JP2018016865A - Surface treatment agent, resin composition, and utilization of them - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a surface treatment agent capable of heightening adhesiveness between material having two different qualities selected from a metal, an inorganic material and a resin material.SOLUTION: There is provided a surface treatment agent containing triazole silane compound shown by chemical formula (I) (X is H, a C1-12 linear/branched alkyl group, amino group, phenyl group or benzyl group; Rand Rare each independently a methyl group or an ethyl group; n is an integer of 1-12; and A and B are each independently an integer of 0-3).SELECTED DRAWING: None

Description

The present invention relates to a surface treatment agent containing a triazolesilane compound, a copper foil, a prepreg, a copper clad laminate, an interlayer insulating material, a resin-coated copper foil, and a printed wiring board using the surface treatment agent.
The present invention also relates to a resin composition containing a resin or a compound before curing thereof and a triazolesilane compound, a solder resist ink, a prepreg, a copper-clad laminate, an interlayer insulating material, and a resin-coated copper foil using the resin composition. The present invention relates to a printed wiring board and a semiconductor sealing material.

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

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

  Patent Document 2 discloses a copper surface conditioning composition and a surface treatment method capable of maintaining the adhesion between copper and an insulating material such as a resin without subjecting the copper surface to a roughening treatment such as etching. The invention is described. In this document, a silane coupling agent having an alkoxyl group, for example, silanol, trisilanol, etc. is preferable as a component of the surface conditioning composition because of its excellent adhesion to an insulating material, and among them, In view of improving adhesion between copper and an insulating material such as an epoxy resin, a silane coupling agent having a mercapto group is preferred. In addition, it is disclosed that a solution containing the surface conditioning composition can be prepared by dissolving the composition in a mixed solvent of water and an organic solvent, and after bringing the solution into contact with the surface of copper It can be dried after washing with water or without washing, and when it is dried after washing with water, a film with a uniform thickness can be obtained, while drying without washing with water. In this case, it is disclosed that high adhesion with an insulating material can be obtained.

  Patent Document 3 describes an invention relating to a method for producing a silane coupling agent solution, a silane coupling agent solution, a surface treatment method for a substrate using the same, and the like. In this document, an organosilicon compound is mixed with water to sufficiently form silanol groups, and further mixed with alcohol, a high silanolation rate can be realized and uniform coating can be achieved. It is disclosed that the adhesiveness is realized, and that the silanolation rate is preferably 60 to 100%, more preferably 80 to 100%. As the organosilicon compound, 3-mercaptopropylmethyldimethoxysilane and 3-mercaptopropyltrimethoxysilane are disclosed. In addition, the point which makes the adhesiveness of the base material comprised from an organic polymer compound or an inorganic material and a liquid crystalline compound is the subject of invention, and the adhesiveness in the case of using copper as a base material Is not mentioned.

  Patent Document 4 describes an invention relating to a silane coupling agent and a polymer composition. This document describes nitrogen-containing heterocycles such as triazole and thiadiazole and silyl groups such as trimethoxysilyl and triethoxysilyl groups as components of silane coupling agents used in glass and metal-rubber adhesion primers. However, various substances having a structure in which they are bonded via an organic group having a thioether (sulfide) bond or the like are disclosed. There is no disclosure that the metal is copper.

Next, in the process leading to the present invention, the findings and results found by the present inventors will be outlined with reference to the literature.
The present inventors have developed a novel triazolesilane compound represented by the chemical formula (II ′), which is suitable as a component of a silane coupling agent, and have proposed various uses (applications) of this substance (patent documents) 5-10).

（式中、Ｘは水素原子、−ＣＨ_３、−ＮＨ_２、−ＳＨまたは−ＳＣＨ_３を表す。Ｙは−ＮＨ−または−Ｓ−を表す。Ｒは−ＣＨ_３または−ＣＨ_２ＣＨ_３を表す。ｍは１〜１２の整数を表し、ｎは０または１〜３の整数を表す。）

(In the formula, X represents a hydrogen atom, —CH ₃ , —NH ₂ , —SH or —SCH _3. Y represents —NH— or —S—. R represents —CH ₃ or —CH ₂ CH ₃ . M represents an integer of 1 to 12, and n represents an integer of 0 or 1 to 3).

  On the other hand, as shown in Reaction Scheme (A) and Reaction Scheme (B), various azole compounds are adopted by introducing a method of introducing an alkoxysilyl group into a nitrogen atom in a heterocyclic ring via a urea bond and an alkylene chain. (See Patent Documents 11 to 12 and Patent Documents 13 to 15).

JP 7-286160 A JP 2009-263790 A JP 2006-045189 A JP 2002-363189 A Japanese Patent Laid-Open No. 2015-010079 JP2015-092020A JP, 2006-056449, A JP 2006-121348 A JP, 2006-125143, A JP, 2006-125144, A Japanese Patent Laying-Open No. 2015-182969 JP2015-206115A Japanese Patent Laying-Open No. 2015-044750 Japanese Patent Laying-Open No. 2015-143395 JP, 2006-117901, A

The objective of this invention is providing the surface treating agent which can improve the adhesiveness of two different materials selected from a metal, an inorganic material, and a resin material.
Moreover, it is providing the copper foil manufactured using this surface treating agent, a prepreg, a copper clad laminated board, an interlayer insulation material, copper foil with resin, and a printed wiring board.
Another object of the present invention is to provide a resin composition capable of forming a resin layer having high adhesion to metals and inorganic materials.
Another object of the present invention is to provide a solder resist ink, a prepreg, a copper-clad laminate, an interlayer insulating material, a resin-coated copper foil, a printed wiring board, and a semiconductor sealing material that are produced using this resin composition.

  As a result of intensive studies to solve the above-mentioned problems, the inventors of the present invention have different materials selected from metals, inorganic materials, and resin materials when a surface treatment agent containing a certain triazolesilane compound is used. It has been found that the adhesion between the two materials, particularly the adhesion between the metal and the resin material, is greatly improved. Moreover, when the resin composition containing this triazole silane compound was used, it discovered that the adhesiveness of resin and a metal or an inorganic material improved significantly. The present invention has been completed based on these findings and further studies.

  That is, the first invention is a surface treatment agent containing a triazolesilane compound represented by the chemical formula (I).

（式中、Ｘは水素原子、炭素数１〜１２の直鎖状もしくは分岐状のアルキル基、アミノ基、フェニル基またはベンジル基を表す。Ｒ_１およびＲ_２は同一または異なって、メチル基もしくはエチル基を表す。ｎは１〜１２の整数を表し、ＡおよびＢは同一または異なって、０〜３の整数を表す。）

(In the formula, X represents a hydrogen atom, a linear or branched alkyl group having 1 to 12 carbon atoms, an amino group, a phenyl group, or a benzyl group. R ₁ and R ₂ may be the same or different, and may be a methyl group or Represents an ethyl group, n represents an integer of 1 to 12, and A and B are the same or different and represent an integer of 0 to 3).

2nd invention is the copper foil which has a film | membrane by the surface treating agent of 1st invention.
3rd invention is a prepreg which has a membrane | film | coat by the surface treating agent of 1st invention.
4th invention is a copper clad laminated board which has a film | membrane by the surface treating agent of 1st invention.
5th invention is the interlayer insulation material which has a film | membrane by the surface treating agent of 1st invention.
6th invention is copper foil with a resin with which copper foil and the resin layer were laminated | stacked through the membrane | film | coat by the surface treating agent of 1st invention.
7th invention is a printed wiring board provided with the member which has a film | membrane by the surface treating agent of 1st invention.
The eighth invention is a resin composition containing a resin or a pre-curing compound thereof and a triazolesilane compound represented by the chemical formula (I).
9th invention is the soldering resist ink comprised from the resin composition of 8th invention.
10th invention is a printed wiring board provided with the soldering resist formed from the soldering resist ink of 9th invention.
The eleventh invention is a prepreg composed of a base material and the resin composition of the eighth invention.
The twelfth invention is a copper clad laminate comprising a copper foil and the prepreg of the eleventh invention.
The thirteenth invention is an interlayer insulating material composed of the resin composition of the eighth invention.
14th invention is a copper foil with resin comprised from the resin layer formed with the copper foil and the resin composition of 8th invention.
15th invention is a printed wiring board provided with the resin layer formed with the resin composition of 8th invention.
The sixteenth invention is a semiconductor encapsulating material composed of the resin composition of the eighth invention.

According to the surface treating agent of the present invention, it is possible to improve the adhesion between two different materials selected from metals, inorganic materials, and resin materials. Therefore, by using the surface treatment agent, copper foil, prepreg, copper-clad laminate, interlayer insulating material, resin-coated copper foil and printed wiring excellent in adhesion to the laminate and its own interlayer adhesion A board etc. can be obtained.
Moreover, according to the resin composition of this invention, the resin layer which has high adhesiveness with respect to a metal or an inorganic material can be formed. Therefore, by using this resin composition, a copper-clad laminate, an interlayer insulating material, a resin-coated copper foil and a printed wiring board, excellent in adhesion to a laminate and its own interlayer adhesion, semiconductor encapsulation Materials etc. can be obtained.

Hereinafter, the present invention will be described in detail.
[Triazole silane compound]
In the practice of the present invention, a triazolesilane compound represented by the above chemical formula (I) is used. Examples of this triazole silane compound include triazole silane compounds represented by chemical formulas (Ia) to (Id) in the case where A and B in chemical formula (I) are the same.

（式中、Ｒ_１、Ｒ_２、Ｘおよびｎは前記と同様である。）

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

That is, the triazole silane compound represented by the chemical formula (Ia) is a triazole silane compound in the case where A and B are 0 in the chemical formula (I) (hereinafter sometimes referred to as triazole silane compound (Ia)). is there.
Similarly, the triazole silane compound represented by the chemical formula (Ib) is a triazole silane compound (hereinafter sometimes referred to as the triazole silane compound (Ib)) when A and B are 1, and the chemical formula (Ic) The triazole silane compound shown is a triazole silane compound when A and B are 2 (hereinafter sometimes referred to as triazole silane compound (Ic)), and the triazole silane compound represented by the chemical formula (Id) is A And a triazole silane compound (hereinafter sometimes referred to as a triazole silane compound (Id)) when B is 3.

  The triazole silane compound represented by the chemical formulas (Ib) to (Id) is a species generated by hydrolysis of the triazole silane compound (Ia) present in the surface treatment agent.

  In the practice of the present invention, it is preferable to use the triazolesilane compound (Ia) as a component of the surface treatment agent and the resin composition.

