JP2016151046A - Surface treatment agent, resin composition, and use of the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a surface treatment agent that can improve adhesiveness between two materials having different quality selected from metal, an inorganic material and a resin material.SOLUTION: A surface treatment agent contains an imidazole silane compound obtained by making a formylimidazole compound react with an aminopropyl silane compound, an imidazole silane compound obtained by making an imidazole compound react with a halopropylsilane compound, or an imidazole silane compound selected from an imidazole silane compound expressed in formula (VI). When the surface treatment agent is used, adhesiveness between two materials having different quality selected from metal, an inorganic material and a resin material, particularly adhesiveness between metal and a resin material can be greatly improved. Further, when a resin composition containing the imidazole silane compound is used, adhesiveness between resin and metal or an inorganic material can be greatly improved.SELECTED DRAWING: None

Description

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

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

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

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

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

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

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

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

  As a result of intensive studies to solve the above problems, the present inventors have selected a material selected from metals, inorganic materials, and resin materials when using a surface treatment agent containing an imidazolesilane compound having a specific structure. It has been found that the adhesion between two materials having different values, particularly the adhesion between a metal and a resin material, can be greatly improved. Moreover, when the resin composition containing the said imidazole silane compound was used, it discovered that the adhesiveness of resin and a metal or an inorganic material could be improved significantly. The present invention has been completed through further studies based on these findings.

［式中、Ｒ¹〜Ｒ³は、同一または異なって、水素原子、炭素数１〜２０のアルキル基、アリル基、ベンジル基またはアリール基を表す。］

［式中、Ｒ¹〜Ｒ³は、前記と同様である。］

［式中、Ｒ⁴〜Ｒ⁶は、同一または異なって、水酸基、炭素数１〜３のアルコキシ基または炭素数１〜３のアルキル基を表す。但し、Ｒ⁴、Ｒ⁵およびＲ⁶が同時にアルキル基である場合を除く。］

［式中、Ｒ⁷〜Ｒ⁹は、同一または異なって、水素原子、炭素数１〜２０のアルキル基、アリル基、ベンジル基またはアリール基を表す。］

［式中、Ｒ¹⁰〜Ｒ¹²は、同一または異なって、水酸基、炭素数１〜３のアルコキシ基または炭素数１〜３のアルキル基を表す。但し、Ｒ¹⁰、Ｒ¹¹およびＲ¹²が同時にアルキル基である場合を除く。Ｘは、フッ素原子、塩素原子、臭素原子または沃素原子を表す。］

［式中、Ｒ¹³〜Ｒ¹⁷は、同一または異なって、水素原子、炭素数１〜２０のアルキル基またはフェニル基を表す。Ｒ¹⁸およびＲ¹⁹は、同一または異なって、水素原子または炭素数１〜３のアルキル基を表す。ｍは１〜３の整数を表す。ｎは０〜５の整数を表す。］
第２の発明は、第１の発明の表面処理剤により処理された銅箔である。
第３の発明は、第１の発明の表面処理剤により処理されたプリプレグである。
第４の発明は、第１の発明の表面処理剤により処理された銅張積層板である。
第５の発明は、第１の発明の表面処理剤により処理された層間絶縁材である。
第６の発明は、銅箔と樹脂層が第１の発明の表面処理剤による皮膜を介して積層された樹脂付銅箔である。
第７の発明は、第１の発明の表面処理剤により処理された部材を備えるプリント配線板である。 That is, the first invention is an imidazolesilane compound obtained by reacting a formylimidazole compound represented by the chemical formula (I) or the chemical formula (II) with an aminopropylsilane compound represented by the chemical formula (III); At least one selected from the group consisting of an imidazolesilane compound obtained by reacting an imidazole compound represented by formula (V) with a halopropylsilane compound represented by formula (V); and an imidazolesilane compound represented by formula (VI) It is a surface treating agent containing the imidazole silane compound.

[Wherein, R ^{1 to} R ³ are the same or different and each represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an allyl group, a benzyl group, or an aryl group. ]

[Wherein, R ^{1 to} R ³ are the same as defined above. ]

[Wherein, R ^{4 to} R ⁶ are the same or different and each represents a hydroxyl group, an alkoxy group having 1 to 3 carbon atoms, or an alkyl group having 1 to 3 carbon atoms. However, the case where R ⁴ , R ⁵ and R ⁶ are simultaneously an alkyl group is excluded. ]

[Wherein, R ^{7 to} R ⁹ are the same or different and each represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an allyl group, a benzyl group, or an aryl group. ]

[In formula, R < ¹⁰ > -R < ¹² > is the same or different and represents a hydroxyl group, a C1-C3 alkoxy group, or a C1-C3 alkyl group. However, the case where R ¹⁰ , R ¹¹ and R ¹² are simultaneously an alkyl group is excluded. X represents a fluorine atom, a chlorine atom, a bromine atom or an iodine atom. ]

[In formula, R < ¹³ > -R < ¹⁷ > is the same or different and represents a hydrogen atom, a C1-C20 alkyl group, or a phenyl group. R ¹⁸ and R ¹⁹ are the same or different and each represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. m represents an integer of 1 to 3. n represents an integer of 0 to 5. ]
The second invention is a copper foil treated with the surface treating agent of the first invention.
The third invention is a prepreg treated with the surface treatment agent of the first invention.
4th invention is the copper clad laminated board processed with the surface treating agent of 1st invention.
5th invention is the interlayer insulation material processed with the surface treating agent of 1st invention.
6th invention is copper foil with a resin with which copper foil and the resin layer were laminated | stacked through the membrane | film | coat by the surface treating agent of 1st invention.
7th invention is a printed wiring board provided with the member processed with the surface treating agent of 1st invention.

［式中、Ｒ¹〜Ｒ³は、同一または異なって、水素原子、炭素数１〜２０のアルキル基、アリル基、ベンジル基またはアリール基を表す。］

［式中、Ｒ¹〜Ｒ³は、前記と同様である。］

［式中、Ｒ⁴〜Ｒ⁶は、同一または異なって、水酸基、炭素数１〜３のアルコキシ基または炭素数１〜３のアルキル基を表す。但し、Ｒ⁴〜Ｒ⁶が同時にアルキル基である場合を除く。］

［式中、Ｒ⁷〜Ｒ⁹は、同一または異なって、水素原子、炭素数１〜２０のアルキル基、アリル基、ベンジル基またはアリール基を表す。］

［式中、Ｒ¹⁰〜Ｒ¹²は、同一または異なって、水酸基、炭素数１〜３のアルコキシ基または炭素数１〜３のアルキル基を表す。但し、Ｒ¹⁰、Ｒ¹¹およびＲ¹²が同時にアルキル基である場合を除く。Ｘは、フッ素原子、塩素原子、臭素原子または沃素原子を表す。］

［式中、Ｒ¹³〜Ｒ¹⁷は、同一または異なって、水素原子、炭素数１〜２０のアルキル基またはフェニル基を表す。Ｒ¹⁸およびＲ¹⁹は、同一または異なって、水素原子または炭素数１〜３のアルキル基を表す。ｍは１〜３の整数を表す。ｎは０〜５の整数を表す。］
第９の発明は、第８の発明の樹脂組成物から構成されたソルダーレジストインクである。
第１０の発明は、第９の発明のソルダーレジストインクから形成されたソルダーレジストを備えるプリント配線板である。
第１１の発明は、基材と第８の発明の樹脂組成物から構成されたプリプレグである。
第１２の発明は、銅箔と第１１の発明のプリプレグから構成された銅張積層板である。
第１３の発明は、第８の発明の樹脂組成物から構成された層間絶縁材である。
第１４の発明は、銅箔と第８の発明の樹脂組成物により形成された樹脂層から構成された樹脂付銅箔である。
第１５の発明は、第８の発明の樹脂組成物により形成された樹脂層を備えるプリント配線板である。
第１６の発明は、第８の発明の樹脂組成物から構成された半導体封止材料である。 The eighth invention relates to an imidazolesilane compound obtained by reacting a formylimidazole compound represented by chemical formula (I) or chemical formula (II) with an aminopropylsilane compound represented by chemical formula (III); At least one imidazole selected from the group consisting of: an imidazole silane compound obtained by reacting an imidazole compound represented by formula (V) with a halopropylsilane compound represented by chemical formula (V); and an imidazole silane compound represented by chemical formula (VI) A resin composition containing a silane compound and a resin or a pre-curing compound thereof.

[Wherein, R ^{1 to} R ³ are the same or different and each represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an allyl group, a benzyl group, or an aryl group. ]

[Wherein, R ^{1 to} R ³ are the same as defined above. ]

[Wherein, R ^{4 to} R ⁶ are the same or different and each represents a hydroxyl group, an alkoxy group having 1 to 3 carbon atoms, or an alkyl group having 1 to 3 carbon atoms. However, the case where R < ⁴ > -R < ⁶ > is an alkyl group simultaneously is remove | excluded. ]

[Wherein, R ^{7 to} R ⁹ are the same or different and each represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an allyl group, a benzyl group, or an aryl group. ]

[In formula, R < ¹⁰ > -R < ¹² > is the same or different and represents a hydroxyl group, a C1-C3 alkoxy group, or a C1-C3 alkyl group. However, the case where R ¹⁰ , R ¹¹ and R ¹² are simultaneously an alkyl group is excluded. X represents a fluorine atom, a chlorine atom, a bromine atom or an iodine atom. ]

[In formula, R < ¹³ > -R < ¹⁷ > is the same or different and represents a hydrogen atom, a C1-C20 alkyl group, or a phenyl group. R ¹⁸ and R ¹⁹ are the same or different and each represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. m represents an integer of 1 to 3. n represents an integer of 0 to 5. ]
9th invention is the soldering resist ink comprised from the resin composition of 8th invention.
10th invention is a printed wiring board provided with the soldering resist formed from the soldering resist ink of 9th invention.
The eleventh invention is a prepreg composed of a base material and the resin composition of the eighth invention.
The twelfth invention is a copper clad laminate comprising a copper foil and the prepreg of the eleventh invention.
The thirteenth invention is an interlayer insulating material composed of the resin composition of the eighth invention.
14th invention is a copper foil with resin comprised from the resin layer formed with the copper foil and the resin composition of 8th invention.
15th invention is a printed wiring board provided with the resin layer formed with the resin composition of 8th invention.
The sixteenth invention is a semiconductor encapsulating material composed of the resin composition of the eighth invention.

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

  Hereinafter, the present invention will be described in detail.

［式中、Ｒ¹〜Ｒ³は、同一または異なって、水素原子、炭素数１〜２０のアルキル基、アリル基、ベンジル基またはアリール基を表す。］

［式中、Ｒ¹〜Ｒ³は、前記と同様である。］

［式中、Ｒ⁴〜Ｒ⁶は、同一または異なって、水酸基、炭素数１〜３のアルコキシ基または炭素数１〜３のアルキル基を表す。但し、Ｒ⁴、Ｒ⁵およびＲ⁶が同時にアルキル基である場合を除く。］

［式中、Ｒ⁷〜Ｒ⁹は、同一または異なって、水素原子、炭素数１〜２０のアルキル基、アリル基、ベンジル基またはアリール基を表す。］

［式中、Ｒ¹⁰〜Ｒ¹²は、同一または異なって、水酸基、炭素数１〜３のアルコキシ基または炭素数１〜３のアルキル基を表す。但し、Ｒ¹⁰、Ｒ¹¹およびＲ¹²が同時にアルキル基である場合を除く。Ｘは、フッ素原子、塩素原子、臭素原子または沃素原子を表す。］

［式中、Ｒ¹³〜Ｒ¹⁷は、同一または異なって、水素原子、炭素数１〜２０のアルキル基またはフェニル基を表す。Ｒ¹⁸およびＲ¹⁹は、同一または異なって、水素原子または炭素数１〜３のアルキル基を表す。ｍは１〜３の整数を表す。ｎは０〜５の整数を表す。］ The surface treating agent of the present invention contains at least one imidazole silane compound selected from the group consisting of the following imidazole silane compound (1), imidazole silane compound (2), and imidazole silane compound (3) as an essential component. It is a surface treatment agent. The resin composition of the present invention includes at least one imidazole silane compound selected from the group consisting of the following imidazole silane compound (1), imidazole silane compound (2), and imidazole silane compound (3), and a resin. Or it is the resin composition which contains the compound before the hardening as an essential component.
Imidazolesilane compound (1): Imidazolesilane compound obtained by reacting a formylimidazole compound represented by chemical formula (I) or chemical formula (II) with an aminopropylsilane compound represented by chemical formula (III) (2): an imidazole silane compound / imidazole silane compound (3) obtained by reacting an imidazole compound represented by chemical formula (IV) with a halopropylsilane compound represented by chemical formula (V): represented by chemical formula (VI) Imidazole silane compounds

[Wherein, R ^{1 to} R ³ are the same or different and each represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an allyl group, a benzyl group, or an aryl group. ]

[Wherein, R ^{1 to} R ³ are the same as defined above. ]

[Wherein, R ^{4 to} R ⁶ are the same or different and each represents a hydroxyl group, an alkoxy group having 1 to 3 carbon atoms, or an alkyl group having 1 to 3 carbon atoms. However, the case where R ⁴ , R ⁵ and R ⁶ are simultaneously an alkyl group is excluded. ]

[Wherein, R ^{7 to} R ⁹ are the same or different and each represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an allyl group, a benzyl group, or an aryl group. ]

[In formula, R < ¹⁰ > -R < ¹² > is the same or different and represents a hydroxyl group, a C1-C3 alkoxy group, or a C1-C3 alkyl group. However, the case where R ¹⁰ , R ¹¹ and R ¹² are simultaneously an alkyl group is excluded. X represents a fluorine atom, a chlorine atom, a bromine atom or an iodine atom. ]

[In formula, R < ¹³ > -R < ¹⁷ > is the same or different and represents a hydrogen atom, a C1-C20 alkyl group, or a phenyl group. R ¹⁸ and R ¹⁹ are the same or different and each represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. m represents an integer of 1 to 3. n represents an integer of 0 to 5. ]

  In the present specification, at least one imidazole silane compound selected from the group consisting of the imidazole silane compound (1), the imidazole silane compound (2), and the imidazole silane compound (3) described above is referred to as “of the present invention. It may be referred to as “imidazolesilane compound”. First, the imidazole silane compound (1), the imidazole silane compound (2), and the imidazole silane compound (3) will be described.

