JP2016125144A - Surface treatment agent, resin composition, and use thereof - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a surface treatment agent capable of enhancing adhesiveness of two different materials selected from metals, inorganic materials, and resin materials.SOLUTION: A surface treatment agent contains an azole silane compound represented by chemical formula (I), wherein X indicates a hydrogen atom, -CH, -NH, -SH, or -SCH; Y indicates -NH- or -S-; R indicates -CHor -CHCH; m indicates an integer of 1-12; and n indicates 0 or an integer of 1-3.SELECTED DRAWING: None

Description

The present invention relates to a surface treatment agent containing an azolesilane compound, a copper foil, a prepreg, a copper clad laminate, an interlayer insulating material, a resin-coated copper foil, and a printed wiring board using the surface treatment agent.
The present invention also relates to a resin composition containing a resin or a pre-curing compound thereof and an azolesilane compound, a solder resist ink, a prepreg, a copper-clad laminate, an interlayer insulating material, and a resin-coated copper foil using the resin composition. The present invention relates to a printed wiring board and a semiconductor sealing material.

  In recent years, printed wiring boards have been multi-layered to cope with the downsizing and thinning of electronic devices and electronic components. So-called multilayer printed wiring boards are provided with a circuit made of copper foil or the like on one or both sides. In addition, an outer layer circuit board or a copper foil is laminated on an inner layer circuit board via a prepreg, and these are integrated. By the way, in such a multilayer printed wiring board, it is important to ensure adhesion between the copper circuit formed on the inner layer circuit board and the insulating adhesive resin of the prepreg on which the outer layer circuit board or copper foil is laminated. It is a difficult issue.

  Patent Document 1 describes an invention relating to a copper foil surface treatment agent that improves the adhesiveness between a copper foil and a prepreg and the solder heat resistance of a copper clad laminate obtained by bonding the copper foil and the prepreg. This document discloses that a trialkoxysilane compound having an imidazole ring and a tetraalkoxysilane compound are used in combination as a component of the surface treatment agent.

  Patent Document 2 discloses a copper surface conditioning composition and a surface treatment method capable of maintaining the adhesion between copper and an insulating material such as a resin without subjecting the copper surface to a roughening treatment such as etching. The invention is described. In this document, a silane coupling agent having an alkoxyl group, for example, silanol, trisilanol, etc. is preferable as a component of the surface conditioning composition because of its excellent adhesion to an insulating material, and among them, In view of improving adhesion between copper and an insulating material such as an epoxy resin, a silane coupling agent having a mercapto group is preferred. In addition, it is disclosed that a solution containing the surface conditioning composition can be prepared by dissolving the composition in a mixed solvent of water and an organic solvent, and after bringing the solution into contact with the surface of copper It can be dried after washing with water or without washing, and when it is dried after washing with water, a film with a uniform thickness can be obtained, while drying without washing with water. In this case, it is disclosed that high adhesion with an insulating material can be obtained.

  Patent Document 3 describes an invention relating to a method for producing a silane coupling agent solution, a silane coupling agent solution, a surface treatment method for a substrate using the same, and the like. In this document, an organosilicon compound is mixed with water to sufficiently form silanol groups, and further mixed with alcohol, a high silanolation rate can be realized, and uniform coating is also possible. It is disclosed that the adhesiveness is realized, and that the silanolation rate is preferably 60 to 100%, more preferably 80 to 100%. As the organosilicon compound, 3-mercaptopropylmethyldimethoxysilane and 3-mercaptopropyltrimethoxysilane are disclosed. In addition, the point which makes the adhesiveness of the base material comprised from an organic polymer compound or an inorganic material and a liquid crystalline compound is the subject of invention, and the adhesiveness in the case of using copper as a base material Is not mentioned.

  Patent Document 4 describes an invention relating to a silane coupling agent and a polymer composition. This document describes nitrogen-containing heterocycles such as triazole and thiadiazole and silyl groups such as trimethoxysilyl and triethoxysilyl groups as components of silane coupling agents used in glass and metal-rubber adhesion primers. However, various substances having a structure in which they are bonded via an organic group having a thioether (sulfide) bond or the like are disclosed. There is no disclosure that the metal is copper.

JP 7-286160 A JP 2009-263790 A JP 2006-045189 A JP 2002-363189 A

The objective of this invention is providing the surface treating agent which can improve the adhesiveness of two different materials selected from a metal, an inorganic material, and a resin material.
Moreover, it is providing the copper foil manufactured using this surface treating agent, a prepreg, a copper clad laminated board, an interlayer insulation material, copper foil with resin, and a printed wiring board.
Another object of the present invention is to provide a resin composition capable of forming a resin layer having high adhesion to metals and inorganic materials.
Another object of the present invention is to provide a solder resist ink, a prepreg, a copper clad laminate, an interlayer insulating material, a resin-coated copper foil, a printed wiring board, and a semiconductor sealing material that are produced using this resin composition.

  As a result of intensive studies to solve the above-mentioned problems, the present inventors use a surface treatment agent containing an azolesilane compound having a specific structure, and a material selected from metals, inorganic materials, and resin materials. It has been found that the adhesion between two materials having different values, particularly the adhesion between a metal and a resin material, can be greatly improved. Moreover, when the resin composition containing the said azole silane compound was used, it discovered that the adhesiveness of resin and a metal or an inorganic material could be improved significantly. The present invention has been completed through further studies based on these findings.

［式（Ｉ）中、Ｘは水素原子、−ＣＨ₃、−ＮＨ₂、−ＳＨまたは−ＳＣＨ₃を表す。Ｙは−ＮＨ−または−Ｓ−を表す。Ｒは−ＣＨ₃または−ＣＨ₂ＣＨ₃を表す。ｍは１〜１２の整数を表し、ｎは０または１〜３の整数を表す］
で示されるアゾールシラン化合物を含有する表面処理剤である。
第２の発明は、第１の発明の表面処理剤による皮膜を有する銅箔である。
第３の発明は、第１の発明の表面処理剤による皮膜を有するプリプレグである。
第４の発明は、第１の発明の表面処理剤による皮膜を有する銅張積層板である。
第５の発明は、第１の発明の表面処理剤による皮膜を有する層間絶縁材である。
第６の発明は、銅箔と樹脂層が第１の発明の表面処理剤による皮膜を介して積層された樹脂付銅箔である。
第７の発明は、第１の発明の表面処理剤による皮膜を有する部材を備えるプリント配線板である。 That is, the first invention is the chemical formula (I)

[In the formula (I), X represents a hydrogen atom, —CH ₃ , —NH ₂ , —SH or —SCH ₃ . Y represents -NH- or -S-. R represents —CH ₃ or —CH ₂ CH ₃ . m represents an integer of 1 to 12, and n represents an integer of 0 or 1].
It is a surface treating agent containing the azole silane compound shown by these.
2nd invention is the copper foil which has a film | membrane by the surface treating agent of 1st invention.
3rd invention is a prepreg which has a membrane | film | coat by the surface treating agent of 1st invention.
4th invention is a copper clad laminated board which has a film | membrane by the surface treating agent of 1st invention.
5th invention is the interlayer insulation material which has a film | membrane by the surface treating agent of 1st invention.
6th invention is copper foil with a resin with which copper foil and the resin layer were laminated | stacked through the membrane | film | coat by the surface treating agent of 1st invention.
7th invention is a printed wiring board provided with the member which has a film | membrane by the surface treating agent of 1st invention.

［式（Ｉ）中、Ｘは水素原子、−ＣＨ₃、−ＮＨ₂、−ＳＨまたは−ＳＣＨ₃を表す。Ｙは−ＮＨ−または−Ｓ−を表す。Ｒは−ＣＨ₃または−ＣＨ₂ＣＨ₃を表す。ｍは１〜１２の整数を表し、ｎは０または１〜３の整数を表す］
で示されるアゾールシラン化合物を含有する樹脂組成物である。
第９の発明は、第８の発明の樹脂組成物から構成されたソルダーレジストインクである。
第１０の発明は、第９の発明のソルダーレジストインクから形成されたソルダーレジストを備えるプリント配線板である。
第１１の発明は、基材と第８の発明の樹脂組成物から構成されたプリプレグである。
第１２の発明は、銅箔と第１１の発明のプリプレグから構成された銅張積層板である。
第１３の発明は、第８の発明の樹脂組成物から構成された層間絶縁材である。
第１４の発明は、銅箔と第８の発明の樹脂組成物により形成された樹脂層から構成された樹脂付銅箔である。
第１５の発明は、第８の発明の樹脂組成物により形成された樹脂層を備えるプリント配線板である。
第１６の発明は、第８の発明の樹脂組成物から構成された半導体封止材料である。 The eighth invention relates to a resin or a pre-curing compound thereof, and a chemical formula (I)

[In the formula (I), X represents a hydrogen atom, —CH ₃ , —NH ₂ , —SH or —SCH ₃ . Y represents -NH- or -S-. R represents —CH ₃ or —CH ₂ CH ₃ . m represents an integer of 1 to 12, and n represents an integer of 0 or 1].
It is a resin composition containing the azole silane compound shown by these.
9th invention is the soldering resist ink comprised from the resin composition of 8th invention.
10th invention is a printed wiring board provided with the soldering resist formed from the soldering resist ink of 9th invention.
The eleventh invention is a prepreg composed of a base material and the resin composition of the eighth invention.
The twelfth invention is a copper clad laminate comprising a copper foil and the prepreg of the eleventh invention.
The thirteenth invention is an interlayer insulating material composed of the resin composition of the eighth invention.
14th invention is a copper foil with resin comprised from the resin layer formed with the copper foil and the resin composition of 8th invention.
15th invention is a printed wiring board provided with the resin layer formed with the resin composition of 8th invention.
The sixteenth invention is a semiconductor encapsulating material composed of the resin composition of the eighth invention.

