KR102185169B1 - Anisotropic conductive adhesive composition - Google Patents

Abstract

[식 중, R¹은 아릴메틸기 또는 알릴기 등이며, R² 및 R³은, 각각 독립적으로, 알킬기 또는 아릴기 등을 나타내고, Y^-는 [P(C₂F₅)₃F₃]^- 또는 [C(CF₃SO₂)₃]^- 등을 나타내되, 단, R² 및 R³은 일체로 되어 환을 형성하고 있을 수도 있고, R¹이 아릴메틸기 등인 경우에는 R² 및 R³ 중 적어도 한쪽이 아릴기 등이며, R¹이 알릴기 등인 경우에는 R² 및 R³은 알킬기이거나, 또는 R² 및 R³이 일체로 되어 형성된 환 등임]An object of the present invention is to provide an anisotropically conductive adhesive composition that can be bonded at a low temperature for a short time, has excellent connection reliability, and has excellent storage stability.
(A) An anisotropically conductive adhesive composition comprising a sulfonium salt compound represented by the following formula (I), (B) a cationic polymerizable substance, and (C) conductive particles is provided.

[In the formula, R ¹ is an arylmethyl group or an allyl group, etc., R ² and R ³ each independently represent an alkyl group or an aryl group, etc., and Y ^- is [P(C ₂ F ₅ ) ₃ F ₃ ] ^- or _{[C (CF 3 SO 2)} 3] - are expressed and the like, with the proviso that, R ² and R ³ are the case in integrated manner may be to form a ring, R ¹ or the like is an aryl group, the R ² and R ³ of the At least one is an aryl group or the like, and when R ¹ is an allyl group, R ² and R ³ are alkyl groups, or a ring formed by combining R ² and R ³ etc.]

Description

Anisotropic conductive adhesive composition {ANISOTROPIC CONDUCTIVE ADHESIVE COMPOSITION}

The present invention relates to an anisotropically conductive adhesive composition.

In recent years, in the fields of semiconductors and liquid crystal displays, various adhesive materials are used to fix electronic components or to perform circuit connection. In these applications, higher density and higher precision are progressing, and high adhesion and connection reliability are also required for adhesives.

In particular, as a circuit connection material in connection of a liquid crystal display and a tape carrier package (TCP), a connection between a flexible printed wiring board (FPC) and a TCP, or a connection between an FPC and a printed wiring board, an anisotropically conductive adhesive in which conductive particles are dispersed in an adhesive. Is being used. In addition, 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, instead of the conventional wire bond, has been carried out, and an anisotropic conductive adhesive is also applied here. Has become.

Further, in recent years, in the field of precision electronic devices, high-density circuits are in progress, and the electrode width and electrode spacing are becoming very narrow. For this reason, in the connection conditions of the conventional epoxy resin-based adhesive for circuit connection, there are problems such as dropping, peeling, and misalignment of the wiring, and in COG mounting, warpage due to the difference in thermal expansion between the chip and the substrate occurs. There is a problem. Further, in order to reduce the cost, there is a need to improve the throughput, and thus an adhesive capable of curing at a low temperature (eg, 100 to 170°C), a short time (eg, within 10 seconds), in other words, at a low temperature is required.

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

[In formula (IX), R _a represents hydrogen, methyl group, acetyl group, methoxycarbonyl group, ethoxycarbonyl group, benzyloxycarbonyl group, benzoyl group, phenoxycarbonyl group, or 9-fluorenylmethoxycarbonyl group, R _b , R _c is independently hydrogen, halogen, any one of 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-nitrobenzyl group, dinitro Benzyl group, trinitrobenzyl group, α-naphthylmethyl group, represents any one of β-naphthylmethyl group, X is any one of SbF ₆ , AsF ₆ , PF ₆ , BF ₄ ]

In addition, 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 formula (X) or the following formula (XI) has been proposed (Patent Document 2). .

[In 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 an optionally substituted naphthyl group. Represents a group, X represents SbF ₆ , AsF ₆ , PF ₆ or BF ₄ ]

[In 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, and R _j represents an alkenyl group, α-alkylbenzyl Group, α,α-dialkylbenzyl group, α-phenylbenzyl group or fluorenyl group, X represents SbF ₆ , AsF ₆ , PF ₆ or BF ₄ ]

Japanese Patent Laid-Open (Hei) No. 3-237107 Japanese Patent Laid-Open (Hei) 6-345726

By the way, as a result of intensive examination by the present inventors, it was found that there is a problem that the anisotropically conductive adhesive obtained is liable to corrode metal and semiconductor wiring when the cationic polymerization initiator described in Patent Document 1 or 2 is used. This is presumed to be because the polymerization initiator has SbF ₆ , AsF ₆ , PF ₆ or BF ₄ as X, but X has a weak bond between a central atom and a fluorine atom, and fluorine ions are easily desorbed. Further, in order to prepare a possible low-temperature fast curing (e.g., within 100 to 170 ℃, 10 seconds) adhesive, SbF _6, AsF _6, PF ₆ and BF ₄ from SbF ₆ the most and preferably as active as X but SbF ₆ had problems in terms of environmental safety.

The present invention has been made in view of the above circumstances, and has an object of providing an anisotropically conductive adhesive composition that can be bonded at a low temperature for a short time, has excellent connection reliability, and has excellent storage stability, and a film-like adhesive comprising them as a film. do. Further, an object of the present invention is to provide a connection structure using these anisotropically conductive adhesive compositions, a method of manufacturing the same, and a semiconductor device.

The present invention provides the anisotropically conductive adhesive compositions described in the following (1) to (10), and the film-like adhesive described in the following (11) comprising them as a film. Further, a connection structure using these anisotropically conductive adhesive compositions, a manufacturing method thereof, and a semiconductor device are provided.

(1) (A) An anisotropically conductive adhesive composition comprising a sulfonium salt compound represented by the following formula (I), (B) a cationic polymerizable substance, and (C) conductive particles.

[In the formula, R ¹ represents a substituted or unsubstituted arylmethyl group or a substituted or unsubstituted allyl group, R ² and R ³ each independently represent an alkyl group or a substituted or unsubstituted aryl group, and Y ⁻ represents [P (R ⁴ ) _a (F) _6-a ] ^- (In the formula, R ⁴ represents an alkyl group in which at least part of a hydrogen atom is substituted with a fluorine atom, a represents an integer of 1 to 6, and a is an integer of 2 or more. In the case, 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 is at least part of a hydrogen atom substituted with a fluorine atom, R ⁵ may be the same as or different from each other), provided that R ² and R ³ may be integrated to form a ring, and R ¹ may be substituted or not In the case of the arylmethyl group of the ring, at least one of R ² and R ³ is a substituted or unsubstituted aryl group, and 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 all It is a ring formed of]

(2) The anisotropically conductive adhesive composition according to (1), which contains a sulfonium salt compound represented by the following general formula (II) as the component (A).

