JP6771603B2 - Resin composition and its use - Google Patents

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 copper foil with a resin, and a printed wiring board using the surface treatment agent.
Further, the present invention relates to a resin composition containing a resin or a compound before curing thereof and a triazolesilane compound, a solder resist ink using the resin composition, a prepreg, a copper-clad laminate, an interlayer insulating material, and a copper foil with resin. , Printed wiring boards and semiconductor encapsulation materials.

In recent years, printed wiring boards have been multi-layered in order to cope with miniaturization and thinning of electronic devices and electronic components, and so-called multi-layer printed wiring boards are provided with circuits made of copper foil or the like on one or both sides. It is manufactured by superimposing a circuit board for an outer layer or a copper foil on a circuit board for an inner layer via a prepreg and integrating them. By the way, in such a multi-layer printed wiring board, it is important to ensure the adhesiveness between the copper circuit formed on the circuit board for the inner layer and the insulating adhesive resin of the prepreg on which the circuit board for the outer layer or the copper foil is laminated. It has become an 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 adhering a copper foil and a 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 describes a copper surface adjusting composition and a surface treatment method capable of maintaining the adhesion between copper and an insulating material such as resin without roughening the surface of copper by etching or the like. The invention is described. In this document, a silane coupling agent having an alkoxyl group such as silanol or trisilanol is also preferable as a component of the surface adjusting composition because it has excellent adhesion to an insulating material, and among them, , A silane coupling agent having a mercapto group is disclosed because it improves the adhesion between copper and an insulating material such as an epoxy resin. Further, it is disclosed that a solution containing the surface adjusting composition can be prepared by dissolving the composition in a mixed solvent of water and an organic solvent, and after the solution is brought into contact with the surface of copper, the solution is prepared. , It may be washed with water and then dried, or it may be dried without washing with water, and when it is washed with water and then dried, a film having a uniform thickness is obtained, while it is dried without washing with water. In this case, it is disclosed that high adhesion to the insulating material can be obtained.

Patent Document 3 describes inventions relating to a method for producing a silane coupling agent solution, a silane coupling agent solution, a surface treatment method for a base material using the silane coupling agent solution, and the like. According to this document, if an organosilicon compound is mixed with water to sufficiently form silanol groups and then alcohol is further mixed, a high silanolization rate can be achieved and uniform coating is possible, which is excellent. It is disclosed that the adhesion is realized, and the silanolization rate is preferably 60 to 100%, more preferably 80 to 100%. And, as the said organosilicon compound, 3-mercaptopropylmethyldimethoxysilane and 3-mercaptopropyltrimethoxysilane are disclosed. It should be noted that the subject of the invention is to improve the adhesion between the base material composed of an organic polymer compound or an inorganic material and the liquid crystal compound, and the adhesion when copper is used as the base material. Is not mentioned.

Patent Document 4 describes inventions relating to silane coupling agents and polymer compositions. In this document, nitrogen-containing heterocycles such as triazole and thiadiazole and silyl groups such as trimethoxysilyl group and triethoxysilyl group are described as components of the silane coupling agent used as a primer for bonding glass or metal to rubber. However, various substances having a structure 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, the findings and results found by the present inventors in the process leading to the present invention 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 methods (uses) of using this substance (Patent Documents). See 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 equation, 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 1-3.)

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

Japanese Unexamined Patent Publication No. 7-286160 JP-A-2009-263790 Japanese Unexamined Patent Publication No. 2006-04518 JP-A-2002-363189 Japanese Unexamined Patent Publication No. 2015-010079 JP-A-2015-092020 Japanese Unexamined Patent Publication No. 2016-056449 JP-A-2016-121348 Japanese Unexamined Patent Publication No. 2016-125143 JP-A-2016-125144 Japanese Unexamined Patent Publication No. 2015-1892969 JP-A-2015-206115 Japanese Unexamined Patent Publication No. 2015-04470 JP 2015-143395 JP-A-2016-117901

An object of the present invention is to provide a surface treatment agent capable of enhancing the adhesiveness of two materials having different materials selected from a metal, an inorganic material and a resin material.
Another object of the present invention is to provide a copper foil, a prepreg, a copper-clad laminate, an interlayer insulating material, a copper foil with a resin, and a printed wiring board manufactured by using this surface treatment agent.
Another object of the present invention is to provide a resin composition capable of forming a resin layer having high adhesiveness to a metal or an inorganic material.
Another object of the present invention is to provide a solder resist ink, a prepreg, a copper-clad laminate, an interlayer insulating material, a copper foil with a resin, a printed wiring board, and a semiconductor encapsulating material produced by using this resin composition.

As a result of intensive research to solve the above problems, the present inventors 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 adhesiveness of the two materials, particularly the adhesiveness between the metal and the resin material, is greatly improved. It has also been found that the use of a resin composition containing this triazole silane compound greatly improves the adhesiveness between the resin and a metal or inorganic material. The present invention has been completed by further studies based on these findings.

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 are the same or different, and are a methyl group or a different group. Represents an ethyl group. N represents an integer of 1-12, and A and B represent the same or different integers of 0-3.)

The second invention is a copper foil having a film formed by the surface treatment agent of the first invention.
The third invention is a prepreg having a film formed by the surface treatment agent of the first invention.
The fourth invention is a copper-clad laminate having a film formed by the surface treatment agent of the first invention.
A fifth invention is an interlayer insulating material having a film formed by the surface treatment agent of the first invention.
The sixth invention is a resin-attached copper foil in which a copper foil and a resin layer are laminated via a film of the surface treatment agent of the first invention.
A seventh invention is a printed wiring board including a member having a film formed by the surface treatment agent of the first invention.
The eighth invention is a resin composition containing a resin or a pre-curing compound thereof and a triazolesilane compound represented by the above chemical formula (I).
The ninth invention is a solder resist ink composed of the resin composition of the eighth invention.
A tenth invention is a printed wiring board including a solder resist formed from the solder resist ink of the ninth 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 composed of a copper foil and the prepreg of the eleventh invention.
A thirteenth invention is an interlayer insulating material composed of the resin composition of the eighth invention.
The fourteenth invention is a resin-attached copper foil composed of a copper foil and a resin layer formed of the resin composition of the eighth invention.
A fifteenth invention is a printed wiring board including a resin layer formed of the resin composition of the eighth invention.
The sixteenth invention is a semiconductor encapsulating material composed of the resin composition of the eighth invention.

According to the surface treatment agent of the present invention, it is possible to enhance the adhesiveness between two materials having different materials selected from metal, inorganic materials and resin materials. Therefore, by using the surface treatment agent, copper foil, prepreg, copper-clad laminate, interlayer insulating material, copper foil with resin, and printed wiring, which are excellent in adhesiveness to the laminated body and the interlayer adhesiveness of itself, are excellent. You can get a board or the like.
Further, according to the resin composition of the present invention, a resin layer having high adhesiveness 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 copper foil with resin and a printed wiring board, and a semiconductor encapsulation, which are excellent in adhesiveness to the laminate and its own interlayer adhesion, are used. Materials and the like can be obtained.

Hereinafter, the present invention will be described in detail.
[Triazole silane compound]
In carrying out the present invention, the triazolesilane compound represented by the above chemical formula (I) is used. Examples of the triazole silane compound include the triazole silane compounds represented by the chemical formulas (Ia) to (Id) when A and B in the 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。）

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

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

The triazole silane compounds represented by the chemical formulas (Ib) to (Id) are species produced by hydrolyzing the triazole silane compound (Ia) present in the surface treatment agent.

