JP2016204725A - Metal surface treatment method, and utilization thereof - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a surface treatment method useful for enhancing the adhesiveness between a metal and a resin, and capable of forming a chemical coating film excellent in chemical resistance on the surface of the metal, and to provide a metal and resin adhering method having the surface treatment method applied thereto.SOLUTION: A surface treatment method comprises: the step of causing a surface treatment liquid containing an azole silane compound of a specific structure having an azole ring and a thioether bond in a molecule to contact as a silane compound with a metal thereby to form a chemical coating film on the surface of a metal; and the step of causing an acid solution or an alkaline solution to contact with the metal after heating the metal formed with the chemical coating film thereby to modify the chemical coating film.SELECTED DRAWING: None

Description

  The present invention relates to a metal surface treatment method for forming a chemical conversion film (surface modified layer) derived from an azolesilane compound on the surface of a metal, and a metal and resin adhesion method using this treatment method.

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 method for forming a silane coupling agent film.
And this forming method is a step of applying a liquid containing a silane coupling agent on the metal surface, a step of drying the metal surface coated with the liquid at a temperature of 25 to 150 ° C. within 5 minutes, By comprising a step of washing the dried metal surface with water, the excess silane coupling agent does not stick, and only the silane coupling agent existing near the metal surface is bonded to the metal, and then fixed by washing with water. By washing away the previous excess silane coupling agent, it is said that it is possible to form a silane coupling agent film having no coating unevenness on the metal surface and maintaining a uniform and sufficient surface silane amount.

  In addition, the invention described in this document is a method for improving the adhesion between a conductor surface made of a metal such as copper or a copper alloy and an insulating resin such as a solder resist or a prepreg in the production of a printed wiring board. In the case of forming a silane coupling agent film on the surface, it is said that it is suitable for solving the problem that the adhesion between the conductor surface and the resin is lowered when the silane coupling film is non-uniform.

Patent Document 2 describes an invention relating to a method for producing a resin-coated metal plate.
In this document, the tin-plated steel sheet is treated with a silane coupling agent, and in the state where the resin is coated, a lot of OH groups remain at the interface between the tin-plated steel sheet and the coated resin film, and the adhesion is low, and When the resin-coated metal plate is heated to a temperature equal to or higher than “the melting point of the coating resin—10 ° C.”, the dehydration condensation reaction of the silane coupling agent proceeds sufficiently, the bonding force between Sn and the film becomes strong, and the adhesiveness is remarkable. Improvements are disclosed.

Patent Document 3 describes an invention relating to an azolesilane compound, a surface treatment liquid, a surface treatment method, and use thereof.
In this document, after contacting the surface treatment solution and the metal, the substrate may be washed with water and dried, or may be dried without washing with water, and drying may be performed at a temperature of room temperature to 150 ° C. A preferable point is disclosed, and it is disclosed that the surface treatment liquid may be brought into contact with the surface of copper or a copper alloy and then contacted with an acidic or alkaline aqueous solution.

JP 2009-019266 A International Publication No. 2011-045833 Pamphlet International Publication No. 2015/002158 Pamphlet

  An object of the present invention is to provide a surface treatment method that is useful for improving the adhesion between a metal and a resin and that can form a chemical conversion film having excellent chemical resistance on the surface of the metal. Moreover, it aims at providing the adhesion method of the metal and resin which applied this surface treatment method.

As a result of intensive studies to solve the above-mentioned problems, the present inventors have used an azole silane compound having a thioether bond (-S-) in the molecule together with an azole ring as a silane compound. It has been found that the purpose of the period is achieved, and the present invention has been completed.
That is, the first invention includes a step of bringing a surface treatment solution containing an azolesilane compound represented by chemical formula (I) or chemical formula (II) into contact with a metal to form a chemical conversion film on the surface of the metal; A method for treating a surface of a metal, comprising the step of modifying the chemical conversion film by heating the metal on which the metal is formed and then bringing the metal into contact with an acidic solution or an alkaline solution.

（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 a step of forming a chemical conversion film on a metal surface by bringing a metal into contact with a surface treatment solution containing the azolesilane compound represented by the chemical formula (I) or the chemical formula (II). Heating the metal that has been formed, contacting the acid solution or alkaline solution with the metal to modify the chemical conversion film, and forming a resin layer on the metal surface through the modified chemical conversion film A method for adhering a metal and a resin characterized by comprising:

  According to the metal surface treatment method of the present invention, a chemical conversion film capable of enhancing the adhesion between the metal and the resin can be formed on the surface of the metal. Moreover, this chemical conversion film is excellent in chemical resistance.

The surface treatment liquid used in the practice of the present invention is represented by the azole silane compound represented by the chemical formula (I) (hereinafter sometimes referred to as the first azole silane compound) or the chemical formula (II). An azole silane compound (hereinafter sometimes referred to as a second azole silane compound) is contained as a silane coupling agent.
In addition, you may use combining a 1st azole silane compound and a 2nd azole silane compound as a silane coupling agent component of the said surface treatment liquid.

  The first azole silane compound includes azole silane compounds represented by chemical formulas (Ia) to (Id).

（式（Ia）〜（Id）中のＸ、Ｙ、Ｒ、ｍは、式（I）中のＸ、Ｙ、Ｒ、ｍと同様である。）

(X, Y, R, and m in formulas (Ia) to (Id) are the same as X, Y, R, and m in formula (I).)

