JP2014084357A - Anisotropically conductive adhesive composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an anisotropically conductive adhesive composition can attach at low temperature for a short time, excellent in connection reliability and storage stability.SOLUTION: An anisotropically conductive adhesive composition containing (A) a sulfonium salt compound represented by the general formula (I), (B) a cationic polymerizable material and (C) a conductive particle is provided. In the formula (I), Ris an arylmethyl group, an allyl group and the like, Rand Rrepresent each independently an alkyl group, an aryl group and the like, Yrepresents [P(CF)F]or [C(CFSO)]and the like, however Rand Rmay form a ring together, at least one of Rand Ris an aryl group and the like when Ris an arylmethyl group and the like, and Rand Ris an alkyl group or a ring formed from Rand Rtogether when Ris an allyl group and the like.

Description

  The present invention relates to an anisotropic conductive adhesive composition.

  In recent years, various adhesive materials have been used to fix electronic components and connect circuits in the fields of semiconductors and liquid crystal displays. In these applications, higher density and higher definition are required, and high adhesive strength and connection reliability are required for adhesives.

  In particular, as a circuit connection material in the connection between the liquid crystal display and the tape carrier package (TCP), the connection between the flexible printed wiring board (FPC) and the TCP, or the connection between the FPC and the printed wiring board, conductive particles are used in the adhesive. A dispersed anisotropic conductive adhesive is used. Recently, even when a semiconductor silicon chip is mounted on a substrate, so-called chip-on-glass (COG) mounting in which the semiconductor silicon chip is directly mounted on the substrate is used instead of the conventional wire bond. A conductive adhesive is applied.

  In recent years, in the field of precision electronic equipment, the density of circuits has been increasing, and the electrode width and electrode interval have become extremely narrow. For this reason, the connection conditions of conventional adhesives for circuit connection using an epoxy resin system have problems such as dropping, peeling, and misalignment of wiring. In COG mounting, this is caused by the difference in thermal expansion between the chip and the substrate. There is a problem that warping occurs. In order to further reduce the cost, it is necessary to improve the throughput, and an adhesive that can be cured at low temperature (for example, 100 to 170 ° C.), for a short time (for example, within 10 seconds), in other words, for low-temperature rapid curing is required. Has been.

  As the cationic polymerization initiator, for example, a polymerization initiator of a cationic polymerizable substance mainly composed of a sulfonium salt compound represented by the following general formula (IX) has been proposed (Patent Document 1).

［式（ＩＸ）中、Ｒ_ａは水素、メチル基、アセチル基、メトキシカルボニル基、エトキシカルボニル基、ベンジルオキシカルボニル基、ベンゾイル基、フェノキシカルボニル基、９−フルオレニルメトキシカルボニル基のいずれかを、Ｒ_ｂ、Ｒ_ｃは独立して水素、ハロゲン、Ｃ_１〜Ｃ_４のアルキル基のいずれかを、Ｒ_ｄはＣ_１〜Ｃ_４のアルキル基を、Ｑはｏ−ニトロベンジル基、ｍ−ニトロベンジル基、ジニトロベンジル基、トリニトロベンジル基、α−ナフチルメチル基、β−ナフチルメチル基のいずれかを示す。ＸはＳｂＦ_６、ＡｓＦ_６、ＰＦ_６、ＢＦ_４のいずれかである。］

[In the formula (IX), _Ra represents any one of hydrogen, methyl group, acetyl group, methoxycarbonyl group, ethoxycarbonyl group, benzyloxycarbonyl group, benzoyl group, phenoxycarbonyl group, and 9-fluorenylmethoxycarbonyl group. , R _b and R _c are each independently hydrogen, halogen, or a C _{1 to} C ₄ alkyl group, R _d is a C _{1 to} C ₄ alkyl group, Q is an o-nitrobenzyl group, m- A nitrobenzyl group, a dinitrobenzyl group, a trinitrobenzyl group, an α-naphthylmethyl group, or a β-naphthylmethyl group is shown. X is SbF ₆ , AsF ₆ , PF ₆ , or BF ₄ . ]

  Further, as a polymerization initiator capable of curing an epoxy resin in a short time by heating, a cationic polymerization initiator containing a sulfonium salt compound represented by the following general formula (X) or the following general formula (XI) has been proposed. (Patent Document 2).

［式（Ｘ）中、Ｒ_ｅは、水素原子、アルキル基、ハロゲン原子、カルボキシル基又はアルコキシカルボニル基を表し、Ｒ_ｆはアルキル基を表し、Ｒ_ｇは置換されていてもよいフェニル基又は置換されていてもよいナフチル基を表し、Ｘは、ＳｂＦ_６、ＡｓＦ_６、ＰＦ_６又はＢＦ_４を表す。］

[In the formula (X), R _e represents a hydrogen atom, an alkyl group, a halogen atom, a carboxyl group or an alkoxycarbonyl group, R _f represents an alkyl group, and R _g represents an optionally substituted phenyl group or a substituted group. Represents an optionally substituted naphthyl group, and X represents SbF ₆ , AsF ₆ , PF ₆ or BF ₄ . ]

［式（ＸＩ）中、Ｒ_ｈは、水素原子、アルキル基、ハロゲン原子、水酸基、アルコキシ基、カルボキシル基又はアルカノイル基を表し、Ｒ_ｉはアルキル基を表し、Ｒ_ｊは、アルケニル基、α−アルキルベンジル基、α，α−ジアルキルベンジル基、α−フェニルベンジル基又はフルオレニル基を表し、ＸはＳｂＦ_６、ＡｓＦ_６、ＰＦ_６又はＢＦ_４を表す。］

[In the formula (XI), R _h represents a hydrogen atom, an alkyl group, a halogen atom, a hydroxyl group, an alkoxy group, a carboxyl group or an alkanoyl group, R _i represents an alkyl group, R _j represents an alkenyl group, α- An alkylbenzyl group, an α, α-dialkylbenzyl group, an α-phenylbenzyl group or a fluorenyl group is represented, and X represents SbF ₆ , AsF ₆ , PF ₆ or BF ₄ . ]

JP-A-3-237107 JP-A-6-345726

By the way, as a result of intensive studies by the present inventors, when the cationic polymerization initiator described in Patent Document 1 or 2 is used, the obtained anisotropic conductive adhesive has a problem that it easily corrodes metal and semiconductor wiring. I found. This is presumed that the above polymerization initiator has SbF ₆ , AsF ₆ , PF ₆ or BF ₄ as X, but X has a weak bond between the central atom and the fluorine atom, and the fluorine ion is easily detached. Is done. Further, in order to prepare an adhesive that can be cured at a low temperature and fast (for example, 100 to 170 ° C. within 10 seconds), SbF ₆ is the most active among SbF ₆ , AsF ₆ , PF ₆ and BF ₄ as X. However, SbF ₆ has a problem from the viewpoint of environmental safety.

  The present invention has been made in view of the above circumstances, and can be bonded in a short time at a low temperature, has excellent connection reliability, and has excellent storage stability, and an anisotropic conductive adhesive composition and a film thereof. An object of the present invention is to provide a film adhesive. It is another object of the present invention to provide a connection structure, a method for manufacturing the same, and a semiconductor device using the anisotropic conductive adhesive composition.

  This invention provides the anisotropic conductive adhesive composition as described in the following (1)-(10), and the film adhesive as described in the following (11) which makes these into a film form. In addition, a connection structure, a manufacturing method thereof, and a semiconductor device using the anisotropic conductive adhesive composition are provided.

［式中、Ｒ^１は置換若しくは未置換のアリールメチル基、又は置換若しくは未置換のアリル基を示し、Ｒ^２及びＲ^３は、それぞれ独立に、アルキル基、又は置換若しくは未置換のアリール基を示し、Ｙ⁻は［Ｐ（Ｒ^４）_ａ（Ｆ）_６−ａ］⁻（式中、Ｒ^４は水素原子の少なくとも一部がフッ素原子で置換されているアルキル基を示し、ａは１〜６の整数を示す。ａが２以上の整数である場合、複数存在するＲ^４は、互いに同一であっても異なっていてもよい。）、又は［Ｃ（（Ｒ^５）ＳＯ_２）_３］⁻（式中、Ｒ^５は水素原子の少なくとも一部がフッ素原子で置換されているアルキル基を示し、複数存在するＲ^５は、互いに同一であっても異なっていてもよい。）を示す。ただし、Ｒ^２及びＲ^３は一緒になって環を形成していてもよく、Ｒ^１が置換又は未置換のアリールメチル基である場合には、Ｒ^２及びＲ^３の少なくとも一方が置換又は未置換のアリール基であり、Ｒ^１が置換又は未置換のアリル基である場合には、Ｒ^２及びＲ^３はアルキル基、又はＲ^２及びＲ^３が一緒になって形成された環である。］
（２）上記（Ａ）成分として、下記一般式（ＩＩ）で表されるスルホニウム塩化合物を含有する、（１）に記載の異方導電性接着剤組成物。

［式中、Ａｒ^１及びＡｒ^２は、それぞれ独立に、置換又は未置換のアリール基を示し、Ｙ⁻は上記と同義である。］
（３）上記（Ａ）成分として、下記一般式（ＩＩＩ）で表されるスルホニウム塩化合物を含有する、（２）に記載の異方導電性接着剤組成物。

［式中、Ｙ⁻は上記と同義である。］
（４）上記（Ａ）成分として、下記一般式（ＩＶ）で表されるスルホニウム塩化合物を含有する、（１）に記載の異方導電性接着剤組成物。

