JP2013057018A - Curable composition and connection structure - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a curable composition that can give a connection structure excellent in migration resistance.SOLUTION: The curable composition comprises a curable compound having no epoxy group or an epoxy group and having a (meth)acryloyl group, and a thermal radical generator. The curable compound is obtained by reacting a (meth)acrylic acid to a part of or all of epoxy groups of a compound expressed by formula (11-1). In formula (11-1), R1 and R2 each represents a 1-5C alkylene group; and four to six groups in the six groups of R3 to R8 represent a hydrogen atom, and groups that are not hydrogen atoms in R3 to R8 represent a group expressed by formula (11a). In formula (11a), R9 represents a 1-5C alkylene group.

Description

  INDUSTRIAL APPLICABILITY The present invention can be used for connecting various connection target members such as electronic components, and includes a curable composition containing a curable compound having a (meth) acryloyl group, and a connection using the curable composition. Concerning the structure.

  A curable composition is used to connect various connection target members such as electronic components. The curable composition contains a photocurable compound that can be cured by light irradiation or a thermosetting compound that can be cured by heating.

  The said curable composition is used for the connection of the semiconductor chip which has a metal bump electrode, and the circuit board which has an electrode, for example.

  Moreover, the curable composition containing electroconductive particle is known. In order to obtain various connection structures, the curable composition containing conductive particles includes, for example, connection between a flexible printed circuit board and a glass substrate (FOG (Film on Glass)), connection between a semiconductor chip and a flexible printed circuit board. (COF (Chip on Film)), connection between semiconductor chip and glass substrate (COG (Chip on Glass)), connection between flexible printed circuit board and glass epoxy substrate (FOB (Film on Board)), etc. Yes.

  As an example of the curable composition, Patent Literature 1 below discloses a thermosetting or photocurable composition containing conductive particles, a base resin, and a hindered phenol polymerization inhibitor. Polyacetal resin and (meth) acrylic resin are described as the base resin.

JP 2003-20455 A

  In the conventional curable composition as described in Patent Document 1, when the connection structure obtained by connecting the electrodes of the electronic component is used in a state of being energized under high humidity, there is a problem that migration easily occurs. is there.

  In recent years, L / S (line / space) which is the electrode width / interelectrode width in the connection structure has been further reduced. As the L / S of the electrode in the connection structure is smaller, there is a problem that an insulation failure is more likely to occur when migration occurs.

  The objective of this invention is providing the curable composition which can obtain the connection structure excellent in migration resistance, and the connection structure using this curable composition.

According to a broad aspect of the present invention, the curable compound includes a curable compound having no epoxy group or having an epoxy group and having a (meth) acryloyl group, and a thermal radical generator. The curable composition obtained by making (meth) acrylic acid react with a part or all of the epoxy group of the compound which has an epoxy group represented by following formula (11-1) is provided.

上記式（１１−１）中、Ｒ１及びＲ２はそれぞれ炭素数１〜５のアルキレン基を表し、Ｒ３、Ｒ４、Ｒ５、Ｒ６、Ｒ７及びＲ８の６個の基の内の４〜６個の基は水素原子を表し、Ｒ３、Ｒ４、Ｒ５、Ｒ６、Ｒ７及びＲ８の内の水素原子ではない基は、下記式（１１ａ）で表される基を表す。

In the above formula (11-1), R1 and R2 each represent an alkylene group having 1 to 5 carbon atoms, and 4 to 6 groups out of 6 groups of R3, R4, R5, R6, R7 and R8 Represents a hydrogen atom, and the group that is not a hydrogen atom among R3, R4, R5, R6, R7, and R8 represents a group represented by the following formula (11a).

上記式（１１ａ）中、Ｒ９は炭素数１〜５のアルキレン基を表す。

In said formula (11a), R9 represents a C1-C5 alkylene group.

  In a specific aspect of the curable composition according to the present invention, the curable compound contains (meth) acrylic acid in part or all of the epoxy group of the compound having an epoxy group represented by the following formula (11). It is obtained by reacting.

上記式（１１）中、Ｒ１及びＲ２はそれぞれ炭素数１〜５のアルキレン基を表し、Ｒ３、Ｒ４、Ｒ５、Ｒ６、Ｒ７及びＲ８の６個の基の内の４〜６個の基は水素原子を表し、Ｒ３、Ｒ４、Ｒ５、Ｒ６、Ｒ７及びＲ８の内の水素原子ではない基は、上記式（１１ａ）で表される基を表す。

In the above formula (11), R1 and R2 each represent an alkylene group having 1 to 5 carbon atoms, and 4 to 6 groups out of 6 groups of R3, R4, R5, R6, R7 and R8 are hydrogen. The group which represents an atom and is not a hydrogen atom among R3, R4, R5, R6, R7 and R8 represents a group represented by the above formula (11a).

  In another specific aspect of the curable composition according to the present invention, the curable compound is obtained by reacting (meth) acrylic acid with 20% or more and 100% or less of the number of epoxy groups.

  In still another specific aspect of the curable composition according to the present invention, the curable compound is obtained by reacting a part of an epoxy group with (meth) acrylic acid, and the curable compound is an epoxy group. And a (meth) acryloyl group.

  In another specific aspect of the curable composition according to the present invention, the curable compound is obtained by reacting (meth) acrylic acid with 20% or more and 80% or less of the number of epoxy groups.

  In still another specific aspect of the curable composition according to the present invention, the curable compound is obtained by reacting (meth) acrylic acid with all of the epoxy groups, and the curable compound has an epoxy group. It has no (meth) acryloyl group.

  According to a broad aspect of the present invention, the curable compound includes a curable compound having no epoxy group or having an epoxy group and having a (meth) acryloyl group, and a thermal radical generator. A curable composition represented by the following formula (1A), the following formula (1B), or the following formula (1C) is provided.

上記式（１Ａ）中、Ｒ１及びＲ２はそれぞれ炭素数１〜５のアルキレン基を表し、Ｒ３、Ｒ４、Ｒ５、Ｒ６、Ｒ７及びＲ８の６個の基の内の４〜６個の基は水素原子を表し、Ｒ３、Ｒ４、Ｒ５、Ｒ６、Ｒ７及びＲ８の内の水素原子ではない基は、下記式（１ａ）又は下記式（１ｂ）で表される基を表し、Ｒ１０及びＲ１１はそれぞれ水素原子又はメチル基を表す。

In the above formula (1A), R1 and R2 each represent an alkylene group having 1 to 5 carbon atoms, and 4 to 6 groups out of 6 groups of R3, R4, R5, R6, R7 and R8 are hydrogen. A group which is an atom and is not a hydrogen atom among R3, R4, R5, R6, R7 and R8 represents a group represented by the following formula (1a) or the following formula (1b), and R10 and R11 are each hydrogen. Represents an atom or a methyl group.

上記式（１Ｂ）中、Ｒ１及びＲ２はそれぞれ炭素数１〜５のアルキレン基を表し、Ｒ３
、Ｒ４、Ｒ５、Ｒ６、Ｒ７及びＲ８の６個の基の内の４〜６個の基は水素原子を表し、Ｒ３、Ｒ４、Ｒ５、Ｒ６、Ｒ７及びＲ８の内の水素原子ではない基は、下記式（１ａ）又は下記式（１ｂ）で表される基を表し、Ｒ１０は水素原子又はメチル基を表す。

In said formula (1B), R1 and R2 represent a C1-C5 alkylene group, respectively, R3
, R4, R5, R6, R7 and R8, 4 to 6 groups represent hydrogen atoms, and R3, R4, R5, R6, R7 and R8 are not hydrogen atoms. Represents a group represented by the following formula (1a) or the following formula (1b), and R10 represents a hydrogen atom or a methyl group.