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 (trialkoxy 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 is represented by the chemical formula (Ic). An azole silane compound (hereinafter sometimes referred to as an azole silane compound (Ic)) is an azole silane compound when n is 2, and an azole silane compound represented by a chemical formula (Id) (hereinafter referred to as an azole silane compound ( Id)) is an azole silane compound when n is 3.

  The azole silane compounds (Ib) to (Id) are species produced 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. In addition, the azolesilane compounds (Ib) to (Id) can be extracted from the surface treatment liquid and used by removing volatile components from the surface treatment liquid, for example.

In the practice of the present invention, when the first azole silane compound is used as a raw material for preparing the surface treatment liquid, it is preferable to use the azole silane compound (Ia).
This azolesilane compound can be synthesized according to the method described in International Publication No. 2015/002158.

As an example of this azole silane compound (Ia),
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 (in the case where Y is “-S—”) and the like.
In the practice of the present invention, two or more selected from these may be used in combination.

In the second azolesilane compound, Y in the chemical formula (II) is
An azole silane compound (hereinafter referred to as an azole silane compound (IIa)) in the case of “—CO—NH— (CH ₂ ) _m —Si (OR) ₃ ”,
An azole silane compound (hereinafter referred to as an azole silane compound (IIb)) in the case of “—CO—NH— (CH ₂ ) _m —Si (OR) ₂ (OH)”,
In the case of “—CO—NH— (CH ₂ ) _m —Si (OR) (OH) ₂ ”, the azole silane compound (hereinafter referred to as azole silane compound (IIc)), and “—CO—NH— (CH ₂ ) _m -Si (OH) ₃ ”(hereinafter referred to as azole silane compound (IId)).

That is, the azole silane compound (IIa) is an azole silane compound when n is 0 in the chemical formula (II).
Similarly, the azole silane compound (IIb) is an azole silane compound when n is 1, the azole silane compound (IIc) is an azole silane compound when n is 2, and the azole silane compound (IId) is It is an azolesilane compound when n is 3.

  As in the case of the first azole silane compound, the azole silane compounds (IIb) to (IId) are species that are generated by hydrolysis of the azole silane compound (IIa) present in the surface treatment liquid. Is suitable as a component of the silane coupling agent together with the trialkoxy azole silane compound (IIa). The azole silane compounds (IIb) to (IId) can be extracted from the surface treatment liquid and used, for example, by removing volatile components from the surface treatment liquid.

In the practice of the present invention, when the second azole silane compound is used as the raw material for preparing the surface treatment liquid, it is preferable to use the azole silane compound (IIa).
This azole silane compound can be synthesized according to the method described in International Publication No. 2015/002158 pamphlet in the same manner as the azole silane compound (Ia) described above.

This azole silane compound (IIa)
2,2'-dithiobis {1- [3- (trimethoxysilyl) propylcarbamoyl] -1H-imidazole},
2,2'-dithiobis {1- [3- (triethoxysilyl) propylcarbamoyl] -1H-imidazole},
2,2'-dithiobis {1- [3- (trimethoxysilyl) propylcarbamoyl] -1H-benzimidazole},
2,2'-dithiobis {1- [3- (triethoxysilyl) propylcarbamoyl] -1H-benzimidazole},
2,2'-dithiobis {5-amino-1- [3- (trimethoxysilyl) propylcarbamoyl] -1H-benzimidazole},
2,2'-dithiobis {5-amino-1- [3- (triethoxysilyl) propylcarbamoyl] -1H-benzimidazole},
3,3′-dithiobis {1- [3- (trimethoxysilyl) propylcarbamoyl] -1H-1,2,4-triazole},
3,3′-dithiobis {1- [3- (triethoxysilyl) propylcarbamoyl] -1H-1,2,4-triazole},
3,3′-dithiobis {5-amino-1- [3- (trimethoxysilyl) propylcarbamoyl] -1H-1,2,4-triazole},
3,3′-dithiobis {5-amino-1- [3- (triethoxysilyl) propylcarbamoyl] -1H-1,2,4-triazole},
4,4′-dithiobis {1- [3- (trimethoxysilyl) propylcarbamoyl] -1H-1,2,3-triazole},
4,4'-dithiobis {1- [3- (triethoxysilyl) propylcarbamoyl] -1H-1,2,3-triazole},
5,5'-dithiobis {1- [3- (trimethoxysilyl) propylcarbamoyl] -1H-tetrazole} and 5,5'-dithiobis {1- [3- (triethoxysilyl) propylcarbamoyl] -1H-tetrazole }.
In the practice of the present invention, two or more selected from these may be used in combination.

The surface treatment liquid used in the practice of the present invention is prepared by dissolving an azole silane compound in water or dissolving an azole silane compound and a solubilizer in water.
As the azole silane compound, the first azole silane compound or the second azole silane compound may be used alone, or the first azole silane compound and the second azole silane compound may be used in combination. Also good.
In preparing the surface treatment solution, a solubilizing agent may be added after mixing the azole silane compound and water, or a mixture of the azole silane compound, water and a solubilizing agent may be mixed, or the azole silane compound. Water may be added after mixing the solubilizing agent.

