JP6523942B2 - Surface treatment liquid of inorganic material or resin material, surface treatment method and use thereof - Google Patents

Description

  The present invention relates to a surface treatment liquid of an inorganic material or resin material using an azole silane compound, a surface treatment method, and use thereof.

In recent years, multilayer printed wiring boards have been promoted to cope with the miniaturization and thinning of electronic devices and electronic parts, and a so-called multilayer printed wiring board is provided with a circuit made of copper foil or the like on one side or both sides. The circuit board for the inner layer is laminated with the circuit board for the outer layer or the copper foil through the prepreg and integrated.
By the way, in such a multilayer printed wiring board, it is important to ensure the adhesion between the copper circuit formed on the circuit board for the inner layer and the insulating adhesive resin of the prepreg on which the circuit board for the outer layer or copper foil is laminated. It is an important issue.

The prior art related to the present invention is described below with reference to the literature.
Patent Document 1 describes an invention relating to a copper foil surface treatment agent that improves the adhesion 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 adhesion between copper and an insulating material such as a resin without roughening the surface of copper. The invention relating to
In this document, a hydroxysilyl group is preferable as a component of the surface conditioning composition because it is excellent in adhesion to an insulating material, and among them, adhesion between copper and an insulating material such as an epoxy resin is preferable. It is disclosed that a silane coupling agent having a mercapto group is preferable because it improves the properties.
Moreover, 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 the solution is brought into contact with the surface of copper, Even if it is washed with water and then dried, it may be dried without being washed with water, and if it is washed with water and then dried, a film of uniform thickness is obtained, while on the other hand, it is dried without being washed with water In that case, it is disclosed that high adhesion to the 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 method for surface treatment of a substrate using the same, and the like.
In this document, after an organosilicon compound is mixed with water to sufficiently form a silanol group, further mixing of an alcohol enables realization of a high silanol conversion rate and also enables uniform coating, which is excellent. It is disclosed that the adhesion is realized and that the silanol ratio is preferably 60 to 100% and more preferably 80 to 100%.
And 3-mercaptopropyl methyl dimethoxysilane and 3-mercaptopropyl trimethoxysilane are disclosed as said organosilicon compound.
In addition, the point which makes the adhesiveness with the base material comprised from an organic polymer compound or an inorganic material, and a liquid crystalline compound excellent is made into the subject of the 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.
In this document, nitrogen-containing heterocycles such as triazole and thiadiazole, and silyl groups such as trimethoxysilyl group and triethoxysilyl group as components of a silane coupling agent used for a primer for adhesion of glass and metal to rubber However, various materials having structures linked via an organic group having a thioether (sulfide) bond or the like are disclosed.

Japanese Patent Laid-Open No. 7-286160 JP, 2009-263790, A JP, 2006-045189, A JP 2002-363189 A

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

As a result of intensive studies to solve the above problems, the present inventors have found that an aqueous solution in which a silane compound having an azole ring and a disulfide bond (-S-S-) is dissolved in the molecule is expected to be obtained. It was found that the object was achieved, and the present invention was completed.
That is, the first invention is a surface treatment liquid of an inorganic material or resin material containing an azole silane compound represented by the chemical formula (I).

2nd invention is the surface treatment method of the inorganic material which makes the surface treatment liquid of 1st invention contact inorganic material.
A third invention is the method for surface treatment of an inorganic material according to the second invention, wherein the inorganic material is silicon, ceramic, glass or an inorganic salt.
A fourth invention is the surface treatment method of the inorganic material of the third invention, wherein the ceramic is alumina, silicon carbide, aluminum nitride, silicon nitride or barium titanate.
5th invention is the surface treatment method of the resin material which makes the resin material contact the surface treatment liquid of 1st invention .
A sixth invention is the surface treatment method of a resin material according to the fifth invention, wherein the resin material is an acrylate resin, an epoxy resin or a polyimide resin.

A seventh invention is a method of bonding metal and resin material, wherein the surface treatment liquid of the first invention is brought into contact with the resin material to form a chemical conversion film on the resin material, and the metal and resin material are formed It is a bonding method of metal and resin material bonded through a film .

An eighth invention is an electronic device comprising a composite material in which a metal and a resin material are bonded to each other via a chemical conversion film formed on the surface of the resin material by the surface treatment liquid of the first invention .
A ninth invention is a printed wiring board comprising a composite material in which a metal and a resin material are bonded to each other via a chemical conversion film formed on the surface of the resin material by the surface treatment liquid of the first invention .

A tenth invention is an insulating composition containing the azole silane compound represented by the chemical formula (I) and a resin material and / or an inorganic material.
The eleventh invention is the insulating composition of the tenth invention, wherein the resin material is an acrylate resin, an epoxy resin or a polyimide resin.
The twelfth invention is the insulating composition of the tenth invention or the eleventh invention, wherein the inorganic material is silicon, ceramic, glass or an inorganic salt.

A thirteenth invention is an insulating material containing the insulating composition according to any one of the tenth to twelfth inventions as a component.
A fourteenth invention is an electronic device having an insulating layer obtained from the insulating composition according to any one of the tenth invention to the twelfth invention.
A fifteenth invention is a printed wiring board having an insulating layer obtained from the insulating composition according to any one of the tenth invention to the twelfth invention.