As this triazole silane compound (Ia), for example,
N- [3- (trimethoxysilyl) propyl] -3- [2- (trimethoxysilyl) ethylthio] -1H-1,2,4-triazole-1-carboxamide,
N- [3- (trimethoxysilyl) propyl] -3- [3- (trimethoxysilyl) propylthio] -1H-1,2,4-triazole-1-carboxamide,
N- [3- (trimethoxysilyl) propyl] -3- [3- (triethoxysilyl) propylthio] -1H-1,2,4-triazole-1-carboxamide,
N- [3- (triethoxysilyl) propyl] -3- [3- (trimethoxysilyl) propylthio] -1H-1,2,4-triazole-1-carboxamide,
N- [3- (triethoxysilyl) propyl] -3- [3- (triethoxysilyl) propylthio] -1H-1,2,4-triazole-1-carboxamide,
N- [3- (trimethoxysilyl) propyl] -5-methyl-3- [3- (trimethoxysilyl) propylthio] -1H-1,2,4-triazole-1-carboxamide,
N- [3- (trimethoxysilyl) propyl] -5-methyl-3- [3- (triethoxysilyl) propylthio] -1H-1,2,4-triazole-1-carboxamide;
N- [3- (triethoxysilyl) propyl] -5-methyl-3- [3- (trimethoxysilyl) propylthio] -1H-1,2,4-triazole-1-carboxamide,
N- [3- (triethoxysilyl) propyl] -5-methyl-3- [3- (triethoxysilyl) propylthio] -1H-1,2,4-triazole-1-carboxamide,
N- [3- (trimethoxysilyl) propyl] -5-ethyl-3- [3- (trimethoxysilyl) propylthio] -1H-1,2,4-triazole-1-carboxamide,
N- [3- (trimethoxysilyl) propyl] -5-ethyl-3- [3- (triethoxysilyl) propylthio] -1H-1,2,4-triazole-1-carboxamide,
N- [3- (triethoxysilyl) propyl] -5-ethyl-3- [3- (trimethoxysilyl) propylthio] -1H-1,2,4-triazole-1-carboxamide,
N- [3- (triethoxysilyl) propyl] -5-ethyl-3- [3- (triethoxysilyl) propylthio] -1H-1,2,4-triazole-1-carboxamide,
N- [3- (trimethoxysilyl) propyl] -5-isopropyl-3- [3- (trimethoxysilyl) propylthio] -1H-1,2,4-triazole-1-carboxamide,
N- [3- (trimethoxysilyl) propyl] -5-propyl-3- [3- (trimethoxysilyl) propylthio] -1H-1,2,4-triazole-1-carboxamide,
N- [3- (trimethoxysilyl) propyl] -5-propyl-3- [3- (triethoxysilyl) propylthio] -1H-1,2,4-triazole-1-carboxamide,
N- [3- (triethoxysilyl) propyl] -5-propyl-3- [3- (trimethoxysilyl) propylthio] -1H-1,2,4-triazole-1-carboxamide,
N- [3- (triethoxysilyl) propyl] -5-propyl-3- [3- (triethoxysilyl) propylthio] -1H-1,2,4-triazole-1-carboxamide;
N- [3- (trimethoxysilyl) propyl] -5-butyl-3- [3- (trimethoxysilyl) propylthio] -1H-1,2,4-triazole-1-carboxamide,
N- [3- (trimethoxysilyl) propyl] -5-butyl-3- [3- (triethoxysilyl) propylthio] -1H-1,2,4-triazole-1-carboxamide,
N- [3- (triethoxysilyl) propyl] -5-butyl-3- [3- (trimethoxysilyl) propylthio] -1H-1,2,4-triazole-1-carboxamide,
N- [3- (triethoxysilyl) propyl] -5-butyl-3- [3- (triethoxysilyl) propylthio] -1H-1,2,4-triazole-1-carboxamide,
N- [3- (trimethoxysilyl) propyl] -5-pentyl-3- [3- (trimethoxysilyl) propylthio] -1H-1,2,4-triazole-1-carboxamide,
N- [3- (trimethoxysilyl) propyl] -5-pentyl-3- [3- (triethoxysilyl) propylthio] -1H-1,2,4-triazole-1-carboxamide;
N- [3- (triethoxysilyl) propyl] -5-pentyl-3- [3- (trimethoxysilyl) propylthio] -1H-1,2,4-triazole-1-carboxamide;
N- [3- (triethoxysilyl) propyl] -5-pentyl-3- [3- (triethoxysilyl) propylthio] -1H-1,2,4-triazole-1-carboxamide;
N- [3- (trimethoxysilyl) propyl] -5-hexyl-3- [3- (trimethoxysilyl) propylthio] -1H-1,2,4-triazole-1-carboxamide,
N- [3- (trimethoxysilyl) propyl] -5-hexyl-3- [3- (triethoxysilyl) propylthio] -1H-1,2,4-triazole-1-carboxamide;
N- [3- (triethoxysilyl) propyl] -5-hexyl-3- [3- (trimethoxysilyl) propylthio] -1H-1,2,4-triazole-1-carboxamide,
N- [3- (triethoxysilyl) propyl] -5-hexyl-3- [3- (triethoxysilyl) propylthio] -1H-1,2,4-triazole-1-carboxamide;
N- [3- (trimethoxysilyl) propyl] -5-heptyl-3- [3- (trimethoxysilyl) propylthio] -1H-1,2,4-triazole-1-carboxamide,
N- [3- (trimethoxysilyl) propyl] -5-heptyl-3- [3- (triethoxysilyl) propylthio] -1H-1,2,4-triazole 1-carboxamide,
N- [3- (triethoxysilyl) propyl] -5-heptyl-3- [3- (trimethoxysilyl) propylthio] -1H-1,2,4-triazole-1-carboxamide,
N- [3- (triethoxysilyl) propyl] -5-heptyl-3- [3- (triethoxysilyl) propylthio] -1H-1,2,4-triazole-1-carboxamide,
N- [3- (trimethoxysilyl) propyl] -5-dodecyl-3- [3- (trimethoxysilyl) propylthio] -1H-1,2,4-triazole-1-carboxamide,
N- [3- (trimethoxysilyl) propyl] -5-amino-3- [3- (trimethoxysilyl) propylthio] -1H-1,2,4-triazole-1-carboxamide,
N- [3- (trimethoxysilyl) propyl] -5-amino-3- [3- (triethoxysilyl) propylthio] -1H-1,2,4-triazole-1-carboxamide,
N- [3- (triethoxysilyl) propyl] -5-amino-3- [3- (trimethoxysilyl) propylthio] -1H-1,2,4-triazole-1-carboxamide;
N- [3- (triethoxysilyl) propyl] -5-amino-3- [3- (triethoxysilyl) propylthio] -1H-1,2,4-triazole-1-carboxamide,
N- [3- (trimethoxysilyl) propyl] -5-amino-3- [12- (trimethoxysilyl) dodecylthio] -1H-1,2,4-triazole-1-carboxamide;
N- [3- (trimethoxysilyl) propyl] -5-phenyl-3- [3- (trimethoxysilyl) propylthio] -1H-1,2,4-triazole-1-carboxamide,
N- [3- (trimethoxysilyl) propyl] -5-phenyl-3- [3- (triethoxysilyl) propylthio] -1H-1,2,4-triazole-1-carboxamide,
N- [3- (triethoxysilyl) propyl] -5-phenyl-3- [3- (trimethoxysilyl) propylthio] -1H-1,2,4-triazole-1-carboxamide,
N- [3- (triethoxysilyl) propyl] -5-phenyl-3- [3- (triethoxysilyl) propylthio] -1H-1,2,4-triazole-1-carboxamide,
N- [3- (trimethoxysilyl) propyl] -5-phenyl-3- [6- (trimethoxysilyl) hexylthio] -1H-1,2,4-triazole-1-carboxamide;
N- [3- (trimethoxysilyl) propyl] -5-benzyl-3- [3- (trimethoxysilyl) propylthio] -1H-1,2,4-triazole-1-carboxamide,
N- [3- (trimethoxysilyl) propyl] -5-benzyl-3- [3- (triethoxysilyl) propylthio] -1H-1,2,4-triazole-1-carboxamide,
N- [3- (triethoxysilyl) propyl] -5-benzyl-3- [3- (trimethoxysilyl) propylthio] -1H-1,2,4-triazole-1-carboxamide,
N- [3- (triethoxysilyl) propyl] -5-benzyl-3- [3- (triethoxysilyl) propylthio] -1H-1,2,4-triazole-1-carboxamide,
And N- [3- (trimethoxysilyl) propyl] -5-benzyl-3- [8- (trimethoxysilyl) octylthio] -1H-1,2,4-triazole-1-carboxamide.
In the practice of the present invention, two or more selected from these compounds may be used in combination.

  The triazole silane compound used in the practice of the present invention comprises a triazole silane compound represented by the chemical formula (II) and an isocyanatopropyl silane compound represented by the chemical formula (III) in an appropriate amount of reaction solvent at an appropriate reaction temperature and reaction. By reacting with time, it is synthesized almost quantitatively (see reaction scheme (C)).

（式中、Ｘ、Ｒ_１、Ｒ_２およびｎは前記と同様である。）

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

Examples of the triazole silane compound represented by the chemical formula (II) (hereinafter sometimes simply referred to as a triazole compound)
3- [2- (trimethoxysilyl) ethylthio] -1H-1,2,4-triazole,
3- [3- (trimethoxysilyl) propylthio] -1H-1,2,4-triazole,
3- [3- (triethoxysilyl) propylthio] -1H-1,2,4-triazole,
3-methyl-5- [3- (trimethoxysilyl) propylthio] -1H-1,2,4-triazole,
3-methyl-5- [3- (triethoxysilyl) propylthio] -1H-1,2,4-triazole,
3-ethyl-5- [3- (trimethoxysilyl) propylthio] -1H-1,2,4-triazole,
3-ethyl-5- [3- (triethoxysilyl) propylthio] -1H-1,2,4-triazole,
3-isopropyl-5- [3- (trimethoxysilyl) propylthio] -1H-1,2,4-triazole,
3-propyl-5- [3- (trimethoxysilyl) propylthio] -1H-1,2,4-triazole,
3-propyl-5- [3- (triethoxysilyl) propylthio] -1H-1,2,4-triazole,
3-butyl-5- [3- (trimethoxysilyl) propylthio] -1H-1,2,4-triazole,
3-butyl-5- [3- (triethoxysilyl) propylthio] -1H-1,2,4-triazole,
3-pentyl-5- [3- (trimethoxysilyl) propylthio] -1H-1,2,4-triazole,
3-pentyl-5- [3- (triethoxysilyl) propylthio] -1H-1,2,4-triazole,
3-hexyl-5- [3- (trimethoxysilyl) propylthio] -1H-1,2,4-triazole,
3-hexyl-5- [3- (triethoxysilyl) propylthio] -1H-1,2,4-triazole,
3-heptyl-5- [3- (trimethoxysilyl) propylthio] -1H-1,2,4-triazole,
3-heptyl-5- [3- (triethoxysilyl) propylthio] -1H-1,2,4-triazole,
3-dodecyl-5- [3- (trimethoxysilyl) propylthio] -1H-1,2,4-triazole,
3-amino-5- [3- (trimethoxysilyl) propylthio] -1H-1,2,4-triazole,
3-amino-5- [3- (triethoxysilyl) propylthio] -1H-1,2,4-triazole,
3-amino-5- [12- (trimethoxysilyl) dodecylthio] -1H-1,2,4-triazole,
3-phenyl-5- [3- (trimethoxysilyl) propylthio] -1H-1,2,4-triazole,
3-phenyl-5- [3- (triethoxysilyl) propylthio] -1H-1,2,4-triazole,
3-phenyl-5- [6- (trimethoxysilyl) hexylthio] -1H-1,2,4-triazole,
3-benzyl-5- [3- (trimethoxysilyl) propylthio] -1H-1,2,4-triazole,
3-benzyl-5- [3- (triethoxysilyl) propylthio] -1H-1,2,4-triazole,
Examples include 3-benzyl-5- [8- (trimethoxysilyl) octylthio] -1H-1,2,4-triazole.