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, dimethylformamide, dimethylacetamide, dimethyl sulfoxide, sulfolane, carbonic acid Dimethyl, 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, succinate Preferable examples include acid, levulinic acid, phenol, benzoic acid, oxalic acid, tartaric acid, malic acid and the like.
These solubilizers may be used in combination of two or more selected from these.

In the practice of the present invention, the pH of the surface treatment liquid is appropriately set (pH 1 to 14) depending on the composition of the surface treatment liquid (type and content of components) and the treatment temperature and treatment time described below. Preferably it is set in the range of 9-13.
In this case, an alkali agent is used to adjust the pH, and when preparing the surface treatment liquid, the alkali agent may be added after mixing the azole silane compound and the solvent, or the azole silane compound, the solvent and the alkali agent. The mixed solution may be mixed, or the solvent may be added after mixing the azolesilane compound and the alkali agent.
In addition, the solvent here refers to the above-mentioned water, a solubilizer, or the liquid mixture of water and a solubilizer.
Moreover, when neutralizing the alkali agent added excessively or making pH low, acids, such as an acetic acid and hydrochloric acid, can be used.

As the alkaline agent,
Alkali metal hydroxides such as sodium hydroxide, potassium hydroxide, magnesium hydroxide, calcium hydroxide, ammonia, methylamine, dimethylamine, trimethylamine, ethylamine, diethylamine, triethylamine, propylamine, isopropylamine, butylamine, allylamine , Ethylenediamine, diethylenetriamine, triethylenetetramine, monoethanolamine, diethanolamine, triethanolamine, monopropanolamine, dipropanolamine, tripropanolamine, monoisopropanolamine, diisopropanolamine, triisopropanolamine, 2-amino-1-propanol , N, N-dimethylethanolamine, cyclohexylamine, aniline, pyrrolidine, piperi Preferred are those that are freely miscible with water such as methylamine, piperazine, pyridine, and the like, methylamine, dimethylamine, trimethylamine, ethylamine, diethylamine, triethylamine, propylamine, isopropylamine, butylamine, allylamine, ethylenediamine, diethylenetriamine, triethylenetetramine, mono Ethanolamine, diethanolamine, triethanolamine, monopropanolamine, dipropanolamine, tripropanolamine, monoisopropanolamine, diisopropanolamine, triisopropanolamine, 2-amino-1-propanol, N, N-dimethylethanolamine, cyclohexyl More amine compounds such as amine, aniline, pyrrolidine, piperidine, piperazine, pyridine Masui.
In preparing the surface treatment liquid, two or more selected from these may be used in combination.

In the practice of the present invention, the azole silane compound (Ia) and the same (IIa) that are preferably used are hydrolyzed when contacted with water as described above, and this hydrolysis mode is shown in Scheme (A).
In this scheme (A), the silyl group of the azolesilane compounds (Ia) to (Ic) and (IIa) to (IIc) is hydrolyzed, that is, trialkoxysilyl groups are gradually A change to a dialkoxyhydroxysilyl group, a dihydroxyalkoxysilyl group, or a trihydroxysilyl group is shown.

In general, it is known that a substance having an alkoxysilyl group or a hydroxysilyl group in the molecule acts as a silane coupling agent.
For example, when the adhesion between copper and a resin is taken as an example when the metal is copper, the azole silane compound preferably used in the practice of the present invention has an azole ring and an alkoxysilyl group (—Si—OR) in the molecule. And the azole ring interacts with the resin and copper to form a chemical bond.
In addition, the alkoxysilyl group is hydrolyzed and converted to a hydroxysilyl group (—Si—OH), which chemically bonds with copper oxide scattered on the surface of copper.
Therefore, when the surface treatment liquid is brought into contact with copper, a chemical film derived from the azole silane compound represented by the chemical formula (I) or the chemical formula (II) is formed on the copper surface by bonding with an azole ring or a hydroxysilyl group. When a resin layer made of resin (resin material) is formed on the surface of this chemical conversion film, the adhesion between copper and resin is greater than when a resin layer is formed directly on the surface of copper. Can increase the sex.

  That is, when the surface treatment liquid and the metal are in contact with each other, a chemical conversion film is formed on the metal surface, and the affinity between the metal and copper is improved by bonding the metal and copper through the layer of the chemical conversion film. Even if it is materials, it adheres more firmly.

In the practice of the present invention, the concentration of the first azole silane compound or the second azole silane compound in the surface treatment solution is converted into the concentration of the corresponding trialkoxy azole silane compound (first azole azole compound). When the silane compound and the second azole silane compound are used in combination, the concentration of the corresponding trialkoxy azole silane compound is preferably 0.001 to 10% by weight. More preferably, the content is 01 to 5% by 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) and (IIb) to (IId) having a hydroxysilyl group generated in the surface treatment liquid gradually react with each other to undergo dehydration condensation, and the hydroxysilyl group is A siloxane bond (Si-O-Si) is formed (see scheme (A)) and converted to a silane oligomer (an azole silane compound having a group represented by chemical formula (e) in scheme (A)) that is hardly soluble in water. The 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 aforementioned solubilizer in the surface treatment liquid.
About content of the solubilizer in a surface treatment liquid, 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 surface treatment liquid used in the practice of the present invention, in order to improve the stability of the surface treatment liquid and the uniformity of the chemical conversion film, halogen ions such as chlorine ions and bromine ions, copper ions, iron ions, zinc ions, etc. A substance that generates metal ions can be added.