According to the surface treating agent of the present invention, it is possible to improve the adhesion between two different materials selected from metals, inorganic materials, and resin materials. Therefore, by using the surface treatment agent, copper foil, prepreg, copper-clad laminate, interlayer insulating material, resin-coated copper foil, printed wiring board, etc. excellent in adhesion to the laminate and its own interlayer adhesion Can be obtained.
Moreover, according to the resin composition of this invention, the resin layer which has high adhesiveness with respect to a metal or an inorganic material can be formed. Therefore, by using this resin composition, a copper-clad laminate, an interlayer insulating material, a resin-coated copper foil and a printed wiring board, and a semiconductor encapsulating material excellent in adhesion to a laminate and interlayer adhesion of itself Etc. can be obtained.

Hereinafter, the present invention will be described in detail.
(Azole silane compound)
The azolesilane compound used in the present invention is represented by the above chemical formula (I).
The azole silane compound includes azole silane compounds represented by chemical formulas (Ia) to (Id).

（式中、Ｘ、Ｙ、Ｒおよびｍは前記と同様である）

(Wherein, X, Y, R and m are the same as above)

That is, the azole silane compound represented by the chemical formula (Ia) is an azole silane compound (hereinafter sometimes referred to as an azole silane compound (Ia)) when n is 0 in the chemical formula (I).
Similarly, the azole silane compound represented by the chemical formula (Ib) is an azole silane compound (hereinafter sometimes referred to as an azole silane compound (Ib)) when n is 1, and is represented by the chemical formula (Ic). The azole silane compound is an azole silane compound when n is 2 (hereinafter sometimes referred to as azole silane compound (Ic)), and the azole silane compound represented by the chemical formula (Id) has n of 3. The azole silane compound (hereinafter sometimes referred to as azole silane compound (Id)).

  The azole silane compound represented by the chemical formulas (Ib) to (Id) is produced by hydrolysis of the azole silane compound (Ia) present in the surface treatment agent.

  In the practice of the present invention, it is preferable to use the azole silane compound (Ia) as a component of the surface treatment agent and the resin composition.

As this azole silane compound (Ia), for example,
3-trimethoxysilylmethylthio-1,2,4-triazole,
3- [3- (trimethoxysilyl) propylthio] -1,2,4-triazole,
3- [3- (triethoxysilyl) propylthio] -1,2,4-triazole,
3- [6- (triethoxysilyl) hexylthio] -1,2,4-triazole,
3- [12- (trimethoxysilyl) dodecylthio] -1,2,4-triazole,
3-methyl-5- [2- (triethoxysilyl) ethylthio] -1,2,4-triazole,
3-methyl-5- [4- (trimethoxysilyl) butylthio] -1,2,4-triazole,
3-methyl-5- [10- (trimethoxysilyl) decylthio] -1,2,4-triazole,
3-amino-5- (triethoxysilyl) methylthio-1,2,4-triazole,
3-amino-5- [3- (trimethoxysilyl) propylthio] -1,2,4-triazole,
3-amino-5- [3- (triethoxysilyl) propylthio] -1,2,4-triazole,
3-amino-5- [6- (trimethoxysilyl) hexylthio] -1,2,4-triazole,
3-amino-5- [12- (trimethoxysilyl) dodecylthio] -1,2,4-triazole,
3-mercapto-5- [2- (trimethoxysilyl) ethylthio] -1,2,4-triazole,
3-mercapto-5- [5- (trimethoxysilyl) pentylthio] -1,2,4-triazole,
3-mercapto-5- [8- (trimethoxysilyl) octylthio] -1,2,4-triazole,
3-methylthio-5- [3- (trimethoxysilyl) propylthio] -1,2,4-triazole,
3-methylthio-5- [4- (triethoxysilyl) butylthio] -1,2,4-triazole,
3-methylthio-5- [10- (trimethoxysilyl) decylthio] -1,2,4-triazole (when Y is —NH—),
2-trimethoxysilylmethylthio-1,3,4-thiadiazole,
2- [6- (trimethoxysilyl) hexylthio] -1,3,4-thiadiazole,
2- [8- (triethoxysilyl) octylthio] -1,3,4-thiadiazole,
5-methyl-2- [3- (trimethoxysilyl) propylthio] -1,3,4-thiadiazole,
5-methyl-2- [5- (trimethoxysilyl) pentylthio] -1,3,4-thiadiazole,
5-methyl-2- [12- (triethoxysilyl) dodecylthio] -1,3,4-thiadiazole,
2-amino-5- [2- (triethoxysilyl) ethylthio] -1,3,4-thiadiazole,
2-amino-5- [3- (trimethoxysilyl) propylthio] -1,3,4-thiadiazole,
2-amino-5- [3- (triethoxysilyl) propylthio] -1,3,4-thiadiazole,
2-amino-5- [8- (trimethoxysilyl) octylthio] -1,3,4-thiadiazole,
2-mercapto-5- [3- (trimethoxysilyl) propylthio] -1,3,4-thiadiazole,
2-mercapto-5- [3- (triethoxysilyl) propylthio] -1,3,4-thiadiazole,
2-mercapto-5- [5- (trimethoxysilyl) pentylthio] -1,3,4-thiadiazole,
2-mercapto-5- [10- (triethoxysilyl) decylthio] -1,3,4-thiadiazole,
2-methylthio-5- [3- (trimethoxysilyl) propylthio] -1,3,4-thiadiazole,
2-mercapto-5- [3- (triethoxysilyl) propylthio] -1,3,4-thiadiazole,
2-methylthio-5- [4- (trimethoxysilyl) butylthio] -1,3,4-thiadiazole,
2-methylthio-5- [3- (triethoxysilyl) propylthio] -1,3,4-thiadiazole,
2-methylthio-5- [8- (triethoxysilyl) octylthio] -1,3,4-thiadiazole (when Y is -S-).
In the practice of the present invention, two or more selected from these compounds may be used in combination.

  The azole silane compound (Ia) includes an azole compound represented by chemical formula (II) (hereinafter referred to as azole compound (II)) and a halogenated alkyltrialkoxysilane compound represented by chemical formula (III) (hereinafter referred to as halogenated). The alkylsilane compound (III)) can be synthesized by reacting in the presence of a dehydrohalogenating agent in an appropriate amount of reaction solvent at an appropriate reaction temperature and reaction time (Scheme (A) )reference).

（式中、Ｘ、Ｙ、Ｒおよびｍは、前記と同様である。Ｈａｌは塩素原子、臭素原子または沃素原子を表す）

(In the formula, X, Y, R and m are the same as described above. Hal represents a chlorine atom, a bromine atom or an iodine atom)

  Examples of the azole compound (II) include 3-mercapto-1,2,4-triazole, 3-methyl-5-mercapto-1,2,4-triazole, 3-amino-5-mercapto-1, 2,4-triazole, 3,5-dimercapto-1,2,4-triazole, 3-mercapto-5-methylthio-1,2,4-triazole, 2-mercapto-1,3,4-thiadiazole, 2- Mercapto-5-methyl-1,3,4-thiadiazole, 2-amino-5-mercapto-1,3,4-thiadiazole, 2,5-dimercapto-1,3,4-thiadiazole and 2-mercapto-5 Examples thereof include methylthio-1,3,4-thiadiazole.

  Examples of the halogenated alkylsilane compound (III) include chloromethyltrimethoxysilane, chloromethyltriethoxysilane, 2-chloroethyltrimethoxysilane, 2-chloroethyltriethoxysilane, and 3-chloropropyltrimethoxysilane. 3-chloropropyltriethoxysilane, 3-bromopropyltrimethoxysilane, 3-bromopropyltriethoxysilane, 3-iodopropyltrimethoxysilane, 3-iodopropyltriethoxysilane, 4-bromobutyltrimethoxysilane, 4 -Bromobutyltriethoxysilane, 5-bromopentyltrimethoxysilane, 5-bromopentyltriethoxysilane, 6-bromohexyltrimethoxysilane, 6-bromohexyltriethoxysilane, 8-bromooctyl Trimethoxysilane, 8-bromo-octyltriethoxysilane, 10-bromo-decyl trimethoxy silane, 10-bromo-decyl triethoxysilane, 12-bromododecyl trimethoxysilane can be mentioned 12-bromo-dodecyl triethoxy silane.

  The reaction solvent is not particularly limited as long as it is an inert solvent for the azole compound (II) and the halogenated alkylsilane compound (III). For example, a hydrocarbon solvent such as hexane, toluene, xylene; Ether solvents such as diethyl ether, tetrahydrofuran, dioxane, cyclopentyl methyl ether; ester solvents such as ethyl acetate and butyl acetate; alcohol solvents such as methanol and ethanol; N, N-dimethylformamide, N, N-dimethylacetamide, Examples include amide solvents such as N-methylpyrrolidone; ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; acetonitrile, dimethyl sulfoxide, hexamethyl phosphoramide, and the like.

