JP6440440B2 - Metal surface treatment liquid, surface treatment method and use thereof - Google Patents

Description

  The present invention relates to a metal surface treatment solution, a surface treatment method and use thereof using an azolesilane compound.

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.

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

The present invention provides a metal surface treatment solution, a surface treatment method and an adhesion method using an azolesilane compound, and a printed wiring board and an electronic device production method using the same, in order to improve the adhesion between the metal and the resin material. The purpose is to do.

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 metal surface treatment liquid characterized by 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).

In a second invention, the metal is a surface treatment solution for metal according to the first invention, wherein the metal is at least one selected from the group consisting of copper, aluminum, titanium, nickel, tin, iron, silver, gold, and alloys thereof. It is.
3rd invention is the surface treatment liquid of the metal of 1st invention whose metal is copper or a copper alloy.
4th invention is the surface treatment method of the metal which makes the surface treatment liquid of 1st invention contact the surface of a metal.
According to a fifth aspect of the present invention, in the metal surface treatment method according to the fourth aspect, the metal is at least one selected from the group consisting of copper, aluminum, titanium, nickel, tin, iron, silver, gold, and alloys thereof. It is.
6th invention is the metal surface treatment method of 4th invention whose metal is copper or a copper alloy.
In the seventh invention, before bringing the surface treatment liquid into contact with the surface of copper or copper alloy, the surface of the copper or copper alloy is selected from pickling treatment, roughening treatment, heat treatment, rust prevention treatment or chemical conversion treatment. It is the metal surface treatment method of 6th invention which performs the at least 1 pretreatment performed.
8th invention is the surface treatment method of the metal of 6th invention which makes the aqueous solution containing a copper ion contact the surface of the said copper or copper alloy before making a surface treatment liquid contact the surface of copper or a copper alloy. .
In a ninth aspect of the invention, any one of the sixth to eighth aspects of the invention wherein the acidic aqueous solution or the alkaline aqueous solution is brought into contact with the surface of the copper or copper alloy after the surface treatment liquid is brought into contact with the surface of the copper or copper alloy. This is one metal surface treatment method.
A tenth invention is a method for adhering a metal and a resin material, wherein the surface treatment liquid of the first invention is brought into contact with the metal surface to form a chemical conversion film on the metal surface, and the chemical conversion film is interposed through the chemical conversion film. This is a method of bonding a metal and a resin material to bond the metal and the resin material.
The eleventh invention is a method for producing a printed wiring board in which a metal and a resin material are bonded via a chemical conversion film formed by the surface treatment liquid of the first invention.
A twelfth invention is a method for manufacturing an electronic device in which a metal and a resin material are bonded via a chemical conversion film formed by the surface treatment liquid of the first invention.

  According to the present invention, the adhesion between a metal and a resin material can be improved.

  Hereinafter, the present invention will be described in detail.

(Surface treatment liquid)
The metal surface treatment liquid of the present invention (hereinafter sometimes simply referred to as “surface treatment liquid” or “treatment liquid”) contains the azole silane compound represented by the chemical formula (I) as an active ingredient. And azolesilane 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 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 the azole silane compound (Ib)) is an azole silane compound in the case where n is 1 in the chemical formula (I). The azole silane compound represented by (Ic) (hereinafter sometimes referred to as azole silane compound (Ic)) is an azole silane compound when n is 2 in the chemical formula (I), and is represented by the chemical formula (Id). The azole silane compound shown (hereinafter sometimes referred to as azole silane compound (Id)) is an azole silane compound when n is 3 in the chemical formula (I).

  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-triethoxysilylmethylthio-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 an organic solvent may be used in combination with water.
In addition, about the preparation method of the surface treatment liquid in the case of using water and an organic solvent together, an organic solvent may be added after mixing the azole silane compound (Ia) and water, or the compound, water and the organic solvent. The mixed solution 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 treatment liquid, pure water, such as ion-exchange water and distilled water, is preferable.