[Imidazolesilane compound (1)]
The steps for synthesizing the imidazole silane compound (1) are shown in Reaction Scheme (A) and Reaction Scheme (B), respectively.

［式中、Ｒ¹〜Ｒ⁶は、前記と同様である。Ｒ²⁰は、炭素数１〜２０のアルキル基、アリル基またはベンジル基を表す。Ｚは、フッ素原子、塩素原子、臭素原子、沃素原子、メシルオキシ基、トシルオキシ基またはトリフロロメチルスルフォニルオキシ基を表す。］

[Wherein, R ^{1 to} R ⁶ are the same as defined above. R ²⁰ represents an alkyl group having 1 to 20 carbon atoms, an allyl group, or a benzyl group. Z represents a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a mesyloxy group, a tosyloxy group or a trifluoromethylsulfonyloxy group. ]

［式中、Ｒ¹〜Ｒ⁶、Ｒ²⁰およびＺは、前記と同様である。］

[Wherein, R ^{1 to} R ⁶ , R ²⁰ and Z are the same as defined above. ]

Reaction scheme (A): By reacting a 2-formylimidazole compound represented by the chemical formula (I) with an aminopropylsilane compound represented by the chemical formula (III), an intermediate represented by the chemical formula (VII) is generated. . Subsequently, by reacting this intermediate with the reducing agent A, an imidazolesilane compound represented by the chemical formula (VIII) is obtained. Further, by reacting an imidazolesilane compound represented by the chemical formula (VIII) with R ²⁰ -Z (for example, an alkylating agent) in the presence of the base A, an imidazolesilane compound represented by the chemical formula (IX) is generated. .
In addition, when the imidazole silane compound represented by the chemical formula (VIII) and the chemical formula (IX) is formed, an oligomer (note: having a siloxane bond (Si-O-Si)) that is a condensate of these imidazole silane compounds is formed. The oligomer is useful as a component of the surface treatment agent and the resin composition, like the imidazole silane compound.
Therefore, in the present invention, the reaction product of the 2-formylimidazole compound represented by the chemical formula (I) and the aminopropylsilane compound represented by the chemical formula (III) is:
(I) a mixture of an imidazolesilane compound represented by the chemical formula (VIII) and an oligomer derived from the compound, or
(B) An imidazolesilane compound represented by the chemical formula (IX), an oligomer derived from the compound, and a chemical formula (VIII) obtained by adding R ²⁰ -Z (for example, an alkylating agent) to the mixture and reacting them. in oligomer and R ²⁰ -Z (e.g., alkylating agents) derived from imidazole silane compound represented refers to a mixture of the reactants with.

Reaction scheme (B): By reacting a 4-formylimidazole compound represented by the chemical formula (II) with an aminopropylsilane compound represented by the chemical formula (III), an intermediate represented by the chemical formula (X) is generated. . Subsequently, by reacting this intermediate with the reducing agent B, an imidazolesilane compound represented by the chemical formula (XI) is obtained. Further, by reacting an imidazolesilane compound represented by the chemical formula (XI) with R ²⁰ -Z (for example, an alkylating agent) in the presence of the base B, an imidazolesilane compound represented by the chemical formula (XII) is generated. .
In addition, when the imidazole silane compound represented by the chemical formula (XI) and the chemical formula (XII) is formed, an oligomer (note: having a siloxane bond (Si-O-Si)) that is a condensate of these imidazole silane compounds is produced. The oligomer is useful as a component of the surface treatment agent and the resin composition, like the imidazole silane compound.
Therefore, in the present invention, the reaction product of the 4-formylimidazole compound represented by the chemical formula (II) and the aminopropylsilane compound represented by the chemical formula (III) is:
(C) a mixture of an imidazolesilane compound represented by the chemical formula (XI) and an oligomer derived from the compound, or
(D) An imidazolesilane compound represented by the chemical formula (XII) obtained by adding R ²⁰ -Z (for example, an alkylating agent) to this mixture and reacting it, an oligomer derived from the compound, and a chemical formula (XI) in oligomer and R ²⁰ -Z (e.g., alkylating agents) derived from imidazole silane compound represented refers to a mixture of the reactants with.

The reaction temperature between the above-mentioned 2-formylimidazole compound or 4-formylimidazole compound (hereinafter sometimes referred to simply as “formylimidazole compound”) and the above-mentioned aminopropylsilane compound is from room temperature to 80 ° C. The reaction time is appropriately determined according to the set reaction temperature, but is preferably in the range of 15 minutes to 2 hours.
Although this reaction proceeds stoichiometrically, the amount of use (formulation amount) of the formylimidazole compound can be set to an appropriate ratio in the range of 0.1 to 10 times mol with respect to the aminopropylsilane compound. .

  In this reaction, as required, methanol, ethanol, propanol, tetrahydrofuran, dioxane, ethyl acetate, acetonitrile, benzene, toluene, xylene, dichloromethane, chloroform, carbon tetrachloride, dimethylformamide, dimethylacetamide, dimethylsulfoxide, An appropriate amount of an appropriate organic solvent selected from hexamethylphosphoric triamide and the like may be used. In addition, the organic solvent used as a reaction solvent may be used individually by 1 type, and may use it combining a solvent from which a kind differs as needed.

The intermediate produced by the reaction of the formylimidazole compound and the aminopropylsilane compound uses 0.001 to 0.5 moles of palladium on carbon as a reduction catalyst relative to the theoretical production amount of the intermediate, It can reduce by making it react. The reaction temperature of the reduction reaction is preferably room temperature to 80 ° C., and the reaction time is appropriately determined according to the set reaction temperature, but is preferably in the range of 1 to 96 hours.
This reduction reaction can also be carried out using sodium borohydride, Raney nickel or the like known as a known reducing agent.
Also in this reaction, the same organic solvent as described above can be used as the reaction solvent.

The imidazolesilane compound represented by the chemical formula (VIII) or the chemical formula (XI) obtained by the reduction reaction and R ²⁰ -Z (for example, an alkylating agent) are converted into a base A or a base B (hereinafter, both are simply referred to as “base”). In the presence of the imidazole silane compound represented by the chemical formula (IX) or (XII).
The R ²⁰ -Z (for example, alkylating agent) can be used in a proportion of 1 to 20 times mol with respect to the starting formylimidazole compound. The reaction temperature of this reaction is preferably room temperature to 150 ° C., and the reaction time is appropriately determined according to the set reaction temperature, but is preferably in the range of 1 to 96 hours.
Also in this reaction, the same organic solvent as described above can be used as a reaction solvent.

As the 2-formylimidazole compound represented by the chemical formula (I),
2-formylimidazole,
4-alkyl-2-formylimidazole,
4-allyl-2-formylimidazole,
4-benzyl-2-formylimidazole,
4-aryl-2-formylimidazole,
4,5-dialkyl-2-formylimidazole,
4,5-diallyl-2-formylimidazole,
4,5-dibenzyl-2-formylimidazole,
4,5-diaryl-2-formylimidazole,
4-alkyl-5-allyl-2-formylimidazole,
4-alkyl-5-benzyl-2-formylimidazole,
4-alkyl-5-aryl-2-formylimidazole,
4-allyl-5-benzyl-2-formylimidazole,
4-allyl-5-aryl-2-formylimidazole,
5-aryl-4-benzyl-2-formylimidazole,
1-alkyl-2-formylimidazole,
1-allyl-2-formylimidazole,
1-benzyl-2-formylimidazole,
1-aryl-2-formylimidazole,
1,4-dialkyl-2-formylimidazole,
1,5-dialkyl-2-formylimidazole,
1-alkyl-4-allyl-2-formylimidazole,
1-alkyl-5-allyl-2-formylimidazole,
1-alkyl-4-benzyl-2-formylimidazole,
1-alkyl-5-benzyl-2-formylimidazole,
1-alkyl-4-aryl-2-formylimidazole,
1-alkyl-5-aryl-2-formylimidazole,
4-alkyl-1-allyl-2-formylimidazole,
5-alkyl-1-allyl-2-formylimidazole,
1,4-diallyl-2-formylimidazole,
1,5-diallyl-2-formylimidazole,
1-allyl-4-benzyl-2-formylimidazole,
1-allyl-5-benzyl-2-formylimidazole,
1-allyl-4-aryl-2-formylimidazole,
1-allyl-5-aryl-2-formylimidazole,
4-alkyl-1-benzyl-2-formylimidazole,
5-alkyl-1-benzyl-2-formylimidazole,
4-allyl-1-benzyl-2-formylimidazole,
5-allyl-1-benzyl-2-formylimidazole,
1,4-dibenzyl-2-formylimidazole,
1,5-dibenzyl-2-formylimidazole,
4-aryl-1-benzyl-2-formylimidazole,
5-aryl-1-benzyl-2-formylimidazole,
4-alkyl-1-aryl-2-formylimidazole,
5-alkyl-1-aryl-2-formylimidazole,
4-allyl-1-aryl-2-formylimidazole,
5-allyl-1-aryl-2-formylimidazole,
1-aryl-4-benzyl-2-formylimidazole,
1-aryl-5-benzyl-2-formylimidazole,
1,4-diaryl-2-formylimidazole,
1,5-diaryl-2-formylimidazole,
1,4,5-trialkyl-2-formylimidazole,
1-alkyl-4,5-diallyl-2-formylimidazole,
1-alkyl-4,5-dibenzyl-2-formylimidazole,
1-alkyl-4,5-diaryl-2-formylimidazole,
1,4-dialkyl-5-allyl-2-formylimidazole,
1,5-dialkyl-4-allyl-2-formylimidazole,
1,4-dialkyl-5-benzyl-2-formylimidazole,
1,5-dialkyl-4-benzyl-2-formylimidazole,
1,4-dialkyl-5-aryl-2-formylimidazole,
1,5-dialkyl-4-aryl-2-formylimidazole,
1-alkyl-4-allyl-5-benzyl-2-formylimidazole,
1-alkyl-5-allyl-4-benzyl-2-formylimidazole,
1-alkyl-4-allyl-5-aryl-2-formylimidazole,
1-alkyl-5-allyl-4-aryl-2-formylimidazole,
1-alkyl-4-aryl-5-benzyl-2-formylimidazole,
1-alkyl-5-aryl-4-benzyl-2-formylimidazole,
4,5-dialkyl-1-allyl-2-formylimidazole,
1,4,5-triallyl-2-formylimidazole,
1-allyl-4,5-dibenzyl-2-formylimidazole,
1-allyl-4,5-diaryl-2-formylimidazole,
5-alkyl-1,4-diallyl-2-formylimidazole,
4-alkyl-1,5-diallyl-2-formylimidazole,
4-alkyl-1-allyl-5-benzyl-2-formylimidazole,
5-alkyl-1-allyl-4-benzyl-2-formylimidazole,
4-alkyl-1-allyl-5-aryl-2-formylimidazole,
5-alkyl-1-allyl-4-aryl-2-formylimidazole,
1,4-diallyl-5-benzyl-2-formylimidazole,
1,5-diallyl-4-benzyl-2-formylimidazole,
1,4-diallyl-5-aryl-2-formylimidazole,
1,5-diallyl-4-aryl-2-formylimidazole,
1-allyl-4-aryl-5-benzyl-2-formylimidazole,
1-allyl-5-aryl-4-benzyl-2-formylimidazole,
4,5-dialkyl-1-benzyl-2-formylimidazole,
4,5-diallyl-1-benzyl-2-formylimidazole,
1,4,5-tribenzyl-2-formylimidazole,
4,5-diaryl-1-benzyl-2-formylimidazole,
4-alkyl-5-allyl-1-benzyl-2-formylimidazole,
5-alkyl-4-allyl-1-benzyl-2-formylimidazole,
4-alkyl-1,5-dibenzyl-2-formylimidazole,
5-alkyl-1,4-dibenzyl-2-formylimidazole,
4-alkyl-5-aryl-1-benzyl-2-formylimidazole,
5-alkyl-4-aryl-1-benzyl-2-formylimidazole,
4-allyl-1,5-dibenzyl-2-formylimidazole,
5-allyl-1,4-dibenzyl-2-formylimidazole,
4-allyl-5-aryl-1-benzyl-2-formylimidazole,
5-allyl-4-aryl-1-benzyl-2-formylimidazole,
4-aryl-1,5-dibenzyl-2-formylimidazole,
5-aryl-1,4-dibenzyl-2-formylimidazole,
4,5-dialkyl-1-aryl-2-formylimidazole,
4,5-diallyl-1-aryl-2-formylimidazole,
1-aryl-4,5-dibenzyl-2-formylimidazole,
1,4,5-triaryl-2-formylimidazole,
4-alkyl-5-allyl-1-aryl-2-formylimidazole,
5-alkyl-4-allyl-1-aryl-2-formylimidazole,
4-alkyl-1-aryl-5-benzyl-2-formylimidazole,
5-alkyl-1-aryl-4-benzyl-2-formylimidazole,
4-alkyl-1,5-diaryl-2-formylimidazole,
5-alkyl-1,4-diaryl-2-formylimidazole,
4-allyl-1-aryl-5-benzyl-2-formylimidazole,
5-allyl-1-aryl-4-benzyl-2-formylimidazole,
4-allyl-1,5-diaryl-2-formylimidazole,
5-allyl-1,4-diaryl-2-formylimidazole,
1,4-diaryl-5-benzyl-2-formylimidazole,
Examples thereof include 1,5-diaryl-4-benzyl-2-formylimidazole.