［式中、Ａ^１及びＡ^２は、それぞれ独立にアルキル基を示し、Ｒ^６、Ｒ^７及びＲ^８は、それぞれ独立に、水素原子、アルキル基、又は置換若しくは未置換のアリール基を示し、Ｙ⁻は上記と同義である。ただし、Ａ^１及びＡ^２は一緒になって環を形成していてもよい。］
（５）上記（Ａ）成分として、一般式（Ｖ）、（ＶＩ）、（ＶＩＩ）又は（ＶＩＩＩ）で表されるスルホニウム塩化合物を含有する、（４）に記載の異方導電性接着剤組成物。

［式中、Ｙ⁻は上記と同義である。］
（６）上記（Ａ）成分として、グリシジルエーテル型エポキシ化合物との混合物についての示差走査熱量測定において、ピーク温度４０〜１５０℃を与えるスルホニウム塩化合物を含有する、（１）〜（５）のいずれかに記載の異方導電性接着剤組成物。
（７）上記（Ｂ）成分として、エポキシ化合物、オキセタン化合物及びビニルエーテル化合物からなる群より選ばれる少なくとも一種を含有する、（１）〜（６）のいずれかに記載の異方導電性接着剤組成物。
（８）（Ｄ）フィルム形成性ポリマーを更に含有する、（１）〜（７）のいずれかに記載の異方導電性接着剤組成物。
（９）回路接続用接着剤として使用される、（１）〜（８）のいずれかに記載の異方導電性接着剤組成物。
（１０）加熱により硬化される、（１）〜（９）のいずれかに記載の異方導電性接着剤組成物。
（１１）（１）〜（１０）のいずれかに記載の異方導電性接着剤組成物をフィルム状にしてなる、フィルム状接着剤。
（１２）第一の回路電極を有する第一の回路部材と、第二の回路電極を有する第二の回路部材と、上記第一の回路部材及び上記第二の回路部材の間に配置され、上記第一の回路電極と上記第二の回路電極とを電気的に接続する回路接続部材と、を備え、上記回路接続部材が（１）〜（１０）のいずれかに記載の異方導電性接着剤組成物の硬化物を含む、接続構造体。
（１３）第一の回路電極を有する第一の回路部材と、第二の回路電極を有する第二の回路部材との間に（１）〜（１０）のいずれかに記載の異方導電性接着剤組成物を配置し、上記異方導電性接着剤組成物を介して、上記第一の回路部材及び上記第二の回路部材を加熱及び加圧して、上記第一の回路電極及び上記第二の回路電極を電気的に接続する工程を備える、接続構造体の製造方法。
（１４）半導体素子と、回路パターンを有する基板と、上記半導体素子及び上記基板の間に配置され、上記半導体素子と上記回路パターンとを電気的に接続する半導体素子接続部材と、を備え、上記半導体素子接続部材が（１）〜（１０）のいずれかに記載の異方導電性接着剤組成物の硬化物を含む、半導体装置。 (1) An anisotropic conductive adhesive composition comprising (A) a sulfonium salt compound represented by the following general formula (I), (B) a cationic polymerizable substance, and (C) conductive particles. .

[Wherein, R ¹ represents a substituted or unsubstituted arylmethyl group or a substituted or unsubstituted allyl group, and R ² and R ³ each independently represents an alkyl group or a substituted or unsubstituted aryl group. shows, Y ^- is _{^{[P (R 4) a (}} F) 6-a] - ( wherein, ^{R 4} represents an alkyl group wherein at least a portion of the hydrogen atoms are substituted by fluorine atoms, a is 1 6 represents an integer of 6. When a is an integer of 2 or more, a plurality of R ⁴ may be the same or different from each other.), Or [C ((R ⁵ ) SO ₂ ) ₃ ] ^- (In the formula, R ⁵ represents an alkyl group in which at least a part of hydrogen atoms are substituted with fluorine atoms, and a plurality of R ⁵ may be the same or different from each other). However, R ² and R ³ may be combined to form a ring, and when R ¹ is a substituted or unsubstituted arylmethyl group, at least one of R ² and R ³ is substituted or unsubstituted. When R ¹ is a substituted aryl group and R ¹ is a substituted or unsubstituted allyl group, R ² and R ³ are alkyl groups or a ring formed by combining R ² and R ³ together. ]
(2) The anisotropic conductive adhesive composition according to (1), which contains a sulfonium salt compound represented by the following general formula (II) as the component (A).

[Wherein, Ar ¹ and Ar ² each independently represent a substituted or unsubstituted aryl group, and Y ⁻ is as defined above]. ]
(3) The anisotropic conductive adhesive composition according to (2), which contains a sulfonium salt compound represented by the following general formula (III) as the component (A).

[Wherein Y ⁻ has the same meaning as described above. ]
(4) The anisotropic conductive adhesive composition according to (1), which contains a sulfonium salt compound represented by the following general formula (IV) as the component (A).

[Wherein, A ¹ and A ² each independently represent an alkyl group, and R ⁶ , R ⁷ and R ⁸ each independently represent a hydrogen atom, an alkyl group, or a substituted or unsubstituted aryl group, Y ⁻ has the same meaning as described above. However, A ¹ and A ² may together form a ring. ]
(5) The anisotropic conductive adhesive according to (4), which contains a sulfonium salt compound represented by the general formula (V), (VI), (VII) or (VIII) as the component (A). Composition.

[Wherein Y ⁻ has the same meaning as described above. ]
(6) Any of (1) to (5), which contains a sulfonium salt compound that gives a peak temperature of 40 to 150 ° C. in the differential scanning calorimetry of the mixture with the glycidyl ether type epoxy compound as the component (A). An anisotropic conductive adhesive composition according to claim 1.
(7) The anisotropic conductive adhesive composition according to any one of (1) to (6), which contains at least one selected from the group consisting of an epoxy compound, an oxetane compound, and a vinyl ether compound as the component (B). object.
(8) The anisotropic conductive adhesive composition according to any one of (1) to (7), further comprising (D) a film-forming polymer.
(9) The anisotropic conductive adhesive composition according to any one of (1) to (8), which is used as an adhesive for circuit connection.
(10) The anisotropic conductive adhesive composition according to any one of (1) to (9), which is cured by heating.
(11) A film adhesive obtained by forming the anisotropic conductive adhesive composition according to any one of (1) to (10) into a film.
(12) The first circuit member having the first circuit electrode, the second circuit member having the second circuit electrode, the first circuit member, and the second circuit member are disposed, A circuit connection member for electrically connecting the first circuit electrode and the second circuit electrode, wherein the circuit connection member is anisotropically conductive according to any one of (1) to (10). A connection structure including a cured product of the adhesive composition.
(13) The anisotropic conductivity according to any one of (1) to (10), between a first circuit member having a first circuit electrode and a second circuit member having a second circuit electrode. An adhesive composition is disposed, and the first circuit member and the second circuit member are heated and pressurized via the anisotropic conductive adhesive composition, and the first circuit electrode and the second circuit member are heated. A method for manufacturing a connection structure, comprising a step of electrically connecting two circuit electrodes.
(14) A semiconductor element, a substrate having a circuit pattern, and a semiconductor element connecting member that is disposed between the semiconductor element and the substrate and electrically connects the semiconductor element and the circuit pattern. The semiconductor device in which a semiconductor element connection member contains the hardened | cured material of the anisotropically conductive adhesive composition in any one of (1)-(10).

  The present invention further includes application of the anisotropic conductive adhesive composition according to any one of (1) to (10) or the film-like adhesive according to (11) as an adhesive for circuit connection, or The anisotropic conductive adhesive composition or the film-like adhesive may be applied to produce an adhesive for circuit connection.

  ADVANTAGE OF THE INVENTION According to this invention, the anisotropic conductive adhesive composition which can be adhere | attached in low temperature for a short time, is excellent in connection reliability, and is excellent in storage stability, and the film adhesive which makes these into a film form are provided. can do. Moreover, the connection structure using the anisotropic conductive adhesive composition, the manufacturing method thereof, and the semiconductor device can be provided.

It is a schematic cross section which shows one Embodiment of a film adhesive. It is a schematic cross section showing one embodiment of a connection structure. (A)-(c) is a series of process drawings which manufacture a connection structure, respectively. It is a fragmentary sectional view showing one embodiment of a semiconductor device. It is a graph which shows the relationship between the curing temperature and the curing rate of the film-like adhesives of Examples 1 to 4 and Comparative Examples 1 and 4 obtained in the curing rate measurement test.

  Hereinafter, preferred embodiments of the present invention will be described in detail. However, the present invention is not limited to the following embodiments.

[Anisotropic conductive adhesive composition]
The anisotropic conductive adhesive composition according to the present embodiment (hereinafter, also simply referred to as “adhesive composition”) is a (A) sulfonium salt compound represented by the general formula (I) (hereinafter referred to as “ (A) component ”), (B) a cationic polymerizable substance (hereinafter, sometimes referred to as“ (B) component ”), and (C) conductive particles.

  The sulfonium salt compound is a compound represented by the following general formula (I).

In the formula, R ¹ represents a substituted or unsubstituted arylmethyl group or a substituted or unsubstituted allyl group, and R ² and R ³ each independently represents an alkyl group or a substituted or unsubstituted aryl group. , Y ⁻ represents a counter anion. However, R ² and R ³ may be combined to form a ring.

