JP2016121348A - Surface treatment liquid, surface treatment method of inorganic material or resin material and use thereof - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a surface treatment liquid, a surface treatment method and an adhesion method of an inorganic material or a resin material using an azole silane compound for enhancing adhesiveness of two materials having different material quality selected from metal, an inorganic material and a resin material and an electronic device and a printed wiring board using them.SOLUTION: There is provided a surface treatment liquid for an inorganic material or a resin material containing an azole silane compound represented by the chemical formula (I), used for adhering two materials selected from a metal, the inorganic material or the resin material, where the metal is copper, aluminum, titanium, nickel, tin, iron, silver, gold or alloy thereof. (I), where X is H, -CH, -NH, -SH or -SCH, Y is -NH- or -S-, R is -CHor -CHCH, m is an integer of 1 to 12, n is 0 or an integer of 1 to 3.SELECTED DRAWING: None

Description

  The present invention relates to a surface treatment liquid for inorganic materials or resin materials using an azolesilane compound, a surface treatment method, and use thereof.

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.

Prior art related to the present invention will be described below with reference to literature.
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 hydroxysilyl group is preferable as a component of the surface conditioning composition because it has excellent adhesion to an insulating material, and among them, adhesion between copper and an insulating material such as an epoxy resin. In view of improving the properties, 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.

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

  The present invention relates to a surface treatment liquid, a surface treatment method and an adhesion method for an inorganic material or a resin material using an azolesilane compound in order to enhance the adhesion of two materials selected from metals, inorganic materials and resin materials. And it aims at providing the electronic device and printed wiring board using these.

As a result of intensive studies to solve the above-mentioned problems, the present inventors have found that an aqueous solution in which a silane compound having an azole ring and a thioether bond (-S-) in the molecule is dissolved has an intended purpose. It has been found that this has been achieved, and the present invention has been completed.
That is, the first invention is a surface treatment liquid for an inorganic material or a resin material containing an azolesilane compound represented by the chemical formula (I).

（式中、Ｘは水素原子、−ＣＨ_３、−ＮＨ_２、−ＳＨまたは−ＳＣＨ_３を表す。Ｙは−ＮＨ−または−Ｓ−を表す。Ｒは−ＣＨ_３または−ＣＨ_２ＣＨ_３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。）

(In the formula, 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 to 3).

According to a second aspect of the present invention, there is provided an inorganic material or a resin material containing an azolesilane compound represented by the chemical formula (I) used for bonding two materials selected from the group consisting of metals, inorganic materials, and resin materials. It is a surface treatment liquid.
3rd invention is the surface treatment liquid of the inorganic material or resin material of 2nd invention whose metal is copper, aluminum, titanium, nickel, tin, iron, silver, gold, or these alloys.
4th invention is the surface treatment liquid of the inorganic material or resin material of 2nd invention whose metal is copper or a copper alloy.
A fifth invention is a surface treatment liquid for an inorganic material or a resin material according to any one of the first to fourth inventions, wherein the inorganic material is silicon, ceramic, glass, or an inorganic salt.
A sixth invention is a surface treatment liquid for an inorganic material or a resin material according to the fifth invention, wherein the ceramic is alumina, silicon carbide, aluminum nitride, silicon nitride, or barium titanate.
7th invention is the surface treatment liquid of the inorganic material or resin material of any one of 1st invention-6th invention whose resin material is an acrylate resin, an epoxy resin, or a polyimide resin.

The eighth invention is an inorganic material surface treatment method in which a surface treatment liquid containing an azolesilane compound represented by the chemical formula (I) is brought into contact with an inorganic material.
A ninth invention is the surface treatment method for an inorganic material according to the eighth invention, wherein the inorganic material is silicon, ceramic, glass, or an inorganic salt.
A tenth invention is the inorganic material surface treatment method of the ninth invention, wherein the ceramic is alumina, silicon carbide, aluminum nitride, silicon nitride or barium titanate.
The eleventh invention is a resin material surface treatment method in which a surface treatment liquid containing an azolesilane compound represented by the chemical formula (I) is brought into contact with the resin material.
The twelfth invention is the surface treatment method for a resin material according to the eleventh invention, wherein the resin material is an acrylate resin, an epoxy resin or a polyimide resin.

A thirteenth invention is a method for bonding a metal and a resin material, wherein a surface treatment liquid containing an azolesilane compound represented by the chemical formula (I) is brought into contact with the resin material to form a chemical conversion film on the resin material. In this method, the metal and the resin material are bonded together via a chemical conversion film.
A fourteenth invention is a method for adhering an inorganic material and a resin material, wherein the surface treatment liquid containing the azolesilane compound represented by the chemical formula (I) is brought into contact with at least one of the inorganic material and the resin material. This is a method for bonding an inorganic material and a resin material, in which a chemical conversion film is formed on at least one and the inorganic material and the resin material are bonded via the chemical conversion film.
A fifteenth invention is a method for bonding a metal and an inorganic material, wherein a surface treatment liquid containing an azolesilane compound represented by the chemical formula (I) is brought into contact with the inorganic material to form a chemical conversion film on the inorganic material. In this method, the metal and the inorganic material are bonded to each other through the chemical conversion film.