  According to the present invention, it is possible to improve the adhesion between two materials of different materials: metal and inorganic material, metal and resin material, and inorganic material and resin material.

  Hereinafter, the present invention will be described in detail.

(Surface treatment solution)
The surface treatment liquid of the present invention is used for surface treatment of an inorganic material or resin material and contains the azole silane compound represented by the above-mentioned chemical formula (I) as an active ingredient, and this azole silane compound has a chemical formula (I) Y in is
An azole silane compound in the case of -CO-NH- (CH ₂ ) ₃ -Si (OR) ₃ (hereinafter referred to as azole silane compound (Ia)),
An azole silane compound (hereinafter referred to as azole silane compound (Ib)) in the case of -CO-NH- (CH ₂ ) ₃ -Si (OR) ₂ (OH),
And azole silane compounds (hereinafter referred to as azole silane compounds (Ic)) in the case of -CO-NH- (CH ₂ ) ₃ -Si (OR) (OH) ₂ and
The azole silane compound (hereinafter referred to as an azole silane compound (Id)) in the case of -CO-NH- (CH ₂ ) ₃ -Si (OH) ₃ is included.
The surface treatment liquid of the present invention may be simply referred to as a surface treatment liquid or a treatment liquid.

That is, the azole silane compound (Ia) is an azole silane compound when n is 0 in the above chemical formula (I).
Similarly, the azole silane compound (Ib) is an azole silane compound when n is 1 and the azole silane compound (Ic) is an azole silane compound when n is 2 and the azole silane compound (Id ) Is an azole silane compound when n is 3.

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

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

The azole silane compound (Ia) is
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 Includes}.
In the practice of the present invention, two or more selected from these may be used in combination.

  In the azole silane compound (Ia), the dithiodiazole compound represented by the chemical formula (II) of the corresponding precursor and the isocyanatopropylsilane compound represented by the chemical formula (III) are appropriately reacted in an appropriate amount of reaction solvent It can synthesize | combine by making it react at temperature and reaction time.

（式中、Ｒは前記と同様である。）

(Wherein R is as defined above)

The dithiodiazole compound to be the above precursor is
2,2'-dithiodi (1H-imidazole),
2,2'-dithiodi (1H-benzimidazole),
2,2'-dithiobis (5-amino-1H-benzimidazole),
3,3'-dithiodi (1H-1,2,4-triazole),
3,3'-dithiobis (5-amino-1H-1,2,4-triazole),
Included are 4,4'-dithiodi (1H-1,2,3-triazole) and 5,5'-dithiodi (1H-tetrazole).

The aforementioned isocyanatopropylsilane compounds are
Including 3-isocyanatopropyltrimethoxysilane and 3-isocyanatopropyltriethoxysilane.

  An example of the reaction when the above precursor is 2,2′-dithiodi (1H-imidazole) is shown in scheme (A).

（式中、Ｒは前記と同様である。）

(Wherein R is as defined above)

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

As said 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, diethylene Glycol monobutyl ether, triethylene glycol dimethyl ether, triethylene glycol diethyl ether, tetrahydrofurfuryl alcohol, furfuryl alcohol, acetone, tetrahydrofuran, dioxane, acetonitrile, 2-pyrrolidone, formamide, N, N-dimethylformamide, N, N-dimethyl formamide Acetamide, dimethyl sulfoxide, sulfolane, dimethyl carbonate, ethylene carbonate, N-methyl pyrrolidone, γ-butyrolactone, 1,3-dimethyl-2-imidazolidinone, formic acid, acetic acid, propionic acid, butyric acid, glycolic acid, lactic acid, gluconic acid Glyceric acid, malonic acid, succinic acid, levulinic acid, phenol, benzoic acid, oxalic acid, tartaric acid, malic acid, methylamine, dimethylamine, trimethyl Amine, ethylamine, diethylamine, triethylamine, propylamine, isopropylamine, butylamine, allylamine, ethylenediamine, diethylenetriamine, triethylenetetramine, monoethanolamine, diethanolamine, triethanolamine, dipropanolamine, dipropanolamine, tripropanolamine, diisopropanolamine, triisopropanol Amine, 1-amino-2-propanol, 3-amino-1-propanol, 2-amino-1-propanol, N, N-dimethylethanolamine, cyclohexylamine, aniline, pyrrolidine, piperidine, piperazine and pyridine are preferred.
In the practice of the present invention, two or more selected from the group consisting of these may be used in combination.

The azole silane compound (Ia) is hydrolyzed when contacted with water as described above, and the mode of this hydrolysis is shown in scheme (B).
In this scheme (B), an embodiment in which the silyl group possessed by the azole silane compounds (Ia) to (Ic) is hydrolyzed, that is, the trialkoxysilyl group gradually becomes a dialkoxyhydroxysilyl group, a dihydroxyalkoxysilyl group. The state of change to a group or trihydroxysilyl group is schematically shown.