  Examples of the dehydrohalogenating agent include metal alkoxides such as sodium methoxide, sodium ethoxide, potassium methoxide, and potassium tert-butoxide; metal carbonates such as sodium carbonate, sodium bicarbonate, and potassium bicarbonate; Examples thereof include organic bases such as zabicycloundecene; metal hydrides such as sodium hydride.

  The reaction between the azole compound (II) and the halogenated alkylsilane compound (III) proceeds stoichiometrically as shown in the above reaction scheme (A), but with respect to the use amount (charge amount) of the azole compound. In addition to the reaction temperature and reaction time, the amount of halogenated alkylsilane compound used (charge amount) is 0.8 to 1.2 times in consideration of factors such as the types of raw materials and reaction solvents used, reaction scale, etc. It is preferable to set it as an appropriate ratio in the molar range. If the charged amount of the halogenated alkylsilane compound is more than 1.2 times mol, the compound may be polymerized and gelled, and if less than 0.8 times mol, the purity of the product decreases. Or the product separation operation becomes complicated. Moreover, since the dehydrohalogenating agent is used to neutralize hydrogen halide by-produced by the reaction of the azole compound and the halogenated alkylsilane compound, the amount used (the amount charged) is the halogenated alkylsilane. What is necessary is just to be equimolar or more with respect to the usage-amount of a compound.

  The reaction temperature is not particularly limited as long as the mercapto group of the azole compound (II) reacts with the halogenated alkylsilane compound (III), but a range of 0 to 150 ° C is preferable, and 5 to 100 ° C. The range of is more preferable. Although the said reaction time is suitably determined according to the set reaction temperature, the range of 30 minutes-10 hours is preferable, and the range of 1-5 hours is more preferable.

(Surface treatment agent)
The surface treating agent of the present invention contains an azole silane compound represented by the chemical formula (I). The surface treating agent of the present invention may contain a solvent together with this azolesilane compound. Examples of the solvent include water, an organic solvent, and a mixed liquid of water and an organic solvent. The surface treating agent in this case can be prepared by mixing the azole silane compound and the solvent using an appropriate mixing means. The surface treatment agent may be referred to as a treatment liquid.

  The organic solvent is not particularly limited as long as it acts as a solubilizing agent, and may be used without limitation, for example, methanol, ethanol, propanol, 2-propanol, butanol, tert-butyl alcohol. , Ethylene glycol, propylene glycol, 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, diethylene glycol monomethyl ether, diethylene Glycol dimethyl ether, diethylene glycol monoethyl ether, diethylene glycol diethyl ether, diethylene glycol monobutyl ether, triethylene glycol dimethyl ether, triethylene glycol diethyl ether, tetrahydrofurfuryl alcohol, furfuryl alcohol, acetone, ethyl methyl ketone, tetrahydrofuran, dioxane, acetonitrile, 2- Pyrrolidone, formamide, N, N-dimethylformamide, N, N-dimethylacetamide, dimethyl sulfoxide, sulfolane, dimethyl carbonate, ethylene carbonate, N-methylpyrrolidone, γ-butyrolactone, 1,3-dimethyl-2-imidazolidinone, Formic acid, acetic acid, propionic acid, butyric acid, glycolic acid, lactic acid, gluconic acid, Glyceric acid, malonic acid, succinic acid, levulinic acid, phenol, benzoic acid, oxalic acid, tartaric acid, malic acid, methyl acetate, ethyl acetate, ethyl formate, methylamine, dimethylamine, trimethylamine, ethylamine, diethylamine, triethylamine, propylamine , Isopropylamine, butylamine, allylamine, ethylenediamine, diethylenetriamine, triethylenetetramine, monoethanolamine, diethanolamine, triethanolamine, dipropanolamine, tripropanolamine, diisopropanolamine, triisopropanolamine, 1-amino-2-propanol, 3-amino-1-propanol, 2-amino-1-propanol, N, N-dimethylethanolamine, cyclohexylamine, Diphosphate, pyrrolidine, piperidine, piperazine, pyridine is preferred. One of these organic solvents (solubilizing agents) may be used alone, or two or more thereof may be used in combination. When a solid solubilizer is used, it is used in combination with water and / or a liquid solubilizer.

  When a mixed solution of water and an organic solvent is used as a solvent, the surface treatment agent may be prepared by mixing an azolesilane compound represented by the chemical formula (I) with water and then adding an organic solvent. A mixed solution of water and an organic solvent may be mixed, or water may be added after mixing the compound and the organic solvent. Moreover, as water used for preparation of a surface treating agent, pure water, such as ion-exchange water and distilled water, is preferable.

  As described above, the azolesilane compound represented by the chemical formula (I) (except when n is 3) is hydrolyzed when contacted with water. The mode of hydrolysis is shown in Scheme (B). In this scheme, the silyl group of the azole silane compounds represented by the chemical formulas (Ia) to (Ic) is hydrolyzed, that is, the trialkoxysilyl group is gradually converted into a dialkoxyhydroxysilyl group, a dihydroxyalkoxy group. The state of changing to a silyl group or a trihydroxysilyl group is simply shown.

（式中、Ｒは前記に同じ。Ｘは繰り返し単位の数を表す整数である）

(In the formula, R is the same as above. X is an integer representing the number of repeating units.)

  In general, it is known that a substance having an alkoxysilyl group in the molecule acts as a silane coupling agent. For example, taking adhesion between copper and a resin material as an example, the azole silane compound used in the practice of the present invention has an azole ring and an alkoxysilyl group (—Si—OR) in the molecule, and the azole ring Interacts with resin and copper to form chemical bonds. In addition, the alkoxysilyl group is hydrolyzed and converted to a hydroxysilyl group (—Si—OH), and this hydroxysilyl group chemically bonds with copper oxide scattered on the surface of copper. Therefore, by bringing the surface treatment agent into contact with copper, a chemical conversion film derived from the azole silane compound represented by the chemical formula (I) is formed on the surface of the copper by bonding with an azole ring or a hydroxysilyl group. When the resin layer is formed on the surface of the chemical conversion film, the adhesion between the copper and the resin can be improved as compared with the case where the resin layer is formed directly on the copper surface.

  In the practice of the present invention, the concentration of the azole silane compound represented by the chemical formula (I) in the surface treatment agent is 0.001 to 10% by weight in terms of the concentration of the trialkoxy azole silane compound (Ia). It is preferable that it is 0.01 to 5 weight%. When this concentration is less than 0.001% by weight, the effect of improving the adhesiveness is not sufficient, and when this concentration exceeds 10% by weight, the effect of improving the adhesiveness almost reaches its peak, and the azolesilane compound It is not economical just because the amount of use increases.

  By the way, the azole silane compounds (Ib) to (Id) having a hydroxysilyl group formed in the surface treatment agent gradually react with each other to undergo dehydration condensation, and the hydroxysilyl group becomes a siloxane bond (Si—O—Si). (See scheme (B)) and converted into a silane oligomer (an azole silane compound having a group represented by the chemical formula (e) in scheme (B)) that is hardly soluble in water.

  When the amount of silane oligomer generated in the surface treatment agent increases, the insoluble matter precipitates (the treatment agent becomes cloudy), and the treatment tank, the pipe connected to the treatment tank, the treatment agent immersed in the treatment agent It may adhere to sensors for detecting temperature and liquid level, and smooth surface treatment may be hindered. In order to avoid this, it is preferable that an organic solvent is contained in the surface treatment agent as a silane oligomer solubilizer that is hardly soluble in water. About content of the organic solvent, it is preferable to set it as the ratio of 0.1-90 weight part with respect to 100 weight part of water, and it is more preferable to set it as the ratio of 1-50 weight part. As this organic solvent, what was illustrated as an above-mentioned organic solvent can be used.

  In the preparation of the surface treatment agent of the present invention, an acid such as acetic acid or hydrochloric acid, or an alkali such as sodium hydroxide or ammonia may be used in order to promote hydrolysis of the azolesilane compound (Ia).

  Similarly, in order to improve the stability of the surface treatment agent and the uniformity of the chemical conversion film, substances that generate halogen ions such as chlorine ions and bromine ions, and metal ions such as copper ions, iron ions, and zinc ions are used. You can also.

  Moreover, you may use a well-known coupling agent together in the range which does not impair the effect of this invention. Known coupling agents include silane coupling agents having a thiol group (mercapto group), vinyl group, epoxy group, (meth) acryl group, amino group, chloropropyl group, and the like.

  Examples of such silane coupling agents include mercaptosilane compounds such as 3-mercaptopropyltrimethoxysilane and 3-mercaptopropylmethyldimethoxysilane, and vinylsilanes such as vinyltrichlorosilane, vinyltrimethoxysilane, and vinyltriethoxysilane. Compounds, vinylphenylsilane compounds such as p-vinylphenyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxy Silane, epoxy silane compounds such as 3-glycidoxypropyltriethoxysilane, acryloxysilane such as 3-acryloxypropyltrimethoxysilane, methacryloxypropylmethyldimethoxysilane, Methacryloxysilane compounds such as taacryloxypropyltrimethoxysilane, methacryloxypropylmethyldiethoxysilane, methacryloxypropyltriethoxysilane, N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, N-2- ( Aminoethyl) -3-aminopropyltrimethoxysilane, N-2- (aminoethyl) -3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl Aminosilane compounds such as -N- (1,3-dimethylbutylidene) propylamine, N-phenyl-3-aminopropyltrimethoxysilane, N- (vinylbenzyl) -2-aminoethyl-3-aminopropyltrimethoxysilane , 3-U Ureidosilane compounds such as idpropyltriethoxysilane, chloropropylsilane compounds such as 3-chloropropyltrimethoxysilane, sulfide silane compounds such as bis (triethoxysilylpropyl) tetrasulfide, isocyanates such as 3-isocyanatopropyltriethoxysilane A silane compound etc. can be mentioned. In addition, an aluminum coupling agent, a titanium coupling agent, a zirconium coupling agent, and the like can also be exemplified.