As the organic solvent,
Methanol, ethanol, propanol, 2-propanol, butanol, ethylene glycol, propylene glycol, glycerin, diethylene glycol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene Glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, acetone, tetrahydrofuran, dioxane, acetonitrile,
Those that are freely miscible with water such as dimethylformamide, dimethylacetamide, dimethyl sulfoxide, formic acid, acetic acid, propionic acid, triethylamine, pyridine and the like are preferable.
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, by bringing the surface treatment solution 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. In the case where a resin layer made of a resin material is formed on the surface of the chemical conversion film, the adhesion between copper and the resin material can be improved as compared with the case where the resin layer is formed directly on the surface of copper.

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 that the surface treatment liquid contains the organic solvent as a silane oligomer solubilizing agent 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.

  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, use substances that generate halogen ions such as chlorine ions and bromine ions, and metal ions such as copper ions, iron ions, and zinc ions. 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,
styrylsilane compounds such as p-styryltrimethoxysilane,
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-dimethyl-butylidene) propylamine,
N-phenyl-3-aminopropyltrimethoxysilane,
Aminosilane compounds such as N- (vinylbenzyl) -2-aminoethyl-3-aminopropyltrimethoxysilane;
Ureidosilane compounds such as 3-ureidopropyltriethoxysilane,
Chloropropylsilane compounds such as 3-chloropropyltrimethoxysilane,
Sulfide silane compounds such as bis (triethoxysilylpropyl) tetrasulfide,
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.

(Processing method)
Preferred examples of the metal to be 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 treated with the surface treatment liquid of the present invention is a foil (for example, electrolytic copper foil, rolled copper foil) used for electronic devices such as printed wiring boards and lead frames, ornaments, building materials, and plating films. (For example, electroless copper plating film, electrolytic copper plating film), granular, needle-like, fibrous, linear, rod-like, tubular, plate-like, etc. 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 resin material include acrylate resin, epoxy resin, polyimide resin, bismaleimide resin, maleimide resin, cyanate resin, polyphenylene ether resin, polyphenylene oxide resin, olefin resin, fluorine-containing resin, polyether imide resin, and polyether ether ketone. Resins, liquid crystal resins and the like can be mentioned, and these may be mixed or modified to be combined with each other.
Among these resin materials, acrylate resins, epoxy resins, and polyimide resins are preferable.

  By treating the surface of the metal using the surface treatment liquid of the present invention, a chemical conversion film can be formed on the metal surface and the adhesion to the resin material can be enhanced.

There is no restriction | limiting in particular as a method of making the surface treatment liquid of this invention contact the surface of a metal, Means, such as immersion, application | coating, a spray, can be employ | adopted.
The time (treatment time) for contacting the surface treatment liquid and the metal 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 metal surface becomes thin and sufficient adhesion to the resin cannot be obtained. There is no great difference in film thickness, 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 metal 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 contacting the surface treatment liquid of the present invention with the metal, it may be washed with water and dried, or may be dried without washing 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 the surface treatment liquid is brought into contact with the copper surface, the copper surface may be subjected to at least one pretreatment selected from pickling treatment, roughening treatment, heat treatment, rust prevention treatment or chemical conversion treatment. .

  The pickling treatment is performed to remove oil and fat components adhering to the copper surface and to remove the oxide film on the copper surface. 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 roughening treatment is performed in order to increase the adhesion between copper and the resin due to the anchor effect. A rough surface is imparted to the surface of the copper, and the adhesion between the copper and the resin material can be enhanced.
In this roughening treatment, methods such as a micro-etching method, electroplating method, electroless plating method, oxidation method (black oxide, brown oxide), oxidation / reduction method, brush polishing method, jet scrub method may be adopted. it can.

In the micro-etching method, for example, organic acid / cupric ion-based, sulfuric acid / hydrogen peroxide-based, persulfate-based, copper chloride-based and iron chloride-based etchants can be used.
In the electroplating method, unevenness is formed on the surface of copper by precipitating fine copper particles on the surface of copper.

