TWI529186B - Thermopolymerization initiator system and adhesive composition - Google Patents

Description

Thermal polymerization initiator system and adhesive composition

The present invention relates to a thermal polymerization initiator system and an adhesive composition.

In recent years, in the field of semiconductors, liquid crystal displays, etc., in order to fix electronic parts, various adhesive materials are used for circuit connection. In such applications, higher density and higher definition are required, and high adhesion or reliability is required for the adhesive.

In particular, in the connection between a liquid crystal display and a TCP, the connection between FPC and TCP, or the connection between an FPC and a printed circuit board, an anisotropic conductive adhesive in which conductive particles are dispersed in an adhesive is used as a circuit connecting material. Further, recently, when a semiconductor germanium wafer is mounted on a substrate, the conventional semiconductor wire is not directly bonded to the substrate, and the semiconductor germanium wafer is directly mounted on the substrate. Anisotropic conductive adhesives are also suitable.

Moreover, in recent years, in the field of precision electronic equipment, accompanying electricity The high density of the road progresses, and the electrode width and electrode spacing become extremely narrow. Therefore, the connection conditions of the conventional epoxy resin-based circuit-connecting adhesive are used to cause problems such as dropping, peeling, and displacement of the wiring, and there is also a difference in thermal expansion between the wafer and the substrate due to COG. The problem of warping. Further, in order to reduce the cost, there is a need to increase the amount of processing, and it is required to have a low temperature (100 to 170 ° C) and a short time (within 10 seconds), in other words, an adhesive which can be hardened at a low temperature.

In the past, as a cationic polymerization initiator, for example, a polymerization initiator of a cationically polymerizable substance having a sulfonium salt represented by the following general formula (II) as a main component has been proposed (Patent Document 1).

[In the formula (II), R _a represents hydrogen, methyl, ethyl fluorenyl, methoxycarbonyl, ethoxycarbonyl, benzyloxycarbonyl, benzinyl, phenoxycarbonyl, 9-fluorenylmethoxy In any of the carbonyl groups, R _b and R _c independently represent any of hydrogen, halogen, or C ₁ -C ₄ alkyl, R _d represents a C ₁ -C ₄ alkyl group, and Q represents an o-nitrobenzyl group. Any one of m-nitrobenzyl, dinitrobenzyl, trinitrobenzyl, α-naphthylmethyl, and β-naphthylmethyl. X is any one of SbF ₆ , AsF ₆ , PF ₆ , and BF ₄ . 〕

Further, a polymerization initiator which cures an epoxy resin in a short time by heating may be a cationic polymerization initiator containing a phosphonium salt represented by the following general formula (III) or the following general formula (IV). (Patent Document 2).

[In the formula (III), 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 a phenyl group which may also be substituted or a naphthyl group which may also be substituted , X represents SbF ₆ , AsF ₆ , PF ₆ or BF ₆ . 〕

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

[Previous Technical Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open No. Hei 3-237107

[Patent Document 2] Japanese Patent Laid-Open No. Hei 6-345726

The polymerization initiator described in Patent Document 1 or 2 is considered to be a bismuth salt by selecting a structure in which a leaving group (-Q, -CH ₂ R _g or R _j ) is easily detached, and attempts to achieve a low temperature. Hardening or hardening for a short time. Further, in the onium salt, the leaving group is considered to be detached by a SN1 reaction or a SN2 reaction of a cation.

Further, the initiator system is known to have a thermal polymerization system and a photopolymerization system. The initiator system of the thermal polymerization system is different from the initiator system of the photopolymerization system, and requires a property such as a general trade-off relationship between low-temperature hardenability and storage stability.

However, in the polymerization initiator described in Patent Document 1 or 2, when the above-mentioned onium salt is used, when a highly cationic polymerizable monomer such as an alicyclic epoxy compound, a propylene oxide compound or a vinyl ether compound is combined There is a problem that the hardening reaction proceeds by itself during storage. In addition, in Patent Document 1, although the storage stability is excellent, the storage conditions are "under shading, 10 ° C or less", and It cannot be said that it is sufficient to preserve stability.

The present invention has been made in view of the above circumstances, and provides an adhesive composition which can be adhered at a low temperature for a short period of time, has good connection reliability, and has excellent storage stability, and is useful in the manufacture of the adhesive composition. The polymerization initiator system is for the purpose.