[In the formula, Ar ¹ and Ar ² each independently represent a substituted or unsubstituted aryl group, and Y ⁻ is the same as described above]

(3) The anisotropically 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 ^- is the same as described above]

(4) The anisotropically conductive adhesive composition according to (1), which contains a sulfonium salt compound represented by the following formula (IV) as the component (A).

[In the formula, A ¹ and A ² each independently represent an alkyl group, R ⁶ , R ⁷ and R ⁸ each independently represent a hydrogen atom, an alkyl group, or a substituted or unsubstituted aryl group, and Y ^- is the above Agree with the foregoing, except that A ¹ and A ² may be integrated to form a ring]

(5) The anisotropically conductive adhesive composition according to (4), which contains a sulfonium salt compound represented by the formula (V), (VI), (VII) or (VIII) as the component (A).

[Wherein, Y ^- is the same as described above]

(6) (1) to (5) containing a sulfonium salt compound giving a peak temperature of 40 to 150°C in the measurement of differential scanning calorimetry for a mixture with a glycidyl ether type epoxy compound as the component (A) ) The anisotropically conductive adhesive composition according to any one of.

(7) The anisotropically conductive adhesive composition according to any one of (1) to (6), containing at least one selected from the group consisting of an epoxy compound, an oxetane compound, and a vinyl ether compound as the component (B).

(8) (D) The anisotropically conductive adhesive composition according to any one of (1) to (7), further containing a film-forming polymer.

(9) The anisotropically conductive adhesive composition according to any one of (1) to (8), which is used as an adhesive for circuit connection.

(10) The anisotropically conductive adhesive composition according to any one of (1) to (9), which is cured by heating.

(11) A film adhesive comprising the anisotropically conductive adhesive composition according to any one of (1) to (10) as a film.

(12) a first circuit member having a first circuit electrode, a second circuit member having a second circuit electrode, and disposed between the first circuit member and the second circuit member, the first circuit electrode and the A connection structure comprising a circuit connection member for electrically connecting a second circuit electrode, wherein the circuit connection member includes a cured product of the anisotropically conductive adhesive composition according to any one of (1) to (10).

(13) An anisotropically conductive adhesive composition according to any one of (1) to (10) is disposed between a first circuit member having a first circuit electrode and a second circuit member having a second circuit electrode, and the anisotropic conductivity A method for manufacturing a connection structure comprising a step of electrically connecting the first circuit member and the second circuit electrode by heating and pressing the first circuit member and the second circuit member through an adhesive composition.

(14) a semiconductor element, a substrate having a circuit pattern, and a semiconductor element connection member disposed between the semiconductor element and the substrate and electrically connecting the semiconductor element and the circuit pattern, the semiconductor element connection member A semiconductor device containing a cured product of the anisotropically conductive adhesive composition according to any one of (1) to (10).

The present invention further provides an application of the anisotropically conductive adhesive composition according to any one of (1) to (10) above or the film adhesive according to (11) as an adhesive for circuit connection, or the anisotropically conductive adhesive composition or film adhesive It may also relate to an application for manufacturing an adhesive for circuit connection of the.

According to the present invention, it is possible to provide an anisotropically conductive adhesive composition that can be bonded at a low temperature for a short time, has excellent connection reliability, and has excellent storage stability, and a film-like adhesive comprising these as a film. Further, a connection structure using these anisotropically conductive adhesive compositions, a method of manufacturing the same, and a semiconductor device can be provided.

1 is a schematic cross-sectional view showing an embodiment of a film adhesive.
2 is a schematic cross-sectional view showing an embodiment of a connection structure.
3A to 3C are a series of process diagrams for manufacturing a connection structure, respectively.
4 is a partial cross-sectional view showing an embodiment of a semiconductor device.
5 is a graph showing the relationship between the curing temperature and curing rate of the film adhesives of Examples 1 to 4 and Comparative Examples 1 and 4 obtained in a curing rate measurement test.

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

[Anisotropically conductive adhesive composition]

The anisotropically conductive adhesive composition (hereinafter, also simply referred to as ``adhesive composition'') according to the present embodiment is (A) a sulfonium salt compound represented by formula (I) (hereinafter, referred to as ``component (A)'' in some cases) And (B) a cationic polymerizable substance (hereinafter, sometimes referred to as "component (B)"), and (C) conductive particles.

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

In the formula, R ¹ represents a substituted or unsubstituted arylmethyl group, or a substituted or unsubstituted allyl group, R ² and R ³ each independently represent an alkyl group or a substituted or unsubstituted aryl group, and Y ⁻ represents a counter anion Show. However, R ² and R ³ may be integrated 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 mentioned. These may have a substituent, and the substitution position of a substituent is not specifically limited, It may be any one position.

Examples of the aryl group include an aryl group having 6 to 12 carbon atoms. More specifically, a phenyl group, a 1-naphthyl group, and a 2-naphthyl group are mentioned. These may have a substituent, and the substitution position of a substituent is not specifically limited, It may be any one position.

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

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

Examples of the substituents each group described above may have include alkyl groups such as methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, t-butyl group, pentyl group, and hexyl group; Aryl groups such as phenyl group and naphthyl group; Alkoxy groups such as methoxy group, ethoxy group, propoxy group, and butoxy group; Alkoxycarbonyl groups such as acetoxy group, propionyloxy group, decylcarbonyloxy group, and dodecylcarbonyloxy group; Ester groups such as methoxycarbonyl group, ethoxycarbonyl group, and benzoyloxy group; Halogen atoms such as fluorine, chlorine, bromine, and iodine; Cyano group, nitro group, and hydroxy group are mentioned. The substitution position of these substituents is not particularly limited and may be any one position.

In addition, in the case of having a cis-trans isomer in the allyl group having a substituent, any isomer may be used.

The counter anion represented by Y ^- is [P(R ⁴ ) _a (F) _6-a ] ^- (in the formula, R ⁴ represents an alkyl group in which at least part of a hydrogen atom is substituted with a fluorine atom, and a is 1 to Represents an integer of 6, and 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 the hydrogen atom is substituted with a fluorine atom, and multiple R ^5s may be the same or different from each other). It is preferable that Y ⁻ has low nucleophilicity.

In addition, as [P(R ⁴ ) _a (F) _6-a ] ^- , it is preferable that at least 80% of the hydrogen atoms in the alkyl group of R ⁴ are substituted with a fluorine atom, and hydrogen in the alkyl group of R ⁴ It is more preferable that 90% or more of the atoms are substituted with fluorine atoms, and it is still more preferable that R ⁴ is a linear or branched perfluoroalkyl group. _{Specifically, [P (CF 3) 3} (F) 3] -, [P (C 2 F 5) 3 (F) 3] - , and _{[P (nC 3 F 7)} 3 (F) 3] - , etc. Can be mentioned. These counter anions may be used alone or in combination of two or more.