  As an alkyl group, a C1-C6 alkyl group is mentioned, for example. More specifically, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a t-butyl group, a pentyl group, and a hexyl group are exemplified. These may have a substituent, and the substitution position of the substituent is not particularly limited, and may be any position.

  As an aryl group, a C6-C12 aryl group is mentioned, for example. More specifically, a phenyl group, 1-naphthyl group, and 2-naphthyl group are exemplified. These may have a substituent, and the substitution position of the substituent is not particularly limited, and may be any position.

  Examples of the arylmethyl group include those in which one of the hydrogen atoms in the methyl group is substituted with the above-described aryl group. More specifically, a benzyl group, 1-naphthylmethyl group, and 2-naphthylmethyl group are exemplified. These may have a substituent, and the substitution position of the substituent is not particularly limited, and may be any position.

Examples of the ring which R ² and R ³ may be formed together include those represented by the following formula (α). These may have a substituent, and the substitution position of the substituent is not particularly limited, and may be any position.

  Examples of the substituent that each group described above may have include, for example, alkyl groups such as a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a t-butyl group, a pentyl group, and a hexyl group. Aryl groups such as phenyl and naphthyl groups; alkoxy groups such as methoxy, ethoxy, propoxy, and butoxy; alkoxycarbonyl groups such as acetoxy, propionyloxy, decylcarbonyloxy, and dodecylcarbonyloxy; Examples thereof include ester groups such as carbonyl group, ethoxycarbonyl group and benzoyloxy group; halogen atoms such as fluorine, chlorine, bromine and iodine; cyano group, nitro group and hydroxy group. The substitution position of these substituents is not particularly limited and may be any position.

  In addition, in the allyl group which has a substituent, when it has a cis-trans isomer, either isomer may be sufficient.

The counter anion represented by Y ⁻ is [P (R ⁴ ) _a (F) _6-a ] ⁻ (wherein R ⁴ represents an alkyl group in which at least a part of hydrogen atoms are substituted with fluorine atoms, a represents an integer of 1 to 6. When a is an integer of 2 or more, a plurality of R ⁴ may be the same or different from each other), or [C ((R ⁵ ) SO ₂ ) ₃ ] ^- (wherein, R ⁵ represents an alkyl group in which at least a part of hydrogen atoms are substituted with fluorine atoms, and a plurality of R ⁵ may be the same or different from each other). ). Y ^- is preferably has a low nucleophilicity.

In addition, as [P (R ⁴ ) _a (F) _6-a ] ^— , it is preferable that 80% or more of the hydrogen atoms in the alkyl group of R ⁴ are substituted with fluorine atoms, and in the alkyl group of R ⁴ More preferably, 90% or more of the hydrogen atoms are substituted with fluorine atoms, and R ⁴ is more preferably a linear or branched perfluoroalkyl group. Specifically, [P (CF ₃ ) ₃ (F) ₃ ] ⁻ , [P (C ₂ F ₅ ) ₃ (F) ₃ ] ⁻ and [P (n—C ₃ F ₇ ) ₃ (F) ₃ ] ^-, and the like. These counter anions may be used alone or in combination of two or more.

_{^{Also, [C ((R 5)}} SO 2) 3] - as is preferably 80% or more of the hydrogen atoms in the alkyl group for ^{R 5} is substituted with a fluorine atom, a hydrogen atom in the alkyl group for ^{R 5} It is more preferable that 90% or more of is substituted with a fluorine atom, and it is more preferable that R ⁵ is a linear or branched perfluoroalkyl group. Specific examples include [C (CF ₃ SO ₂ ) ₃ ] ⁻ , [C (C ₂ F ₅ SO ₂ ) ₃ ] ⁻ and [C (n—C ₃ F ₇ SO ₂ ) ₃ ] ^−. . These counter anions may be used alone or in combination of two or more.

The sulfonium salt compound is represented by the general formula (II) in which R ¹ is a substituted or unsubstituted arylmethyl group, R ² is a substituted or unsubstituted aryl group, and R ³ is a methyl group. A sulfonium salt compound is preferred. An adhesive composition containing such a sulfonium salt compound is excellent in storage stability and low temperature fast curability.

The R ¹ is a substituted or unsubstituted allyl group, the R ² and R ³ are alkyl groups, or the ring formed by combining R ² and R ³ is represented by the general formula (IV). Also preferred are the sulfonium salt compounds. An adhesive composition containing such a sulfonium salt compound is excellent in storage stability and low temperature fast curability.

  Specific examples of the sulfonium salt compound include α-naphthylmethyl-4-hydroxyphenylmethylsulfonium tris (perfluoroethyl) trifluorophosphate, biphenylmethyl-4-hydroxyphenylmethylsulfonium trinium (perfluoroethyl) trifluorophosphate, phenyl Methyl-4-hydroxyphenylmethylsulfonium tris (perfluoroethyl) trifluorophosphate, 1-methyl-phenylmethyl-4-hydroxyphenylmethylsulfonium tris (perfluoroethyl) trifluorophosphate, 2-methyl-phenylmethyl-4- Hydroxyphenylmethylsulfonium tris (perfluoroethyl) trifluorophosphate, fluorenylmethyl-4-hydroxyphenyl Tylsulfonium tris (perfluoroethyl) trifluorophosphate, α-naphthylmethyl-4-acetylphenylmethylsulfonium tris (perfluoroethyl) trifluorophosphate, biphenylmethyl-4-acetylphenylmethylsulfonium tris (perfluoroethyl) trifluoro Phosphate, phenylmethyl-4-acetylphenylmethylsulfonium tris (perfluoroethyl) trifluorophosphate, 1-methyl-phenylmethyl-4-acetylphenylmethylsulfonium tris (perfluoroethyl) trifluorophosphate, 2-methyl-phenylmethyl -4-acetylphenylmethylsulfonium tris (perfluoroethyl) trifluorophosphate, fluorenylmethyl -4-acetylphenylmethylsulfonium tris (perfluoroethyl) trifluorophosphate, α-naphthylmethyl-4-methoxyphenylmethylsulfonium tris (perfluoroethyl) trifluorophosphate, biphenylmethyl-4-methoxyphenylmethylsulfonium tris (per Fluoroethyl) trifluorophosphate, phenylmethyl-4-methoxyphenylmethylsulfonium tris (perfluoroethyl) trifluorophosphate, 1-methyl-phenylmethyl-4-methoxyphenylmethylsulfonium tris (perfluoroethyl) trifluorophosphate, 2 -Methyl-phenylmethyl-4-methoxyphenylmethylsulfonium tris (perfluoroethyl) trifluorophosphate , Fluorenylmethyl-4-methoxyphenylmethylsulfonium tris (perfluoroethyl) trifluorophosphate, 2-butenyldimethylsulfonium tris (perfluoroethyl) trifluorophosphate, 3-methyl-2-butenyldimethylsulfonium tris (Perfluoroethyl) trifluorophosphate, cinnamyldimethylsulfonium tris (perfluoroethyl) trifluorophosphate, 2-butenyltetramethylenesulfonium tris (perfluoroethyl) trifluorophosphate, 3-methyl-2-butenyltetramethylene Sulfonium tris (perfluoroethyl) trifluorophosphate, cinnamyltetramethylenesulfonium tris (perfluoroethyl) trifluoro Sulfate, α-naphthylmethyl-4-hydroxyphenylmethylsulfonium tris (trifluoromethanesulfonyl) methide, biphenylmethyl-4-hydroxyphenylmethylsulfonium tris (trifluoromethanesulfonyl) methide, phenylmethyl-4-hydroxyphenylmethylsulfonium tris (trifluoro) Lomethanesulfonyl) methide, 1-methyl-phenylmethyl-4-hydroxyphenylmethylsulfonium tris (trifluoromethanesulfonyl) methide, 2-methyl-phenylmethyl-4-hydroxyphenylmethylsulfonium tris (trifluoromethanesulfonyl) methide, fluorenyl Methyl-4-hydroxyphenylmethylsulfonium tris (trifluoromethanesulfonyl) methide, α-naphthylmethyl-4-acetylphenylmethylsulfonium tris (trifluoromethanesulfonyl) methide, biphenylmethyl-4-acetylphenylmethylsulfonium tris (trifluoromethanesulfonyl) methide, phenylmethyl-4-acetylphenylmethylsulfonium tris (trifluoromethanesulfonyl) ) Methide, 1-methyl-phenylmethyl-4-acetylphenylmethylsulfonium tris (trifluoromethanesulfonyl) methide, 2-methyl-phenylmethyl-4-acetylphenylmethylsulfonium tris (trifluoromethanesulfonyl) methide, fluorenylmethyl- 4-acetylphenylmethylsulfonium tris (trifluoromethanesulfonyl) methide, α-naphthylmethyl-4-methyl Toxiphenylmethylsulfonium tris (trifluoromethanesulfonyl) methide, biphenylmethyl-4-methoxyphenylmethylsulfonium tris (trifluoromethanesulfonyl) methide, phenylmethyl-4-methoxyphenylmethylsulfonium tris (trifluoromethanesulfonyl) methide, 1-methyl- Phenylmethyl-4-methoxyphenylmethylsulfonium tris (trifluoromethanesulfonyl) methide, 2-methyl-phenylmethyl-4-methoxyphenylmethylsulfonium tris (trifluoromethanesulfonyl) methide, fluorenylmethyl-4-methoxyphenylmethylsulfonium tris (Trifluoromethanesulfonyl) methide, 2-butenyldimethylsulfonium tris (trifluoro Lomethanesulfonyl) methide, 3-methyl-2-butenyldimethylsulfonium tris (trifluoromethanesulfonyl) methide, cinnamyldimethylsulfonium tris (trifluoromethanesulfonyl) methide, 2-butenyltetramethylenesulfonium tris (trifluoromethanesulfonyl) methide, Examples include 3-methyl-2-butenyltetramethylenesulfonium tris (trifluoromethanesulfonyl) methide, cinnamyltetramethylenesulfonium tris (trifluoromethanesulfonyl) methide, and the like. As the component (A), one of the sulfonium salt compounds may be used alone, or two or more may be used in combination.