As a result of intensive review, the present inventors have found that by combining the onium salt compound represented by the following general formula (I) with a radical polymerization initiator, even when a glycidyl ether compound is used, When any of the alicyclic epoxy compound, the propylene oxide compound, and the vinyl ether compound is used as a polymerizable substance, the curability at low temperature and the practical storage stability can be coexisted, and the present invention has been completed.

In other words, the present invention provides the initiator system described in the following (1) to (6) and the adhesive composition described in the following (7) to (17).

(1) A thermal polymerization initiator system comprising (A) an onium salt compound represented by the following general formula (I) and (B) a radical polymerization initiator.

R ¹ -I ⁺ -R ² Y ^- (I) wherein R ¹ and R ² each independently represent a substituted or unsubstituted aryl group, and Y ^- represents an anionic residue. 〕

(2) The thermal polymerization initiator system according to (1) above, wherein the above Y ^- is SbF ₆ ^- , [P(R ⁶ ) _a (F) _6-a ] ^- (wherein R ⁶ represents a hydrogen atom At least a part of the alkyl group substituted by a fluorine atom, a represents an integer of 0 to 5. When a is an integer of 2 or more, the plural R ⁶ may be the same or different from each other, and B (C ₆ F _{5 )} ) ₄ ^- or C(CF ₃ SO ₂ ) ₃ ^- .

(3) The thermal polymerization initiator system according to (1) or (2) above, wherein the radical polymerization initiator is an organic peroxide.

(4) The thermal polymerization initiator system according to (3) above, wherein the organic peroxide has a one-minute half-life temperature of from 80 to 170 °C.

(5) The thermal polymerization initiator system according to any one of the above (1) to (4), which is used for curing the cationically polymerizable material.

(6) The thermal polymerization initiator system according to any one of the above (1) to (5), which is used for hardening by heating.

(7) An adhesive composition comprising (A) an onium salt compound represented by the following general formula (I), (B) a radical polymerization initiator, and (C) a cationically polymerizable substance.

R ¹ -I ⁺ -R ² Y ^- (I) wherein R ¹ and R ² each independently represent a substituted or unsubstituted aryl group, and Y ^- represents an anionic residue. 〕

(8) The adhesive composition according to the above (7), wherein the above Y ^- is SbF ₆ ^- , [P(R ⁶ ) _a (F) _6-a ] ^- (wherein R ⁶ represents at least a part of a hydrogen atom The alkyl group substituted by a fluorine atom, a represents an integer of 0 to 5. When a is an integer of 2 or more, the plural R ⁶ may be the same or different from each other.), B(C ₆ F ₅ ) ₄ ^- or _{C (CF 3 SO 2) 3} -.

(9) The adhesive composition according to (7) or (8) above, wherein the radical polymerization initiator is an organic peroxide.

(10) The adhesive composition according to (9) above, wherein the organic peroxide has a one-minute half-life temperature of from 80 to 170 °C.

(11) The adhesive composition according to any one of the above (7), wherein the cationically polymerizable substance contains at least one compound selected from the group consisting of an epoxy compound, a propylene oxide compound, and a vinyl ether compound. .

(12) The adhesive composition according to any one of (7) to (11) above which further comprises (D) a film-forming polymer.

(13) The adhesive composition according to any one of (7) to (12) above which further contains (E) conductive particles.

(14) The adhesive composition according to (13) above, which is characterized by anisotropic conductivity.

(15) The adhesive composition according to any one of the above (7) to (14), which is used as an adhesive composition for circuit connection.

(16) The adhesive composition according to any one of the above (7) to (15) which is hardened by heating.

(17) A film-like adhesive composition which is made above (7) The adhesive composition according to any one of (16) is formed into a film.