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

Examples of this triazole silane compound (Ia) include
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,
Examples thereof include N- [3- (trimethoxysilyl) propyl] -5-benzyl-3- [8- (trimethoxysilyl) octylthio] -1H-1,2,4-triazole-1-carboxamide.
In carrying out the present invention, two or more kinds selected from these compounds and the like may be used in combination.

The triazolesilane compound used in the practice of the present invention is a triazolesilane compound represented by the chemical formula (II) and an isocyanatopropylsilane compound represented by the chemical formula (III) in an appropriate reaction temperature and reaction in an appropriate amount of reaction solvent. 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。）

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

As an example of the triazolesilane compound represented by the chemical formula (II) (hereinafter, may be 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 thereof include 3-benzyl-5- [8- (trimethoxysilyl) octylthio] -1H-1,2,4-triazole.

The isocyanatopropylsilane compound represented by the chemical formula (III) (hereinafter, may be simply referred to as an isocyanato compound) is
Represents 3-isocyanatopropyltrimethoxysilane and 3-isocyanatopropyltriethoxysilane.

As the reaction solvent, any solvent inert to the triazole compound and the isocyanato compound can be used without particular limitation, and for example, alcohol-based solvents such as methanol, ethanol, propanol and 2-propanol; pentane, Hydrocarbon solvents such as hexane, heptane, toluene and xylene; ether solvents such as diethyl ether, tetrahydrofuran, 1,4-dioxane and cyclopentylmethyl ether; ester solvents such as ethyl acetate and butyl acetate; formamide, N, N Amido solvents such as -dimethylformamide, N, N-dimethylacetamide, 2-pyrrolidone, N-methylpyrrolidone; ketone solvents such as acetone, methylethylketone, methylisobutylketone, cyclohexanone, dimethylsulfoxide, acetonitrile and the like.

The amount of isocyanato compound used (charged amount) relative to the amount of triazole compound used (charged amount) is 0 in consideration of factors such as the reaction temperature and reaction time, the type of raw material used, the reaction solvent, and the reaction scale. It is preferable to set an appropriate ratio in the range of 8. to 1.2 times the molar amount.
If the amount of the isocyanato compound charged is more than 1.2 times the molar amount, the compound may polymerize and gel, and if it is less than 0.8 times the molar amount, the purity of the product may decrease or the product may be produced. There is a concern that the operation of separating objects 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, more preferably in the range of 1 to 5 hours.

[Surface treatment agent]
The surface treatment agent of the present invention contains the triazolesilane compound represented by the above chemical formula (I). The surface treatment 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 solution of water and an organic solvent. The surface treatment agent in this case can be prepared by mixing the triazolesilane compound and the solvent by adopting an appropriate mixing means. Hereinafter, the surface treatment agent may be referred to as a treatment liquid.

The organic solvent may be liquid or solid as long as it acts as a solubilizer, and is not particularly limited. 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. , Ethylene 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, ethylmethyl Ketone, tetrahydrofuran, dioxane, acetonitrile, 2-pyrrolidone, formamide, N, N-dimethylformamide, N, N-dimethylacetamide, dimethylsulfoxide, 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, apple Acid, methyl acetate, ethyl acetate, ethyl formate, methylamine, dimethylamine, trimethylamine, ethylamine, diethylamine, triethylamine, propylamine, isopropylamine, butylamine, allylamine, ethylenediamine, diethylenetriamine, triethylenetetramine, monoethanolamine, diethanolamine, tri Ethanolamine, dipropanolamine, tripropanolamine, diisopropanolamine, triisopropanolamine, 1-amino-2-propanol, 3-amino-1-propanol, 2-amino-1-propanol, N, N-dimethylethanolamine , Cyclohexylamine, Aniline, pyrrolidine, piperidine, piperazine and pyridine are 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 a water and / or liquid solubilizer.

When a mixed solution of water and an organic solvent is used as the 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 mixed solution of water and an organic solvent may be mixed, or water may be added after mixing the compound and the organic solvent. Further, as the water used for preparing the surface treatment agent, pure water such as ion-exchanged water or 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 it comes into contact with water, and the mode of this hydrolysis is defined in the scheme (D). Indicated. In this scheme, the embodiment in which 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 changed to a dialkoxyhydroxysilyl group or a dihydroxy. The change to an alkoxysilyl group and a trihydroxysilyl group is briefly shown.

（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 equation, R indicates the above-mentioned R ₁ or R _2. Y is an integer representing the number of repeating units.)

Generally, a substance having an alkoxysilyl group in the molecule is known to act as a silane coupling agent. For example, taking the 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 resins and copper to form chemical bonds. In addition, the alkoxysilyl group is hydrolyzed and converted into a hydroxysilyl group (-Si-OH), and this hydroxysilyl group chemically bonds with copper oxide scattered on the surface of copper. Therefore, when copper is brought into contact with the surface treatment agent, a chemical conversion film derived from the triazole silane compound represented by the chemical formula (I) is formed on the surface of 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 adhesiveness between the copper and the resin can be enhanced as compared with the case where the resin layer is formed directly on the surface of the copper.

In the practice of the present invention, the concentration of the triazolesilane 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 triazolesilane compound (Ia) of the trialkoxy. It is preferably 0.01 to 5% by weight, and more preferably 0.01 to 5% by weight. When this concentration is less than 0.001% by weight, the effect of improving the adhesiveness is not sufficient, and when this concentration exceeds 10% by weight, the effect of improving the adhesiveness is almost leveled off, and the triazolesilane compound It is not economical because it only increases the amount of silane used.

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 dehydrate and condense, and the hydroxysilyl group becomes a siloxane bond (Si). -O-Si) is formed (see scheme (D)) and converted to a water-insoluble silane oligomer (a triazolesilane compound having a group represented by the chemical formula (e) in scheme (D)).

When the amount of silane oligomer produced in the surface treatment agent increases, insoluble matter precipitates (the surface treatment agent becomes cloudy) and is immersed in the treatment tank, the piping connected to the treatment tank, or the surface treatment agent. There is a risk that it will adhere to sensors for detecting the temperature and liquid level of the treatment agent, and smooth surface treatment will be hindered. In order to avoid this, it is preferable to include an organic solvent in the surface treatment agent as a dissolving agent for the silane oligomer which is poorly soluble in water. The content of the organic solvent is preferably 0.1 to 900 parts by weight, more preferably 1 to 500 parts by weight, based on 100 parts by weight of water, and is particularly specified in this ratio. It's not something. As the organic solvent, those exemplified as the above-mentioned organic solvent can be used.

In the preparation of the surface treatment 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 the 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, a substance that generates halogen ions such as chlorine ion and bromine ion and metal ions such as copper ion, iron ion and zinc ion is used. You can also do it.

Further, a known coupling agent may be used in combination as long as the effect of the present invention is not impaired. Examples of known coupling agents include silane coupling agents having a thiol group (mercapto group), a vinyl group, an epoxy group, a (meth) acrylic group, an amino group, a chloropropyl group and the like.

