JP6421073B2 - Metal surface treatment liquid and use thereof - Google Patents

Description

  The present invention relates to a metal surface treatment liquid and use thereof.

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

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

Patent Document 2 discloses a copper surface conditioning composition and a surface treatment method capable of maintaining the adhesion between copper and an insulating material such as a resin without subjecting the copper surface to a roughening treatment such as etching. The invention is described.
This document discloses that the surface conditioning composition contains a silane coupling agent at a concentration of 50 to 10,000 ppm, and the condensation rate of the silane coupling agent is 50% or more. Examples of ring agents include ureidosilanes such as 3-ureidopropyltriethoxysilane (NH ₂ —CO—NH—C ₃ H ₆ —Si (OC ₂ H ₅ ) ₃ ), which are excellent in adhesion to insulating materials. For this reason, silanol, trisilanol and the like are disclosed as the components of the surface conditioning composition.
In addition, it is disclosed that a solution containing the surface conditioning composition can be prepared by dissolving the composition in a mixed solvent of water and an organic solvent, and after bringing the solution into contact with the surface of copper It can be dried after washing with water or without washing, and when it is dried after washing with water, a film with a uniform thickness can be obtained, while drying without washing with water. In this case, it is disclosed that high adhesion with an insulating material can be obtained.

Patent Document 3 describes an invention relating to a method for producing a silane coupling agent solution, a silane coupling agent solution, a surface treatment method for a substrate using the same, and the like.
In this document, an organosilicon compound is mixed with water to sufficiently form silanol groups, and further mixed with alcohol, a high silanolation rate can be realized, and uniform coating is also possible. It is disclosed that the adhesiveness is realized, and that the silanolation rate is preferably 60 to 100%, more preferably 80 to 100%.
An example of the organosilicon compound is 3-ureidopropyltriethoxysilane.
In addition, the point which makes the adhesiveness of the base material comprised from an organic polymer compound or an inorganic material and a liquid crystalline compound is the subject of invention, and the adhesiveness in the case of using a metal 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, as a component of a silane coupling agent used for a primer for bonding glass or metal and rubber, a nitrogen-containing heterocyclic ring such as triazole, and a silyl group such as a trimethoxysilyl group or a triethoxysilyl group, Various substances having a structure bonded via an organic group are disclosed.

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

  The present invention can enhance the adhesion between a metal surface and an insulating resin such as a prepreg or a solder resist, a metal surface treatment solution, a metal surface treatment method, a metal-resin adhesion method, and these An object of the present invention is to provide a printed wiring board to which the means is adapted.

As a result of intensive studies in order to solve the above-mentioned problems, the present inventors have found that an aqueous solution in which a silane compound having a triazole ring is dissolved via a ureido (urea) structure at the end has an intended purpose. It has been found that this has been achieved, and the present invention has been completed.
That is, the first invention is a metal surface treatment liquid characterized by being an aqueous solution containing a triazolesilane compound represented by the chemical formula (I).

（式中、Ｘ^１が水素原子である場合は、Ｘ^２が水素原子を表し、Ｘ^１がメチル基の場合は、Ｘ^２が水素原子、メチル基またはエチル基を表し、Ｘ^１がエチル基の場合は、Ｘ^２が水素原子、メチル基またはエチル基を表し、Ｘ^１が−ＮＨ_２である場合は、Ｘ^２が水素原子、メチル基、エチル基、−ＮＨ_２または−ＳＨを表し、Ｘ^１が−ＳＨである場合は、Ｘ^２が水素原子、メチル基、エチル基、−ＮＨ_２または−ＳＨを表し、Ｘ^１が−ＳＣＨ_３である場合は、Ｘ^２が水素原子、メチル基、エチル基、−ＮＨ_２、−ＳＨまたは−ＳＣＨ_３を表す。Ｒはメチル基またはエチル基を表す。ｎは０〜３の整数を表す。）

(In the formula, when X ¹ is a hydrogen atom, X ² represents a hydrogen atom, and when X ¹ is a methyl group, X ² represents a hydrogen atom, a methyl group or an ethyl group, and X ¹ represents an ethyl group. In the case of X ² represents a hydrogen atom, a methyl group or an ethyl group, and when X ¹ is —NH ₂ , X ² represents a hydrogen atom, a methyl group, an ethyl group, —NH ₂ or —SH, If X ¹ is -SH is, ^{X 2} is a hydrogen atom, a methyl group, an ethyl group, -NH ₂ or an -SH, if ^{X 1} is -SCH _3, ^{X 2} is a hydrogen atom, a methyl group And represents an ethyl group, —NH ₂ , —SH or —SCH ₃ , R represents a methyl group or an ethyl group, and n represents an integer of 0 to _3. )

