increases, and it is expected to obtain a uniform cured product.

Embodiments for Carrying Out the Invention

[0011] The present invention will be described in detail below. 1. Silane compound 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 formula (I-1) to chemical formula (I-47).

[0012]

Chemical formula

[0013] <000010,7>

Chemical formula

[0014]

Chemical formula

[0015]

Chemical formula

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

[0017] 2.Synthesis method The compounds 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 as described above.)

[0019] Aromatic carboxylic acids represented by chemical formula (II) include those represented by chemical formulas (II-1) to (II-16).

[0020] [ka]

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

[0022] Examples of aminoalkylsilanes represented by chemical formula (III) include those represented by chemical formulas (III-1) to (III-32).

[0023] [ka]

[0024] [ka]

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

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

[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)carbodiimidemethiozide, 1-cyclohexyl-3-(2-morpholinoethyl)carbodiimidemetho-p-toluenesulfonate, and 1-hydroxybenzotriazole. Examples include diphenyl phosphate azide, hexafluorophosphate (benzotriazole-1-yloxy) tripyrrolidinophosphonium (PyBOP), hexafluorophosphate (7-azabenzotriazole-1-yloxy) tripyrrolidinophosphonium (PyAOP), hexafluorophosphate bromotris(dimethylamino)phosphonium (BroP), hexafluorophosphate chlorotrispirolidinophosphonium (PyCloP), hexafluorophosphate bromotrisspirolidinophosphonium (PyBroP), and 3-(diethoxyphosphoryloxy)-1,2,3-benzotriazine-4(3H)-one (BEPBT). These may be used individually or in combination of two or more. The amount of condensing agent (i) used (charged) is preferably in an appropriate ratio within the range of 0.1 to 10 times the molar amount of the aromatic carboxylic acid shown in chemical formula (II).

[0028] In carrying out this reaction, a base (ii) may be used to accelerate the reaction. Additionally, a reaction solvent (iii) may be used as appropriate, if necessary.

[0029] Examples of bases (ii) include trimethylamine, triethylamine, tributylamine, N,N-diisopropylethylamine, N-methylmorpholine, 1,5-diazabicyclo[4.3.0]nona-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, sodium carbonate Examples include potassium carbonate, cesium carbonate, lithium bicarbonate, sodium bicarbonate, potassium bicarbonate, cesium bicarbonate, trilithium phosphate, trisodium phosphate, tripotassium phosphate, tricesium phosphate, dilithium hydrogen phosphate, disodium hydrogen phosphate, dipotassium hydrogen phosphate, dicesium hydrogen phosphate, lithium dihydrogen phosphate, sodium dihydrogen phosphate, potassium dihydrogen phosphate, cesium dihydrogen phosphate, lithium acetate, sodium acetate, potassium acetate, cesium acetate, lithium alkoxide (lithium methoxide, etc.), sodium alkoxide (sodium methoxide, sodium ethoxide, etc.), potassium alkoxide (t-butoxypotassium, etc.), etc. These may be used individually or in combination of two or more. The amount of base (ii) used (charged) is preferably in an appropriate ratio within the range of 0.1 to 10 times the molar amount of the aromatic carboxylic acid represented by chemical formula (II).

[0030] The reaction solvent (iii) is not particularly limited as long as it does not inhibit the reaction, and examples include methanol, ethanol, propanol, tetrahydrofuran, dioxane, ethyl acetate, acetone, acetonitrile, benzene, toluene, xylene, dichloromethane, chloroform, carbon tetrachloride, tetrachloroethane, dichlorobenzene, dimethylformamide, dimethylacetamide, dimethyl sulfoxide, hexamethylphosphate triamide, etc., and these can be combined as needed 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 set appropriately according to the set reaction temperature, but it is preferably set in the range of 1 to 96 hours.

[0032] After the reaction is complete, the compound of the present invention, which is the target product, can be extracted from the resulting reaction solution by means of, for example, concentration of the reaction solution by distillation of the reaction solvent or solvent extraction. Furthermore, if necessary, the product can be purified using methods such as washing with water, activated carbon treatment, silica gel chromatography, and recrystallization.