Examples of such a silane coupling agent include mercaptosilane compounds such as 3-mercaptopropyltrimethoxysilane and 3-mercaptopropylmethyldimethoxysilane, and vinylsilanes such as vinyltricrolsilane, vinyltrimethoxysilane, and vinyltriethoxysilane. Compounds, vinylphenylsilane compounds such as p-vinylphenyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxy Epoxysilane compounds such as silane, 3-glycidoxypropyltriethoxysilane, acryloxisilane such as 3-acryloxypropyltrimethoxysilane, methaloxypropylmethyldimethoxysilane, methaloxypropyltrimethoxysilane, methaloxypropylmethyldi Methacryloxysilane compounds such as ethoxysilane and metharoxypropyltriethoxysilane, N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, N-2- (aminoethyl) -3-aminopropyltrimethoxysilane, N-2- (aminoethyl) -3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N- (1,3-dimethylbutylidene) Aminosilane compounds such as propylamine, N-phenyl-3-aminopropyltrimethoxysilane, N- (vinylbenzyl) -2-aminoethyl-3-aminopropyltrimethoxysilane, ureidosilanes such as 3-ureidopropyltriethoxysilane Examples thereof include compounds, chloropropylsilane compounds such as 3-chloropropyltrimethoxysilane, sulfidesilane compounds such as bis (triethoxysilylpropyl) tetrasulfide, and isocyanatesilane compounds such as 3-isocyanoxidetriethoxysilane. In addition, aluminum-based coupling agents, titanium-based coupling agents, zirconium-based coupling agents, and the like can also be mentioned.

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), application, 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, fibrous, thin-film, plate-like, and amorphous materials formed from metals, inorganic materials, resin materials, and the like. Be done.

Examples of the metal include copper, aluminum, titanium, nickel, tin, iron, silver, gold and alloys thereof. Specific examples of the alloy are not particularly limited as long as it is an alloy containing copper, and examples thereof include Cu-Ag type, Cu-Te type, Cu-Mg type, Cu-Sn type, and Cu-Si type. , Cu-Mn series, Cu-Be-Co series, Cu-Ti series, Cu-Ni-Si series, Cu-Zn-Ni series, Cu-Cr series, Cu-Zr series, Cu-Fe series, Cu-Al Examples thereof include based alloys, Cu—Zn based, Cu—Co based alloys and the like. Examples of other alloys include aluminum alloys (Al—Si alloys), nickel alloys (Ni—Cr alloys), iron alloys (Fe—Ni alloys, stainless steel) and the like. Among these metals, copper and copper alloys are preferred.
Further, as a metal aspect, foils (for example, electrolytic copper foil, rolled copper foil) used for electronic devices such as printed wiring boards and lead frames, ornaments, building materials, etc., and plating films (for example, electroless copper plating). (Film, electrolytic copper plating film), thin film formed by vapor deposition method, sputtering method, damascene method, etc., and used in applications and forms such as granular, needle-like, fibrous, linear, rod-like, tubular, and plate-like. Things can be mentioned. In the case of copper wiring in which a high-frequency electric signal flows in recent years, it is preferable that the copper surface is a smooth surface having an average roughness of 0.1 μm or less. The surface of copper may be plated with nickel, zinc, chromium, tin or the like as a pretreatment.

Examples of the inorganic material include silicon, ceramics, carbon used as a filler, inorganic salts, glass and the like. Specifically, silicon compounds such as silicon, silicon carbide, silica, glass, diatomaceous earth, calcium silicate, talc, glass beads, sericite active white clay, bentonite, alumina, zinc oxide, iron oxide, magnesium oxide, tin oxide, and oxidation. Oxides such as titanium, hydroxides such as magnesium hydroxide, aluminum hydroxide, basic magnesium carbonate, calcium carbonate, zinc carbonate, hydrotalcite, carbonates such as magnesium carbonate, sulfates such as barium sulfate and graphite, Titanates such as barium titanate, nitrides such as aluminum nitride and silicon nitride, graphites such as scaly graphite (natural graphite), expanded graphite, expanded graphite (synthetic graphite), activated carbons, carbon fibers, carbon Black and the like can be mentioned. Among these inorganic materials, silicon, ceramics (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, and fluorine-containing resin, which have excellent heat resistance and insulation properties. , Polyetherimide resin, polyetherether ketone resin, liquid crystal resin and the like, and these may be mixed or modified with each other to be combined. Further, the degree of polymerization of these resins is not particularly limited, and may be appropriately polymerized (cured) after surface treatment. Among these resin materials, acrylate resin, epoxy resin and polyimide resin are preferable.

[Surface treatment method]
The method of bringing the surface treatment agent of the present invention into contact with the surface of the material to be treated is not particularly limited, and means such as dipping, coating and spraying can be adopted. The time (treatment time) for contacting the surface treatment agent with 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 adhesive force between materials of different materials cannot be obtained, while even if it is longer than 10 minutes. , There is no big difference in the film thickness, and improvement of adhesiveness cannot be expected. 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 appropriately set in relation to the treatment time.

After the surface treatment agent of the present invention is brought into contact with the material to be treated, it may be washed with water and then dried, or it may be dried without washing with water. Drying is preferably at a temperature of room temperature to 150 ° C. As the water used for washing with water, pure water such as ion-exchanged water or distilled water is preferable, but the method and time of washing with water are not particularly limited, and an appropriate time by means such as spraying or dipping may be used.

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

Further, before the surface treatment agent of the present invention is brought 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, alkaline washing treatment, roughening treatment or heat resistance treatment. At least one pretreatment selected from may be performed.

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

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

The roughening treatment forms an uneven shape on the surface of the metal, inorganic material or resin material, and the adhesiveness (adhesion) of the two materials selected from the metal, the inorganic material and the resin material is improved by the anchor effect thereof. It is done to enhance. For this roughening treatment, a method such as a desmear method, a plasma etching method, a metal sputtering method, an electroless plating method, an electroplating method, a rust prevention treatment, an oxidation / reduction method, a brush polishing method, or a jet scrub method shall be adopted. Can be done.

In the desmear method, for example, a potassium permanganate-based or sodium permanganate-based desmear agent can be used. Further, a swelling treatment or a neutralization treatment may be performed before and after the roughening treatment by the desmear method.
In the metal sputtering method and the electroless plating method, irregularities are formed on the surface of the metal, the inorganic material or the resin material by precipitating fine metal particles on the surface of the metal, the inorganic material or the 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 metal, inorganic or resin materials. At least one type of film is formed.
A known electroless plating method can be adopted for forming this film, but vapor deposition or other means may also be used.

The above-mentioned rust preventive treatment is performed to prevent oxidative corrosion of the metal surface, and a method of forming a zinc or zinc alloy composition plating film or an electrolytic chromate plating film on the metal surface. Can be adopted.

As the chemical conversion treatment, a method of forming a passivation film of tin or a method of forming a passivation film of copper oxide can be adopted.

When the surface treatment agent of the present invention is brought 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. The 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. Ammonia, hydrochloric acid, or the like may be used in combination to solubilize the copper salt in water.

Further, after the surface treatment agent of the present invention is brought into contact with the surface of the metal, inorganic material or resin material, an acidic aqueous solution or an alkaline aqueous solution may be brought into contact with the surface of the metal, inorganic material or resin material. This acidic aqueous solution or alkaline aqueous solution also 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, like the above-mentioned 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 mineral acids such as sulfuric acid, nitric acid and hydrochloric acid, and aqueous solutions containing organic acids such as formic acid, acetic acid, lactic acid, glycolic acid and amino acids. it can. Examples of the alkaline aqueous solution include aqueous solutions containing alkali metal hydroxides such as sodium hydroxide and potassium hydroxide and amines such as ammonia, ethanolamine and monopropanolamine.