In addition, as [C((R ⁵ )SO ₂ ) ₃ ] ^- , it is preferable that at least 80% of the hydrogen atoms in the alkyl group of R ⁵ are substituted with fluorine atoms, and the hydrogen atom in the alkyl group of R ⁵ It is more preferable that 90% or more is substituted with a fluorine atom, and it is still more preferable that R ⁵ is a linear or branched perfluoroalkyl group. _{Specifically, [C (CF 3 SO 2} ) 3] - , and the like ^{_{-, [C (C 2 F}} 5 SO 2) 3] - , and _{[C (nC 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 preferably a sulfonium salt compound represented by formula (II) wherein 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. The adhesive composition containing such a sulfonium salt compound is excellent in storage stability and low temperature curing properties.

Further, a sulfonium salt compound represented by Formula (IV) wherein R ¹ is a substituted or unsubstituted allyl group, and R ² and R ³ are an alkyl group or a ring formed by uniting R ² and R ³ is also preferred. The adhesive composition containing such a sulfonium salt compound is excellent in storage stability and low temperature curing properties.

Specific examples of the sulfonium salt compound include α-naphthylmethyl-4-hydroxyphenylmethylsulfonium tris (perfluoroethyl) trifluorophosphate and biphenylmethyl-4-hydroxyphenylmethylsulfonium tris (perfluoro Ethyl) trifluorophosphate, phenylmethyl-4-hydroxyphenylmethylsulfonium tris (perfluoroethyl) trifluorophosphate, 1-methyl-phenylmethyl-4-hydroxyphenylmethylsulfonium tris (perfluoro Ethyl) trifluorophosphate, 2-methyl-phenylmethyl-4-hydroxyphenylmethylsulfonium tris (perfluoroethyl) trifluorophosphate, fluorenylmethyl-4-hydroxyphenylmethylsulfonium tris (purple Luoroethyl) trifluorophosphate, α-naphthylmethyl-4-acetylphenylmethylsulfonium tris (perfluoroethyl) trifluorophosphate, biphenylmethyl-4-acetylphenylmethylsulfonium tris (perfluoro Ethyl) trifluorophosphate, 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 (perfluoroethyl) 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 (perfluoro Ethyl) trifluorophosphate, 2-butenyldimethylsulfonium tris (perfluoroethyl) trifluorophosphate, 3-methyl-2-butenyldimethylsulfonium tris (perfluoroethyl) trifluorophosphate, thinner Mildimethylsulfonium tris(perfluoroethyl)trifluorophosphate, 2-butenyltetramethylenesulfonium tris(perfluoroethyl)trifluorophosphate, 3-methyl-2-butenyltetramethylenesulfonium Tris (perfluoroethyl) trifluorophosphate, cinnamyltetramethylenesulfonium tris (perfluoroethyl) trifluorophosphate, α-naphthylmethyl-4-hydroxyphenylmethylsulfonium tris (trifluoromethane Sulfonyl) methide, biphenylmethyl-4-hydroxyphenylmethylsulfonium tris (trifluoromethanesulfonyl) methide, phenylmethyl-4-hydroxyphenylmethylsulfonium tris (trifluoromethanesulfonyl) Metide, 1-methyl-phenylmethyl-4-hydroxyphenylmethylsulfonium tris (trifluoromethanesulfonyl) methide, 2-methyl-phenylmethyl-4-hydroxyphenylmethylsulfonium tris (trifluoro Methanesulfonyl)methide, fluorenylmethyl-4-hydroxyphenylmethylsulfonium tris (trifluoromethanesulfonyl)methide, α-naphthylmethyl-4-acetylphenylmethylsulfonium tris (trifluoro Methanesulfonyl)methide, biphenylmethyl-4-acetylphenylmethylsulfonium tris(trifluoromethanesulfonyl)methide, phenylmethyl-4-acetylphenylmethylsulfonium tris(trifluoromethanesulfonyl)me Tides, 1-methyl-phenylmethyl-4-acetylphenylmethylsulfonium tris(trifluoromethanesulfonyl)methide, 2-methyl-phenylmethyl-4-acetylphenylmethylsulfonium tris(trifluoromethanesulfonyl) )Metide, fluorenylmethyl-4-acetylphenylmethylsulfonium tris (trifluoromethanesulfonyl) methide, α-naphthylmethyl-4-methoxyphenylmethylsulfonium 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) Phonyl) methide, fluorenylmethyl-4-methoxyphenylmethylsulfonium tris (trifluoromethanesulfonyl) methide, 2-butenyldimethylsulfonium tris (trifluoromethanesulfonyl) methide, 3 -Methyl-2-butenyldimethylsulfonium tris(trifluoromethanesulfonyl)methide, cinnamyldimethylsulfonium tris(trifluoromethanesulfonyl)methide, 2-butenyltetramethylenesulfonium tris(tri Fluoromethanesulfonyl)methide, 3-methyl-2-butenyltetramethylenesulfonium tris(trifluoromethanesulfonyl)methide, cinnamyltetramethylenesulfonium tris(trifluorome) Tansulfonyl)methide and the like. As the component (A), one type of sulfonium salt compound may be used alone, or two or more types may be used in combination.

In particular, α-naphthylmethyl-4-hydroxyphenylmethylsulfonium tris (perfluoroethyl) trifluorophosphate, 3-methyl-2-butenyldimethylsulfonium tris (perfluoroethyl) trifluorophosphate , Cinnamyldimethylsulfonium tris (perfluoroethyl) trifluorophosphate, 3-methyl-2-butenyl tetramethylenesulfonium tris (perfluoroethyl) trifluorophosphate, cinnamyl tetramethylenesulfonium 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, The adhesive composition containing cinnamyl tetramethylenesulfonium tris (trifluoromethanesulfonyl) methide is further excellent in storage stability and curing at low temperature.

From the viewpoint of storage stability of the adhesive composition containing the component (A), as the component (A), the component (A) and the glycidyl ether type epoxy compound YL980 (product name of Japan Epoxy Resin Co., Ltd., bisphenol A type epoxy resin) In the measurement of differential scanning calorimetry for a mixture of ), it is preferable to give an exothermic peak at 40 to 150°C. In particular, it is more preferable to give an exothermic peak at 70 to 130°C.