  Moreover, you may add a well-known coupling agent to a surface treatment liquid 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,
Acryloxysilane compounds 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.

  In the practice of the present invention, first, the surface treatment liquid is brought into contact with the metal. When the surface treatment liquid comes into contact with the metal, the azole silane compound dissolved in the surface treatment liquid interacts with the metal to deposit the azole silane compound on the surface of the metal, thereby forming a chemical conversion film derived from the azole silane compound. Is done.

There is no restriction | limiting in particular about the method of making a surface treatment liquid and a metal contact, Means, such as spray, immersion, and application | coating, are employable.
About the time (processing time) which makes a surface treatment liquid and a metal contact, it is preferable to set in the range of 1 second-10 minutes, and it is more preferable to set in the range of 5 seconds-3 minutes. When the treatment time is shorter than 1 second, the film thickness of the chemical film formed on the metal surface becomes thin, and sufficient adhesion between the metal and the resin cannot be obtained. There is no great difference in film thickness, and improvement in adhesion cannot be expected.
Further, the temperature of the surface treatment liquid (treatment temperature) when the surface treatment liquid is brought into contact with the metal is preferably set in the range of 5 to 50 ° C., but may be appropriately set in relation to the treatment time. That's fine.

In addition, after making a surface treatment liquid and a metal contact, you may wash a metal with water as needed.
The water used for washing is preferably pure water such as ion-exchanged water or distilled water, but the washing method and temperature / time are not particularly limited, and may be any appropriate temperature / time by means such as spraying or dipping. .

  Subsequently, the metal on which the chemical conversion film is formed is heated. When the chemical conversion film formed on the surface of the metal is heated, dehydration condensation between the azole silane compounds is promoted, and the chemical bond between the chemical conversion film and the metal becomes strong.

The heating temperature is preferably set in the range of 50 to 260 ° C, more preferably in the range of 100 to 150 ° C.
When the heating temperature is lower than 50 ° C, the chemical resistance of the chemical conversion film cannot be sufficiently obtained. On the other hand, when the heating temperature is higher than 260 ° C, the oxidation of the chemical conversion film is promoted and the chemical resistance is lowered.
The heating time is preferably set in the range of 1 second to 120 minutes, more preferably in the range of 10 seconds to 60 minutes.
When the heating time is shorter than 1 second, the chemical resistance is not sufficiently obtained. On the other hand, when the heating time is longer than 120 minutes, the oxidation of the chemical conversion film is promoted and the chemical resistance is lowered.
Such heat treatment can be performed in an air atmosphere or a nitrogen atmosphere (oxygen-free).

After heating the metal, the metal is brought into contact with an acidic solution or an alkaline solution.
As described above, the chemical conversion film formed on the surface of the metal is heated to promote dehydration condensation between the azole silane compounds, and the bond between the chemical conversion film derived from the azole silane compound and the metal is strong. The chemical film undergoes a chemical change (the chemical film is denatured). And as a result, it is estimated that the characteristic (function) of a chemical conversion film improves.
However, even if heated, the azole silane compound which is in a free or near free state is taken into the chemical conversion film, and it is expected that the properties of the chemical conversion film will be further improved by removing these compounds. The
After heating the chemical conversion film together with the metal, the azole silane compound in the free or near free state is removed from the chemical conversion film by bringing the metal on which the chemical conversion film is formed into contact with an acidic solution or an alkaline solution.

Examples of the acidic solution include an aqueous solution containing a mineral acid such as sulfuric acid, nitric acid and hydrochloric acid, an aqueous solution containing an organic acid such as formic acid, acetic acid, lactic acid, glycolic acid and amino acid, methanol, ethanol and glycol. Examples thereof include alcohol solutions containing the like.
Examples of the alkaline solution include alkaline solutions such as alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, and amines such as ammonia, ethanolamine, and propanolamine. Can be mentioned.
In addition, in the acidic solution and alkaline solution, you may contain the above-mentioned solubilizer with an acidic substance and an alkaline substance.

The concentration of the acidic substance in the acidic solution and the concentration of the alkaline substance in the alkaline solution are both preferably 0.01 to 50% by weight, and more preferably 0.5 to 10% by weight. If the concentration is lower than 0.01% by weight, a sufficient treatment effect cannot be obtained. On the other hand, if it is higher than 50% by weight, the effect of improving the chemical resistance almost reaches its peak, and the amount of use of an acidic substance or alkaline substance increases. Not right.
The temperature of the acidic solution or alkaline solution (treatment temperature) is not particularly limited, but is preferably set in the range of 0 to 80 ° C.
The contact time (treatment time) between the acidic solution or alkaline solution and the metal is preferably set in the range of 1 second to 10 minutes, more preferably in the range of 30 seconds to 5 minutes.
If the treatment time is shorter than 1 second, sufficient chemical resistance cannot be obtained. On the other hand, even if the treatment time is longer than 10 minutes, the effect of improving chemical resistance almost reaches its peak.