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, treatments such as plasma, laser, ion beam, ozone, heating or humidification are performed to carry out treatment such as plasma, inorganic material or resin material. Alternatively, the surface of the resin material may be modified. Further, cleaning for the purpose of removing resin / ion residues of a metal, an inorganic material or a resin material may be performed by mechanical polishing of a plasma, a laser, an ion beam, a permis brush or the like, or processing of a drill or the like.

In particular, in the step of performing metal plating or the step of mounting a component, the surface of the metal in contact with the surface treatment agent of the present invention is treated with plasma, laser, ion beam, ozone, heating or humidification, etc. It is preferable to carry out reforming and cleaning for the purpose of removing residues.

Further, in the step of performing metal plating or the step of mounting a component, a primer treatment for forming an organic film, a metal film, or the like on the surface of a metal in contact with the surface treatment agent of the present invention in order to improve adhesion. May be done.

These pretreatments and posttreatments may be carried out in appropriate combinations.

The surface treatment agent of the present invention can be suitably used for the surface treatment of the above-mentioned metal. By treating the surface of the metal with the surface treatment agent of the present invention, a film can be formed on the metal surface and the adhesiveness with other materials can be enhanced. This film has high heat resistance, and for example, the adhesive strength is maintained even by solder reflow heating (about 260 ° C.).
In addition, in order to enhance the effect of this treatment, the surface-treated material to be treated 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 adhesiveness between the metal and the resin can be formed on the surface of the metal. Then, when the chemical conversion film is brought into contact with an organic solvent or a corrosive chemical solution after the metal and the resin are adhered to each other, the chemical resistance is not affected by the organic solvent or the corrosive chemical solution. It can be an excellent and strong chemical conversion film.

Further, such a surface treatment method includes, for example, a copper circuit (copper wiring layer), a prepreg, a solder resist (insulating resin layer), gold plating, silver plating, nickel plating, palladium plating, tin plating, solder plating, etc. It is suitable for surface treatment of copper for the purpose of enhancing the adhesiveness (adhesion) between the plating resist and the dry film resist layer such as the etching resist.

[Adhesion method]
In practicing the present invention, two materials selected from the above-mentioned metal, inorganic material and resin material can be adhered using the surface treatment agent of the present invention. By adhering the two materials through the film formed by the surface treatment agent of the present invention, the affinity between the two materials can be improved, so that even materials of different materials can be adhered more firmly. Can be done. The thickness of the film is 0.0001 to 1 μm, preferably 0.001 to 0.5 μm.

As the bonding method, a known method can be adopted. The surface treatment agent of the present invention is brought into contact with the surface of a material to be treated selected from a metal, an inorganic material or a resin material to form a film, and another material to be treated is applied to a part or the whole of the formed film. , Crimping, mixing, etc., the use of adhesives, adhesive sheets (films), and the combination of these means for bonding.

Further, the surface treatment agent of the present invention is brought into contact with the surfaces of two materials to be treated selected from a metal, an inorganic material, and a resin material to form a film on each surface, and the two materials to be treated are pressure-bonded. Examples include means such as mixing, use of an adhesive and an adhesive sheet (film), and a method of combining and adhering these means.

According to such an bonding method, as in the case described above, the copper circuit and the prepreg or solder resist, gold plating, silver plating, nickel plating, palladium plating, plating resist such as tin plating or solder plating, or etching resist. It is possible to enhance the adhesiveness between the dry film resist layer and the like.
That is, even if the bonded portion between the copper circuit and the resists (resin) is exposed to various corrosive chemicals (chemicals) used in various plating steps, soldering steps, and etching steps, it is unlikely to deteriorate. Therefore, good adhesion (adhesion) between copper and resin can be maintained.
Chemical solutions used in these steps include pickling aqueous solutions such as hydrochloric acid and sulfuric acid used for pretreatment of various plating treatments, alkaline degreasing agents containing sodium hydroxide and amines, organic solvents, and hydrogen peroxide. -Copper etching agents such as sulfuric acid and persulfate, resin oxidizing agents such as permanganate (Desmia solution), various plating agents such as copper plating, gold plating, silver plating, nickel plating, palladium plating, tin plating, solder Examples include post flux used during 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 manufactured by any method such as electroless plating method, electrolytic plating method, thin film deposition method, sputtering method, damascene method, etc., and includes an inner via hole, a through hole, a connection terminal, and the like. It may be.

[Use of surface treatment agent]
By using the surface treatment agent of the present invention, it is possible to bond two materials, particularly two materials having different materials, as described above, and thus for electrical / electronic applications (various electrical / electronic parts, printed wiring boards, etc.). It can be suitably used for electronic devices), construction applications, civil engineering applications, automobile applications, medical material applications, and the like.

The surface treatment agent of the present invention can be suitably used for a material to be treated, which is formed of a metal, particularly copper or a copper alloy. For example, the purpose is to improve the adhesiveness (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). This is suitable in some cases, and in a printed wiring board having an insulating resin layer in contact with the copper wiring layer, the adhesiveness 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 the surface treatment of a material, a copper foil, a prepreg, a copper-clad laminate, an interlayer insulating material, a sheet-like member having a film formed by the treatment with the surface treatment agent, and the like. In addition to a copper foil with a resin 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 and the like can be mentioned.

The printed wiring board can be manufactured, for example, by contacting the surface treatment agent of the present invention with the surface of the copper wiring layer, then washing and drying with water, and then forming an insulating resin layer on the surface of the copper wiring layer. it can. The method of this contact is as described above, and immersion of the copper wiring layer in the surface treatment agent or spraying on the surface of the copper wiring layer by the surface treatment agent is convenient, reliable and preferable.

Further, in the process of removing a part of the insulating resin for mounting the components and conducting the upper and lower wiring after forming the insulating resin layer on the surface of the copper wiring layer, the plasma is combined with the removal of the residue on the copper circuit. , Laser, ion beam, machine polishing of permis brush, etc., processing of drills, etc., cleaning with acidic aqueous solution, alkaline aqueous solution, solvent, etc. may be performed alone or in combination.

Although the method of washing with water is not limited, it is preferable to immerse the copper wiring layer in the washing water or spray the surface of the copper wiring layer with the washing water because it is simple and reliable. For the formation of the insulating resin layer, a known method, for example, a method of attaching a semi-cured resin material, a means of applying a liquid resin material containing a solvent, or the like can be adopted. Next, a via hole is formed in order to make the upper and lower wiring conductive. By repeating this process, a multilayer printed wiring board can be manufactured.

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

By the way, Japanese Patent Application Laid-Open No. 2009-19266 describes 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. The present invention describes a method for forming a silane coupling agent film, which comprises a step of performing the above step and a step of washing the dried metal surface with water. Further, it is said that an adhesive metal layer such as tin may be formed on the metal surface by a dip plating solution in advance as a surface treatment. The surface treatment agent of the present invention can be used as a liquid containing the above-mentioned silane coupling agent. The matters described in this patent gazette shall form a part of the present specification by citation.

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

The "resin or its pre-cured compound" includes a thermoplastic resin, a thermosetting or active energy ray-curable resin (cured product), a raw material monomer thereof, and a partial polymer or semi-cured product of the monomer. In the case of a thermosetting or active energy ray-curable resin, the resin may be in any state selected from A stage resin, B stage resin and 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, and poly, which have excellent heat resistance and insulating properties. Examples thereof include an etherimide resin, a polyether ether ketone resin, and a liquid crystal resin, and these may be mixed or modified with each other to be combined. Among these resin materials, acrylate resin, epoxy resin and polyimide resin 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, more preferably 0.01 to 5% by weight. .. When the content of the triazolesilane compound is less than 0.001% by weight, the effect of improving the adhesiveness is not sufficient, and when this content exceeds 10% by weight, the effect of improving the adhesiveness is almost the same. It has reached a plateau, and the amount of triazole silane compound used has only increased, which is not economical.