The second invention is an aqueous solution containing a triazolesilane compound represented by the chemical formula (I), and is a metal surface treatment solution used for bonding a metal and a resin. That is, the metal surface treatment liquid according to the first aspect of the present invention is used for bonding a metal and a resin.
A third invention is a metal surface treatment method, wherein the surface treatment liquid of the first invention or the second invention is brought into contact with a metal.
According to a fourth aspect of the present invention, before bringing the surface treatment liquid into contact with the surface of the metal, the surface of the metal is subjected to at least one selected from pickling treatment, roughening treatment, heat resistance treatment, rust prevention treatment or chemical conversion treatment. A metal surface treatment method according to a third aspect of the invention, characterized in that the treatment is performed.
5th invention is the surface treatment method of the metal of 3rd invention characterized by making the aqueous solution containing a copper ion contact the surface of the said metal, before making a surface treatment liquid contact the surface of a metal. .
A sixth aspect of the invention is the metal surface treatment method according to the third aspect of the invention, wherein after the surface treatment liquid is brought into contact with the surface of the metal, an acidic aqueous solution or an alkaline aqueous solution is brought into contact with the surface of the metal. .
A seventh invention is a method for adhering a metal and a resin, wherein a resin layer is formed on the surface of the metal after the surface treatment liquid of the first or second invention is brought into contact with the metal.
An eighth invention is a printed wiring board characterized in that a resin layer is formed on the surface of the metal after the surface treatment liquid of the first invention or the second invention is brought into contact with the metal.
According to a ninth aspect of the invention, in the metal surface treatment solution according to the first or second aspect, the metal is copper, aluminum, titanium, nickel, tin, iron, silver, gold, or an alloy thereof. It is.
In a tenth aspect of the invention, the metal is copper, aluminum, titanium, nickel, tin, iron, silver, gold, or an alloy of any of the third to sixth aspects. This is a surface treatment method.
An eleventh invention is the metal-resin bonding method according to the seventh invention, wherein the metal is copper, aluminum, titanium, nickel, tin, iron, silver, gold, or an alloy thereof.
A twelfth invention is the printed wiring board according to the eighth invention, wherein the metal is copper, aluminum, titanium, nickel, tin, iron, silver, gold or an alloy thereof.

  ADVANTAGE OF THE INVENTION According to this invention, the adhesiveness of metal surfaces and resin, such as a prepreg and a soldering resist, can be improved.

Hereinafter, the present invention will be described in detail.
The metal surface treatment liquid of the present invention (hereinafter sometimes simply referred to as a surface treatment liquid or a treatment liquid) contains the triazole silane compound represented by the chemical formula (I) as an active ingredient. Includes triazolesilane compounds represented by the chemical formulas (Ia) to (Id).

（式中、Ｘ^１、Ｘ^２およびＲは、前記と同様である。）

(Wherein X ¹ , X ² and R are the same as described above.)

Note that the triazole silane compound represented by the chemical formula (Ia) is a triazole silane compound (hereinafter sometimes referred to as a triazole trialkoxysilane compound) when n is 0 in the chemical formula (I).
Similarly, the triazole silane compound represented by the chemical formula (Ib) is a triazole silane compound when n is 1, and the triazole silane compound represented by the chemical formula (Ic) is a triazole silane compound when n is 2. The triazole silane compound represented by the chemical formula (Id) is a triazole silane compound when n is 3.

  The triazole silane compound represented by the chemical formulas (Ib) to (Id) is a compound (seed) produced by hydrolysis of the triazole trialkoxysilane compound represented by the chemical formula (Ia) present in the surface treatment liquid.

  In the practice of the present invention, it is preferable to use a triazole trialkoxysilane compound represented by the chemical formula (Ia) as a raw material of components in the surface treatment liquid.