  In addition to the above, the surface treatment agent of the present invention may contain an appropriate additive depending on the type of the material to be treated (described later), the application, and the like.

(Material to be treated)
Examples of the material to be treated to which the surface treatment agent of the present invention is applied include granular, needle-like, fiber-like, thin-film-like, plate-like, and amorphous ones formed from metals, inorganic materials, resin materials, and the like. It is done.

Examples of the metal include copper, aluminum, titanium, nickel, tin, iron, silver, gold, and alloys thereof. As a specific example of the alloy, a copper alloy is not particularly limited as long as it is an alloy containing copper. For example, Cu-Ag, Cu-Te, Cu-Mg, Cu-Sn, and Cu-Si Cu-Mn, Cu-Be-Co, Cu-Ti, Cu-Ni-Si, Cu-Zn-Ni, Cu-Cr, Cu-Zr, Cu-Fe, Cu-Al Alloy of Cu type, Cu-Zn type, Cu-Co type and the like. Other alloys include aluminum alloy (Al—Si alloy), nickel alloy (Ni—Cr alloy), iron alloy (Fe—Ni alloy, stainless steel) and the like. Of these metals, copper and copper alloys are preferred.
Moreover, as a metal aspect, the foil (for example, electrolytic copper foil, rolled copper foil), plating film (for example, electroless copper plating film) used for electronic devices, such as a printed wiring board and a lead frame, decorations, and building materials , Electrolytic copper plating film), thin films formed by vapor deposition, sputtering, damascene, etc., and those used in applications and forms such as granular, needle-like, fiber-like, linear, rod-like, tubular, plate-like Can be mentioned. In the case of copper wiring through which a high-frequency electric signal flows in recent years, the copper surface is preferably a smooth surface having an average roughness of 0.1 μm or less. As a pretreatment, the surface of copper may be plated with nickel, zinc, chromium, tin or the like.

  Examples of the inorganic material include silicon, ceramic, carbon used as a filler, inorganic salt, and glass. Specifically, silicon, silicon carbide, silica, glass, diatomaceous earth, calcium silicate, talc, glass beads, sericite activated clay, bentonite and other silicon compounds, alumina, zinc oxide, iron oxide, magnesium oxide, tin oxide, oxidation Oxides such as titanium, hydroxides such as magnesium hydroxide, aluminum hydroxide, basic magnesium carbonate, carbonates such as calcium carbonate, zinc carbonate, hydrotalcite, 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, expanded graphite (synthetic graphite), activated carbons, carbon fibers, carbon Black etc. are mentioned. Among these inorganic materials, silicon, ceramic (alumina, silicon carbide, aluminum nitride, silicon nitride and barium titanate), glass and inorganic salts are preferable.

  The resin material may be either a thermoplastic resin or a thermosetting resin. Specifically, acrylate resin, epoxy resin, polyimide resin, bismaleimide resin, maleimide resin, cyanate resin, polyphenylene ether resin, polyphenylene oxide resin, polybutadiene resin, olefin resin, fluorine-containing resin having excellent heat resistance and insulation properties , Polyetherimide resin, polyetheretherketone resin, liquid crystal resin, and the like. These may be combined or modified with each other. Moreover, there is no restriction | limiting in particular in the polymerization degree of these resin, After superposing | polymerizing (curing) suitably after surface treatment. Among these resin materials, acrylate resins, epoxy resins, and polyimide resins are preferable.

(Surface treatment method)
There is no restriction | limiting in particular as a method of making the surface treating agent of this invention contact the surface of a to-be-processed material, Means, such as immersion, application | coating, a spray, can be employ | adopted. The time (treatment time) for contacting the surface treatment agent and the material to be treated is preferably 1 second to 10 minutes, and more preferably 5 seconds to 3 minutes. When the treatment time is less than 1 second, the film thickness formed on the surface of the material to be treated becomes thin, and sufficient adhesion between different materials cannot be obtained. There is no great difference in the film thickness of the film, and no improvement in adhesion can be expected. Moreover, about the temperature of the processing agent at the time of making a surface processing agent contact the to-be-processed material surface, it is preferable to set it as 5-50 degreeC, However, What is necessary is just to set suitably in relation to the said processing time.

  After the surface treatment agent of the present invention and the material to be treated are brought into contact with each other, the substrate may be washed with water and then dried, or may be dried without being washed with water. Drying is preferably performed at a temperature of room temperature to 150 ° C. The water used for washing is preferably pure water such as ion-exchanged water or distilled water, but the washing method and time are not particularly limited, and may be an appropriate time by means such as spraying or dipping.

  Before bringing the surface treatment agent of the present invention into contact with the metal surface, the surface of the metal is selected from pickling treatment, alkali washing treatment, roughening treatment, heat treatment, rust prevention treatment or chemical conversion treatment. At least one pretreatment may be performed.

  In addition, before bringing the surface treatment agent of the present invention into contact with the surface of the inorganic material or resin material, the surface of the inorganic material or resin material is subjected to pickling treatment, alkali washing treatment, roughening treatment, or heat resistance treatment. At least one pre-processing selected from may be performed.

  The pickling treatment is performed to remove oil and fat components adhering to the surface of the metal, inorganic material or resin material and to remove the oxide film on the surface of the metal. For this pickling treatment, solutions such as hydrochloric acid solution, sulfuric acid solution, nitric acid solution, sulfuric acid-hydrogen peroxide solution, organic acid solution, inorganic acid-organic solvent solution, organic acid-organic solvent solution, etc. Can be used.

  The alkali washing treatment is performed to remove oil and fat components adhering to the surface of the metal, inorganic material, or resin material. This alkali washing treatment includes sodium hydroxide solution, kalim hydroxide solution, magnesium hydroxide solution, calcium hydroxide solution, amine solution, inorganic alkali-organic solvent solution, amine-organic solvent solution, etc. Can be used.

  The roughening treatment forms an uneven shape on the surface of the metal, inorganic material, or resin material, and has an anchor effect to improve the adhesion (adhesion) of two materials selected from the metal, inorganic material, and resin material. It is done to increase. For this roughening treatment, desmear method, plasma etching method, metal sputtering method, electroless plating method, electroplating method, rust prevention treatment, oxidation / reduction method, brush polishing method, jet scrub method, etc. should be adopted. Can do.

In the desmear method, for example, a potassium permanganate or sodium permanganate desmear agent can be used. Further, swelling treatment or neutralization treatment may be performed before or after the roughening treatment by the desmear method.
In the metal sputtering method or the electroless plating method, fine metal particles are deposited on the surface of the metal, inorganic material, or resin material, thereby forming irregularities on the surface of the metal, inorganic material, or resin material.

The heat-resistant treatment is selected from nickel, nickel-phosphorus, zinc, zinc-nickel, copper-zinc, copper-nickel, copper-nickel-cobalt or nickel-cobalt on the surface of a metal, inorganic material or resin material. At least one film is formed.
In forming this film, a known electroless plating method can be employed, but vapor deposition or other means may be used.

  The rust prevention treatment is performed to prevent oxidative corrosion of the metal surface, and a method of forming a zinc or zinc alloy composition plating film or electrolytic chromate plating film on the metal surface. Can be adopted.

  For the chemical conversion treatment, a method of forming a passive film of tin or a method of forming a passive film of copper oxide can be employed.

  Before bringing the surface treatment agent of the present invention into contact with the surface of a metal, inorganic material or resin material, an aqueous solution containing copper ions may be brought into contact with the surface of the metal, inorganic material or resin material. This aqueous solution containing copper ions has a function of making the thickness of the chemical conversion film formed on the surface of the metal, inorganic material or resin material uniform. The copper ion source of 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. In order to solubilize the copper salt in water, ammonia or hydrochloric acid may be used in combination.

Moreover, after making the surface treating agent of this invention contact the surface of a metal, an inorganic material, or a resin material, you may make acidic aqueous solution or alkaline aqueous solution contact the surface of the said metal, inorganic material, or resin material. This acidic aqueous solution or alkaline aqueous solution also has the function of making the thickness of the chemical conversion film formed on the surface of the metal, inorganic material, or resin material uniform, like the aqueous solution containing copper ions.
The acidic aqueous solution or alkaline aqueous solution is not particularly limited, and examples of the acidic aqueous solution include an aqueous solution containing a mineral acid such as sulfuric acid, nitric acid, and hydrochloric acid, and an organic acid such as formic acid, acetic acid, lactic acid, glycolic acid, and amino acid. it can. Examples of the alkaline aqueous solution include aqueous solutions containing alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, and amines such as ammonia, ethanolamine and monopropanolamine.