The resin composition includes a resin or a compound before curing thereof, a triazolesilane compound represented by the chemical formula (I), a solvent (water, an organic solvent, a mixed solution of water and an organic solvent), depending on the intended use. Additives (curing agent, curing accelerator, flame retardant, dye, pigment, ultraviolet absorber, lubricant, filler, etc.) and the like may be appropriately contained. As the organic solvent, those exemplified as the above-mentioned organic solvent (solubilizer) can be used.

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

[Use of resin composition]
Since the resin composition of the present invention contains the triazolesilane compound represented by the chemical formula (I), the cured resin layer adheres to an adjacent layer or member, for example, a layer or member of a metal or inorganic material with high strength. (Adhesion). Therefore, it can be suitably used for various electric / electronic applications (electric / electronic parts and the like, electronic devices such as printed wiring boards), construction 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 by the solder resist ink, and a substrate (paper). , Glass cloth, glass non-woven 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, and an interlayer insulating material (interlayer) composed of the resin composition of the present invention. Insulation film, etc.), a copper foil with a resin composed of a copper foil and a resin layer formed of the resin composition of the present invention, a printed wiring board provided with a resin layer formed of the resin composition of the present invention, a book. Examples thereof include a semiconductor encapsulating material composed of the resin composition of the present invention.

For the solder resist, a solder resist ink composed of a triazole silane compound represented by the chemical formula (I) and a resin or a resin composition of the present invention containing a resin or a compound before curing (curable compound) thereof is applied onto an appropriate substrate. , The curable resin layer formed by drying is cured by 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 base material (paper, glass cloth, glass non-woven fabric, etc.) or by immersing the base material in the resin composition and impregnating it.
The copper-clad laminate can be manufactured by laminating the prepreg and the copper foil.
The interlayer insulating material can be produced by applying the resin composition of the present invention on an appropriate substrate and drying, semi-curing or curing it.
The resin-attached copper foil can be produced by applying the resin composition of the present invention on the copper foil and drying, semi-curing or curing the resin composition.
The "resin layer formed by the resin composition of the present invention" in the printed wiring board may be formed in layers regardless of the shape, but the solder resist, the prepreg, and the interlayer insulating material are preferable. , Resin in copper foil with resin. The resin composition of the present invention can be suitably used as a semiconductor encapsulating material.

Further, since excellent adhesiveness, heat resistance, insulating property and the like can be imparted to the member to which the surface treatment agent and the resin composition of the present invention are applied, conductivity can be provided by incorporating an appropriate auxiliary agent as necessary. With sex pastes, underfills, die attach materials, semiconductor chip mounting materials, non-conductive adhesives, liquid crystal sealants, display materials, reflectors, paints, adhesives, hardeners, varnishes, elastomers, inks, waxes, sealants, etc. can do.

Hereinafter, the present invention will be specifically described with reference to Examples and Comparative Examples, but the present invention is not limited thereto.
Examples of synthesis of the silane coupling agent component (triazole silane compound) used in the examples are shown in Reference Examples 1-1 to 6-1. Then, 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 Examples 1-1 to 6-1, examples of synthesis of the precursor (triazolesilane compound) used as a raw material are shown in Reference Examples 1-2 to 6-2.
The main raw materials used in these reference examples are as follows.

[Main raw materials used in the reference example]
-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-A-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: Special Table No. 5-509176 It was synthesized 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-A-5-509176.
・ 3-Isocyanatopropyltriethoxysilane: manufactured by Momentive Performance Materials Japan Co., Ltd. ・ 3-Isocyanatopropyltriethoxysilane: manufactured by 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>
3- [3- (Trimethoxysilyl) propylthio] -1H-1,2,4-triazole 10.0 g (38 mmol) 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 dropping, the mixture was heated and stirred at 65 ° C. for 4 hours, the volatile matter was distilled off from the reaction solution under reduced pressure, and 17.8 g (38.) of the triazolesilane compound of the title represented by the chemical formula (Ia-1) as a colorless liquid. 0 mmol, yield 100%) was obtained.

[Reference Example 1-2]
<Synthesis of precursor 3- [3- (trimethoxysilyl) propylthio] -1H-1,2,4-triazole>
A suspension consisting 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 a 28% sodium methoxide methanol solution was added. After making a uniform solution, the mixture was 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 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 the obtained 12.5 g of white viscous substance was extracted 3 times with 40 ml of diethyl ether, the insoluble matter was filtered off from the extract, and the filtrate was concentrated under reduced pressure to give the title of slightly yellowish brown oil. 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>
3-Methyl-5- [3- (trimethoxysilyl) propylthio] -1H-1,2,4-triazole in a solution consisting of 8.40 g (30 mmol) and 50 ml of tetrahydrofuran at room temperature, 3-isocyanatopropyltrimethoxy. 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 the mixture was stirred at 63 ° C. for 5 hours.
The volatile matter was distilled off from the reaction solution 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>
A 28% sodium methoxide methanol solution 42 in 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. .0 g (0.218 mol) was added and the mixture was stirred for 20 minutes. To this, 43.1 g (0.217 mol) of (3-chloropropyl) trimethoxysilane was added, and the mixture was further stirred at 76 ° C. for 3 hours.
After cooling the reaction solution to room temperature, the insoluble material was filtered off, 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>
3-Amino-5- [3- (trimethoxycisilyl) propylthio] -1H-1,2,4-triazole 8.34 g (30 mmol) was dissolved in 50 ml of tetrahydrofuran, and 0.7 g (7 mmol) of triethylamine was dissolved therein. 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, the volatile matter was distilled off from the reaction solution under reduced pressure, and 15.8 g (30) of the triazolesilane compound of the title represented by the chemical formula (Ia-3) as a pale yellow liquid. 0.0 mmol, yield 100%) was obtained.

[Reference Example 3-2]
<Synthesis of precursor 3-amino-5- [3- (trimethoxysilyl) propylthio] -1H-1,2,4-triazole>
A suspension consisting 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 cooled. ) To make a uniform solution, the mixture was returned to room temperature and stirred for 30 minutes, and a solution consisting of 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, and 26.4 g of the obtained white viscous substance was extracted three times with 100 ml of diethyl ether. The extract was filtered and then concentrated under reduced pressure to obtain 9.20 g (33 mmol) of the triazole compound of the title of a slightly yellowish brown oil. , Yield 55.1%) was obtained.

[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. After that, 7.4 g (30 mmol) of 3-isocyanatopropyltriethoxysilane was added dropwise at room temperature. After completion of the dropping, the mixture was heated and stirred at 65 ° C. for 4 hours, the volatile matter was distilled off from the reaction solution under reduced pressure, and 17.0 g (30) of the title triazolesilane compound represented by the chemical formula (Ia-4) as a pale yellow liquid was obtained. 0.0 mmol, yield 100%) was obtained.