Further, according to the investigation of the present inventors, the onium salt compound represented by the above general formula (I) is less likely to cause a SN1 reaction or a substituent due to the SN2 reaction of the cation than the onium salt described in Patent Document 1 or 2. Separation. Therefore, when the onium salt compound represented by the above general formula (I) is used alone in combination with a radical polymerization initiator, hardening at a low temperature (100 to 170 ° C) and a short time (within 10 seconds) becomes difficult. . The present inventors have found that the above-mentioned onium salt compound and the radical polymerization initiator which are difficult to harden at a low temperature for a short period of time alone can be used together to obtain an initiator system which can be hardened at a low temperature for a short period of time. One thing. The reason why such an initiator system can be obtained is not entirely clear, but it is considered that the above-mentioned onium salt compound or the above-mentioned onium salt compound is induced by a radical generated from a radical polymerization initiator.

According to the present invention, it is possible to provide an adhesive composition which is excellent in adhesion at a low temperature for a short period of time, excellent in connection reliability, and excellent in storage stability, and an initiator system useful in the production of the adhesive composition.

[Fig. 1] shows differential scanning heat of Examples 1, 2 and Comparative Example 1. A graph of the measurement results.

Fig. 2 is a graph showing the results of measurement of differential scanning calorimetry in Example 3 and Comparative Example 2.

Fig. 3 is a graph showing the results of measurement of differential scanning calorimetry in Example 4 and Comparative Example 3.

Fig. 4 is a graph showing the results of measurement of differential scanning calorimetry in Example 5 and Comparative Example 4.

Fig. 5 is a graph showing the relationship between the curing temperature and the curing rate of the film-like adhesive compositions of Examples 1 to 4 obtained in the curing rate measurement test.

Fig. 6 is a graph showing the relationship between the curing temperature and the curing rate of the film-like adhesive compositions of Comparative Examples 1 to 8 obtained in the curing rate measurement test.

Fig. 7 is a graph showing the relationship between the curing temperature and the curing rate of the film-like adhesive compositions of Comparative Examples 9 to 11 obtained in the curing rate measurement test.

Fig. 8 is a graph showing the relationship between the elapsed time and the hardening rate of the film-like adhesive compositions of Examples 1 to 4 obtained in the storage stability test.

Fig. 9 is a graph showing the relationship between the elapsed time and the hardening rate of the film-like adhesive compositions of Comparative Examples 1 to 8 obtained in the storage stability test.

Fig. 10 is a graph showing the relationship between the elapsed time and the hardening rate of the film-like adhesive compositions of Comparative Examples 9 to 11 obtained in the storage stability test.

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

(starter system)

The initiator system of the present embodiment contains (A) an onium salt compound represented by the general formula (I) (hereinafter, referred to as "(A) component" depending on the case), and (B) a radical polymerization initiator. (Hereinafter, it is called "(B) component" depending on the situation).

[Chemical 6] R ¹ -I ⁺ -R ² Y ^- (I)

In the formula, R ¹ and R ² each independently represent a substituted or unsubstituted aryl group, and Y ^- represents an anionic residue.

The aryl group may, for example, be 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 position of substitution of the substituent is not particularly limited, and may be any position.

Examples of the substituent which may have each of the above groups include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, and a t-butyl group. An alkyl group such as a pentyl group or a hexyl group; an aryl group such as a phenyl group or a naphthyl group; an alkoxy group such as a methoxy group, an ethoxy group, a propoxy group or a butoxy group; an ethoxy group or a propyloxy group; An alkoxycarbonyl group such as a mercaptocarbonyloxy group or a dodecylcarbonyloxy group; an ester group such as a methoxycarbonyl group, an ethoxycarbonyl group or a benzhydryloxy group; a halogen atom such as fluorine, chlorine, bromine or iodine; Cyano group, nitro group, hydroxyl group, and the like. The position of substitution of these substituents is not particularly limited and may be any position.

The anion residue may be a monovalent relative anion such as BF ₄ ^- , SbF ₆ ^- , AsF ₆ ^- , [P(R ⁶ ) _a (F) _6-a ] ^- (wherein R ⁶ represents a hydrogen atom At least a part of the alkyl group substituted by a fluorine atom, a represents an integer of 0 to 5. When a is an integer of 2 or more, the plural R ⁶ may be the same or different from each other, and B (C ₆ F _{5 ) 4} ^- , Ga(C ₆ F ₅ ) ₄ ^- , Ga(C ₆ F ₅ ) ₂ F ₂ ^- , Ga(C ₆ F ₅ )F ₃ ^- , C(CF ₃ SO ₂ ) ₃ ^- and the like.