This triazole trialkoxysilane compound is
1- [3- (trimethoxysilyl) propylcarbamoyl] -1H-1,2,4-triazole,
1- [3- (triethoxysilyl) propylcarbamoyl] -1H-1,2,4-triazole,
5-methyl-1- [3- (trimethoxysilyl) propylcarbamoyl] -1H-1,2,4-triazole,
5-methyl-1- [3- (triethoxysilyl) propylcarbamoyl] -1H-1,2,4-triazole,
3,5-dimethyl-1- [3- (trimethoxysilyl) propylcarbamoyl] -1H-1,2,4-triazole,
3,5-dimethyl-1- [3- (triethoxysilyl) propylcarbamoyl] -1H-1,2,4-triazole,
3-ethyl-5-methyl-1- [3- (trimethoxysilyl) propylcarbamoyl] -1H-1,2,4-triazole,
3-ethyl-5-methyl-1- [3- (triethoxysilyl) propylcarbamoyl] -1H-1,2,4-triazole,
5-ethyl-1- [3- (trimethoxysilyl) propylcarbamoyl] -1H-1,2,4-triazole,
5-ethyl-1- [3- (triethoxysilyl) propylcarbamoyl] -1H-1,2,4-triazole,
5-ethyl-3-methyl-1- [3- (trimethoxysilyl) propylcarbamoyl] -1H-1,2,4-triazole,
5-ethyl-3-methyl-1- [3- (triethoxysilyl) propylcarbamoyl] -1H-1,2,4-triazole,
3,5-diethyl-1- [3- (trimethoxysilyl) propylcarbamoyl] -1H-1,2,4-triazole,
3,5-diethyl-1- [3- (triethoxysilyl) propylcarbamoyl] -1H-1,2,4-triazole,
5-amino-1- [3- (trimethoxysilyl) propylcarbamoyl] -1H-1,2,4-triazole,
5-amino-1- [3- (triethoxysilyl) propylcarbamoyl] -1H-1,2,4-triazole,
5-amino-3-methyl-1- [3- (trimethoxysilyl) propylcarbamoyl] -1H-1,2,4-triazole,
5-amino-3-methyl-1- [3- (triethoxysilyl) propylcarbamoyl] -1H-1,2,4-triazole,
5-amino-3-ethyl-1- [3- (trimethoxysilyl) propylcarbamoyl] -1H-1,2,4-triazole,
5-amino-3-ethyl-1- [3- (triethoxysilyl) propylcarbamoyl] -1H-1,2,4-triazole,
3,5-diamino-1- [3- (trimethoxysilyl) propylcarbamoyl] -1H-1,2,4-triazole,
3,5-diamino-1- [3- (triethoxysilyl) propylcarbamoyl] -1H-1,2,4-triazole,
5-amino-3-mercapto-1- [3- (trimethoxysilyl) propylcarbamoyl] -1H-1,2,4-triazole,
5-amino-3-mercapto-1- [3- (triethoxysilyl) propylcarbamoyl] -1H-1,2,4-triazole,
5-mercapto-1- [3- (trimethoxysilyl) propylcarbamoyl] -1H-1,2,4-triazole,
5-mercapto-1- [3- (triethoxysilyl) propylcarbamoyl] -1H-1,2,4-triazole,
5-mercapto-3-methyl-1- [3- (trimethoxysilyl) propylcarbamoyl] -1H-1,2,4-triazole,
5-mercapto-3-methyl-1- [3- (triethoxysilyl) propylcarbamoyl] -1H-1,2,4-triazole,
3-ethyl-5-mercapto-1- [3- (trimethoxysilyl) propylcarbamoyl] -1H-1,2,4-triazole,
3-ethyl-5-mercapto-1- [3- (triethoxysilyl) propylcarbamoyl] -1H-1,2,4-triazole,
3-amino-5-mercapto-1- [3- (trimethoxysilyl) propylcarbamoyl] -1H-1,2,4-triazole,
3-amino-5-mercapto-1- [3- (triethoxysilyl) propylcarbamoyl] -1H-1,2,4-triazole,
3,5-dimercapto-1- [3- (trimethoxysilyl) propylcarbamoyl] -1H-1,2,4-triazole,
3,5-dimercapto-1- [3- (triethoxysilyl) propylcarbamoyl] -1H-1,2,4-triazole,
5-methylthio-1- [3- (trimethoxysilyl) propylcarbamoyl] -1H-1,2,4-triazole,
5-methylthio-1- [3- (triethoxysilyl) propylcarbamoyl] -1H-1,2,4-triazole,
3-methyl-5-methylthio-1- [3- (trimethoxysilyl) propylcarbamoyl] -1H-1,2,4-triazole,
3-methyl-5-methylthio-1- [3- (triethoxysilyl) propylcarbamoyl] -1H-1,2,4-triazole,
3-ethyl-5-methylthio-1- [3- (trimethoxysilyl) propylcarbamoyl] -1H-1,2,4-triazole,
3-ethyl-5-methylthio-1- [3- (triethoxysilyl) propylcarbamoyl] -1H-1,2,4-triazole,
3-amino-5-methylthio-1- [3- (trimethoxysilyl) propylcarbamoyl] -1H-1,2,4-triazole,
3-amino-5-methylthio-1- [3- (triethoxysilyl) propylcarbamoyl] -1H-1,2,4-triazole,
3-mercapto-5-methylthio-1- [3- (trimethoxysilyl) propylcarbamoyl] -1H-1,2,4-triazole,
3-mercapto-5-methylthio-1- [3- (triethoxysilyl) propylcarbamoyl] -1H-1,2,4-triazole,
3,5-bis (methylthio) -1- [3- (trimethoxysilyl) propylcarbamoyl] -1H-1,2,4-triazole and 3,5-bis (methylthio) -1- [3- (triethoxy Silyl) propylcarbamoyl] -1H-1,2,4-triazole (included).
In the practice of the present invention, two or more selected from these may be used in combination.

  The triazole trialkoxysilane compound is obtained by reacting a triazole compound represented by the chemical formula (II) with an isocyanatopropylsilane compound represented by the chemical formula (III) in an appropriate amount of reaction solvent at an appropriate reaction temperature and reaction time. Therefore, it is synthesized almost quantitatively (see reaction scheme (A)).

（式中、Ｘ^１、Ｘ^２およびＲは、前記と同様である。）

(Wherein X ¹ , X ² and R are the same as described above.)

The triazole compound is
1,2,4-triazole,
3-methyl-1,2,4-triazole,
3,5-dimethyl-1,2,4-triazole,
3-ethyl-5-methyl-1,2,4-triazole,
3-ethyl-1,2,4-triazole,
3,5-diethyl-1,2,4-triazole,
3-amino-1,2,4-triazole,
3-amino-5-methyl-1,2,4-triazole,
3-amino-5-ethyl-1,2,4-triazole,
3,5-diamino-1,2,4-triazole,
3-mercapto-1,2,4-triazole,
3-mercapto-5-methyl-1,2,4-triazole,
5-ethyl-3-mercapto-1,2,4-triazole,
5-amino-3-mercapto-1,2,4-triazole,
3,5-dimercapto-1,2,4-triazole,
3-methylthio-1,2,4-triazole,
3-methylthio-5-methyl-1,2,4-triazole,
5-ethyl-3-methylthio-1,2,4-triazole,
5-amino-3-methylthio-1,2,4-triazole,
Represents (includes) 5-mercapto-3-methylthio-1,2,4-triazole and 3,5-bis (methylthio) -1,2,4-triazole.

The isocyanatopropylsilane compound is
Represents (includes) 3-isocyanatopropyltrimethoxysilane and 3-isocyanatopropyltriethoxysilane.

The surface treatment liquid of the present invention is prepared by mixing the triazole trialkoxysilane compound represented by the chemical formula (Ia) and water, but an organic solvent may be used in combination with water.
In addition, about the preparation method of a surface treatment liquid, you may add the organic solvent after mixing the said triazole trialkoxysilane compound and water, you may mix the liquid mixture of this compound, water, and an organic solvent, Water may be added after mixing the compound and the organic solvent.
Moreover, as water used for preparation of a surface treatment liquid, pure water, such as ion-exchange water and distilled water, is preferable.