[Reference Example 4-2]
<Synthesis of precursor 3-amino-5- [3- (triethoxysilyl) propylthio] -1H-1,2,4-triazole>
A suspension consisting 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 (10. 30 mmol) was added to make a uniform solution, and the mixture was returned to room temperature and stirred for 30 minutes. A solution consisting of 6.74 g (30 mmol) of (3-chloropropyl) triethoxysilane and 10 ml of dehydrated ethanol was added dropwise over 10 minutes, and the mixture was further stirred at 78 ° C. for 6 hours.
The reaction solution was concentrated under reduced pressure to extract 10.8 g of a white viscous substance with 40 ml of diethyl ether three times, and after removing the insoluble matter from the extract, the filtrate was concentrated under reduced pressure to form a low melting point crystalline solid. 8.2 g (25.7 mmol, yield 85.6%) of the title triazole compound was obtained.

[Reference Example 5-1]
<Synthesis of N- [3- (trimethoxysilyl) propyl] -5-phenyl-3- [3- (trimethoxysilyl) propylthio] -1H-1,2,4-triazole-1-carboxamide>
3-Phenyl-5-[3- (trimethoxysilyl) propylthio] -1H-1,2,4-triazole in a solution consisting of 9.50 g (28 mmol) and 50 ml of tetrahydrofuran at room temperature, 3-isocyanatopropyltrimethoxy. 5.74 g (28 mmol) of silane was added dropwise over 5 minutes, followed by stirring for 10 minutes. To this, 1.14 g (11 mmol) of triethylamine was added, and the mixture was stirred at 63 ° C. for 4 hours and 30 minutes.
The volatile matter was distilled off from the reaction solution 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>
28% sodium methoxide methanol in a suspension consisting 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 at room temperature. 27.3 g (0.142 mol) of the solution was added and the mixture was stirred for 20 minutes. To this, 28.0 g (0.141 mol) of (3-chloropropyl) trimethoxysilane was added, and the mixture was further stirred at 73 ° C. for 4 hours.
The reaction mixture was cooled to room temperature, the insoluble material was filtered off, and the filtrate was dried under reduced pressure to give 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>
3-Benzyl-5- [3- (trimethoxysilyl) propylthio] -1H-1,2,4-triazole in a solution consisting of 9.03 g (26 mmol) and 50 ml of tetrahydrofuran at room temperature, 3-isocyanatopropyltrimethoxy. 5.23 g (25 mmol) of silane was added dropwise over 5 minutes, followed by stirring for 10 minutes. To this, 1.0 g (10 mmol) of triethylamine was added, and the mixture was stirred at 63 ° C. for 5 hours.
The volatile matter was distilled off from the reaction solution 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>
A 28% sodium methoxide methanol solution in 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 25 at room temperature. .6 g (0.133 mol) was added and the mixture was stirred for 10 minutes. To this, 26.2 g (0.132 mol) of (3-chloropropyl) trimethoxysilane was added, and the mixture was further stirred at 73 ° C. for 3 hours.
The reaction mixture was cooled to room temperature, the insoluble material was filtered off, and the filtrate was concentrated under reduced pressure to give 48.0 g (0.134 mol, yield 102.2%) of the triazole compound entitled as a pale yellow liquid.

[Reference Example 7]
<Synthesis of imidazole silane compound>
3. Melting 3.4 g (0.05 mol) of imidazole at 95 ° C. and stirring under 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 transparent 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 the chemical formulas (IV-1) to (IV-3).

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

[Adhesiveness evaluation test (a)]
(1) Metal As the metal, an electrolytic copper foil (thickness: 18 μm) was used.
(2) Metal surface treatment The following steps a to c were performed.
I. Acid cleaning (5% sulfuric acid aqueous solution) / 1 minute (room temperature), washing with water b. Acid cleaning (same as above) / 1 minute (room temperature), washing with water, drying / 1 minute (100 ° C)
C. Immerse in surface treatment agent / 1 minute (room temperature), 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 electrolytic copper foil, and the copper foil and prepreg were adhered to prepare 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)", subjected to pressure cooker treatment (121 ° C./humidity100%/100 hours), and then copper. The peeling strength of the foil was measured.

[Adhesiveness evaluation test (b)]
Instead of "laminating and pressing a glass cloth epoxy resin impregnated prepreg (FR-4 grade)" on the S surface of the electrolytic copper foil, "resin for build-up wiring board (manufactured by Ajinomoto Fine-Techno, product name" GX-13 ") The adhesiveness between the copper foil and the resin was evaluated by the same procedure as in the evaluation test (a) except that the copper foil and the resin were laminated.

[Adhesiveness 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) Metal surface treatment The following steps a to d were performed.
I. Acid cleaning / 1 minute (room temperature), washing with water b. Micro-etching with hydrogen peroxide / sulfuric acid / 1 minute (room temperature), washing with water c. Acid cleaning / 1 minute (room temperature), washing with water, drying / 1 minute (100 ° C)
D. Immerse in surface treatment agent / 1 minute (room temperature), wash with water, dry / 1 minute (100 ° C)
(3) Formation of Resin Layer on Metal Solder resist ink (manufactured by Taiyo Ink Mfg. Co., Ltd., acrylate / epoxy resin, product name "PSR-4000AUS308") is applied to the treated electrolytic copper foil, and then dried (80 ° C./30). Minutes) and curing (150 ° C./60 minutes) to form a 13 μm-thick resin layer (coating film).
(4) Evaluation of Adhesiveness According to "JIS K5400-8.5 (1990)", the coating film formed on the electrolytic copper foil was cross-cut (100 squares) on a 1 mm x 1 mm grid and treated with a pressure cooker (121 ° C.). / Humidity 100% / 100 hours), then a tape peel test was performed to measure the number of squares in which the coating film did not peel off. In addition, the degree of damage to the coating film was visually observed.
The criteria for determining the adhesiveness are shown in Table 1.

[Adhesiveness evaluation test (d)]
(1) Metal As the metal, an aluminum foil (thickness: 50 μm) was used.
(2) Metal surface treatment The following steps a to b were performed.
I. Acid cleaning / 1 minute (room temperature), washing with water b. Immerse in surface treatment agent / 1 minute (room temperature), wash with water, dry / 1 minute (100 ° C)
(3) Adhesion of Metal and Resin A prepreg (FR-4 grade) impregnated with a glass cloth epoxy resin was laminated and pressed on the treated aluminum foil, and the aluminum foil and the prepreg were bonded to prepare a laminated plate.
(4) Evaluation of Adhesiveness A test piece having a width of 10 mm was prepared from this laminated plate according to "JIS C6481 (1996)", and the peeling strength of the aluminum foil was measured.

[Adhesiveness evaluation test (e)]
(1) Resin material As the resin material, a glass cloth epoxy resin impregnated prepreg (FR-4 grade) was used.
(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 prepare a copper-clad laminate.
(4) Evaluation of Adhesiveness A test piece having a width of 10 mm was prepared from this copper-clad laminate according to "JIS C6481 (1996)", and the peeling strength of the copper foil was measured.

[Adhesiveness 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 the mixture was 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 To 100 parts by weight of solder resist ink (same as above), 1 part by weight of barium sulfate carrying a silane coupling agent component was added, and the mixture was stirred for 30 minutes to prepare the resin composition. (Solder resist ink composition) was prepared.
(3) Preparation of Printed Wiring Board The obtained resin composition is used as 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). Then, it was heated in an oven at 150 ° C. for 1 hour to prepare a printed wiring board in which a cured product of this resin composition and a copper foil were adhered to each other.
(4) Evaluation of Adhesiveness From this printed wiring board, a test piece having a width of 10 mm was prepared according to "JIS C6481 (1996)", and the peeling strength of the copper foil was measured.