In the heat-resistant treatment, at least one film selected from nickel, nickel-phosphorus, zinc, zinc-nickel, copper-zinc, copper-nickel, copper-nickel-cobalt, or nickel-cobalt is formed on the surface of copper. Is formed.
This film can be formed by employing a known electroplating method, but is not limited to electroplating, and vapor deposition or other means may be used.

  The rust prevention treatment is to prevent the copper surface from being oxidized and corroded, and a method of forming a zinc or zinc alloy composition plating film or electrolytic chromate plating film on the copper surface. Can be adopted.

  In 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 liquid of the present invention into contact with the copper surface, an aqueous solution containing copper ions may be brought into contact with the copper surface. This aqueous solution containing copper ions has a function of making the thickness of the chemical conversion film formed on the surface of copper 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 added.

After bringing the surface treatment liquid of the present invention into contact with the copper surface, an acidic or alkaline aqueous solution may be brought into contact with the copper surface. This acidic or alkaline aqueous solution also has a function of making the thickness of the chemical conversion film formed on the surface of copper uniform, similarly to the aqueous solution containing copper ions.
The acidic aqueous solution and the alkaline aqueous solution are not particularly limited, and examples of the acidic aqueous solution include aqueous solutions containing mineral acids such as sulfuric acid, nitric acid, and hydrochloric acid, and 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.

(Adhesion method)
A known method can be adopted as a method of bonding the metal having a chemical conversion film formed on the surface thereof by contacting the surface treatment liquid of the present invention and the resin material. For example, the surface treatment liquid of the present invention is contacted with a metal surface to form a chemical conversion film, and a resin material is applied to a part or the whole of the formed chemical conversion film, followed by pressure bonding, an adhesive, an adhesive sheet (film ) And a method of bonding and bonding the metal on which the chemical conversion film is formed and a resin material, or a method of combining them.

  Since the surface treatment liquid of the present invention can be used to improve the adhesion between the metal and the resin material, it is a material (raw material) for producing electronic devices such as various electric / electronic parts and printed wiring boards. ).

  In particular, the surface treatment liquid of the present invention can be preferably applied to metals, particularly copper. For example, it is suitable for copper surface treatment for the purpose of improving the adhesion (adhesion) between the copper circuit (copper wiring layer) and the prepreg or solder resist (insulating resin layer). In the printed wiring board having the insulating resin layer in contact therewith, the adhesion between the copper wiring layer and the insulating resin layer can be enhanced.

The printed wiring board can be produced by bringing the surface treatment liquid of the present invention and the surface of the copper wiring into contact with each other, then washing and drying, and then forming an insulating resin layer on the surface of the copper wiring. The contact method is as described above, and immersion of the copper wiring in the surface treatment liquid, spraying of the copper wiring with the treatment liquid, and the like are simple and reliable, and are preferable.
Further, the water washing method is not particularly limited, but immersion of the copper wiring in the washing water and spraying on the surface of the copper wiring with the washing water are preferable because they are simple and reliable.
The insulating resin layer can be formed by using a known method, for example, a method of applying a semi-cured resin material or a means of applying a liquid resin material containing a solvent. Next, a via hole is formed to connect the upper and lower wirings. By repeating this process, a multilayer printed wiring board can be produced.

  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.

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. An invention relating to a method for forming a silane coupling agent film is described, which 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 immersion plating as a surface treatment.
The surface treatment liquid 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.