In general, substances having an alkoxysilyl group in the molecule are known to act as a silane coupling agent.
For example, taking adhesion of copper and a resin material as an example, in the practice of the present invention, the azole silane compound (Ia) preferably used as a component in the surface treatment liquid has an azole ring and an alkoxysilyl group The azole ring interacts with the resin and copper to form a chemical bond.
In addition, the alkoxysilyl group is hydrolyzed to be converted to a hydroxysilyl group (-Si-OH), and the hydroxysilyl group chemically bonds to copper oxide scattered on the copper surface.
Therefore, by bringing the resin material and the surface treatment liquid into contact with each other, the chemical conversion film derived from the azole silane compound represented by the chemical formula (I) formed on the surface of the resin layer adheres copper to the surface of this chemical conversion film. In this case, the adhesion between the copper and the resin material can be enhanced as compared to the case where copper is directly adhered to the resin layer.

In the practice of the present invention, the concentration of the azole silane compound (I) in the surface treatment liquid is 0.001 to 10% by weight in terms of the concentration of the trialkoxy compound azole silane compound (Ia) Preferably, it is 0.01 to 5% by weight.
If this concentration is less than 0.001% by weight, the adhesive improvement effect is not sufficient, and if this concentration exceeds 10% by weight, the adhesive improvement effect almost reaches a plateau, and the azole silane compound It is not economical because the use amount of

  By the way, the azole silane compounds (Ib) to (Id) having a hydroxysilyl group generated in the surface treatment solution gradually react with each other to be dehydrated and condensed, and the hydroxysilyl group is a siloxane bond (Si-O-Si) (See scheme (B)) and converted to a water-insoluble silane oligomer (an azole silane compound having a group represented by chemical formula (e) in scheme (B)). In addition, X of group shown by Chemical formula (e) is an integer showing the number of repeating units.

When the amount of silane oligomers generated in the surface treatment solution increases, insolubles precipitate (the treatment solution becomes turbid), the treatment tank and the piping connected to the treatment vessel, and the treatment solution immersed in the treatment solution It adheres to sensors for detecting temperature and liquid level, and smooth surface treatment may be inhibited.
In order to avoid this, it is preferable to include the above-mentioned solubilizer in the surface treatment solution.
The content of the solubilizer is preferably 0.1 to 90 parts by weight, and more preferably 1 to 50 parts by weight with respect to 100 parts by weight of water.

  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 to accelerate the hydrolysis of the azole silane compound (Ia).

  Similarly, in order to improve the stability of the surface treatment solution and the uniformity of the chemical conversion film, a substance that generates a halogen ion such as chlorine ion or bromine ion or a metal ion such as copper ion, iron ion or zinc ion is used. It can also be done.

  In addition, known coupling agents may be used in combination as long as the effects of the present invention are not impaired. As a well-known coupling agent, the silane type coupling agent which has a thiol group (mercapto group), a vinyl group, an epoxy group, a (meth) acryl group, an amino group, a chloropropyl group etc. is mentioned.

Examples of such silane coupling agents are:
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,
Epoxysilane compounds such as 3-glycidoxypropyltriethoxysilane,
Acryloxysilanes such as 3-acryloxypropyltrimethoxysilane,
Methacryloxypropylmethyldimethoxysilane,
Methacryloxypropyl trimethoxysilane,
Methacryloxypropylmethyldiethoxysilane,
Methacryloxysilane compounds such as methacryloxypropyl triethoxysilane,
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,
Ureido silane compounds such as 3-ureidopropyltriethoxysilane,
Chloropropylsilane compounds such as 3-chloropropyltrimethoxysilane,
Sulfide silane compounds such as bis (triethoxysilylpropyl) tetrasulfide,
The isocyanate silane compounds, such as 3-isocyanate propyl triethoxysilane, etc. can be mentioned.
In addition, aluminum based coupling agents, titanium based coupling agents, zirconium based coupling agents and the like can also be mentioned.

(Surface treatment method)
Examples of the inorganic material to be treated with the surface treatment liquid of the present invention include silicon, ceramics, carbon used as a filler, inorganic salts, glass and the like.
Specifically, silicon, silicon carbide, silica, glass, diatomaceous earth, calcium silicate, talc, glass beads, sericite activated clay, silicon compounds such as bentonite, alumina, zinc oxide, iron oxide, magnesium oxide, tin oxide, oxide Oxides such as titanium, hydroxides such as magnesium hydroxide, aluminum hydroxide and basic magnesium carbonate, carbonates such as calcium carbonate, zinc carbonate, hydrotalcite and magnesium carbonate, and sulfates such as barium sulfate and gypsum Titanates such as barium titanate, nitrides such as aluminum nitride and silicon nitride, flaky graphite (natural graphite), expanded graphite, graphites such as expanded graphite (synthetic graphite), activated carbons, carbon fibers, carbon Black etc. are mentioned.
Among these inorganic materials, silicon, ceramics (alumina, silicon carbide, aluminum nitride, silicon nitride and barium titanate), glass and inorganic salts are preferred.