[Adhesiveness evaluation test (g)]
(1) Preparation of resin composition To 100 parts by weight of solder resist ink (same as above), 1 part by weight of a silane coupling agent component (hydrolyzate) having a hydroxysilyl group was added, and the mixture was stirred for 30 minutes. , A resin composition (solder resist ink composition) was prepared.
(2) Preparation of Printed Wiring Board The obtained resin composition is used as 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). Then, it was dried (80 ° C./30 minutes) and cured (150 ° C./60 minutes) to prepare a printed wiring board in which a cured product of this resin composition and a copper foil were adhered to each other.
(3) Evaluation of Adhesiveness A test piece having a width of 10 mm was prepared from this printed wiring board according to "JIS C6481 (1996)", and the peeling strength of the copper foil was measured.

[Example 1]
As a silane coupling agent component, add 10 g of "N- [3- (trimethoxysilyl) propyl] -3- [3- (trimethoxysilyl) propylthio] -1H-1,2,4-triazole-1-carboxamide". , 200 g of ethylene glycol monobutyl ether was added, and then 790 g of water was added, and the mixture was stirred overnight at room temperature to prepare a surface treatment agent (hereinafter referred to as treatment liquid A).
With respect to this treatment liquid A, it was confirmed that the methoxysilyl group of the triazolesilane compound was hydrolyzed to the hydroxysilyl group, and the adhesiveness evaluation tests (a) to (f) were carried out.
Subsequently, the volatile matter 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 adhesiveness 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] as in Example 1. In the same manner, a surface treatment agent (hereinafter referred to as treatment liquid B) was prepared.
Regarding this treatment liquid B, it was confirmed that the methoxysilyl group of the triazolesilane compound was hydrolyzed to the hydroxysilyl group, and the adhesiveness evaluation tests (a) to (f) were carried out.
Further, in the same manner as in Example 1, a hydrolyzate of the silane coupling agent component was obtained from the treatment liquid B, and an adhesiveness evaluation test (g) was conducted.
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- To 10 g of carboxamide, 200 g of ethylene glycol monobutyl ether was added, then 789 g of water and 1 g of acetic acid were added, and the mixture was stirred at room temperature for 2 hours to prepare a surface treatment agent (hereinafter referred to as treatment liquid C).
With respect to this treatment liquid C, it was confirmed that the methoxysilyl group of the triazolesilane compound was hydrolyzed to the hydroxysilyl group, and the adhesiveness evaluation tests (a) to (f) were carried out.
Further, in the same manner as in Example 1, a hydrolyzate of the silane coupling agent component was obtained from the treatment liquid C, and an adhesiveness evaluation test (g) was conducted.
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", " Except for the use of N- [3- (triethoxysilyl) propyl] -5-amino-3- [3- (triethoxysilyl) propylthio] -1H-1,2,4-triazole-1-carboxamide. A surface treatment agent (hereinafter referred to as treatment liquid D) was prepared in the same manner as in Example 3.
With respect to this treatment liquid D, it was confirmed that the ethoxysilyl group of the triazolesilane compound was hydrolyzed to the hydroxysilyl group, and the adhesiveness evaluation tests (a) to (f) were carried out.
Further, in the same manner as in Example 1, a hydrolyzate of the silane coupling agent component was obtained from the treatment liquid D, and an adhesiveness evaluation test (g) was conducted.
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", subsequently 790 g of water was added, and the mixture was stirred at 50 ° C. for 2 hours to prepare a surface treatment agent (hereinafter referred to as treatment liquid E).
Regarding this treatment liquid E, it was confirmed that the methoxysilyl group of the triazolesilane compound was hydrolyzed to the hydroxysilyl group, and the adhesiveness evaluation tests (a) to (f) were carried out.
Further, in the same manner as in Example 1, a hydrolyzate of the silane coupling agent component was obtained from the treatment liquid E, and an adhesiveness evaluation test (g) was conducted.
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", " Except for the use of N- [3- (trimethoxysilyl) propyl] -5-benzyl-3- [3- (trimethoxysilyl) propylthio] -1H-1,2,4-triazole-1-carboxamide] A surface treatment agent (hereinafter referred to as treatment liquid F) was prepared in the same manner as in Example 5.
Regarding this treatment liquid F, it was confirmed that the methoxysilyl group of the triazolesilane compound was hydrolyzed to the hydroxysilyl group, and the adhesiveness evaluation tests (a) to (f) were carried out.
Further, in the same manner as in Example 1, a hydrolyzate of the silane coupling agent component was obtained from the treatment liquid F, and an adhesiveness evaluation test (g) was conducted.
The test results obtained were as shown in Table 2.

[Comparative Example 1]
"Imidazolesilane compound" instead of "N- [3- (trimethoxysilyl) propyl] -3- [3- (trimethoxysilyl) propylthio] -1H-1,2,4-triazole-1-carboxamide" A surface treatment agent (hereinafter referred to as treatment liquid G) was prepared in the same manner as in Example 1 except that the above was used.
With respect to this treatment liquid G, it was confirmed that the methoxysilyl group of the imidazole silane compound was hydrolyzed to the hydroxysilyl group, and the adhesiveness evaluation tests (a) to (f) were carried out.
Further, in the same manner as in Example 1, a hydrolyzate of the silane coupling agent component was obtained from the treatment liquid G, and an adhesiveness evaluation test (g) was conducted.
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.
With respect to this treatment liquid H, it was confirmed that the methoxysilyl group of 3-aminopropyltrimethoxysilane was hydrolyzed to the hydroxysilyl group, and the adhesiveness evaluation tests (a) to (f) were carried out.
Further, in the same manner as in Example 1, a hydrolyzate of the silane coupling agent component was obtained from the treatment liquid H, and an adhesiveness evaluation test (g) was conducted.
The test results obtained were as shown in Table 2.

[Comparative Example 3]
Without using a silane coupling agent, 200 g of ethylene glycol 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).
When the adhesiveness evaluation tests (a) to (f) were performed on this treatment liquid I, the test results obtained were as shown in Table 2.
The adhesiveness evaluation test (g) was carried out without adding anything to the solder resist. The test results obtained were as shown in Table 2.

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

[Adhesiveness evaluation test (h)]
(1) Metal As the metal, an electrolytic copper foil (thickness: 18 μm) was used.
(2) Metal Surface Treatment Any one selected from the following three treatment methods (α to γ) was carried out.
<Processing method α>
I. Acid cleaning (5% sulfuric acid aqueous solution) / 1 minute (room temperature), washing with water b. Micro etching (etching amount 3 μm) / 1 minute (room temperature), washing with water, drying / 1 minute (100 ° C)
C. Immerse in surface treatment agent / 1 minute (room temperature), wash with water, dry / 1 minute (100 ° C)
<Processing method β>
I. Acid cleaning (5% sulfuric acid aqueous solution) / 1 minute (room temperature), washing with water b. Micro etching (etching amount 3 μm) / 1 minute (room temperature), washing with water, drying / 1 minute (100 ° C)
C. Brush the surface treatment agent and dry / 1 minute (100 ° C)
<Processing method γ>
I. Acid cleaning (5% sulfuric acid aqueous solution) / 1 minute (room temperature), washing with water b. Micro etching (etching amount 3 μm) / 1 minute (room temperature), washing with water, drying / 1 minute (100 ° C)
C. Brush the surface treatment agent, heat / 5 minutes (100 ° C), methanol wash, water wash, 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 prepare a copper-clad laminate.
(4) Evaluation of Adhesiveness A test piece having a width of 10 mm was prepared from this copper-clad laminate according to "JIS C6481 (1996)", and the peeling strength of the copper foil was measured. The peeling strength after two reflow heatings (peak temperature 260 ° C., atmosphere) 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- To 10 g of carboxamide, 990 g of a 1: 1 mixed solution of water and methanol was added and stirred at room temperature for 2 hours to prepare a surface treatment agent (hereinafter referred to as treatment solution J).
With respect to this treatment liquid J, it was confirmed that the methoxysilyl group of the triazolesilane compound was hydrolyzed to the hydroxysilyl group, and an adhesiveness evaluation test (h) (treatment method γ) was carried out.
The test results obtained were as shown in Table 3.