  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)
3- [3- (triethoxysilyl) propylthio] -1,2,4-triazole (Synthesis example shown in Reference Example 2) 3-amino-5- [3- (trimethoxysilyl) propylthio] -1 Of 2,2,4-triazole (Synthesis example was shown in Reference Example 3)
3-amino-5- [3- (triethoxysilyl) propylthio] -1,2,4-triazole (Synthesis example shown in Reference Example 4)
3-amino-5- [6- (trimethoxysilyl) hexylthio] -1,2,4-triazole (Synthesis example shown in Reference Example 5)
5-methyl-2- [3- (trimethoxysilyl) propylthio] -1,3,4-thiadiazole (Synthesis example shown in Reference Example 6)
5-methyl-2- [5- (trimethoxysilyl) pentylthio] -1,3,4-thiadiazole (Synthesis example shown in Reference Example 7)
2-amino-5- [3- (trimethoxysilyl) propylthio] -1,3,4-thiadiazole (Synthesis example shown in Reference Example 8)
2-amino-5- [3- (triethoxysilyl) propylthio] -1,3,4-thiadiazole (Synthesis example shown in Reference Example 9)
2-mercapto-5- [3- (trimethoxysilyl) propylthio] -1,3,4-thiadiazole (Synthesis example shown in Reference Example 10)
2-mercapto-5- [3- (triethoxysilyl) propylthio] -1,3,4-thiadiazole (Synthesis example shown in Reference Example 11)
2-methylthio-5- [3- (trimethoxysilyl) propylthio] -1,3,4-thiadiazole (Synthesis example shown in Reference Example 12)
2-methylthio-5- [3- (triethoxysilyl) propylthio] -1,3,4-thiadiazole (Synthesis example shown in Reference Example 13)
-Imidazolesilane compound (Synthesis method was shown in Reference Example 14)
・ 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 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 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- [3- (triethoxysilyl) 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 ethanol was cooled to 10 ° C., and 10.2 g (30 mmol) of a 20% sodium ethoxide ethanol 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 6.74 g (30 mmol) of 3-chloropropyltriethoxysilane and 10 mL of dehydrated ethanol was added dropwise at room temperature over 10 minutes, and further to 78 ° C. And stirred for 6 hours.
The reaction solution was concentrated under reduced pressure, and 10.8 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 (Ia-2) as a slightly tan oil. 7.8 g (25 mmol, yield 85.7%) of the title azole silane compound represented by

[Reference Example 3]
<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. 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 (Ia-3 ) 9.2 g (33 mmol, yield 55.1%) of the title azole silane compound represented by

[Reference Example 4]
<Synthesis of 3-amino-5- [3- (triethoxysilyl) propylthio] -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 ethanol was cooled to 10 ° C., and 10.2 g (30 mmol) of a 20% sodium ethoxide ethanol 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 6.74 g (30 mmol) of 3-chloropropyltriethoxysilane and 10 mL of dehydrated ethanol was added dropwise at the same temperature over 10 minutes. The mixture was further stirred at 78 ° C. for 6 hours.
The reaction solution was concentrated under reduced pressure, and 10.8 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 (Ia-4) as slightly yellowish brown crystals. 7.8 g (25 mmol, yield 85.7%) of the title azole silane compound represented by

[Reference Example 5]
<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 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 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-5 as a slightly yellowish brown oily substance). ) 5.3g (16mmol, 52% yield) of the title azole silane compound represented by

[Reference Example 6]
<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. 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 (Ia-6) as a pale yellowish brown oily substance. 16.9 g (60 mmol, yield 99.9%) of the title azole silane compound represented by

[Reference Example 7]
<Synthesis of 5-methyl-2- [5- (trimethoxysilyl) pentylthio] -1,3,4-thiadiazole>
A suspension composed of 3.3 g (25 mmol) of 2-mercapto-5-methyl-1,3,4-thiadiazole and 40 mL of dehydrated methanol was cooled to 10 ° C., and 4.8 g (25 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 6.8 g (25 mmol) of 5-bromopentyltrimethoxysilane and 10 mL of dehydrated methanol was added dropwise at room temperature over 10 minutes, and The mixture was stirred at 60 ° C. for 6 hours.
The reaction mixture was concentrated under reduced pressure, and 10.4 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-7) as a pale yellowish brown oily substance. ) 6.1 g (19 mmol, yield 75.7%) of the title azole silane compound represented by