The sixteenth invention comprises a composite material in which a metal and a resin material are bonded via a chemical conversion film formed on the surface of the resin material by a surface treatment liquid containing an azolesilane compound represented by the chemical formula (I). It is an electronic device.
In a seventeenth aspect of the invention, an inorganic material and a resin material are passed through a chemical conversion film formed on at least one surface of the inorganic material and the resin material by the surface treatment liquid containing the azolesilane compound represented by the chemical formula (I). An electronic device comprising a bonded composite material.
The eighteenth invention comprises a composite material in which a metal and an inorganic material are bonded via a chemical conversion film formed on the surface of the inorganic material by a surface treatment liquid containing the azolesilane compound represented by the chemical formula (I). It is an electronic device.
A nineteenth invention comprises a composite material in which a metal and a resin material are bonded via a chemical conversion film formed on the surface of the resin material by a surface treatment liquid containing an azolesilane compound represented by the chemical formula (I). It is a printed wiring board.
In a twentieth aspect of the invention, the inorganic material and the resin material are passed through a chemical conversion film formed on at least one surface of the inorganic material and the resin material by the surface treatment liquid containing the azolesilane compound represented by the chemical formula (I). It is a printed wiring board provided with the bonded composite material.
A twenty-first invention comprises a composite material in which a metal and an inorganic material are bonded through a chemical conversion film formed on the surface of the inorganic material by a surface treatment liquid containing the azolesilane compound represented by the chemical formula (I). It is a printed wiring board.

A twenty-second invention is an insulating composition containing an azolesilane compound represented by the chemical formula (I) and a resin material and / or an inorganic material.
A twenty-third invention is the insulating composition of the twenty-second invention, wherein the resin material is an acrylate resin, an epoxy resin, or a polyimide resin.
A twenty-fourth invention is the insulating composition of the twenty-second invention or the twenty-third invention, wherein the inorganic material is silicon, ceramic, glass, or an inorganic salt.

A twenty-fifth aspect of the invention is an insulating material containing the insulating composition according to any one of the twenty-second to twenty-fourth aspects as a component.
A twenty-sixth invention is an electronic device having an insulating layer obtained from the insulating composition of any one of the twenty-second to twenty-fourth inventions.
A twenty-seventh invention is a printed wiring board having an insulating layer obtained from the insulating composition of any one of the twenty-second to twenty-fourth inventions.

  According to the present invention, adhesion between two different materials, that is, a metal and an inorganic material, a metal and a resin material, and an inorganic material and a resin material can be enhanced.

  Hereinafter, the present invention will be described in detail.

(Surface treatment liquid)
The surface treatment liquid of the present invention is used for the surface treatment of an inorganic material or a resin material, and contains an azole silane compound represented by the above chemical formula (I) as an active ingredient. The azole silane compound has the chemical formula (Ia) The azole silane compound shown by-(Id) is included.
The surface treatment liquid of the present invention may be simply referred to as a surface treatment liquid or a treatment liquid.

（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 described above.)

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

  The azole silane compounds (Ib) to (Id) are species generated by hydrolysis of the azole silane compound (Ia) present in the surface treatment liquid, and these are trialkoxy azole silane compounds (Ia). In addition, it is suitable as a component of the silane coupling agent. Further, the azole silane compounds (Ib) to (Id) can be used by being extracted from the surface treatment liquid by removing volatile components from the surface treatment liquid, for example.

  In the practice of the present invention, it is preferable to use the azolesilane compound (Ia) as a raw material for the components in the surface treatment liquid.

Examples of the azole silane compound (Ia) include
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 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 alkyl halide). Silane compound (III)) can be synthesized by reacting in an appropriate amount of reaction solvent at an appropriate reaction temperature and reaction time in the presence of a dehydrohalogenating agent. (See Scheme (A)).

（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,
Examples include 2,5-dimercapto-1,3,4-thiadiazole and 2-mercapto-5-methylthio-1,3,4-thiadiazole.