As the 4-formylimidazole compound represented by the chemical formula (II),
4-formylimidazole,
2-alkyl-4-formylimidazole,
5-alkyl-4-formylimidazole,
2-allyl-4-formylimidazole,
5-allyl-4-formylimidazole,
2-benzyl-4-formylimidazole,
5-benzyl-4-formylimidazole,
2-aryl-4-formylimidazole,
5-aryl-4-formylimidazole,
2,5-dialkyl-4-formylimidazole,
2-alkyl-5-allyl-4-formylimidazole,
5-alkyl-2-allyl-4-formylimidazole,
2-alkyl-5-benzyl-4-formylimidazole,
5-alkyl-2-benzyl-4-formylimidazole,
2-alkyl-5-aryl-4-formylimidazole,
5-alkyl-2-aryl-4-formylimidazole,
2,5-diallyl-4-formylimidazole,
2-allyl-5-benzyl-4-formylimidazole,
5-allyl-2-benzyl-4-formylimidazole,
2-allyl-5-aryl-4-formylimidazole,
5-allyl-2-aryl-4-formylimidazole,
2,5-dibenzyl-4-formylimidazole,
2-aryl-5-benzyl-4-formylimidazole,
5-aryl-2-benzyl-4-formylimidazole,
2,5-diaryl-4-formylimidazole,
1,2,5-trialkyl-4-formylimidazole,
1,2-dialkyl-5-allyl-4-formylimidazole,
1,5-dialkyl-2-allyl-4-formylimidazole,
1,2-dialkyl-5-benzyl-4-formylimidazole,
1,5-dialkyl-2-benzyl-4-formylimidazole,
1,2-dialkyl-5-aryl-4-formylimidazole,
1,5-dialkyl-2-aryl-4-formylimidazole,
1-alkyl-2,5-diallyl-4-formylimidazole,
1-alkyl-2-allyl-5-benzyl-4-formylimidazole,
1-alkyl-5-allyl-2-benzyl-4-formylimidazole,
1-alkyl-2-allyl-5-aryl-4-formylimidazole,
1-alkyl-5-allyl-2-aryl-4-formylimidazole,
1-alkyl-2,5-dibenzyl-4-formylimidazole,
1-alkyl-2-aryl-5-benzyl-4-formylimidazole,
1-alkyl-5-aryl-2-benzyl-4-formylimidazole,
1-alkyl-2,5-diaryl-4-formylimidazole,
2,5-dialkyl-1-allyl-4-formylimidazole,
2-alkyl-1,5-diallyl-4-formylimidazole,
5-alkyl-1,2-diallyl-4-formylimidazole,
2-alkyl-1-allyl-5-benzyl-4-formylimidazole,
5-alkyl-1-allyl-2-benzyl-4-formylimidazole,
2-alkyl-1-allyl-5-aryl-4-formylimidazole,
5-alkyl-1-allyl-2-aryl-4-formylimidazole,
1,2,5-triallyl-4-formylimidazole,
1,2-diallyl-5-benzyl-4-formylimidazole,
1,5-diallyl-2-benzyl-4-formylimidazole,
1,2-diallyl-5-aryl-4-formylimidazole,
1,5-diallyl-2-aryl-4-formylimidazole,
1-allyl-2,5-dibenzyl-4-formylimidazole,
1-allyl-2-aryl-5-benzyl-4-formylimidazole,
1-allyl-5-aryl-2-benzyl-4-formylimidazole,
1-allyl-2,5-diaryl-4-formylimidazole,
2,5-dialkyl-1-benzyl-4-formylimidazole,
2-alkyl-5-allyl-1-benzyl-4-formylimidazole,
5-alkyl-2-allyl-1-benzyl-4-formylimidazole,
2-alkyl-1,5-dibenzyl-4-formylimidazole,
5-alkyl-1,2-dibenzyl-4-formylimidazole,
2-alkyl-5-aryl-1-benzyl-4-formylimidazole,
5-alkyl-2-aryl-1-benzyl-4-formylimidazole,
2,5-diallyl-1-benzyl-4-formylimidazole,
2-allyl-1,5-dibenzyl-4-formylimidazole,
5-allyl-1,2-dibenzyl-4-formylimidazole,
2-allyl-5-aryl-1-benzyl-4-formylimidazole,
5-allyl-2-aryl-1-benzyl-4-formylimidazole,
1,2,5-tribenzyl-4-formylimidazole,
2-aryl-1,5-dibenzyl-4-formylimidazole,
5-aryl-1,2-dibenzyl-4-formylimidazole,
2,5-diaryl-1-benzyl-4-formylimidazole,
2,5-dialkyl-1-aryl-4-formylimidazole,
2-alkyl-5-allyl-1-aryl-4-formylimidazole,
5-alkyl-2-allyl-1-aryl-4-formylimidazole,
2-alkyl-1-aryl-5-benzyl-4-formylimidazole,
5-alkyl-1-aryl-2-benzyl-4-formylimidazole,
2-alkyl-1,5-diaryl-4-formylimidazole,
5-alkyl-1,2-diaryl-4-formylimidazole,
2,5-diallyl-1-aryl-4-formylimidazole,
2-allyl-1-aryl-5-benzyl-4-formylimidazole,
5-allyl-1-aryl-2-benzyl-4-formylimidazole,
2-allyl-1,5-diaryl-4-formylimidazole,
5-allyl-1,2-diaryl-4-formylimidazole,
1-aryl-2,5-dibenzyl-4-formylimidazole,
1,2-diaryl-5-benzyl-4-formylimidazole,
1,5-diaryl-2-benzyl-4-formylimidazole,
Examples thereof include 1,2,5-triaryl-4-formylimidazole.

"Alkyl" appearing in these substance names
Represents a group (alkyl group) such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, icosyl.

In addition, "aryl" appearing in the same substance name is
Phenyl,
1-naphthyl, 2-naphthyl,
2-thienyl, 3-thienyl,
2-benzothienyl, 3-benzothienyl, 4-benzothienyl, 5-benzothienyl, 6-benzothienyl, 7-benzothienyl,
1-pyrrolyl, 2-pyrrolyl, 3-pyrrolyl,
1-in drill, 2-in drill, 3-in drill, 4-in drill, 5-in drill, 6-in drill, 7-in drill,
2-furyl, 3-furyl,
2-benzofuryl, 3-benzofuryl, 4-benzofuryl, 5-benzofuryl, 6-benzofuryl, 7-benzofuryl,
2-pyridyl, 3-pyridyl, 4-pyridyl,
2-quinolyl, 3-quinolyl, 4-quinolyl, 5-quinolyl, 6-quinolyl, 7-quinolyl, 8-quinolyl,
1-isoquinolyl, 3-isoquinolyl, 4-isoquinolyl, 5-isoquinolyl, 6-isoquinolyl, 7-isoquinolyl, 8-isoquinolyl,
1-imidazolyl, 2-imidazolyl, 4-imidazolyl,
1-benzimidazolyl, 2-benzimidazolyl, 4-benzoimidazolyl, 5-benzoimidazolyl, 6-benzimidazolyl, 7-benzimidazolyl,
2-oxazolyl, 4-oxazolyl, 5-oxazolyl,
2-benzoxazolyl, 4-benzoxazolyl, 5-benzoxazolyl, 6-benzoxazolyl, 7-benzoxazolyl,
2-thiazolyl, 4-thiazolyl, 5-thiazolyl,
2-benzothiazolyl, 4-benzothiazolyl, 5-benzothiazolyl, 6-benzothiazolyl, 7-benzothiazolyl,
1-pyrazolyl, 3-pyrazolyl, 4-pyrazolyl, 5-pyrazolyl,
3-isoxazolyl, 4-isoxazolyl, 5-isoxazolyl,
2-pyrazyl,
2-pyrimidyl, 4-pyrimidyl, 5-pyrimidyl,
3-pyridazyl, 4-pyridazyl,
2-triazyl,
2-quinoxalyl, 3-quinoxalyl, 5-quinoxalyl, 6-quinoxalyl,
2-quinazolyl, 4-quinazolyl, 5-quinazolyl, 6-quinazolyl, 7-quinazolyl, 8-quinazolyl,
It represents a group (aryl group) such as 3-cinnolyl, 4-cinnolyl, 5-cinnolyl, 6-cinnolyl, 7-cinnolyl, and 8-cinnolyl, and these aryl groups may be substituted with the aforementioned alkyl group.

As the aminopropylsilane compound represented by the chemical formula (III),
3-aminopropyltrimethoxysilane,
3-aminopropylmethyldimethoxysilane,
3-aminopropyldimethylmethoxysilane,
3-aminopropyltriethoxysilane,
3-aminopropylmethyldiethoxysilane,
3-aminopropyldimethylethoxysilane,
3-aminopropyltripropoxysilane,
3-aminopropylmethyldipropoxysilane,
An example is 3-aminopropyldimethylpropoxysilane.

Examples of R ²⁰ -Z (for example, alkylating agent) include trialkyloxonium tetrafluoroborate, alkyl triflate, dialkyl sulfate, alkyl tosylate, alkyl mesylate, alkyl iodide, alkyl bromide, alkyl chloride, fluorine An alkyl halide can be exemplified.
“Alkyl” appearing in these substance names is the same as the aforementioned alkyl group.

As the base A and the base B, trimethylamine, triethylamine, diisopropylethylamine, diazabicycloundecene, diazabicyclononene, pyridine, lithium hydroxide, sodium hydroxide, potassium hydroxide, cesium hydroxide, Lithium carbonate, sodium carbonate, potassium carbonate, cesium carbonate, lithium bicarbonate, sodium bicarbonate, potassium bicarbonate, cesium bicarbonate, trilithium phosphate, trisodium phosphate, tripotassium phosphate, tricesium phosphate, phosphoric acid Dilithium hydrogen, disodium hydrogen phosphate, dipotassium hydrogen phosphate, dicesium hydrogen phosphate, lithium dihydrogen phosphate, sodium dihydrogen phosphate, potassium dihydrogen phosphate, cesium dihydrogen phosphate, lithium acetate, acetic acid Sodium, potassium acetate, acetic acid It can be exemplified Siumu like.
These are used for the purpose of capturing by-produced hydrogen halide, and the amount of the base used is an appropriate ratio in the range of 1 to 20 times equivalent to R ²⁰ -Z (eg, alkylating agent). It is preferable to do.

As the imidazole silane compound represented by the chemical formula (VIII),
3- (imidazol-2-ylmethylamino) propyltrimethoxysilane,
3- (1-methylimidazol-2-ylmethylamino) propyltrimethoxysilane,
3- (4-methylimidazol-2-ylmethylamino) propyltrimethoxysilane,
3- (4-phenylimidazol-2-ylmethylamino) propyltrimethoxysilane,
3- (imidazol-2-ylmethylamino) propyltriethoxysilane,
Examples thereof include 3- (imidazol-2-ylmethylamino) propyltrihydroxysilane and the like.