Examples of the organic solvent include methanol, ethanol, propanol, 2-propanol, butanol, tert-butanol, ethylene glycol, propylene glycol, glycerin, diethylene glycol, triethylene glycol, ethylene glycol monomethyl ether, ethylene glycol dimethyl ether, and 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 dimethyl ether, diethylene glycol diethyl ether, triethylene glycol dimethyl ether, triethylene glycol diethyl Ether, tetrahydrofurfuryl alcohol, furfuryl alcohol, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, 1-butoxy-2-propanol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, acetone, In addition to tetrahydrofuran and dioxane, acetonitrile, 2-pyrrolidone, formamide, 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 Ruamine, dimethylamine, trimethylamine, ethylamine, diethylamine, triethylamine, propylamine, isopropylamine, butylamine, allylamine, ethylenediamine, diethylenetriamine, triethylenetetramine, monoethanolamine, diethanolamine, triethanolamine, dipropanolamine, tripropanolamine, mono Isopropanolamine, diisopropanolamine, triisopropanolamine, 1-amino-2-propanol, 3-amino-1-propanol, 2-amino-1-propanol, N, N-dimethylethanolamine, cyclohexylamine, aniline, pyrrolidine, Piperidine, piperazine, pyridine, N, N-dimethylformamide, N, N-dimethylacetate Bromide, which freely miscible with water, such as dimethyl sulfoxide are preferred.
In the practice of the present invention, two or more selected from these may be used in combination.

  As the metal of the material to be treated to which the surface treatment liquid of the present invention can be applied, copper or a copper alloy is preferable. It is expected that this surface treatment solution can be applied.

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.

  Hereinafter, in the specification of the present application, “copper” refers to both so-called metallic copper and copper alloy, and foil (electrolytic copper) used for electronic parts such as electronic boards and lead frames, ornaments, building materials, and the like. Foil, rolled copper foil), plating film (electroless copper plating film, electrolytic copper plating film), wire, bar, tube, plate and the like. In the case of copper wiring through which a high-frequency electric signal flows in recent years, the copper surface is preferably a smooth surface having an average roughness of 0.1 μm or less.

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

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

In the practice of the present invention, the concentration of the triazolesilane compound represented by the chemical formula (I) in the surface treatment liquid is preferably 0.001 to 10% by weight in terms of the concentration of the triazoletrialkoxysilane compound. More preferably, the content is 0.01 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 triazole trialkoxy. Not only is the amount of silane compound used increased, but it is not economical.

  By the way, the triazolesilane compound having a hydroxysilyl group formed in the surface treatment liquid (see the above chemical formulas (Ib) to (Id)) gradually reacts with each other to undergo dehydration condensation, and the hydroxysilyl group is bonded to a siloxane bond ( Si-O-Si) (see scheme (B)), a silane oligomer that is hardly soluble in water (a triazolesilane compound having a group represented by the chemical formula (e) in scheme (B), and x in the formula represents polymerization) Represents the degree).

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 above-mentioned organic solvent in the surface treatment liquid as a silane oligomer solubilizing agent that is hardly soluble in water.
About content of the organic solvent, it is preferable to set it as the ratio of 0.1-90 weight part with respect to 100 weight part of water, and it is more preferable to set it as the ratio of 1-50 weight part.

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

  Similarly, in order to improve the stability of the surface treatment solution and the uniformity of the chemical conversion film derived from the triazole silane compound, halogen ions such as chlorine ions and bromine ions, copper ions, iron ions, zinc ions, etc. Substances that generate metal ions can also be used (added).

  In addition, a known coupling agent may be used (added) as long as the effects of the present invention are not impaired. Known coupling agents include silane coupling agents having a thiol group (mercapto group), vinyl group, epoxy group, (meth) acryl group, amino group, chloropropyl group, and the like.

Examples of such silane coupling agents include
3-mercaptopropyltrimethoxysilane,
Mercaptosilane compounds such as 3-mercaptopropylmethyldimethoxysilane,
Vinyltrichlorosilane,
Vinyltrimethoxysilane,
Vinylsilane compounds such as vinyltriethoxysilane,
styrylsilane compounds such as p-styryltrimethoxysilane,
2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane,
3-glycidoxypropyltrimethoxysilane,
3-glycidoxypropylmethyldiethoxysilane,
Epoxy silane compounds such as 3-glycidoxypropyltriethoxysilane,
Acryloxysilane compounds such as 3-acryloxypropyltrimethoxysilane,
3-methacryloxypropylmethyldimethoxysilane,
3-methacryloxypropyltrimethoxysilane,
3-methacryloxypropylmethyldiethoxysilane,
Methacryloxysilane compounds such as 3-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.

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

After bringing the surface treatment liquid of the present invention into contact with the metal, it is preferable to wash the metal with water.
By washing with water, the triazolesilane compound adhering to the metal can be simply removed without chemically bonding to the metal, and the triazolesilane compound adhering to the surface of the member made of a material other than the metal can also be removed.
In this way, by simply removing the adhering triazolesilane compound, it is possible to prevent contamination of the chemical used in the subsequent process (for example, plating treatment).
After the metal is washed with water, it is preferably dried at a temperature of room temperature to 150 ° C.
The water used for washing is preferably pure water such as ion-exchanged water or distilled water, but the washing method and time are not particularly limited, and may be an appropriate time by means such as dipping or spraying.

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

  The pickling treatment is performed to remove oil and fat components adhering to the metal surface and to remove the oxide film on the metal surface. This pickling treatment uses 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 do.

The roughening treatment is performed to enhance the adhesion between the metal and the resin due to the anchor effect. By this pretreatment, an uneven shape is imparted to the surface of the metal, and the adhesion between the metal and the resin material can be enhanced.
In this pretreatment, roughening means such as micro-etching method, electroplating method, electroless plating method, oxidation method (black oxide, brown oxide), oxidation / reduction method, brush polishing method, jet scrub method, etc. should be adopted. Can do.