上記式（１Ｃ）中、Ｒ１及びＲ２はそれぞれ炭素数１〜５のアルキレン基を表し、Ｒ３、Ｒ４、Ｒ５、Ｒ６、Ｒ７及びＲ８の６個の基の内の４〜６個の基は水素原子を表し、Ｒ３、Ｒ４、Ｒ５、Ｒ６、Ｒ７及びＲ８の内の水素原子ではない基は、下記式（１ａ）又は下記式（１ｂ）で表される基を表し、Ｒ１１は水素原子又はメチル基を表す。

In the above formula (1C), R1 and R2 each represent an alkylene group having 1 to 5 carbon atoms, and 4 to 6 groups out of 6 groups of R3, R4, R5, R6, R7 and R8 are hydrogen. A group which is an atom and is not a hydrogen atom among R3, R4, R5, R6, R7 and R8 represents a group represented by the following formula (1a) or the following formula (1b), and R11 is a hydrogen atom or methyl Represents a group.

上記式（１ａ）中、Ｒ９は炭素数１〜５のアルキレン基を表す。

In said formula (1a), R9 represents a C1-C5 alkylene group.

上記式（１ｂ）中、Ｒ９は炭素数１〜５のアルキレン基を表し、Ｒ１２は水素原子又はメチル基を表す。

In said formula (1b), R9 represents a C1-C5 alkylene group, R12 represents a hydrogen atom or a methyl group.

  In a specific aspect of the curable composition according to the present invention, the curable compound is represented by the above formula (1A), and among R3, R4, R5, R6, R7 and R8 in the above formula (1A), The group which is not a hydrogen atom is a group represented by the above formula (1b), and includes a curable compound having no epoxy group and having a (meth) acryloyl group.

  In another specific aspect of the curable composition according to the present invention, the curable compound is represented by the above formula (1B) or the above formula (1C), has an epoxy group, and (meth) acryloyl group. A curable compound having

  In another specific aspect of the curable composition according to the present invention, a photocuring initiator is further included.

  In another specific aspect of the curable composition according to the present invention, conductive particles are further included.

  A connection structure according to the present invention includes a first connection target member, a second connection target member, and a connection portion that connects the first and second connection target members. It is formed with the curable composition mentioned above.

  The curable composition which concerns on this invention is obtained by making (meth) acrylic acid react with a part or all of the epoxy group of the compound which has an epoxy group represented by the said Formula (11-1), and an epoxy group Since it contains a curable compound having no epoxy or having an epoxy group and having a (meth) acryloyl group, and a thermal radical generator, a connection structure having excellent migration resistance can be obtained.

  The curable composition according to the present invention is represented by the above formula (1A), the above formula (1B) or the above formula (1C), and has no epoxy group or has an epoxy group, and (meth) acryloyl. Since the curable compound having a group and the thermal radical generator are included, a connection structure having excellent migration resistance can be obtained.

FIG. 1 is a partially cutaway cross-sectional view schematically showing an example of a connection structure using a curable composition according to an embodiment of the present invention.

  Details of the present invention will be described below.

  The curable composition concerning this invention contains the curable compound which does not have an epoxy group or has an epoxy group, and has a (meth) acryloyl group, and a thermal radical generator.

  The curable composition which concerns on this invention is a curable compound obtained by making (meth) acrylic acid react with a part or all of the epoxy group of the compound which has an epoxy group represented by Formula (11-1). Since the thermal radical generator is contained, a connection structure having excellent migration resistance can be obtained by using the curable composition according to the present invention. Therefore, a connection structure having high insulation reliability can be obtained.

  Moreover, since the curable composition which concerns on this invention contains the curable compound represented by Formula (1A), Formula (1B) or Formula (1C), and a thermal radical generator, the sclerosis | hardenability which concerns on this invention By using the composition, a connection structure excellent in migration resistance can be obtained. Therefore, a connection structure having high insulation reliability can be obtained.

  The curable composition concerning this invention may further contain other thermosetting agents other than a thermal radical generator. The curable composition concerning this invention may further contain the photocuring initiator. The curable composition according to the present invention may further contain conductive particles.

(Curable compound)
It is preferable that the said curable compound is obtained by making (meth) acrylic acid react with a part or all of the epoxy group of the compound which has an epoxy group represented by following formula (11-1). The said curable compound is epoxy (meth) acrylate obtained by making (meth) acrylic acid react with a part or all of the epoxy group of the compound which has an epoxy group. The curable compound is a compound obtained by modifying a part or all of the epoxy group of a compound having an epoxy group with a (meth) acryloyl group. This curable compound has at least one (meth) acryloyl group. The “(meth) acryl” refers to acryl and methacryl. The above “(meth) acryloyl” refers to acryloyl and methacryloyl. The “(meth) acrylate” refers to acrylate and methacrylate.

上記式（１１−１）中、Ｒ１及びＲ２はそれぞれ炭素数１〜５のアルキレン基を表す。Ｒ３、Ｒ４、Ｒ５、Ｒ６、Ｒ７及びＲ８の６個の基の内の４〜６個の基は水素原子を表す。Ｒ３、Ｒ４、Ｒ５、Ｒ６、Ｒ７及びＲ８の内の水素原子ではない基は、下記式（１１ａ）で表される基を表す。Ｒ３、Ｒ４、Ｒ５、Ｒ６、Ｒ７及びＲ８の６個の基の全てが水素原子であってもよい。Ｒ３、Ｒ４、Ｒ５、Ｒ６、Ｒ７及びＲ８の６個の基の内の１個又は２個が下記式（１１ａ）で表される基であり、かつＲ３、Ｒ４、Ｒ５、Ｒ６、Ｒ７及びＲ８の内の下記式（１１ａ）で表される基ではない基は水素原子であってもよい。

In said formula (11-1), R1 and R2 represent a C1-C5 alkylene group, respectively. 4 to 6 groups out of 6 groups of R3, R4, R5, R6, R7 and R8 represent a hydrogen atom. The group which is not a hydrogen atom among R3, R4, R5, R6, R7 and R8 represents a group represented by the following formula (11a). All of the six groups of R3, R4, R5, R6, R7 and R8 may be hydrogen atoms. One or two of the six groups of R3, R4, R5, R6, R7 and R8 are groups represented by the following formula (11a), and R3, R4, R5, R6, R7 and R8 Of these, a group that is not a group represented by the following formula (11a) may be a hydrogen atom.

上記式（１１ａ）中、Ｒ９は炭素数１〜５のアルキレン基を表す。

In said formula (11a), R9 represents a C1-C5 alkylene group.

  The curable compound is preferably represented by the following formula (1A), the following formula (1B), or the following formula (1C). This curable compound has at least one (meth) acryloyl group.

上記式（１Ａ）中、Ｒ１及びＲ２はそれぞれ炭素数１〜５のアルキレン基を表す。Ｒ３、Ｒ４、Ｒ５、Ｒ６、Ｒ７及びＲ８の６個の基の内の４〜６個の基は水素原子を表す。Ｒ３、Ｒ４、Ｒ５、Ｒ６、Ｒ７及びＲ８の内の水素原子ではない基は、下記式（１ａ）又は下記式（１ｂ）で表される基を表す。Ｒ１０及びＲ１１はそれぞれ水素原子又はメチル基を表す。Ｒ３、Ｒ４、Ｒ５、Ｒ６、Ｒ７及びＲ８の６個の基の内の１個又は２個が下記式（１ａ）又は下記式（１ｂ）で表される基であり、かつＲ３、Ｒ４、Ｒ５、Ｒ６、Ｒ７及びＲ８の内の下記式（１ａ）又は下記式（１ｂ）で表される基ではない基は水素原子であってもよい。上記式（１Ａ）で表される硬化性化合物がエポキシ基を有さない場合には、上記式（１Ａ）中のＲ３、Ｒ４、Ｒ５及びＲ６の内の水素原子ではない基は下記式（１ｂ）で表される基を表す。

In said formula (1A), R1 and R2 represent a C1-C5 alkylene group, respectively. 4 to 6 groups out of 6 groups of R3, R4, R5, R6, R7 and R8 represent a hydrogen atom. The group which is not a hydrogen atom among R3, R4, R5, R6, R7 and R8 represents a group represented by the following formula (1a) or the following formula (1b). R10 and R11 each represent a hydrogen atom or a methyl group. One or two of the six groups of R3, R4, R5, R6, R7 and R8 are groups represented by the following formula (1a) or the following formula (1b), and R3, R4, R5 , R 6, R 7 and R 8, a group that is not a group represented by the following formula (1a) or the following formula (1b) may be a hydrogen atom. When the curable compound represented by the above formula (1A) does not have an epoxy group, the group that is not a hydrogen atom among R3, R4, R5 and R6 in the above formula (1A) is represented by the following formula (1b). ) Represents a group represented by