As the halogenated alkylsilane compound (III), for example,
Chloromethyltrimethoxysilane,
Chloromethyltriethoxysilane,
2-chloroethyltrimethoxysilane,
2-chloroethyltriethoxysilane,
3-chloropropyltrimethoxysilane,
3-chloropropyltriethoxysilane,
3-bromopropyltrimethoxysilane,
3-bromopropyltriethoxysilane,
3-iodopropyltrimethoxysilane,
3-iodopropyltriethoxysilane,
4-bromobutyltrimethoxysilane,
4-bromobutyltriethoxysilane,
5-bromopentyltrimethoxysilane,
5-bromopentyltriethoxysilane,
6-bromohexyltrimethoxysilane,
6-bromohexyltriethoxysilane,
8-bromooctyltrimethoxysilane,
8-bromooctyltriethoxysilane,
10-bromodecyltrimethoxysilane,
10-bromodecyltriethoxysilane,
Examples thereof include 12-bromododecyltrimethoxysilane and 12-bromododecyltriethoxysilane.

The surface treatment liquid of the present invention is prepared by mixing the azole silane compound (Ia) and water, but a solubilizer may be used in combination with water.
Regarding the method for preparing the surface treatment liquid when water and a solubilizing agent are used in combination, the solubilizing agent may be added after the azole silane compound (Ia) and water are mixed, or the compound, water and A mixed solution of solubilizers may be mixed, or water may be added after mixing the compound and the solubilizer.
Moreover, as water used for preparation of a surface treatment liquid, pure water, such as ion-exchange water and distilled water, is preferable.

As the solubilizer,
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, polyethylene Glycol monobutyl ether, triethylene glycol dimethyl ether, triethylene glycol diethyl ether, tetrahydrofurfuryl alcohol, furfuryl alcohol, acetone, tetrahydrofuran, dioxane, acetonitrile, 2-pyrrolidone, formamide, N, N-dimethylformamide, N, N-dimethyl Acetamide, 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, methylamine, dimethylamine, trimethyl Amine, ethylamine, diethylamine, triethylamine, propylamine, isopropylamine, butylamine, allylamine, ethylenediamine, diethylenetriamine, triethylenetetramine, monoethanolamine, diethanolamine, triethanolamine, dipropanolamine, tripropanolamine, diisopropanolamine, triisopropanol Amine, 1-amino-2-propanol, 3-amino-1-propanol, 2-amino-1-propanol, N, N-dimethylethanolamine, cyclohexylamine, aniline, pyrrolidine, piperidine, piperazine and pyridine are preferred.
In the practice of the present invention, two or more selected from these may be used in combination.

As described above, the azole silane compound (Ia) is hydrolyzed when contacted with water. The mode of hydrolysis is shown in Scheme (B).
In this scheme (B), the silyl group of the azole silane compounds (Ia) to (Ic) is hydrolyzed, that is, the trialkoxysilyl group is gradually dialkoxyhydroxysilyl group, dihydroxyalkoxysilyl. A state of changing to a group, a trihydroxysilyl group is simply shown.

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

In the practice of the present invention, the concentration of the azole silane compound (I) in the surface treatment liquid is 0.001 to 10% by weight in terms of the concentration of the trialkoxy azole silane compound (Ia). Preferably, 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 generated in the surface treatment liquid 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. In addition, X of group shown by Chemical formula (e) is an integer showing the number of repeating units.

When the amount of silane oligomer generated in the surface treatment liquid increases, the insoluble matter precipitates (the treatment liquid becomes cloudy), and the treatment tank, the pipe connected to the treatment tank, the treatment liquid immersed in the treatment liquid 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 to include the solubilizer in the surface treatment liquid.
About content of a solubilizer, 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.

  In the preparation of the surface treatment liquid 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 solution and the uniformity of the chemical conversion film, a substance that generates halogen ions such as chlorine ions and bromine ions and metal ions such as copper ions, iron ions, and zinc ions is 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
3-mercaptopropyltrimethoxysilane,
Mercaptosilane compounds such as 3-mercaptopropylmethyldimethoxysilane,
Vinyltrichlorosilane,
Vinyltrimethoxysilane,
Vinylsilane compounds such as vinyltriethoxysilane,
vinylphenylsilane compounds such as p-vinylphenyltrimethoxysilane,
2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane,
3-glycidoxypropyltrimethoxysilane,
3-glycidoxypropylmethyldiethoxysilane,
Epoxy silane compounds such as 3-glycidoxypropyltriethoxysilane,
Acryloxysilanes such as 3-acryloxypropyltrimethoxysilane;
Methacryloxypropylmethyldimethoxysilane,
Methacryloxypropyltrimethoxysilane,
Methacryloxypropylmethyldiethoxysilane,
Methacryloxysilane compounds such as 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,
Sulfide silane compounds such as bis (triethoxysilylpropyl) tetrasulfide,
Examples include isocyanate silane compounds such as 3-isocyanatopropyltriethoxysilane.
In addition, an aluminum coupling agent, a titanium coupling agent, a zirconium coupling agent, and the like can also be exemplified.