The isocyanatopropylsilane compound represented by the chemical formula (III) (hereinafter sometimes simply referred to as an isocyanato compound)
It represents 3-isocyanatopropyltrimethoxysilane and 3-isocyanatopropyltriethoxysilane.

  The reaction solvent can be used without particular limitation as long as it is an inert solvent for the triazole compound and the isocyanato compound. For example, alcohol solvents such as methanol, ethanol, propanol, 2-propanol; pentane, Hydrocarbon solvents such as hexane, heptane, toluene, xylene; ether solvents such as diethyl ether, tetrahydrofuran, 1,4-dioxane, cyclopentyl methyl ether; ester solvents such as ethyl acetate, butyl acetate; formamide, N, N Amide solvents such as dimethylformamide, N, N-dimethylacetamide, 2-pyrrolidone, N-methylpyrrolidone; ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, dimethyl sulfoxide, acetate Nitrile, and the like.

The amount of isocyanato compound used (the amount charged) relative to the amount of triazole compound used (the amount charged) is 0 in consideration of factors such as the reaction temperature and reaction time, the type of raw materials used, the reaction solvent, and the reaction scale. It is preferable to set it as an appropriate ratio in the range of 0.8 to 1.2 moles.
If the amount of the isocyanato compound charged is more than 1.2 times mol, the compound may be polymerized and gelled. If the amount is less than 0.8 times mol, the purity of the product may be lowered or produced. There is a possibility that the separation operation of the object becomes complicated.

The reaction temperature is preferably in the range of 0 to 100 ° C, more preferably in the range of 5 to 65 ° C.
The reaction time is appropriately determined according to the set reaction temperature, but is preferably in the range of 30 minutes to 10 hours, and more preferably in the range of 1 to 5 hours.

[Surface treatment agent]
The surface treating agent of the present invention contains a triazole silane compound represented by the above chemical formula (I). The surface treating agent of the present invention may contain a solvent together with this triazole silane compound. Examples of the solvent include water, an organic solvent, and a mixed liquid of water and an organic solvent. The surface treating agent in this case can be prepared by mixing the triazole silane compound and the solvent using an appropriate mixing means. Hereinafter, the surface treatment agent may be referred to as a treatment liquid.

  The organic solvent is not particularly limited as long as it acts as a solubilizing agent, and may be used without limitation, for example, 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, ethyl methyl ketone, tetrahydrofuran, dioxane, acetonitrile, 2- Pyrrolidone, formamide, N, N-dimethylformamide, N, N-dimethylacetamide, dimethyl sulfoxide, sulfolane, dimethyl carbonate, ethylene carbonate, N-methylpyrrolidone, γ-butyrolactone, 1,3-dimethyl-2-imidazolidinone, Formic acid, acetic acid, propionic acid, butyric acid, glycolic acid, lactic acid, gluconic acid, Glyceric acid, malonic acid, succinic acid, levulinic acid, phenol, benzoic acid, oxalic acid, tartaric acid, malic acid, methyl acetate, ethyl acetate, ethyl formate, methylamine, dimethylamine, trimethylamine, ethylamine, diethylamine, triethylamine, propylamine , Isopropylamine, butylamine, allylamine, ethylenediamine, diethylenetriamine, triethylenetetramine, monoethanolamine, diethanolamine, triethanolamine, dipropanolamine, tripropanolamine, diisopropanolamine, triisopropanolamine, 1-amino-2-propanol, 3-amino-1-propanol, 2-amino-1-propanol, N, N-dimethylethanolamine, cyclohexylamine, Diphosphate, pyrrolidine, piperidine, piperazine, pyridine is preferred. These organic solvents (solubilizers) may be used in combination of two or more. When a solid solubilizer is used, it is used in combination with water and / or a liquid solubilizer.

  When using a mixed solution of water and an organic solvent as a solvent, the surface treatment agent may be prepared by mixing the triazolesilane compound represented by the chemical formula (I) with water and then adding the organic solvent. A mixture of water, water and organic solvent may be mixed, or water may be added after mixing the compound and organic solvent. Moreover, as water used for preparation of a surface treating agent, pure water, such as ion-exchange water and distilled water, is preferable.

  As described above, the triazolesilane compound represented by the chemical formula (I) (except when A and B are 3 at the same time) is hydrolyzed when contacted with water, and this hydrolysis mode is shown in Scheme (D). Indicated. In this scheme, the silyl group of the triazolesilane compound exemplified by the above chemical formulas (Ia) to (Ic) is hydrolyzed, that is, the trialkoxysilyl group is gradually converted into a dialkoxyhydroxysilyl group, a dihydroxy group. It is simply shown that it changes to an alkoxysilyl group or a trihydroxysilyl group.

（式中、Ｒは前記のＲ_１またはＲ_２を示す。Ｙは繰り返し単位の数を表す整数である。）

(In the formula, R represents R ₁ or R ₂ described above. Y is an integer representing the number of repeating units.)

  In general, it is known that a substance having an alkoxysilyl group in the molecule acts as a silane coupling agent. For example, taking adhesion between copper and a resin material as an example, the triazole silane 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 resin and copper to form chemical bonds. In addition, the alkoxysilyl group is hydrolyzed and converted to a hydroxysilyl group (—Si—OH), and this hydroxysilyl group chemically bonds with copper oxide scattered on the surface of copper. Therefore, by bringing the surface treatment agent 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 triazole silane compound represented by the chemical formula (I) in the surface treatment agent is 0.001 to 10% by weight in terms of the concentration of the trialkoxy triazole silane compound (Ia). It is preferable that it is 0.01 to 5 weight%. When this concentration is less than 0.001% by weight, the effect of improving the adhesiveness is not sufficient, and when this concentration exceeds 10% by weight, the effect of improving the adhesiveness almost reaches its peak, and the triazolesilane compound It is not economical just because the amount of use increases.

  By the way, for example, the above-mentioned triazolesilane compounds (Ib) to (Id) having a hydroxysilyl group generated in the surface treatment agent gradually react with each other to undergo dehydration condensation, and the hydroxysilyl group is bonded to a siloxane bond (Si -O-Si) (see Scheme (D)) and converted into a silane oligomer (triazole silane compound having a group represented by the chemical formula (e) in Scheme (D)) that is hardly soluble in water.

  When the amount of silane oligomer produced in the surface treatment agent increases, the insoluble matter precipitates (the surface treatment agent becomes cloudy), and the treatment tank, the pipe connected to the treatment tank, the immersion in the surface treatment agent There is a risk that smooth surface treatment may be hindered by adhesion to sensors for detecting the temperature and liquid level of the treatment agent. In order to avoid this, it is preferable that an organic solvent is contained in the surface treatment agent as a silane oligomer solubilizer that is hardly soluble in water. The content of the organic solvent is preferably 0.1 to 900 parts by weight and more preferably 1 to 500 parts by weight with respect to 100 parts by weight of water. It is not something. As this organic solvent, what was illustrated as an above-mentioned organic solvent can be used.

  In the preparation of the surface treating agent of the present invention, an acid such as acetic acid or hydrochloric acid, or an alkali such as sodium hydroxide or ammonia may be used in order to promote hydrolysis of the triazolesilane compound (Ia).

  Similarly, in order to improve the stability of the surface treatment agent and the uniformity of the chemical conversion film, substances that generate halogen ions such as chlorine ions and bromine ions, and metal ions such as copper ions, iron ions, and zinc ions are used. You can also.

  Moreover, you may use a well-known coupling agent together in the range which does not impair the effect of this invention. Known coupling agents include silane coupling agents having a thiol group (mercapto group), vinyl group, epoxy group, (meth) acryl group, amino group, chloropropyl group, and the like.

  Examples of such silane coupling agents include mercaptosilane compounds such as 3-mercaptopropyltrimethoxysilane and 3-mercaptopropylmethyldimethoxysilane, and vinylsilanes such as vinyltrichlorosilane, vinyltrimethoxysilane, and vinyltriethoxysilane. Compounds, vinylphenylsilane compounds such as p-vinylphenyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxy Silane, epoxy silane compounds such as 3-glycidoxypropyltriethoxysilane, acryloxysilane such as 3-acryloxypropyltrimethoxysilane, methacryloxypropylmethyldimethoxysilane, Methacryloxysilane compounds such as taacryloxypropyltrimethoxysilane, methacryloxypropylmethyldiethoxysilane, methacryloxypropyltriethoxysilane, N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, N-2- ( Aminoethyl) -3-aminopropyltrimethoxysilane, N-2- (aminoethyl) -3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl Aminosilane compounds such as -N- (1,3-dimethylbutylidene) propylamine, N-phenyl-3-aminopropyltrimethoxysilane, N- (vinylbenzyl) -2-aminoethyl-3-aminopropyltrimethoxysilane , 3-U Ureidosilane compounds such as idpropyltriethoxysilane, chloropropylsilane compounds such as 3-chloropropyltrimethoxysilane, sulfide silane compounds such as bis (triethoxysilylpropyl) tetrasulfide, isocyanates such as 3-isocyanatopropyltriethoxysilane A silane compound etc. can be mentioned. In addition, an aluminum coupling agent, a titanium coupling agent, a zirconium coupling agent, and the like can also be exemplified.

  In addition to the above, the surface treatment agent of the present invention may contain an appropriate additive depending on the type of material to be treated (described later), the use, and the like.

[Material to be treated]
Examples of the material to be treated to which the surface treatment agent of the present invention is applied include granular, needle-like, fiber-like, thin-film-like, plate-like, and amorphous ones formed from metals, inorganic materials, resin materials, and the like. It is done.

Examples of the metal include copper, aluminum, titanium, nickel, tin, iron, silver, gold, and alloys thereof. As a specific example of the alloy, a 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, and Cu-Si Cu-Mn, Cu-Be-Co, Cu-Ti, Cu-Ni-Si, Cu-Zn-Ni, Cu-Cr, Cu-Zr, Cu-Fe, Cu-Al Alloy of Cu type, Cu-Zn type, Cu-Co type and the like. Other alloys include aluminum alloy (Al—Si alloy), nickel alloy (Ni—Cr alloy), iron alloy (Fe—Ni alloy, stainless steel) and the like. Of these metals, copper and copper alloys are preferred.
Moreover, as a metal aspect, foil (for example, electrolytic copper foil, rolled copper foil), plating film (for example, electroless copper plating) used for electronic devices such as printed wiring boards and lead frames, ornaments, building materials, etc. Film, electrolytic copper plating film), thin film formed by vapor deposition, sputtering, damascene, etc., and used in applications and forms such as granular, needle-like, fibrous, linear, rod-like, tubular, and plate-like Things. In the case of copper wiring through which a high-frequency electric signal flows in recent years, the copper surface is preferably a smooth surface having an average roughness of 0.1 μm or less. As a pretreatment, the surface of copper may be plated with nickel, zinc, chromium, tin or the like.