上記式（１Ｂ）中、Ｒ１及びＲ２はそれぞれ炭素数１〜５のアルキレン基を表す。Ｒ３、Ｒ４、Ｒ５、Ｒ６、Ｒ７及びＲ８の６個の基の内の４〜６個の基は水素原子を表す。Ｒ３、Ｒ４、Ｒ５、Ｒ６、Ｒ７及びＲ８の内の水素原子ではない基は、下記式（１ａ）又は下記式（１ｂ）で表される基を表す。Ｒ１０は水素原子又はメチル基を表す。Ｒ３、Ｒ４、Ｒ５、Ｒ６、Ｒ７及びＲ８の６個の基の内の１個又は２個が下記式（１ａ）又は下記式（１ｂ）で表される基であり、かつＲ３、Ｒ４、Ｒ５、Ｒ６、Ｒ７及びＲ８の内の下記式（１ａ）又は下記式（１ｂ）で表される基ではない基は水素原子であってもよい。

In said formula (1B), R1 and R2 represent a C1-C5 alkylene group, respectively. 4 to 6 groups out of 6 groups of R3, R4, R5, R6, R7 and R8 represent a hydrogen atom. The group which is not a hydrogen atom among R3, R4, R5, R6, R7 and R8 represents a group represented by the following formula (1a) or the following formula (1b). R10 represents a hydrogen atom or a methyl group. One or two of the six groups of R3, R4, R5, R6, R7 and R8 are groups represented by the following formula (1a) or the following formula (1b), and R3, R4, R5 , R 6, R 7 and R 8, a group that is not a group represented by the following formula (1a) or the following formula (1b) may be a hydrogen atom.

上記式（１Ｃ）中、Ｒ１及びＲ２はそれぞれ炭素数１〜５のアルキレン基を表す。Ｒ３、Ｒ４、Ｒ５、Ｒ６、Ｒ７及びＲ８の６個の基の内の４〜６個の基は水素原子を表す。Ｒ３、Ｒ４、Ｒ５、Ｒ６、Ｒ７及びＲ８の内の水素原子ではない基は、下記式（１ａ）又は下記式（１ｂ）で表される基を表す。Ｒ１１は水素原子又はメチル基を表す。Ｒ３、Ｒ４、Ｒ５、Ｒ６、Ｒ７及びＲ８の６個の基の内の１個又は２個が下記式（１ａ）又は下記式（１ｂ）で表される基であり、かつＲ３、Ｒ４、Ｒ５、Ｒ６、Ｒ７及びＲ８の内の下記式（１ａ）又は下記式（１ｂ）で表される基ではない基は水素原子であってもよい。

In said formula (1C), R1 and R2 represent a C1-C5 alkylene group, respectively. 4 to 6 groups out of 6 groups of R3, R4, R5, R6, R7 and R8 represent a hydrogen atom. The group which is not a hydrogen atom among R3, R4, R5, R6, R7 and R8 represents a group represented by the following formula (1a) or the following formula (1b). R11 represents a hydrogen atom or a methyl group. One or two of the six groups of R3, R4, R5, R6, R7 and R8 are groups represented by the following formula (1a) or the following formula (1b), and R3, R4, R5 , R 6, R 7 and R 8, a group that is not a group represented by the following formula (1a) or the following formula (1b) may be a hydrogen atom.

上記式（１ａ）中、Ｒ９は炭素数１〜５のアルキレン基を表す。

In said formula (1a), R9 represents a C1-C5 alkylene group.

上記式（１ｂ）中、Ｒ９は炭素数１〜５のアルキレン基を表し、Ｒ１２は水素原子又はメチル基を表す。

In said formula (1b), R9 represents a C1-C5 alkylene group, R12 represents a hydrogen atom or a methyl group.

  The curable compound represented by the above formula (1A), the above formula (1B) or the above formula (1C) and having no epoxy group or having an epoxy group and having a (meth) acryloyl group has the above formula. It can be obtained by reacting (meth) acrylic acid with part or all of the epoxy group of the compound having an epoxy group represented by (11-1). The curable compound represented by the above formula (1A), the above formula (1B) or the above formula (1C) and having no epoxy group or having an epoxy group and having a (meth) acryloyl group has the above formula. You may synthesize | combine by methods other than the method of making a part or all of the epoxy group of the compound which has an epoxy group represented by (11-1) react with (meth) acrylic acid.

  From the viewpoint of further improving the reactivity of the curable composition and obtaining a connection structure that is more excellent in migration resistance, the curable compound preferably has two or more (meth) acryloyl groups. The said curable compound may have an epoxy group and does not need to have an epoxy group. That is, the curable compound includes a compound in which a part of the epoxy group remains without being converted to a (meth) acryloyl group.

  From the viewpoint of improving the reactivity of the curable composition and obtaining a connection structure that is more excellent in migration resistance, the curable compound represented by the above formula (11-1) is represented by the following formula (11). It is preferable that it is a curable compound.

上記式（１１）中、Ｒ１及びＲ２はそれぞれ炭素数１〜５のアルキレン基を表す。Ｒ３、Ｒ４、Ｒ５、Ｒ６、Ｒ７及びＲ８の６個の基の内の４〜６個の基は水素原子を表す。Ｒ３、Ｒ４、Ｒ５、Ｒ６、Ｒ７及びＲ８の内の水素原子ではない基は、上記式（１１ａ）で表される基を表す。

In said formula (11), R1 and R2 represent a C1-C5 alkylene group, respectively. 4 to 6 groups out of 6 groups of R3, R4, R5, R6, R7 and R8 represent a hydrogen atom. The group which is not a hydrogen atom among R3, R4, R5, R6, R7 and R8 represents a group represented by the above formula (11a).

  From the viewpoint of further improving the reactivity of the curable composition, the curable compound represented by the above formula (11-1) is a curable compound represented by the following formula (11A-1). Is preferred. It is preferable that all six groups of R3, R4, R5, R6, R7 and R8 in the above formula (11-1) represent a hydrogen atom.

上記式（１１Ａ−１）中、Ｒ１及びＲ２はそれぞれ炭素数１〜５のアルキレン基を表す。

In said formula (11A-1), R1 and R2 represent a C1-C5 alkylene group, respectively.

  From the viewpoint of further improving the reactivity of the curable composition and obtaining a connection structure further excellent in migration resistance, the compound represented by the above formula (11) is represented by the following formula (11A). A curable compound is preferable. It is preferable that all six groups of R3, R4, R5, R6, R7 and R8 in the above formula (11) represent hydrogen atoms.

上記式（１１Ａ）中、Ｒ１及びＲ２はそれぞれ炭素数１〜５のアルキレン基を表す。

In said formula (11A), R1 and R2 represent a C1-C5 alkylene group, respectively.

  From the viewpoint of further improving the reactivity of the curable composition and obtaining a connection structure further excellent in migration resistance, it is represented by the above formula (1A), the above formula (1B) or the above formula (1C). The curable compound is preferably a compound represented by the following formula (1AA), the following formula (1BB), or the following formula (1CC). It is preferable that all six groups of R3, R4, R5, R6, R7 and R8 in the above formula (1A), the above formula (1B) or the above formula (1C) represent a hydrogen atom.

上記式（１ＡＡ）中、Ｒ１及びＲ２はそれぞれ炭素数１〜５のアルキレン基を表す。Ｒ１０及びＲ１１はそれぞれ水素原子又はメチル基を表す。

In said formula (1AA), R1 and R2 represent a C1-C5 alkylene group, respectively. R10 and R11 each represent a hydrogen atom or a methyl group.

上記式（１ＢＢ）中、Ｒ１及びＲ２はそれぞれ炭素数１〜５のアルキレン基を表す。Ｒ１０は水素原子又はメチル基を表す。

In said formula (1BB), R1 and R2 represent a C1-C5 alkylene group, respectively. R10 represents a hydrogen atom or a methyl group.