(Surface treatment method)
Examples of the inorganic material to be treated with the surface treatment liquid of the present invention include silicon, ceramic, carbon used as a filler, inorganic salts, 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.
Of these inorganic materials, silicon, ceramics (alumina, silicon carbide, aluminum nitride, silicon nitride and barium titanate), glass and inorganic salts are preferred.

Examples of resin materials to be treated with the surface treatment liquid of the present invention include acrylate resins, epoxy resins, polyimide resins, bismaleimide resins, maleimide resins, cyanate resins, polyphenylene ether resins, polyphenylene oxide resins, polybutadiene resins, olefin resins, A fluorine-containing resin, a polyetherimide resin, a polyetheretherketone resin, a liquid crystal resin, and the like can be given. These may be mixed or modified to be combined 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.

Preferred examples of the metal to be bonded to the inorganic material or resin material treated with the surface treatment liquid of the present invention include copper, aluminum, titanium, nickel, tin, iron, silver, gold, and alloys thereof.
Examples of the copper alloy are not particularly limited as long as it is an alloy containing copper. For example, Cu-Ag, Cu-Te, Cu-Mg, Cu-Sn, Cu-Si, and Cu-Mn are available. Cu-Be-Co, Cu-Ti, Cu-Ni-Si, Cu-Zn-Ni, Cu-Cr, Cu-Zr, Cu-Fe, Cu-Al, Cu-Zn And alloys such as Cu-Co alloys.
Examples of other alloys include an aluminum alloy (Al—Si alloy), a nickel alloy (Ni—Cr alloy), and an iron alloy (Fe—Ni alloy, stainless steel).
Among these metals, copper and copper alloys (hereinafter, both may be referred to simply as copper) are more preferable.

  In addition, the metal to be bonded to the inorganic material or resin material treated with the surface treatment liquid of the present invention is a foil (for example, an electrolytic copper foil, an electronic device such as a printed wiring board and a lead frame, a decorative article, and a building material. Rolled copper foil), plating film (for example, electroless copper plating film, electrolytic copper plating film), thin film formed by vapor deposition method, sputtering method, damascene method, etc., granular, needle-like, fibrous, linear, rod-like , Tubular, plate-like and other uses / forms. 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.

There is no restriction | limiting in particular as a method of making the surface treatment liquid of this invention contact the surface of an inorganic material or a resin material, Means, such as immersion, application | coating, a spray, are employable.
The time (treatment time) for bringing the surface treatment liquid into contact with the inorganic material or the resin material 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 of the chemical conversion film formed on the surface of the inorganic material or the resin material becomes thin, and sufficient adhesion between different materials cannot be obtained. Even if the length is increased, there is no great difference in the film thickness of the chemical conversion film, and improvement in adhesion cannot be expected.
Moreover, about the temperature of the processing liquid at the time of making a surface processing liquid contact the surface of an inorganic material or a resin material, 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 contacting the surface treatment liquid of the present invention with the inorganic material or the resin material, it may be washed with water and then dried, or may be dried without being washed with water.
The drying temperature is preferably 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 washed for an appropriate time by means such as dipping or spraying.

  Before bringing the surface treatment liquid 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 at least one selected from pickling treatment, alkali washing treatment, roughening treatment, or heat treatment. One pretreatment may be performed.

  The pickling treatment is performed to remove oil and fat components adhering to the surface of the inorganic material or resin material. 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 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 inorganic material or resin material, and enhances the adhesion (adhesion) of two materials selected from metal, inorganic material and resin material by the anchor effect. To do. 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 inorganic material or resin material, thereby forming irregularities on the surface of the inorganic material or resin material.

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

Before bringing the surface treatment liquid of the present invention into contact with the surface of the inorganic material or resin material, an aqueous solution containing copper ions may be brought into contact with the surface of the 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 inorganic material or resin material uniform.
The copper ion source 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.

After bringing the surface treatment liquid of the present invention into contact with the surface of the inorganic material or resin material, an acidic or alkaline aqueous solution may be brought into contact with the surface of the inorganic material or resin material. This acidic or alkaline aqueous solution also has a function of making the thickness of the chemical conversion film formed on the surface of the inorganic material or the resin material uniform, like the aqueous solution containing copper ions.
The acidic aqueous solution and the alkaline aqueous solution are not particularly limited. Examples of the acidic aqueous solution include 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. 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 liquid of the present invention is brought into contact with the surface of the inorganic material or resin material, a treatment such as plasma, laser, ion beam, ozone, heating or humidification is performed, and the inorganic material or resin material is treated. The surface may be modified. In addition, cleaning for the purpose of removing resin / ion residues of inorganic materials or resin materials may be performed using mechanical polishing such as plasma, laser, ion beam, permis brush, or a drilling method.