As the imidazole silane compound represented by the chemical formula (XI),
3- (imidazol-4-ylmethylamino) propyltrimethoxysilane,
3- (4-methylimidazol-5-ylmethylamino) propyltrimethoxysilane,
3- (2-methylimidazol-4-ylmethylamino) propyltrimethoxysilane,
3- (2-phenyl-4-methylimidazol-5-ylmethylamino) propyltrimethoxysilane,
3- (imidazol-4-ylmethylamino) propyltriethoxysilane,
3- (imidazol-4-ylmethylamino) propyltrihydroxysilane,
3- (4-methylimidazol-5-ylmethylamino) propyltrihydroxysilane,
Examples include 3- (2-phenyl-4-methylimidazol-5-ylmethylamino) propyltrihydroxysilane.

As the imidazole silane compound represented by the chemical formula (IX),
3-[(imidazol-2-ylmethyl) methylamino] propyltrimethoxysilane,
3-[(imidazol-2-ylmethyl) ethylamino] propyltrimethoxysilane,
3-[(1-methylimidazol-2-ylmethyl) methylamino] propyltrimethoxysilane,
3-[(1-methylimidazol-2-ylmethyl) ethylamino] propyltrimethoxysilane,
3-[(4-methylimidazol-2-ylmethyl) methylamino] propyltrimethoxysilane,
3-[(4-methylimidazol-2-ylmethyl) ethylamino] propyltrimethoxysilane,
3-[(4-phenylimidazol-2-ylmethyl) methylamino] propyltrimethoxysilane,
3-[(4-phenylimidazol-2-ylmethyl) ethylamino] propyltrimethoxysilane,
3-[(imidazol-2-ylmethyl) methylamino] propyltriethoxysilane,
3-[(imidazol-2-ylmethyl) ethylamino] propyltriethoxysilane,
3-[(imidazol-2-ylmethyl) methylamino] propyltrihydroxysilane,
3-[(imidazol-2-ylmethyl) ethylamino] propyltrihydroxysilane and the like can be exemplified.

As the imidazole silane compound represented by the chemical formula (XII),
3-[(imidazol-4-ylmethyl) methylamino] propyltrimethoxysilane,
3-[(imidazol-4-ylmethyl) ethylamino] propyltrimethoxysilane,
3-[(4-methylimidazol-5-ylmethyl) methylamino] propyltrimethoxysilane,
3-[(4-methylimidazol-5-ylmethyl) ethylamino] propyltrimethoxysilane,
3-[(2-methylimidazol-4-ylmethyl) methylamino] propyltrimethoxysilane,
3-[(2-methylimidazol-4-ylmethyl) ethylamino] propyltrimethoxysilane,
3-[(2-phenyl-4-methylimidazol-5-ylmethyl) methylamino] propyltrimethoxysilane,
3-[(2-phenyl-4-methylimidazol-5-ylmethyl) ethylamino] propyltrimethoxysilane,
3-[(imidazol-4-ylmethyl) methylamino] propyltriethoxysilane,
3-[(imidazol-4-ylmethyl) ethylamino] propyltriethoxysilane,
3-[(imidazol-4-ylmethyl) methylamino] propyltrihydroxysilane,
3-[(imidazol-4-ylmethyl) ethylamino] propyltrihydroxysilane,
3-[(4-methylimidazol-5-ylmethyl) methylamino] propyltrihydroxysilane,
3-[(4-methylimidazol-5-ylmethyl) ethylamino] propyltrihydroxysilane,
3-[(2-phenyl-4-methylimidazol-5-ylmethyl) methylamino] propyltrihydroxysilane,
Examples include 3-[(2-phenyl-4-methylimidazol-5-ylmethyl) ethylamino] propyltrihydroxysilane and the like.

  The chemical formula (VIII) and chemical formula (IX), the chemical formula (XI) and chemical formula (XII), and these oligomers may be simply referred to as “imidazolesilane compound (1)”.

[Imidazolesilane compound (2)]
The process of synthesizing the imidazole silane compound (2) is shown in the reaction scheme (C).

［式中、Ｒ⁷〜Ｒ¹²およびＸは、前記と同様である。］

[Wherein, R ^{7 to} R ¹² and X are the same as defined above. ]

Reaction scheme (C): an imidazole represented by the chemical formula (XIII) by reacting an imidazole compound represented by the chemical formula (IV) with a halopropylsilane compound represented by the chemical formula (V) in the presence of the base C. A silane compound is produced.
In addition, when the imidazolesilane compound represented by the chemical formula (XIII) is produced, an oligomer (note: having a siloxane bond (Si-O-Si)) is produced as a side reaction product. However, this oligomer is useful as a component of the surface treatment agent and the resin composition, like the imidazolesilane compound.
Therefore, in the present invention, the reaction product of the imidazole compound represented by the chemical formula (IV) and the halopropylsilane compound represented by the chemical formula (V) includes the imidazole silane compound represented by the chemical formula (XIII) and the compound. It refers to a mixture with the derived oligomer.

The reaction temperature between the imidazole compound and the halopropylsilane compound is preferably 50 to 150 ° C., and the reaction time is appropriately determined according to the set reaction temperature. A range of time is preferred.
This reaction proceeds stoichiometrically, but the amount of imidazole compound used (amount charged) can be set to an appropriate ratio in the range of 0.1 to 10 moles relative to the halopropylsilane compound.

The base C is the same as the base described above.
The amount of the base C used is preferably an appropriate ratio in the range of 1 to 20 times equivalent to the halopropylsilane compound.

  Also in this reaction, the same organic solvent as described above can be used as a reaction solvent.

As the imidazole compound represented by the chemical formula (IV),
Imidazole,
2-alkylimidazole,
4-alkylimidazole,
2-allylimidazole,
4-allylimidazole,
2-benzylimidazole,
4-benzylimidazole,
2-arylimidazole,
4-arylimidazole,
2,4-dialkylimidazole,
2-alkyl-4-allylimidazole,
2-alkyl-4-benzylimidazole,
2-alkyl-4-arylimidazole,
2-allyl-4-alkylimidazole,
2,4-diallylimidazole,
2-allyl-4-benzylimidazole,
2-allyl-4-arylimidazole,
2-benzyl-4-alkylimidazole,
2-benzyl-4-allylimidazole,
2,4-dibenzylimidazole,
2-benzyl-4-arylimidazole,
2-aryl-4-alkylimidazole,
2-aryl-4-allylimidazole,
2-aryl-4-benzylimidazole,
2,4-diarylimidazole,
4,5-dialkylimidazole,
4-alkyl-5-allylimidazole,
4-alkyl-5-benzylimidazole,
4-alkyl-5-arylimidazole,
4,5-diallylimidazole,
4-allyl-5-benzylimidazole,
4-allyl-5-arylimidazole,
4,5-dibenzylimidazole,
4-benzyl-5-arylimidazole,
4,5-diarylimidazole,
2,4,5-trialkylimidazole,
2,4-dialkyl-5-allylimidazole,
2,4-dialkyl-5-benzylimidazole,
2,4-dialkyl-5-arylimidazole,
2-alkyl-4,5-diallylimidazole,
2-alkyl-4-allyl-5-benzylimidazole,
2-alkyl-4-allyl-5-arylimidazole,
2-alkyl-4-benzyl-5-allylimidazole,
2-alkyl-4,5-dibenzylimidazole,
2-alkyl-4,5-diarylimidazole,
2-allyl-4,5-dialkylimidazole,
2,5-diallyl-4-alkylimidazole,
2-allyl-4-alkyl-5-benzylimidazole,
2-allyl-4-alkyl-5-arylimidazole,
2,4,5-triallylimidazole,
2,4-diallyl-5-benzylimidazole,
2,4-diallyl-5-arylimidazole,
2-allyl-4,5-dibenzylimidazole,
2-allyl-4-benzyl-5-arylimidazole,
2-allyl-4,5-diarylimidazole,
2-benzyl-4,5-dialkylimidazole,
2-benzyl-4-alkyl-5-allylimidazole,
2,5-dibenzyl-4-alkylimidazole,
2-benzyl-4-alkyl-5-arylimidazole,
2-benzyl-4-allyl-5-alkylimidazole,
2-benzyl-4,5-diallylimidazole,
2,5-dibenzyl-4-allylimidazole,
2-benzyl-4-allyl-5-arylimidazole,
2,4-dibenzyl-5-alkylimidazole,
2,4-dibenzyl-5-allylimidazole,
2,4,5-tribenzylimidazole,
2,4-dibenzyl-5-arylimidazole,
2-benzyl-4-aryl-5-alkylimidazole,
2-benzyl-4-aryl-5-allylimidazole,
2,5-dibenzyl-4-arylimidazole,
2-benzyl-4,5-diarylimidazole,
2-aryl-4,5-dialkylimidazole,
2-aryl-4-alkyl-5-allylimidazole,
2-aryl-4-alkyl-5-benzylimidazole,
2,5-diaryl-4-alkylimidazole,
2-aryl-4-allyl-5-alkylimidazole,
2-aryl-4,5-diallylimidazole,
2-aryl-4-allyl-5-benzylimidazole,
2,5-diaryl-4-allylimidazole,
2-aryl-4-benzyl-5-alkylimidazole,
2-aryl-4-benzyl-5-allylimidazole,
2-aryl-4,5-benzylimidazole,
2,5-diaryl-4-benzylimidazole,
2,4-diaryl-5-alkylimidazole,
2,4-diaryl-5-allylimidazole,
2,4-diaryl-5-benzylimidazole,
Examples include 2,4,5-triarylimidazole.
“Alkyl” and “aryl” appearing in these substance names are the same as the aforementioned alkyl group and aryl group, respectively.

As the halopropylsilane compound represented by the chemical formula (V),
3-chloropropyltrimethoxysilane,
3-chloropropylmethyldimethoxysilane,
3-chloropropyldimethylmethoxysilane,
3-chloropropyltriethoxysilane,
3-chloropropylmethyldiethoxysilane,
3-chloropropyldimethylethoxysilane,
3-chloropropyltripropoxysilane,
3-chloropropylmethyldipropoxysilane,
3-chloropropyldimethylpropoxysilane,
3-bromopropyltrimethoxysilane,
3-bromopropylmethyldimethoxysilane,
3-bromopropyldimethylmethoxysilane,
3-bromopropyltriethoxysilane,
3-bromopropylmethyldiethoxysilane,
3-bromopropyldimethylethoxysilane,
3-bromopropyltripropoxysilane,
3-bromopropylmethyldipropoxysilane,
3-bromopropyldimethylpropoxysilane,
3-iodopropyltrimethoxysilane,
3-iodopropylmethyldimethoxysilane,
3-iodopropyldimethylmethoxysilane,
3-iodopropyltriethoxysilane,
3-iodopropylmethyldiethoxysilane,
3-iodopropyldimethylethoxysilane,
3-iodopropyltripropoxysilane,
3-iodopropylmethyldipropoxysilane,
Examples thereof include 3-iodopropyldimethylpropoxysilane.

As the imidazolesilane compound represented by the chemical formula (XIII),
3- (2-methylimidazol-1-yl) propyltrimethoxysilane,
3- (2-phenylimidazol-1-yl) propyltrimethoxysilane,
3- (2-ethyl-4-methylimidazol-1-yl) propyltrimethoxysilane,
3- (2-undecylimidazol-1-yl) propyltrimethoxysilane,
3- (2-methylimidazol-1-yl) propyltriethoxysilane,
3- (2-methylimidazol-1-yl) propyltrihydroxysilane,
Examples include 3- (2-phenylimidazol-1-yl) propyltrihydroxysilane.

  The imidazole silane compound represented by the above chemical formula (XIII) and the oligomer may be simply referred to as “imidazole silane compound (2)”.

[Imidazolesilane compound (3)]
The steps of synthesizing the imidazole silane compound (3) are shown in Reaction Scheme (D) and Reaction Scheme (E), respectively.

［式中、Ｒ¹³〜Ｒ¹⁹、ｍおよびｎは、前記と同様である。Ｒ²¹は炭素数１〜２０のアルキル基またはフェニル基を表す。］

[Wherein, R ^{13 to} R ¹⁹ , m and n are the same as described above. R ²¹ represents an alkyl group having 1 to 20 carbon atoms or a phenyl group. ]

  Reaction Scheme (D): By reacting an imidazole carbamate compound represented by the chemical formula (XIVa) with a 3-aminopropylsilane compound represented by the chemical formula (XVa), an imidazole silane compound represented by the chemical formula (VI) is generated. To do.

The reaction temperature between the imidazole carbamate compound and the 3-aminopropylsilane compound is preferably 50 to 250 ° C., and the reaction time is appropriately determined according to the set reaction temperature, but 30 minutes to A range of 48 hours is preferred.
This reaction proceeds stoichiometrically, but depending on the conditions such as reaction temperature, reaction time, type and amount of reaction solvent used, reaction scale, etc., the amount of imidazole carbamate compound used (amount charged) was changed to 3-amino It can be set as the appropriate ratio in the range of 0.1-10 times mole with respect to a propylsilane compound.