Further, in [P(R ⁶ ) _a (F) _6-a ] ^- , R ⁶ is preferably an alkyl group in which 80% or more of a hydrogen atom is substituted by a fluorine atom, and 90% or more of a hydrogen atom is fluorine. The alkyl group substituted by an atom is preferred, and a linear or branched perfluoroalkyl group is more preferred.

The anionic residue is preferably one having a low nucleophilicity. Therefore, the anionic residue is SbF ₆ ^- , [P(R ⁶ ) _a (F) _6-a ] ^- (wherein R ⁶ represents an alkyl group in which at least a part of a hydrogen atom is replaced by a fluorine atom, and a represents 0. An integer of ~5. When a is an integer of 2 or more, the plural R ⁶ may be the same or different from each other, and B(C ₆ F ₅ ) ₄ ^- , C(CF ₃ SO ₂ ) ₃ ^{- is} preferable. Preferably, SbF ₆ ^- , B(C ₆ F ₅ ) ₄ ^- , C(CF ₃ SO ₂ ) ₃ ^- is preferred. When the nucleophilicity of the anion residue is low, the growth reaction rate of the cationically polymerizable compound becomes high, and it becomes polymerizable at a low temperature and for a short period of time.

The onium salt compound is preferably a diarylsulfonium salt compound in which R ¹ and R ² are a substituted or unsubstituted aryl group. The initiator system containing such an onium salt compound is more excellent in storage stability and rapid low-temperature hardenability.

Specific examples of the onium salt compound include diphenylphosphonium hexafluoride arsenide, bis(4-chlorophenyl)phosphonium hexafluoride arsenide, bis(4-bromophenyl)phosphonium hexafluoride hexafluoride, and benzene. Base (4-methoxyphenyl) ruthenium hexafluoride, UVE series manufactured by General Electric Co., Ltd., FC series manufactured by Minnesota Mining & Manufacturing Co., Ltd., UV-9310C manufactured by Toshiba Silicon Co., Ltd. ( Relative anion: SbF ₆ ^- ) and PhotoInitiator 2074 (relative anion: (C ₆ F ₅ ) ₄ B ^- ) manufactured by Rhône-Poulenc.

In the initiator system of the present embodiment, one of the onium salt compounds may be used alone as the component (A), and two or more of them may be used in combination. In the initiator system of the present embodiment, the component (A) has a function as a cationic polymerization initiator.

The component (A) is preferably one in which the activity is exhibited at a temperature of from 140 to 250 ° C from the viewpoint of preserving stability, and the differential scanning calorimetry for the mixture with the epoxy propyl ether type epoxy compound is given. It is better to give a peak temperature of 140~250 °C.

As the component (B), a conventionally known peroxide or azo compound can be used, and an organic peroxide is preferred from the viewpoint of further improving storage stability and rapid hardening at a low temperature.

Examples of the organic peroxide include diethylhydrazine peroxide, peroxydicarbonate, peroxyester, peroxyketal, dialkyl peroxide, hydroperoxide, and perylene alkyl. Among these, from the viewpoint of stability and reactivity, peroxy ester and diethylperoxy peroxide are preferred. Further, the peroxyester has a structure represented by -C(=O)-O-O-, and the peroxydiamine group has a structure represented by -C(=O)-O-O-C(=O)-. Further, the organic peroxide has a one-minute half-life temperature of 80 to 170 ° C, and a peroxy ester having a molecular weight of 180 to 1,000 or a diethylperoxy peroxide group is more preferable. By synthesizing the acid compound as such, it is possible to provide an initiator system which is excellent in preservation stability and low-temperature rapid hardening property.