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 metal particles are deposited on the surface of the metal to form irregularities on the surface of the metal.

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.
This film can be formed by using a known electroplating method, but vapor deposition or other means may be employed.

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

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

Before bringing the surface treatment liquid of the present invention into contact with the metal surface, an aqueous solution containing copper ions may be brought into contact with the metal surface. This aqueous solution containing copper ions has a function of making the thickness of the chemical conversion film formed on the surface of the metal uniform.
The copper ion source is not particularly limited as long as it is a copper salt that dissolves in water, and examples thereof include copper salts such as copper sulfate, copper nitrate, copper chloride, copper formate, and copper acetate. In order to solubilize the copper salt in water, ammonia or hydrochloric acid may be added.

After the surface treatment liquid of the present invention is brought into contact with the metal surface, an acidic aqueous solution or an alkaline aqueous solution may be brought into contact with the metal surface. This acidic or alkaline aqueous solution also has a function of making the thickness of the chemical conversion film formed on the surface of the metal uniform, like the aqueous solution containing copper ions.
The acidic aqueous solution and the alkaline aqueous solution are not particularly limited, and examples of the acidic aqueous solution include aqueous solutions containing mineral acids such as sulfuric acid, nitric acid, and hydrochloric acid, and organic acids such as formic acid, acetic acid, lactic acid, glycolic acid, and amino acids. it can. Examples of the alkaline aqueous solution include aqueous solutions containing alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, and amines such as ammonia, ethanolamine and monopropanolamine.

The surface treatment liquid of the present invention is suitable for, for example, copper surface treatment for the purpose of enhancing the adhesion (adhesion) between a copper circuit (copper wiring layer) and a prepreg (insulating resin layer).
ADVANTAGE OF THE INVENTION According to this invention, the adhesiveness between a copper wiring layer and an insulating resin layer can be improved in the laminated body (for example, printed wiring board which has a multilayer wiring structure) which has an insulating resin layer in contact with a copper wiring layer. it can.

The laminate can be produced by bringing the surface treatment liquid of the present invention and the surface of the copper wiring into contact with each other and then washing with water to form an insulating resin layer on the surface of the copper wiring. The contact method is as described above, and it is preferable that immersion of the copper wiring in the surface treatment liquid or spraying of the copper wiring with the treatment liquid is simple and reliable.
Moreover, there is no restriction | limiting in particular also about the method of the said water washing, but the immersion to the copper wiring in washing | cleaning water or the spray to the copper wiring surface by washing water is simple and reliable, and preferable.
For the formation of the insulating resin layer, a known method such as a method of attaching a semi-cured resin or a method of applying a liquid resin containing a solvent can be employed. Next, a via hole is formed to connect the upper and lower wirings. By repeating this process, a multilayer printed wiring board can be produced.

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

The insulating resin layer may be made of a known resin.
Specific resins include acrylate resins, epoxy resins, polyimide resins, bismaleimide resins, maleimide resins, cyanate resins, polyphenylene ether (polyphenylene oxide) resins, olefin resins, fluorine-containing resins, which are excellent in heat resistance and insulation. A liquid crystal polymer, a polyetherimide resin, a polyetheretherketone resin, and the like can be given. These may be combined or modified with each other.

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

  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 materials used in the examples and comparative examples are as follows.

[Main ingredients]
1- [3- (Trimethoxysilyl) propylcarbamoyl] -1H-1,2,4-triazole (Synthesis example shown in Reference Example 1)
5-amino-1- [3- (trimethoxysilyl) propylcarbamoyl] -1H-1,2,4-triazole (Synthesis example shown in Reference Example 2)
5-Amino-3-methyl-1- [3- (trimethoxysilyl) propylcarbamoyl] -1H-1,2,4-triazole (Synthesis example shown in Reference Example 3)
3,5-diamino-1- [3- (trimethoxysilyl) propylcarbamoyl] -1H-1,2,4-triazole (Synthesis example shown in Reference Example 4)
3-mercapto-5-amino-1- [3- (trimethoxysilyl) propylcarbamoyl] -1H-1,2,4-triazole and 3-amino-5-mercapto-1- [3- (trimethoxysilyl) ) Propylcarbamoyl] -1H-1,2,4-triazole mixture (Synthesis example shown in Reference Example 5)
5-Mercapto-1- [3- (trimethoxysilyl) propylcarbamoyl] -1H-1,2,4-triazole (Synthesis example shown in Reference Example 6)
3-amino-5-methylthio-1- [3- (trimethoxysilyl) propylcarbamoyl] -1H-1,2,4-triazole (Synthesis example shown in Reference Example 7)
・ Imidazolesilane compound (The synthesis method was shown in Reference Example 8)
・ 3-Aminopropyltrimethoxysilane (Shin-Etsu Chemical Co., Ltd., product name “KBM-903”)
・ Ethylene glycol monobutyl ether (Wako Pure Chemical Industries, Reagent)
Solder resist (acrylate / epoxy resin, manufactured by Taiyo Ink Manufacturing Co., Ltd., product name “PSR-4000AUS308”)

[Reference Example 1]
<Synthesis of 1- [3- (trimethoxysilyl) propylcarbamoyl] -1H-1,2,4-triazole>
While stirring at room temperature, 30 g of methanol was charged with 2.8 g (0.04 mol) of 1,2,4-triazole, followed by 8.2 g of 3-isocyanatopropyltrimethoxysilane. (0.04 mol) was added dropwise.
After the exotherm due to the reaction had subsided, the mixture was stirred at room temperature for 4 hours, and then the volatile component was distilled off from the reaction solution under reduced pressure to give the title compound represented by the chemical formula (Ia-1) as an candy-like liquid. 10.9 g (99.5% yield) of a triazole trialkoxysilane compound was obtained.