  Also in this reaction, the same organic solvent as described above can be used as a reaction solvent.

［式中、Ｒ¹³〜Ｒ¹⁶、Ｒ¹⁸、Ｒ¹⁹、ｍおよびｎは、前記と同様である。］

[Wherein, R ^{13 to} R ¹⁶ , R ¹⁸ , R ¹⁹ , m and n are the same as described above. ]

Reaction scheme (E): an imidazole represented by the chemical formula (VI ′) by reacting a 1-aminoalkylimidazole compound represented by the chemical formula (XIVb) with a 3-isocyanatopropylsilane compound represented by the chemical formula (XVb). A silane compound is produced.
The chemical formula (VI ′) is equivalent to the chemical formula (VI) in which R ¹⁷ is specified as a hydrogen atom.

The reaction temperature between the 1-aminoalkylimidazole compound and the 3-isocyanatopropylsilane compound is preferably -20 to 80 ° C., and the reaction time is appropriately determined according to the set reaction temperature. However, the range of 15 minutes to 12 hours is preferable.
This reaction also proceeds stoichiometrically as in the reaction shown in Reaction Scheme (D), but due to the same situation as described above, the amount of 1-aminoalkylimidazole compound used (feed amount) was changed to 3-isocyanate. It can be set as the appropriate ratio in the range of 0.1-10 times mole with respect to a natopropylsilane compound.

  In addition, this reaction may be performed without a solvent, or may be performed using the same solvent as the reaction solvent shown in the reaction scheme (D) as a reaction solvent.

In the chemical formulas appearing in the claims and the specification of the present application, the alkyl group having 1 to 20 carbon atoms that R ^{13 to} R ¹⁷ and R ²¹ can adopt is:
Represents a saturated hydrocarbon group such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, icosyl.

In addition, the alkyl group having 1 to 3 carbon atoms that can be adopted by R ¹⁸ and R ¹⁹ is
Represents a saturated hydrocarbon group such as methyl, ethyl, propyl and the like.

As an imidazole carbamate compound represented by the chemical formula (XIVa),
1-methoxycarbonylaminomethylimidazole,
1- (2-methoxycarbonylaminoethyl) -2-methylimidazole,
1- (2-ethoxycarbonylaminoethyl) -2-methylimidazole,
1- (2-propoxycarbonylaminoethyl) -2-methylimidazole,
1- (2-butoxycarbonylaminoethyl) -2-methylimidazole,
1- (2-phenoxycarbonylaminoethyl) -2-methylimidazole,
1- (3-methoxycarbonylaminopropyl) -2-methylimidazole,
1- (3-ethoxycarbonylaminopropyl) -2-methylimidazole,
1- (3-propoxycarbonylaminopropyl) -2-methylimidazole,
1- (3-butoxycarbonylaminopropyl) -2-methylimidazole,
1- (3-phenoxycarbonylaminopropyl) -2-methylimidazole,
1- (2-methoxycarbonylaminoethyl) -2-phenylimidazole,
1- (3-methoxycarbonylaminopropyl) -2-phenylimidazole,
1- (3-methoxycarbonylaminopropyl) -2-ethyl-4-methylimidazole,
1- (3-methoxycarbonylaminopropyl) -2-phenyl-4-methylimidazole,
1- (3-methoxycarbonylaminopropyl) -2-undecylimidazole and the like can be mentioned.

As the 3-aminopropylsilane compound represented by the chemical formula (XVa),
3-aminopropyltrimethoxysilane,
3-aminopropyltriethoxysilane,
3-aminopropyltripropoxysilane,
N-methyl-3-aminopropyltrimethoxysilane,
N-phenyl-3-aminopropyltrimethoxysilane,
3-aminopropyldimethoxymethylsilane,
Examples include 3-aminopropylmethoxydimethylsilane.

As the 1-aminoalkylimidazole compound represented by the chemical formula (XIVb),
1- (2-aminoethyl) imidazole,
1- (3-aminopropyl) imidazole,
1- (2-aminoethyl) -2-methylimidazole,
1- (3-aminopropyl) -2-methylimidazole,
1- (2-aminoethyl) -2-phenylimidazole,
1- (3-aminopropyl) -2-phenylimidazole,
1- (3-aminopropyl) -2-undecylimidazole,
1- (3-aminopropyl) -2-ethyl-4-methylimidazole,
Examples include 1- [2- (methylamino) ethyl] -2-phenylimidazole.

As the 3-isocyanatopropylsilane compound represented by the chemical formula (XVb),
3-isocyanatopropyltrimethoxysilane,
3-isocyanatopropyltriethoxysilane,
3-isocyanatopropyl tripropoxysilane,
3-isocyanatopropyldimethoxymethylsilane,
3-isocyanatopropylmethoxydimethylsilane etc. are mentioned.

As an imidazole silane compound represented by the chemical formula (VI),
1- [3- (imidazol-1-yl) propyl] -3- [3- (trimethoxysilyl) propyl] urea,
1- [2- (2-methylimidazol-1-yl) ethyl] -3- [3- (trimethoxysilyl) propyl] urea,
1- [3- (2-methylimidazol-1-yl) propyl] -3- [3- (trimethoxysilyl) propyl] urea,
1- [2- (2-methylimidazol-1-yl) ethyl] -3- [3- (triethoxysilyl) propyl] urea,
1- [3- (2-methylimidazol-1-yl) propyl] -3- [3- (triethoxysilyl) propyl] urea,
1- [2- (2-methylimidazol-1-yl) ethyl] -3- [3- (dimethoxymethylsilyl) propyl] urea,
1- [2- (2-methylimidazol-1-yl) ethyl] -1-methyl-3- [3- (trimethoxysilyl) propyl] urea,
1- [2- (2-methylimidazol-1-yl) ethyl] -3-phenyl-3- [3- (trimethoxysilyl) propyl] urea,
1- [2- (2-ethyl-4-methylimidazol-1-yl) ethyl] -3- [3- (trimethoxysilyl) propyl] urea,
1- [3- (2-ethyl-4-methylimidazol-1-yl) propyl] -3- [3- (trimethoxysilyl) propyl] urea,
1- [2- (2-undecylimidazol-1-yl) ethyl] -3- [3- (trimethoxysilyl) propyl] urea,
1- [3- (2-undecylimidazol-1-yl) propyl] -3- [3- (trimethoxysilyl) propyl] urea,
1- [2- (2-phenylimidazol-1-yl) ethyl] -3- [3- (trimethoxysilyl) propyl] urea,
1- [3- (2-phenylimidazol-1-yl) propyl] -3- [3- (trimethoxysilyl) propyl] urea,
Examples include 1- [2- (2-phenylimidazol-1-yl) ethyl] -1-methyl-3- [3- (trimethoxysilyl) propyl] urea.

(Surface treatment agent)
The surface treating agent of the present invention contains the imidazole silane compound of the present invention as an essential component. The surface treating agent of the present invention may contain a solvent together with the imidazolesilane compound of the present invention. Examples of the solvent include water, an organic solvent, and a mixed liquid of water and an organic solvent. The surface treating agent in this case can be prepared by mixing the imidazolesilane compound of the present invention and a solvent using an appropriate mixing means. The surface treatment agent may be referred to as a treatment liquid.

  The organic solvent is not particularly limited as long as it acts as a solubilizing agent, and may be used without limitation, for example, methanol, ethanol, propanol, 2-propanol, butanol, tert-butyl alcohol. , Ethylene glycol, propylene glycol, glycerin, diethylene glycol, triethylene glycol, ethylene glycol monomethyl ether, ethylene glycol dimethyl ether, ethylene glycol monoethyl ether, ethylene glycol diethyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether , Propylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene Glycol dimethyl ether, diethylene glycol monoethyl ether, diethylene glycol diethyl ether, diethylene glycol monobutyl ether, triethylene glycol dimethyl ether, triethylene glycol diethyl ether, tetrahydrofurfuryl alcohol, furfuryl alcohol, acetone, tetrahydrofuran, dioxane, acetonitrile, 2-pyrrolidone, formamide, N, N-dimethylformamide, N, N-dimethylacetamide, dimethyl sulfoxide, sulfolane, dimethyl carbonate, ethylene carbonate, N-methylpyrrolidone, γ-butyrolactone, 1,3-dimethyl-2-imidazolidinone, formic acid, acetic acid, Propionic acid, butyric acid, glycolic acid, lactic acid, gluconic acid, glyceric acid, malon Acid, succinic acid, levulinic acid, phenol, benzoic acid, oxalic acid, tartaric acid, malic acid, methylamine, dimethylamine, trimethylamine, ethylamine, diethylamine, triethylamine, propylamine, isopropylamine, butylamine, allylamine, ethylenediamine, diethylenetriamine, tri Ethylenetetramine, monoethanolamine, diethanolamine, triethanolamine, dipropanolamine, tripropanolamine, diisopropanolamine, triisopropanolamine, 1-amino-2-propanol, 3-amino-1-propanol, 2-amino-1 -Propanol, N, N-dimethylethanolamine, cyclohexylamine, aniline, pyrrolidine, piperidine, piperazine, pyridine Masui. One of these organic solvents (solubilizing agents) may be used alone, or two or more thereof may be used in combination. When a solid solubilizer is used, it is used in combination with water and / or a liquid solubilizer.

  When using a mixed solution of water and an organic solvent as a solvent, the surface treatment agent may be prepared by adding the organic solvent after mixing the imidazolesilane compound of the present invention and water, or with the imidazolesilane compound of the present invention. A mixed solution of water and an organic solvent may be mixed, or water may be added after mixing the imidazolesilane compound of the present invention and the organic solvent. Moreover, as water used for preparation of a surface treating agent, pure water, such as ion-exchange water and distilled water, is preferable.

The concentration of the imidazolesilane compound (total amount) of the present invention in the surface treatment agent of the present invention is preferably in the range of 0.001 to 20% by weight.
When the concentration of the imidazolesilane compound is less than 0.001% by weight, there is a possibility that the effect of improving the adhesiveness may not be sufficiently obtained. When the concentration exceeds 20% by weight, the effect of improving the adhesiveness is almost flattened, It is not economical because only the amount of imidazolesilane compound used is increased.

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

  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 ions and bromine ions and metal ions such as copper ions, iron ions, and zinc ions is used. You can also.

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

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

  In addition to the above, the surface treatment agent of the present invention may contain an appropriate additive depending on the type of the material to be treated (described later), the 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, fiber-like, thin-film-like, plate-like, and amorphous ones formed from metals, inorganic materials, resin materials, and the like. It is done.

Examples of the metal include copper, aluminum, titanium, nickel, tin, iron, silver, gold, and alloys thereof. As a specific example of the alloy, a copper alloy is not particularly limited as long as it is an alloy containing copper. For example, Cu-Ag, Cu-Te, Cu-Mg, Cu-Sn, and Cu-Si Cu-Mn, Cu-Be-Co, Cu-Ti, Cu-Ni-Si, Cu-Zn-Ni, Cu-Cr, Cu-Zr, Cu-Fe, Cu-Al Alloy of Cu type, Cu-Zn type, Cu-Co type and the like. Other alloys include aluminum alloy (Al—Si alloy), nickel alloy (Ni—Cr alloy), iron alloy (Fe—Ni alloy, stainless steel) and the like. Of these metals, copper and copper alloys are preferred.
Moreover, as a metal aspect, the foil (for example, electrolytic copper foil, rolled copper foil), plating film (for example, electroless copper plating film) used for electronic devices, such as a printed wiring board and a lead frame, decorations, and building materials , Electrolytic copper plating film), thin films formed by vapor deposition, sputtering, damascene, etc., and those used in applications and forms such as granular, needle-like, fiber-like, linear, rod-like, tubular, plate-like Can be mentioned. In the case of copper wiring through which a high-frequency electric signal flows in recent years, the copper surface is preferably a smooth surface having an average roughness of 0.1 μm or less. As a pretreatment, the surface of copper may be plated with nickel, zinc, chromium, tin or the like.

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

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

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

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

  Before bringing the surface treatment agent of the present invention into contact with the metal surface, an aqueous solution containing copper ions may be brought into contact with the metal surface. This aqueous solution containing copper ions has a function of making the thickness of the chemical conversion film formed on the surface of the metal uniform. The copper ion source of the aqueous solution containing copper ions is not particularly limited as long as it is a copper salt that dissolves in water, and examples thereof include copper salts such as copper sulfate, copper nitrate, copper chloride, copper formate, and copper acetate. In order to solubilize the copper salt in water, ammonia or hydrochloric acid may be added. Moreover, after making the surface treating agent of this invention contact the surface of a metal, you may make acidic surface or alkaline aqueous solution contact the surface of the said metal. 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 uniform, similarly to the aqueous solution containing copper ions. The acidic aqueous solution and the alkaline aqueous solution are not particularly limited. Examples of the acidic aqueous solution include an aqueous solution containing a mineral acid such as sulfuric acid, nitric acid and hydrochloric acid, and an aqueous solution containing an organic acid such as formic acid, acetic acid, lactic acid, glycolic acid and amino acid. Can be mentioned. Examples of the alkaline aqueous solution include aqueous solutions containing hydroxides of alkali metals such as sodium hydroxide and potassium hydroxide, amines such as ammonia, ethanolamine and monopropanolamine.