[Reference Example 8]
<Synthesis of 2-amino-5- [3- (trimethoxysilyl) propylthio] -1,3,4-thiadiazole>
To a suspension composed of 8.0 g (60 mmol) of 2-amino-5-mercapto-1,3,4-thiadiazole and 90 mL of dehydrated methanol, 3.24 g (60 mmol) of sodium methoxide (solid) was added at room temperature. After preparing a uniform solution, the mixture was stirred for 30 minutes, and a solution consisting of 17.4 g (60 mmol) of 3-iodopropyltrimethoxysilane and 17 mL of dehydrated methanol was added dropwise over 30 minutes, and the mixture was further stirred at 37 to 40 ° C. for 5 hours. .
The reaction solution was concentrated under reduced pressure, and 100 mL of diethyl ether was added to 27.1 g of the resulting white viscous product and stirred. The insoluble material was removed by filtration and then concentrated under reduced pressure to give a chemical formula (Ia-8) as slightly yellowish brown crystals. 17.5 g (59 mmol, yield 98.7%) of the title azole silane compound represented by

[Reference Example 9]
<Synthesis of 2-amino-5- [3- (triethoxysilyl) propylthio] -1,3,4-thiadiazole>
A suspension composed of 3.99 g (30 mmol) of 2-amino-5-mercapto-1,3,4-thiadiazole and 50 mL of dehydrated ethanol was cooled to 10 ° C., and 10.2 g (30 mmol) of a 20% sodium ethoxide ethanol 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 6.74 g (30 mmol) of 3-chloropropyltriethoxysilane and 10 mL of dehydrated ethanol was added dropwise at room temperature over 10 minutes, The mixture was further stirred at 78 ° C. for 6 hours.
The reaction solution was concentrated under reduced pressure, and 11.6 g of the resulting white viscous product was extracted three times with 40 mL of diethyl ether. The extract was filtered and then concentrated under reduced pressure to give a chemical formula (Ia-9) as slightly yellowish brown crystals. 9.1 g (26 mmol, yield 89.8%) of the title azole silane compound represented by

[Reference Example 10]
<Synthesis of 2-mercapto-5- [3- (trimethoxysilyl) propylthio] -1,3,4-thiadiazole>
To a suspension composed of 9.0 g (60 mmol) of 2,5-dimercapto-1,3,4-thiadiazole and 90 mL of dehydrated methanol, 3.24 g (60 mmol) of sodium methoxide (solid) was added at room temperature to obtain a homogeneous solution. Then, the mixture was stirred for 30 minutes, and a solution composed of 17.4 g (60 mmol) of 3-iodopropyltrimethoxysilane and 17 mL of dehydrated methanol was added dropwise at 15-17 ° C. over 30 minutes under water cooling, and further 42-44 Stir at 4 ° C. for 4 hours.
The reaction mixture was concentrated under reduced pressure, and 100 mL of diethyl ether was added to 27.5 g of the resulting white viscous substance and stirred. The insoluble material was removed by filtration, and then concentrated under reduced pressure to give a chemical formula (Ia- 16.7 g (53 mmol, yield 89.1%) of the title azolesilane compound represented by 10) was obtained.

[Reference Example 11]
<Synthesis of 2-mercapto-5- [3- (triethoxysilyl) propylthio] -1,3,4-thiadiazole>
A suspension composed of 4.50 g (30 mmol) of 2,5-dimercapto-1,3,4-thiadiazole and 50 mL of dehydrated ethanol was cooled to 10 ° C., and 10.2 g (30 mmol) of a 20% sodium ethoxide ethanol solution was added. Then, the solution was returned to room temperature and stirred for 30 minutes, and a solution composed of 6.74 g (30 mmol) of 3-chloropropyltriethoxysilane and 10 mL of dehydrated ethanol was added dropwise at room temperature over 10 minutes, and further to 78 ° C. And stirred for 6 hours.
The reaction mixture was concentrated under reduced pressure, and 14.8 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-11 as a pale yellowish brown oil). ) 9.0 g (25 mmol, yield 84.6%) of the title azole silane compound represented by