[Reference Example 2]
<Synthesis of 5-amino-1- [3- (trimethoxysilyl) propylcarbamoyl] -1H-1,2,4-triazole>
While stirring at room temperature, 100 g of tetrahydrofuran was added to and suspended in 5.04 g (0.06 mol) of 3-amino-1,2,4-triazole, followed by 3-isocyanatopropyltri Methoxysilane 12.3g (0.06mol) was dripped and it stirred for 1 hour.
After charging 0.83 g (0.008 mol) of triethylamine, the mixture was stirred for 4.5 hours under reflux, and then volatile components were distilled off from the reaction solution under reduced pressure to obtain a candy-like liquid. 17.5 g (yield 100.9%) of the title triazole trialkoxysilane compound represented by (Ia-2) was obtained.

[Reference Example 3]
<Synthesis of 5-amino-3-methyl-1- [3- (trimethoxysilyl) propylcarbamoyl] -1H-1,2,4-triazole>
While stirring 14 g of methanol at room temperature, 2.0 g (0.02 mol) of 3-amino-5-methyl-1,2,4-triazole was added thereto and dissolved, followed by 3-isocyanate. 4.1 g (0.02 mol) of natopropyltrimethoxysilane was added dropwise.
After the exotherm due to the reaction had subsided, the mixture was stirred at room temperature for 2 hours, and then the volatile matter was distilled off from the reaction solution under reduced pressure to give the title compound represented by the chemical formula (Ia-3) as an candy-like liquid. The triazole trialkoxysilane compound 6.2g (yield 100.2%) was obtained.

[Reference Example 4]
<Synthesis of 3,5-diamino-1- [3- (trimethoxysilyl) propylcarbamoyl] -1H-1,2,4-triazole>
While stirring at 40 ° C., 41 g of dimethylformamide was dissolved by adding 2.0 g (0.02 mol) of 3,5-diamino-1,2,4-triazole, followed by 3-isocyanate. 4.1 g (0.02 mol) of natopropyltrimethoxysilane was added dropwise.
After the exotherm due to the reaction had subsided, the mixture was stirred at 40 ° C. for 2 hours, and then the volatile component was distilled off from the reaction solution under reduced pressure to give a candy-like liquid represented by the chemical formula (Ia-4). 6.3 g (yield 98.1%) of the triazole trialkoxysilane compound was obtained.

[Reference Example 5]
<3-Mercapto-5-amino-1- [3- (trimethoxysilyl) propylcarbamoyl] -1H-1,2,4-triazole and 3-amino-5-mercapto-1- [3- (trimethoxysilyl) ) Synthesis of Propylcarbamoyl] -1H-1,2,4-triazole>
While stirring at room temperature, 20 g of dimethylformamide was charged with 2.3 g (0.02 mol) of 3-amino-5-mercapto-1,2,4-triazole and dissolved therein. Subsequently, this solution was cooled to 5 ° C., and 4.1 g (0.02 mol) of 3-isocyanatopropyltrimethoxysilane was added dropwise so as not to exceed 10 ° C.
After the exotherm due to the reaction had subsided, the mixture was stirred at 5 to 10 ° C. for 2 hours, and then the volatile component was distilled off from the reaction solution under reduced pressure. As a result, 6.6 g (yield: 102.8%) of a mixture of the title triazole trialkoxysilane compound and the title triazole trialkoxysilane compound represented by the chemical formula (Ia-6) was obtained.
In addition, from the ¹ H-NMR spectrum data, it was recognized that the ratio of both was 4: 6 (molar ratio).

[Reference Example 6]
<Synthesis of 5-mercapto-1- [3- (trimethoxysilyl) propylcarbamoyl] -1H-1,2,4-triazole>
While stirring 30 g of methanol at room temperature, 2.0 g (0.02 mol) of 3-mercapto-1,2,4-triazole was added thereto and dissolved, followed by 3-isocyanatopropyltrimethoxy. 4.1 g (0.02 mol) of silane was added dropwise.
After the exotherm due to the reaction had subsided, the mixture was stirred at room temperature for 2 hours, and then the volatile component was distilled off from the reaction solution under reduced pressure to give the title compound represented by the chemical formula (Ia-7) as an candy-like liquid. 6.3 g (yield 103.9%) of a triazole trialkoxysilane compound was obtained.

[Reference Example 7]
<Synthesis of 3-amino-5-methylthio-1- [3- (trimethoxysilyl) propylcarbamoyl] -1H-1,2,4-triazole>
While stirring at room temperature, 14 g of dimethylformamide was dissolved in 2.6 g (0.02 mol) of 5-amino-3-methylthio-1,2,4-triazole. 4.1 g (0.02 mol) of isocyanatopropyltrimethoxysilane was added dropwise.
After the exotherm due to the reaction had subsided, the mixture was stirred at room temperature for 2 hours, and then the volatile component was distilled off from the reaction mixture under reduced pressure to give the title compound represented by the chemical formula (Ia-8) as an candy-like liquid. 6.8 g (yield 101.4%) of a triazole trialkoxysilane compound was obtained.

[Reference Example 8]
<Synthesis of imidazole silane compound>
3.4 g (0.05 mol) of imidazole was melted at 95 ° C., and 11.8 g (0.05 mol) of 3-glycidoxypropyltrimethoxysilane was added dropwise over 30 minutes while stirring in an argon atmosphere. After completion of dropping, the reaction was further carried out at a temperature of 95 ° C. for 1 hour.
The reaction product was obtained as a clear orange viscous liquid (cited from JP-A-5-186479).
Note: According to JP-A-5-186479, the reaction product is a mixture of imidazole silane compounds represented by chemical formulas (IV-1) to (IV-3).