  Examples of the inorganic material include silicon, ceramic, carbon used as a filler, inorganic salt, and glass. Specifically, silicon, silicon carbide, silica, glass, diatomaceous earth, calcium silicate, talc, glass beads, sericite activated clay, bentonite and other silicon compounds, alumina, zinc oxide, iron oxide, magnesium oxide, tin oxide, oxidation Oxides such as titanium, hydroxides such as magnesium hydroxide, aluminum hydroxide, basic magnesium carbonate, carbonates such as calcium carbonate, zinc carbonate, hydrotalcite, magnesium carbonate, sulfates such as barium sulfate and gypsum, Titanates such as barium titanate, nitrides such as aluminum nitride and silicon nitride, graphites such as flake graphite (natural graphite), expanded graphite, expanded graphite (synthetic graphite), activated carbons, carbon fibers, carbon Black etc. are mentioned. Among these inorganic materials, silicon, ceramic (alumina, silicon carbide, aluminum nitride, silicon nitride and barium titanate), glass and inorganic salts are preferable.

  The resin material may be either a thermoplastic resin or a thermosetting resin. Specifically, acrylate resin, epoxy resin, polyimide resin, bismaleimide resin, maleimide resin, cyanate resin, polyphenylene ether resin, polyphenylene oxide resin, polybutadiene resin, olefin resin, fluorine-containing resin having excellent heat resistance and insulation properties , Polyetherimide resin, polyetheretherketone resin, liquid crystal resin, and the like. These may be combined or modified with each other. Moreover, there is no restriction | limiting in particular in the polymerization degree of these resin, After superposing | polymerizing (curing) suitably after surface treatment. Among these resin materials, acrylate resins, epoxy resins, and polyimide resins are preferable.

[Surface treatment method]
There is no restriction | limiting in particular as a method of making the surface treating agent of this invention contact the surface of a to-be-processed material, Means, such as immersion, application | coating, a spray, can be employ | adopted. The time (treatment time) for contacting the surface treatment agent and the material to be treated is preferably 1 second to 10 minutes, and more preferably 5 seconds to 3 minutes. When the treatment time is less than 1 second, the film thickness formed on the surface of the material to be treated becomes thin, and sufficient adhesion between different materials cannot be obtained. There is no great difference in the film thickness of the film, and no improvement in adhesion can be expected. Further, the temperature of the treatment agent when the surface treatment agent is brought into contact with the surface of the material to be treated is preferably 5 to 50 ° C., but may be set as appropriate in relation to the treatment time.

  After the surface treatment agent of the present invention and the material to be treated are brought into contact with each other, the substrate may be washed with water and then dried, or may be dried without being washed with water. Drying is preferably performed 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 of spraying or dipping.

  Before bringing the surface treatment agent of the present invention into contact with the metal surface, the surface of the metal is selected from pickling treatment, alkali washing treatment, roughening treatment, heat treatment, rust prevention treatment or chemical conversion treatment. At least one pretreatment may be performed.

  In addition, before bringing the surface treatment agent of the present invention into contact with the surface of the inorganic material or resin material, the surface of the inorganic material or resin material is subjected to pickling treatment, alkali washing treatment, roughening treatment, or heat resistance treatment. At least one pre-processing selected from may be performed.

  The pickling treatment is performed to remove oil and fat components adhering to the surface of the metal, inorganic material or resin material and to remove the oxide film on the surface of the metal. For this pickling treatment, solutions such as hydrochloric acid solution, sulfuric acid solution, nitric acid solution, sulfuric acid-hydrogen peroxide solution, organic acid solution, inorganic acid-organic solvent solution, organic acid-organic solvent solution, etc. Can be used.

  The alkali washing treatment is performed to remove oil and fat components adhering to the surface of the metal, inorganic material, or resin material. This alkali washing treatment includes sodium hydroxide solution, kalim hydroxide solution, magnesium hydroxide solution, calcium hydroxide solution, amine solution, inorganic alkali-organic solvent solution, amine-organic solvent solution, etc. The solution can be used.

  The roughening treatment forms an uneven shape on the surface of the metal, inorganic material, or resin material, and has an anchor effect to improve the adhesion (adhesion) of two materials selected from the metal, inorganic material, and resin material. It is done to increase. For this roughening treatment, desmear method, plasma etching method, metal sputtering method, electroless plating method, electroplating method, rust prevention treatment, oxidation / reduction method, brush polishing method, jet scrub method, etc. should be adopted. Can do.

In the desmear method, for example, a potassium permanganate or sodium permanganate desmear agent can be used. Further, swelling treatment or neutralization treatment may be performed before or after the roughening treatment by the desmear method.
In the metal sputtering method or the electroless plating method, fine metal particles are deposited on the surface of the metal, inorganic material, or resin material, thereby forming irregularities on the surface of the metal, inorganic material, or resin material.

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

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

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

Moreover, after making the surface treating agent of this invention contact the surface of a metal, an inorganic material, or a resin material, you may make acidic aqueous solution or alkaline aqueous solution contact the surface of the said metal, inorganic material, or resin material. This acidic aqueous solution or alkaline aqueous solution also has the function of making the thickness of the chemical conversion film formed on the surface of the metal, inorganic material, or resin material uniform, like the aqueous solution containing copper ions.
The acidic aqueous solution or alkaline aqueous solution is not particularly limited, and examples of the acidic aqueous solution include an aqueous solution containing a mineral acid such as sulfuric acid, nitric acid, and hydrochloric acid, and an organic acid such as formic acid, acetic acid, lactic acid, glycolic acid, and amino acid. it can. Examples of the alkaline aqueous solution include aqueous solutions containing alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, and amines such as ammonia, ethanolamine and monopropanolamine.

  Before or after the surface treatment agent of the present invention is brought into contact with the surface of the metal, inorganic material or resin material, treatment such as plasma, laser, ion beam, ozone, heating or humidification is carried out to obtain a metal or inorganic material. Alternatively, the surface of the resin material may be modified. In addition, cleaning for the purpose of removing resin / ion residues of metal, inorganic material, or resin material may be performed by mechanical polishing such as plasma, laser, ion beam, permis brush, or drilling.

  In particular, the surface of the metal contacted with the surface treatment agent of the present invention is subjected to a treatment such as plasma, laser, ion beam, ozone, heating or humidification in the step of performing metal plating or the step of mounting a component. It is preferable to perform cleaning for the purpose of modification or residue removal.

  In addition, in the step of performing metal plating or the step of mounting components, a primer treatment for forming an organic film or a metal film on the surface of the metal contacted with the surface treatment agent of the present invention in order to improve adhesion May be performed.

  These pre-treatments and post-treatments may be implemented in combination as appropriate.

The surface treating agent of the present invention can be suitably used for the surface treatment of the metal. By treating the surface of the metal using the surface treating agent of the present invention, a film can be formed on the metal surface, and the adhesion to other materials can be enhanced. This film has high heat resistance, and for example, the adhesive force is maintained even by solder reflow heating (about 260 ° C.).
In order to enhance the effect of this treatment, the surface-treated material may be heat-treated.

  According to the surface treatment method using the surface treatment agent of the present invention, a chemical conversion film for enhancing the adhesion between the metal and the resin can be formed on the surface of the metal. And, in the case where the organic solvent or corrosive chemical solution comes into contact with the chemical film after bonding the metal and the resin, it is not affected by the organic solvent or corrosive chemical solution. An excellent and strong chemical conversion film can be obtained.

  Such surface treatment methods include, for example, copper circuits (copper wiring layers), prepregs, solder resists (insulating resin layers), gold plating, silver plating, nickel plating, palladium plating, tin plating, solder plating, etc. It is suitable for the surface treatment of copper for the purpose of improving the adhesion (adhesion) with a dry film resist layer such as a plating resist or an etching resist.

[Adhesion method]
In the practice of the present invention, two materials selected from the metals, inorganic materials, and resin materials can be bonded using the surface treating agent of the present invention. By adhering two materials through a film formed by the surface treatment agent of the present invention, the affinity between each other can be improved, so even different materials can be bonded more firmly. Can do. The thickness of the film is 0.0001 to 1 μm, preferably 0.001 to 0.5 μm.

  As a bonding method, a known method can be adopted. A surface treatment agent selected from metals, inorganic materials, or resin materials is contacted with the surface treatment agent of the present invention to form a film, and another treatment material is applied to part or all of the formed film. , Pressure bonding, mixing, and the like, use of an adhesive and an adhesive sheet (film), and a method of bonding by combining these means.

  Moreover, the surface treatment agent of the present invention is brought into contact with the surfaces of two materials to be treated selected from metals, inorganic materials, and resin materials, a film is formed on each surface, and the two materials to be treated are pressure-bonded. Examples thereof include a method of mixing, use of an adhesive and an adhesive sheet (film), and a method of bonding these means in combination.

According to such an adhesion method, as in the case described above, a copper circuit and a prepreg, solder resist, gold plating, silver plating, nickel plating, palladium plating, tin plating, solder plating, or other plating resist, or etching resist The adhesion between the dry film resist layer and the like can be improved.
That is, even if the adhesion part of a copper circuit and said resist (resin) is exposed to the various corrosive chemical | medical solution (chemical | medical agent) used in various plating processes, soldering processes, and an etching process, it is hard to deteriorate. Therefore, good adhesiveness (adhesion) between copper and resin can be maintained.
The chemicals used in these processes include pickling aqueous solutions such as hydrochloric acid and sulfuric acid used for pretreatment of various plating processes, alkaline degreasing agents including sodium hydroxide and amines, organic solvents, hydrogen peroxide -Copper etching agents such as sulfuric acid and persulfates, resin oxidizing agents such as permanganate (desmear solution), various plating agents such as copper plating, gold plating, silver plating, nickel plating, palladium plating and tin plating, solder Examples thereof include post flux used at the time of plating and soldering.
The organic solvent is generally used in various fields, and includes, for example, those exemplified in paragraphs 0029 and 0033 of the present specification.

  The copper circuit 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.

[Use of surface treatment agent]
By using the surface treating agent of the present invention, it is possible to bond two materials as described above, in particular, two different materials, so that it can be used for electric / electronic applications (various electric / electronic components, printed wiring boards, etc. The electronic device), architectural use, civil engineering use, automobile use, medical material use and the like can be suitably used.

  The surface treating agent of the present invention can be suitably used for a material to be treated formed of a metal, particularly copper or a copper alloy. For example, the purpose is to improve the adhesion (adhesion) between a copper circuit (copper wiring layer) and a semi-cured or cured prepreg or solder resist, or a semi-cured or cured dry film (insulating resin layer). In a printed wiring board having an insulating resin layer in contact with the copper wiring layer, the adhesion between the copper wiring layer and the insulating resin layer can be enhanced.

  As an example of using the surface treatment agent of the present invention for surface treatment of a material, a copper foil having a film formed by treatment with the surface treatment agent, a prepreg, a copper-clad laminate, an interlayer insulating material, a sheet-like member, In addition to a resin-coated copper foil in which a copper foil and a resin layer are laminated via a film of the surface treatment agent, a printed wiring board provided with these members can be used.

  The printed wiring board can be produced, for example, by bringing the surface treatment agent of the present invention into contact with the surface of the copper wiring layer, then washing and drying, and then forming an insulating resin layer on the surface of the copper wiring layer. it can. The contact method is as described above, and immersion of the copper wiring layer in the surface treating agent or spraying on the surface of the copper wiring layer with the surface treating agent is preferable because it is simple and reliable.