上記式（１ＣＣ）中、Ｒ１及びＲ２はそれぞれ炭素数１〜５のアルキレン基を表す。Ｒ１１はそれぞれ水素原子又はメチル基を表す。

In said formula (1CC), R1 and R2 represent a C1-C5 alkylene group, respectively. R11 represents a hydrogen atom or a methyl group, respectively.

All of the compounds having an epoxy group represented by the above formula (11-1), formula (11A-1), formula (11) and formula (11A) have at least two epoxy groups. In addition, a group having an epoxy group is bonded to the naphthalene ring. Since it has such a structure, by heating the curable composition containing a curable compound obtained by reacting (meth) acrylic acid with part or all of the epoxy group of the compound having the epoxy group Thus, the migration resistance of the resulting connection structure can be improved. Moreover, since a naphthalene ring has a planar structure, it makes it possible to harden a curable composition rapidly.

  Formula (11-1), Formula (11A-1), Formula (11), Formula (11A), Formula (1A), Formula (1AA), Formula (1B), Formula (1BB), Formula (1C) and R1 and R2 in Formula (1CC), and R9 in Formula (11a), Formula (1a), and Formula (1b) are all alkylene groups having 1 to 5 carbon atoms. When carbon number of this alkylene group exceeds 5, the hardening rate of the said curable composition will fall easily. The alkylene group having 1 to 5 carbon atoms is preferably an alkylene group having 1 to 3 carbon atoms, and more preferably a methylene group. The alkylene group may be an alkylene group having a straight chain structure or an alkylene group having a branched structure.

  The reaction itself of reacting (meth) acrylic acid with part or all of the epoxy group of the compound having an epoxy group can be carried out by a conventionally known method. That is, (meth) acrylic acid can be reacted with part or all of the epoxy group by carrying out the reaction in the presence of a catalyst according to a conventional method.

  A solvent may be used when (meth) acrylic acid is reacted with part or all of the epoxy group of the compound having an epoxy group. Further, the compound having an epoxy group and the (meth) acrylic acid may be added to a solvent and used as a solution. Examples of the solvent include water and organic solvents. Examples of the organic solvent include methanol, ethanol, toluene, and the like.

  The solvent is preferably used in an amount of 50 parts by weight or more, and preferably 300 parts by weight or less based on 100 parts by weight of the compound having an epoxy group. When the amount of the solvent used is not less than the above lower limit and not more than the above upper limit, the (meth) acryloyl group can be more efficiently introduced.

  A catalyst or a polymerization inhibitor may be used in the reaction of the compound having an epoxy group with the (meth) acrylic acid.

  Examples of the catalyst include triethylamine, benzyldimethylamine, N, N′-dimethylpiperidine, 2,4,6-tris (dimethylaminomethyl) phenol, triethylenediamine, trimethylbenzylammonium chloride, tetra-n-butylammonium bromide, and chloride. Examples include lithium and triphenylphosphine. Examples of the polymerization inhibitor include hydroquinone, hydroquinone monomethyl ether, benzoquinone, pt-butylcatechol, and 2,6-dibutyl-4-methylphenol.

  The catalyst is preferably used in an amount of 0.5 parts by weight or more, preferably 5 parts by weight or less based on 100 parts by weight of the compound having an epoxy group. When the usage-amount of the said catalyst is more than the said minimum and below the said upper limit, a (meth) acryloyl group can be introduce | transduced still more efficiently. The polymerization inhibitor is preferably used in an amount of 0.2 parts by weight or more, and preferably 1.5 parts by weight or less based on 100 parts by weight of the compound having an epoxy group. When the usage-amount of the said polymerization inhibitor is more than the said minimum and below the said upper limit, the polymerization reaction of the radically polymerizable double bonds in a raw material or a product can be suppressed effectively.

The curable compound is obtained by reacting (meth) acrylic acid in excess of 0% with respect to 100% of the total number of epoxy groups, and reacting (meth) acrylic acid to 20% or more. Preferably obtained by reacting (meth) acrylic acid with 30% or more, and obtained by reacting (meth) acrylic acid with 40% or more. More preferably. The above curable compound is obtained by reacting (meth) acrylic acid to 100% or less with respect to 100% of the total number of epoxy groups, and reacting (meth) acrylic acid to 80% or less. It is preferably obtained, more preferably obtained by reacting (meth) acrylic acid to 70% or less, and obtained by reacting (meth) acrylic acid to 60% or less. Is more preferable. When (meth) acrylic acid is reacted with 100% of the number of epoxy groups, a curable compound in which (meth) acrylic acid is reacted with all of the epoxy groups is obtained.

  From the viewpoint of improving the reactivity of the curable composition, the curable compound is preferably obtained by reacting (meth) acrylic acid with 20% to 100% of the number of epoxy groups.

  In addition, from the viewpoint of further improving the thermosetting property due to the presence of the epoxy group, the curable compound is obtained by reacting a part of the epoxy group with (meth) acrylic acid, and has an epoxy group. And having a (meth) acryloyl group. From the viewpoint of further improving the thermosetting property by the presence of the epoxy group, the curable compound should be obtained by reacting (meth) acrylic acid to 20% or more and 80% or less of the number of epoxy groups. Is preferred.

  From the viewpoint of increasing the number of (meth) acryloyl groups and further improving the reactivity of the curable composition, the curable compound is obtained by reacting (meth) acrylic acid with all of the epoxy groups. It is preferable to have an epoxy group and a (meth) acryloyl group. That is, the curable compound is preferably obtained by reacting (meth) acrylic acid with 100% of the number of epoxy groups.

  From the viewpoint of increasing the number of (meth) acryloyl groups and further improving the reactivity of the curable composition, the curable compound is represented by the formula (1A), and the formula (1A) The group which is not a hydrogen atom among R3, R4, R5, R6, R7 and R8 is a group represented by the above formula (1b), has no epoxy group, and has a (meth) acryloyl group. It is preferable that an active compound is included.

  From the viewpoint of further improving the thermosetting property by the presence of the epoxy group, the curable compound is represented by the above formula (1B) or the above formula (1C), has an epoxy group, and (meth) It preferably contains a curable compound having an acryloyl group.

  In addition, the curable composition has a first curable compound having no epoxy group and having a (meth) acryloyl group, and a second curing having an epoxy group and having a (meth) acryloyl group. Both of them may be included. In this case, the number of (meth) acryloyl groups in the total 100% of the total number of epoxy groups and (meth) acryloyl groups of the curable compound exceeds 0%, preferably 20% or more, more preferably 30% or more, more preferably 40% or more and less than 100%, preferably 80% or less, more preferably 70% or less, and still more preferably 60% or less.

(Thermosetting agent)
In order to cure the curable composition by heating, the curable composition contains a thermosetting agent. In the curable composition according to the present invention, the thermosetting agent essentially contains a thermal radical generator. By using the thermal radical generator, the migration resistance of the connection structure is improved. Furthermore, the connection reliability between electrodes and the connection reliability of the connection structure under high temperature and high humidity are also improved.

  The thermal radical generator is not particularly limited. As the thermal radical generator, a conventionally known thermal radical generator can be used. As for the said thermal radical generator, only 1 type may be used and 2 or more types may be used together. The “thermal radical generator” means a compound that generates radical species by heating.

  The thermal radical generator is not particularly limited, and examples thereof include azo compounds and peroxides. Examples of the peroxide include diacyl peroxide compounds, peroxyester compounds, hydroperoxide compounds, peroxydicarbonate compounds, peroxyketal compounds, dialkyl peroxide compounds, and ketone peroxide compounds.

  Examples of the azo compound include 2,2′-azobisisobutyronitrile, 2,2′-azobis (2-methylbutyronitrile), and 2,2′-azobis (2,4-dimethylvaleronitrile). 1,1′-azobis-1-cyclohexanecarbonitrile, dimethyl-2,2′-azobisisobutyrate, dimethyl-2,2′-azobis (2-methylpropionate), dimethyl-1,1 ′ -Azobis (1-cyclohexanecarboxylate), 4,4'-azobis (4-cyanovaleric acid), 2,2'-azobis (2-amidinopropane) dihydrochloride, 2-tert-butylazo-2-cyanopropane 2,2′-azobis (2-methylpropionamide) dihydrate, 2,2′-azobis (2,4,4-trimethylpentane), and the like.