  In the process of metal plating or mounting on the surface of the inorganic material or resin material in contact with the surface treatment liquid of the present invention, plasma, laser, ion beam, ozone, heating, humidification or the like is performed to improve the surface. Further, cleaning for the purpose of removing the residue may be performed.

  In the step of metal plating or mounting on the surface of the inorganic material or resin material in contact with the surface treatment liquid of the present invention, primer treatment such as organic film or metal film for the purpose of improving adhesion may be performed.

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

  The surface treatment liquid of the present invention can be used for treating the surface of the inorganic material or resin material. By treating the surface of the inorganic material or resin material using the surface treatment liquid of the present invention, a chemical conversion film can be formed on the surface of the inorganic material or resin material, and the adhesion to other materials can be enhanced.

  In the present invention, two materials selected from the group consisting of the metals, inorganic materials, and resin materials can be bonded using the surface treatment liquid of the present invention. By using the chemical conversion film (chemical conversion film layer) formed by the surface treatment liquid of the present invention, mutual affinity can be improved, so even different materials can be bonded more firmly. it can.

(Adhesion method)
As a bonding method, a known method can be used.
The surface treatment liquid of the present invention is brought into contact with the surface of the inorganic material and / or resin material to form a chemical conversion film on the surface of one of the materials or both materials, and the two materials are applied, pressure bonded, Examples thereof include a method of mixing, the use of an adhesive, an adhesive sheet (film), or a method of bonding by combining these means.
In addition, the surface treatment liquid of the present invention is contacted with the surface of the inorganic material or resin material to form a chemical conversion film, and a part or the whole of the formed chemical conversion film is subjected to means such as pressure bonding, an adhesive, and an adhesive sheet The use of (film) or a method of adhering these means in combination.

  By using the surface treatment liquid of the present invention, a composite material obtained by adhering two materials, particularly two materials different from each other, as described above can be obtained. Therefore, various electrical components equipped with such a composite material It can be suitably used for electronic devices such as electronic components and printed wiring boards.

  The surface treatment liquid of the present invention is a semi-cured or cured prepreg, a solder resist, a semi-cured or cured dry film (insulating resin layer), and an adhesive property (adhesion) between the copper circuit (copper wiring layer). It is suitable for surface treatment of a resin material for the purpose of enhancing the adhesive strength, and in a printed wiring board having an insulating resin layer in contact with the copper wiring layer, enhancing the adhesion between the copper wiring layer and the insulating resin layer Can do.

The printed wiring board can be produced by bringing the surface treatment liquid of the present invention and the surface of the insulating resin layer into contact with each other, then washing and drying, and then bonding the insulating resin layer and the surface of the copper wiring layer. . The contact method is as described above, and it is preferable that immersion of the insulating resin layer in the surface treatment liquid or spraying on the surface of the insulating resin layer with the treatment liquid is simple and reliable.
The washing method is not particularly limited, but immersion of the insulating resin layer in washing water or spraying on the surface of the insulating resin layer with washing water is preferable because it is simple and reliable.
As a method of adhering the insulating resin layer and the copper wiring layer, a known method, for example, a method of attaching a semi-cured resin material or the like can be employed.
In the case of producing a multilayer printed wiring board, a process of adhering an insulating resin layer and a copper wiring layer may be repeated a desired number of times to form via holes in order to make the upper and lower wirings conductive.

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

  In addition, “copper” used in the present invention is a foil (electrolytic copper foil, rolled copper foil), plating film (electroless copper plating) used for electronic devices such as printed wiring boards and lead frames, ornaments, and building materials. Film, electrolytic copper plating film), wire, rod, tube, plate and the like. 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.

(Insulating composition)
The azole silane compound represented by the chemical formula (I) can be made into an insulating composition by being contained in a resin material and / or an inorganic material as a silane coupling agent.
Moreover, an insulating composition can also be obtained by dissolving the azole silane compound represented by the chemical formula (I) in an organic solvent and mixing it with a resin material and / or an inorganic material.

The content of the azolesilane compound in the insulating composition is preferably 0.001 to 10% by weight, and more preferably 0.01 to 5% by weight. When the content of the azole silane compound is less than 0.001% by weight in the insulating composition, the effect of improving the adhesiveness is not sufficient, and when the concentration exceeds 10% by weight, the adhesive property The improvement effect has almost reached its peak, and the amount of the azolesilane compound used is increased, which is not economical.
The insulating composition can be produced by a known method. For example, the insulating composition can be produced by dissolving the azole silane compound in an organic solvent and mixing it with a solid or liquid resin material. Alternatively, the azole silane compound may be directly added to and mixed with a liquid resin material to produce an insulating composition. Furthermore, a conventionally well-known inorganic material can be added to the said component, and an insulating composition can be produced. As the organic solvent, a normal organic solvent used as a paint or a diluent for the paint can be used.