  In particular, α-naphthylmethyl-4-hydroxyphenylmethylsulfonium tris (perfluoroethyl) trifluorophosphate, 3-methyl-2-butenyldimethylsulfonium tris (perfluoroethyl) trifluorophosphate, cinnamyldimethylsulfonium tris (per Fluoroethyl) trifluorophosphate, 3-methyl-2-butenyltetramethylenesulfonium tris (perfluoroethyl) trifluorophosphate, cinnamyltetramethylenesulfonium tris (perfluoroethyl) trifluorophosphate, α-naphthylmethyl-4- Hydroxyphenylmethylsulfonium tris (trifluoromethanesulfonyl) methide, 3-methyl-2-butenyldimethylsulfonium tris (tri Fluoromethanesulfonyl) methide, cinnamyldimethylsulfonium tris (trifluoromethanesulfonyl) methide, 3-methyl-2-butenyltetramethylenesulfonium tris (trifluoromethanesulfonyl) methide, cinnamyltetramethylenesulfonium tris (trifluoromethanesulfonyl) methide The adhesive composition to be contained is further excellent in storage stability and low temperature fast curability.

  From the viewpoint of storage stability of the adhesive composition containing the component (A), the component (A) includes the component (A) and a glycidyl ether type epoxy compound YL980 (product name of Japan Epoxy Resin Co., Ltd., bisphenol A). What gives an exothermic peak to 40-150 degreeC in the differential scanning calorimetry about a mixture with a type epoxy resin) is preferable. In particular, those giving an exothermic peak at 70 to 130 ° C. are more preferable.

  The content ratio of the component (A) in the adhesive composition according to this embodiment is preferably 0.5 to 50% by mass, and 2 to 25% by mass based on the total amount of the component (B). More preferred. When the content ratio of the component (A) is 0.5% by mass or more, more sufficient curing tends to be obtained, and when it is 50% by mass or less, the adhesive strength tends to be further improved.

  Examples of the component (B) include an epoxy compound, an oxetane compound, and a vinyl ether compound. Examples of the epoxy compound include a glycidyl ether type epoxy compound and an alicyclic epoxy compound.

  The glycidyl ether type epoxy compound may be any compound having a glycidyl ether group in the molecule and capable of being cured by irradiation with actinic rays or heating in the presence or absence of a curing agent. Among them, those having two or more epoxy groups in one molecule are preferable because the crosslink density when cured is high. The glycidyl ether type epoxy compound is not particularly limited as long as it is a compound having a glycidyl ether group, and known compounds can be used. More specifically, bisphenol type epoxy resins derived from epichlorohydrin and bisphenol A or bisphenol F and the like, and glycidyl ether type epoxy compounds having an alicyclic structure obtained by hydrogenating the aromatic structure of these bisphenol type epoxy resins, Cresol novolac epoxy resin, novolak glycidyl ether compound such as phenol novolac epoxy resin, glycidyl amine epoxy compound, glycidyl ester epoxy compound, biphenyl diglycidyl ether, triglycidyl isocyanurate, polyglycidyl methacrylate or glycidyl methacrylate, and And a copolymer with a vinyl monomer copolymerizable therewith. These may be used alone or in combination of two or more.

  An alicyclic epoxy compound is a compound having in its molecule an epoxy group consisting of two of the carbon atoms constituting the cyclic hydrocarbon skeleton and an oxygen atom, and is irradiated with actinic rays in the presence or absence of a curing agent. Or what should just be hardened | cured by heating is sufficient. Among them, those having two or more epoxy groups in one molecule are preferable because the crosslink density when cured is high. The alicyclic epoxy compound is not particularly limited as long as it is a compound having an alicyclic epoxy group, and known compounds can be used. Examples thereof include a cyclohexene oxide-containing compound obtained by oxidizing a cyclohexene ring-containing compound and a cyclopentene oxide-containing compound obtained by oxidizing a cyclopentene ring-containing compound. More specifically, 2- (3,4-epoxycyclohexyl-5,5-spiro-3,4-epoxy) cyclohexane-metadioxane, 3,4-epoxy-1-methylcyclohexyl-3,4-epoxy- 1-methylhexanecarboxylate, 3,4-epoxy-3-methylcyclohexylmethyl-3,4-epoxy-3-methylcyclohexanecarboxylate, 3,4-epoxy-5-methylcyclohexylmethyl-3,4-epoxy 5-methylcyclohexanecarboxylate, 3,4-epoxy-6-methylcyclohexylcarboxylate, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, 6-methyl-3,4-epoxycyclohexylmethyl-6 -Methyl-3,4-epoxy Hexane carboxylate, ethylenebis (3,4-epoxycyclohexane carboxylate), dicyclopentadiene diepoxide, bis (3,4-epoxycyclohexylmethyl) adipate, methylenebis (3,4-epoxycyclohexane), and the like. These may be used alone or in combination of two or more.

  The oxetane compound may be an oxetane compound having an oxetanyl group in the molecule and can be cured by irradiation with actinic rays or heating in the presence or absence of a curing agent. Among these, a compound having two or more oxetane rings is preferable because the crosslink density when cured is high. Furthermore, an aliphatic or alicyclic compound having 2 to 6 oxetane rings and 1 to 6 hydroxyl groups in the molecule is preferable from the viewpoint of excellent curability.

  Examples of the oxetane compound include compounds represented by the following general formula (XII).

In the formula, R ⁹ represents a hydrogen atom, a fluorine atom or a monovalent hydrocarbon group, R ¹⁰ represents a hydrogen atom, an n-valent aliphatic hydrocarbon group or an n-valent aromatic hydrocarbon group, and n is 1 Represents an integer of ~ 6. However, n is 1 when R ¹⁰ is a hydrogen atom. When n is an integer of 2 or more, a plurality of oxygen atom bonding to R ¹⁰ may be bonded to the same carbon atom of R ¹⁰ may be mutually bonded to different carbon atoms of R ^10.

  More specifically, as the oxetane compound, 1,4-di [(3-oxetanyl-n-butoxy) methyl] benzene, 4,4′-bis [(3-oxetanyl-n-butoxy) methyl] biphenyl, Examples include 3-ethyl-3 {[(3-ethyloxetane-3-yl) methoxy] methyl} oxetane, 3-ethyl-3-hydroxymethyloxetane, 2-ethylhexyloxetane, and the like.

  Any vinyl ether compound may be used as long as it is a compound having a vinyl ether group in the molecule and is cured by irradiation with actinic rays or heating in the presence or absence of a curing agent. Among them, those having two or more vinyl ether groups in one molecule are preferable because the crosslinking density when cured is increased.

  Examples of the vinyl ether compound include compounds represented by the following general formula (XIII).

In the formula, R ¹¹ represents an m-valent aliphatic hydrocarbon group or an m-valent aromatic hydrocarbon group, and m represents an integer of 1 to 4. when m is an integer of 2 or more, a plurality of oxygen atoms bonded to R ¹¹ may be bonded to the same carbon atom of R ¹¹ may be mutually bonded to different carbon atoms of R ^11.

  More specific examples of the vinyl ether compound include 1,4-butanediol divinyl ether, cyclohexane dimethanol divinyl ether, diethylene glycol divinyl ether, and triethylene glycol divinyl ether.

  (B) As for the cation polymerizable substituent equivalent of a component, 43-1000 are preferable, 50-800 are more preferable, 73-600 are more preferable. There exists a tendency for adhesive strength to improve more at the time of the connection of the electrode mentioned later that a cationically polymerizable substituent equivalent is 43-1000. The cationic polymerizable substituent equivalent is a value obtained by dividing the average molecular weight of one molecule of the cationic polymerizable substance contained by the number of cationic polymerizable substituents in one molecule of the cationic polymerizable substance, that is, unit cationic polymerizable. Refers to the average molecular weight per substituent.

As the component (B), it is preferable to use a high-purity product in which the content of impurity ions (Na ⁺ , Cl ^−, etc.) and hydrolyzable chlorine is reduced to 300 ppm or less, from the viewpoint of preventing corrosion.

  The content ratio of the component (B) in the adhesive composition according to this embodiment is preferably 10 to 90% by mass and more preferably 25 to 75% by mass based on the total amount of the adhesive composition. . When the content ratio of the component (B) is 10% by mass or more, the physical properties (elastic modulus, etc.) of the cured product tend to be further improved. Power tends to improve more.

  In the adhesive composition according to this embodiment, the component (B) may be used alone or in combination of two or more.