The content ratio of the component (A) in the adhesive composition according to the present embodiment is preferably 0.5 to 50% by mass, and more preferably 2 to 25% by mass, based on the total amount of the component (B). 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, and 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 a compound having a glycidyl ether group in its molecule, and may be cured by irradiation with active light 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 crosslinking density when cured becomes high. As the glycidyl ether type epoxy compound, a known compound can be used without particular limitation as long as it is a compound having a glycidyl ether group. More specifically, a bisphenol type epoxy resin derived from epichlorohydrin and bisphenol A or bisphenol F, and a glycidyl ether type epoxy compound having an alicyclic structure obtained by hydrogenating the aromatic structure of these bisphenol type epoxy resins, cresol Novolak type glycidyl ether compounds such as novolak type epoxy resins and phenol novolak type epoxy resins, glycidylamine type epoxy compounds, glycidyl ester type epoxy compounds, biphenyl diglycidyl ether, triglycidyl And a copolymer of isocyanurate, polyglycidyl methacrylate, or glycidyl methacrylate, and a vinyl monomer copolymerizable therewith. These may be used alone or in combination of two or more.

The alicyclic epoxy compound is a compound having an epoxy group containing two of the carbon atoms constituting the cyclic hydrocarbon skeleton and an oxygen atom in its molecule, and may be cured by irradiation with active light 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 crosslinking density when cured becomes high. As the alicyclic epoxy compound, a known one can be used without particular limitation as long as it is a compound having an alicyclic epoxy group. 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-methadioxane, 3,4-epoxy-1-methylcyclohexyl-3,4 -Epoxy-1-methylhexanecarboxylate, 3,4-epoxy-3-methylcyclohexylmethyl-3,4-epoxy-3-methylcyclohexanecarboxylate, 3,4-epoxy-5-methylcyclohexyl Methyl-3,4-epoxy-5-methylcyclohexanecarboxylate, 3,4-epoxy-6-methylcyclohexylcarboxylate, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxyl Rate, 6-methyl-3,4-epoxycyclohexylmethyl-6-methyl-3,4-epoxycyclohexanecarboxylate, ethylenebis(3,4-epoxycyclohexanecarboxylate), dicyclopentadiene diepoxy De, bis(3,4-epoxycyclohexylmethyl) adipate, methylenebis(3,4-epoxycyclohexane), etc. are mentioned. These may be used alone or in combination of two or more.

As an oxetane compound, it is an oxetane compound which has an oxetanyl group in a molecule|numerator, and what is necessary is just to be hardened|cured by irradiation of actinic light or heating in the presence or absence of a curing agent. Among them, a compound having two or more oxetane rings is preferable because the crosslinking density when cured becomes high. Further, 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 represents an integer of 1 to 6. However, when R ¹⁰ is a hydrogen atom, n is 1. when n is an integer of 2 or more, a plurality of oxygen atoms bonded to R ¹⁰ may be bonded to the same carbon atom of R ¹⁰ each may be bonded to different carbon atoms of R ^10.

As the oxetane compound, more specifically, 1,4-di[(3-oxetanyl-n-butoxy)methyl]benzene, 4,4'-bis[(3-oxetanyl-n-butoxy) )Methyl]biphenyl, 3-ethyl-3{[(3-ethyloxetan-3-yl)methoxy]methyl}oxetane, 3-ethyl-3-hydroxymethyloxetane, 2-ethylhexyloxetane And the like.

The vinyl ether compound may be a compound having a vinyl ether group in its molecule, and may be cured by irradiation of active light 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 becomes high.

As a vinyl ether compound, a compound represented by the following general formula (XIII) is mentioned.

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 each may be bonded to different carbon atoms of R ^11.

More specifically, as a vinyl ether compound, 1,4-butanediol divinyl ether, cyclohexane dimethanol divinyl ether, diethylene glycol divinyl ether, triethylene glycol divinyl ether, etc. are mentioned.

The cationically polymerizable substituent equivalent of the component (B) is preferably 43 to 1000, more preferably 50 to 800, and still more preferably 73 to 600. When the cationically polymerizable substituent equivalent is 43 to 1000, the adhesive strength tends to be further improved at the time of connection of an electrode described later. In addition, the cationic polymerizable substituent equivalent is the value obtained by dividing the average molecular weight of one molecule of the cationic polymerizable substance to be contained by the number of cationic polymerizable substituents in one molecule of the cationic polymerizable substance, that is, the average molecular weight per unit cationic polymerizable substituent. Point.

(B) as components, the impurity ^ion-to use high-purity products with reduced content of such as (Na ^+, Cl, etc.) and hydrolyzable chlorine to less than 300ppm, it is preferable in terms of corrosion protection.

The content ratio of the component (B) in the adhesive composition according to the present 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.) at the time of making a cured product tend to be improved, and when it is 90% by mass or less, the curing shrinkage tends to be small and the adhesive strength tends to be further improved. have.

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

The adhesive composition according to the present embodiment further contains (C) conductive particles. Examples of the conductive particles include metal particles such as Au, Ag, Ni, Cu, and solder, and carbon. In addition, a non-conductive glass, ceramic, plastic, or the like may be used as a core, and the core may be coated with the metal, metal particles, or carbon. When the conductive particles are made of plastic as a core, and the core is coated with the metal, metal particles, or carbon, and are hot-melted metal particles, they are deformed by heating and pressurization, and the contact area with the electrode increases at the time of connection. It is desirable because it improves reliability. Further, when the surface of the conductive particles is again coated with a polymer resin or the like, when the blending amount of the conductive particles is increased, short circuit due to contact between the particles can be suppressed, and insulation between electrode circuits can be improved. Therefore, microparticles in which the surface of the conductive particles is suitably coated with a polymer resin or the like can be used alone or in combination with the conductive particles.

The average particle diameter of this conductive particle can be calculated|required by SEM observation. The average particle diameter of the conductive particles is preferably 1 to 18 µm from the viewpoint of improving dispersibility and conductivity. Although the content ratio of the conductive particles in the adhesive composition according to the present embodiment is not particularly limited, it is preferably 0.1 to 30% by volume, more preferably 0.1 to 10% by volume, based on 100% by volume of the adhesive composition. Do. When the content ratio of the conductive particles is 0.1% by volume or more, the conductivity tends to be further improved, and when it is 30% by volume or less, short circuit of the circuit can be further prevented. In addition, "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 the mass using specific gravity. In addition, the volume of each component can also be obtained from the volume increased by adding the component to a volumetric cylinder or the like into a suitable solvent (water, alcohol, etc.). In addition, a suitable solvent means that the component is well wetted without dissolving or swelling.

In the adhesive composition according to the present embodiment, for the purpose of preventing corrosion of an adherend, a metal hydroxide or a corrosion inhibitor containing a metal oxide can be added and mixed. As the corrosion inhibitor, more specifically, at least one or more selected from the group consisting of aluminum hydroxide, magnesium hydroxide, calcium hydroxide, silicon oxide, aluminum oxide, magnesium oxide, antimony oxide, tin oxide, titanium oxide, manganese oxide and zirconium oxide desirable. When the corrosion inhibitor is in the form of particles, the particle diameter is preferably 10 μm or less from the viewpoint of dispersion in the adhesive composition, high adhesion to the adherend, and the ability to prevent corrosion of the adherend.