[0033] 3. Surface treatment agent The surface treatment agent of the present invention contains the compound of the present invention, but may contain one or more of the 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 solvents include water, organic solvents, and mixtures of water and organic solvents. Furthermore, a solubilizer (acid, alkali) can be used to promote the dissolution (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 solubilizer using appropriate means.

[0034] Examples of the aforementioned organic solvents 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 include 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, 1,3-dimethyl-2-imidazolidinone, etc. These organic solvents may be used individually or in combination of two or more.

[0035] Examples of the aforementioned acids include inorganic acids such as hydrochloric acid, sulfuric acid, nitric acid, and phosphoric acid, as well as 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 individually or in combination of two or more.

[0036] Examples of the alkalis mentioned above 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, trippropanolamine, monoisopropanolamine, diisopropanolamine, triisopropanolamine, 2-amino-1-propanol, N,N-dimethylethanolamine, cyclohexylamine, aniline, pyrrolidine, piperidine, piperazine, and pyridine. These alkalis may be used individually or in combination of two or more.

[0037] When using a mixture of water and an organic solvent 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, or 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, pure water such as ion-exchanged water or distilled water is preferred as the water used in preparing the surface treatment agent.

[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 adhesive improvement effect will not be sufficiently obtained, and if it exceeds 20% by weight, the adhesive improvement effect will almost plateau, and the amount of the compound of the present invention used will only increase, which is not economical.

[0039] To improve the stability of surface treatment agents and the uniformity of chemical conversion films, substances that generate halide ions such as fluoride ions, chloride ions, bromide ions, and iodide ions, as well as metal ions such as copper ions, iron ions, and zinc ions, can also be used.

[0040] Halide ions have the effect of uniformly forming flat surfaces in the 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, cupric bromide, etc. Halogen compounds may also be present as impurities in other components.

[0041] The content of halide ions in the surface treatment agent is not particularly limited, but is 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 enhance the adhesive strength between metals and resins. The valence of copper ions can be either monovalent or divalent. Examples of substances that generate copper ions include metallic copper, copper sulfate (and its hydrates, especially pentahydrate), copper formate (and its hydrates, especially tetrahydrate), copper nitrate, cuprous chloride, cupric chloride, copper acetate (and its hydrates, especially monohydrate), copper hydroxide, copper oxide, copper sulfide, copper carbonate, cuprous bromide, cupric bromide, copper phosphate, and copper benzoate. Furthermore, the copper ions in the surface treatment agent may include copper ions that have eluted from metallic copper or copper oxide contained in the copper circuit during the treatment of the copper circuit with the surface treatment agent.

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

[0044] Furthermore, known coupling agents may be used in combination, to the extent that they do not impair the effects of the present invention. Examples of known coupling agents include silane-based coupling agents having thiol groups (mercapto groups), vinyl groups, epoxy groups, (meth)acrylic groups, amino groups, chloropropyl groups, etc., aluminum-based coupling agents, titanium-based coupling agents, zirconium-based coupling agents, and the like.

[0045] Examples of the silane coupling agent mentioned above include, 3-mercaptopropyltrimethoxysilane, Mercaptosilane compounds such as 3-mercaptopropylmethyldimethoxysilane, Vinyltrichlorosilane, Vinyltrimethoxysilane, Vinyl silane 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-dimethylbutylidene)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, Sulfidosilane 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. Preferably, the surface treatment agent of the present invention has a pH of 3 to 11.5. More preferably, if it is in the acidic range, it has a pH of 3 to 7, if it is in the basic range, it has a pH of 8 to 11.5, and even more preferably, it 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), its application, etc.

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

[0049] Examples of the aforementioned metals include copper, aluminum, titanium, nickel, tin, iron, silver, gold, and alloys thereof. Specific examples of these alloys include copper alloys, which are not particularly limited as long as they contain copper, such as 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. Furthermore, examples of metal forms include foils (e.g., electrolytic copper foil, rolled copper foil) used in electronic devices such as printed circuit boards and lead frames, decorative items, and building materials; plating films (e.g., electroless copper plating films, electrolytic copper plating films); thin films formed by vapor deposition, sputtering, damascene methods, etc.; and metals used in various applications and forms such as granular, needle-shaped, fibrous, linear, rod-shaped, tubular, and plate-shaped. In the case of copper wiring carrying high-frequency electrical signals in recent years, it is preferable that the copper surface be a smooth surface 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 aforementioned inorganic materials include silicon, ceramics, carbon used as a filler, inorganic salts, and glass. Specifically, these 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 aforementioned resin material may be either a thermoplastic resin or a thermosetting resin. Specifically, 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, polyetheretherketone resins, and liquid crystal resins, which have excellent heat resistance and insulation properties. These may be mixed or modified and combined. Furthermore, there are no particular restrictions on the degree of polymerization of these resins, and they may be polymerized (cured) as appropriate after surface treatment. Among these resin materials, acrylate resins, epoxy resins, and polyimide resins are preferred.