Examples of the resin material to be treated with the surface treatment liquid of the present invention include acrylate resin, epoxy resin, polyimide resin, bismaleimide resin, maleimide resin, cyanate resin, polyphenylene ether resin, polyphenylene oxide resin, polybutadiene resin, olefin resin, A fluorine-containing resin, a polyether imide resin, a polyether ether ketone resin, a liquid crystal resin, etc. may be mentioned, and these may be mixed or modified with each other to be combined. Moreover, there is no restriction | limiting in particular in the polymerization degree of these resin, You may superpose | polymerize (harden) suitably after surface treatment.
Among these resin materials, acrylate resin, epoxy resin and polyimide resin are preferable.

As metals to be bonded to the inorganic material or resin material treated with the surface treatment liquid of the present invention, copper, aluminum, titanium, nickel, tin, iron, silver, gold and alloys thereof can be preferably mentioned.
It will not specifically limit, if it is an alloy containing copper as an example of a copper alloy, For example, Cu-Ag type, Cu-Te type, Cu-Mg type, Cu-Sn type, Cu-Si type, Cu-Mn type , Cu-Be-Co system, Cu-Ti system, Cu-Ni-Si system, Cu-Zn-Ni system, Cu-Cr system, Cu-Zr system, Cu-Fe system, Cu-Al system, Cu-Zn system Alloys, such as a system and a Cu-Co system, can be mentioned.
Moreover, aluminum alloy (Al-Si alloy), nickel alloy (Ni-Cr alloy), iron alloy (Fe-Ni alloy, stainless steel) etc. can be mentioned as another alloy.
Among these metals, copper and copper alloys (hereinafter, both may be simply referred to as copper) are more preferable.

  The metal to be bonded to the inorganic material or resin material treated with the surface treatment liquid of the present invention is a foil used for electronic devices such as printed wiring boards and lead frames, decorative articles, building materials, etc. Rolled copper foil), plating film (for example, electroless copper plating film, electrolytic copper plating film), thin film formed by vapor deposition method, sputtering method, damascene method, etc., granular, needle-like, fibrous, linear, rod-like , Tubular, plate-like and the like. In addition, in the case of the copper wiring in which the high frequency electric signal in recent years flows, it is preferable that the surface of copper is a smooth surface whose average roughness is 0.1 micrometer or less. The surface of copper may be plated with nickel, zinc, chromium, tin or the like as a pretreatment.

There is no restriction | limiting in particular as a method of making the surface treatment liquid of this invention contact the surface of an inorganic material or resin material, Means, such as immersion, application | coating, a spray, are employable.
It is preferable to set it as 1 second-10 minutes about the time (process time) which makes a surface treatment liquid and an inorganic material or resin material contact, and it is more preferable to set it as 5 seconds-3 minutes. If the treatment time is less than 1 second, the film thickness of the chemical conversion film formed on the surface of the inorganic material or resin material becomes thin, and sufficient adhesion between different materials can not be obtained. Even if it is long, the film thickness of the chemical conversion film does not greatly change, and no improvement in adhesion can be expected.
The temperature of the treatment liquid when the surface treatment liquid is brought into contact with the surface of the inorganic material or resin material is preferably 5 to 50 ° C., but it may be set appropriately in relation to the above-mentioned treatment time. .

After the surface treatment liquid of the present invention is brought into contact with the inorganic material or resin material, it may be washed with water and then dried, or may be dried without being washed with water.
The drying temperature is preferably room temperature to 150 ° C.
As water used for water washing, pure water such as ion exchanged water or distilled water is preferable, but there is no particular limitation on the method and time of water washing, and washing may be carried out for a suitable time by means such as immersion or spray.

  Before bringing the surface treatment liquid of the present invention into contact with the surface of the inorganic material or resin material, at least one selected from acid pickling treatment, alkali washing treatment, roughening treatment or heat resistance treatment on the surface of the inorganic material or resin material. Pre-processing may be performed.

  The above-mentioned pickling treatment is carried out in order to remove the oil and fat component adhering to the surface of the inorganic material or the resin material. For this pickling treatment, solutions such as hydrochloric acid solution, sulfuric acid solution, nitric acid solution, sulfuric acid-hydrogen peroxide solution, organic acid solution, inorganic acid-organic solvent solution, organic acid-organic solvent solution Can be used.

  The above-mentioned alkali cleaning treatment is carried out to remove the fat and oil component adhering to the surface of the inorganic material or the resin material. For this alkaline cleaning treatment, a sodium hydroxide solution, a potassium hydroxide solution, a magnesium hydroxide solution, a calcium hydroxide solution, an amine solution, an inorganic alkali-organic solvent solution, an amine-organic solvent solution, etc. The following solutions can be used.

  The roughening process described above forms a concavo-convex shape on the surface of the inorganic material or resin material, and enhances the adhesion (adhesion) of two materials selected from metal, inorganic material and resin material by the anchor effect thereof. To do For this roughening treatment, adopt methods such as desmear method, plasma etching method, metal sputtering method, electroless plating method, electroplating method, rust prevention treatment, oxidation / reduction method, brush polishing method, jet scrub method etc. Can.

In the desmear method, for example, a permanganate potassium salt type or a permanganate sodium salt type desmear agent can be used. Further, swelling treatment or neutralization treatment may be performed before or after the roughening treatment by the desmear method.
In the metal sputtering method or the electroless plating method, unevenness is formed on the surface of the inorganic material or resin material by depositing fine metal particles on the surface of the inorganic material or resin material.