[Reference Example 12]
<Synthesis of 2-methylthio-5- [3- (trimethoxysilyl) propylthio] -1,3,4-thiadiazole>
To a suspension of 2-mercapto-5-methylthio-1,3,4-thiadiazole 11.4 g (69.4 mmol) and 120 mL of dehydrated methanol, 3.75 g (69.4 mmol) of sodium methoxide (solid) at room temperature. ) To obtain a homogeneous solution, followed by stirring for 30 minutes. A solution composed of 20.1 g (69.3 mmol) of 3-iodopropyltrimethoxysilane and 20 mL of dehydrated methanol was added dropwise over 30 minutes, and further, 34 to 37 ° C. For 5 hours.
The reaction mixture was concentrated under reduced pressure, and 130 mL of diethyl ether was added to 32.6 g of the white viscous substance obtained and stirred. The insoluble material was removed by filtration, and the filtrate was concentrated under reduced pressure to give a chemical formula (Ia-12) as a pale yellow oil. 22.5 g (68.9 mmol, yield 99.3%) of the title azole silane compound represented by

[Reference Example 13]
<Synthesis of 2-methylthio-5- [3- (triethoxysilyl) propylthio] -1,3,4-thiadiazole>
A suspension consisting of 4.93 g (30 mmol) of 2-mercapto-5-methylthio-1,3,4-thiadiazole and 50 mL of dehydrated ethanol was cooled to 10 ° C., and 10.2 g (30 mmol) of a 20% sodium ethoxide ethanol 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 6.74 g (30 mmol) of 3-chloropropyltriethoxysilane and 10 mL of dehydrated ethanol was added dropwise at room temperature over 10 minutes, The mixture was further stirred at 78 ° C. for 6 hours.
The reaction mixture was concentrated under reduced pressure, and 15.4 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-13) as a pale yellowish brown oily substance. 9.8 g (26 mmol, yield 88.6%) of the title azole silane compound represented by

[Reference Example 14]
<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 the dropwise addition, the reaction was further carried out at 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 (d) of the adhesion between the metal and the resin material performed in the following examples and comparative examples are as follows.

[Adhesion Evaluation Test (a)]
(1) Metal An electrolytic copper foil (thickness: 18 μm) was used as the metal.
(2) Processing of metal It carried out according to the following processes i-iii.
i. Acid clean / 1 minute (room temperature), water wash ii. Acid cleaning / 1 minute (room temperature), water washing, drying / 1 minute (100 ° C)
iii. Immersion in surface treatment solution / 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 copper foil, and the copper foil and the resin 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 C6418 (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, electrolytic copper foil thickness: 18 μm, length 120 mm × width 110 mm) was used.
(2) Processing of metal It carried out according to the following processes i-iv.
i. Acid clean / 1 minute (room temperature), water wash ii. Micro etching with hydrogen peroxide / sulfuric acid / 1 minute (room temperature), water washing iii. Acid cleaning / 1 minute (room temperature), water washing, drying / 1 minute (100 ° C)
iv. Immersion in surface treatment solution / 1 minute (room temperature), water washing, drying / 1 minute (100 ° C.)
(3) Formation of resin layer on metal After applying a solder resist (product name “PSR-4000AUS308”, manufactured by Taiyo Ink Manufacturing Co., Ltd.) to the treated electrolytic copper foil, drying (80 ° C./30 minutes), post-cure ( 150 ° C./60 minutes) 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.
The criteria for determining adhesiveness are as shown in Table 1.

[Adhesion Evaluation Test (d)]
(1) Metal An aluminum foil (thickness: 50 μm) was used as the metal.
(2) Processing of metal It carried out according to the following processes i-ii.
i. Acid clean / 1 minute (room temperature), water wash ii. Immersion in surface treatment solution / 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 resin 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.

[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”).
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)-(d).
The test results obtained were as shown in Table 2.