  Moreover, the evaluation tests (A) to (C) of the adhesion between the metal and the resin performed in the examples and comparative examples are as follows.

[Adhesion evaluation test (I)]
(1) Base material of test piece As a base material of the test piece, an electrolytic copper foil (thickness: 18 μm) was used.
(2) Processing of base material It carried out according to the following processes ac.
a. Acid clean / 1 minute (room temperature), water wash b. Acid cleaning / 1 minute (room temperature), water washing, drying / 1 minute (100 ° C)
c. Immersion in copper surface treatment solution / 1 minute (room temperature), water washing, drying / 1 minute (100 ° C.)
(3) Adhesion of substrate and resin A glass cloth epoxy resin-impregnated prepreg (FR-4 grade) was laminated and pressed on the S surface of the treated substrate, and the substrate and the resin were adhered to produce a printed wiring board.
(4) Evaluation of adhesiveness From this printed wiring board, a test piece having a width of 10 mm was prepared according to “JIS C6481”, pressure cooked (121 ° C./humidity 100% / 100 hours), and then stripped of the copper foil. Strength was measured.

[Adhesion evaluation test (b)]
Instead of “Lamination press of glass cloth epoxy resin impregnated prepreg (FR-4 grade)” on the S side of the substrate, “Resin for build-up wiring board (product name“ GX-13 ”manufactured by Ajinomoto Fine Techno Co., Ltd.) Except for “lamination”, the adhesion between the metal and the resin was evaluated in the same procedure as in the evaluation test (A).

[Adhesion evaluation test (c)]
(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) Treatment of base material It was performed according to the following steps a to d.
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 copper surface treatment solution / 1 minute (room temperature), water washing, drying / 1 minute (100 ° C.)
(3) Formation of resin layer on substrate After applying a solder resist (product name “PSR-4000AUS308”, manufactured by Taiyo Ink Manufacturing Co., Ltd.) to the treated substrate, drying (80 ° C./30 minutes), post-cure ( 150 ° C./60 minutes), a 13 μm thick resin layer (coating film) was formed, and a test piece of a printed wiring board 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 pressure cooker treatment (121 ° C./humidity) 100% / 100 hours), a tape peel test was performed, and the number of squares where the coating film did not peel was measured. Moreover, the damage condition of the coating film was observed visually.
The criteria for determining adhesiveness are as shown in Table 1.

[Example 1]
As a silane coupling agent component, 200 g of ethylene glycol monobutyl ether was added to 10 g of 1- [3- (trimethoxysilyl) propylcarbamoyl] -1H-1,2,4-triazole, and subsequently 790 g of water was added. Was stirred for 2 hours to prepare a copper surface treatment solution (hereinafter referred to as treatment solution A).
About this processing liquid A, it confirmed that the methoxy silyl group of the said triazole trialkoxysilane compound was hydrolyzed to the hydroxy silyl group, and performed the adhesive evaluation test (a)-(c).
The test results obtained were as shown in Table 2.

[Example 2]
As a silane coupling agent component, instead of “1- [3- (trimethoxysilyl) propylcarbamoyl] -1H-1,2,4-triazole”, “5-amino-1- [3- (trimethoxysilyl) A surface treatment solution for copper (hereinafter referred to as treatment solution B) was prepared in the same manner as in Example 1 except that [1) Propylcarbamoyl] -1H-1,2,4-triazole ”was used.
About this processing liquid B, it confirmed that the methoxy silyl group of the said triazole trialkoxysilane compound was hydrolyzed to the hydroxy silyl group, and performed the adhesive evaluation test (a)-(c).
The test results obtained were as shown in Table 2.

[Example 3]
As a silane coupling agent component, instead of “1- [3- (trimethoxysilyl) propylcarbamoyl] -1H-1,2,4-triazole”, “5-amino-3-methyl-1- [3- A copper surface treatment solution (hereinafter referred to as treatment solution C) was prepared in the same manner as in Example 1 except that (trimethoxysilyl) propylcarbamoyl] -1H-1,2,4-triazole ”was used.
About this processing liquid C, it confirmed that the methoxysilyl group of the said triazole trialkoxysilane compound was hydrolyzed to the hydroxysilyl group, and performed the adhesive evaluation test (a)-(c).
The test results obtained were as shown in Table 2.

[Example 4]
As a silane coupling agent component, instead of “1- [3- (trimethoxysilyl) propylcarbamoyl] -1H-1,2,4-triazole”, “3,5-diamino-1- [3- (tri A copper surface treatment solution (hereinafter referred to as treatment solution D) was prepared in the same manner as in Example 1 except that “methoxysilyl) propylcarbamoyl] -1H-1,2,4-triazole” was used.
About this process liquid D, it confirmed that the methoxysilyl group of the said triazole trialkoxysilane compound was hydrolyzed to the hydroxysilyl group, and performed the adhesive evaluation test (I)-(C).
The test results obtained were as shown in Table 2.

[Example 5]
As a silane coupling agent component, instead of “1- [3- (trimethoxysilyl) propylcarbamoyl] -1H-1,2,4-triazole”, “3-mercapto-5-amino-1- [3- (Trimethoxysilyl) propylcarbamoyl] -1H-1,2,4-triazole and 3-amino-5-mercapto-1- [3- (trimethoxysilyl) propylcarbamoyl] -1H-1,2,4-triazole A surface treatment solution for copper (hereinafter referred to as treatment solution E) was prepared in the same manner as in Example 1 except that the mixture was used.
About this process liquid E, it confirmed that the methoxysilyl group of the said triazole trialkoxysilane compound was hydrolyzed to the hydroxysilyl group, and performed the adhesive evaluation test (I)-(C).
The test results obtained were as shown in Table 2.