  In addition, after forming an insulating resin layer on the surface of the copper wiring layer, in the process of removing part of the insulating resin for mounting parts and conducting the upper and lower wirings, in addition to removing residues on the copper circuit, plasma In addition, mechanical polishing such as laser, ion beam, permis brush, processing such as drill, cleaning with acidic aqueous solution, alkaline aqueous solution or solvent may be performed alone or in combination.

  Although there is no restriction | limiting in the method of the said water washing, the immersion to the copper wiring layer in washing | cleaning water or the spray to the copper wiring layer 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 material or a means of applying a liquid resin material containing a solvent can be employed. Next, a via hole is formed to connect the upper and lower wirings. A multilayer printed wiring board can be manufactured by repeating this process.

  In addition, “copper” according to the present invention is the same as that described above, but foils (electrolytic copper foil, rolled copper foil) used for electronic devices such as printed wiring boards and lead frames, ornaments, building materials, etc. ), Plating film (electroless copper plating film, electrolytic copper plating film), thin film formed by vapor deposition, sputtering, damascene, etc., granular, needle-like, fibrous, linear, rod-like, tubular, plate-like It is used in such applications and forms. In the case of copper wiring through which a high-frequency electric signal flows in recent years, the copper surface is preferably a smooth surface having an average roughness of 0.1 μm or less. As a pretreatment, the surface of copper may be plated with nickel, zinc, chromium, tin or the like.

  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. And a method for forming a silane coupling agent film, characterized in that it 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 a surface plating as an immersion plating solution. The surface treating agent of the present invention can be used as a liquid containing the silane coupling agent. In addition, the matter described in this patent gazette shall constitute a part of this specification by reference.

[Resin composition]
The resin composition of the present invention contains a resin or its pre-curing compound and a triazolesilane compound represented by the chemical formula (I).

  The “resin or its pre-curing compound” includes thermoplastic resins, heat or active energy ray-curable resins (cured products), raw material monomers thereof, partially polymerized products or semi-cured products of the monomers. In the case of a heat or active energy ray curable resin, the resin may be in any state selected from an A stage resin, a B stage resin, and a C stage resin.

  Examples of the resin include acrylate resin, epoxy resin, polyimide resin, bismaleimide resin, maleimide resin, cyanate resin, polyphenylene ether resin, polyphenylene oxide resin, olefin resin, fluorine-containing resin, Examples include ether imide resins, polyether ether ketone resins, liquid crystal resins, and the like, and these may be mixed or combined with each other. Among these resin materials, acrylate resins, epoxy resins, and polyimide resins are preferable.

  The content of the triazolesilane compound represented by the chemical formula (I) in the resin composition of the present invention is preferably 0.001 to 10% by weight, and more preferably 0.01 to 5% by weight. . When the content of the triazole silane compound is less than 0.001% by weight, the effect of improving the adhesiveness is not sufficient, and when the content exceeds 10% by weight, the effect of improving the adhesiveness is almost zero. It is not economical because the amount of use of the triazolesilane compound is increased.

  In addition to the resin or its pre-curing compound and the triazolesilane compound represented by the chemical formula (I), the resin composition includes a solvent (water, an organic solvent, a mixture of water and an organic solvent), Additives (such as curing agents, curing accelerators, flame retardants, dyes, pigments, ultraviolet absorbers, lubricants, fillers) and the like may be included as appropriate. As the organic solvent, those exemplified as the aforementioned organic solvent (solubilizing agent) can be used.

  The resin composition can be prepared by a known method. For example, a resin composition can be prepared by dissolving a triazolesilane compound represented by the chemical formula (I) in an organic solvent and mixing it in a solid or liquid resin material. Further, the resin composition may be prepared by directly adding and mixing the triazolesilane compound represented by the chemical formula (I) to the liquid resin material.

[Use of resin composition]
Since the resin composition of the present invention contains a triazolesilane compound represented by the chemical formula (I), the cured resin layer adheres to an adjacent layer or member, for example, a metal or inorganic material layer or member with high strength. (Adhere). Therefore, it can be suitably used for various electrical / electronic applications (electronic devices such as electrical / electronic components and printed wiring boards), architectural applications, civil engineering applications, automobile applications, medical material applications, and the like.

  Specific examples of using the resin composition of the present invention include, for example, a solder resist ink composed of the resin composition of the present invention, a printed wiring board including a solder resist formed from the solder resist ink, and a base material (paper , A glass cloth, a glass nonwoven fabric, etc.) and a prepreg composed of the resin composition of the present invention, a copper-clad laminate composed of the prepreg and a copper foil, an interlayer insulating material composed of the resin composition of the present invention (interlayer) Insulating film, etc.), copper foil, and resin-coated copper foil composed of a resin layer formed of the resin composition of the present invention, a printed wiring board comprising a resin layer formed of the resin composition of the present invention, the present The semiconductor sealing material comprised from the resin composition of invention can be mentioned.

The solder resist is prepared by applying a solder resist ink comprising a resin composition of the present invention containing a triazolesilane compound represented by the chemical formula (I) and a resin or a pre-curing compound (curing compound) on an appropriate substrate. It is obtained by curing a curable resin layer formed by drying using heat or active energy rays.
The printed wiring board can be manufactured by a known method using the solder resist ink. The prepreg can be produced, for example, by applying the resin composition of the present invention to a substrate (paper, glass cloth, glass nonwoven fabric, etc.), or immersing and impregnating the substrate in the resin composition.
The said copper clad laminated board can be manufactured by laminating | stacking the said prepreg and copper foil.
The interlayer insulating material can be produced by applying the resin composition of the present invention on a suitable substrate and drying, semi-curing or curing.
The copper foil with resin can be produced by applying the resin composition of the present invention on a copper foil and drying, semi-curing or curing.
The “resin layer formed from the resin composition of the present invention” in the printed wiring board may be any layer as long as it is formed in any shape, preferably the solder resist, the prepreg, and the interlayer insulating material. It is resin in copper foil with resin. The resin composition of the present invention can be suitably used as a semiconductor sealing material.

  In addition, since a member to which the surface treatment agent or the resin composition of the present invention is applied can be provided with excellent adhesiveness, heat resistance, insulation, etc., by adding an appropriate auxiliary agent as necessary, Paste, underfill, die attach material, semiconductor chip mounting material, non-conductive adhesive, liquid crystal sealant, display material, reflector, paint, adhesive, curing agent, varnish, elastomer, ink, wax, sealant, etc. can do.

EXAMPLES Hereinafter, although an Example and a comparative example demonstrate this invention concretely, this invention is not limited to these.
Synthesis examples of the silane coupling agent component (triazole silane compound) used in the examples are shown in Reference Examples 1-1 to 6-1. A synthesis example of the silane coupling agent component (imidazole silane compound) used in the comparative example is shown in Reference Example 7.
In Reference Example 1-1 to Reference Example 6-1, synthesis examples of the precursor (triazolesilane compound) used as a raw material are shown in Reference Example 1-2 to Reference Example 6-2.
The main raw materials used in these reference examples are as follows.

[Main raw materials used in Reference Examples]
3-mercapto-1H-1,2,4-triazole: manufactured by Tokyo Chemical Industry Co., Ltd.3-methyl-5-mercapto-1H-1,2,4-triazole: described in JP-T-5-509176 Synthesized according to the method.
・ 3-Amino-5-mercapto-1H-1,2,4-triazole: manufactured by Tokyo Chemical Industry Co., Ltd. ・ 3-Phenyl-5-mercapto-1H-1,2,4-triazole: JP-T 5-509176 Synthesis was performed according to the method described in the publication.
3-Benzyl-5-mercapto-1H-1,2,4-triazole: synthesized according to the method described in JP-T-5-509176.
-3-isocyanatopropyltrimethoxysilane: Momentive Performance Materials Japan, Ltd.-3-isocyanatopropyltriethoxysilane: Shin-Etsu Chemical Co., Ltd., trade name "KBE-9007"
・ (3-Iodopropyl) trimethoxysilane: manufactured by ALDRICH ・ (3-chloropropyl) trimethoxysilane: manufactured by Shin-Etsu Chemical Co., Ltd., trade name “KBM-703”
・ (3-Chloropropyl) triethoxysilane: manufactured by Tokyo Chemical Industry Co., Ltd.

[Reference Example 1-1]
<Synthesis of N- [3- (trimethoxysilyl) propyl] -3- [3- (trimethoxysilyl) propylthio] -1H-1,2,4-triazole-1-carboxamide>
10.0 g (38 mmol) of 3- [3- (trimethoxysilyl) propylthio] -1H-1,2,4-triazole was dissolved in 50 ml of tetrahydrofuran, 0.7 g (7 mmol) of triethylamine was added, and then at room temperature. 7.8 g (38 mmol) of 3-isocyanatopropyltrimethoxysilane was added dropwise. After completion of the dropwise addition, the mixture was heated and stirred at 65 ° C. for 4 hours, and the reaction solution was evaporated under reduced pressure to distill off the volatile matter. As a colorless liquid, 17.8 g (38. 0 mmol, 100% yield).

[Reference Example 1-2]
<Synthesis of Precursor 3- [3- (Trimethoxysilyl) propylthio] -1H-1,2,4-triazole>
A suspension composed of 3.0 g (30 mmol) of 3-mercapto-1H-1,2,4-triazole and 50 ml of dehydrated methanol was cooled to 10 ° C., and 5.8 g (30 mmol) of 28% sodium methoxide methanol solution was added. To a homogeneous solution, and then returned to room temperature and stirred for 30 minutes. A solution consisting of 8.7 g (30 mmol) of (3-iodopropyl) trimethoxysilane and 10 ml of dehydrated methanol was added dropwise thereto over 10 minutes, and the mixture was further stirred at 27 to 30 ° C. for 3 hours and 30 minutes.
The reaction solution was concentrated under reduced pressure, and 12.5 g of white viscous substance obtained by extraction with 40 ml of diethyl ether was extracted 3 times. The insoluble matter was removed from the extract by filtration, and then the filtrate was concentrated under reduced pressure to give a slightly yellowish brown oily title. 7.3 g (27.7 mmol, yield 92.3%) of the triazole compound was obtained.

[Reference Example 2-1]
<Synthesis of N- [3- (trimethoxysilyl) propyl] -5-methyl-3- [3- (trimethoxysilyl) propylthio] -1H-1,2,4-triazole-1-carboxamide>
To a solution consisting of 8.40 g (30 mmol) of 3-methyl-5- [3- (trimethoxysilyl) propylthio] -1H-1,2,4-triazole and 50 ml of tetrahydrofuran was added 3-isocyanatopropyltrimethoxy at room temperature. 6.28 g (31 mmol) of silane was added dropwise over 5 minutes, followed by stirring for 10 minutes. To this, 1.2 g (12 mmol) of triethylamine was added and stirred at 63 ° C. for 5 hours.
The reaction solution was distilled off volatile components under reduced pressure to obtain 14.2 g (29.4 mmol, yield 98.1%) of the title triazolesilane compound represented by the chemical formula (Ia-2) as a pale yellow liquid. .