The content ratio of the corrosion inhibitor in the adhesive composition according to the present 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). When the content ratio of the corrosion inhibitor is 0.1% by mass or more, the corrosion prevention effect can be sufficiently exhibited, and when it is 60% by mass or less, the dispersibility increases, and the connection reliability of the adhesive composition tends to be further improved.

The adhesive composition according to the present 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 the alicyclic epoxy compound is contained as the component (B), by further containing a chain or cyclic ether compound, the curing behavior of the alicyclic epoxy compound can be more easily and reliably controlled.

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 the chain ether compound include polyethylene glycols such as triethylene glycol and tetraethylene glycol; Derivatives functionalized with an ether bond or an ester bond of a terminal hydroxyl group of polyethylene glycols; Polymers of monofunctional epoxy compounds such as ethylene oxide, propylene oxide, and cyclohexene oxide; Polymers of polyfunctional epoxy compounds; Polymers of monofunctional or polyfunctional oxetane compounds; Monofunctional or polyfunctional tetrahydrofuran polymers, etc. are mentioned. In addition, as a cyclic ether compound, 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, polyethylene glycol ring And a cyclized product of a polymer of an epoxy compound and the like. These may be used alone or in combination of two or more.

Among the above, a cyclic ether compound is preferable from the viewpoint of the 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 more preferably 0.01 to 5 mol%, based on the component (A). 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 higher.

The adhesive composition according to the present embodiment, as long as it is within a range that does not impair the effect of the present invention, may include various known additives such as inorganic fillers; Reinforcing agent; coloring agent; Stabilizers (heat stabilizers, weatherability improvers, etc.); extender; Viscosity modifiers; Tackifiers typified by terpenephenol copolymers, terpene resins, rosin derivatives and alicyclic hydrocarbon resins; Flame retardant; Ultraviolet absorbers; Antioxidants; Discoloration inhibitors; Antibacterial agents; Fungicides; Anti-aging agents; Antistatic agent; Plasticizer; Lubricant; blowing agent; It may contain a release agent or the like.

Examples of the colorant include dyes such as direct dyes, acid dyes, basic dyes, and metal complex dyes; Inorganic pigments such as carbon black and mica; Organic pigments, such as a coupling azo system, a condensed azo system, an anthraquinone system, a thioindigo system, a dioxazone system, and a phthalocyanine system, etc. are mentioned. Further, examples of the stabilizer include compounds such as hindered phenol type, hydrazine type, phosphorus type, benzophenone type, benzotriazole type, and oxalic acid anilide type. Examples of the inorganic filler include glass fibers; Asbestos fiber; Carbon fiber; Silica fibers; Alumina fibers; Zirconia fibers; Boron nitride fibers; Silicon nitride fibers; Basic magnesium sulfate fibers; Boron fibers; Stainless steel fibers; Inorganic substances such as aluminum, titanium, copper, brass, and magnesium, and metal fibers containing them; Metal powders such as copper, iron, nickel, zinc, tin, lead, stainless steel, aluminum, gold and silver; Wood flour; Aluminum silicate; Talc; Clay; lead carbonate; sulfate; phosphate; Borate; Borosilicate; Aluminosilicate; Titanate; Basic salts such as basic sulfate and basic carbonate; Glass materials such as glass hollow spheres and glass flakes; Silicon carbide; Aluminum nitride; Mullite; Cordierite and the like.

The adhesive composition according to the present embodiment may appropriately contain various polymers for the purpose of thickening and filming. 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 epoxy modified products thereof, and SEBS (styrene ethylene butyl Renstyrene block copolymer) and a modified product thereof, and the like can be used. These may be used alone or in combination of two or more. Moreover, a siloxane bond or a fluorine substituent may be contained in these polymers. 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 becomes cloudy. In particular, in the case of film formation, it is preferable to contain film-forming polymers such as phenoxy resins and polyvinyl butyrals.

When the molecular weight of the polymer is large, film-forming properties are easily obtained, and the melt viscosity that affects the fluidity of the adhesive composition can be widely set. The weight average molecular weight of the polymer is not particularly limited, but is preferably 5000 to 150000, more preferably 10000 to 80000. When the weight average molecular weight is 5000 or more, the film formation property tends to be more excellent, and when it is 150000 or less, the compatibility with other components tends to be better. Here, the weight average molecular weight means a value measured by using a calibration curve using standard polystyrene from a gel permeation chromatography (GPC) according to the conditions described below.

(Measuring conditions)

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 Kasei High School Co., Ltd.

Sample concentration: 120mg/3mL

Solvent: tetrahydrofuran

Injection volume: 60 μL

Pressure: 2.9MPa(30kgf/㎠)

Flow: 1.00 mL/mim

The content of the polymer in the adhesive composition according to the present embodiment is preferably 20 to 320 parts by mass, and more preferably 50 to 150 parts by mass based on 100 parts by mass of the component (B). When the content ratio of the polymer is 20 to 320 parts by mass, the fluidity and adhesiveness of the adhesive composition tend to be further improved.

When the adhesive composition according to the present embodiment is liquid at room temperature, it can be used in a paste form. In the case of solid at room temperature, in addition to heating and using, it can also be pasted using a solvent. The solvent that can be used is not particularly limited as long as it has no reactivity with the adhesive composition and additives, and exhibits sufficient solubility, but the boiling point at normal pressure is preferably 50 to 150°C. In the case of a solvent having a boiling point of 50°C or higher, it is difficult to volatilize even when left at room temperature, and there are few restrictions when used in an open system. In addition, in a solvent having a boiling point of 150°C or less, the solvent is liable to volatilize, and connection reliability after adhesion tends to be further improved.

The adhesive composition according to the present 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 the heating temperature is 180°C or less, undesirable side reactions tend to be suppressed and connection reliability tends to be further improved. In addition, when the heating time is 0.1 second or more, the curing reaction tends to proceed easily, and when the heating time is 10 hours or less, the productivity of the cured product is further improved, and undesirable side reactions are difficult to proceed, and the connection reliability tends to be further improved. There is this.

The adhesive composition according to the present embodiment can adhere to an adherend by using heating and pressing together. The heating temperature in the case of bonding by combining heating and pressing 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), it is generally preferably 0.1 to 30 MPa. Further, in the case of COG mounting, 10 to 100 MPa is preferred. It is preferable to perform these heating and pressurization in the range of 0.5 second-120 second.

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

[Film adhesive]

1 is a schematic cross-sectional view showing an embodiment of a film adhesive. The film adhesive 1 shown in FIG. 1 is obtained by forming the above-described adhesive composition including the adhesive component 5 and the conductive particles 7 into a film. According to the film-like adhesive 1, handling is easy, it can be easily installed on an adherend, and connection work can be performed easily.