  Since the insulating composition of the present invention provides an insulating material having high strength, it can be suitably used for electronic devices such as various electric parts and electronic parts, printed wiring boards, and the like.

  EXAMPLES Hereinafter, although an Example and a comparative example demonstrate this invention concretely, this invention is not limited to these. The main raw materials used in the examples are as follows.

[Main ingredients]
3- [3- (Trimethoxysilyl) propylthio] -1,2,4-triazole (Synthesis example shown in Reference Example 1)
Synthesis of 3-amino-5- [3- (trimethoxysilyl) propylthio] -1,2,4-triazole (Synthesis example shown in Reference Example 2)
3-amino-5- [6- (trimethoxysilyl) hexylthio] -1,2,4-triazole (Synthesis example shown in Reference Example 3)
5-methyl-2- [3- (trimethoxysilyl) propylthio] -1,3,4-thiadiazole (Synthesis example shown in Reference Example 4)
・ Imidazolesilane compound (The synthesis method was shown in Reference Example 5)
・ 3-Aminopropyltrimethoxysilane (Shin-Etsu Chemical Co., Ltd., product name “KBM-903”)
・ Ethylene glycol monobutyl ether (Wako Pure Chemical Industries, Reagent)
Solder resist (acrylate / epoxy resin, manufactured by Taiyo Ink Manufacturing Co., Ltd., product name “PSR-4000AUS308”)

[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 consisting 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 Stir for 3 hours and 30 minutes at ° C.
The reaction mixture was concentrated under reduced pressure, and 12.5 g of the resulting white viscous substance was extracted with 40 mL of diethyl ether three times. The extract was filtered and concentrated under reduced pressure to give a chemical formula (Ia-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 consisting of 7.0 g (60 mmol) of 3-amino-5-mercapto-1,2,4-triazole and 100 mL of dehydrated methanol was cooled to 10 ° C., and 3.2 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 17.4 g (60 mmol) of 3-iodopropyltrimethoxysilane and 20 mL of dehydrated methanol was added dropwise over 30 minutes at room temperature. It stirred at 27-30 degreeC for 3 hours and 30 minutes.
The reaction mixture 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 concentrated under reduced pressure to give a chemical formula (Ia-2) as a pale tan oil. ) 9.2 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 3.5 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 homogeneous 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 solution 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 (Ia-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 2-mercapto-5-methyl-1,3,4-thiadiazole and 100 mL of dehydrated methanol was cooled to 10 ° C., and 11.6 g (60 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 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 solution 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 (Ia-4 as a slightly tan oil). 16.9 g (60 mmol, yield 99.9%) of the title azole silane compound represented by

[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 Japanese Patent Laid-Open No. 5-186479, the reaction product is a mixture of imidazole silane compounds represented by chemical formulas (IV-1) to (IV-3).

<Adhesion evaluation test>
Evaluation tests (a) to (c) of the adhesion between the resin material and the metal performed in the following examples and comparative examples are as follows.

[Adhesion Evaluation Test (a)]
(1) Resin Material Glass cloth epoxy resin impregnated prepreg (FR-4 grade) was used as the resin material.
(2) Treatment of resin material The surface of the resin material was treated with a surface treatment liquid by a spray method.
(3) Production of Printed Wiring Board An electrolytic copper foil (thickness: 35 μm) S surface was laminated and pressed on the processed resin material, and the resin material and copper were bonded to produce a printed wiring board.
(4) Evaluation of adhesiveness From this printed wiring board, according to "JIS C6481 (1996)", the test piece of width 10mm was produced, and the peeling strength of copper foil was measured.

[Adhesion Evaluation Test (b)]
(1) Treatment of inorganic material 10 parts by weight of barium sulfate was added to 100 parts by weight of the surface treatment solution and stirred for 5 minutes. Subsequently, the barium sulfate carrying the silane coupling agent was filtered and dried in an oven at 100 ° C. for 1 hour.
(2) Preparation of resin composition 1 part by weight of barium sulfate carrying a silane coupling agent was added to 100 parts by weight of the solder resist before curing, and stirred for 30 minutes to prepare a resin composition.
(3) Production of Printed Wiring Board 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 60 minutes to cure this resin composition. The printed wiring board which the thing (resin material) and copper foil adhered was produced.
(4) Evaluation of adhesiveness From this printed wiring board, according to "JIS C6481 (1996)", the test piece of width 10mm was produced, and the peeling strength of copper foil was measured.