[0052] (Surface treatment method) There are no particular limitations on the method for bringing the surface treatment agent of the present invention into contact with the surface of the material to be treated; immersion, coating, spraying, and other methods can be employed. The contact time between the surface treatment agent and the material to be treated (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 thickness formed on the surface of the material to be treated will be thin, and sufficient adhesion between materials of different materials cannot be obtained. On the other hand, if the contact time is longer than 10 minutes, there will be no significant difference in the film thickness, and no improvement in adhesion can be expected. Furthermore, the temperature of the surface treatment agent when it is brought into contact with the surface of the material to be treated is preferably 5 to 50°C, but it can be set appropriately in relation to the above-mentioned treatment time.

[0053] After the surface treatment agent of the present invention comes into contact with the material to be treated, it may be washed with water and then dried, or it may be dried without washing with water. The drying temperature is preferably in the range of room temperature to 150°C. While pure water such as deionized water or distilled water is preferred for washing, there are no particular restrictions on the washing method or duration; it may be done for an appropriate amount of time by means such as spraying or immersion.

[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 has the function of making the thickness (film thickness) of the film formed on the metal surface uniform. 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 include 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. Alternatively, after bringing the surface treatment agent of the present invention into contact with the metal surface, an acidic aqueous solution or an alkaline aqueous solution may be brought into contact with the metal surface. This acidic aqueous solution or alkaline aqueous solution also has the function of making the thickness of the film formed on the metal surface uniform, similar to the aqueous solution containing copper ions described above. The acidic aqueous solution and alkaline aqueous solution 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 aforementioned metals, inorganic materials, and resin materials. By treating the surface of a workpiece with the surface treatment agent of the present invention, a film is formed on the surface of the workpiece, improving its adhesion to other materials. This film has high heat resistance, and the adhesive strength is maintained even by solder reflow heating (around 260°C), for example. In addition, to enhance the effect of this treatment, the surface-treated workpiece may be heat-treated.

[0056] (Adhesion method) Two materials selected from the aforementioned metals, inorganic materials, and resin materials can be bonded together 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 affinity for each other can be improved, allowing for stronger bonding even between materials of different materials. The thickness of the film is preferably 0.0001 to 1 μm, and more preferably 0.001 to 0.5 μm.

[0057] As for bonding methods, known methods can be employed. For example, a surface treatment agent of the present invention may be brought into contact with the surface of a material to be treated, selected from metals, inorganic materials, and resin materials, to form a film. Other methods include applying, pressing, or mixing other materials to a part or the entirety of the formed film, or using adhesives, adhesive sheets (films), or a combination of these methods.

[0058] Furthermore, the surface treatment agent of the present invention is brought into contact with the surfaces of two materials to be treated, selected from metal, inorganic material, and resin material, to form a film on each of the two materials, and the two materials are bonded together by means such as pressing or mixing, or by using an adhesive, adhesive sheet (film), or 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 materials, and can therefore be suitably used in the manufacture of materials for electrical and electronic applications (various electrical and electronic components and electronic devices such as printed circuit boards), building applications, civil engineering applications, automotive applications, medical applications, and the like.

[0060] The surface treatment agent of the present invention can be suitably used on materials to be treated that are made of metal, particularly copper or copper alloys. For example, it is suitable when the purpose is to improve the 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 in a printed circuit board having an insulating resin layer in contact with the copper wiring layer, the adhesion between the copper wiring layer and the insulating resin layer can be improved.

[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, as well as resin-coated copper foil in which copper foil and a resin layer are laminated with a film of the surface treatment agent in between, and printed circuit boards equipped with these members.