[Example 8]
The adhesiveness evaluation test (h) (treatment method β) was carried out using the treatment liquid J prepared in Example 7. 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 adhesiveness evaluation test (h) (treatment method γ).
The test results obtained were as shown in Table 3.

[Example 10]
The adhesiveness evaluation test (h) (treatment method β) was carried out using the treatment liquid K. The test results obtained were as shown in Table 3.

[Example 11]
A surface treatment agent (hereinafter referred to as treatment liquid L) was added in the same manner as in Example 7 except that 200 g of ethylene glycol monobutyl ether was added instead of the 1: 1 mixture of water and methanol, and then 790 g of water was added. ) Was prepared.
With respect to this treatment liquid L, it was confirmed that the methoxysilyl group of the triazolesilane compound was hydrolyzed to the hydroxysilyl group, and an adhesiveness evaluation test (h) (treatment method α) was carried out.
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.
With respect to this treatment liquid M, it was confirmed that the methoxysilyl group of 3-mercaptopropyltrimethoxysilane was hydrolyzed to the hydroxysilyl group, and an adhesiveness evaluation test (h) (treatment method γ) was carried out.
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) is used in the same manner as in Example 7 except that "3-glycidoxypropyltrimethoxysilane" (manufactured by Shin-Etsu Chemical Co., Ltd., trade name "KBM-403") is used. Was prepared.
With respect to this treatment liquid N, it was confirmed that the methoxysilyl group of 3-glycidoxypropyltrimethoxysilane was hydrolyzed to the hydroxysilyl group, and an adhesiveness 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 the adhesiveness evaluation test (h) (treatment method α) was performed on this treatment liquid O, the test results obtained were as shown in Table 3.

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

[Adhesiveness evaluation test (i)]
(1) Resin material As the resin material, a glass cloth epoxy resin impregnated prepreg (FR-4 grade) was used.
(2) Surface Treatment of Resin Material Any one selected from the following three treatment methods (α to γ) was carried out.
<Processing method α>
I. Acid cleaning (5% sulfuric acid aqueous solution) / 1 minute (room temperature), washing with water b. Immerse in surface treatment agent / 1 minute (room temperature), wash with water, dry / 1 minute (100 ° C)
<Processing method β>
I. Acid cleaning (5% sulfuric acid aqueous solution) / 1 minute (room temperature), washing with water b. Brush the surface treatment agent and dry / 1 minute (100 ° C)
<Processing method γ>
I. Acid cleaning (5% sulfuric acid aqueous solution) / 1 minute (room temperature), washing with water b. Brush the surface treatment agent, heat / 10 minutes (100 ° C), methanol wash, water wash, 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 the copper foil were adhered to prepare a copper-clad laminate.
(4) Evaluation of Adhesiveness This copper-clad laminate was subjected to the same procedure as in the adhesiveness 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 the mixture was stirred at room temperature for 2 hours to prepare a surface treatment agent (hereinafter referred to as treatment liquid P).
This treatment liquid P was subjected to an adhesiveness 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- To 10 g of carboxamide, 990 g of a 1: 1 mixed solution of water and methanol was added, and the mixture was stirred at 50 ° C. for 1 hour to prepare a surface treatment agent (hereinafter referred to as treatment solution Q).
With respect to this treatment liquid Q, it was confirmed that the methoxysilyl group of the triazolesilane compound was hydrolyzed to the hydroxysilyl group, and the same adhesiveness evaluation test as in Example 12 was carried out.
The test results obtained were as shown in Table 4.

[Example 14]
Adhesiveness evaluation test (i) (treatment method β) was carried out using the treatment liquid Q prepared in Example 13. The test results obtained were as shown in Table 4.

[Comparative Example 7]
Using the treatment liquid M prepared in Comparative Example 4, an adhesiveness evaluation test similar to that in Example 12 was performed. The test results obtained were as shown in Table 4.

[Comparative Example 8]
Imidazole 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 R) was prepared in the same manner as in Example 13 except that a silane compound was used.
Regarding this treatment liquid R, it was confirmed that the methoxysilyl group of the imidazole silane compound was hydrolyzed to the hydroxysilyl group, and an adhesiveness evaluation test similar to that in Example 12 was carried out.
The test results obtained were as shown in Table 4.

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

[Adhesiveness evaluation test (j)]
(1) Metal As the metal, a silver foil plated with silver (thickness: 0.1 to 0.3 μm) was used.
(2) Metal surface treatment The following steps a to b were performed.
I. Acid cleaning (5% sulfuric acid aqueous solution) / 1 minute (room temperature), washing with water b. Brush the surface treatment agent, heat / 5 minutes (100 ° C), methanol wash, water wash, 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 produced.
(4) Evaluation of Adhesiveness A test piece having a width of 10 mm was prepared from this silver-plated copper-clad laminate according to "JIS C6481 (1996)", and the peeling strength of the silver-plated copper foil was measured.

[Example 15]
The adhesiveness evaluation test (j) was carried out using the treatment liquid Q prepared in Example 13. The test results obtained were as shown in Table 5.

[Comparative Example 9]
Using the treatment liquid O prepared in Comparative Example 6, an adhesiveness evaluation test similar to that in Example 13 was carried out. The test results obtained were as shown in Table 5.

According to the present invention, since the adhesiveness (adhesiveness) of the metal, inorganic material and resin material can be sufficiently ensured, 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 miniaturization, thinning, high frequency, high density, etc. of the multilayer printed wiring board, and therefore has great industrial applicability.

Claims (9)

A resin composition containing a resin or a compound before curing thereof and a triazolesilane compound represented by the chemical formula (I) as a silane coupling agent , wherein the resin is an acrylate resin, an epoxy resin, a polyimide resin, a bismaleimide resin, or a maleimide. A resin selected from a resin, a cyanate resin, a polyphenylene ether resin, a polyphenylene oxide resin, an olefin resin, a fluorine-containing resin, a polyetherimide resin, a polyether ether ketone resin, or a liquid crystal resin, and the triazole in the resin composition. A resin composition having a silane compound content of 0.001 to 10% by weight .

(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 are the same or different, and are a methyl group or a different group. Represents an ethyl group. N represents an integer of 1-12, and A and B represent the same or different integers of 0-3.) A solder resist ink composed of the resin composition according to claim 1. A printed wiring board comprising a solder resist formed from the solder resist ink according to claim 2. A prepreg composed of a base material and the resin composition according to claim 1. A copper-clad laminate composed of a copper foil and the prepreg according to claim 4. An interlayer insulating material composed of the resin composition according to claim 1. A copper foil with a resin composed of a copper foil and a resin layer formed of the resin composition according to claim 1. A printed wiring board including a resin layer formed of the resin composition according to claim 1. A semiconductor encapsulating material composed of the resin composition according to claim 1.