  The adhesive composition according to this embodiment further contains (C) conductive particles. Examples of the conductive particles include metal particles such as Au, Ag, Ni, Cu, and solder, and carbon. Further, non-conductive glass, ceramic, plastic, or the like may be used as a core, and the core, metal particles, or carbon may be coated on the core. When the conductive particles are plastic cores and the cores are coated with the above metal, metal particles or carbon, and hot-melt metal particles, they are deformed by heat and pressure, increasing the contact area with the electrodes during connection. This is preferable because reliability is improved. In addition, fine particles whose surfaces are further coated with a polymer resin or the like can suppress short circuit due to contact between particles and improve insulation between electrode circuits when the amount of conductive particles is increased. . Accordingly, the fine particles obtained by coating the surface of the conductive particles with a polymer resin or the like can be used alone or mixed with the conductive particles as appropriate.

  The average particle diameter of the conductive particles can be obtained by SEM observation. The average particle diameter of the conductive particles is preferably 1 to 18 μm from the viewpoint of good dispersibility and conductivity. The content ratio of the conductive particles in the adhesive composition according to this embodiment is not particularly limited, but is preferably 0.1 to 30% by volume with respect to 100% by volume of the adhesive composition. It is more preferable that it is 1-10 volume%. There exists a tendency for electroconductivity to improve more that the content rate of electroconductive particle is 0.1 volume% or more, and it can prevent the short circuit of a circuit more as it is 30 volume% or less. The “volume%” is determined based on the volume of each component before curing at 23 ° C., but the volume of each component can also be calculated by converting mass using specific gravity. Moreover, the volume of each component can also be calculated | required from what added the appropriate solvent (water, alcohol, etc.) to the graduated cylinder etc., and added the component, and increased. An appropriate solvent means a solvent that does not dissolve or swell the components but wets well.

  In the adhesive composition according to this embodiment, a corrosion inhibitor made of a metal hydroxide or a metal oxide can be added and mixed for the purpose of preventing corrosion of the adherend. More specifically, the corrosion inhibitor includes aluminum hydroxide, magnesium hydroxide, calcium hydroxide, silicon oxide, aluminum oxide, magnesium oxide, antimony oxide, tin oxide, titanium oxide, manganese oxide, and zirconium oxide. At least one selected from the above is preferred. When the corrosion inhibitor is in the form of particles, the particle size may be 10 μm or less from the viewpoints of dispersion in the adhesive composition, high adhesion to the adherend and ability to prevent corrosion of the adherend. preferable.

  The content ratio of the corrosion inhibitor in the adhesive composition according to this embodiment is preferably 0.1 to 60% by mass and more preferably 1 to 30% by mass based on the total amount of the component (A). preferable. When the content of the corrosion inhibitor is 0.1% by mass or more, the corrosion prevention effect can be sufficiently exerted, and when the content is 60% by mass or less, the dispersibility is increased and the connection reliability of the adhesive composition is improved. There is a tendency to improve.

  The adhesive composition according to this embodiment may further contain a chain ether compound or a cyclic ether compound having two or more ether bonds in one molecule. In particular, when an alicyclic epoxy compound is contained as the component (B), the curing behavior of the alicyclic epoxy compound can be more easily and reliably controlled by further containing a chain or cyclic ether compound.

  The chain or cyclic ether compound is not particularly limited as long as it has two or more ether bonds in one molecule, and a known one can be used. Examples of chain ether compounds include polyethylene glycols such as triethylene glycol and tetraethylene glycol; derivatives obtained by functionalizing terminal hydroxyl groups of polyethylene glycols with ether bonds or ester bonds; monofunctional epoxies such as ethylene oxide, propylene oxide, and cyclohexene oxide Polymers of compounds; polymers of polyfunctional epoxy compounds; polymers of monofunctional or polyfunctional oxetane compounds; polymers of monofunctional or polyfunctional tetrahydrofurans. Examples of cyclic ether compounds include 12-crown-4-ether, 14-crown-4-ether, 15-crown-5-ether, 18-crown-6-ether, 21-crown-7-ether, 24- Crown-8-ether, 30-crown-7-ether, benzo-18-crown-6-ether, dibenzo-18-crown-6-ether, tribenzo-18-crown-6-ether, cyclized product of polyethylene glycols And cyclized products of polymers of epoxy compounds. These may be used alone or in combination of two or more.

  Among these, cyclic ether compounds are preferable from the viewpoint of reaction control ability, and 12-crown-4-ether, 14-crown-4-ether, 15-crown-5-ether, 18-crown-6-ether, 21- Crown-7-ether, 24-crown-8-ether, 30-crown-7-ether, benzo-18-crown-6-ether, dibenzo-18-crown-6-ether, tribenzo-18-crown-6 Ether is more preferred.

  The content of the chain or cyclic ether compound in the adhesive composition according to the present embodiment is preferably 0.005 to 10 mol%, and 0.01 to 5 mol% with respect to the component (A). More preferably. When the content of the chain or cyclic ether compound is 0.005 mol% or more, the adhesive strength is further improved, and when it is 20 mol% or less, curing is promoted and the crosslinking density tends to be further increased.

  The adhesive composition according to this embodiment has various known additives such as an inorganic filler; a reinforcing agent; a colorant; a stabilizer (thermal stabilizer, weather resistance) as long as the effects of the present invention are not impaired. Extenders; viscosity modifiers; tackifiers represented by terpene phenol copolymers, terpene resins, rosin derivatives and alicyclic hydrocarbon resins; flame retardants; ultraviolet absorbers; antioxidants Anti-discoloring agent; Antifungal agent; Anti-aging agent; Antistatic agent; Plasticizer; Lubricant; Foaming agent; Release agent and the like may be contained.

  Examples of the colorant include direct dyes, acid dyes, basic dyes, metal complex dyes and the like; inorganic pigments such as carbon black and mica; coupling azo series, condensed azo series, anthraquinone series, thioindigo series, dioxazone series And organic pigments such as phthalocyanine. Examples of the stabilizer include compounds such as hindered phenol, hydrazine, phosphorus, benzophenone, benzotriazole, and oxalic acid anilide. Examples of the inorganic filler include glass fiber, asbestos fiber, carbon fiber, silica fiber, alumina fiber, zirconia fiber, boron nitride fiber, silicon nitride fiber, basic magnesium sulfate fiber, boron fiber, stainless steel fiber, aluminum, titanium, Inorganic materials such as copper, brass and magnesium and metal fibers made of these; metal powders such as copper, iron, nickel, zinc, tin, lead, stainless steel, aluminum, gold and silver; wood powder; aluminum silicate; talc; Carbonates; sulfates; phosphates; borates; borosilicates; aluminosilicates; titanates; basic salts such as basic sulfates and basic carbonates; glasses such as glass hollow spheres and glass flakes Materials: silicon carbide; aluminum nitride; mullite; cordierite.

  The adhesive composition according to the present embodiment may appropriately contain various polymers for the purpose of thickening and forming a film. The polymer to be contained is not limited as long as it does not significantly inhibit the curing of the component (B), and a known polymer can be used. Examples of such polymers include phenoxy resins, polymethacrylates, polyacrylates, polyesters, polyvinyl butyrals, SBS (styrene butadiene styrene block copolymer) and its epoxy modified products, and SEBS (styrene ethylene butylene styrene block). Copolymer) and modified products thereof. These may be used alone or in combination of two or more. Furthermore, these polymers may contain siloxane bonds or fluorine substituents. These can be suitably used as an adhesive composition as long as the resins to be mixed are completely compatible with each other or microphase separation occurs and the mixture becomes cloudy. In particular, when aiming at film formation, it is preferable to contain a film-forming polymer such as phenoxy resins and polyvinyl butyrals.

When the molecular weight of the polymer is large, film formability can be easily obtained, and the melt viscosity that affects the fluidity of the adhesive composition can be set in a wide range. The weight average molecular weight of the polymer is not particularly limited, but is preferably 5,000 to 150,000, and more preferably 10,000 to 80,000. When the weight average molecular weight is 5000 or more, the film formability tends to be more excellent, and when it is 150,000 or less, the compatibility with other components tends to be better. Here, the weight average molecular weight refers to a value measured from a gel permeation chromatograph (GPC) using a standard polystyrene calibration curve according to the following conditions.
(Measurement condition)
Device: GPC-8020 manufactured by Tosoh Corporation
Detector: RI-8020 manufactured by Tosoh Corporation
Column: Gelpack GL-A-160-S + GL-A150 manufactured by Hitachi Chemical Co., Ltd.
Sample concentration: 120 mg / 3 mL
Solvent: Tetrahydrofuran Injection volume: 60 μL
Pressure: 2.9 MPa (30 kgf / cm ² )
Flow rate: 1.00 mL / mim

  The content of the polymer in the adhesive composition according to this embodiment is preferably 20 to 320 parts by mass, and more preferably 50 to 150 parts by mass with respect to 100 parts by mass of the component (B). There exists a tendency for the fluidity | liquidity and adhesiveness of an adhesive composition to improve that the content rate of the said polymer is 20-320 mass parts.

  The adhesive composition according to this embodiment can be used in the form of a paste when it is liquid at room temperature. In the case of a solid at room temperature, it may be heated and used, or may be made into a paste using a solvent. The solvent that can be used is not particularly limited as long as it is not reactive with the adhesive composition and the additive and exhibits sufficient solubility, but has a boiling point of 50 to 150 ° C. at normal pressure. Those are preferred. A solvent having a boiling point of 50 ° C. or higher is less likely to volatilize even when left at room temperature, and there are few restrictions when used in an open system. Moreover, in the solvent whose boiling point is 150 degrees C or less, it is easy to volatilize a solvent and there exists a tendency for the connection reliability after adhesion | attachment to improve more.