[0062] The aforementioned printed circuit board can be manufactured, for example, by bringing the surface treatment agent of the present invention into contact with the surface of a copper wiring layer formed on a copper-clad laminate, followed by washing and drying, and then forming an insulating resin layer on the surface of the copper wiring layer. As for the method of contact, as described above, immersion of the copper wiring layer in the surface treatment agent or spraying the surface treatment agent onto the surface of the copper wiring layer is simple, reliable, and preferable.

[0063] Furthermore, there are no particular restrictions on the method of washing, but immersion of the copper wiring layer in washing water or spraying the surface of the copper wiring layer with washing water is simple, reliable, and preferred. For forming the insulating resin layer, known methods can be employed, such as a method of attaching a semi-cured resin material or a means of applying a liquid resin material containing a solvent. Next, via holes are formed to allow electrical conductivity between the upper and lower wiring. By repeating this process, a multilayer printed circuit board can be manufactured.

[0064] The aforementioned copper wiring layer may be manufactured using 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] Incidentally, Japanese Patent Publication No. 2009-19266 describes an invention for a method of forming a silane coupling agent film, characterized by comprising the steps of applying a liquid containing a silane coupling agent to a metal surface, drying the metal surface to which the liquid has been applied at a temperature of 25 to 150°C for no more than 5 minutes, and washing the dried metal surface with water. Furthermore, it is stated 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 described above. The matters described in this patent publication shall be 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 of the compounds of the present invention.

[0067] The aforementioned "resin or curable compound" includes thermoplastic resins, monomers of thermal or active energy ray curable resins, and partially polymerized or semi-cured products of said monomers. In the case of thermal or active energy ray curable resins, they may be in any of the following states: A-stage resin, B-stage resin, or C-stage resin.

[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, polyetheretherketone resins, and liquid crystal resins, all of which have excellent heat resistance and insulation properties. These may be mixed or modified to form combinations. Among 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, and 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 plateaus, and the amount of triazine compound used increases without being economical.

[0070] The resin composition of the present invention may contain, in addition to the compound of the present invention and a resin or curable compound, 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 application. The organic solvent can be any of the organic solvents described in section 3. Surface Treatment Agents above.

[0071] The resin composition of the present invention can be prepared by known methods. For example, it can be prepared by dissolving the compound of the present invention in an organic solvent and mixing it with a solid or liquid resin or curable compound. Alternatively, the resin composition may be prepared by directly adding and mixing the compound of the present invention with a resin or curable compound.

[0072] (Use of resin compositions) Since the resin composition of the present invention contains the compound of the present invention, the cured resin layer adheres with high strength to adjacent (contacting) layers or components, such as metal or inorganic material layers or components. Therefore, it can be suitably used in the manufacture of materials for various electrical and electronic applications (electrical and electronic components, electronic devices such as printed circuit boards), building applications, civil engineering applications, automotive applications, medical applications, and more.

[0073] Specific examples of using the resin composition of the present invention include, for example, a solder resist ink comprising the resin composition of the present invention, a printed circuit board having a solder resist layer formed by 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 by the resin composition of the present invention, a printed circuit board having a resin layer formed by the resin composition of the present invention, and a semiconductor encapsulation material comprising the resin composition of the present invention.

[0074] The aforementioned solder resist layer is obtained by applying the aforementioned solder resist ink onto a suitable substrate, drying it to form a resin layer, and then curing the resulting layer using heat or active energy rays. The aforementioned printed circuit board can be manufactured using the aforementioned solder resist ink by a known method. The aforementioned prepreg can be manufactured, for example, by applying the resin composition of the present invention to a substrate (paper, glass cloth, glass nonwoven fabric, etc.) or by immersing and impregnating the substrate in the resin composition of the present invention. The aforementioned copper-clad laminate can be manufactured by laminating the aforementioned prepreg and copper foil. The aforementioned resin-coated copper foil can be manufactured by applying the resin composition of the present invention onto copper foil and then drying, semi-curing, or curing it. Examples of the "resin layer formed by the resin composition of the present invention" in the printed circuit board mentioned above include the solder resist, prepreg, and resin in the resin-coated copper foil. The resin composition of the present invention can also be used as a semiconductor encapsulation material.