  Examples of the diacyl peroxide compound include benzoyl peroxide, diisobutyryl peroxide, di (3,5,5-trimethylhexanoyl) peroxide, dilauroyl peroxide, and disuccinic acid peroxide. Examples of the peroxyester compound include cumylperoxyneodecanoate, 1,1,3,3-tetramethylbutylperoxyneodecanoate, tert-hexylperoxyneodecanoate, and tert-butylperoxyneo. Decanoate, tert-butylperoxyneoheptanoate, tert-hexylperoxypivalate, 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate, 2,5-dimethyl-2 , 5-di (2-ethylhexanoylperoxy) hexane, tert-hexylperoxy-2-ethylhexanoate, tert-butylperoxypivalate, tert-butylperoxy-2-ethylhexanoate, tert -Butyl peroxyisobutyrate, tert-butyl per Kishiraureto, tert- butylperoxy isophthalate, tert- butylperoxy acetate, tert- butylperoxy octoate and tert- butyl peroxybenzoate, and the like. Examples of the hydroperoxide compound include cumene hydroperoxide and p-menthane hydroperoxide. Examples of the peroxydicarbonate compound include di-sec-butyl peroxydicarbonate, di (4-t-butylcyclohexyl) peroxydicarbonate, di-n-propyl peroxydicarbonate, diisopropyl peroxycarbonate, and di- (2-ethylhexyl) peroxycarbonate and the like. Other examples of the peroxide include methyl ethyl ketone peroxide, potassium persulfate, and 1,1-bis (tert-butylperoxy) -3,3,5-trimethylcyclohexane.

  The decomposition temperature for obtaining the 10-hour half-life of the thermal radical generator is preferably 30 ° C. or higher, more preferably 40 ° C. or higher, preferably 90 ° C. or lower, more preferably 80 ° C. or lower. When the decomposition temperature for obtaining the 10-hour half-life of the thermal radical generator is less than 30 ° C., the storage stability of the curable composition tends to decrease, and when it exceeds 90 ° C., the curable composition There is a tendency that it is difficult to sufficiently heat cure.

  The content of the thermal radical generator is not particularly limited. The content of the thermal radical generator is preferably 0.01 parts by weight or more, more preferably 0.05 parts by weight or more, preferably 10 parts by weight or less, more preferably 100 parts by weight of the curable compound. 5 parts by weight or less. When the content of the thermal radical generator is not less than the above lower limit and not more than the above upper limit, the curable composition is sufficiently thermally cured.

  When the said curable compound has an epoxy group etc., the said curable compound may further contain the other thermosetting agent different from the said thermal radical generator.

  Examples of the other thermosetting agent include a thermal cation initiator, an imidazole curing agent, an amine curing agent, a phenol curing agent, a polythiol curing agent, and an acid anhydride. As for said other thermosetting agent, only 1 type may be used and 2 or more types may be used together.

  From the viewpoint of curing the curable composition more rapidly at a low temperature, the other curing agent is an imidazole curing agent, an amine curing agent, a phenol curing agent, a polythiol curing agent, an acid anhydride, or a thermal cation initiator. It is preferably an imidazole curing agent, a polythiol curing agent, an amine curing agent, or a thermal cation initiator.

  Moreover, since the storage stability of a curable composition can be improved, a latent hardening | curing agent is preferable. The latent curing agent is preferably a latent imidazole curing agent, a latent polythiol curing agent or a latent amine curing agent. The other thermosetting agent may be coated with a polymer substance such as polyurethane resin or polyester resin.

  The imidazole curing agent is not particularly limited, and 2-methylimidazole, 2-ethyl-4-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-phenylimidazolium trimellitate, 2, 4-Diamino-6- [2'-methylimidazolyl- (1 ')]-ethyl-s-triazine and 2,4-diamino-6- [2'-methylimidazolyl- (1')]-ethyl-s- Examples include triazine isocyanuric acid adducts.

  The polythiol curing agent is not particularly limited, and examples include trimethylolpropane tris-3-mercaptopropionate, pentaerythritol tetrakis-3-mercaptopropionate, and dipentaerythritol hexa-3-mercaptopropionate. .

  The amine curing agent is not particularly limited, and hexamethylene diamine, octamethylene diamine, decamethylene diamine, 3,9-bis (3-aminopropyl) -2,4,8,10-tetraspiro [5.5]. Examples include undecane, bis (4-aminocyclohexyl) methane, metaphenylenediamine, and diaminodiphenylsulfone.

  The other curing agent is preferably a thermal cation initiator. The curable composition preferably contains a thermal cation initiator. As the thermal cation initiator, iodonium salts and sulfonium salts are preferably used. For example, commercially available products of the above thermal cation initiator include San-Aid SI-45L, SI-60L, SI-80L, SI-100L, SI-110L, SI-150L manufactured by Sanshin Chemical Co., Ltd., and ADEKA manufactured by ADEKA Optomer SP-150, SP-170 etc. are mentioned.

Preferred anionic portions of the thermal cationic initiator include SbF ₆ , PF ₆ , BF ₄ , and B (C ₆ F ₅ ) ₄ .

  The content of the other thermosetting agent is not particularly limited. The content of the other thermosetting agent with respect to 100 parts by weight of the curable compound is preferably 0.01 parts by weight or more, more preferably 0.05 parts by weight or more, still more preferably 5 parts by weight or more. Preferably it is 10 weight part or more, Preferably it is 40 weight part or less, More preferably, it is 30 weight part or less, More preferably, it is 20 weight part or less. When the content of the thermosetting agent is not less than the above lower limit and not more than the above upper limit, the curable composition is sufficiently thermoset.

  When the other curing agent is a thermal cation initiator, the content of the thermal cation initiator is preferably 0.01 parts by weight or more, more preferably 0 with respect to 100 parts by weight of the curable compound. 0.05 parts by weight or more, preferably 10 parts by weight or less, more preferably 5 parts by weight or less. When the content of the thermal cation initiator is not less than the above lower limit and not more than the above upper limit, the curable composition is sufficiently thermally cured.

(Photocuring initiator)
In order to cure the curable composition not only by heating but also by irradiation with light, the curable composition may contain a photocuring initiator. The photocuring initiator is not particularly limited. Conventionally known photocuring initiators can be used as the photocuring initiator. From the viewpoint of further improving the reactivity of the curable composition, the curable composition preferably contains a photoradical generator. By using the photo radical generator, the conduction reliability between the electrodes and the connection reliability of the connection structure are increased. As for the said photocuring initiator, only 1 type may be used and 2 or more types may be used together.

  The photocuring initiator is not particularly limited, and is not limited to acetophenone photocuring initiator (acetophenone photoradical generator), benzophenone photocuring initiator (benzophenone photoradical generator), thioxanthone, ketal photocuring initiator (ketal photoradical). Generator), halogenated ketones, acyl phosphinoxides, acyl phosphonates, and the like. Examples of the photocuring initiator include a photocationic initiator.

  Specific examples of the acetophenone photocuring initiator include 4- (2-hydroxyethoxy) phenyl (2-hydroxy-2-propyl) ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, methoxy Examples include acetophenone, 2,2-dimethoxy-1,2-diphenylethane-1-one, and 2-hydroxy-2-cyclohexylacetophenone. Specific examples of the ketal photocuring initiator include benzyldimethyl ketal.

  The curable composition preferably contains a photocationic initiator. By using a photocationic initiator, curing of the curable composition after light irradiation can be rapidly advanced. Furthermore, the curable composition portion that is blocked by the conductive particles and not directly irradiated with light can be sufficiently cured by the cation reaction due to the action of the photocation initiator.