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

Before contacting the surface treatment liquid of the present invention with the surface of the inorganic material or resin material, an aqueous solution containing copper ions may be contacted with the surface of the inorganic material or resin material. The aqueous solution containing this copper ion has a function to make the thickness of the chemical conversion film formed on the surface of the inorganic material or resin material uniform.
The copper ion source is not particularly limited as long as it is a copper salt dissolved in water, and copper salts such as copper sulfate, copper nitrate, copper chloride, copper formate, copper acetate and the like can be mentioned. In order to solubilize the copper salt in water, ammonia, hydrochloric acid or the like may be used in combination.

After bringing the surface treatment liquid of the present invention into contact with the surface of the inorganic material or resin material, an acidic or alkaline aqueous solution may be brought into contact with the surface of the inorganic material or resin material. This acidic or alkaline aqueous solution also has a function to make the thickness of the chemical conversion film formed on the surface of the inorganic material or resin material uniform, as in the above-described 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 hydroxides of alkali metals such as sodium hydroxide and potassium hydroxide, and amines such as ammonia, ethanolamine and monopropanolamine.

  Before or after bringing the surface treatment liquid of the present invention into contact with the surface of the above-mentioned inorganic material or resin material, treatment such as plasma, laser, ion beam, ozone, heating or humidification is performed to obtain inorganic material or resin material The surface may be modified. Alternatively, the inorganic material or the resin material may be cleaned for the purpose of resin / ion residue removal, using a processing method such as mechanical polishing such as plasma, laser, ion beam, Permis-brush, or drill.

  In the process of metal plating or mounting on the surface of the inorganic material or resin material in contact with the surface treatment liquid of the present invention, the surface is reformed by processing such as plasma, laser, ion beam, ozone, heating or humidification. And washing for the purpose of removing the residue.

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

  The above pretreatment and post treatment may be carried out in combination as appropriate.

  The surface treatment liquid of the present invention can be used to treat the surface of the above-mentioned inorganic material or resin material. By treating the surface of the inorganic material or resin material with the surface treatment liquid of the present invention, a chemical conversion film can be formed on the surface of the inorganic material or resin material, and the adhesiveness with other materials can be enhanced.

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

(Bonding method)
As a bonding method, it can carry out by a well-known method.
The surface treatment liquid of the present invention is brought into contact with the surface of the inorganic material and / or resin material to form a chemical conversion film on the surface of one or both materials, and the two materials are applied, crimped, Means such as mixing, use of an adhesive, an adhesive sheet (film) or a method of bonding by combining these means may be mentioned.
Further, the surface treatment liquid of the present invention is brought into contact with the surface of the inorganic material or resin material to form a chemical conversion film, and a metal is pressed onto part or all of the formed chemical film, an adhesive, an adhesive sheet There is a method of using (film) or combining these means and adhering.

  By using the surface treatment liquid of the present invention, as described above, a composite material in which two materials, in particular, two different materials are adhered to each other is obtained. Therefore, various electric components provided with such a composite material And electronic devices such as electronic components and printed wiring boards.

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

The printed wiring board can be produced by bringing the surface treatment liquid of the present invention into contact with the surface of the insulating resin layer, and then washing with water and drying, and then bonding the insulating resin layer and the copper wiring layer surface. . The method for this contact is as described above, and immersion of the insulating resin layer in the surface treatment solution or spraying of the treatment solution onto the surface of the insulating resin layer is preferred because it is simple and reliable.
The method of washing with water is also not particularly limited, but immersion of the insulating resin layer in washing water or spraying of the washing resin with the washing water onto the surface of the insulating resin layer is preferred because it is simple and reliable.
As a method of bonding the insulating resin layer and the copper wiring layer, a known method such as a method of bonding a semi-hardened resin material can be adopted.
In the case of producing a multilayer printed wiring board, a process of bonding the insulating resin layer and the copper wiring layer may be repeated as many times as desired to form via holes in order to electrically connect the upper and lower wirings.

  The copper wiring may be manufactured by any method such as electroless plating, electrolytic plating, vapor deposition, sputtering, damascene, etc., including inner via holes, through holes, connection terminals, etc. May be.

  In addition, “copper” used in the present invention refers to foils (electrolytic copper foil, rolled copper foil) used for printed wiring boards, electronic devices such as lead frames, decorative articles, building materials, etc., plating films (electroless copper plating) Film, electrolytic copper plating film), wire, rod, tube, plate and the like. In addition, in the case of the copper wiring in which the high frequency electric signal in recent years flows, it is preferable that the surface of copper is a smooth surface whose average roughness is 0.1 micrometer or less.