[Example 2]
Instead of “3- [3- (trimethoxysilyl) propylthio] -1,2,4-triazole”, “3- [3- (triethoxysilyl) propylthio] -1,2,4-triazole” is used. A surface treatment liquid (hereinafter referred to as treatment liquid B) was prepared in the same manner as in Example 1 except that.
About this processing liquid B, it confirmed that the ethoxy silyl group of the said azole silane compound was hydrolyzed to the hydroxy silyl group, and performed the adhesive evaluation test (a)-(d).
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- [3- (trimethoxysilyl) propylthio] -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 processing liquid C, 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)-(d).
The test results obtained were as shown in Table 2.

[Example 4]
Instead of “3- [3- (trimethoxysilyl) propylthio] -1,2,4-triazole”, “3-amino-5- [3- (triethoxysilyl) propylthio] -1,2,4- A surface treatment liquid (hereinafter referred to as treatment liquid D) was prepared in the same manner as in Example 1 except that “triazole” was used.
About this processing liquid D, it confirmed that the ethoxy silyl group of the said azole silane compound was hydrolyzed to the hydroxy silyl group, and performed the adhesive evaluation test (a)-(d).
The test results obtained were as shown in Table 2.

[Example 5]
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 E) was prepared in the same manner as in Example 1 except that “triazole” was used.
About this processing liquid E, 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)-(d).
The test results obtained were as shown in Table 2.

[Example 6]
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 F) was prepared in the same manner as in Example 1 except that “thiadiazole” was used.
About this process liquid F, 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)-(d).
The test results obtained were as shown in Table 2.

[Example 7]
Instead of “3- [3- (trimethoxysilyl) propylthio] -1,2,4-triazole”, “5-methyl-2- [5- (trimethoxysilyl) pentylthio] -1,3,4- A surface treatment liquid (hereinafter referred to as treatment liquid G) was prepared in the same manner as in Example 1 except that “thiadiazole” was used.
About this processing liquid G, 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)-(d).
The test results obtained were as shown in Table 2.

[Example 8]
Instead of “3- [3- (trimethoxysilyl) propylthio] -1,2,4-triazole”, “2-amino-5- [3- (trimethoxysilyl) propylthio] -1,3,4- A surface treatment liquid (hereinafter referred to as treatment liquid H) was prepared in the same manner as in Example 1 except that “thiadiazole” was used.
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 (a)-(d).
The test results obtained were as shown in Table 2.

[Example 9]
Instead of “3- [3- (trimethoxysilyl) propylthio] -1,2,4-triazole”, “2-amino-5- [3- (triethoxysilyl) propylthio] -1,3,4- A surface treatment liquid (hereinafter referred to as treatment liquid I) was prepared in the same manner as in Example 1 except that “thiadiazole” was used.
About this processing liquid I, 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)-(d).
The test results obtained were as shown in Table 2.

[Example 10]
Instead of “3- [3- (trimethoxysilyl) propylthio] -1,2,4-triazole”, “2-mercapto-5- [3- (trimethoxysilyl) propylthio] -1,3,4- A surface treatment liquid (hereinafter referred to as treatment liquid J) was prepared in the same manner as in Example 1 except that “thiadiazole” was used.
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 (a)-(d).
The test results obtained were as shown in Table 2.

[Example 11]
Instead of “3- [3- (trimethoxysilyl) propylthio] -1,2,4-triazole”, “2-mercapto-5- [3- (triethoxysilyl) propylthio] -1,3,4- A surface treatment liquid (hereinafter referred to as treatment liquid K) was prepared in the same manner as in Example 1 except that “thiadiazole” was used.
About this processing liquid K, it confirmed that the ethoxy silyl group of the said azole silane compound was hydrolyzed to the hydroxy silyl group, and performed the adhesive evaluation test (a)-(d).
The test results obtained were as shown in Table 2.

[Example 12]
Instead of “3- [3- (trimethoxysilyl) propylthio] -1,2,4-triazole”, “2-methylthio-5- [3- (trimethoxysilyl) propylthio] -1,3,4- A surface treatment liquid (hereinafter referred to as treatment liquid L) was prepared in the same manner as in Example 1 except that “thiadiazole” was used.
About this processing liquid L, 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)-(d).
The test results obtained were as shown in Table 2.