Specific examples of the component (B) include cumene peroxy neodecanoate, 1,1,3,3-tetramethylbutyl neodecanoate, and 1-cyclohexyl-1-? Oxidized methyl ethyl neodecanoate, t-hexyl neodecanoate peroxide, t-butyl neodecanoate peroxide, t-butyl trimethyl acetate, 1, 1, 3,3-tetramethylbutyl-2-ethylhexanoate, 2,5-dimethyl-2,5-di(2-ethylhexyl)peroxide, t-hexyl peroxide 2-ethyl hexanoate, 2-ethyl peroxybutyl t-butylhexanoate, t-butyl neoheptanoate peroxide, t-pentylhexanoic acid-2-B Ester, di-t-butyl hexahydrophthalate, t-pentylhexanoic acid-3,5,5-trimethyl ester, 3-hydroxy-1,1-dimethylbutyl peroxide Neodecanoate, 1,1,3,3-tetramethylhexanoic acid-2-ethyl ester, t-pentyl neodecanoate peroxide, t-pentylhexanoic acid-2-ethyl peroxide , 2,2'-azobis-2,4-dimethylvaleronitrile, 1,1'-azobis(1-ethenyloxy-1-phenylethane), 2,2'-even Nitrogen bisisobutyronitrile, 2,2'-azobis(2-methylbutyronitrile), dimethyl-2,2'-azobisisobutyronitrile, 4,4'-azobis(4- Cyanovalerate, 1,1'-azobis(1-cyclohexanecarbonitrile), isopropyl t-hexyl monocarbonate, t-butyl maleic acid peroxide, t-butyl peroxide Caproic acid-3,5,5-trimethyl ester, t-butyl laurate peroxide, 2,5-dimethyl-2,5-bis(3-methylbenzylidene)hexane, peroxidation T-butyl-monoethyl-2-ethylhexylate, t-hexylbenzyl peroxide, 2,5-dimethyl-2,5-di(benzylidene peroxide)hexane, peroxidation -butyl benzyl ester, trimethyl butyl peroxy adipate, t-pentyl n-octanoate peroxide, t-pentyl isocyanate peroxide, t-pentyl benzyl peroxide Peroxidized laurel醯基等.

The 1-minute half-life temperature is 80-170 ° C, and the molecular weight is 180-1000 peroxy ester, specifically 2,5-dimethyl-2,5-di(2-ethylhexyl peroxide) Hexane, etc.

Further, the one-minute half-life temperature is 80 to 170 ° C, and the peroxydiethyl sulfhydryl group having a molecular weight of 180 to 1,000 is specifically a lauric acid peroxide group.

(B) The radical polymerization initiator may be used singly or in combination of two or more.

The content ratio of the component (B) in the initiator system of the present embodiment is preferably 25% by mass or more, and more preferably 50% by mass or more based on the total amount of the component (A). When the content ratio of the component (B) is within the above range, an initiator system which is more excellent in both storage stability and low-temperature rapid hardenability can be obtained. When the content ratio of the component (B) is less than the above range, the initial species of cationic polymerization tends not to be sufficiently formed.

When the initiator system of the present embodiment contains an organic peroxide as the component (B), the one-minute half-life temperature β of the organic peroxide and the mixture of the component (A) and the epoxy propyl ether-type epoxy compound are The difference α-β between the peak temperatures α in the differential scanning calorimetry is preferably 30 to 200 °C.

The initiator system of the present invention may also be a group of an onium salt compound and a phosphonium salt compound having a peak temperature of 140 to 250 ° C in a differential scanning calorimetry selected from a mixture of a glycidyl ether type epoxy compound. At least one of the cerium salts is formed with an organic peroxide having a half-life temperature of 80 to 170 ° C for 1 minute. In the same manner as the initiator system of the above-described embodiment, the cationically polymerizable material such as an epoxy compound can be polymerized at a low temperature for a short period of time, and the storage stability is excellent. Here, the phosphonium salt compound and the organic acidified compound can be used. Use the same as above.

In the initiator system of the present embodiment, the cationically polymerizable substance such as an epoxy compound can be polymerized at a low temperature for a short period of time, and the storage stability is excellent. Therefore, the initiator system of the present embodiment can produce an adhesive composition which is adhered at a low temperature for a short period of time, has excellent connection reliability, and is excellent in storage stability. The reason why the effect of such an effect can be effectively achieved by the combination of a sulfonium salt compound and a radical polymerization initiator is not completely clear, and it is considered that since the stability of the sulfonium salt compound is excellent, the storage stability becomes good, from the radical polymerization. The radical generated by the initiator induces the formation of a cationic species formed by decomposition of the onium salt compound, thereby enabling rapid hardening at a low temperature.