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

The content of the azole silane compound in the insulating composition is preferably 0.001 to 10% by weight, and more preferably 0.01 to 5% by weight. When the content of the azole silane compound is less than 0.001% by weight in the insulating composition, the effect of improving adhesion is not sufficient, and when the concentration exceeds 10% by weight, the adhesive property is improved. The improvement effect almost plateaus, and the amount of use of the azole silane compound is increased, which is not economical.
The insulating composition can be produced by a known method. For example, the insulating composition can be produced by dissolving the azole silane compound in an organic solvent and mixing it with a solid or liquid resin material. Alternatively, the azole silane compound may be directly added to a liquid resin material and mixed to prepare an insulating composition. Furthermore, a conventionally known inorganic material can be added to the above components to produce an insulating composition. As the organic solvent, a conventional organic solvent used as a paint or a dilution liquid of a paint can be used.

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

  Hereinafter, the present invention will be specifically described by way of Examples and Comparative Examples, but the present invention is not limited thereto. In addition, the main raw materials used in the Example are as follows.

[Main raw material]
・ 2,2'-dithiobis {1- [3- (trimethoxysilyl) propylcarbamoyl] -1H-imidazole} (the synthesis example is shown in the reference example 1)
・ 3,3'-Dithiobis {1- [3- (trimethoxysilyl) propylcarbamoyl] -1H-1,2,4-triazole (the synthesis example is shown in Reference Example 2)
・ 3,3'-Dithiobis {5-amino-1- [3- (trimethoxysilyl) propylcarbamoyl] -1H-1,2,4-triazole} (the synthesis example is shown in Reference Example 3)
・ 4,4'-Dithiobis {1- [3- (trimethoxysilyl) propylcarbamoyl] -1H-1,2,3-triazole} (The synthesis example is shown in Reference Example 4)
-Imidazole silane compound (The synthesis method was shown in the reference example 5)
3-Aminopropyltrimethoxysilane (Shin-Etsu Chemical Co., Ltd., product name "KBM-903")
· Ethylene glycol monobutyl ether (Wako Pure Chemical Industries, reagent)
-Solder resist (acrylate epoxy resin, manufactured by Solar Ink Mfg. Co., product name "PSR-4000AUS308")

[Reference Example 1]
<Synthesis of 2,2′-Dithiobis {1- [3- (trimethoxysilyl) propylcarbamoyl] -1H-imidazole}
2.0 g (10 mmol) of 2,2'-dithiodi (1H-imidazole) is added to 45 g of dehydrated N, N-dimethylformamide and dissolved by stirring at room temperature, in which 3-isocyanatopropyltrimethoxysilane is dissolved. 4.1 g (20 mmol) was added dropwise.
After the exotherm has subsided, the reaction solution is stirred at 40 ° C. for 6 hours, concentrated under reduced pressure, and 6.5 g (10 mmol, 100% yield) of the title azolesilane compound represented by the chemical formula (I-1) as a brown liquid. Got).

[Reference Example 2]
<Synthesis of 3,3′-dithiobis {1- [3- (trimethoxysilyl) propylcarbamoyl] -1H-1,2,4-triazole>
4.02 g (20.1 mmol) of 3,3'-dithiodi (1H-1,2,4-triazole) is added to 150 g of dehydrated N, N-dimethylformamide and dissolved by stirring at room temperature. 9.49 g (46.2 mmol) of 3-isocyanatopropyltrimethoxysilane was added dropwise. Ten minutes after that, 0.92 g (9.1 mmol) of triethylamine was added and stirred at 60 ° C. for 8 hours.
The reaction solution was concentrated under reduced pressure to obtain 12.3 g (20.1 mmol, yield 100%) of the title azole silane compound represented by the chemical formula (I-2) as a pale yellow liquid.

[Reference Example 3]
Synthesis of 3,3′-Dithiobis {5-amino-1- [3- (trimethoxysilyl) propylcarbamoyl] -1H-1,2,4-triazole}
2.00 g (8.7 mmol) of 3,3'-dithiobis (5-amino-1H-1,2,4-triazole) was added to 45 g of dehydrated N, N-dimethylformamide and dissolved at room temperature with stirring To this, 3.56 g (17.3 mmol) of 3-isocyanatopropyltrimethoxysilane was added dropwise. After 5 minutes, 0.3 g (3 mmol) of triethylamine was added, and the mixture was stirred at 55 ° C. for 5 hours.
The reaction solution is concentrated under reduced pressure, and the obtained concentrate is recrystallized twice from dehydrated methanol and dried under reduced pressure to give 3.65 g of the title azole silane compound represented by the chemical formula (I-3) as white crystals. (5.7 mmol, 65.5% yield) was obtained.

[Reference Example 4]
Synthesis of 4,4′-Dithiobis {1- [3- (trimethoxysilyl) propylcarbamoyl] -1H-1,2,3-triazole}
8.67 g (43.3 mmol) of 4,4'-dithiodi (1H-1,2,3-triazole) is added to 50 g of dehydrated N, N-dimethylformamide and dissolved by stirring at room temperature. Then, 18.7 g (91.1 mmol) of 3-isocyanatopropyltrimethoxysilane was added dropwise, and after 20 minutes, 1.84 g (18.2 mmol) of triethylamine was added, followed by stirring at room temperature for 15 hours.
The reaction mixture is concentrated under reduced pressure, and the liquid concentrate is washed with 130 mL of hexane and dried under reduced pressure to give 26.0 g of the title azole silane compound represented by the chemical formula (I-4) as a brown liquid (42. 6 mmol, yield 98.3%).