[Example 6]
As a silane coupling agent component, instead of “1- [3- (trimethoxysilyl) propylcarbamoyl] -1H-1,2,4-triazole”, “5-mercapto-1- [3- (trimethoxysilyl) A surface treatment solution for copper (hereinafter referred to as treatment solution F) was prepared in the same manner as in Example 1 except that [] propylcarbamoyl] -1H-1,2,4-triazole ”was used.
About this process liquid F, it confirmed that the methoxysilyl group of the said triazole trialkoxysilane compound was hydrolyzed to the hydroxysilyl group, and performed the adhesive evaluation test (I)-(C).
The test results obtained were as shown in Table 2.

[Example 7]
As a silane coupling agent component, instead of “1- [3- (trimethoxysilyl) propylcarbamoyl] -1H-1,2,4-triazole”, “3-amino-5-methylthio-1- [3- A copper surface treatment solution (hereinafter referred to as treatment solution G) was prepared in the same manner as in Example 1 except that (trimethoxysilyl) propylcarbamoyl] -1H-1,2,4-triazole ”was used.
About this process liquid G, it confirmed that the methoxysilyl group of the said triazole trialkoxysilane compound was hydrolyzed to the hydroxysilyl group, and performed the adhesive evaluation test (I)-(C).
The test results obtained were as shown in Table 2.

[Comparative Example 1]
Example 1 except that “imidazole silane compound” was used in place of “1- [3- (trimethoxysilyl) propylcarbamoyl] -1H-1,2,4-triazole” as the silane coupling agent component. In the same manner as above, a copper surface treatment solution (hereinafter referred to as treatment solution H) was prepared.
About this processing liquid H, it confirmed that the methoxy silyl group of the imidazole silane compound was hydrolyzed to the hydroxy silyl group, and performed the adhesive evaluation test (ii)-(iii).
The test results obtained were as shown in Table 2.

[Comparative Example 2]
As the silane coupling agent component, “3-aminopropyltrimethoxysilane” was used instead of “1- [3- (trimethoxysilyl) propylcarbamoyl] -1H-1,2,4-triazole”. In the same manner as in Example 1, a copper surface treatment solution (hereinafter referred to as treatment solution I) was prepared.
For this treatment liquid I, it was confirmed that the methoxysilyl group of 3-aminopropyltrimethoxysilane was hydrolyzed to a hydroxysilyl group, and adhesive evaluation tests (a) to (c) were conducted.
The test results obtained were as shown in Table 2.

[Comparative Example 3]
Without using a silane coupling agent, 200 g of ethylene glycol monobutyl ether and 790 g of water were mixed and stirred at room temperature for 2 hours to prepare a copper surface treatment liquid (hereinafter referred to as treatment liquid J).
About this processing liquid J, when the adhesive evaluation tests (a) to (c) were performed, the test results obtained were as shown in Table 2.

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

Claims (12)

A metal surface treatment solution, which is an aqueous solution containing a triazolesilane compound represented by the chemical formula (I).

(In the formula, when X ¹ is a hydrogen atom, X ² represents a hydrogen atom, and when X ¹ is a methyl group, X ² represents a hydrogen atom, a methyl group or an ethyl group, and X ¹ represents an ethyl group. In the case of X ² represents a hydrogen atom, a methyl group or an ethyl group, and when X ¹ is —NH ₂ , X ² represents a hydrogen atom, a methyl group, an ethyl group, —NH ₂ or —SH, If X ¹ is -SH is, ^{X 2} is a hydrogen atom, a methyl group, an ethyl group, -NH ₂ or an -SH, if ^{X 1} is -SCH _3, ^{X 2} is a hydrogen atom, a methyl group And represents an ethyl group, —NH ₂ , —SH or —SCH ₃ , R represents a methyl group or an ethyl group, and n represents an integer of 0 to _3. ) Claim 1 surface treatment liquid metal, wherein the used to bond metals and resins.   A metal surface treatment method, wherein the surface treatment liquid according to claim 1 or 2 is brought into contact with a metal.   Before bringing the surface treatment liquid into contact with the metal surface, the metal surface is subjected to at least one pretreatment selected from pickling treatment, roughening treatment, heat treatment, rust prevention treatment or chemical conversion treatment. The metal surface treatment method according to claim 3.   The metal surface treatment method according to claim 3, wherein an aqueous solution containing copper ions is brought into contact with the surface of the metal before the surface treatment liquid is brought into contact with the surface of the metal.   4. The metal surface treatment method according to claim 3, wherein after the surface treatment liquid is brought into contact with the surface of the metal, an acidic aqueous solution or an alkaline aqueous solution is brought into contact with the surface of the metal.   A method for bonding a metal and a resin, comprising: forming a resin layer on a metal surface after bringing the surface treatment liquid according to claim 1 or 2 into contact with the metal.   A printed wiring board comprising a resin layer formed on a surface of a metal after the surface treatment liquid according to claim 1 or 2 is brought into contact with the metal.   The metal surface treatment solution according to claim 1 or 2, wherein the metal is copper, aluminum, titanium, nickel, tin, iron, silver, gold, or an alloy thereof.   The metal surface treatment method according to claim 3, wherein the metal is copper, aluminum, titanium, nickel, tin, iron, silver, gold, or an alloy thereof.   The metal-resin bonding method according to claim 7, wherein the metal is copper, aluminum, titanium, nickel, tin, iron, silver, gold, or an alloy thereof. The printed wiring board according to claim 8, wherein the metal is copper, aluminum, titanium, nickel, tin, iron, silver, gold, or an alloy thereof.