[Reference Example 2-2]
<Synthesis of Precursor 3-Methyl-5- [3- (trimethoxysilyl) propylthio] -1H-1,2,4-triazole>
To a solution consisting of 25.0 g (0.217 mol) of 3-methyl-5-mercapto-1H-1,2,4-triazole and 120 ml of dehydrated N, N-dimethylformamide at room temperature, a 28% sodium methoxide methanol solution 42 0.0 g (0.218 mol) was added and stirred for 20 minutes. To this was added 43.1 g (0.217 mol) of (3-chloropropyl) trimethoxysilane, and the mixture was further stirred at 76 ° C. for 3 hours.
After cooling the reaction solution to room temperature, insolubles were removed by filtration, and the filtrate was dried under reduced pressure to obtain 60.7 g (0.219 mol, yield 100.8%) of the title triazole compound as a white solid.

[Reference Example 3-1]
<Synthesis of N- [3- (trimethoxysilyl) propyl] -5-amino-3- [3- (trimethoxysilyl) propylthio] -1H-1,2,4-triazole-1-carboxamide>
8.34 g (30 mmol) of 3-amino-5- [3- (trimethoxysilyl) propylthio] -1H-1,2,4-triazole was dissolved in 50 ml of tetrahydrofuran, and 0.7 g (7 mmol) of triethylamine was added thereto. After the addition, 6.15 g (30 mmol) of 3-isocyanatopropyltrimethoxysilane was added dropwise at room temperature. After completion of the dropwise addition, the mixture was heated and stirred at 65 ° C. for 4 hours, and the reaction solution was evaporated under reduced pressure to distill off the volatile matter. As a pale yellow liquid, 15.8 g (30) of the title triazolesilane compound represented by the chemical formula (Ia-3) 0.0 mmol, yield 100%).

[Reference Example 3-2]
<Synthesis of Precursor 3-Amino-5- [3- (trimethoxysilyl) propylthio] -1H-1,2,4-triazole>
A suspension composed of 6.96 g (60 mmol) of 3-amino-5-mercapto-1H-1,2,4-triazole and 100 ml of dehydrated methanol was cooled to 10 ° C., and 3.24 g (60 mmol) of sodium methoxide (solid) was obtained. ) To obtain a homogeneous solution, and the mixture was returned to room temperature and stirred for 30 minutes. A solution comprising 17.42 g (60 mmol) of 3-iodopropyltrimethoxysilane and 20 ml of dehydrated methanol was added dropwise over 30 minutes. The mixture was stirred at -30 ° C for 3 hours and 30 minutes.
The reaction mixture was concentrated under reduced pressure. 26.4 g of the white viscous substance obtained was extracted 3 times with 100 ml of diethyl ether, and the extract was filtered and concentrated under reduced pressure to give 9.20 g (33 mmol) of the title triazole compound as a slightly tan oil. Yield 55.1%).

[Reference Example 4-1]
<Synthesis of N- [3- (triethoxysilyl) propyl] -5-amino-3- [3- (triethoxysilyl) propylthio] -1H-1,2,4-triazole-1-carboxamide>
9.6 g (30 mmol) of 3-amino-5- [3- (triethoxysilyl) propylthio] -1H-1,2,4-triazole was dissolved in 50 ml of tetrahydrofuran, and 0.7 g (7 mmol) of triethylamine was added thereto. Thereafter, 7.4 g (30 mmol) of 3-isocyanatopropyltriethoxysilane was added dropwise at room temperature. After completion of the dropwise addition, the mixture was heated and stirred at 65 ° C. for 4 hours, and the reaction solution was evaporated under reduced pressure to distill off the volatile matter. As a pale yellow liquid, 17.0 g (30 of the title triazolesilane compound represented by the chemical formula (Ia-4) 0.0 mmol, yield 100%).

[Reference Example 4-2]
<Synthesis of Precursor 3-Amino-5- [3- (triethoxysilyl) propylthio] -1H-1,2,4-triazole>
A suspension composed of 3.48 g (30 mmol) of 3-amino-5-mercapto-1H-1,2,4-triazole and 50 ml of dehydrated ethanol was cooled to 10 ° C., and 10.2 g of a 20% sodium ethoxide ethanol solution ( 30 mmol) was added to obtain a homogeneous solution, and the mixture was returned to room temperature and stirred for 30 minutes. A solution consisting of 6.74 g (30 mmol) of (3-chloropropyl) triethoxysilane and 10 ml of dehydrated ethanol was added dropwise thereto over 10 minutes, and the mixture was further stirred at 78 ° C. for 6 hours.
The reaction solution was concentrated under reduced pressure, and 10.8 g of white viscous substance obtained by extraction with 40 ml of diethyl ether was extracted three times. Insoluble matter was removed from the extract by filtration, and the filtrate was concentrated under reduced pressure to obtain a low melting crystalline solid. There were obtained 8.2 g (25.7 mmol, yield 85.6%) of the title triazole compound.

[Reference Example 5-1]
<Synthesis of N- [3- (trimethoxysilyl) propyl] -5-phenyl-3- [3- (trimethoxysilyl) propylthio] -1H-1,2,4-triazole-1-carboxamide>
To a solution consisting of 9.50 g (28 mmol) of 3-phenyl-5- [3- (trimethoxysilyl) propylthio] -1H-1,2,4-triazole and 50 ml of tetrahydrofuran was added 3-isocyanatopropyltrimethoxy at room temperature. After dripping 5.74 g (28 mmol) of silane over 5 minutes, the mixture was stirred for 10 minutes. To this was added 1.14 g (11 mmol) of triethylamine, and the mixture was stirred at 63 ° C. for 4 hours and 30 minutes.
The reaction solution was distilled off volatile components under reduced pressure to obtain 14.62 g (26.8 mmol, yield 95.8%) of the title triazolesilane compound represented by the chemical formula (Ia-5) as a pale yellow liquid. .

[Reference Example 5-2]
<Synthesis of Precursor 3-Phenyl-5- [3- (trimethoxysilyl) propylthio] -1H-1,2,4-triazole>
To a suspension composed of 25.0 g (0.141 mol) of 3-phenyl-5-mercapto-1H-1,2,4-triazole and 140 ml of dehydrated N, N-dimethylformamide, 28% sodium methoxide methanol at room temperature. 27.3 g (0.142 mol) of the solution was added and stirred for 20 minutes. To this was added 28.0 g (0.141 mol) of (3-chloropropyl) trimethoxysilane, and the mixture was further stirred at 73 ° C. for 4 hours.
The reaction solution was cooled to room temperature, insolubles were removed by filtration, and the filtrate was dried under reduced pressure to obtain 49.8 g (0.147 mol, yield 104.0%) of the title triazole compound as a pale yellow solid.

[Reference Example 6-1]
<Synthesis of N- [3- (trimethoxysilyl) propyl] -5-benzyl-3- [3- (trimethoxysilyl) propylthio] -1H-1,2,4-triazole-1-carboxamide>
To a solution consisting of 9.03 g (26 mmol) of 3-benzyl-5- [3- (trimethoxysilyl) propylthio] -1H-1,2,4-triazole and 50 ml of tetrahydrofuran at room temperature, 3-isocyanatopropyltrimethoxy was added. Silane 5.23 g (25 mmol) was added dropwise over 5 minutes, followed by stirring for 10 minutes. To this, 1.0 g (10 mmol) of triethylamine was added and stirred at 63 ° C. for 5 hours.
The reaction solution was distilled off volatile components under reduced pressure to obtain 13.73 g (24.6 mmol, yield 98.3%) of the title triazolesilane compound represented by the chemical formula (Ia-6) as a pale yellow liquid. .

[Reference Example 6-2]
<Synthesis of Precursor 3-Benzyl-5- [3- (trimethoxysilyl) propylthio] -1H-1,2,4-triazole>
To a solution consisting of 25.0 g (0.131 mol) of 3-benzyl-5-mercapto-1H-1,2,4-triazole and 120 ml of dehydrated N, N-dimethylformamide at room temperature, 28% sodium methoxide methanol solution 25 0.6 g (0.133 mol) was added and stirred for 10 minutes. To this was added 26.2 g (0.132 mol) of (3-chloropropyl) trimethoxysilane, and the mixture was further stirred at 73 ° C. for 3 hours.
The reaction solution was cooled to room temperature, insolubles were removed by filtration, and the filtrate was concentrated under reduced pressure to obtain 48.0 g (0.134 mol, yield 102.2%) of the title triazole compound as a pale yellow liquid.

[Reference Example 7]
<Synthesis of imidazole silane compound>
While melting 3.4 g (0.05 mol) of imidazole at 95 ° C. and stirring in an argon atmosphere, 3-glycidoxypropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., trade name “KBM-403”) 11. 8 g (0.05 mol) was added dropwise over 30 minutes. After completion of the 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).

  The adhesive evaluation tests (a) to (g) employed in Examples 1 to 6 and Comparative Examples 1 to 3 are as follows.

[Adhesion Evaluation Test (a)]
(1) Metal An electrolytic copper foil (thickness: 18 μm) was used as the metal.
(2) Surface treatment of metal It carried out according to the following processes i to c.
A. Acid cleaning (5% sulfuric acid aqueous solution) / 1 minute (room temperature), water washing b. Acid cleaning (same as above) / 1 minute (room temperature), water washing, drying / 1 minute (100 ° C.)
C. Immersion in surface treatment agent / 1 minute (room temperature), water washing, drying / 1 minute (100 ° C.)
(3) Adhesion of metal and resin A glass cloth epoxy resin-impregnated prepreg (FR-4 grade) was laminated and pressed on the S surface of the treated electrolytic copper foil, and the copper foil and prepreg were adhered to produce a copper-clad laminate. .
(4) Evaluation of adhesiveness From this copper-clad laminate, a test piece having a width of 10 mm was prepared according to “JIS C6481 (1996)” and subjected to pressure cooker treatment (121 ° C./humidity 100% / 100 hours), and then copper The peel strength of the foil was measured.

[Adhesion Evaluation Test (b)]
Instead of “Lamination press of glass cloth epoxy resin impregnated prepreg (FR-4 grade)” on the S surface of the electrolytic copper foil, “Resin for build-up wiring board (product name“ GX-13 ”manufactured by Ajinomoto Fine Techno Co., Ltd.)” The adhesiveness between the copper foil and the resin was evaluated in the same procedure as in the evaluation test (a) except that “laminate”.

[Adhesion Evaluation Test (c)]
(1) Metal As the metal, an electrolytic copper foil of a double-sided copper clad laminate (base material: FR4, plate thickness: 1.0 mm, copper foil thickness: 18 μm, length 120 mm × width 110 mm) was used.
(2) Surface treatment of metal It carried out according to the following processes ai.
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 surface treatment agent / 1 minute (room temperature), water washing, drying / 1 minute (100 ° C.)
(3) Formation of resin layer on metal Solder resist ink (manufactured by Taiyo Ink Manufacturing Co., Ltd., acrylate / epoxy resin, product name “PSR-4000AUS308”) is applied to the treated electrolytic copper foil and then dried (80 ° C./30 Min) and curing (150 ° C./60 min) to form a 13 μm thick resin layer (coating film).
(4) Evaluation of adhesiveness According to “JIS K5400-8.5 (1990)”, the coating formed on the electrolytic copper foil was cross-cut (100 squares) on a 1 mm × 1 mm grid, and pressure cooker treatment (121 ° C. / Humidity 100% / 100 hours), a tape peel test was performed, and the number of squares where the coating film did not peel was measured. Moreover, the damage condition of the coating film was observed visually.
Table 1 shows the criteria for determining adhesiveness.