After contacting the metal with the acidic solution or alkaline solution, the metal may be washed with water and then dried.
The drying temperature is preferably set in the range of room temperature to 150 ° C.
The water used for washing is preferably pure water such as ion-exchanged water or distilled water, but the washing method and temperature / time are not particularly limited, and can be set at an appropriate temperature / time by means of spraying or dipping. I do not care.

  In carrying out the present invention, an aqueous solution containing copper ions may be brought into contact with the surface of the metal before bringing the surface treatment liquid into contact with the metal. The copper ion source of copper ions is not particularly limited as long as it is a copper compound 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.

  Further, before bringing the surface treatment liquid into contact with the metal, the metal surface may be subjected to at least one pretreatment selected from pickling treatment, roughening treatment, heat resistance treatment, rust prevention treatment or chemical conversion treatment.

The pickling treatment is performed to remove oil and fat components adhering to the metal surface and to remove the oxide film on the metal 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.
In addition, you may use the said acidic solution as these solutions.

The roughening treatment is performed in order to increase the adhesion between the metal and the resin due to the anchor effect.
In this roughening treatment, an uneven shape is imparted to the copper surface. As means for this purpose, micro etching method, electroplating method, electroless plating method, oxidation method (black oxide, brown oxide), oxidation / Methods such as a reduction method, a brush polishing method, and a jet scrub method can be employed.

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, fine copper particles are deposited on the surface of copper, thereby imparting an uneven shape to 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 metal surface. Is formed.
The formation of this film can be performed by employing a known electroplating method, but may be performed by using other means such as vapor deposition.

The rust prevention treatment is performed to prevent oxidative corrosion of the metal surface.
As this means, a method of forming a zinc or zinc alloy plating film or electrolytic chromate plating film on the surface of the metal can be employed.

  In the practice of the present invention, copper or a copper alloy is suitable as the metal to be treated by the surface treatment liquid, but the present invention is also applicable to aluminum, titanium, nickel, tin, iron, silver, gold, or alloys thereof. It is expected that the inventive surface treatment method can be adapted.

The copper alloy is not particularly limited as long as it is an alloy containing copper. For example, Cu-Ag, Cu-Te, Cu-Mg, Cu-Sn, Cu-Si, Cu-Mn, Cu -Be-Co, Cu-Ti, Cu-Ni-Si, Cu-Cr, Cu-Zr, Cu-Fe, Cu-Al, Cu-Zn, Cu-Co, and other alloys Can be mentioned.
As an alloy of aluminum, titanium, nickel, tin, iron, silver or gold, for example, an aluminum alloy (Al—Si series), a nickel alloy (Ni—Cr series), an iron alloy (Fe—Ni series, stainless steel), etc. Can be mentioned.

Moreover, in the implementation of the present invention, the metal treated using the surface treatment liquid is a foil used for electronic devices such as printed wiring boards and lead frames, ornaments, building materials, etc. (for example, electrolytic copper foil, Rolled copper foil, copper foil with resin, copper foil with carrier, electroless copper foil, sputtered copper foil, thin copper foil), plating film (for example, electroless copper plating film, electrolytic copper plating film), vapor deposition method, sputtering method It is used in the form of a thin film formed by a damascene method or the like, or granular, needle-like, fiber-like, linear, rod-like, tubular or plate-like.
When a recent high-frequency electric signal flows, the copper surface is preferably a smooth surface with 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.

  Moreover, the copper foil with a carrier exemplified as the metal foil is used for a printed wiring board in which a circuit is formed by any one of a semi-additive method, a subtractive method, a partly additive method, or a modified semi-additive method. It is an ultrathin electrolytic copper foil, and has a copper foil carrier, a release layer laminated on the copper foil carrier, and an ultrathin copper layer laminated on the release layer.

Even before or after the surface treatment liquid is brought into contact with the metal, irradiation or exposure with plasma, laser, ion beam, ozone, or treatment such as heating or humidification may be performed to modify the surface of the metal. Good.
Also, the resin / ion residue on the metal surface may be removed (cleaned) by polishing with means such as plasma, laser, ion beam, permis brush, or processing with a drill.
For metal surfaces to which the surface treatment method of the present invention is applied in the metal plating process or electronic component mounting process, surface modification or resin / ion residue is achieved by means of plasma, laser, ion beam, ozone, heating, humidification, etc. May be removed.

In the practice of the present invention, a known method can be adopted as means for bonding (compositing) a resin having a chemical conversion film formed on the surface thereof by contacting the surface treatment solution and the resin.
For example, a method in which a chemical conversion film is formed on a metal surface, a resin is applied to a part or the whole of the chemical conversion film, and then subjected to pressure bonding, or a metal in which the chemical conversion film is formed using an adhesive or an adhesive sheet (film) And a method in which the resin and the resin are bonded together, or a method in which these are combined.

Examples of the resin include acrylate resin, epoxy resin, polyimide resin, bismaleimide resin, maleimide resin, cyanate resin, polyphenylene ether resin, polyphenylene oxide resin, olefin resin, fluorine-containing resin, polyetherimide resin, and polyether ether ketone resin. Liquid crystal resins and the like can be mentioned, and these may be combined or modified with each other. Moreover, there is no restriction | limiting in particular in the polymerization degree of these resin, Resin after uncured, semi-cured or cured, or uncrosslinked or crosslinked may be used.
Among these resins, acrylate resins, epoxy resins, and polyimide resins are preferable.