[Adhesion Evaluation Test (c)]
(1) Preparation of insulating composition With respect to 100 parts by weight of the solder resist before curing, 1 part by weight of a hydrolyzate described later was added and stirred for 30 minutes to prepare an insulating composition.
(2) Production of Printed Wiring Board After applying the obtained insulating composition onto the S surface of the electrolytic copper foil (thickness: 35 μm), drying (80 ° C./30 minutes), post-cure (150 ° C./60 To obtain a printed wiring board in which the cured product (resin material) of the insulating composition and the copper foil were bonded.
(3) Evaluation of adhesiveness From this printed wiring board, according to "JIS C6481 (1996)", the test piece of width 10mm was produced, and the peeling strength of copper foil was measured.

[Example 1]
200 g of ethylene glycol monobutyl ether was added to 10 g of 3- [3- (trimethoxysilyl) propylthio] -1,2,4-triazole, followed by addition of 790 g of water, and the mixture was stirred at room temperature for 2 hours. (Hereinafter, referred to as “treatment liquid A”) was prepared.
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) and (b).
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 (c).
The test results obtained were as shown in Table 1.

[Example 2]
Instead of “3- [3- (trimethoxysilyl) propylthio] -1,2,4-triazole”, “3-amino-5- [3- (trimethoxysilyl) propylthio] -1,2,4- A surface treatment liquid (hereinafter referred to as treatment liquid B) was prepared in the same manner as in Example 1 except that “triazole” was used.
About this processing liquid B, 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) and (b).
Subsequently, the volatile component in the treatment liquid B was removed under reduced pressure to obtain a hydrolyzate of an azolesilane compound. The obtained hydrolyzate was subjected to an adhesive evaluation test (c).
The test results obtained were as shown in Table 1.

[Example 3]
Instead of “3- [3- (trimethoxysilyl) propylthio] -1,2,4-triazole”, “3-amino-5- [6- (trimethoxysilyl) hexylthio] -1,2,4- A surface treatment liquid (hereinafter referred to as treatment liquid C) was prepared in the same manner as in Example 1 except that “triazole” was used.
About this process liquid C, it confirmed that the methoxysilyl group of the said azole silane compound was hydrolyzed to the hydroxysilyl group, and performed the adhesive evaluation test (a) and (b).
Subsequently, the volatile component in the treatment liquid C was removed under reduced pressure to obtain a hydrolyzate of an azolesilane compound. The obtained hydrolyzate was subjected to an adhesive evaluation test (c).
The test results obtained were as shown in Table 1.

[Example 4]
Instead of “3- [3- (trimethoxysilyl) propylthio] -1,2,4-triazole”, “5-methyl-2- [3- (trimethoxysilyl) propylthio] -1,3,4- A surface treatment liquid (hereinafter referred to as treatment liquid D) was prepared in the same manner as in Example 1 except that “thiadiazole” was used.
About this processing liquid D, 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) and (b).
Subsequently, the volatile component in the treatment liquid D was removed under reduced pressure to obtain a hydrolyzate of an azolesilane compound. The obtained hydrolyzate was subjected to an adhesive evaluation test (c).
The test results obtained were as shown in Table 1.

[Comparative Example 1]
A surface treatment solution (hereinafter, referred to as “imidazole silane compound”) was used in the same manner as in Example 1 except that “imidazolesilane compound” was used instead of “3- [3- (trimethoxysilyl) propylthio] -1,2,4-triazole”. Treatment liquid E) was prepared.
About this process liquid E, it confirmed that the methoxy silyl group of the said imidazole silane compound was hydrolyzed to the hydroxy silyl group, and performed the adhesive evaluation test (a) and (b).
Subsequently, the volatile component in the treatment liquid E was removed under reduced pressure to obtain a hydrolyzate of an imidazolesilane compound. The obtained hydrolyzate was subjected to an adhesive evaluation test (c).
The test results obtained were as shown in Table 1.

[Comparative Example 2]
Surface treatment in the same manner as in Example 1 except that “3-aminopropyltrimethoxysilane” was used instead of “3- [3- (trimethoxysilyl) propylthio] -1,2,4-triazole”. A liquid (hereinafter referred to as “treatment liquid F”) was prepared.
About this process liquid F, it confirmed that the methoxysilyl group of 3-aminopropyl trimethoxysilane was hydrolyzed to the hydroxysilyl group, and performed the adhesive evaluation test (a) and (b).
Subsequently, the volatile matter in the treatment liquid F was removed under reduced pressure to obtain a hydrolyzate of 3-aminopropyltrimethoxysilane. The obtained hydrolyzate was subjected to an adhesive evaluation test (c).
The test results obtained were as shown in Table 1.

[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 liquid (hereinafter referred to as treatment liquid G).
This treatment liquid G was subjected to adhesive evaluation tests (a) and (b). The test results obtained were as shown in Table 1.
The adhesive evaluation test (c) was carried out without adding anything to the solder resist. The test results obtained were as shown in Table 1.

  According to the present invention, the adhesion (adhesiveness) of the metal, the inorganic material, and the resin material can be sufficiently ensured, so that the surface of the base material 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 (27)

A surface treatment liquid of an inorganic material or a resin material containing an azolesilane compound represented by the chemical formula (I).