[Adhesion Evaluation Test (d)]
(1) Metal An aluminum foil (thickness: 50 μm) was used as the metal.
(2) Surface treatment of metal It carried out according to the following processes (a) to (b).
A. Acid clean / 1 minute (room temperature), water wash b. Immersion in surface treatment agent / 1 minute (room temperature), water washing, drying / 1 minute (100 ° C.)
(3) Adhesion of metal and resin A glass cloth epoxy resin-impregnated prepreg (FR-4 grade) was laminated and pressed on the treated aluminum foil, and the aluminum foil and the prepreg were adhered to produce a laminate.
(4) Evaluation of adhesiveness From this laminated board, according to "JIS C6481 (1996)", the test piece of width 10mm was produced, and the peeling strength of aluminum foil was measured.

[Adhesion evaluation test (e)]
(1) Resin material Glass cloth epoxy resin impregnated prepreg (FR-4 grade) was used as a resin material.
(2) Surface treatment of resin material The surface of the prepreg was treated with a surface treatment agent by a spray method.
(3) Adhesion of resin material and copper foil An electrolytic copper foil (thickness: 35 μm) S surface was laminated and pressed on the treated prepreg, and the prepreg and the copper foil were adhered to produce a copper-clad laminate.
(4) Evaluation of adhesiveness From this copper clad laminate, according to "JIS C6481 (1996)", a test piece having a width of 10 mm was prepared, and the peel strength of the copper foil was measured.

[Adhesion evaluation test (f)]
(1) Surface treatment of inorganic material 10 parts by weight of barium sulfate was added to 100 parts by weight of the surface treatment agent and stirred for 5 minutes. Subsequently, barium sulfate was filtered off and dried in an oven at 100 ° C. for 1 hour to prepare barium sulfate carrying a silane coupling agent component.
(2) Preparation of resin composition 1 part by weight of barium sulfate carrying a silane coupling agent component is added to 100 parts by weight of solder resist ink (same as above), and stirred for 30 minutes to obtain a resin composition. (Solder resist ink composition) was prepared.
(3) Production of Printed Wiring Board Electrolytic copper foil of double-sided copper-clad laminate (base material: FR4, board thickness: 1.0 mm, copper foil thickness: 18 μm, length 120 mm × width 110 mm) Then, it was heated in an oven at 150 ° C. for 1 hour to produce a printed wiring board in which the cured product of the resin composition and the copper foil were bonded.
(4) Evaluation of adhesiveness From this printed wiring board, according to "JIS C6481 (1996)", the test piece of width 10mm was produced, and the peeling strength of copper foil was measured.

[Adhesion evaluation test (g)]
(1) Preparation of resin composition 1 part by weight of a silane coupling agent component (hydrolyzate) having a hydroxysilyl group is added to 100 parts by weight of solder resist ink (same as above) and stirred for 30 minutes. A resin composition (solder resist ink composition) was prepared.
(2) Production of Printed Wiring Board Electrolytic copper foil of double-sided copper-clad laminate (base material: FR4, board thickness: 1.0 mm, copper foil thickness: 18 μm, length 120 mm × width 110 mm) Then, drying (80 ° C./30 minutes) and curing (150 ° C./60 minutes) were performed to produce a printed wiring board in which the cured product of the resin composition and the copper foil were bonded.
(3) Evaluation of adhesiveness From this printed wiring board, according to "JIS C6481 (1996)", the test piece of width 10mm was produced, and the peeling strength of copper foil was measured.

[Example 1]
As a silane coupling agent component, 10 g of “N- [3- (trimethoxysilyl) propyl] -3- [3- (trimethoxysilyl) propylthio] -1H-1,2,4-triazole-1-carboxamide” Then, 200 g of ethylene glycol monobutyl ether was added, followed by 790 g of water, and the mixture was stirred overnight at room temperature to prepare a surface treatment agent (hereinafter referred to as treatment liquid A).
About this processing liquid A, it confirmed that the methoxysilyl group of the triazole silane compound was hydrolyzed to the hydroxysilyl group, and performed the adhesive evaluation test (a)-(f).
Subsequently, the volatile component in the treatment liquid A was removed under reduced pressure to obtain a hydrolyzate of the silane coupling agent component (silane coupling agent component having a hydroxysilyl group). The obtained hydrolyzate was subjected to an adhesive evaluation test (g).
The test results obtained were as shown in Table 2.

[Example 2]
Instead of “N- [3- (trimethoxysilyl) propyl] -3- [3- (trimethoxysilyl) propylthio] -1H-1,2,4-triazole-1-carboxamide”, “N- [3 -(Trimethoxysilyl) propyl] -5-methyl-3- [3- (trimethoxysilyl) propylthio] -1H-1,2,4-triazole-1-carboxamide " Similarly, a surface treatment agent (hereinafter referred to as treatment liquid B) was prepared.
About this processing liquid B, it confirmed that the methoxysilyl group of the triazole silane compound was hydrolyzed to the hydroxysilyl group, and performed the adhesive evaluation test (a)-(f).
Moreover, it carried out similarly to Example 1, obtained the hydrolyzate of the silane coupling agent component from the processing liquid B, and performed the adhesive evaluation test (g).
The test results obtained were as shown in Table 2.

Example 3
As a silane coupling agent component, “N- [3- (trimethoxysilyl) propyl] -5-amino-3- [3- (trimethoxysilyl) propylthio] -1H-1,2,4-triazole-1- 200 g of ethylene glycol monobutyl ether was added to 10 g of carboxamide, and then 789 g of water and 1 g of acetic acid were added, followed by stirring at room temperature for 2 hours to prepare a surface treatment agent (hereinafter referred to as “treatment liquid C”).
About this process liquid C, it confirmed that the methoxysilyl group of the triazole silane compound was hydrolyzed to the hydroxysilyl group, and performed the adhesive evaluation test (a)-(f).
Moreover, it carried out similarly to Example 1, obtained the hydrolyzate of the silane coupling agent component from the processing liquid C, and performed the adhesive evaluation test (g).
The test results obtained were as shown in Table 2.

Example 4
Instead of “N- [3- (trimethoxysilyl) propyl] -5-amino-3- [3- (trimethoxysilyl) propylthio] -1H-1,2,4-triazole-1-carboxamide” N- [3- (triethoxysilyl) propyl] -5-amino-3- [3- (triethoxysilyl) propylthio] -1H-1,2,4-triazole-1-carboxamide ”was used, A surface treatment agent (hereinafter referred to as treatment liquid D) was prepared in the same manner as in Example 3.
About this process liquid D, it confirmed that the ethoxysilyl group of the triazole silane compound was hydrolyzed to the hydroxysilyl group, and performed the adhesive evaluation test (a)-(f).
Moreover, it carried out similarly to Example 1, obtained the hydrolyzate of the silane coupling agent component from the processing liquid D, and performed the adhesive evaluation test (g).
The test results obtained were as shown in Table 2.

Example 5
As a silane coupling agent component, “N- [3- (trimethoxysilyl) propyl] -5-phenyl-3- [3- (trimethoxysilyl) propylthio] -1H-1,2,4-triazole-1- 200 g of ethylene glycol monobutyl ether was added to 10 g of carboxamide, and then 790 g of water was added, followed by stirring at 50 ° C. for 2 hours to prepare a surface treatment agent (hereinafter referred to as “treatment liquid E”).
About this processing liquid E, it confirmed that the methoxysilyl group of the triazole silane compound was hydrolyzed to the hydroxysilyl group, and performed the adhesive evaluation test (a)-(f).
Moreover, it carried out similarly to Example 1, obtained the hydrolyzate of the silane coupling agent component from the processing liquid E, and performed the adhesive evaluation test (g).
The test results obtained were as shown in Table 2.

Example 6
Instead of “N- [3- (trimethoxysilyl) propyl] -5-phenyl-3- [3- (trimethoxysilyl) propylthio] -1H-1,2,4-triazole-1-carboxamide”, N- [3- (trimethoxysilyl) propyl] -5-benzyl-3- [3- (trimethoxysilyl) propylthio] -1H-1,2,4-triazole-1-carboxamide ”was used, A surface treatment agent (hereinafter referred to as treatment liquid F) was prepared in the same manner as in Example 5.
About this processing liquid F, it confirmed that the methoxysilyl group of the triazole silane compound was hydrolyzed to the hydroxysilyl group, and performed the adhesive evaluation test (a)-(f).
Moreover, it carried out similarly to Example 1, obtained the hydrolyzate of the silane coupling agent component from the processing liquid F, and performed the adhesive evaluation test (g).
The test results obtained were as shown in Table 2.

[Comparative Example 1]
Instead of “N- [3- (trimethoxysilyl) propyl] -3- [3- (trimethoxysilyl) propylthio] -1H-1,2,4-triazole-1-carboxamide”, “imidazolesilane compound” A surface treatment agent (hereinafter referred to as treatment liquid G) was prepared in the same manner as in Example 1 except that was used.
About this process liquid G, it confirmed that the methoxysilyl group of the imidazole silane compound was hydrolyzed to the hydroxysilyl group, and performed the adhesive evaluation test (a)-(f).
Moreover, it carried out similarly to Example 1, obtained the hydrolyzate of the silane coupling agent component from the processing liquid G, and performed the adhesive evaluation test (g).
The test results obtained were as shown in Table 2.

[Comparative Example 2]
Instead of “N- [3- (trimethoxysilyl) propyl] -3- [3- (trimethoxysilyl) propylthio] -1H-1,2,4-triazole-1-carboxamide”, “3-aminopropyl A surface treatment agent (hereinafter referred to as treatment liquid H) was prepared in the same manner as in Example 1 except that trimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., product name “KBM-903”) ”was used.
For this treatment liquid H, it was confirmed that the methoxysilyl group of 3-aminopropyltrimethoxysilane was hydrolyzed to a hydroxysilyl group, and adhesive evaluation tests (a) to (f) were conducted.
Moreover, it carried out similarly to Example 1, obtained the hydrolyzate of the silane coupling agent component from the processing liquid H, and performed the adhesive evaluation test (g).
The test results obtained were as shown in Table 2.

[Comparative Example 3]
Without using a silane coupling agent, 200 g of ethylene glycol butyl ether and 790 g of water were mixed and stirred at room temperature for 2 hours to prepare a surface treatment agent (hereinafter referred to as treatment liquid I).
About this processing liquid I, when the adhesive evaluation tests (a) to (f) were performed, the test results obtained were as shown in Table 2.
The adhesive evaluation test (g) was carried out without adding anything to the solder resist. The test results obtained were as shown in Table 2.

  The adhesive evaluation test (h) employed in Examples 7 to 11 and Comparative Examples 4 to 6 is as follows.