[Example 13]
Instead of “3- [3- (trimethoxysilyl) propylthio] -1,2,4-triazole”, “2-methylthio-5- [3- (triethoxysilyl) propylthio] -1,3,4- A surface treatment liquid (hereinafter referred to as treatment liquid M) was prepared in the same manner as in Example 1 except that “thiadiazole” was used.
About this processing liquid M, it confirmed that the ethoxy silyl group of the said azole silane compound was hydrolyzed to the hydroxy silyl group, and performed the adhesive evaluation test (a)-(d).
The test results obtained were as shown in Table 2.

[Comparative Example 1]
Surface treatment solution (hereinafter referred to as treatment) in the same manner as in Example 1 except that “imidazolesilane” was used instead of “3- [3- (trimethoxysilyl) propylthio] -1,2,4-triazole”. Liquid N) was prepared.
About this process liquid N, it confirmed that the methoxy silyl group of imidazole silane was hydrolyzed to the hydroxy silyl group, and performed the adhesive evaluation test (a)-(d).
The test results obtained were as shown in Table 2.

[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 O”) was prepared.
About this processing liquid O, it confirmed that the methoxysilyl group of 3-aminopropyl trimethoxysilane was hydrolyzed to the hydroxysilyl group, and performed the adhesive evaluation test (a)-(d).
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 liquid (hereinafter referred to as treatment liquid P).
When the adhesive evaluation tests (a) to (d) were performed on the treatment liquid P, the test results obtained were as shown in Table 2.

  According to the present invention, the adhesiveness (adhesion) between the metal and the resin material can be sufficiently ensured, which can greatly contribute to the realization of the multilayer printed wiring board such as miniaturization, thinning, high frequency, high density, etc. Therefore, industrial applicability is great.

Claims (12)

A metal surface treatment solution comprising 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).   The metal surface treatment solution according to claim 1, wherein the metal is at least one selected from the group consisting of copper, aluminum, titanium, nickel, tin, iron, silver, gold, and alloys thereof.   The metal surface treatment solution according to claim 1, wherein the metal is copper or a copper alloy.   A metal surface treatment method in which the surface treatment liquid according to claim 1 is brought into contact with a metal surface.   The metal surface treatment method according to claim 4, wherein the metal is at least one selected from the group consisting of copper, aluminum, titanium, nickel, tin, iron, silver, gold, and alloys thereof.   The metal surface treatment method according to claim 4, wherein the metal is copper or a copper alloy.   Before contacting the surface treatment liquid with the surface of the copper or copper alloy, the surface of the copper or copper alloy is subjected to at least one selected from pickling treatment, roughening treatment, heat treatment, rust prevention treatment or chemical conversion treatment. The metal surface treatment method according to claim 6, wherein the treatment is performed.   The metal surface treatment method according to claim 6, wherein an aqueous solution containing copper ions is brought into contact with the surface of the copper or copper alloy before the surface treatment liquid is brought into contact with the surface of copper or the copper alloy.   The surface of the metal according to any one of claims 6 to 8, wherein after the surface treatment liquid is brought into contact with the surface of copper or a copper alloy, an acidic aqueous solution or an alkaline aqueous solution is brought into contact with the surface of the copper or copper alloy. Processing method.   A method for bonding a metal and a resin material, wherein the surface treatment liquid according to claim 1 is brought into contact with the surface of the metal to form a chemical conversion film on the surface of the metal, and the metal and the resin material are bonded via the chemical conversion film. Bonding method between metal and resin material to be bonded. The manufacturing method of the printed wiring board which adhere | attached the metal and resin material through the chemical conversion film formed with the surface treatment liquid of Claim 1. The manufacturing method of the electronic device which adhere | attached the metal and the resin material through the chemical conversion film formed with the surface treatment liquid of Claim 1.