  The adhesive composition according to this embodiment can be cured by heating. The heating temperature is preferably 40 to 180 ° C., more preferably 50 to 150 ° C., and the heating time is preferably 0.1 second to 10 hours, more preferably 1 second to 1 hour. When the heating temperature is 40 ° C. or higher, the curing rate tends to be further improved, and when it is 180 ° C. or lower, undesirable side reactions are suppressed, and the connection reliability tends to be further improved. In addition, if the heating time is 0.1 seconds or more, the curing reaction tends to proceed, and if it is 10 hours or less, the productivity of the cured product is further improved and unwanted side reactions are less likely to proceed. Connection reliability tends to improve more.

  The adhesive composition according to the present embodiment can adhere an adherend by using both heating and pressing. The heating temperature in the case of bonding using heating and pressurization in combination is not particularly limited, but a temperature of 50 to 190 ° C. is preferable. The pressure is not particularly limited as long as it does not damage the adherend, but in the case of TCP and chip-on-flex (COF), generally 0.1 to 30 MPa is preferable. In the case of COG mounting, 10 to 100 MPa is preferable. These heating and pressurization are preferably performed in the range of 0.5 seconds to 120 seconds.

  The adhesive composition according to this embodiment can be used as an adhesive for different types of adherends having different thermal expansion coefficients, and can also be used as a film. Specifically, an adhesive for circuit connection for bonding between circuit members having circuit electrodes, such as silver paste and silver film, an elastomer for chip size package (CSP), an underfill material for CSP, and a lead-on chip It can be used as an adhesive for connecting a semiconductor element, such as (LOC) tape, for bonding a semiconductor element and a semiconductor element mounting instruction member having a circuit pattern.

[Film adhesive]
FIG. 1 is a schematic cross-sectional view showing an embodiment of a film adhesive. A film adhesive 1 shown in FIG. 1 is obtained by forming the above-described adhesive composition, which is composed of an adhesive component 5 and conductive particles 7, into a film shape. According to this film adhesive 1, it is easy to handle, can be easily installed on the adherend, and can be easily connected.

  In addition, the film adhesive 1 is good also as a multilayer structure (not shown) which consists of two or more layers using different types of adhesive compositions. In the two or more layers, the Tg (glass transition temperature) of each layer can be different by, for example, 5 ° C. or more.

  The film adhesive 1 is, for example, a temperature at which an adhesive composition is dissolved in a solvent and applied on a support (PET (polyethylene terephthalate) film or the like) using a coating apparatus, and the adhesive composition is not cured. And can be produced by drying with hot air for a predetermined time. Moreover, the thickness of the film adhesive 1 can be 10-50 micrometers, for example.

[Connection structure]
FIG. 2 is a schematic cross-sectional view showing an embodiment of a connection structure. As shown in FIG. 2, the connection structure of the present embodiment includes a first circuit member 20 and a second circuit member 30 that face each other, and the first circuit member 20 and the second circuit member. A circuit connection member 10 is provided between 30 and 30. The first circuit member 20 or the second circuit member 30 may be made of an inorganic material. Further, at least a part of the adhesion surface with the connection member may be made of an inorganic material.

  The first circuit member 20 includes a circuit board (first circuit board) 21 and a circuit electrode (first circuit electrode) 22 formed on the main surface 21 a of the circuit board 21. Note that an insulating layer (not shown) may be formed on the main surface 21a of the circuit board 21 in some cases.

  On the other hand, the second circuit member 30 includes a circuit board (second circuit board) 31 and a circuit electrode (second circuit electrode) 32 formed on the main surface 31 a of the circuit board 31. In addition, an insulating layer (not shown) may be formed on the main surface 31a of the circuit board 31 according to circumstances.

The first circuit member 20 and the second circuit member 30 are not particularly limited as long as electrodes that require electrical connection are formed. Specific examples include glass or plastic substrates with electrodes formed of ITO or the like used for liquid crystal displays, printed wiring boards, ceramic wiring boards, flexible wiring boards, semiconductor silicon chips, and the like. Used in combination accordingly. As described above, in the present embodiment, the printed wiring board, polyimide, and other organic materials, copper, aluminum, and other metals, ITO (indium tinoxide), silicon nitride (SiN _x ), silicon dioxide (SiO ₂ ), and the like are used. Circuit members having various surface states such as materials made of inorganic materials can be used.

  The circuit connection member 10 is formed of a cured product of the adhesive composition, and contains the insulating substance 11 and the conductive particles 7. The conductive particles 7 are disposed not only between the circuit electrode 22 and the circuit electrode 32 facing each other, but also between the main surface 21a and the main surface 31a. In the connection structure, the circuit electrode 22 and the circuit electrode 32 are electrically connected through the conductive particles 7. That is, the conductive particles 7 are in direct contact with both the circuit electrode 22 and the circuit electrode 32.

  In this connection structure, as described above, the circuit electrode 22 and the circuit electrode 32 that face each other are electrically connected via the conductive particles 7. For this reason, the connection resistance between the circuit electrode 22 and the circuit electrode 32 is sufficiently reduced. Therefore, the flow of current between the circuit electrode 22 and the circuit electrode 32 can be made smooth, and the functions of the circuit can be fully exhibited.

[Method of manufacturing connection structure]
Next, the manufacturing method of the connection structure mentioned above is demonstrated.

  First, the first circuit member 20 and the film adhesive 1 described above are prepared (see FIG. 3A).

  The thickness of the film adhesive 1 is preferably 10 to 50 μm. By setting the thickness of the film adhesive 1 to 10 μm or more, the circuit connection material between the circuit electrode 22 and the circuit electrode 32 is reliably filled. On the other hand, by setting the thickness of the film adhesive 1 to 50 μm or less, it is possible to prevent the circuit connection material between the circuit electrode 22 and the circuit electrode 32 from protruding further.

  Next, the film adhesive 1 is placed on the surface of the first circuit member 20 on which the circuit electrodes 22 are formed. In addition, when the film adhesive 1 has adhered on the support body (not shown), the 1st circuit member 20 is made so that the film adhesive 1 side faces the first circuit member 20. Put it on top. At this time, the film adhesive 1 is film-like and easy to handle. For this reason, the film adhesive 1 can be easily interposed between the first circuit member 20 and the second circuit member 30, and the connection between the first circuit member 20 and the second circuit member 30 is possible. Work can be done easily.

  And the film adhesive 1 is pressurized to the arrow A and B direction of Fig.3 (a), and the film adhesive 1 is temporarily connected to the 1st circuit member 20 (refer FIG.3 (b)). At this time, you may pressurize, heating.

  Subsequently, as shown in FIG. 3 (c), the second circuit member 30 is arranged so that the second circuit electrode 32 faces the first circuit member 20 (that is, the first circuit electrode 22 and the first circuit member 22). The second circuit electrode 32 is placed on the film adhesive 1 in a state of being opposed to each other. In addition, when the film adhesive 1 has adhered on the support body (not shown), after peeling a support body, the 2nd circuit member 30 is mounted on the film adhesive 1.

  And it heats through the 1st circuit member 20 and the 2nd circuit member 30 in the arrow A and B direction of FIG.3 (c), heating the film adhesive 1. FIG. In this way, the film adhesive 1 is cured, the main connection is performed, and a connection structure as shown in FIG. 2 is obtained.

  When the connection structure is manufactured as described above, in the obtained connection structure, the conductive particles 7 can be brought into contact with both the circuit electrode 22 and the circuit electrode 32 facing each other. The connection resistance between them can be sufficiently reduced.

  In addition, the adhesive component 5 is cured by the heating of the film adhesive 1 in a state where the distance between the circuit electrode 22 and the circuit electrode 32 is sufficiently small, and becomes the insulating material 11, and the first circuit member 20. And the second circuit member 30 are firmly connected via the circuit connection member 10. That is, in the obtained connection structure, since the circuit connection member 10 is made of a cured product of the circuit connection material containing the adhesive composition, the first circuit member 20 or the second circuit member 30 is used. The adhesive strength of the circuit connecting member 10 to the above is sufficiently high, and the adhesive strength is sufficiently high particularly under high temperature and high humidity conditions. In the connection structure, a sufficiently high adhesive strength is maintained for a long period. Therefore, the obtained connection structure is sufficiently prevented from changing with time in the distance between the circuit electrode 22 and the circuit electrode 32, and is excellent in long-term reliability of electrical characteristics between the circuit electrode 22 and the circuit electrode 32.

  Moreover, in the said embodiment, although the connection structure is manufactured using the film adhesive 1, it replaces with the film adhesive 1 and may use the adhesive composition which is not formed in the film form. . Even in this case, if the adhesive composition is dissolved in a solvent and the solution is applied to either the first circuit member 20 or the second circuit member 30 and dried, the first circuit member 20 and the first circuit member 20 An adhesive composition can be interposed between the two circuit members 30.

[Semiconductor device]
Next, an embodiment of a semiconductor device according to the present invention will be described. FIG. 4 is a schematic cross-sectional view showing an embodiment of the semiconductor device of the present invention. As shown in FIG. 4, the semiconductor device 2 of the present embodiment includes a semiconductor element 50 and a substrate 60 that serves as a support member for the semiconductor element, and these are electrically connected between the semiconductor element 50 and the substrate 60. A semiconductor element connection member 80 is provided for connection. The semiconductor element connection member 80 is stacked on the main surface 60 a of the substrate 60, and the semiconductor element 50 is further stacked on the semiconductor element connection member 80.