  According to the metal surface treatment method of the present invention, a chemical conversion film for enhancing the adhesion between the metal and the resin can be formed on the metal surface. The chemical film is not affected by organic solvents or corrosive chemicals when the metal is contacted with organic solvents or corrosive chemicals before the metal and resin are bonded. It is possible to obtain a strong chemical conversion film having excellent resistance.

  The metal surface treatment method of the present invention includes, for example, a copper circuit (copper wiring layer), prepreg, solder resist (insulating resin layer), gold plating, silver plating, nickel plating, palladium plating, tin plating, solder plating, etc. It is suitable for the surface treatment of copper for the purpose of improving the adhesion (adhesion) with a dry film resist layer such as a plating resist or an etching resist.

As described above, the metal and resin bonding method of the present invention includes a copper circuit, a prepreg, solder resist, gold plating, silver plating, nickel plating, palladium plating, tin plating, solder plating, or other plating resist or etching resist. Adhesiveness with the dry film resist layer can be improved.
That is, by applying the metal / resin bonding method of the present invention, the adhesive portion between the copper circuit and the resists (resins) described above has various corrosive properties used in various plating processes, soldering processes, and etching processes. Even when exposed to a chemical solution (medicine), it is difficult to deteriorate, so that good adhesion (adhesion) between copper and resin can be maintained.
The chemicals used in these processes include aqueous pickling solutions such as hydrochloric acid and sulfuric acid used for pretreatment of various plating treatments, alkaline degreasing agents containing sodium hydroxide and amines, hydrogen peroxide-sulfuric acid, excess Copper etching agents such as sulfates, resin oxidants such as permanganate (desmear solution), copper plating, gold plating, silver plating, nickel plating, palladium plating, tin plating, and other plating agents, solder plating, soldering The post flux etc. which are sometimes used are mentioned.

  The copper circuit 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.

The metal surface treatment method and metal-resin adhesion method of the present invention are suitable as elemental technologies for manufacturing electronic devices such as various electric / electronic components and printed wiring boards.
The printed wiring board forms a chemical film on the surface of the copper circuit by the metal surface treatment method of the present invention, and subsequently forms a chemical film on the surface of the copper circuit by the metal and resin bonding method of the present invention. It can manufacture by forming an insulating resin layer via.
The insulating resin layer is formed by using known means, for example, a method of attaching a semi-cured resin (resin material), a method of applying a liquid resin (resin material) containing a solvent, or the like. can do. Next, a via hole is formed to connect the upper and lower wirings. A multilayer printed wiring board can be manufactured by repeating this process.

  EXAMPLES Hereinafter, although this invention is demonstrated in detail based on an Example and a comparative example, this invention is not limited to these. The main raw material azolesilane compounds used in Examples and Comparative Examples are as follows.

[Main ingredients]
3-amino-5- [6- (trimethoxysilyl) hexylthio] -1,2,4-triazole (synthesized according to the method described in International Publication No. 2015/002158 pamphlet. See chemical formula (Ia-1))
2,2'-dithiobis {1- [3- (triethoxysilyl) propylcarbamoyl] -1H-imidazole (see above, chemical formula (IIa-1))
3- [3- (Trimethoxysilyl) propylthio] -1,2,4-triazole (same as above, see chemical formula (Ia-2))

  The chemical resistance evaluation tests (a) and (b) conducted in the examples and comparative examples are as follows.

[Chemical resistance evaluation test (I)]
(1) Base material of test piece As a base material of test piece, double-sided copper-clad laminate (substrate: FR4, plate thickness: 1.0 mm, copper foil thickness: 18 μm) subjected to electrolytic copper plating (plating thickness: 20 μm), 120 mm long × 110 mm wide) was used.
(2) Processing of base material It performed according to the following processes af.
a. Acid clean / 1 minute (room temperature), water wash b. Micro etching with hydrogen peroxide / sulfuric acid / 1 minute (room temperature), water washing c. Acid cleaning / 1 minute (room temperature), water washing, drying / 1 minute (100 ° C)
d. Immersion in metal surface treatment solution / 1 minute (room temperature), water washing e. Heating (Note: Refer to the heating conditions listed in Table 2)
f. Immersion in acidic solution or alkaline solution / 1 minute (room temperature), washing with water (3) Formation of resin layer on substrate surface Solder resist (trade name “PSR-4000AUS308” manufactured by Taiyo Ink Manufacturing Co., Ltd.) on the treated substrate Then, drying (80 ° C./30 minutes) and post-cure (150 ° C./60 minutes) were performed to form a 13 μm-thick resin layer (coating film), and a printed wiring board test piece was prepared.
(4) Evaluation of adhesiveness According to “JIS K5400-8.5”, the coating film formed on the surface of the test piece was cross-cut (100 squares) on a 1 mm × 1 mm grid and shown in the following steps g to i. Then, a tape peel test was performed, the number of squares where the coating film was not peeled was measured, and the degree of damage to the coating film was visually observed.
g. 10% hydrochloric acid aqueous solution clean / 10 minutes immersion (room temperature)
h. Water washing i. Drying / 1 minute (100 ° C)
The criteria for determining adhesiveness are as shown in Table 1.
The higher the rank of the determination represented by A to F, the better the adhesion between the metal and the resin, and the better adhesion even when subjected to contact with 10% hydrochloric acid aqueous solution (step g). It is determined that sex is maintained. That is, it is judged that the adhesive performance excellent in chemical resistance is obtained.