  The surface treating agent of the present invention can be used for treating the surface of at least one material to be treated selected from the metals, inorganic materials, and resin materials. By treating the surface of the material to be treated with the surface treatment agent of the present invention, a film can be formed on the surface of the material to be treated, and the adhesion to other materials can be improved. This film has high heat resistance, and for example, the adhesive force is maintained even by solder reflow heating (about 260 ° C.). In order to enhance the effect of this treatment, the surface-treated material may be heat-treated.

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

  As a bonding method, a known method can be adopted. A coating is formed by bringing the surface treatment agent of the present invention into contact with the surface of a material to be treated selected from metals, inorganic materials, or resin materials, and another material to be treated is applied and pressure-bonded to part or all of the formed film. And means such as mixing, use of an adhesive, an adhesive sheet (film), or a combination of these means.

  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 films on the surfaces of the two materials to be treated, respectively. Examples thereof include means for applying a treatment material, pressure bonding, mixing, and the like, use of an adhesive, an adhesive sheet (film), or a combination of these means.

(Use of surface treatment agent)
By using the surface treating agent of the present invention, it is possible to bond two materials as described above, particularly two different materials, so that it can be used for electric / electronic applications (such as various electric / electronic parts and printed wiring boards). It can be suitably used for electronic devices), architectural applications, civil engineering applications, automobile applications, medical material applications, and the like.

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

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

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

  The washing method is not particularly limited, but immersion of the copper wiring layer in the washing water or spraying on the surface of the copper wiring layer with the washing water is preferable because it is simple and reliable. For the formation of the insulating resin layer, a known method such as a method of attaching a semi-cured resin material or a means of applying a liquid resin material containing a solvent can be employed. Next, a via hole is formed to connect the upper and lower wirings. A multilayer printed wiring board can be manufactured by repeating this process.

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

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

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

(Resin composition)
The resin composition of the present invention contains the imidazole silane compound of the present invention and a resin or a compound before curing as essential components.

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

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

  The content (total amount) of the imidazolesilane compound of the present invention in the resin composition of the present invention is preferably 0.001 to 10% by weight, and more preferably 0.01 to 5% by weight. When the content of the imidazolesilane compound of the present invention is less than 0.001% by weight in the resin composition, the effect of improving the adhesiveness is not sufficient, and when the content exceeds 10% by weight, the adhesiveness The improvement effect is almost flat, and the amount of the imidazolesilane compound of the present invention is increased, which is not economical.

  In addition to the resin or its pre-curing compound and the imidazolesilane compound of the present invention, the resin composition includes a solvent (water, an organic solvent, a mixture of water and an organic solvent), an additive (curing) An appropriate amount of an agent, a curing accelerator, a flame retardant, a dye, a pigment, an ultraviolet absorber, a lubricant, a filler, and the like). As the organic solvent, those exemplified as the aforementioned organic solvent (solubilizing agent) can be used.

  The resin composition can be prepared by a known method. For example, the resin composition can be prepared by dissolving the imidazolesilane compound of the present invention in an organic solvent and mixing it in a solid or liquid resin material. Further, the resin composition may be prepared by directly adding and mixing the imidazolesilane compound of the present invention to a liquid resin material.

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

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

  The solder resist is formed by applying a solder resist ink made of the resin composition of the present invention containing the imidazolesilane compound of the present invention and a pre-curing compound (curable compound) on an appropriate substrate and drying it. It can be obtained by curing the conductive resin layer using heat or active energy rays. The printed wiring board can be manufactured by a known method using the solder resist ink. The prepreg can be produced, for example, by applying the resin composition of the present invention to a substrate (paper, glass cloth, glass nonwoven fabric, etc.), or immersing and impregnating the substrate in the resin composition. The said copper clad laminated board can be manufactured by laminating | stacking the said prepreg and copper foil. The interlayer insulating material can be produced by applying the resin composition of the present invention on a suitable substrate and drying, semi-curing or curing. The copper foil with resin can be produced by applying the resin composition of the present invention on a copper foil and drying, semi-curing or curing. In the printed wiring board, the “resin layer formed of the resin composition of the present invention” includes various types of resin other than the solder resist, the prepreg, the interlayer insulating material, and the resin-coated copper foil. The resin composition of the present invention can be used as a semiconductor sealing material.

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

EXAMPLES Hereinafter, although an Example and a comparative example demonstrate this invention concretely, this invention is not limited to these. In addition, the synthesis example of the imidazole silane compound used in the Example is shown in Reference Examples 1-13. The main raw materials used for these syntheses are as follows.
2-formylimidazole: manufactured by Shikoku Kasei Kogyo Co., Ltd. 3-aminopropyltrimethoxysilane: manufactured by Wako Pure Chemical Industries, Ltd. Synthesized in compliance.
・ 2-Phenyl-4-methyl-5-formylimidazole: Same as above ・ 2-Methylimidazole: Shikoku Kasei Kogyo Co., Ltd. ・ 3-Chloropropyltrimethoxysilane: Tokyo Kasei Kogyo Co., Ltd. ・ 2-Phenylimidazole: Shikoku Kasei Kogyo Co., Ltd. 1- (3-aminopropyl) imidazole manufactured by Tokyo Chemical Industry Co., Ltd. And synthesized.
1- (3-aminopropyl) -2-methylimidazole: synthesized according to the method described in “JP 2010-126464 A”.
1- (3-aminopropyl) -2-ethyl-4-methylimidazole: same as above 1- (3-aminopropyl) -2-undecylimidazole: same as above 1- (2-aminoethyl) -2-phenyl Imidazole: Same as above. 1- (3-Aminopropyl) -2-phenylimidazole: Same as above. 1- [2- (Methylamino) ethyl] -2-phenylimidazole: As described in “International Publication No. 2005/123066 pamphlet” Synthesized according to the method.
・ 3-isocyanatopropyltrimethoxysilane: manufactured by Momentive

[Reference Example 1]
<Synthesis of an imidazolesilane compound (abbreviated as “IMZ · S-1”) using 2-formylimidazole and 3-aminopropyltrimethoxysilane as raw materials>
To 100 ml of methanol, 8.96 g (50.0 mmol) of 3-aminopropyltrimethoxysilane and 4.80 g (50.0 mmol) of 2-formylimidazole were added to prepare a reaction solution. Reacted for hours.
Subsequently, this reaction solution was ice-cooled, 0.76 g (20.0 mmol) of sodium borohydride was added, and the mixture was reacted at room temperature for 1 hour.
Next, the reaction solution was concentrated, 100 ml of water was added, water was removed by decantation, and the volatile matter was distilled off to obtain 10.71 g of a yellow viscous material. Since the obtained viscous body is completely dissolved in a solvent such as methanol, it is recognized that the viscous body is not gelled.

^{From the 1} H-NMR spectrum data and the IR spectrum data, the obtained viscous material was obtained from an imidazole silane compound represented by the chemical formula (XVI) and an imidazole silane compound represented by the chemical formulas (XVI-1) to (XVI-3). Is estimated to be a mixture of

  The imidazole silane compounds represented by the chemical formulas (XVI-1) to (XVI-3) were by-produced due to the dehydration condensation of silanol (Si-OH) of the imidazole silane compounds represented by the chemical formula (XVI). Although it is an oligomer having a siloxane bond (Si—O—Si), it is useful as a component of a surface treatment agent and a resin composition in the same manner as the imidazolesilane compound represented by the chemical formula (XVI).

[Reference Example 2]
<Synthesis of an imidazolesilane compound (abbreviated as “IMZ · S-2”) using 4-methyl-5-formylimidazole and 3-aminopropyltrimethoxysilane as raw materials>
A yellow viscous material was obtained in the same manner as in Reference Example 1, except that 4-methyl-5-formylimidazole was used instead of 2-formylimidazole. Since the obtained viscous body is completely dissolved in a solvent such as methanol, it is recognized that the viscous body is not gelled.
Further, from the ¹ H-NMR spectrum data and the IR spectrum data, the obtained viscous material was obtained from the imidazole silane compound represented by the chemical formula (XVII) and the imidazole silane represented by the chemical formulas (XVII-1) to (XVII-3). Presumed to be a mixture with the compound.

  The imidazole silane compounds represented by the chemical formulas (XVII-1) to (XVII-3) were by-produced due to the dehydration condensation of silanol (Si-OH) of the imidazole silane compounds represented by the chemical formula (XVII). Although it is an oligomer having a siloxane bond (Si—O—Si), it is useful as a component of a surface treatment agent and a resin composition in the same manner as the imidazolesilane compound represented by the chemical formula (XVII).

[Reference Example 3]
<Synthesis of an imidazolesilane compound (abbreviated as “IMZ · S-3”) using 2-phenyl-4-methyl-5-formylimidazole and 3-aminopropyltrimethoxysilane as raw materials>
A light yellow solid was obtained in the same manner as in Reference Example 1 except that 2-phenyl-4-methyl-5-formylimidazole was used instead of 2-formylimidazole. Since the obtained solid is completely dissolved in a solvent such as methanol, it is recognized that it is not gelled.
Further, from the ¹ H-NMR spectrum data and IR spectrum data, the obtained solid was obtained from an imidazole silane compound represented by chemical formula (XVIII) and an imidazole silane compound represented by chemical formulas (XVIII-1) to (XVIII-3). It is estimated that

  The imidazole silane compounds represented by the chemical formulas (XVIII-1) to (XVIII-3) were by-produced due to the dehydration condensation of silanol (Si-OH) of the imidazole silane compounds represented by the chemical formula (XVIII). Although it is an oligomer having a siloxane bond (Si—O—Si), it is useful as a component of a surface treatment agent and a resin composition in the same manner as the imidazolesilane compound represented by the chemical formula (XVIII).

[Reference Example 4]
<Synthesis of an imidazolesilane compound (abbreviated as “IMZ · S-4”) using 2-methylimidazole and 3-chloropropyltrimethoxysilane as raw materials>
4.93 g (60.0 mmol) of 2-methylimidazole, 3.24 g (60.0 mmol) of sodium methoxide and 11.92 g (60.0 mmol) of 3-chloropropyltrimethoxysilane were mixed and stirred at 120 ° C. for 5 hours. Reacted.
The reaction mixture was added to 120 ml of water and stirred at room temperature for 1 hour. The water was removed by decantation, and volatile components were distilled off to obtain 10.64 g of a brown solid. Since the obtained solid is completely dissolved in a solvent such as methanol, it is recognized that it is not gelled.
Further, from the ¹ H-NMR spectrum data and IR spectrum data, the obtained solid was obtained from the following formula: It is estimated that

  The imidazole silane compounds represented by the chemical formulas (XIX-1) to (XIX-3) were by-produced due to the dehydration condensation of silanol (Si-OH) of the imidazole silane compounds represented by the chemical formula (XIX). Although it is an oligomer having a siloxane bond (Si—O—Si), it is useful as a component of a surface treatment agent and a resin composition in the same manner as the imidazolesilane compound represented by the chemical formula (XIX).

[Reference Example 5]
<Synthesis of an imidazolesilane compound (abbreviated as “IMZ · S-5”) using 2-phenylimidazole and 3-chloropropyltrimethoxysilane as raw materials>
A light brown solid was obtained in the same manner as in Reference Example 4 except that 2-phenylimidazole was used instead of 2-methylimidazole. Since the obtained solid is completely dissolved in a solvent such as methanol, it is recognized that it is not gelled.
Further, from the ¹ H-NMR spectrum data and the IR spectrum data, the obtained solid was obtained from the imidazole silane compound represented by the chemical formula (XX) and the imidazole silane compound represented by the chemical formulas (XX-1) to (XX-3). It is estimated that

  The imidazole silane compounds represented by the chemical formulas (XX-1) to (XX-3) were by-produced due to the dehydration condensation of silanol (Si-OH) of the imidazole silane compound represented by the chemical formula (XX). Although it is an oligomer having a siloxane bond (Si—O—Si), it is useful as a component of a surface treatment agent and a resin composition, like the imidazolesilane compound represented by the chemical formula (XX).