  Examples of the photocationic curing agent include iodonium-based photocationic curing agents, oxonium-based photocationic curing agents, and sulfonium-based photocationic curing agents. Examples of the iodonium-based photocationic curing agent include bis (4-tert-butylphenyl) iodonium hexafluorophosphate. Examples of the oxonium-based photocationic curing agent include trimethyloxonium tetrafluoroborate. Examples of the sulfonium-based photocationic curing agent include tri-p-tolylsulfonium hexafluorophosphate and triphenylsulfonium bromide. Of these, a sulfonium-based photocationic curing agent is preferable from the viewpoint of further improving the reactivity of the curable composition and further improving the conduction reliability between the electrodes.

  The content of the photocuring initiator is not particularly limited. The content of the photocuring initiator (the content of the photocationic initiator when the photocuring initiator is a photocationic initiator) is preferably 0.1 wt. Part or more, more preferably 0.2 part by weight or more, preferably 2 parts by weight or less, more preferably 1 part by weight or less. When the content of the photocuring initiator is not less than the above lower limit and not more than the above upper limit, the curable composition is appropriately photocured. The flow of the curable composition can be suppressed by irradiating the curable composition with light to form a B-stage.

(Conductive particles)
The curable composition may contain conductive particles. A curable composition containing conductive particles can be used as an anisotropic conductive material.

  The conductive particles contained in the anisotropic conductive material electrically connect the electrodes of the first and second connection target members. The conductive particles are not particularly limited as long as they are conductive particles. The surface of the conductive layer of the conductive particles may be covered with an insulating layer. The surface of the conductive layer of the conductive particles may be covered with insulating particles. In these cases, the insulating layer or insulating particles between the conductive layer and the electrode are excluded when the connection target member is connected. Examples of the conductive particles include conductive particles obtained by coating the surfaces of organic particles, inorganic particles, organic-inorganic hybrid particles, or metal particles with a metal layer, and metal particles that are substantially composed of only metal. It is done. The metal layer is not particularly limited. Examples of the metal layer include a gold layer, a silver layer, a copper layer, a nickel layer, a palladium layer, and a metal layer containing tin.

  From the viewpoint of further improving the conduction reliability between the electrodes, the conductive particles preferably include resin particles and a conductive layer disposed on the surface of the resin particles.

  The content of the conductive particles is not particularly limited. In 100% by weight of the curable composition, the content of the conductive particles is preferably 0.1% by weight or more, more preferably 0.5% by weight or more, preferably 20% by weight or less, more preferably 15% by weight or less. It is. A conductive particle can be easily arrange | positioned between the upper and lower electrodes which should be connected as content of the said electroconductive particle is more than the said minimum and below the said upper limit. Furthermore, it becomes difficult to electrically connect adjacent electrodes that should not be connected via a plurality of conductive particles. That is, a short circuit between adjacent electrodes can be prevented.

(Other ingredients)
The curable composition according to the present invention preferably further contains a phenolic compound. The phenolic compound has a phenolic hydroxyl group in which a hydroxyl group is bonded to a benzene ring. Examples of the phenolic compound include polyphenol, triol, hydroquinone, and tocopherol (vitamin E). As for the said phenolic compound, only 1 type may be used and 2 or more types may be used together.

  The curable composition according to the present invention preferably further contains a filler. By using the filler, latent heat expansion of the cured product of the curable composition can be suppressed. Specific examples of the filler include silica, aluminum nitride, and alumina. As for a filler, only 1 type may be used and 2 or more types may be used together.

  The content of the filler is not particularly limited. The content of the filler is preferably 5 parts by weight or more, more preferably 15 parts by weight or more, preferably 200 parts by weight or less, more preferably 100 parts by weight or less with respect to 100 parts by weight of the total amount of the curable compound. When the content of the filler is not less than the above lower limit and not more than the above upper limit, latent heat expansion of the cured product can be sufficiently suppressed, and the filler can be sufficiently dispersed in the curable composition.

  The curable composition according to the present invention may contain a solvent. By using the solvent, the viscosity of the curable composition can be easily adjusted.

  Examples of the solvent include ethyl acetate, methyl cellosolve, toluene, acetone, methyl ethyl ketone, cyclohexane, n-hexane, tetrahydrofuran, and diethyl ether.

  The curable composition concerning this invention may further contain the storage stabilizer, the ion-trapping agent, the silane coupling agent, etc. as needed.

(Use of curable composition)
The curable composition concerning this invention can be used in order to adhere | attach various connection object members.

  When the curable composition according to the present invention is an anisotropic conductive material containing conductive particles, the anisotropic conductive material can be used as an anisotropic conductive paste, an anisotropic conductive film, or the like. When the anisotropic conductive material is an anisotropic conductive film, a film not containing conductive particles may be laminated on the anisotropic conductive film containing conductive particles. The film includes a sheet. The curable composition according to the present invention is preferably a paste-like anisotropic conductive paste.

  The anisotropic conductive material is suitably used for obtaining a connection structure in which the first and second connection target members are electrically connected.

  In FIG. 1, an example of the connection structure using the curable composition which concerns on one Embodiment of this invention is typically shown with sectional drawing.

  A connection structure 1 shown in FIG. 1 includes a first connection target member 2, a second connection target member 4, and a connection part 3 connecting the first and second connection target members 2 and 4. Prepare. The connection part 3 is formed by hardening the curable composition containing the electroconductive particle 5, ie, an anisotropic conductive material.

  The first connection target member 2 has a plurality of electrodes 2b on the upper surface 2a. The second connection target member 4 has a plurality of electrodes 4b on the lower surface 4a. The electrode 2b and the electrode 4b are electrically connected by one or a plurality of conductive particles 5. Therefore, the first and second connection target members 2 and 4 are electrically connected by the conductive particles 5.

  The curable composition according to the present invention is a paste-like anisotropic conductive paste, and is preferably an anisotropic conductive paste applied on the first connection target member in a paste-like state.

  The said 1st, 2nd connection object member is not specifically limited. Specific examples of the first and second connection target members include electronic components such as semiconductor chips, capacitors, and diodes, and electronic components such as printed circuit boards, flexible printed circuit boards, and glass substrates. It is done. The first and second connection target members are preferably electronic components. The curable composition according to the present invention is preferably a curable composition for connecting electronic components.

  The manufacturing method of the connection structure is not particularly limited. As an example of a method for manufacturing a connection structure, the curable composition is disposed between a first connection target member and a second connection target member to obtain a laminate, and then the laminate is heated and heated. The method of pressing is mentioned.

  In addition, the said curable composition does not need to contain electroconductive particle. In this case, the curable composition is used to bond and connect the first and second connection target members without electrically connecting the first and second connection target members.

When the curable composition according to the present invention is an anisotropic conductive material, the anisotropic conductive material is, for example, a connection between a flexible printed circuit board and a glass substrate (FOG (Film on Glass)), a semiconductor chip, and the like. Connection with flexible printed circuit board (COF (Chip on
Film)), connection between a semiconductor chip and a glass substrate (COG (Chip on Glass)), connection between a flexible printed circuit board and a glass epoxy substrate (FOB (Film on Board)), or the like. Especially, the said anisotropic conductive material is suitable for a FOG use or a COG use, and is more suitable for a COG use. The curable composition according to the present invention is preferably an anisotropic conductive material used for connection between a flexible printed circuit board and a glass substrate, or between a semiconductor chip and a flexible printed circuit board. It is more preferable that the conductive material is an anisotropic conductive material used for connection to the.

  In the connection structure according to the present invention, it is preferable to use a flexible printed circuit board and a glass substrate as the second connection target member and the first connection target member, or use a semiconductor chip and a glass substrate, It is more preferable to use a semiconductor chip and a glass substrate.

  In FOG applications, since the L / S is relatively wide, the particle size of the conductive particles is large and the concentration is low, so the pressure at the time of connection is low, sufficient indentation and resin filling properties cannot be obtained, and conduction reliability between electrodes And the occurrence of voids in the cured product layer is often a problem. On the other hand, the use of the curable composition according to the present invention can effectively increase the conduction reliability between the electrodes in the FOG application, and effectively generate voids in the cured product layer. It is possible to suppress.

  In COG applications, since the L / S is a relatively narrow pitch, if the fluidity when the anisotropic conductive material is heated is insufficient, the anisotropic conductive material is not sufficiently filled between the electrode lines. The reliability of conduction and the occurrence of voids in the cured product layer often become problems. On the other hand, the use of the curable composition according to the present invention can effectively increase the conduction reliability between electrodes in COG applications, and effectively suppress the generation of voids in the cured product layer. Is possible.