[Chemical resistance evaluation test (b)]
The treatment shown in Step g is the same as in the chemical resistance evaluation test (A) except that a 5% aqueous sodium hydroxide solution was used instead of the 10% aqueous hydrochloric acid solution.

[Example 1]
As a silane coupling agent component, 200 g of ethylene glycol monobutyl ether was added to 10 g of 3-amino-5- [6- (trimethoxysilyl) hexylthio] -1,2,4-triazole, followed by 790 g of water, The mixture was stirred at room temperature for 2 hours to prepare a metal surface treatment liquid (hereinafter referred to as treatment liquid A).
About this processing liquid A, it confirmed that the said azole silane compound was hydrolyzed, and performed the chemical-resistant evaluation tests (ii) and (ii).
In addition, about the conditions (temperature / time) of the heat processing shown to the process e, it was 100 degreeC / 60 minutes, and 5% hydrochloric acid aqueous solution was used about the acidic or alkaline solution used for the process shown to the process f. .
The test results obtained were as shown in Table 2.

[Example 2]
For the treatment liquid A prepared in Example 1, the heat treatment conditions (temperature / hour) shown in step e were changed from 100 ° C./60 minutes to 125 ° C./20 minutes and used for the treatment shown in step f. Chemical resistance evaluation tests (a) and (b) were conducted in the same manner as in Example 1 except that the 5% hydrochloric acid aqueous solution was changed to a 1% sodium hydroxide aqueous solution.
The test results obtained were as shown in Table 2.

[Example 3]
For the treatment liquid A prepared in Example 1, the heat treatment conditions (temperature / hour) shown in step e were changed from 100 ° C./60 minutes to 150 ° C./10 minutes and used for the treatment shown in step f. Chemical resistance evaluation tests (A) and (B) were conducted in the same manner as in Example 1 except that the 5% hydrochloric acid aqueous solution was changed to a 10% hydrochloric acid aqueous solution.
The test results obtained were as shown in Table 2.

[Example 4]
As a silane coupling agent component, instead of “3-amino-5- [6- (trimethoxysilyl) hexylthio] -1,2,4-triazole”, “2,2′-dithiobis {1- [3- A metal surface treatment solution (hereinafter referred to as treatment solution B) was prepared in the same manner as in Example 1 except that (triethoxysilyl) propylcarbamoyl] -1H-imidazole ”was used.
Subsequently, with respect to this treatment liquid B, the heat treatment conditions (temperature / hour) shown in step e were changed from 100 ° C./60 minutes to 125 ° C./20 minutes, in the same manner as in Example 1, with the result that the Chemical evaluation tests (A) and (B) were conducted.
The test results obtained were as shown in Table 2.

[Example 5]
As a silane coupling agent component, instead of “3-amino-5- [6- (trimethoxysilyl) hexylthio] -1,2,4-triazole”, “3- [3- (trimethoxysilyl) propylthio]” A metal surface treatment liquid (hereinafter referred to as treatment liquid C) was prepared in the same manner as in Example 1 except that “-1,2,4-triazole” was used.
Subsequently, for this treatment liquid C, the heat treatment condition (temperature / hour) shown in step e was changed from 100 ° C./60 minutes to 125 ° C./20 minutes, and 5% used for the treatment shown in step f. The chemical resistance evaluation tests (a) and (b) were conducted in the same manner as in Example 1 except that the hydrochloric acid aqueous solution was changed to a 10% hydrochloric acid aqueous solution.
The test results obtained were as shown in Table 2.

[Comparative Example 1]
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 metal surface treatment liquid (hereinafter referred to as treatment liquid D).
Subsequently, for this treatment liquid D, the chemical resistance evaluation test (A) and (A) were conducted in the same manner as in Example 1 except that the heat treatment shown in step e and the treatment shown in step f were not performed. B)
The test results obtained were as shown in Table 2.

[Comparative Example 2]
For the treatment liquid B prepared in Example 4, the chemical resistance evaluation test (A) was performed in the same manner as in Example 4 except that the heat treatment shown in Step e and the treatment shown in Step f were not performed. And (b) were performed.

[Comparative Example 3]
About the processing liquid B prepared in Example 4, the chemical resistance evaluation tests (A) and (B) were performed in the same manner as in Example 4 except that the processing shown in Step f was not performed.
The test results obtained were as shown in Table 2.

[Comparative Example 4]
The chemical resistance evaluation tests (A) and (B) were performed in the same manner as in Example 4 except that the treatment liquid B prepared in Example 4 was used and the heat treatment shown in Step e was not performed. It was.
The test results obtained were as shown in Table 2.

According to the metal surface treatment method of the present invention, a chemical conversion film for enhancing the adhesion between the metal and the resin can be formed on the metal surface. The chemical film is not affected by organic solvents or corrosive chemicals when the metal is contacted with organic solvents or corrosive chemicals before the metal and resin are bonded. It is possible to obtain a strong chemical conversion film having excellent resistance.
The surface treatment method is, for example, copper circuit (copper wiring layer), prepreg, solder resist (insulating resin layer), gold plating, silver plating, nickel plating, palladium plating, tin plating, solder plating, or the like. It is suitable for the surface treatment of copper for the purpose of improving the adhesion (adhesion) between a resist or a dry film resist layer such as an etching resist.
Therefore, the present invention can greatly contribute to the realization of downsizing, thinning, high frequency, high density and the like of electronic devices and the like, and thus the industrial applicability is great.