[Reference Example 6]
<Synthesis of 1- [3- (imidazol-1-yl) propyl] -3- [3- (trimethoxysilyl) propyl] urea (abbreviated as “IMZ · S-6”)>
1.26 g (10.0 mmol) of 1- (3-aminopropyl) imidazole was dissolved in 20 ml of toluene, and 2.06 g (10.0 mmol) of 3-isocyanatopropyltrimethoxysilane was added dropwise while keeping the temperature at 40 ° C. or lower. .
Next, the reaction solution was stirred at room temperature for 1 hour, and then the volatile matter was distilled off to obtain 3.31 g (10.0 mmol) of the title imidazolesilane compound represented by the chemical formula (XXI) as a pale yellow viscous liquid. Yield: 100%).

[Reference Example 7]
<Synthesis of 1- [2- (2-methylimidazol-1-yl) ethyl] -3- [3- (trimethoxysilyl) propyl] urea (abbreviated as “IMZ · S-7”)>
The same operation as in Reference Example 6 was performed except that 1.26 g (10.0 mmol) of 1- (2-aminoethyl) -2-methylimidazole was used instead of 1- (3-aminopropyl) imidazole. As a pale yellow viscous liquid, 3.31 g (10.0 mmol, yield: 100%) of the title imidazolesilane compound represented by the chemical formula (XXII) was obtained.

[Reference Example 8]
<Synthesis of 1- [3- (2-methylimidazol-1-yl) propyl] -3- [3- (trimethoxysilyl) propyl] urea (abbreviated as “IMZ · S-8”)>
The same operation as in Reference Example 6 was performed except that 1.40 g (10.0 mmol) of 1- (3-aminopropyl) -2-methylimidazole was used instead of 1- (3-aminopropyl) imidazole. As a pale yellow viscous liquid, 3.45 g (10.0 mmol, yield: 100%) of the title imidazolesilane compound represented by the chemical formula (XXIII) was obtained.

[Reference Example 9]
Synthesis of <1- [3- (2-ethyl-4-methylimidazol-1-yl) propyl] -3- [3- (trimethoxysilyl) propyl] urea (abbreviated as “IMZ · S-9”) >
The same as Reference Example 6 except that 1.68 g (10.0 mmol) of 1- (3-aminopropyl) -2-ethyl-4-methylimidazole was used instead of 1- (3-aminopropyl) imidazole. The operation was performed to obtain 3.73 g (10.0 mmol, yield: 100%) of the title imidazolesilane compound represented by the chemical formula (XXIV) as a pale yellow viscous liquid.

[Reference Example 10]
<Synthesis of 1- [3- (2-undecylimidazol-1-yl) propyl] -3- [3- (trimethoxysilyl) propyl] urea (abbreviated as “IMZ · S-10”)>
The same operation as in Reference Example 6 was performed except that 2.80 g (10.0 mmol) of 1- (3-aminopropyl) -2-undecylimidazole was used instead of 1- (3-aminopropyl) imidazole. As a pale yellow viscous liquid, 4.85 g (10.0 mmol, yield: 100%) of the title imidazolesilane compound represented by the chemical formula (XXV) was obtained.

[Reference Example 11]
<Synthesis of 1- [2- (2-phenylimidazol-1-yl) ethyl] -3- [3- (trimethoxysilyl) propyl] urea (abbreviated as “IMZ · S-11”)>
The same operation as in Reference Example 6 was performed except that 1.88 g (10.0 mmol) of 1- (2-aminoethyl) -2-phenylimidazole was used instead of 1- (3-aminopropyl) imidazole. As a pale yellow viscous liquid, 3.93 g (10.0 mmol, yield: 100%) of the title imidazolesilane compound represented by the chemical formula (XXVI) was obtained.

[Reference Example 12]
<Synthesis of 1- [3- (2-phenylimidazol-1-yl) propyl] -3- [3- (trimethoxysilyl) propyl] urea (abbreviated as “IMZ · S-12”)>
The same operation as in Reference Example 6 was performed except that 2.02 g (10.0 mmol) of 1- (3-aminopropyl) -2-phenylimidazole was used instead of 1- (3-aminopropyl) imidazole. As a pale yellow viscous liquid, 4.07 g (10.0 mmol, yield: 100%) of the title imidazolesilane compound represented by the chemical formula (XXVII) was obtained.

[Reference Example 13]
Synthesis of <1- [2- (2-phenylimidazol-1-yl) ethyl] -1-methyl-3- [3- (trimethoxysilyl) propyl] urea (abbreviated as “IMZ · S-13”) >
The same operation as in Reference Example 6 except that 2.01 g (10.0 mmol) of 1- [2- (methylamino) ethyl] -2-phenylimidazole was used instead of 1- (3-aminopropyl) imidazole. As a pale yellow viscous liquid, 4.07 g (10.0 mmol, yield: 100%) of the title imidazolesilane compound represented by the chemical formula (XXVIII) was obtained.

The imidazole silane compounds used in the comparative examples and the known silane coupling agents used in the examples and comparative examples are as follows.
A mixture of imidazole silane compounds represented by chemical formulas (XXIX-1) to (XXIX-3): synthesized according to the method described in “JP-A-5-186479”. Hereinafter, it is abbreviated as “IMZ · S-14”.
3-glycidoxypropyltrimethoxysilane: manufactured by Shin-Etsu Chemical Co., Ltd., trade name “KBM-403”, hereinafter abbreviated as “epoxysilane”.
3-Aminopropyltrimethoxysilane: manufactured by Shin-Etsu Chemical Co., Ltd., trade name “KBM-903”, hereinafter abbreviated as “aminosilane”.
3-mercaptopropyltrimethoxysilane: manufactured by Shin-Etsu Chemical Co., Ltd., trade name “KBM-803”, hereinafter abbreviated as “mercaptosilane”.

Main raw materials other than the imidazole silane compound and the silane coupling agent used in Examples and Comparative Examples are as follows.
・ Phenol novolac resin (manufactured by DIC, trade name “TD-2131”)
・ Orthocresol novolac epoxy resin (manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., trade name “YDCN-704”)
2-ethyl-4-methylimidazole (manufactured by Shikoku Kasei Kogyo Co., Ltd., trade name “2E4MZ”, hereinafter abbreviated as “2E4MZ”)
Brominated bisphenol A type epoxy resin (Mitsubishi Chemical Corporation, trade name “jER5046B80”)
・ Biphenyl type epoxy resin (Mitsubishi Chemical Corporation, trade name “YX4000”)
・ Phenolic resin (Sumitomo Bakelite)
・ Silicone powder (trade name “MSP-150 (M)”, manufactured by Nikko Rica)
・ Triphenylphosphine (Wako Pure Chemical Industries, Ltd.)
・ Carnauba wax (manufactured by Toa Kasei)
・ Carbon black (Mitsubishi Chemical Corporation)
・ Filler (manufactured by Tatsumori Co., Ltd., trade name “MSR-25”, fused silica)

  The adhesion test methods employed in the examples and comparative examples are as follows.

[Adhesion test (I)]
Brass was plated on a mat surface of a 25 cm × 25 cm electrolytic copper foil (thickness: 33 μm), and then zinc or a mixture of zinc oxide and chromium oxide was plated and used as a test piece. Next, the test piece was immersed in a surface treatment agent, taken out, drained, and then dried in a dryer at 100 ° C. for 5 minutes. And the mat | matte surface of this test piece was adhere | attached on the base material which impregnated the epoxy resin to the glass fiber cloth, and the normal peel strength was measured based on "JIS C6481".

[Adhesion test (b)]
(1) Base material of test piece As a base material of the test piece, an electrolytic copper foil (thickness: 18 μm) was used.
(2) Processing of base material It carried out according to the following processes ac.
a. Acid clean / 1 minute (room temperature), water wash b. Acid cleaning / 1 minute (room temperature), water washing, drying / 1 minute (100 ° C)
c. Immersion in surface treatment agent / 1 minute (room temperature), water washing, drying / 1 minute (100 ° C.)
(3) Adhesion of base material and resin A printed wiring board is obtained by laminating and pressing a glass cloth epoxy resin-impregnated prepreg (FR-4 grade) on the S surface (shiny surface) of the treated base material. It was created.
(4) Evaluation of adhesiveness From this printed wiring board, a test piece having a width of 10 mm was prepared in accordance with “JIS C6481” and subjected to pressure cooker treatment (121 ° C./humidity 100% / 100 hours). The peel strength was measured.

[Adhesion test (C)]
Instead of “lamination press of glass cloth epoxy resin impregnated prepreg (FR-4 grade)” on the S surface (shiny surface) of the base material, “resin for build-up wiring board (manufactured by Ajinomoto Fine Techno Co., Ltd., trade name“ GX ”) The peel strength of the copper foil was measured in the same procedure as in the adhesion test (b) except that “-13”) was laminated ”.

[Adhesion test (d)]
(1) Base material of test piece As a base material of test piece, double-sided copper-clad laminate (substrate: FR4, plate thickness: 1.0 mm, copper foil thickness: 18 μm) subjected to electrolytic copper plating (plating thickness: 20 μm), 120 mm long × 110 mm wide) was used.
(2) Treatment of base material It was performed according to the following steps a to d.
a. Acid clean / 1 minute (room temperature), water wash b. Micro etching with hydrogen peroxide / sulfuric acid / 1 minute (room temperature), water washing c. Acid cleaning / 1 minute (room temperature), water washing, drying / 1 minute (100 ° C)
d. Immersion in surface treatment agent / 1 minute (room temperature), water washing, drying / 1 minute (100 ° C.)
(3) Formation of resin layer on substrate After applying a solder resist (product name “PSR-4000AUS308”, manufactured by Taiyo Ink Manufacturing Co., Ltd.) to the treated substrate, drying (80 ° C./30 minutes), post-cure ( 150 ° C./60 minutes), a 13 μm thick resin layer (coating film) was formed, and a test piece of a printed wiring board was prepared.
(4) Evaluation of adhesiveness According to “JIS K5400-8.5”, the coating film formed on the surface of the test piece was cross-cut (100 squares) on a 1 mm × 1 mm grid, and pressure cooker treatment (121 ° C./humidity) 100% / 100 hours), a tape peel test was performed, and the number of squares where the coating film was not peeled was measured. Moreover, the damage condition of the coating film was observed visually.
The criteria for determining adhesiveness are as shown in Table 1.

[Example 1]
A surface treating agent was prepared by dissolving IMZ · S-1 in methanol so as to have the composition shown in Table 2. Subsequently, when this surface treating agent was used for the adhesion test (A), the test results obtained were as shown in Table 2.

[Examples 2 to 5, Comparative Example 1]
In the same manner as in Example 1, a surface treatment agent having the composition shown in Table 2 was prepared. Subsequently, when the adhesion test (A) was performed using these surface treatment agents, the test results obtained were as shown in Table 2.

[Comparative Example 2]
An adhesion test (I) was performed without subjecting the copper foil to surface treatment. The test results were as shown in Table 2.

[Examples 6 to 13]
In the same manner as in Example 1, surface treatment agents having the compositions described in Table 3 were prepared. Subsequently, when these surface-treating agents were used to conduct an adhesion test (A), the test results obtained were as shown in Table 3.

  According to the test results shown in Tables 2 and 3, the adhesion between copper and the resin can be improved by using the surface treating agent of the present invention.

Example 14
200 g of ethylene glycol monobutyl ether (hereinafter abbreviated as EGBE) was added to 10 g of IMZ · S-1, followed by addition of 790 g of water, and the mixture was stirred at room temperature for 2 hours to prepare a surface treatment agent. .
When this surface treatment agent was used to conduct adhesive evaluation tests (b) to (d), the test results obtained were as shown in Table 4.

[Examples 15 to 18]
A surface treating agent having the composition described in Table 4 was prepared in the same manner as in Example 14 except that IMZ · S-2 to IMZ · S-5 were used instead of IMZ · S-1.
When these surface treatment agents were used for adhesive evaluation tests (b) to (d), the test results obtained were as shown in Table 4.

[Comparative Examples 3 to 4]
A surface treating agent was prepared in the same manner as in Example 14 except that IMZ · S-14 and aminosilane were used instead of IMZ · S-1.
When these surface treatment agents were used for adhesive evaluation tests (b) to (d), the test results obtained were as shown in Table 4.

[Comparative Example 5]
200 g of EGBE and 790 g of water were mixed and stirred at room temperature for 2 hours to prepare a surface treating agent.
When this surface treatment agent was used to conduct adhesive evaluation tests (b) to (d), the test results obtained were as shown in Table 4.

[Examples 19 to 26]
A surface treating agent having the composition described in Table 5 was prepared in the same manner as in Example 14 except that IMZ · S-6 to IMZ · S-13 were used instead of IMZ · S-1.
When these surface treatment agents were used for adhesive evaluation tests (b) to (d), the test results obtained were as shown in Table 5.

[Comparative Example 6]
When the adhesion tests (b) to (d) were performed without subjecting the copper foil to surface treatment, the test results obtained were as shown in Table 5.

  According to the test results shown in Table 4 and Table 5, the adhesion between the metal and the resin can be improved by using the surface treating agent of the present invention.