[Adhesion evaluation test (h)]
(1) Metal An electrolytic copper foil (thickness: 18 μm) was used as the metal.
(2) Surface treatment of metal Any one selected from the following three treatment methods (α to γ) was performed.
<Treatment method α>
A. Acid cleaning (5% sulfuric acid aqueous solution) / 1 minute (room temperature), water washing b. Micro etching (etching amount 3 μm) / 1 minute (room temperature), water washing, drying / 1 minute (100 ° C.)
C. Immersion in surface treatment agent / 1 minute (room temperature), water washing, drying / 1 minute (100 ° C.)
<Processing method β>
A. Acid cleaning (5% sulfuric acid aqueous solution) / 1 minute (room temperature), water washing b. Micro etching (etching amount 3 μm) / 1 minute (room temperature), water washing, drying / 1 minute (100 ° C.)
C. Brush the surface treatment agent, dry / 1 minute (100 ° C)
<Processing method γ>
A. Acid cleaning (5% sulfuric acid aqueous solution) / 1 minute (room temperature), water washing b. Micro etching (etching amount 3 μm) / 1 minute (room temperature), water washing, drying / 1 minute (100 ° C.)
C. Brush the surface treatment agent, heat / 5 minutes (100 ° C.), wash with methanol, wash with water, dry / 1 minute (100 ° C.)
(3) Adhesion of metal and resin A glass cloth epoxy resin-impregnated prepreg (FR-4 grade) was laminated and pressed on the S surface of the treated copper foil, and the copper foil and the prepreg were adhered to produce a copper-clad laminate.
(4) Evaluation of adhesiveness From this copper clad laminate, according to "JIS C6481 (1996)", a test piece having a width of 10 mm was prepared, and the peel strength of the copper foil was measured. The peel strength after 2 reflow heatings (peak temperature 260 ° C., air) was also measured.

Example 7
As a silane coupling agent component, “N- [3- (trimethoxysilyl) propyl] -5-amino-3- [3- (trimethoxysilyl) propylthio] -1H-1,2,4-triazole-1- 990 g of a 1: 1 mixture of water and methanol was added to 10 g of carboxamide, and the mixture was stirred at room temperature for 2 hours to prepare a surface treatment agent (hereinafter referred to as treatment liquid J).
About this processing liquid J, it confirmed that the methoxysilyl group of the triazole silane compound was hydrolyzed to the hydroxysilyl group, and performed the adhesive evaluation test (h) (processing method (gamma)).
The test results obtained were as shown in Table 3.

Example 8
Using the treatment liquid J prepared in Example 7, an adhesive evaluation test (h) (treatment method β) was performed. The test results obtained were as shown in Table 3.

Example 9
A surface treatment agent (hereinafter referred to as treatment liquid K) was prepared in the same manner as in Example 7 except that methanol was used instead of the 1: 1 mixture of water and methanol.
This treatment liquid K was subjected to an adhesion evaluation test (h) (treatment method γ).
The test results obtained were as shown in Table 3.

Example 10
Using the treatment liquid K, an adhesion evaluation test (h) (treatment method β) was performed. The test results obtained were as shown in Table 3.

Example 11
Instead of the 1: 1 mixture of water and methanol, 200 g of ethylene glycol monobutyl ether was added, followed by the addition of 790 g of water. ) Was prepared.
About this processing liquid L, it confirmed that the methoxy silyl group of the triazole silane compound was hydrolyzed to the hydroxy silyl group, and performed the adhesive evaluation test (h) (processing method (alpha)).
The test results obtained were as shown in Table 3.

[Comparative Example 4]
Instead of “N- [3- (trimethoxysilyl) propyl] -5-amino-3- [3- (trimethoxysilyl) propylthio] -1H-1,2,4-triazole-1-carboxamide” A surface treatment agent (hereinafter referred to as treatment liquid M) was prepared in the same manner as in Example 7 except that 3-mercaptopropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., trade name “KBM-803”) was used. did.
For this treatment liquid M, it was confirmed that the methoxysilyl group of 3-mercaptopropyltrimethoxysilane was hydrolyzed to a hydroxysilyl group, and an adhesive evaluation test (h) (treatment method γ) was conducted.
The test results obtained were as shown in Table 3.

[Comparative Example 5]
Instead of “N- [3- (trimethoxysilyl) propyl] -5-amino-3- [3- (trimethoxysilyl) propylthio] -1H-1,2,4-triazole-1-carboxamide” A surface treatment agent (hereinafter referred to as treatment liquid N) was used in the same manner as in Example 7 except that “3-glycidoxypropyltrimethoxysilane” (manufactured by Shin-Etsu Chemical Co., Ltd., trade name “KBM-403”) was used. Was prepared.
For this treatment liquid N, it was confirmed that the methoxysilyl group of 3-glycidoxypropyltrimethoxysilane was hydrolyzed to a hydroxysilyl group, and an adhesive evaluation test (h) (treatment method γ) was performed. It was.
The test results obtained were as shown in Table 3.

[Comparative Example 6]
Without using a silane coupling agent, 500 g of methanol and 500 g of water were mixed and stirred at room temperature for 1 hour to prepare a surface treatment agent (hereinafter referred to as treatment liquid O).
When this treatment solution O was subjected to an adhesive evaluation test (h) (treatment method α), the test results obtained were as shown in Table 3.

  The adhesive evaluation test (i) employed in Examples 12 to 14 and Comparative Examples 7 to 8 is as follows.

[Adhesion evaluation test (i)]
(1) Resin material Glass cloth epoxy resin impregnated prepreg (FR-4 grade) was used as a resin material.
(2) Surface treatment of resin material Any one selected from the following three treatment methods (α to γ) was performed.
<Treatment method α>
A. Acid cleaning (5% sulfuric acid aqueous solution) / 1 minute (room temperature), water washing b. Immersion in surface treatment agent / 1 minute (room temperature), water washing, drying / 1 minute (100 ° C.)
<Processing method β>
A. Acid cleaning (5% sulfuric acid aqueous solution) / 1 minute (room temperature), water washing b. Brush the surface treatment agent, dry / 1 minute (100 ° C)
<Processing method γ>
A. Acid cleaning (5% sulfuric acid aqueous solution) / 1 minute (room temperature), water washing b. Brush the surface treatment agent, heat / 10 minutes (100 ° C), wash with methanol, wash with water, dry / 1 minute (100 ° C)
(3) Adhesion of Resin Material and Copper Foil An electrolytic copper foil (thickness: 35 μm) S surface was laminated and pressed on the surface-treated prepreg, and the prepreg and copper foil were adhered to produce a copper-clad laminate.
(4) Evaluation of adhesiveness About this copper clad laminated board, it carried out similarly to the case of the adhesive evaluation test (h).

Example 12
As a silane coupling agent component, “N- [3- (trimethoxysilyl) propyl] -5-methyl-3- [3- (trimethoxysilyl) propylthio] -1H-1,2,4-triazole-1- 990 g of methanol was added to 10 g of “carboxamide” and stirred at room temperature for 2 hours to prepare a surface treatment agent (hereinafter referred to as “treatment liquid P”).
The treatment liquid P was subjected to an adhesion evaluation test (i) (treatment method γ).
The test results obtained were as shown in Table 4.

Example 13
As a silane coupling agent component, “N- [3- (trimethoxysilyl) propyl] -5-amino-3- [3- (trimethoxysilyl) propylthio] -1H-1,2,4-triazole-1- 990 g of a 1: 1 mixture of water and methanol was added to 10 g of carboxamide, and the mixture was stirred at 50 ° C. for 1 hour to prepare a surface treatment agent (hereinafter referred to as treatment liquid Q).
For this treatment liquid Q, it was confirmed that the methoxysilyl group of the triazolesilane compound was hydrolyzed to a hydroxysilyl group, and the same adhesive evaluation test as in Example 12 was performed.
The test results obtained were as shown in Table 4.

Example 14
Using the treatment liquid Q prepared in Example 13, an adhesive evaluation test (i) (treatment method β) was performed. The test results obtained were as shown in Table 4.

[Comparative Example 7]
Using the treatment liquid M prepared in Comparative Example 4, the same adhesive evaluation test as in Example 12 was performed. The test results obtained were as shown in Table 4.

[Comparative Example 8]
Instead of “N- [3- (trimethoxysilyl) propyl] -5-amino-3- [3- (trimethoxysilyl) propylthio] -1H-1,2,4-triazole-1-carboxamide”, imidazole A surface treatment agent (hereinafter referred to as treatment liquid R) was prepared in the same manner as in Example 13 except that the silane compound was used.
About this processing liquid R, it confirmed that the methoxy silyl group of the imidazole silane compound was hydrolyzed to the hydroxy silyl group, and the adhesive evaluation test similar to the case of Example 12 was done.
The test results obtained were as shown in Table 4.

  The adhesive evaluation test (j) employed in Example 15 and Comparative Example 9 is as follows.

[Adhesion evaluation test (j)]
(1) Metal As a metal, copper foil which gave silver plating (thickness: 0.1-0.3 micrometer) was used.
(2) Surface treatment of metal It carried out according to the following processes (a) to (b).
A. Acid cleaning (5% sulfuric acid aqueous solution) / 1 minute (room temperature), water washing b. Brush the surface treatment agent, heat / 5 minutes (100 ° C.), wash with methanol, wash with water, dry / 1 minute (100 ° C.)
(3) Adhesion of metal and resin A glass cloth epoxy resin-impregnated prepreg (FR-4 grade) is laminated and pressed on the silver-plated surface of the surface-treated silver-plated copper foil, and the silver-plated copper foil and prepreg are bonded and silver-plated A copper clad laminate was prepared.
(4) Evaluation of adhesiveness From this silver-plated copper-clad laminate, a test piece having a width of 10 mm was prepared according to “JIS C6481 (1996)”, and the peel strength of the silver-plated copper foil was measured.

Example 15
Using the treatment liquid Q prepared in Example 13, an adhesive evaluation test (j) was conducted. The test results obtained were as shown in Table 5.

[Comparative Example 9]
Using the treatment liquid O prepared in Comparative Example 6, the same adhesive evaluation test as in Example 13 was performed. The test results obtained were as shown in Table 5.

According to the present invention, the adhesion (adhesion) between the metal, the inorganic material, and the resin material can be sufficiently ensured, so that the surface of the material to be treated 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 (16)

A surface treatment agent containing a triazolesilane compound represented by the chemical formula (I).

(In the formula, X represents a hydrogen atom, a linear or branched alkyl group having 1 to 12 carbon atoms, an amino group, a phenyl group, or a benzyl group. R ₁ and R ₂ may be the same or different, and may be a methyl group or Represents an ethyl group, n represents an integer of 1 to 12, and A and B are the same or different and represent an integer of 0 to 3).   The copper foil which has a film | membrane by the surface treating agent of Claim 1.   The prepreg which has a film | membrane by the surface treating agent of Claim 1.   The copper clad laminated board which has a film | membrane by the surface treating agent of Claim 1.   The interlayer insulation material which has a film | membrane by the surface treating agent of Claim 1.   A copper foil with a resin in which a copper foil and a resin layer are laminated via a film made of the surface treatment agent according to claim 1.   A printed wiring board provided with the member which has a film | membrane by the surface treating agent of Claim 1.   A resin composition comprising a resin or a compound before curing thereof, and a triazolesilane compound represented by the chemical formula (I).   The solder resist ink comprised from the resin composition of Claim 8.   A printed wiring board provided with the soldering resist formed from the soldering resist ink of Claim 9.   The prepreg comprised from the base material and the resin composition of Claim 8.   The copper clad laminated board comprised from the copper foil and the prepreg of Claim 11.   The interlayer insulation material comprised from the resin composition of Claim 8.   The copper foil with resin comprised from the resin layer formed with the copper foil and the resin composition of Claim 8.   A printed wiring board provided with the resin layer formed with the resin composition of Claim 8. The semiconductor sealing material comprised from the resin composition of Claim 8.