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

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

[Evaluation test of adhesion (a)]
(1) Resin Material A glass cloth epoxy resin impregnated prepreg (FR-4 grade) was used as the resin material.
(2) Treatment of resin material The surface treatment liquid was treated by a spray method on the surface of the resin material.
(3) Preparation of Printed Wiring Board The treated resin material was laminated and pressed on the S surface of an electrolytic copper foil (thickness: 35 μm), and the resin material and copper were adhered to produce a printed wiring board.
(4) Evaluation of adhesiveness From this printed wiring board, according to "JIS C 6481 (1996)", the test piece of width 10 mm was produced and the tearing-off strength of copper foil was measured.

[Evaluation test of adhesion (b)]
(1) Treatment of Inorganic Material 10 parts by weight of barium sulfate was added to 100 parts by weight of the surface treatment solution and stirred for 5 minutes. Subsequently, the barium sulfate supporting a silane coupling agent was filtered and dried in an oven at 100 ° C. for 1 hour.
(2) Preparation of resin composition 1 part by weight of barium sulfate carrying a silane coupling agent was added to 100 parts by weight of the solder resist before curing, and the mixture was stirred for 30 minutes to prepare a resin composition.
(3) Preparation of printed wiring board After apply | coating the obtained resin composition on S surface of an electrolytic copper foil (thickness: 35 micrometers), 60 minutes of heating in a 150 degreeC oven are carried out, and hardening of this resin composition is carried out. A printed wiring board in which an object (resin material) and a copper foil were bonded was produced.
(4) Evaluation of adhesiveness From this printed wiring board, according to "JIS C 6481 (1996)", the test piece of width 10 mm was produced and the tearing-off strength of copper foil was measured.

[Evaluation test of adhesion (c)]
(1) Preparation of Insulating Composition 1 part by weight of a hydrolyzate described later was added to 100 parts by weight of a solder resist before curing, and the mixture was stirred for 30 minutes to prepare an insulating composition.
(2) Preparation of Printed Wiring Board The obtained insulating composition is applied onto the S surface of an electrolytic copper foil (thickness: 35 μm) and then dried (80 ° C./30 minutes), post cure (150 ° C./60 minutes) A part was carried out to prepare a printed wiring board in which a cured product (resin material) of the insulating composition and a copper foil were adhered.
(3) Evaluation of adhesiveness From this printed wiring board, according to "JIS C 6481 (1996)", the test piece of width 10 mm was produced, and the tearing-off strength of copper foil was measured.

Example 1
To 10 g of 2,2'-dithiobis {1- [3- (trimethoxysilyl) propylcarbamoyl] -1H-imidazole}, 200 g of ethylene glycol monobutyl ether is added, followed by 790 g of water, and stirred at room temperature for 2 hours The surface treatment solution (hereinafter referred to as treatment solution A) was prepared.
With respect to this treatment liquid A, it was confirmed that the methoxysilyl group of the azole silane compound was hydrolyzed to a hydroxysilyl group, and adhesion evaluation tests (a) and (b) were conducted.
Subsequently, the volatile matter in the treatment liquid A was removed under reduced pressure to obtain a hydrolyzate of the azole silane compound. The evaluation test (c) of adhesiveness was done about the obtained hydrolyzate.
The test results obtained were as shown in Table 1.

Example 2
Instead of “2,2′-dithiobis {1- [3- (trimethoxysilyl) propylcarbamoyl] -1H-imidazole}”, “3,3′-dithiobis {1- [3- (trimethoxysilyl) propyl] A surface treatment solution (hereinafter referred to as treatment solution B) was prepared in the same manner as in Example 1 except that carbamoyl] -1H-1,2,4-triazole was used.
With regard to this treatment liquid B, it was confirmed that the methoxysilyl group of the azole silane compound was hydrolyzed to a hydroxysilyl group, and adhesion evaluation tests (a) and (b) were performed.
Subsequently, the volatile matter in the treatment liquid B was removed under reduced pressure to obtain a hydrolyzate of the azole silane compound. The evaluation test (c) of adhesiveness was done about the obtained hydrolyzate.
The test results obtained were as shown in Table 1.

[Example 3]
Instead of “2,2′-dithiobis {1- [3- (trimethoxysilyl) propylcarbamoyl] -1H-imidazole}”, “3,3′-dithiobis {5-amino-1- [3- (tri) A surface treatment solution (hereinafter referred to as treatment solution C) was prepared in the same manner as in Example 1 except that methoxysilyl) propylcarbamoyl] -1H-1,2,4-triazole} was used.
With regard to this treatment liquid C, it was confirmed that the methoxysilyl group of the azole silane compound was hydrolyzed to a hydroxysilyl group, and adhesion evaluation tests (a) and (b) were performed.
Subsequently, the volatile matter in the treatment liquid C was removed under reduced pressure to obtain a hydrolyzate of the azole silane compound. The evaluation test (c) of adhesiveness was done about the obtained hydrolyzate.
The test results obtained were as shown in Table 1.