Example 27
5 g of IMZ · S-1 was added to 45 g of phenol novolac resin melted at 100 ° C. and stirred for 5 minutes. This was cooled and then pulverized to prepare a curing agent (hereinafter referred to as “IMZ · S-1 curing agent”).
Subsequently, an ortho-cresol novolac type epoxy resin and an IMZ · S-1 curing agent were blended at room temperature so as to have the composition shown in Table 6, and then melt-kneaded at 90 to 100 ° C. After cooling this, it grind | pulverized and the epoxy resin composition (semiconductor sealing material) was prepared.
Next, two copper alloy plates (C-7025, size: 50 mm × 25 mm) were bonded together with the epoxy resin composition and heat-cured under the conditions of 175 ° C. × 8 hours to prepare test pieces.
About this test piece, according to “JIS K6850”, using AUTOGRAPH AG-X (manufactured by Shimadzu Corporation) at room temperature, the two test pieces were pulled in the reverse direction at a tensile speed of 5 mm / min, and the maximum load was measured. Shear strength was calculated by dividing the maximum load by the bonding area. The test results obtained were as shown in Table 6.

[Examples 28 to 31]
Curing agents were prepared in the same manner as in Example 27 except that IMZ · S-2 to IMZ · S-5 were added in place of IMZ · S-1, respectively (hereinafter referred to as “IMZ · S-2”). Curing agents ”to“ IMZ · S-5 curing agents ”).
Then, after preparing the epoxy resin composition which has a composition of Table 6 like Example 27, the test piece was produced and the shear strength was measured.
The test results obtained were as shown in Table 6.

[Comparative Example 7]
An epoxy resin composition having the composition shown in Table 6 was prepared in the same manner as in Example 27 except that the phenol novolac resin, 2E4MZ and epoxysilane were blended in place of the IMZ · S-1 curing agent. .
Subsequently, a test piece was prepared in the same manner as in Example 27, and the shear strength was measured.
The test results obtained were as shown in Table 6.

[Examples 32-39]
Curing agents were prepared in the same manner as in Example 27, except that IMZ · S-6 to IMZ · S-13 were blended in place of IMZ · S-1, respectively (hereinafter referred to as “IMZ · S-6”). Curing agents ”to“ IMZ · S-13 curing agent ”).
Subsequently, in the same manner as in Example 27, after preparing an epoxy resin composition having the composition shown in Table 7, a test piece was prepared and the shear strength was measured.
The test results obtained were as shown in Table 7.

  According to the test results shown in Tables 6 and 7, the shear strength of the cured product of the epoxy resin composition can be improved by using the resin composition of the present invention.

Example 40
A brominated bisphenol A type epoxy resin, an orthocresol novolac type epoxy resin and an IMZ · S-1 curing agent were blended so as to have the composition shown in Table 8 to prepare an epoxy resin composition. Subsequently, acetone was added to the epoxy resin composition to prepare a varnish.
Subsequently, the varnish was impregnated in a specification 7628 type glass woven fabric base (non-alkali plain woven glass cloth for laminate) so that the resin content was approximately 50%, and then dried to prepare a prepreg.
Subsequently, 8 sheets of this prepreg were stacked and a copper foil (thickness: 35 μm) was stacked on one side, and then this was pressed for 90 minutes at 175 ° C. under a heating / pressurizing condition of 40 kg / cm ^2. A laminate was prepared.
About this copper clad laminated board, the test piece of width 10mm was created according to "JISC6418", and the peel strength of copper foil was measured. The test results obtained were as shown in Table 8.

[Examples 41 to 44]
An epoxy resin having the composition shown in Table 8 in the same manner as in Example 40 except that each of IMZ · S-2 curing agent to IMZ · S-5 curing agent was blended in place of the IMZ · S-1 curing agent. A composition was prepared.
Subsequently, acetone was added to the epoxy resin composition to prepare a varnish.
Next, in the same manner as in Example 40, after producing a copper-clad laminate, the peel strength was measured.
The test results obtained were as shown in Table 8.

[Comparative Example 8]
An epoxy resin composition having the composition described in Table 8 was prepared in the same manner as in Example 40 except that the phenol novolac resin and 2E4MZ were blended in place of the IMZ · S-1 curing agent.
Subsequently, acetone was added to the epoxy resin composition to prepare a varnish.
Next, in the same manner as in Example 40, after producing a copper-clad laminate, the peel strength was measured.
The test results obtained were as shown in Table 8.

[Examples 45-52]
An epoxy resin having the composition described in Table 9 in the same manner as in Example 40 except that each of IMZ · S-6 curing agent to IMZ · S-13 curing agent was blended in place of the IMZ · S-1 curing agent. A composition was prepared.
Subsequently, acetone was added to the epoxy resin composition to prepare a varnish.
Next, in the same manner as in Example 40, after producing a copper-clad laminate, the peel strength was measured.
The test results obtained were as shown in Table 9.

  According to the test results shown in Tables 8 and 9, the peel strength of the copper-clad laminate can be improved by using the resin composition of the present invention.

Example 53
5 g of IMZ · S-1 was dissolved in 5 g of methanol, 20 g of silicone powder and 20 g of methanol were added to the solution and stirred for 30 minutes, and then the methanol was removed by heating to 80 ° C. under reduced pressure. After cooling, the mixture was pulverized and shaken using a 90 μm shaker to prepare an additive (hereinafter referred to as “IMZ · S-1 additive”).
Subsequently, after blending biphenyl type epoxy resin, phenol resin, IMZ · S-1 additive, triphenylphosphine, carnauba wax, carbon black, filler, epoxy silane, and mercaptosilane to the composition shown in Table 10, Melt-kneaded at 90 ° C. After cooling this, it grind | pulverized and the epoxy resin composition (semiconductor sealing material) was prepared.
Subsequently, two metal plates were bonded together with the epoxy resin composition and heat-cured under the conditions of 175 ° C. × 6 hours to prepare test pieces.
About this test piece, according to “JIS K6850”, using AUTOGRAPH AG-X (manufactured by Shimadzu Corporation) at room temperature, the two test pieces were pulled in the reverse direction at a tensile speed of 5 mm / min, and the maximum load was measured. Shear strength was calculated by dividing the maximum load by the bonding area. The test results obtained were as shown in Table 10.

In addition, the following three types of metal plates were used.
Copper alloy plate: Copper strike plating of about 0.1 μm was performed on a copper alloy (C7025, size: 50 × 25 × 0.15 mm). Hereinafter, it is abbreviated as “copper plate”.
Silver plating plate: Silver plating of about 5 μm was performed on a copper alloy (C7025, size: 50 × 25 × 0.15 mm). Hereinafter, it is abbreviated as “silver plate”.
Gold plating plate: Ni plating of about 0.5 μm is performed on a copper alloy (C7025, size: 50 × 25 × 0.15 mm), followed by Pd plating of about 0.05 μm, and then about 0.00 mm. 005 μm Au plating was performed. Hereinafter, it is abbreviated as “metal plate”.

[Examples 54 to 57]
Each additive was prepared in the same manner as in Example 53 except that each of IMZ · S-2 to IMZ · S-5 was used instead of IMZ · S-1 (hereinafter referred to as “IMZ · S-2”). Additives ”to“ IMZ · S-5 additive ”).
Then, after preparing an epoxy resin composition so that it might become a composition of Table 10 like Example 53, the test piece was produced and the shear strength was measured. The test results obtained were as shown in Table 10.

[Comparative Example 9]
An epoxy resin composition having the composition described in Table 10 was prepared in the same manner as in Example 53 except that silicone powder was used instead of the IMZ · S-1 additive.
Subsequently, a test piece was prepared in the same manner as in Example 53, and the shear strength was measured. The test results obtained were as shown in Table 10.

[Examples 58 to 65]
Each additive was prepared in the same manner as in Example 53 except that each of IMZ · S-6 to IMZ · S-13 was used instead of IMZ · S-1 (hereinafter referred to as “IMZ · S-6”). Additives ”to“ IMZ · S-13 additive ”).
Subsequently, in the same manner as in Example 53, an epoxy resin composition was prepared so as to have the composition shown in Table 11, a test piece was prepared, and shear strength was measured. The test results obtained were as shown in Table 11.

  According to the test results shown in Table 10 and Table 11, the shear strength of the sealed product (cured product) can be improved by using the resin composition of the present invention as a semiconductor sealant.

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

Claims (16)

An imidazole silane compound obtained by reacting a formylimidazole compound represented by chemical formula (I) or chemical formula (II) with an aminopropylsilane compound represented by chemical formula (III); an imidazole compound represented by chemical formula (IV); A surface containing at least one imidazolesilane compound selected from the group consisting of an imidazolesilane compound obtained by reacting with a halopropylsilane compound represented by chemical formula (V); and an imidazolesilane compound represented by chemical formula (VI) Processing agent.

[Wherein, R ^{1 to} R ³ are the same or different and each represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an allyl group, a benzyl group, or an aryl group. ]

[Wherein, R ^{1 to} R ³ are the same as defined above. ]

[Wherein, R ^{4 to} R ⁶ are the same or different and each represents a hydroxyl group, an alkoxy group having 1 to 3 carbon atoms, or an alkyl group having 1 to 3 carbon atoms. However, the case where R ⁴ , R ⁵ and R ⁶ are simultaneously an alkyl group is excluded. ]

[Wherein, R ^{7 to} R ⁹ are the same or different and each represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an allyl group, a benzyl group, or an aryl group. ]

[In formula, R < ¹⁰ > -R < ¹² > is the same or different and represents a hydroxyl group, a C1-C3 alkoxy group, or a C1-C3 alkyl group. However, the case where R ¹⁰ , R ¹¹ and R ¹² are simultaneously an alkyl group is excluded. X represents a fluorine atom, a chlorine atom, a bromine atom or an iodine atom. ]

[In formula, R < ¹³ > -R < ¹⁷ > is the same or different and represents a hydrogen atom, a C1-C20 alkyl group, or a phenyl group. R ¹⁸ and R ¹⁹ are the same or different and each represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. m represents an integer of 1 to 3. n represents an integer of 0 to 5. ]   A copper foil treated with the surface treating agent according to claim 1.   A prepreg treated with the surface treating agent according to claim 1.   The copper clad laminated board processed with the surface treating agent of Claim 1.   An interlayer insulating material treated with the surface treating agent according to claim 1.   A copper foil with a resin in which a copper foil and a resin layer are laminated via a film made of the surface treatment agent according to claim 1.   A printed wiring board comprising a member treated with the surface treating agent according to claim 1. An imidazole silane compound obtained by reacting a formylimidazole compound represented by chemical formula (I) or chemical formula (II) with an aminopropylsilane compound represented by chemical formula (III); an imidazole compound represented by chemical formula (IV); An imidazolesilane compound obtained by reacting with a halopropylsilane compound represented by the chemical formula (V); and at least one imidazolesilane compound selected from the group consisting of an imidazolesilane compound represented by the chemical formula (VI), and a resin Or the resin composition containing the compound before the hardening.

[Wherein, R ^{1 to} R ³ are the same or different and each represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an allyl group, a benzyl group, or an aryl group. ]

[Wherein, R ^{1 to} R ³ are the same as defined above. ]

[Wherein, R ^{4 to} R ⁶ are the same or different and each represents a hydroxyl group, an alkoxy group having 1 to 3 carbon atoms, or an alkyl group having 1 to 3 carbon atoms. However, the case where R < ⁴ > -R < ⁶ > is an alkyl group simultaneously is remove | excluded. ]

[Wherein, R ^{7 to} R ⁹ are the same or different and each represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an allyl group, a benzyl group, or an aryl group. ]

[In formula, R < ¹⁰ > -R < ¹² > is the same or different and represents a hydroxyl group, a C1-C3 alkoxy group, or a C1-C3 alkyl group. However, the case where R ¹⁰ , R ¹¹ and R ¹² are simultaneously an alkyl group is excluded. X represents a fluorine atom, a chlorine atom, a bromine atom or an iodine atom. ]

[In formula, R < ¹³ > -R < ¹⁷ > is the same or different and represents a hydrogen atom, a C1-C20 alkyl group, or a phenyl group. R ¹⁸ and R ¹⁹ are the same or different and each represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. m represents an integer of 1 to 3. n represents an integer of 0 to 5. ]   The solder resist ink comprised from the resin composition of Claim 8.   A printed wiring board provided with the soldering resist formed from the soldering resist ink of Claim 9.   The prepreg comprised from the base material and the resin composition of Claim 8.   The copper clad laminated board comprised from the copper foil and the prepreg of Claim 11.   The interlayer insulation material comprised from the resin composition of Claim 8.   The copper foil with resin comprised from the resin layer formed with the copper foil and the resin composition of Claim 8.   A printed wiring board provided with the resin layer formed with the resin composition of Claim 8.   The semiconductor sealing material comprised from the resin composition of Claim 8.