  The substrate 60 includes a circuit pattern 61, and the circuit pattern 61 is electrically connected to the semiconductor element 50 via the semiconductor element connection member 80 on the main surface 60 a of the substrate 60 or directly. And these are sealed with the sealing material 70, and the semiconductor device 2 is formed.

  The material of the semiconductor element 50 is not particularly limited, but silicon, germanium group 4 semiconductor element, GaAs, InP, GaP, InGaAs, InGaAsP, AlGaAs, InAs, GaInP, AlInP, AlGaInP, GaNAs, GaNP, GaInNAs, GaInNP, III-V group compound semiconductor elements such as GaSb, InSb, GaN, AlN, InGaN, InNAsP, II-VI group compound semiconductor elements such as HgTe, HgCdTe, CdMnTe, CdS, CdSe, MgSe, MgS, ZnSe, and ZeTe, and Various materials such as CuInSe (CIS) can be used.

  The semiconductor element connecting member 80 is formed of a cured product of the adhesive composition according to the present invention, and contains the insulating substance 11 and the conductive particles 7. The conductive particles 7 are disposed not only between the semiconductor element 50 and the circuit pattern 61 but also between the semiconductor element 50 and the main surface 60a. In the semiconductor device 2 of the present embodiment, the semiconductor element 50 and the circuit pattern 61 are electrically connected via the conductive particles 7. For this reason, the connection resistance between the semiconductor element 50 and the circuit pattern 61 is sufficiently reduced. Therefore, the current flow between the semiconductor element 50 and the circuit pattern 61 can be made smooth, and the functions of the semiconductor can be fully exhibited. Moreover, it is also possible to show the anisotropy of electrical connection by setting the conductive particles 7 to the above-described mixing ratio.

  The semiconductor element connection member 80 is made of a cured product of a circuit connection material made of the adhesive composition according to the present invention. From this, the adhesive strength of the semiconductor element connection member 40 to the semiconductor element 50 and the substrate 60 is sufficiently high, and the connection resistance between the semiconductor element 50 and the circuit pattern 61 can be sufficiently reduced. And this state can be maintained over a long period of time. In addition, since the semiconductor element connecting member can be formed by heating in a short time at a low temperature, the influence on the semiconductor element or the like can be reduced. Therefore, the long-term reliability of the electrical characteristics between the semiconductor element 50 and the substrate 60 can be sufficiently increased.

  The preferred embodiment of the present invention has been described above, but the present invention is not limited to the above embodiment.

  EXAMPLES Hereinafter, although this invention is demonstrated further more concretely based on an Example and a comparative example, this invention is not limited to an Example at all.

Example 1
TA-60 (San Apro Co., Ltd. product name, α-naphthylmethyl-4-hydroxyphenylmethylsulfonium tris (perfluoroethyl) trifluorophosphate) as component (A), and glycidyl ether type epoxy compound YL980 (Japan) as component (B) Epoxy Resin Co., Ltd. product name, bisphenol A type epoxy resin) was used. A phenoxy resin (YP-70, trade name manufactured by Toto Kasei Co., Ltd.) was used as the film-forming polymer. Further, a nickel layer having a thickness of 0.2 μm is provided on the surface of particles having polystyrene as a core, and a gold layer having a thickness of 0.02 μm is provided outside the nickel layer. Particles were made and used. Moreover, aluminum hydroxide powder was used as a corrosion inhibitor.

  (A) A component, (B) component, and a film-forming polymer are mix | blended with the mixing ratio shown in Table 1, Furthermore, 8 volume% of electroconductive particles are mix-dispersed and it uses a coating apparatus for PET resin film of thickness 40 micrometers. The film-like adhesive having a thickness of 20 μm was obtained by applying and drying with hot air at 70 ° C. for 5 minutes.

(Example 2)
A film adhesive was obtained in the same manner as in Example 1 except that α-naphthylmethyl-4-hydroxyphenylmethylsulfonium tris (trifluoromethanesulfonyl) methide (PMNS TFSM) was used as the component (A). Table 1 shows the mixing ratio of each component.

(Example 3)
A film-like adhesive was obtained in the same manner as in Example 1 except that 3-methyl-2-butenyltetramethylenesulfonium tris (perfluoroethyl) trifluorophosphate (MBTS TFEP) was used as the component (A). . Table 1 shows the mixing ratio of each component.

(Example 4)
A film adhesive was obtained in the same manner as in Example 1 except that cinnamyltetramethylenesulfonium tris (perfluoroethyl) trifluorophosphate (CMS TFEP) was used as the component (A). Table 1 shows the mixing ratio of each component.

(Comparative Example 1)
(A) In the same manner as in Example 1 except that SI-60 (product name of Sanshin Chemical Industry Co., Ltd., α-naphthylmethyl-4-hydroxyphenylmethylsulfonium hexafluoroantimonate) was used as the component. An adhesive was obtained. Table 1 shows the mixing ratio of each component.

(Comparative Example 2)
A film adhesive was obtained in the same manner as in Example 1 except that CPI-100A (product name of San Apro Co., Ltd., 4-phenylthiophenyldiphenylsulfonium hexafluoroantimonate) was used as the component (A). Table 1 shows the mixing ratio of each component.

(Comparative Example 3)
(A) A film adhesive in the same manner as in Example 1 except that CPI-200K (product name of San Apro Co., Ltd., 4-phenylthiophenyldiphenylsulfonium tris (perfluoroethyl) trifluorophosphate) was used as the component. Got. Table 1 shows the mixing ratio of each component.

(Comparative Example 4)
A film adhesive was obtained in the same manner as in Example 1 except that tetramethylene α-naphthylmethylsulfonium tris (perfluoroethyl) trifluorophosphate (MPS TFEP) was used as the component (A). Table 1 shows the mixing ratio of each component.

(Comparative Example 5)
A film adhesive was obtained in the same manner as in Example 1 except that 4-hydroxyphenylmethylcinnamylsulfonium tris (perfluoroethyl) trifluorophosphate (PMCS TFEP) was used as the component (A). Table 1 shows the mixing ratio of each component. In Table 1, the mixing ratio is expressed in parts by mass.

  Table 2 shows the sulfonium salt compounds of the component (A) used in Examples and Comparative Examples.

[Differential scanning calorimetry]
Differential scanning calorimetry of the film-like adhesives obtained in Examples and Comparative Examples was performed to examine the presence or absence of an exothermic peak.
In the film-like adhesives obtained in Comparative Examples 2 and 3, no exothermic peak was observed. Moreover, the film adhesive obtained in Comparative Example 5 was cured before measurement. The film adhesives obtained in Examples 1 to 4 and Comparative Examples 1 and 4 gave an exothermic peak. Table 3 shows the temperature at that time.

In differential scanning calorimetry, TA-60 (Y ⁻ = [P (C ₂ F ₅ ) ₃ F ₃ ] ⁻ , Example 1) in which the component (A) has α-naphthylmethyl-4-hydroxyphenylmethylsulfonium. And PMNS TFSM (Y ⁻ = [C (CF ₃ SO ₂ ) ₃ ] ⁻ , Example 2), similarly to SI-60 (Y ⁻ = [SbF ₆ ] ⁻ , Comparative Example 1), an exothermic peak Was observed at around 110 ° C., and an equivalent low-temperature curability was observed.

  In differential scanning calorimetry, when the component (A) is a sulfonium salt compound having three aryl groups (Comparative Examples 2 and 3), no exothermic peak was observed, but the substituted arylmethyl group and the substituted aryl group And a sulfonium salt compound having an exothermic peak near 110 ° C. and having an allyl group substituted with a methyl group or a phenyl group and an alkyl group (implementation) In Examples 3 and 4), there was an exothermic peak near 120 ° C., and the same low-temperature curability was observed. On the other hand, in the case of a sulfonium salt compound having a substituted arylmethyl group and an alkyl group (Comparative Example 4), there is an exothermic peak near 150 ° C., and curability is recognized at a high temperature as compared with the component (A) of the Example. It was. In the case of a sulfonium salt compound having a substituted allyl group and a substituted aryl group (Comparative Example 5), it was confirmed that the curing proceeded before measurement and the storage stability was poor.

[Curing rate measurement test]
The film adhesives of Examples 1 to 4 and Comparative Examples 1 and 4 were heated and cured at 100 to 160 ° C. for 10 seconds on a hot plate, respectively. From the infrared absorption spectrum, the difference between the area values of the signal intensity of the epoxy group before and after heating was divided by the area value of the signal intensity before heating was determined as the curing rate. The results are shown in FIG.

Example 1 and PMNS TFSM (Y ⁻ =) using TA-60 (Y ⁻ = [P (C ₂ F ₅ ) ₃ F ₃ ] ⁻ ), which is an α-naphthylmethyl-4-hydroxyphenylmethylsulfonium salt compound. Example 2 using [C (CF ₃ SO ₂ ) ₃ ] ⁻ ) is high in a short time of 10 seconds as in Comparative Example 1 using SI-60 (Y ⁻ = [SbF ₆ ] ⁻ ). A curing rate was exhibited, and an equivalent low-temperature rapid curing property was observed.

  Examples 3 and 4 using a sulfonium salt compound having a methyl group or phenyl group-substituted allyl group and an alkyl group showed the same low-temperature fast curing properties as in Examples 1 and 2 and Comparative Example 1. On the other hand, in Comparative Example 4 using a sulfonium salt compound having a substituted arylmethyl group and an alkyl group, curing hardly proceeded.