Example 4
Instead of “2,2′-dithiobis {1- [3- (trimethoxysilyl) propylcarbamoyl] -1H-imidazole}”, “4,4′-dithiobis {1- [3- (trimethoxysilyl) propyl] A surface treatment solution (hereinafter referred to as treatment solution D) was prepared in the same manner as in Example 1 except that carbamoyl] -1H-1,2,3-triazole was used.
With respect to this treatment liquid D, it was confirmed that the methoxysilyl group of the azole silane compound was hydrolyzed to a hydroxysilyl group, and adhesion evaluation tests (a) and (b) were performed.
Subsequently, the volatile components in the treatment liquid D were removed under reduced pressure to obtain a hydrolyzate of the azole silane compound. The evaluation test (c) of adhesiveness was done about the obtained hydrolyzate.
The test results obtained were as shown in Table 1.

Comparative Example 1
A surface treatment liquid (hereinafter referred to as “Example 1”) was used in the same manner as in Example 1 except that “imidazole silane compound” was used instead of “3- [3- (trimethoxysilyl) propylthio] -1,2,4-triazole”. A treatment solution E) was prepared.
With respect to this treatment liquid E, it was confirmed that the methoxysilyl group of the imidazole silane compound was hydrolyzed to a hydroxysilyl group, and adhesion evaluation tests (a) and (b) were performed.
Subsequently, the volatile matter in the treatment liquid E was removed under reduced pressure to obtain a hydrolyzate of the imidazole silane compound. The evaluation test (c) of adhesiveness was done about the obtained hydrolyzate.
The test results obtained were as shown in Table 1.

Comparative Example 2
Surface treatment in the same manner as in Example 1 except that “3-aminopropyltrimethoxysilane” was used instead of “3- [3- (trimethoxysilyl) propylthio] -1,2,4-triazole” A solution (hereinafter referred to as treatment solution F) was prepared.
About this processing liquid F, it was confirmed that the methoxy silyl group of 3-aminopropyl trimethoxysilane was hydrolyzed to a hydroxy silyl group, and evaluation test (a) and (b) of adhesiveness was done.
Subsequently, the volatiles in the treatment solution F were removed under reduced pressure to obtain a hydrolyzate of 3-aminopropyltrimethoxysilane. The evaluation test (c) of adhesiveness was done about the obtained hydrolyzate.
The test results obtained were as shown in Table 1.

Comparative Example 3
Without using a silane coupling agent, 200 g of ethylene glycol monobutyl ether and 790 g of water were mixed and stirred at room temperature for 2 hours to prepare a surface treatment solution (hereinafter referred to as treatment solution G).
About this processing liquid G, when the evaluation test (a) and (b) of adhesiveness was done, the obtained test result was as having shown in Table 1.
Moreover, about the evaluation test (c) of adhesiveness, it implemented without adding anything to a solder resist. The test results obtained were as shown in Table 1.

According to the present invention, the adhesiveness (adhesion) of the metal, the inorganic material and the resin material can be sufficiently secured, so that the surface of the substrate can be kept in a smooth state without being roughened. Therefore, since the present invention can greatly contribute to the realization of the miniaturization, thinning, high frequency, high densification and the like of the multilayer printed wiring board, industrial applicability is great.

Claims (15)

The surface treatment liquid of the inorganic material or resin material containing the azole silane compound shown by Chemical formula (I).

The surface treatment method of the inorganic material which makes the surface treatment liquid of Claim 1 contact an inorganic material. The surface treatment method of an inorganic material according to claim 2 , wherein the inorganic material is silicon, ceramic, glass or an inorganic salt. The surface treatment method of an inorganic material according to claim 3 , wherein the ceramic is alumina, silicon carbide, aluminum nitride, silicon nitride or barium titanate. A surface treatment method of a resin material, wherein the surface treatment liquid according to claim 1 is brought into contact with the resin material. The surface treatment method of a resin material according to claim 5 , wherein the resin material is an acrylate resin, an epoxy resin or a polyimide resin. A method of bonding metal and resin material,
A method of bonding metal and resin material, wherein the surface treatment liquid according to claim 1 is brought into contact with the resin material to form a chemical conversion film on the resin material, and bonding the metal and the resin material through the chemical conversion film. An electronic device comprising a composite material in which a metal and a resin material are adhered to each other via a chemical conversion film formed on the surface of the resin material by the surface treatment liquid according to claim 1 . A printed wiring board comprising a composite material in which a metal and a resin material are adhered to each other via a chemical conversion film formed on the surface of the resin material by the surface treatment liquid according to claim 1 . Structural Formula azole silane compound represented by (I), a resin material and / or inorganic material and an insulating composition containing.

The insulating composition according to claim 10 , wherein the resin material is an acrylate resin, an epoxy resin or a polyimide resin. The insulating composition according to claim 10 or 11 , wherein the inorganic material is silicon, ceramic, glass or an inorganic salt. An insulating material comprising the insulating composition according to any one of claims 10 to 12 as a component. An electronic device having an insulating layer obtained from the insulating composition according to any one of claims 10 to 12 . A printed wiring board having an insulating layer obtained from the insulating composition according to any one of claims 10 to 12 .