  Before or after the surface treatment agent of the present invention is brought into contact with the surface of the metal, inorganic material or resin material, treatment such as plasma, laser, ion beam, ozone, heating or humidification is carried out to obtain a metal or inorganic material. Alternatively, the surface of the resin material may be modified. Further, cleaning for the purpose of removing resin / ion residue of metal, inorganic material, or resin material may be performed using mechanical polishing such as plasma, laser, ion beam, permis brush, and drilling.

  In the process of metal plating or mounting on the surface of the metal, inorganic material, or resin material in contact with the surface treatment agent of the present invention, plasma, laser, ion beam, ozone, heating or humidification is performed to improve the surface. Cleaning for the purpose of quality and residue removal may be performed.

  Even if the surface of the metal, inorganic material or resin material in contact with the surface treatment agent of the present invention is subjected to primer treatment such as organic coating or metal coating for the purpose of improving adhesion in the process of metal plating or mounting. Good.

  The pre-processing and post-processing described above may be implemented in combination as appropriate.

  The surface treating agent of the present invention can be used for treating the surface of at least one material to be treated selected from the metals, inorganic materials, and resin materials. By treating the surface of the material to be treated with the surface treatment agent of the present invention, a film can be formed on the surface of the material to be treated, and the adhesion to other materials can be improved. This film has high heat resistance, and for example, the adhesive force is maintained even by solder reflow heating (about 260 ° C.). In order to enhance the effect of this treatment, the surface-treated material may be heat-treated.

(Adhesion method)
In the present invention, two materials selected from the metals, inorganic materials, and resin materials can be bonded using the surface treating agent of the present invention. By adhering two materials through a film formed by the surface treatment agent of the present invention, the affinity between each other can be improved, so even different materials can be bonded more firmly. Can do. The thickness of the film is 0.0001 to 1 μm, preferably 0.001 to 0.5 μm.

  As a bonding method, a known method can be adopted. A coating is formed by bringing the surface treatment agent of the present invention into contact with the surface of a material to be treated selected from metals, inorganic materials, or resin materials, and another material to be treated is applied and pressure-bonded to part or all of the formed film. And means such as mixing, use of an adhesive, an adhesive sheet (film), or a combination of these means.

  Further, the surface treatment agent of the present invention is brought into contact with the surfaces of two materials to be treated selected from a metal, an inorganic material, and a resin material to form films on the surfaces of the two materials to be treated, respectively. Examples thereof include means for applying a treatment material, pressure bonding, mixing, and the like, use of an adhesive, an adhesive sheet (film), or a combination of these means.

(Use of surface treatment agent)
By using the surface treating agent of the present invention, it is possible to bond two materials as described above, particularly two different materials, so that it can be used for electric / electronic applications (such as various electric / electronic parts and printed wiring boards). It can be suitably used for electronic devices), architectural applications, civil engineering applications, automobile applications, medical material applications, and the like.

  The surface treating agent of the present invention can be suitably used for a material to be treated formed of a metal, particularly copper or a copper alloy. For example, the purpose is to improve the adhesion (adhesion) between a copper circuit (copper wiring layer) and a semi-cured or cured prepreg or solder resist, or a semi-cured or cured dry film (insulating resin layer). In a printed wiring 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 enhanced.

  Examples of using the surface treatment agent of the present invention for surface treatment of materials include copper foils, prepregs, copper-clad laminates, interlayer insulation materials, sheet-like members, and copper having a film formed by treatment with the surface treatment agent. In addition to a resin-coated copper foil in which a foil and a resin layer are laminated via a film of the surface treatment agent, a printed wiring board including these members can be used.

  The printed wiring board can be produced, for example, by bringing the surface treatment agent of the present invention into contact with the surface of the copper wiring layer, and then washing and drying, and then forming an insulating resin layer on the surface of the copper wiring layer. it can. The contact method is as described above, and immersion of the copper wiring layer in the surface treatment agent or spraying on the surface of the copper wiring layer with the surface treatment agent is preferable because it is simple and reliable.

  The washing method is not particularly limited, but immersion of the copper wiring layer in the washing water or spraying on the surface of the copper wiring layer with the washing water is preferable because it is simple and reliable. For the formation of the insulating resin layer, a known method such as a method of attaching a semi-cured resin material or a means of applying a liquid resin material containing a solvent can be employed. Next, a via hole is formed to connect the upper and lower wirings. A multilayer printed wiring board can be manufactured by repeating this process.

  The copper wiring may be produced by any method such as an electroless plating method, an electrolytic plating method, a vapor deposition method, a sputtering method, or a damascene method, and includes an inner via hole, a through hole, a connection terminal, etc. But you can.

  In addition, “copper” according to the present invention is a foil (electrolytic copper foil, rolled copper foil), plating film (electroless copper plating film) used for electronic devices such as printed wiring boards and lead frames, decorations, and building materials. , Electrolytic copper plating film), thin films formed by vapor deposition, sputtering, damascene, etc., and used in applications and forms such as granular, needle-like, fiber-like, linear, rod-like, tubular, and plate-like is there. In the case of copper wiring through which a high-frequency electric signal flows in recent years, the copper surface is preferably a smooth surface having an average roughness of 0.1 μm or less. As a pretreatment, the surface of copper may be plated with nickel, zinc, chromium, tin or the like.

  By the way, JP 2009-19266 A discloses a step of applying a liquid containing a silane coupling agent to a metal surface, and drying the metal surface to which the liquid is applied at a temperature of 25 to 150 ° C. within 5 minutes. And a method for forming a silane coupling agent film, characterized in that it includes a step of performing a step of washing and washing a dried metal surface with water. Further, it is said that an adhesive metal layer such as tin may be formed on the metal surface in advance by a surface plating as an immersion plating solution. The surface treatment agent of the present invention can be used as a liquid containing the silane coupling agent. In addition, the matter described in this patent gazette shall constitute a part of this specification by reference.

(Resin composition)
The resin composition of the present invention contains a resin or a pre-curing compound thereof and an azolesilane compound represented by the chemical formula (I).

  The “resin or its pre-curing compound” includes thermoplastic resins, heat or active energy ray-curable resins (cured products), raw material monomers thereof, partially polymerized products or semi-cured products of the monomers. In the case of heat or active energy ray curable resin, any state of A stage resin, B stage resin, and C stage resin may be used.

  Examples of the resin include acrylate resin, epoxy resin, polyimide resin, bismaleimide resin, maleimide resin, cyanate resin, polyphenylene ether resin, polyphenylene oxide resin, olefin resin, fluorine-containing resin, Examples include ether imide resins, polyether ether ketone resins, liquid crystal resins, and the like, and these may be mixed or combined with each other. Among these resin materials, acrylate resins, epoxy resins, and polyimide resins are preferable.

  The content of the azolesilane compound represented by the chemical formula (I) in the resin composition of the present invention is preferably 0.001 to 10% by weight, and more preferably 0.01 to 5% by weight. . When the content of the azolesilane compound is less than 0.001% by weight in the resin composition, the effect of improving the adhesiveness is not sufficient, and when the concentration exceeds 10% by weight, the adhesiveness is improved. The effect has almost reached its peak, and the amount of azolesilane compound used is increased, which is not economical.

  In addition to the resin or its pre-curing compound and the azolesilane compound represented by the chemical formula (I), the resin composition includes a solvent (water, an organic solvent, a mixture of water and an organic solvent), Additives (such as curing agents, curing accelerators, flame retardants, dyes, pigments, ultraviolet absorbers, lubricants, fillers) and the like may be included as appropriate. As the organic solvent, those exemplified as the aforementioned organic solvent (solubilizing agent) can be used.

  The resin composition can be prepared by a known method. For example, the resin composition can be prepared by dissolving the azole silane compound represented by the chemical formula (I) in an organic solvent and mixing it with a solid or liquid resin material. Alternatively, the resin composition may be prepared by directly adding and mixing the azole silane compound represented by the chemical formula (I) to the liquid resin material.

(Use of resin composition)
Since the resin composition of the present invention contains an azolesilane compound represented by the chemical formula (I), the cured resin layer adheres to an adjacent layer or member, for example, a metal or inorganic material layer or member with high strength. (Adhere). Therefore, it can be suitably used for various electrical / electronic applications (electronic devices such as electrical / electronic components and printed wiring boards), architectural applications, civil engineering applications, automobile applications, medical material applications, and the like.

  Specific examples using the resin composition of the present invention include, for example, a solder resist ink composed of the resin composition of the present invention, a printed wiring board including a solder resist formed from the solder resist ink, and a base material (paper , A glass cloth, a glass nonwoven fabric, etc.) and a prepreg composed of the resin composition of the present invention, a copper-clad laminate composed of the prepreg and a copper foil, an interlayer insulating material composed of the resin composition of the present invention (interlayer) Insulating film, etc.), copper foil, and resin-coated copper foil composed of a resin layer formed of the resin composition of the present invention, a printed wiring board comprising the resin layer formed of the resin composition of the present invention, the present The semiconductor sealing material comprised from the resin composition of invention can be mentioned.

  The solder resist is prepared by applying a solder resist ink made of the resin composition of the present invention containing an azolesilane compound represented by the chemical formula (I) and a pre-curing compound (curing compound) on an appropriate substrate, and drying. It is obtained by curing the curable resin layer to be formed using heat or active energy rays. The printed wiring board can be manufactured 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 immersing and impregnating the substrate in the resin composition. The said copper clad laminated board can be manufactured by laminating | stacking the said prepreg and copper foil. The interlayer insulating material can be produced by applying the resin composition of the present invention on a suitable substrate and drying, semi-curing or curing. The copper foil with resin can be produced by applying the resin composition of the present invention on a copper foil and drying, semi-curing or curing. In the printed wiring board, the “resin layer formed of the resin composition of the present invention” includes various types of resin other than the solder resist, the prepreg, the interlayer insulating material, and the resin-coated copper foil. The resin composition of the present invention can be used as a semiconductor sealing material.