[Storage stability test]
The film adhesives of Examples 1 to 4 and Comparative Examples 1 to 5 were left in a thermostatic apparatus at 40 ° C. for 5 days. From the infrared absorption spectrum, the curing rate after standing was determined. The results are shown in Table 3.

  In Examples 1 to 4 and Comparative Examples 1 to 4, curing hardly progressed and the storage stability was good. On the other hand, Comparative Example 5 was cured before the test and had low storage stability.

[Measurement of fluoride ion concentration]
The film adhesives of Examples 1 to 4 and Comparative Examples 1 to 5 were diluted 100 times with pure water, and then extracted by heating for 15 hours in an environment of 121 ° C./100% RH. After filtering the extracted water, the fluorine ion concentration was measured with an anion chromatograph (IC-20 manufactured by DIONEX). The results are shown in Table 3.

Y ^- _{as, [P (C 2 F 5} ) 3 F 3] - or _{[C (CF 3 SO 2)} 3] - In Examples 1 to 4 and Comparative Examples 3-5 were used sulfonium salt compound having the Although the fluorine ion concentration was as low as less than 100 ppm, it was confirmed that Comparative Examples 1 and 2 using a sulfonium salt compound having [SbF ₆ ] ^— had extremely high fluorine ion concentrations of 10500 ppm and 6800 ppm, respectively.

[Production of connection structure]
Implemented on a glass substrate (Corning # 1737, external dimensions 38 mm x 28 mm, thickness 0.5 mm, ITO (indium tin oxide) wiring pattern (pattern width 50 μm, pitch 50 μm) on the surface with a size of 2 x 20 mm Each film adhesive of Examples 1-4 and Comparative Examples 1-5 was transferred from a PET resin film. An IC chip (outside 1.7 mm × 17.2 mm, thickness 0.55 mm, bump size 50 μm × 50 μm, bump pitch 50 μm) under the mounting conditions (temperature and time) shown in Table 4 is 80 MPa (bump area conversion) ) It was mounted by heating and pressing under load. Moreover, the film adhesive after a storage stability test was similarly mounted.

[Evaluation of connection resistance]
A resistance value (maximum value among 14 terminals measured) between adjacent circuits of the connection structure produced as described above was measured. Table 4 shows the obtained results.

  In the case where the film-like adhesives of Examples 1 to 4 and Comparative Example 1 were used, both the values before and after the storage stability test showed a good value of less than 5Ω. When the film adhesives of Comparative Examples 2 and 3 were used, curing did not proceed and connection could not be made. Further, when the film adhesive of Comparative Example 4 was used, a high resistance value was obtained. In Comparative Example 5, curing proceeded before the connection structure was produced.

[Observation of wiring corrosion of connection structure]
The appearance of the ITO wiring after treating the connection structure produced as described above (using a film-like adhesive that has not been subjected to a storage stability test) in an environment of 85 ° C. and 85% RH for 24 hours. Observed. Table 4 shows the obtained results.

Y ^- a, _[SbF 6] ^- Comparative Example 1 and 2 using a sulfonium salt compound having, the occurrence of corrosion of significant wiring was observed, Y ^- _{as, [P (C 2 F 5} ) 3 F _3] ^- or _{[C (CF 3 SO 2)} 3] - corrosion in examples 1-4 and Comparative examples 3-5 were used sulfonium salt compound having a was not observed.

From the above, Y ⁻ is represented by [P (R ⁴ ) _a (F) _6-a ] ⁻ or [C ((R ⁵ ) SO ₂ ) ₃ ] ⁻ , especially [P (C ₂ F ₅ ) ₃ F ₃ ] ^— or [C (CF ₃ SO ₂ ) ₃ ] ^— , the adhesive composition containing the sulfonium salt compound represented by the above general formula (I) comprises [SbF ₆ ] ^— It has been found that it has low-temperature rapid curability and storage stability equivalent to those contained, and further, since fluorine ions are not easily desorbed, the occurrence of corrosion is suppressed and the connection reliability is excellent. In the sulfonium salt compound represented by the general formula (I), R ¹ is a substituted or unsubstituted arylmethyl group, R ² is a substituted or unsubstituted aryl group, and R ³ is a methyl group. In some cases, when R ¹ is a substituted or unsubstituted allyl group, R ² and R ³ are alkyl groups, or R ² and R ³ are a ring formed together, they can be connected at a low temperature in a short time. It was found to be suitable as a polymerization initiator for the adhesive composition that can be produced.

DESCRIPTION OF SYMBOLS 1 ... Film adhesive, 2 ... Semiconductor device, 5 ... Adhesive component, 7 ... Conductive particle ((C) component), 10 ... Circuit connection member, 11 ... Insulating substance, 20 ... First circuit member, 21 ... Circuit board (first circuit board), 21a ... Main surface, 22 ... Circuit electrode (first circuit electrode), 30 ... Second circuit member, 31 ... Circuit board (second circuit board), 31a ... Main surface 32... Circuit electrode (second circuit electrode) 50. Semiconductor element 60. Substrate 61 Circuit pattern 70 Sealing material 80 Semiconductor element connecting member

Claims (14)

(A) a sulfonium salt compound represented by the following general formula (I);
(B) a cationically polymerizable substance;
(C) conductive particles;
An anisotropic conductive adhesive composition comprising:

[Wherein, R ¹ represents a substituted or unsubstituted arylmethyl group or a substituted or unsubstituted allyl group, and R ² and R ³ each independently represents an alkyl group or a substituted or unsubstituted aryl group. shows, Y ^- is _{^{[P (R 4) a (}} F) 6-a] - ( wherein, ^{R 4} represents an alkyl group wherein at least a portion of the hydrogen atoms are substituted by fluorine atoms, a is 1 6 represents an integer of 6. When a is an integer of 2 or more, a plurality of R ⁴ may be the same or different from each other.), Or [C ((R ⁵ ) SO ₂ ) ₃ ] ^- (In the formula, R ⁵ represents an alkyl group in which at least a part of hydrogen atoms are substituted with fluorine atoms, and a plurality of R ⁵ may be the same or different from each other). However, R ² and R ³ may be combined to form a ring, and when R ¹ is a substituted or unsubstituted arylmethyl group, at least one of R ² and R ³ is substituted or unsubstituted. When R ¹ is a substituted aryl group and R ¹ is a substituted or unsubstituted allyl group, R ² and R ³ are alkyl groups or a ring formed by combining R ² and R ³ together. ] The anisotropic conductive adhesive composition of Claim 1 containing the sulfonium salt compound represented by the following general formula (II) as said (A) component.

[Wherein, Ar ¹ and Ar ² each independently represent a substituted or unsubstituted aryl group, and Y ⁻ is as defined above]. ] The anisotropic conductive adhesive composition of Claim 2 containing the sulfonium salt compound represented by the following general formula (III) as said (A) component.

[Wherein Y ⁻ has the same meaning as described above. ] The anisotropic conductive adhesive composition of Claim 1 containing the sulfonium salt compound represented by the following general formula (IV) as said (A) component.

[Wherein, A ¹ and A ² each independently represent an alkyl group, and R ⁶ , R ⁷ and R ⁸ each independently represent a hydrogen atom, an alkyl group, or a substituted or unsubstituted aryl group, Y ⁻ has the same meaning as described above. However, A ¹ and A ² may together form a ring. ] The anisotropic conductive adhesive composition of Claim 4 containing the sulfonium salt compound represented by general formula (V), (VI), (VII) or (VIII) as said (A) component.

[Wherein Y ⁻ has the same meaning as described above. ]   The said (A) component contains the sulfonium salt compound which gives the peak temperature of 40-150 degreeC in the differential scanning calorimetry about the mixture with a glycidyl ether type epoxy compound, The any one of Claims 1-5. An anisotropic conductive adhesive composition.   The anisotropic conductive adhesive composition as described in any one of Claims 1-6 containing at least 1 type chosen from the group which consists of an epoxy compound, an oxetane compound, and a vinyl ether compound as said (B) component.   (D) The anisotropic conductive adhesive composition as described in any one of Claims 1-7 which further contains a film-forming polymer.   The anisotropic conductive adhesive composition according to any one of claims 1 to 8, which is used as an adhesive for circuit connection.   The anisotropic conductive adhesive composition according to any one of claims 1 to 9, which is cured by heating.   The film adhesive which makes the anisotropic conductive adhesive composition as described in any one of Claims 1-10 into a film form. A first circuit member having a first circuit electrode; a second circuit member having a second circuit electrode; and being disposed between the first circuit member and the second circuit member, A circuit connection member for electrically connecting the circuit electrode and the second circuit electrode,
The connection structure in which the said circuit connection member contains the hardened | cured material of the anisotropically conductive adhesive composition as described in any one of Claims 1-10.   The anisotropic conductive adhesive composition according to claim 1, between a first circuit member having a first circuit electrode and a second circuit member having a second circuit electrode. The first circuit electrode and the second circuit are arranged by heating and pressurizing the first circuit member and the second circuit member via the anisotropic conductive adhesive composition. A method for manufacturing a connection structure, comprising a step of electrically connecting electrodes. A semiconductor element, a substrate having a circuit pattern, and a semiconductor element connecting member disposed between the semiconductor element and the substrate, and electrically connecting the semiconductor element and the circuit pattern,
The semiconductor device in which the said semiconductor element connection member contains the hardened | cured material of the anisotropically conductive adhesive composition as described in any one of Claims 1-10.

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