  Hereinafter, the present invention will be specifically described with reference to Examples and Comparative Examples. The present invention is not limited only to the following examples.

(Synthesis Example 1)
In the above formula (11), R1 and R2 each represents a methylene group, and a compound having an epoxy group in which all six groups R4, R5, R6, R7, and R8 represent hydrogen atoms was prepared. That is, a compound having an epoxy group represented by the following formula (11AA) was prepared.

上記式（１１ＡＡ）で表される硬化性化合物１００重量部と、アクリル酸５１重量部と、テトラ−ｎ−ブチルアンモニウムブロミド１重量部とを混合し、窒素雰囲気下で、１２０℃に加熱し、エポキシ基の数の１００％（エポキシ基の数の（メタ）アクリロイル基で変換された割合である転化率）がアクリロイル基で変換された硬化性化合物を得た。

100 parts by weight of the curable compound represented by the above formula (11AA), 51 parts by weight of acrylic acid, and 1 part by weight of tetra-n-butylammonium bromide are mixed and heated to 120 ° C. in a nitrogen atmosphere. A curable compound was obtained in which 100% of the number of epoxy groups (conversion rate, which is the ratio of epoxy groups converted by (meth) acryloyl groups) was converted by acryloyl groups.

¹ H-NMR of the obtained curable compound was measured using chloroform as a solvent. As a result, the signal in the region of 6.5 to 7.5 ppm indicating the presence of the epoxy group disappeared, and the signal appeared in the region of 2.5 to 3.5 ppm indicating the presence of the hydroxyl group. In addition, a signal in the region of 4 to 6 ppm indicating the presence of acryloyl group appeared. The obtained curable compound was a curable compound represented by the following formula (1AAA).

(Synthesis Examples 2 to 5)
A compound having an epoxy group represented by the above formula (11AA) was prepared.

  Curability in which the conversion rate, which is the ratio converted by the (meth) acryloyl group of the number of epoxy groups, is the value shown in Table 1 below, except that the amount of acrylic acid used was changed A compound was obtained.

¹ H-NMR of the obtained curable compound was measured using chloroform as a solvent. As a result, the signal in the 6.5 to 7.5 ppm region indicating the presence of the epoxy group was reduced, and the signal appeared in the 2.5 to 3.5 ppm region indicating the presence of the hydroxyl group. In addition, a signal in the region of 4 to 6 ppm indicating the presence of acryloyl group appeared. The obtained curable compound includes a curable compound represented by the above formula (1AAA), a curable compound represented by the following formula (1BBB), and a curable compound represented by the following formula (1CCC). Included.

(Synthesis Examples 6-8)
The number of epoxy groups was the same as in Synthesis Example 1 except that the compound having the epoxy group represented by the formula (11) shown in Table 1 below was used and the amount of acrylic acid used was changed. The curable compound whose conversion rate which is the ratio converted by the (meth) acryloyl group was the value shown in Table 1 below was obtained.

(Synthesis Example 9)
Conversion which is the ratio converted by the (meth) acryloyl group of the number of epoxy groups in the same manner as in Synthesis Example 1 except that methacrylic acid was used instead of acrylic acid and the amount of methacrylic acid used was changed. The curable compound whose rate is the value shown in Table 1 below was obtained.

  In Examples and Comparative Examples, the following materials were used as components other than the curable compounds obtained in Synthesis Examples 1 to 9.

(Other curable compounds)
Curable compound A (epoxy acrylate, "Epoxy ester 3000A" manufactured by Kyoeisha Chemical Co., Ltd.)
Curable compound B (epoxy acrylate, “Epoxy ester M-600A” manufactured by Kyoeisha Chemical Co., Ltd.)

(Thermal radical generator)
Thermal radical generator A (Nippon "Perbutyl O")
Thermal radical generator B (Nippon "Perhexyl PV")

(Photocuring initiator)
Photopolymerization initiator A ("DAROCUR TPO" manufactured by BASF)
Photoinitiator B ("IRGUCURE 819" manufactured by BASF)

(Filler)
Silica (average particle size 0.25μm)
Alumina (average particle size 0.5μm)

(Conductive particles)
Conductive particles (having a metal layer in which a nickel plating layer is formed on the surface of divinylbenzene resin particles and a gold plating layer is formed on the surface of the nickel plating layer)

Example 1
Using the curable compound obtained in Synthesis Example 1, the components shown in Table 2 below were blended in the blending amounts shown in Table 2 below, and the mixture was stirred at 2000 rpm for 5 minutes using a planetary stirrer. A formulation was obtained. The obtained composition was filtered using a nylon filter paper (pore diameter: 10 μm) to obtain a curable composition (anisotropic conductive paste).

(Examples 2 to 13 and Comparative Examples 1 and 2)
A curable composition (anisotropic conductive paste) was obtained in the same manner as in Example 1 except that the types and amounts of the ingredients were changed as shown in Table 2 below.

(Evaluation)
(1) Storage stability of curable composition The curable composition immediately after preparation was left to stand at 25 degreeC for 24 hours. The storage stability of the curable composition was evaluated from the change in viscosity of the curable composition before and after standing. In the viscosity measurement, an E-type viscosity measuring device (manufactured by Toki Sangyo Co., Ltd., trade name: VISCOMETER TV-22, rotor used: φ15 mm, temperature: 25 ° C.) The viscosity (10 rpm) was measured. The storage stability of the curable composition was determined according to the following criteria.

[Criteria for Storage Stability of Curable Composition]
◯: The viscosity after 24 hours is 1 time or more and less than 1.1 times the initial viscosity ○: The viscosity after 24 hours is 1.1 times or more and less than 1.3 times the initial viscosity ×: After 24 hours Is 1.3 times or more of the initial viscosity.

(2) Fabrication of connection structure (COG):
A glass substrate (first connection target member) having an Al—Nd electrode pattern with an L / S of 15 μm / 15 μm on the upper surface was prepared. Further, a semiconductor chip (second connection target member) having a Cu electrode pattern with L / S of 15 μm / 15 μm on the lower surface was prepared.

  On the said glass substrate, the curable composition was apply | coated using the dispenser so that it might become thickness 20 micrometers, and the curable composition layer was formed. Next, the semiconductor chip was laminated on the curable composition layer so that the electrodes face each other.

  When the curable compositions of Examples 1 to 11 and Comparative Examples 1 and 2 were used, BD-02 manufactured by Ohashi Seisakusho was used, and the temperature of the curable composition layer was 170 ° C. (main press bonding temperature). While adjusting the temperature of the thermocompression bonding head, the pressure bonding head is placed on the upper surface of the semiconductor chip, the pressure of 1 MPa is applied and the curable composition layer is cured at 170 ° C. for 5 seconds, and the connection structure (COG) is formed. Obtained.

When the curable compositions of Examples 12 and 13 were used, the semiconductor chip was laminated on the curable composition layer so that the electrodes were opposed to each other. A 365 nm ultraviolet ray was irradiated for 3 seconds so that the light irradiation intensity was 3000 mW / cm ^2, and the curable composition layer was semi-cured by photopolymerization to form a B stage. Then, using a BD-02 manufactured by Ohashi Seisakusho, adjusting the temperature of the thermocompression bonding head so that the temperature of the curable composition layer is 170 ° C. (main compression bonding temperature), the pressure bonding head is placed on the upper surface of the semiconductor chip. The curable composition layer was cured by applying a pressure of 1 MPa at 170 ° C. for 5 seconds to obtain a connection structure (COG).

(3) Fabrication of connection structure (FOG):
A glass substrate (first connection target member) having an Au electrode pattern with an L / S of 50 μm / 50 μm on the upper surface was prepared. Moreover, the flexible printed circuit board (2nd connection object member) which has Cu electrode pattern whose L / S is 40 micrometers / 40 micrometers on the lower surface was prepared.

  On the said glass substrate, the curable composition was apply | coated using the dispenser so that it might become thickness 40 micrometers, and the curable composition layer was formed. Next, the flexible printed circuit board was laminated on the curable composition layer so that the electrodes face each other.