  In addition, since a member to which the surface treatment agent or the resin composition of the present invention is applied can be provided with excellent adhesiveness, heat resistance, insulation, etc., by adding an appropriate auxiliary agent as necessary, Paste, underfill, die attach material, semiconductor chip mounting material, non-conductive adhesive, liquid crystal sealant, display material, reflector, paint, adhesive, curing agent, varnish, elastomer, ink, wax, sealant, etc. can do.

  EXAMPLES Hereinafter, although an Example and a comparative example demonstrate this invention concretely, this invention is not limited to these.

In addition, the synthesis example of the azole silane compound used in the Example is shown in Reference Examples 1-4.
The raw material azole compound and halogenated alkylsilane compound used in the synthesis are as follows.
[Azole compounds]
・ 3-mercapto-1,2,4-triazole: manufactured by Tokyo Chemical Industry Co., Ltd. ・ 3-amino-5-mercapto-1,2,4-triazole: same as above ・ 5-methyl-1,3,4-thiadiazole-2 -Thiol: Same as above

[Halogenated alkylsilane compounds]
3-iodopropyltrimethoxysilane: manufactured by Sigma-Aldrich Corp. 6-bromohexyltrimethoxysilane: synthesized according to the method described in “D. Zhang et al., Tetrahedron 2007, 63 (23), 5076-5082”. .

[Reference Example 1]
<Synthesis of 3- [3- (trimethoxysilyl) propylthio] -1,2,4-triazole>
A suspension composed of 3.0 g (30 mmol) of 3-mercapto-1,2,4-triazole and 50 mL of dehydrated methanol was cooled to 10 ° C., and 5.8 g (30 mmol) of 28% sodium methoxide methanol solution was added to be homogeneous. After preparing the solution, the solution was returned to room temperature and stirred for 30 minutes, and a solution composed of 8.7 g (30 mmol) of 3-iodopropyltrimethoxysilane and 10 mL of dehydrated methanol was added dropwise at room temperature over 10 minutes, and further 27-30 The mixture was stirred at 3 ° C for 3 hours and 30 minutes.
The reaction solution was concentrated under reduced pressure, and 12.5 g of the resulting white viscous product was extracted with 40 mL of diethyl ether three times. The extract was filtered and then concentrated under reduced pressure to give a chemical formula (I-1 ) 7.3 g (27 mmol, yield 92.3%) of the title azole silane compound represented by

[Reference Example 2]
<Synthesis of 3-amino-5- [3- (trimethoxysilyl) propylthio] -1,2,4-triazole>
A suspension composed of 6.96 g (60 mmol) of 3-amino-5-mercapto-1,2,4-triazole and 100 mL of dehydrated methanol was cooled to 10 ° C., and 3.24 g (60 mmol) of sodium methoxide (solid) was added. After adding a uniform solution, the mixture was returned to room temperature and stirred for 30 minutes, and a solution consisting of 17.42 g (60 mmol) of 3-iodopropyltrimethoxysilane and 20 mL of dehydrated methanol was added dropwise at room temperature over 30 minutes. The mixture was stirred at 27 to 30 ° C. for 3 hours and 30 minutes.
The reaction solution was concentrated under reduced pressure, and 26.4 g of the resulting white viscous product was extracted with 100 mL of diethyl ether three times. The extract was filtered and then concentrated under reduced pressure to give a chemical formula (I-2 ) 9.20 g (33 mmol, yield 55.1%) of the title azole silane compound represented by

[Reference Example 3]
<Synthesis of 3-amino-5- [6- (trimethoxysilyl) hexylthio] -1,2,4-triazole>
A suspension composed of 3.48 g (30 mmol) of 3-amino-5-mercapto-1,2,4-triazole and 50 mL of dehydrated methanol was cooled to 10 ° C., and 5.8 g (30 mmol) of 28% sodium methoxide methanol solution. Was added to make a uniform solution, and the mixture was returned to room temperature and stirred for 30 minutes. A solution consisting of 9.4 g (30 mmol) of 6-bromohexyltrimethoxysilane and 10 mL of dehydrated methanol was added dropwise at room temperature over 10 minutes, Furthermore, it stirred at 60 degreeC for 6 hours.
The reaction mixture was concentrated under reduced pressure, and 14.2 g of the resulting white viscous product was extracted with 40 mL of diethyl ether three times. The extract was filtered and concentrated under reduced pressure to give a chemical formula (I-3 ) 5.3g (16mmol, 52% yield) of the title azole silane compound represented by

[Reference Example 4]
<Synthesis of 5-methyl-2- [3- (trimethoxysilyl) propylthio] -1,3,4-thiadiazole>
A suspension composed of 7.9 g (60 mmol) of 5-methyl-1,3,4-thiadiazole-2-thiol and 100 mL of dehydrated methanol was cooled to 10 ° C., and 11.6 g (60 mmol) of 28% sodium methoxide methanol solution. To obtain a homogeneous solution, and the mixture was returned to room temperature and stirred for 30 minutes. A solution consisting of 17.4 g (60 mmol) of 3-iodopropyltrimethoxysilane and 20 mL of dehydrated methanol was added dropwise at room temperature over 30 minutes, Furthermore, it stirred at 34-40 degreeC for 4 hours.
The reaction mixture was concentrated under reduced pressure, and 26.5 g of the resulting white viscous product was extracted with 80 mL of diethyl ether three times. The extract was filtered and concentrated under reduced pressure to give a chemical formula (I-4 16.9 g (60 mmol, yield 99.9%) of the title azole silane compound represented by

  A synthesis example of the imidazolesilane compound used in the comparative example is shown in Reference Example 5.

[Reference Example 5]
<Synthesis of imidazole silane compound>
3.4 g (0.05 mol) of imidazole was melted at 95 ° C., and 11.8 g (0.05 mol) of 3-glycidoxypropyltrimethoxysilane was added dropwise over 30 minutes while stirring in an argon atmosphere. After completion of dropping, the reaction was further carried out at a temperature of 95 ° C. for 1 hour.
The reaction product was obtained as a clear orange viscous liquid (cited from JP-A-5-186479).
Note: According to JP-A-5-186479, the reaction product is a mixture of imidazole silane compounds represented by chemical formulas (IV-1) to (IV-3).

<Adhesive evaluation test-I>
The adhesive evaluation tests (a) to (g) conducted in Examples (1 to 4) and Comparative Examples (1 to 3) are as follows.

[Adhesion Evaluation Test (a)]
(1) Metal An electrolytic copper foil (thickness: 18 μm) was used as the metal.
(2) Surface treatment of metal It carried out according to the following processes i to c.
A. Acid clean / 1 minute (room temperature), water wash b. Acid cleaning / 1 minute (room temperature), water washing, drying / 1 minute (100 ° C)
C. Immersion in surface treatment agent / 1 minute (room temperature), water washing, drying / 1 minute (100 ° C.)
(3) Adhesion of metal and resin A glass cloth epoxy resin-impregnated prepreg (FR-4 grade) was laminated and pressed on the S surface of the treated electrolytic copper foil, and the copper foil and prepreg were adhered to produce a copper-clad laminate. .
(4) Evaluation of adhesiveness From this copper-clad laminate, a test piece having a width of 10 mm was prepared according to “JIS C6481 (1996)” and subjected to pressure cooker treatment (121 ° C./humidity 100% / 100 hours), and then copper The peel strength of the foil was measured.

[Adhesion Evaluation Test (b)]
Instead of “Lamination press of glass cloth epoxy resin impregnated prepreg (FR-4 grade)” on the S surface of the electrolytic copper foil, “Resin for build-up wiring board (product name“ GX-13 ”manufactured by Ajinomoto Fine Techno Co., Ltd.)” The adhesiveness between the copper foil and the resin was evaluated in the same procedure as in the evaluation test (a) except that “laminate”.

[Adhesion Evaluation Test (c)]
(1) Metal As the metal, an electrolytic copper foil of a double-sided copper clad laminate (base material: FR4, plate thickness: 1.0 mm, copper foil thickness: 18 μm, length 120 mm × width 110 mm) was used.
(2) Surface treatment of metal It carried out according to the following processes ai.
A. Acid clean / 1 minute (room temperature), water wash b. Micro etching with hydrogen peroxide / sulfuric acid / 1 minute (room temperature), water washing c. Acid cleaning / 1 minute (room temperature), water washing, drying / 1 minute (100 ° C)
D. Immersion in surface treatment agent / 1 minute (room temperature), water washing, drying / 1 minute (100 ° C.)
(3) Formation of resin layer on metal Solder resist ink (manufactured by Taiyo Ink Manufacturing Co., Ltd., acrylate / epoxy resin, product name “PSR-4000AUS308”) is applied to the treated electrolytic copper foil and then dried (80 ° C./30 Min) and curing (150 ° C./60 min) to form a 13 μm thick resin layer (coating film).
(4) Evaluation of adhesiveness According to “JIS K5400-8.5 (1990)”, the coating formed on the electrolytic copper foil was cross-cut (100 squares) on a 1 mm × 1 mm grid, and pressure cooker treatment (121 ° C. / Humidity 100% / 100 hours), a tape peel test was performed, and the number of squares where the coating film did not peel was measured. Moreover, the damage condition of the coating film was observed visually.
In addition, the criteria for determining adhesiveness are as shown in Table 1 below.