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, ethyl methyl ketone, tetrahydrofuran, dioxane, acetonitrile, 2-pyrrolidone, formamide, dimethylformamide, dimethylacetamide, dimethyl sulfoxide , Sulfolane, dimethyl carbonate, ethylene carbonate, N-methylpyrrolidone, γ-butyrolactone, 1,3-dimethyl-2-imidazolidinone, formic acid, acetic acid, propionic acid, butyric acid, glycolic acid, lactic acid, gluconic acid, glyceric acid, Malonic acid, succinic acid, levulinic acid, phenol, benzoic acid, oxalic acid, tartaric acid, malic acid , methyl acetate, ethyl acetate, ethyl formate, etc. Those miscible with water are preferred.
These solubilizers may be used in combination of two or more selected from these.

As the alkaline agent,
Sodium hydroxide, potassium hydroxide, magnesium hydroxide, calcium hydroxide, barium hydroxide and other alkali metal , alkaline earth metal hydroxides, and alkali metal carbonates such as sodium carbonate, sodium bicarbonate, potassium carbonate , Quaternary ammonium hydroxide compounds such as tetramethylammonium hydroxide, tetraethylammonium hydroxide , ammonia, methylamine, dimethylamine, trimethylamine, ethylamine, diethylamine, triethylamine, propylamine, isopropylamine, butylamine, allylamine, ethylenediamine, diethylenetriamine, Triethylenetetramine, monoethanolamine, diethanolamine, triethanolamine, monopropanolamine, dipropanolamine Free with water such as tripropanolamine, monoisopropanolamine, diisopropanolamine, triisopropanolamine, 2-amino-1-propanol, N, N-dimethylethanolamine, cyclohexylamine, aniline, pyrrolidine, piperidine, piperazine, pyridine Those that are miscible are preferred, methylamine, dimethylamine, trimethylamine, ethylamine, diethylamine, triethylamine, propylamine, isopropylamine, butylamine, allylamine, ethylenediamine, diethylenetriamine, triethylenetetramine, monoethanolamine, diethanolamine, triethanolamine, monopropanol Amine, dipropanolamine, tripropanolamine, monoisopropanol Emissions, diisopropanolamine, triisopropanolamine, 2-amino-1-propanol, N, N-dimethylethanolamine, cyclohexylamine, aniline, pyrrolidine, piperidine, piperazine, amine compounds such as pyridine are more preferred.
In preparing the surface treatment liquid, two or more selected from these may be used in combination.

In addition, before bringing the surface treatment liquid into contact with the metal, the metal surface is subjected to at least one pretreatment selected from pickling treatment, alkali washing treatment, roughening treatment, heat treatment, rust prevention treatment or chemical conversion treatment. May be.
The alkali washing treatment is performed to remove oil and fat components adhering to the copper surface. 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. The solution can be used.

Before or after contacting the surface treatment solution with the metal, at least one treatment selected from plasma, laser, ion beam, ozone irradiation or exposure, heating, humidification, etc. Surface modification may be performed.
Also, the resin / ion residue on the metal surface may be removed (cleaned) by polishing with means such as plasma, laser, ion beam, permis brush, or processing with at least one selected from a drill or the like.
Further, at least one means selected from plasma, laser, ion beam, ozone, heating, humidification, etc., on the metal surface to which the surface treatment method of the present invention is applied in the metal plating process or the electronic component mounting process. Thus, surface modification and removal of resin / ion residues may be performed.

Examples of the resin include acrylate resin, epoxy resin, polyimide resin, bismaleimide resin, maleimide resin, cyanate resin, polyphenylene ether resin, polybutadiene resin, polyphenylene oxide resin, olefin resin, fluorine-containing resin, polyetherimide resin, polyether. An ether ketone resin, a liquid crystal resin, and the like can be given, and these may be combined or modified with each other. Moreover, there is no restriction | limiting in particular in the polymerization degree of these resin, Resin after uncured, semi-cured or cured, or uncrosslinked or crosslinked may be used.
Among these resins, acrylate resins, epoxy resins, and polyimide resins are preferable.

Claims (2)

After the surface treatment liquid containing the azolesilane compound represented by the chemical formula (I) or the chemical formula (II) is brought into contact with the metal to form a chemical conversion film on the surface of the metal, and after the metal that has formed the chemical conversion film is heated A method for treating a metal surface, comprising the step of modifying the chemical conversion film by bringing the metal into contact with an acidic solution or an alkaline solution.

(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 step of forming a chemical conversion film on the surface of the metal by contacting the surface treatment liquid containing the azolesilane compound represented by the chemical formula (I) or chemical formula (II) with the metal, and heating the metal on which the chemical conversion film is formed After that, the method includes a step of contacting the metal with an acidic solution or an alkaline solution to modify the chemical conversion film, and a step of forming a resin layer on the surface of the metal through the modified chemical conversion film. Bonding method between metal and resin.