[0075] Furthermore, the surface treatment agent or resin composition of the present invention can be applied to components to which excellent adhesion, heat resistance, insulation, etc. can be imparted. By including appropriate auxiliary agents as needed, it can be used to create 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. [Examples]

[0076] The present invention will be described in detail 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) • 3-aminopropyltriethoxysilane (see chemical formula (III-3), manufactured by Fujifilm Wako Pure Chemical Industries) • 4-(N,N-dimethylamino)pyridine (manufactured by Fujifilm Wako Pure Chemical Industries) • 1,3-Diisopropylcarbodiimide (manufactured by Fujifilm Wako Pure Chemical Industries)

[0078] The silane compounds used in the comparative example (evaluation test) 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 (measurement of surface free energy) methods used in the examples and comparative examples are as follows.

[0081] [Measurement of surface free energy] A 4cm x 4cm electrolytic copper foil (thickness: 33μm) was plated with brass on the M side, and then plated with a mixture of zinc and chromium oxide to create a test specimen. Next, this specimen was immersed in a surface treatment agent (room temperature x 5 minutes), removed, drained, and then immersed in THF to remove excess surface treatment agent. It was then dried at room temperature for 24 hours. For the S side of the surface-treated specimen, a contact angle meter (Kyowa Interface Science, DropMaster 500) was used to measure the surface free energy dispersion force component γ. d and polar force component γ p The contact angles on the specimen surfaces were measured using water and diiodomethane, for which the properties are known. From the obtained contact angle results, the γ of the solid surface was calculated using Owen's approximation formula. S d and gamma S p Calculate the surface free energy γ from the following equation. S The result was calculated. γ S =γ S d +γ S p

[0082] [Example 1] <Synthesis of 2,3,5-triiodo-N-[3-(triethoxysilyl)propyl]benzamide> In a 500 mL flask, 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 were mixed and stirred at 40°C for 20 hours. The resulting reaction mixture was concentrated and purified by silica gel column chromatography (chloroform / ethanol = 10 / 1 (wt / wt)) to obtain 6.75 g of a pale yellow solid (yield: 32%).

[0083] The pale yellow solid obtained 1 The H-NMR spectral data were 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). Based on these spectral data, the obtained pale yellow solid was identified as the compound shown in the title, represented by chemical formula (I-8).

[0084] [Example 2] THF and deionized water were mixed in a 95:5 ratio, 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 to a total weight of 2%, and the mixture was stirred at room temperature for 5 minutes to prepare the surface treatment agent. When an evaluation test (measurement of surface free energy) was performed using this surface treatment agent, the test results obtained are shown in Table 1.

[0085] [Comparative Example 1] Evaluation tests (measurement of surface free energy) were performed using test specimens that had not been treated with a surface treatment agent, and the results obtained are shown in Table 1.

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

[0087] [Table 1]

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

[0089] The silane compound of the present invention, by having two or more iodine atoms in its molecule, is expected to increase the surface free energy of the treated material surface when used as a component of a surface treatment agent, thereby improving the adhesion between the treated material and the resin. Therefore, sufficient adhesion to the resin can be ensured while maintaining a smooth surface without roughening the surface of the treated material. Therefore, the present invention can greatly contribute to the miniaturization, thinning, high-frequency operation, and high-density operation of various electronic components and devices, and thus has great industrial potential.

Claims

1. A silane compound represented by chemical formula (I). 【Chemistry 1】 (In the formula, R １ R represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, either identical or different. ２ R represents an alkyl group or phenyl group having 1 to 3 carbon atoms. ３ (where 'n' represents a hydrogen atom, an alkyl group with 1 to 3 carbon atoms, or a phenyl group; 'X' represents an iodine atom; 'n' represents an integer from 1 to 5; 'm' represents an integer from 2 to 5; and 'p' represents an integer from 1 to 3.)

2. A surface treatment agent containing the compound described in claim 1.

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

4. A bonding method characterized by bringing the surface treatment agent described in claim 2 into contact with at least one selected from the group consisting of metal, inorganic material, and resin material to form a chemical conversion film on at least one of the materials, and bonding them to each other via the chemical conversion film.

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

6. A resin composition comprising the compound described in claim 1 and a resin or a curable compound.

7. A cured product obtained by curing the resin composition described in claim 6.

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