[Adhesion Evaluation Test (d)]
(1) Metal An aluminum foil (thickness: 50 μm) was used as the metal.
(2) Surface treatment of metal It carried out according to the following processes (a) to (b).
A. Acid clean / 1 minute (room temperature), water wash b. Immersion in surface treatment agent / 1 minute (room temperature), water washing, drying / 1 minute (100 ° C.)
(3) Adhesion of metal and resin A glass cloth epoxy resin-impregnated prepreg (FR-4 grade) was laminated and pressed on the treated aluminum foil, and the aluminum foil and the prepreg were adhered to produce a laminate.
(4) Evaluation of adhesiveness From this laminated board, according to "JIS C6481 (1996)", the test piece of width 10mm was produced, and the peeling strength of aluminum foil was measured.

[Adhesion evaluation test (e)]
(1) Resin Material Glass cloth epoxy resin impregnated prepreg (FR-4 grade) was used as the resin material.
(2) Surface treatment of resin material The surface of the prepreg was treated with a surface treatment agent by a spray method.
(3) Adhesion of resin material and copper foil An electrolytic copper foil (thickness: 35 μm) S surface was laminated and pressed on the treated prepreg, and the prepreg and the copper foil were adhered to produce a copper-clad laminate.
(4) Evaluation of adhesiveness From this copper clad laminate, according to "JIS C6481 (1996)", a test piece having a width of 10 mm was prepared, and the peel strength of the copper foil was measured.

[Adhesion evaluation test (f)]
(1) Surface treatment of inorganic material 10 parts by weight of barium sulfate was added to 100 parts by weight of the surface treatment agent and stirred for 5 minutes. Subsequently, barium sulfate was separated by filtration and dried in an oven at 100 ° C. for 1 hour to prepare barium sulfate carrying an azolesilane compound.
(2) Preparation of resin composition To 100 parts by weight of the solder resist ink, 1 part by weight of barium sulfate carrying an azolesilane compound was added and stirred for 30 minutes to prepare a resin composition.
(3) Preparation of copper-clad laminate After the obtained resin composition was applied on the S surface of an electrolytic copper foil (thickness: 35 μm), it was heated in an oven at 150 ° C. for 1 hour, A copper-clad laminate in which the cured product and copper foil were bonded was produced.
(4) Evaluation of adhesiveness From this copper clad laminate, according to "JIS C6481 (1996)", a test piece having a width of 10 mm was prepared, and the peel strength of the copper foil was measured.

[Adhesion evaluation test (g)]
(1) Preparation of resin composition To 100 parts by weight of the solder resist ink, 1 part by weight of a hydrolyzate described later was added and stirred for 30 minutes to prepare a resin composition.
(2) Production of copper-clad laminate After applying the obtained resin composition on the S surface of the electrolytic copper foil (thickness: 35 μm), drying (80 ° C./30 minutes), curing (150 ° C./60 minutes) ) To prepare a copper-clad laminate in which the cured product of this resin composition and the copper foil were bonded.
(3) Evaluation of adhesiveness From this copper clad laminate, according to "JIS C6481 (1996)", the test piece of width 10mm was produced, and the peeling strength of copper foil was measured.

[Example 1]
As a silane coupling agent component, 200 g of ethylene glycol monobutyl ether was added to 10 g of 3- [3- (trimethoxysilyl) propylthio] -1,2,4-triazole, and then 790 g of water was added. The mixture was stirred for a time to prepare a surface treatment agent (hereinafter referred to as treatment liquid A).
About this processing liquid A, it confirmed that the methoxy silyl group of the said azole silane compound was hydrolyzed to the hydroxy silyl group, and performed the adhesive evaluation test (a)-(f).
Subsequently, the volatile component in the treatment liquid A was removed under reduced pressure to obtain a hydrolyzate of an azolesilane compound. The obtained hydrolyzate was subjected to an adhesive evaluation test (g).
The test results obtained were as shown in Table 2.

[Example 2]
Instead of “3- [3- (trimethoxysilyl) propylthio] -1,2,4-triazole”, “3-amino-5- [3- (trimethoxysilyl) propylthio] -1,2,4- A surface treatment agent (hereinafter referred to as “treatment liquid B”) was prepared in the same manner as in Example 1 except that “triazole” was used, and adhesive evaluation tests (a) to (g) were performed on this treatment liquid B. It was.
The test results obtained were as shown in Table 2.

[Example 3]
Instead of “3- [3- (trimethoxysilyl) propylthio] -1,2,4-triazole”, “3-amino-5- [6- (trimethoxysilyl) hexylthio] -1,2,4- A surface treatment agent (hereinafter referred to as “treatment liquid C”) was prepared in the same manner as in Example 1 except that “triazole” was used, and this treatment liquid C was subjected to adhesive evaluation tests (a) to (g). It was.
The test results obtained were as shown in Table 2.

[Example 4]
Instead of “3- [3- (trimethoxysilyl) propylthio] -1,2,4-triazole”, “5-methyl-2- [3- (trimethoxysilyl) propylthio] -1,3,4- A surface treatment agent (hereinafter referred to as “treatment liquid D”) was prepared in the same manner as in Example 1 except that “thiadiazole” was used, and this treatment liquid D was subjected to adhesive evaluation tests (a) to (g). It was.
The test results obtained were as shown in Table 2.

[Comparative Example 1]
A surface treatment agent (hereinafter referred to as “the imidazole silane compound”) was used in the same manner as in Example 1 except that “imidazole silane compound” was used instead of “3- [3- (trimethoxysilyl) propylthio] -1,2,4-triazole”. Treatment liquid E) was prepared.
About this processing liquid E, it confirmed that the methoxy silyl group of the imidazole silane compound was hydrolyzed to the hydroxy silyl group, and it is the same as that of the case of Example 1 below, and adhesive evaluation test (a)-( g) was performed.
The test results obtained were as shown in Table 2.

[Comparative Example 2]
Instead of “3- [3- (trimethoxysilyl) propylthio] -1,2,4-triazole”, “3-aminopropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., product name“ KBM-903 ”)” A surface treatment agent (hereinafter referred to as treatment liquid F) was prepared in the same manner as in Example 1 except that it was used.
For this treatment liquid F, it was confirmed that the methoxysilyl group of 3-aminopropyltrimethoxysilane was hydrolyzed to a hydroxysilyl group. Hereinafter, in the same manner as in Example 1, an adhesive evaluation test ( a) to (g) were performed.
The test results obtained were as shown in Table 2.

[Comparative Example 3]
Without using a silane coupling agent, 200 g of ethylene glycol monobutyl ether and 790 g of water were mixed and stirred at room temperature for 2 hours to prepare a surface treatment agent (hereinafter referred to as treatment liquid G).
When this treatment liquid G was subjected to adhesive evaluation tests (a) to (f), the test results obtained were as shown in Table 2.
The adhesive evaluation test (g) was carried out without adding anything to the solder resist. The test results obtained were as shown in Table 2.

<Adhesion evaluation test-II>
The adhesive evaluation tests (h) to (j) performed in Examples (5 to 13) and Comparative Examples (4 to 9) are as follows.

[Adhesion evaluation test (h)]
(1) Metal An electrolytic copper foil (thickness: 18 μm) was used as the metal.
(2) Surface treatment of metal Any one selected from the following three treatment methods (α to γ) was employed.
<Treatment method α>
A. Acid cleaning (5% sulfuric acid aqueous solution) / 1 minute (room temperature), water washing b. Micro etching (etching amount 3 μm) / 1 minute (room temperature), water washing, drying / 1 minute (100 ° C.)
C. Immersion in surface treatment agent / 1 minute (room temperature), water washing, drying / 1 minute (100 ° C.)
<Processing method β>
A. Acid cleaning (5% sulfuric acid aqueous solution) / 1 minute (room temperature), water washing b. Micro etching (etching amount 3 μm) / 1 minute (room temperature), water washing, drying / 1 minute (100 ° C.)
C. Brush the surface treatment agent, wash with methanol, wash with water, dry / 1 minute (100 ° C)
<Processing method γ>
A. Acid cleaning (5% sulfuric acid aqueous solution) / 1 minute (room temperature), water washing b. Micro etching (etching amount 3 μm) / 1 minute (room temperature), water washing, drying / 1 minute (100 ° C.)
C. Brush the surface treatment agent, dry / 1 minute (100 ° C)
(3) Adhesion of metal and resin A glass cloth epoxy resin-impregnated prepreg (FR-4 grade) was laminated and pressed on the S surface of the treated copper foil, and the copper foil and the prepreg were adhered to produce a copper-clad laminate.
(4) Evaluation of adhesiveness From this copper clad laminate, according to "JIS C6481 (1996)", a test piece having a width of 10 mm was prepared, and the peel strength of the copper foil was measured. The peel strength after 2 reflow heatings (peak temperature 260 ° C., air) was also measured.