(In the formula, 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 to 3).   A surface treatment liquid for an inorganic material or a resin material containing an azolesilane compound represented by the above chemical formula (I), which is used for bonding two materials selected from the group consisting of metals, inorganic materials, and resin materials.   The surface treatment liquid for an inorganic material or a resin material according to claim 2, wherein the metal is copper, aluminum, titanium, nickel, tin, iron, silver, gold, or an alloy thereof.   The surface treatment liquid for an inorganic material or a resin material according to claim 2, wherein the metal is copper or a copper alloy.   The surface treatment solution for an inorganic material or a resin material according to any one of claims 1 to 4, wherein the inorganic material is silicon, ceramic, glass, or an inorganic salt.   The surface treatment liquid for an inorganic material or a resin material according to claim 5, wherein the ceramic is alumina, silicon carbide, aluminum nitride, silicon nitride, or barium titanate.   The resin material is an acrylate resin, an epoxy resin, or a polyimide resin. The surface treatment liquid for an inorganic material or a resin material according to any one of claims 1 to 6.   A surface treatment method for an inorganic material, wherein a surface treatment liquid containing an azolesilane compound represented by the chemical formula (I) is brought into contact with the inorganic material.   The inorganic material surface treatment method according to claim 8, wherein the inorganic material is silicon, ceramic, glass, or an inorganic salt.   The surface treatment method for an inorganic material according to claim 9, wherein the ceramic is alumina, silicon carbide, aluminum nitride, silicon nitride, or barium titanate.   A surface treatment method for a resin material, wherein a surface treatment liquid containing an azolesilane compound represented by the chemical formula (I) is brought into contact with the resin material.   The resin material surface treatment method according to claim 11, wherein the resin material is an acrylate resin, an epoxy resin, or a polyimide resin. A method for bonding a metal and a resin material,
A metal for forming a chemical conversion film on the resin material by bringing the surface treatment liquid containing the azolesilane compound represented by the chemical formula (I) into contact with the resin material, and bonding the metal and the resin material through the chemical conversion film And bonding method of resin material. An adhesion method between an inorganic material and a resin material,
A surface treatment liquid containing the azolesilane compound represented by the chemical formula (I) is brought into contact with at least one of an inorganic material and a resin material to form a chemical conversion film on the at least one, and the inorganic material and the resin material are converted into a chemical conversion film. A method for bonding an inorganic material and a resin material to be bonded via a metal. A method for bonding a metal and an inorganic material,
A surface treatment liquid containing an azolesilane compound represented by the chemical formula (I) is contacted with an inorganic material to form a chemical conversion film on the inorganic material, and a metal that bonds the metal and the inorganic material through the chemical conversion film; Inorganic material bonding method.   An electronic device comprising a composite material in which a metal and a resin material are bonded through a chemical conversion film formed on the surface of the resin material by a surface treatment liquid containing an azolesilane compound represented by the chemical formula (I).   A composite material in which an inorganic material and a resin material are bonded to each other through a chemical conversion film formed on the surface of at least one of the inorganic material and the resin material by a surface treatment liquid containing the azolesilane compound represented by the chemical formula (I). Electronic devices.   An electronic device comprising a composite material obtained by bonding a metal and an inorganic material through a chemical conversion film formed on the surface of the inorganic material by a surface treatment liquid containing an azolesilane compound represented by the chemical formula (I).   A printed wiring board comprising a composite material obtained by bonding a metal and a resin material through a chemical conversion film formed on the surface of the resin material by a surface treatment liquid containing an azolesilane compound represented by the chemical formula (I).   A composite material in which an inorganic material and a resin material are bonded to each other through a chemical conversion film formed on the surface of at least one of the inorganic material and the resin material by a surface treatment liquid containing the azolesilane compound represented by the chemical formula (I). Printed wiring board.   A printed wiring board comprising a composite material obtained by bonding a metal and an inorganic material through a chemical conversion film formed on the surface of the inorganic material by a surface treatment liquid containing an azolesilane compound represented by the chemical formula (I).   An insulating composition comprising an azolesilane compound represented by the chemical formula (I), a resin material and / or an inorganic material.   The insulating composition according to claim 22, wherein the resin material is an acrylate resin, an epoxy resin, or a polyimide resin.   The insulating composition according to claim 22 or 23, wherein the inorganic material is silicon, ceramic, glass, or an inorganic salt.   The insulating material which uses the insulating composition as described in any one of Claims 22-24 as a component.   The electronic device which has an insulating layer obtained from the insulating composition as described in any one of Claims 22-24.   The printed wiring board which has an insulating layer obtained from the insulating composition as described in any one of Claims 22-24.