In addition, the film adhesive 1 can also be made into a multilayer structure (not shown) including two or more layers using different kinds of adhesive compositions. In the above two or more layers, the Tg (glass transition temperature) of each layer can be different from, for example, 5°C or more.

The film-like adhesive (1) is applied by using a coating device on a support (PET (polyethylene terephthalate) film, etc.), for example, of an adhesive composition dissolved in a solvent, and hot air drying for a predetermined time at a temperature at which the adhesive composition does not cure. It can be produced by doing. In addition, the thickness of the film adhesive 1 can be, for example, 10 to 50 µm.

[Connection structure]

2 is a schematic cross-sectional view showing an embodiment of a connection structure. As shown in FIG. 2, the connection structure of this embodiment is provided with the 1st circuit member 20 and the 2nd circuit member 30 opposing each other, and the 1st circuit member 20 and the 2nd circuit Between the members 30, a circuit connecting member 10 connecting them is provided. 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 surface to be adhered to 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 21a of the circuit board 21. In addition, 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 31a of the circuit board 31, have. Also, an insulating layer (not shown) may be formed on the main surface 31a of the circuit board 31 in some cases.

The first circuit member 20 and the second circuit member 30 are not particularly limited as long as electrodes requiring electrical connection are formed. Specifically, there may be mentioned glass or plastic substrates, printed wiring boards, ceramic wiring boards, flexible wiring boards, semiconductor silicon chips, etc. on which electrodes are formed of ITO or the like used in liquid crystal displays, and these are combined and used as necessary. As described above, in the present embodiment, in addition to materials containing organic substances such as printed wiring boards and polyimide, metals such as copper and aluminum, indium tin oxide (ITO), silicon nitride (SiNX), and silicon dioxide (SiO Circuit members having a wide variety of surface states, such as materials containing inorganic materials such as ₂ ), can be used.

The circuit connecting member 10 is formed of a cured product of the adhesive composition, and contains an insulating material 11 and conductive particles 7. The conductive particles 7 are disposed not only between the opposing circuit electrode 22 and the circuit electrode 32 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 opposing circuit electrode 22 and the circuit electrode 32 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. Accordingly, the flow of current between the circuit electrode 22 and the circuit electrode 32 can be smoothed, and the function of the circuit can be sufficiently exhibited.

[Method of manufacturing connection structure]

Next, a method of manufacturing the above-described connection structure will be described.

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

It is preferable that the thickness of the film adhesive 1 is 10 to 50 μm. When the thickness of the film-like adhesive 1 is 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 more highly prevent the circuit connection material between the circuit electrode 22 and the circuit electrode 32 from being pushed out.

Next, the film adhesive 1 is mounted on the surface of the first circuit member 20 on which the circuit electrode 22 is formed. In addition, when the film-like adhesive 1 is attached on a support (not shown), the film-like adhesive 1 is mounted on the first circuit member 20 with the side facing the first circuit member 20. do. At this time, the film adhesive 1 is in the form of a film and is easy to handle. For this reason, the film-like adhesive 1 can be easily interposed between the first circuit member 20 and the second circuit member 30, so that the first circuit member 20 and the second circuit member 30 Connection operation can be easily performed.

Then, the film-like adhesive 1 is pressed in the directions of arrows A and B in FIG. 3A to temporarily connect the film-like adhesive 1 to the first circuit member 20 (FIG. 3(b) ) Reference). At this time, it is also possible to pressurize while heating.

Subsequently, as shown in Fig. 3(c), the second circuit member 30 and the second circuit electrode 32 are directed toward the first circuit member 20 (that is, the first circuit electrode ( 22) and the second circuit electrode 32 are placed on the film-like adhesive 1). In addition, when the film adhesive 1 is attached on a support (not shown), the second circuit member 30 is mounted on the film adhesive 1 after peeling the support.

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

When the connection structure is manufactured as described above, in the connection structure obtained, it becomes possible to make the conductive particles 7 contact with both the opposing circuit electrode 22 and the circuit electrode 32, and the circuit electrode 22 ) And the connection resistance between the circuit electrode 32 can be sufficiently reduced.

Further, by heating the film-like adhesive 1, the adhesive component 5 is cured in a state in which the distance between the circuit electrode 22 and the circuit electrode 32 is sufficiently reduced to become an insulating material 11, The first circuit member 20 and the second circuit member 30 are firmly connected through the circuit connecting member 10. That is, in the obtained connection structure, since the circuit connection member 10 is constituted by a cured product of a circuit connection material containing the adhesive composition, the first circuit member 20 or the second circuit member 30 ), the adhesive strength of the circuit connection member 10 is sufficiently high, particularly under high temperature and high humidity conditions. Further, in the connection structure, a state in which the adhesive strength is sufficiently high is maintained over a long period of time. Therefore, the obtained connection structure is sufficiently prevented from changing over time in the distance between the circuit electrode 22 and the circuit electrode 32, and has excellent long-term reliability of the electrical properties between the circuit electrode 22 and the circuit electrode 32 Do.

In addition, in the said embodiment, although the connection structure is manufactured using the film adhesive 1, instead of the film adhesive 1, the adhesive composition which is not formed in a film can also be used. Even in this case, when the adhesive composition is dissolved in a solvent and the solution is applied to either of the first circuit member 20 or the second circuit member 30 and dried, the first circuit member 20 and the second circuit member 20 An adhesive composition may be interposed between the circuit members 30.

[Semiconductor device]

Next, an embodiment of a semiconductor device according to the present invention will be described. 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 serving as a support member for the semiconductor element, and the semiconductor element 50 and the substrate ( Between 60), a semiconductor element connecting member 80 for electrically connecting them is provided. Further, the semiconductor element connecting member 80 is stacked on the main surface 60a of the substrate 60, and the semiconductor element 50 is further stacked on the semiconductor element connecting member 80.

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

The material of the semiconductor device 50 is not particularly limited, but semiconductor devices of group 4 of silicon and germanium, GaAs, InP, GaP, InGaAs, InGaAsP, AlGaAs, InAs, GaInP, AlInP, AlGaInP, GaNAs, GaNP, GaInNAs, GaInNP , Group III-V compound semiconductor devices such as GaSb, InSb, GaN, AlN, InGaN, InNAsP, and II-VI compound semiconductor devices such as HgTe, HgCdTe, CdMnTe, CdS, CdSe, MgSe, MgS, ZnSe, ZeTe, and , CuInSe (CIS), etc. 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 an insulating material 11 and 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 through the conductive particles 7. For this reason, the connection resistance between the semiconductor element 50 and the circuit pattern 61 is sufficiently reduced. Accordingly, the flow of current between the semiconductor element 50 and the circuit pattern 61 can be smoothed, and the function of the semiconductor can be sufficiently exhibited. In addition, it is also possible to exhibit anisotropy of electrical connection by setting the conductive particles 7 in the above-described mixing ratio.