[Adhesion evaluation test (i)]
(1) Resin Material Glass cloth epoxy resin impregnated prepreg (FR-4 grade) was used as the resin material.
(2) Surface treatment of resin material Any one selected from the following three treatment methods (α to γ) was employed.
<Treatment method α>
A. Acid cleaning (5% sulfuric acid aqueous solution) / 1 minute (room temperature), water washing b. Immersion in surface treatment agent / 1 minute (room temperature), water washing, drying / 1 minute (100 ° C.)
<Processing method β>
A. Acid cleaning (5% sulfuric acid aqueous solution) / 1 minute (room temperature), water washing b. Brush the surface treatment agent, wash with methanol, wash with water, dry / 1 minute (100 ° C)
<Processing method γ>
A. Acid cleaning (5% sulfuric acid aqueous solution) / 1 minute (room temperature), water washing b. Brush the surface treatment agent, dry / 1 minute (100 ° C)
(3) Adhesion of resin material and copper foil An electrolytic copper foil (thickness: 35 μm) S surface was laminated and pressed on the treated prepreg, and the prepreg and the copper foil were adhered to produce a copper-clad laminate.
(4) Evaluation of adhesiveness About this copper clad laminated board, it carried out similarly to the case of the adhesive evaluation test (h).

[Adhesion evaluation test (j)]
(1) Metal As the metal, a copper foil subjected to silver plating (thickness: 0.1 to 0.3 μm) was used.
(2) Surface treatment of metal It carried out according to the following processes (a) to (b).
A. Acid cleaning (5% sulfuric acid aqueous solution) / 1 minute (room temperature), water washing b. Brush the surface treatment agent, wash with methanol, wash with water, dry / 1 minute (100 ° C)
(3) Adhesion of metal and resin A glass cloth epoxy resin-impregnated prepreg (FR-4 grade) is laminated and pressed on the silver-plated surface of the treated silver-plated copper foil, and the silver-plated copper foil and prepreg are bonded together to form silver-plated copper. A tension laminate was produced.
(4) Evaluation of adhesiveness About this silver plating copper clad laminated board, it carried out similarly to the case of the adhesive evaluation test (h). Note that the peel strength after two reflow heatings has not been measured.

[Example 5]
As a silane coupling agent component, 990 g of a 1: 1 mixture of water and methanol was added to 10 g of 3-amino-5- [3- (trimethoxysilyl) propylthio] -1,2,4-triazole at room temperature. The mixture was stirred for 2 hours to prepare a surface treatment agent (hereinafter referred to as treatment liquid H).
About this processing liquid H, it confirmed that the methoxy silyl group of the said azole silane compound was hydrolyzed to the hydroxy silyl group, and performed the adhesive evaluation test (h) (processing method (gamma)).
The test results obtained were as shown in Table 3.

[Example 6]
Using the treatment liquid H, an adhesive evaluation test (h) (treatment method β) was performed. The test results obtained were as shown in Table 3.

[Example 7]
A surface treatment agent (hereinafter referred to as treatment liquid I) was prepared in the same manner as in Example 5 except that methanol was used instead of the 1: 1 mixture of water and methanol.
This treatment liquid I was subjected to an adhesive evaluation test (h) (treatment method γ).
The test results obtained were as shown in Table 3.

[Example 8]
Using the treatment liquid I, an adhesion evaluation test (h) (treatment method β) was performed. The test results obtained were as shown in Table 3.

[Example 9]
Instead of adding 990 g of a 1: 1 mixture of water and methanol, 200 g of ethylene glycol monobutyl ether was added, and subsequently, 790 g of water was added. J).
About this processing liquid J, it confirmed that the methoxy silyl group of the said azole silane compound was hydrolyzed to the hydroxy silyl group, and performed the adhesive evaluation test (h) (processing method (alpha)).
The test results obtained were as shown in Table 3.

[Comparative Example 4]
Instead of 3-amino-5- [3- (trimethoxysilyl) propylthio] -1,2,4-triazole, 3-mercaptopropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., product name “KBM-803”) was used. A surface treatment agent (hereinafter referred to as treatment liquid K) was prepared in the same manner as in Example 5 except that it was used.
About this processing liquid K, it confirmed that the methoxysilyl group of this silane compound was hydrolyzed to the hydroxysilyl group, and performed the adhesive evaluation test (h) (processing method (gamma)).
The test results obtained were as shown in Table 3.

[Comparative Example 5]
Instead of 3-amino-5- [3- (trimethoxysilyl) propylthio] -1,2,4-triazole, 3-glycidoxypropyltrimethoxysilane (trade name “KBM-403” manufactured by Shin-Etsu Chemical Co., Ltd.) ) Was used in the same manner as in Example 5 to prepare a surface treating agent (hereinafter referred to as “treatment liquid L”).
About this processing liquid L, it confirmed that the methoxysilyl group of this silane compound was hydrolyzed to the hydroxysilyl group, and performed the adhesive evaluation test (h) (processing method (gamma)).
The test results obtained were as shown in Table 3.

[Comparative Example 6]
Without using a silane coupling agent, 500 g of methanol and 500 g of water were mixed and stirred at room temperature for 1 hour to prepare a surface treatment agent (hereinafter referred to as treatment liquid M).
When this treatment solution M was subjected to an adhesive evaluation test (h) (treatment method α), the test results obtained were as shown in Table 3.

[Example 10]
As a silane coupling agent component, 990 g of methanol was added to 10 g of 3- [3- (trimethoxysilyl) propylthio] -1,2,4-triazole, and the mixture was stirred at room temperature for 2 hours. Liquid N) was prepared.
About this processing liquid N, it confirmed that the methoxy silyl group of the said azole silane compound was hydrolyzed to the hydroxy silyl group, and performed the adhesive evaluation test (i) (processing method (gamma)).
The test results obtained were as shown in Table 4.

[Example 11]
As a silane coupling agent component, 990 g of a 1: 1 mixture of water and methanol was added to 10 g of 3-amino-5- [3- (trimethoxysilyl) propylthio] -1,2,4-triazole at room temperature. The mixture was stirred for 2 hours to prepare a surface treatment agent (hereinafter referred to as treatment liquid O).
About this process liquid O, the adhesive evaluation test similar to the case of Example 10 was done.
The test results obtained were as shown in Table 4.

[Example 12]
Using the treatment liquid O, an adhesive evaluation test (i) (treatment method β) was performed. The test results obtained were as shown in Table 4.

[Comparative Example 7]
Using the treatment liquid K, the same adhesive evaluation test as in Example 10 was performed. The test results obtained were as shown in Table 4.

[Comparative Example 8]
In the same manner as in Example 11 except that an imidazolesilane compound was used instead of 3-amino-5- [3- (trimethoxysilyl) propylthio] -1,2,4-triazole, a surface treatment agent (hereinafter referred to as a surface treatment agent) , Treatment liquid P).
For this treatment liquid P, it was confirmed that the methoxysilyl group of the imidazolesilane compound was hydrolyzed to a hydroxysilyl group, and the same adhesive evaluation test as in Example 10 was performed.
The test results obtained were as shown in Table 4.

[Example 13]
Using the treatment liquid N, an adhesive evaluation test (j) was performed. The test results obtained were as shown in Table 5.

[Comparative Example 9]
Using the treatment liquid M, the same adhesive evaluation test as in Example 13 was performed. The test results obtained were as shown in Table 5.

  According to the present invention, the adhesion (adhesion) between the metal, the inorganic material, and the resin material can be sufficiently ensured, so that the surface of the material to be treated can be maintained in a smooth state without being roughened. Therefore, the present invention can greatly contribute to the realization of the multilayer printed wiring board, such as miniaturization, thinning, high frequency, high density, etc., and thus the industrial applicability is great.

Claims (16)

Chemical formula (I)

[In the formula (I), X represents a hydrogen atom, —CH ₃ , —NH ₂ , —SH or —SCH ₃ . Y represents -NH- or -S-. R represents —CH ₃ or —CH ₂ CH ₃ . m represents an integer of 1 to 12, and n represents an integer of 0 or 1].
The surface treating agent containing the azole silane compound shown by these.   The copper foil which has a film | membrane by the surface treating agent of Claim 1.   The prepreg which has a film | membrane by the surface treating agent of Claim 1.   The copper clad laminated board which has a film | membrane by the surface treating agent of Claim 1.   The interlayer insulation material which has a film | membrane by the surface treating agent of Claim 1.   A copper foil with a resin in which a copper foil and a resin layer are laminated via a film made of the surface treatment agent according to claim 1.   A printed wiring board provided with the member which has a film | membrane by the surface treating agent of Claim 1. A resin or a pre-cured compound thereof and a chemical formula (I)

[In the formula (I), X represents a hydrogen atom, —CH ₃ , —NH ₂ , —SH or —SCH ₃ . Y represents -NH- or -S-. R represents —CH ₃ or —CH ₂ CH ₃ . m represents an integer of 1 to 12, and n represents an integer of 0 or 1].
The resin composition containing the azole silane compound shown by these.   The solder resist ink comprised from the resin composition of Claim 8.   A printed wiring board provided with the soldering resist formed from the soldering resist ink of Claim 9.   The prepreg comprised from the base material and the resin composition of Claim 8.   The copper clad laminated board comprised from the copper foil and the prepreg of Claim 11.   The interlayer insulation material comprised from the resin composition of Claim 8.   The copper foil with resin comprised from the resin layer formed with the copper foil and the resin composition of Claim 8.   A printed wiring board provided with the resin layer formed with the resin composition of Claim 8.   The semiconductor sealing material comprised from the resin composition of Claim 8.