  When the curable compositions of Examples 1 to 11 and Comparative Examples 1 and 2 were used, BD-02 manufactured by Ohashi Seisakusho was used, and the temperature of the curable composition layer was 170 ° C. (main press bonding temperature). While adjusting the temperature of the thermocompression bonding head, the pressure bonding head is placed on the upper surface of the flexible printed circuit board, the pressure of 1 MPa is applied and the curable composition layer is cured at 170 ° C. for 5 seconds, and the connection structure (COG) Got.

When the curable compositions of Examples 12 and 13 were used, 365 nm ultraviolet rays were irradiated for 3 seconds so that the light irradiation intensity was 3000 mW / cm ^2, and the curable composition layer was semi-cured by photopolymerization. , B stage. Then, using a BD-02 manufactured by Ohashi Seisakusho, adjusting the temperature of the thermocompression bonding head so that the temperature of the curable composition layer is 170 ° C. (main compression bonding temperature), the pressure bonding head is placed on the upper surface of the semiconductor chip. The curable composition layer was cured by applying a pressure of 1 MPa at 170 ° C. for 5 seconds to obtain a connection structure (COG).

(4) Migration resistance The obtained connection structure (COG) and the obtained connection structure (FOG) at 85 ° C. and 85% RH with a voltage of 20 V applied between measurement terminals insulated from each other. Exposure was performed for 500 hours in an atmosphere (insulation reliability test). During this time, the change in resistance value between the measurement terminals was measured. The case where the resistance value was 10 ⁵ Ω or less was judged as an insulation failure. Migration resistance was determined according to the following criteria.

[Judgment criteria for migration resistance]
◯: Among 10 connection structures, there is no connection structure in which an insulation failure occurs, and the average resistance value after the insulation reliability test is 10 ⁷ Ω or more. ○: Among 10 connection structures, There is no connection structure in which insulation failure has occurred, and the average resistance value after the insulation reliability test is 10 ⁶ Ω or more and less than 10 ⁷ Ω Δ: Of 10 connection structures, connection in which insulation failure has occurred There is no structure, and the average resistance value after the insulation reliability test is 10 ⁵ Ω or more and less than 10 ⁶ Ω x: Among 10 connection structures, there is one or more connection structures in which insulation failure occurs

(5) Conductivity 20-point resistance values of the obtained connection structure (COG) and the obtained connection structure (FOG) were evaluated by a four-terminal method. The conductivity was determined according to the following criteria.

[Conductivity criteria]
○: The resistance value is 3Ω or less in all locations. Δ: There are one or more locations where the resistance value exceeds 3Ω. ×: There are one or more locations that are not conducting at all.

(6) Connection reliability after thermal history The obtained connection structure (COG) and the obtained connection structure (FOG) 100 pieces were each held at −30 ° C. for 5 minutes, and then to 120 ° C. for 25 minutes. The temperature was raised at 120 ° C., held at 120 ° C. for 5 minutes, and then subjected to a cooling / heating cycle test in which the process of lowering the temperature to −30 ° C. in 25 minutes was one cycle. After 1000 cycles, the connection structure was removed.

  About 100 connection structures after the thermal cycle test, it was evaluated whether or not conduction failure between the upper and lower electrodes occurred. Of the 100 connection structures, the case where the number of defective conductions is 1 or less is “◯”, the case of 2 or more, 3 or less is “Δ”, the case of 4 or more It was determined as “x”.

  The results are shown in Table 2 below.

DESCRIPTION OF SYMBOLS 1 ... Connection structure 2 ... 1st connection object member 2a ... Upper surface 2b ... 1st electrode 3 ... Connection part 4 ... 2nd connection object member 4a ... Lower surface 4b ... 2nd electrode 5 ... Conductive particle

Claims (12)

A curable compound having no epoxy group or having an epoxy group and having a (meth) acryloyl group, and a thermal radical generator,
The curable composition obtained by making (meth) acrylic acid react with a part or all of the epoxy group of the compound in which the said curable compound has an epoxy group represented by following formula (11-1).

In the formula (11-1), R1 and R2 each represent an alkylene group having 1 to 5 carbon atoms, and 4 to 6 groups out of 6 groups of R3, R4, R5, R6, R7 and R8. Represents a hydrogen atom, and the group that is not a hydrogen atom among R3, R4, R5, R6, R7, and R8 represents a group represented by the following formula (11a).

In said formula (11a), R9 represents a C1-C5 alkylene group. The curable compound according to claim 1, wherein the curable compound is obtained by reacting (meth) acrylic acid with part or all of the epoxy group of the compound having an epoxy group represented by the following formula (11). Composition.

In the formula (11), R1 and R2 each represent an alkylene group having 1 to 5 carbon atoms, and 4 to 6 groups out of 6 groups of R3, R4, R5, R6, R7 and R8 are hydrogen. The group which represents an atom and is not a hydrogen atom among R3, R4, R5, R6, R7 and R8 represents a group represented by the formula (11a).   The curable composition according to claim 1 or 2, wherein the curable compound is obtained by reacting (meth) acrylic acid with 20% or more and 100% or less of the number of epoxy groups. The curable compound is obtained by reacting a part of the epoxy group with (meth) acrylic acid,
The curable composition according to any one of claims 1 to 3, wherein the curable compound has an epoxy group and a (meth) acryloyl group.   The curable composition according to claim 4, wherein the curable compound is obtained by reacting (meth) acrylic acid with 20% or more and 80% or less of the number of epoxy groups. The curable compound is obtained by reacting all of the epoxy groups with (meth) acrylic acid,
The curable composition according to any one of claims 1 to 3, wherein the curable compound does not have an epoxy group and has a (meth) acryloyl group. A curable compound having no epoxy group or having an epoxy group and having a (meth) acryloyl group, and a thermal radical generator,
The curable composition in which the curable compound is represented by the following formula (1A), the following formula (1B), or the following formula (1C).

In the formula (1A), R1 and R2 each represent an alkylene group having 1 to 5 carbon atoms, and 4 to 6 groups out of 6 groups of R3, R4, R5, R6, R7 and R8 are hydrogen. A group which is an atom and is not a hydrogen atom among R3, R4, R5, R6, R7 and R8 represents a group represented by the following formula (1a) or the following formula (1b), and R10 and R11 are each hydrogen. Represents an atom or a methyl group.

In the formula (1B), R1 and R2 each represent an alkylene group having 1 to 5 carbon atoms, and 4 to 6 groups out of 6 groups of R3, R4, R5, R6, R7 and R8 are hydrogen. A group which is an atom and is not a hydrogen atom among R3, R4, R5, R6, R7 and R8 represents a group represented by the following formula (1a) or the following formula (1b), and R10 is a hydrogen atom or methyl Represents a group.

In the formula (1C), R1 and R2 each represent an alkylene group having 1 to 5 carbon atoms, and 4 to 6 groups out of 6 groups of R3, R4, R5, R6, R7 and R8 are hydrogen. A group which is an atom and is not a hydrogen atom among R3, R4, R5, R6, R7 and R8 represents a group represented by the following formula (1a) or the following formula (1b), and R11 is a hydrogen atom or methyl Represents a group.

In said formula (1a), R9 represents a C1-C5 alkylene group.

In said formula (1b), R9 represents a C1-C5 alkylene group, R12 represents a hydrogen atom or a methyl group.   The curable compound is represented by the formula (1A), and the group that is not a hydrogen atom among R3, R4, R5, R6, R7 and R8 in the formula (1A) is represented by the formula (1b). The curable composition according to claim 7, which comprises a curable compound that is a group that has no epoxy group and has a (meth) acryloyl group.     The said curable compound is represented by the said Formula (1B) or the said Formula (1C), has an epoxy group, and contains the curable compound which has a (meth) acryloyl group. Curable composition.   The curable composition of any one of Claims 1-9 which further contains a photocuring initiator.   The curable composition of any one of Claims 1-10 which further contains electroconductive particle. A first connection target member, a second connection target member, and a connection part connecting the first and second connection target members;
The connection structure in which the said connection part is formed with the curable composition of any one of Claims 1-11.

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