The semiconductor element connecting member 80 is constituted by a cured product of a circuit connecting material containing 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 is sufficiently reduced. I can. And this state can be sustained over a long period of time. Further, since the semiconductor element connecting member can be formed by heating at a low temperature for a short time, the influence on the semiconductor element or the like can be reduced. Accordingly, it becomes possible to sufficiently increase the long-term reliability of the electrical properties between the semiconductor element 50 and the substrate 60.

As mentioned above, although preferred embodiment of this invention was demonstrated, this invention is not limited to the said embodiment.

Hereinafter, the present invention will be described in more detail based on Examples and Comparative Examples, but the present invention is not limited to the Examples at all.

(Example 1)

(A) TA-60 (product name of Acid-Apro Co., Ltd., α-naphthylmethyl-4-hydroxyphenylmethylsulfonium tris (perfluoroethyl) trifluorophosphate), (B) gly Cydyl ether type epoxy compound YL980 (Japan Epoxy Resin Co., Ltd. product name, bisphenol A type epoxy resin) was used. As the film-forming polymer, a phenoxy resin (YP-70, a brand name manufactured by Toto Kasei Co., Ltd.) was used. In addition, a nickel layer having a thickness of 0.2 μm was formed on the surface of particles having a core of polystyrene, and a gold layer having a thickness of 0.02 μm was formed on the outside of the nickel layer, and conductive particles having an average particle diameter of 3 μm and a specific gravity of 2.5 were prepared. Used. In addition, aluminum hydroxide powder was used as the corrosion inhibitor.

Component (A), component (B), and film-forming polymer were blended at the mixing ratio shown in Table 1, and 8% by volume of conductive particles were blended and dispersed, and applied to a PET resin film having a thickness of 40 µm using a coating device. Then, by hot air drying at 70°C for 5 minutes, a film adhesive having a thickness of the adhesive layer of 20 μm was obtained.

(Example 2)

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

(Example 3)

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

(Example 4)

(A) 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. Table 1 shows the mixing ratio of each component.

(Comparative Example 1)

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

(Comparative Example 2)

(A) Film-like adhesive in the same manner as in Example 1, except that CPI-100A (product name, 4-phenylthiophenyl diphenylsulfonium hexafluoroantimonate) was used as the component. Got it. Table 1 shows the mixing ratio of each component.

(Comparative Example 3)

(A) The same as in Example 1, except that CPI-200K (product name, 4-phenylthiophenyldiphenylsulfonium tris (perfluoroethyl) trifluorophosphate) was used as the component. A film-like adhesive was obtained by the method. Table 1 shows the mixing ratio of each component.

(Comparative Example 4)

(A) 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. Table 1 shows the mixing ratio of each component.

(Comparative Example 5)

(A) 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. Table 1 shows the mixing ratio of each component. In addition, in Table 1, the mixing ratio is expressed by mass parts.

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

[Differential Scanning Calorimetry Measurement]

Differential scanning calorimetry of the film-like adhesives obtained by Examples and Comparative Examples was performed, and the presence or absence of an exothermic peak was examined.

In the film adhesives obtained by Comparative Examples 2 and 3, no exothermic peak was observed. Further, the film-like adhesive obtained by Comparative Example 5 was cured before measurement. The film adhesives obtained by 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, (A) component is α- naphthyl-4-hydroxyphenyl methyl sulfonium having a ^{TA-60 (Y - = [} P (C 2 F 5) 3 F 3] -, performed example 1) and PMNS TFSM (Y- = [C ( CF 3 SO 2) 3] -, example 2) in case ^{of, SI-60 (Y - =} [SbF 6] - Similar to Comparative example 1), heat The peak was observed around 110°C, and equivalent low-temperature curing properties were confirmed.

In addition, in the differential scanning calorimetry measurement, when the component (A) is a sulfonium salt compound having three aryl groups (Comparative Examples 2 and 3), an exothermic peak was not confirmed, but a sulfonium salt compound having a substituted arylmethyl group and a substituted aryl group In the case of (Examples 1 and 2 and Comparative Example 1), there was an exothermic peak at around 110°C, and in the case of a sulfonium salt compound having an allyl group and an alkyl group substituted with a methyl or phenyl group (Examples 3 and 4), at around 120°C There was an exothermic peak, and each equivalent low-temperature curing property was confirmed. 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 was an exothermic peak at around 150°C, and curability was confirmed at high temperature compared to the component (A) of Example. 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 curing proceeded before measurement and storage stability was inferior.

[Hardening rate measurement test]

The film adhesives of Examples 1 to 4 and Comparative Examples 1 and 4 were cured by heating on a hot plate for 10 seconds at 100 to 160°C, respectively. From the infrared absorption spectrum, the difference in the area value of the signal intensity of the epoxy group before and after heating was divided by the area value of the signal intensity before heating to obtain a curing rate. The results are shown in FIG. 5.

α- naphthyl-4-hydroxyphenyl methyl sulfonium salt ^{compound, TA-60 (Y - =} [P (C 2 F 5) 3 F 3] -) with the examples 1 and PMNS TFSM (Y ^- = _{[C (CF 3 SO 2)} 3] - carried out using a) example ^{2, SI-60 (Y - =} [SbF 6] -) as in Comparative example 1 using a, exhibits a high cure rate in a short time of 10 seconds , The same low temperature stability was confirmed.

Examples 3 and 4 using the sulfonium salt compound having an allyl group substituted with a methyl group or a phenyl group and an alkyl group exhibited the same low-temperature 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, hardly curing proceeded.

[Storage stability test]

The film adhesives of Examples 1 to 4 and Comparative Examples 1 to 5 were allowed to stand in a thermostat at 40°C for 5 days. From the infrared absorption spectrum, the curing rate after standing was determined. Table 3 shows the results.

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

[Measurement of fluorine ion concentration]

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

Y ^- _{a, [P (C 2 F 5} ) 3 F 3] - or _{[C (CF 3 SO 2)} 3] - The sulfonate embodiment using a salt compound Examples 1 to 4 and Comparative Examples 3 to 5 having, a fluorine low, but the ion concentration of less than 100ppm, [SbF _6] ^- the Comparative examples 1 and 2 with a sulfonium salt compound having it was confirmed that the fluoride ion concentration is very high, each 10500ppm, 6800ppm.

[Manufacture of connection structure]

On a glass substrate (Corning #1737, external shape 38 mm × 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 × 20 mm Each of the film adhesives of 1 to 4 and Comparative Examples 1 to 5 was transferred from the PET resin film. IC chip (appearance 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, 80 MPa (bump area conversion) load Was added, heated and pressurized to mount. In addition, the film-like adhesive after the storage stability test was similarly mounted.

[Evaluation of connection resistance]

The resistance value (maximum value during measurement of 14 terminals) between adjacent circuits of the connection structure fabricated as described above was measured. Table 4 shows the obtained results.

In the case of using the film adhesives of Examples 1 to 4 and Comparative Example 1, both before and after the storage stability test showed a good value of less than 5 Ω. In the case of using the film adhesives of Comparative Examples 2 and 3, the curing did not proceed and the connection could not be made. In addition, when the film-like adhesive of Comparative Example 4 was used, it became a high resistance value. In Comparative Example 5, hardening proceeded before production of the connection structure.

[Observation of wiring corrosion of connection structure]

The external appearance of the ITO wiring was observed after treating the connection structure produced as described above (a film-like adhesive not subjected to a storage stability test) in an environment of 85°C and 85% RH for 24 hours. Table 4 shows the obtained results.

Y ^- a, [SbF _6] ^- sulfonate in Comparative Examples 1 and 2 using the salt compound, was identified to have a corrosion of significant wiring, Y having a ^- _{a, [P (C 2 F 5} ) 3 F 3] - In Examples 1 to 4 and Comparative Examples 3 to 5 using the sulfonium salt compound having [C(CF ₃ SO ₂ ) ₃ ] ^- , corrosion was not observed.

From the above, Y ^- is _{^{[P (R 4) a (}} F) 6-a] - , or ^{[C ((R 5) SO} 2) 3] - is represented by, in particular, _{[P (C 2 F 5)} 3 F _3] ^- or _{[C (CF 3 SO 2)} 3] - the adhesive composition comprising the sulfonium salt compound represented by the above formula (I), [SbF _6] ^- low-temperature fast-curing equivalent to those comprising the And storage stability, and since fluorine ions are less likely to be desorbed, the occurrence of corrosion is suppressed, and it has been found that the connection reliability is excellent. In addition, in the sulfonium salt compound represented by the formula (I), when R ¹ is a substituted or unsubstituted arylmethyl group, R ² is a substituted or unsubstituted aryl group, R ³ is a methyl group, or R ¹ is substituted or When it is an unsubstituted allyl group, and R ² and R ³ are an alkyl group or a ring formed integrally with R ² and R ³ , it has been found that it is suitable as a polymerization initiator of an adhesive composition that can be connected in a short time at a low temperature.

1: film adhesive
2: semiconductor device
5: adhesive component
7: conductive particles (component (C))
10: circuit connection member
11: insulating material
20: first circuit member
21: circuit board (first circuit board)
21a: if you give
22: circuit electrode (first circuit electrode)
30: second circuit member
31: circuit board (second circuit board)
31a: if you give
32: circuit electrode (second circuit electrode)
50: semiconductor device
60: substrate
61: circuit pattern
70: sealing material
80: semiconductor element connection member

Claims (14)

(A) a sulfonium salt compound represented by the following formula (I), and
(B) a cationic polymerizable substance,
(C) conductive particles
Anisotropically conductive adhesive composition comprising a.

[In the formula, R ¹ represents a substituted or unsubstituted arylmethyl group or a substituted or unsubstituted allyl group, R ² and R ³ each independently represent an alkyl group or a substituted or unsubstituted aryl group, and Y ⁻ represents [P (R ⁴ ) _a (F) _6-a ] ^- (In the formula, R ⁴ represents an alkyl group in which at least part of a hydrogen atom is substituted with a fluorine atom, a represents an integer of 1 to 6, and a is an integer of 2 or more. In the case, 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 is at least part of a hydrogen atom substituted with a fluorine atom, R ⁵ may be the same as or different from each other), provided that R ² and R ³ may be integrated to form a ring, and R ¹ may be substituted or not In the case of an arylmethyl group of the ring, at least one of R ² and R ³ is a substituted or unsubstituted aryl group, and 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 all It is a ring formed of] The anisotropically conductive adhesive composition according to claim 1, containing a sulfonium salt compound represented by the following formula (II) as the component (A).

[In the formula, Ar ¹ and Ar ² each independently represent a substituted or unsubstituted aryl group, and Y ⁻ is the same as described above] The anisotropically conductive adhesive composition according to claim 2, wherein the component (A) contains a sulfonium salt compound represented by the following general formula (III).

[Wherein, Y ^- is the same as described above] The anisotropically conductive adhesive composition according to claim 1, wherein the component (A) contains a sulfonium salt compound represented by the following general formula (IV).

[In the formula, A ¹ and A ² each independently represent an alkyl group, R ⁶ , R ⁷ and R ⁸ each independently represent a hydrogen atom, an alkyl group, or a substituted or unsubstituted aryl group, and Y ^- is the above Agree with the foregoing, except that A ¹ and A ² may be integrated to form a ring] The anisotropically conductive adhesive composition according to claim 4, wherein the component (A) contains a sulfonium salt compound represented by the formula (V), (VI), (VII) or (VIII).

[Wherein, Y ^- is the same as described above] The sulfonium salt according to any one of claims 1 to 5, which provides a peak temperature of 40 to 150°C in the measurement of differential scanning calorimetry for a mixture with a glycidyl ether-type epoxy compound as the component (A). An anisotropically conductive adhesive composition containing a compound. The anisotropically conductive adhesive composition according to any one of claims 1 to 5, wherein the component (B) contains at least one selected from the group consisting of an epoxy compound, an oxetane compound, and a vinyl ether compound. The anisotropically conductive adhesive composition according to any one of claims 1 to 5, further comprising (D) a film-forming polymer. The anisotropically conductive adhesive composition according to any one of claims 1 to 5, which is used as an adhesive for circuit connection. The anisotropically conductive adhesive composition according to any one of claims 1 to 5, which is cured by heating. A film adhesive comprising the anisotropically conductive adhesive composition according to any one of claims 1 to 5 as a film. A first circuit member having a first circuit electrode, a second circuit member having a second circuit electrode, and disposed between the first circuit member and the second circuit member, the first circuit electrode and the second circuit A circuit connecting member for electrically connecting the electrodes is provided,
A connection structure in which the circuit connection member contains a cured product of the anisotropically conductive adhesive composition according to any one of claims 1 to 5. An anisotropically conductive adhesive composition according to any one of claims 1 to 5 is disposed between a first circuit member having a first circuit electrode and a second circuit member having a second circuit electrode, and the anisotropically conductive adhesive composition A step of electrically connecting the first circuit electrode and the second circuit electrode by heating and pressing the first circuit member and the second circuit member through the method. A semiconductor element, a substrate having a circuit pattern, and a semiconductor element connection member disposed between the semiconductor element and the substrate and electrically connecting the semiconductor element and the circuit pattern,
A semiconductor device in which the semiconductor element connecting member contains a cured product of the anisotropically conductive adhesive composition according to any one of claims 1 to 5.

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