(adhesive composition)

The adhesive composition of the present embodiment contains (A) an onium salt compound represented by the general formula (I), (B) a radical polymerization initiator, and (C) a cationically polymerizable substance (hereinafter, referred to as the case) "(C) component").

The onium salt compound and the radical polymerization initiator may be the same as those of the component (A) and the component (B) in the above-mentioned initiator system.

The content ratio of the component (A) in the adhesive composition of the present embodiment is preferably 0.05 to 30% by mass, more preferably 0.1 to 15% by mass based on the total amount of the component (C). If the content ratio of the component (A) is less than the above range, the curing may be insufficient. If it is outside the above range, the compatibility tends to decrease.

The content ratio of the component (B) in the adhesive composition of the present embodiment is preferably 25% by mass or more based on the total amount of the component (A), and more preferably 50% by mass or more. When the content ratio of the component (B) is within the above range, an initiator system which is more excellent in both storage stability and low-temperature rapid hardenability can be obtained. If the content ratio of the component (B) is less than the above range, the initial species of the cationic polymerization tends to be insufficiently formed.

The (C) component may, for example, be an epoxy compound, a propylene oxide compound or a vinyl ether compound, and the epoxy compound may, for example, be a glycidyl ether epoxy compound or an alicyclic epoxy compound.

The cationically polymerizable substituent of the component (C) is preferably from 43 to 1,000, more preferably from 50 to 800, more preferably from 73 to 600. When the cationically polymerizable substituent equivalent is less than 43 or exceeds 1,000, the adhesion strength tends to decrease at the time of connection of the electrodes to be described later. Further, the cationically polymerizable substituent equivalent means that the average molecular weight of one of the cationically polymerizable compounds contained in the molecule is a quotient of a cationically polymerizable substituent in one molecule of the cationically polymerizable compound, that is, per unit cationically polymerizable substituent. Average molecular weight.

From the viewpoint of corrosion prevention, the component (C) is preferably a high-purity product in which the content of impurities (Na ⁺ , Cl ^{- ,} etc.) or hydrolyzable chlorine is reduced to 300 ppm or less.

The content ratio of the component (C) in the adhesive composition of the present embodiment is preferably from 10 to 90% by mass, more preferably from 25 to 75% by mass based on the total mass of the adhesive composition. When the content of the component (C) is less than 10% by mass, the composition of the adhesive having poor physical properties (glass transition temperature, modulus, etc.) is insufficient, and if it exceeds 90% by mass, there is hardening shrinkage. Large and weak adhesion.

The epoxy propyl ether type epoxy compound of the component (C) is a compound which has a glycidyl ether group in a molecule and is hardened by irradiation or heating of active light in the presence or absence of a hardener. Just fine. Among them, those having two or more epoxy groups in one molecule are preferred because the crosslinking density at the time of hardening is increased. The epoxypropyl ether type epoxy compound is not particularly limited as long as it is a compound having a glycidyl ether group, and a known one can also be used. More specifically, a bisphenol type epoxy resin derived from epichlorohydrin, bisphenol A or bisphenol F, or a polyepoxypropyl ether, a polyepoxypropyl ester, or an aromatic ring may be mentioned. Oxygen compound, alicyclic epoxy compound, cresol novolac type epoxy resin, phenol novolak type epoxy resin, etc., novolac type epoxy compound, epoxypropylamine epoxy compound, glycidyl ester Epoxy compound, biphenyl diepoxypropyl ether, triepoxypropyl isomeric cyanurate, polyepoxypropyl methacrylate, glycidyl methacrylate and copolymerizable a copolymer of ethylene monomer or the like. These may be used alone or in combination of two or more.

The alicyclic epoxy compound of the component (C) is a compound having an epoxy group composed of two of the carbon atoms constituting the cyclic hydrocarbon skeleton in the molecule and an oxygen atom, and in the presence of a hardener or It can be cured in the absence of irradiation or heating by active light. Among them, those having two or more epoxy groups in one molecule are preferred because the crosslinking density at the time of curing is increased. The alicyclic epoxy compound is not particularly limited as long as it is a compound having an alicyclic epoxy group, and a known one can also be used. For example, a compound containing cyclohexene oxide or cyclopentene oxide obtained by oxidizing a compound containing a cyclohexene or a cyclopentene ring can be mentioned. More specifically, 2-(3,4-epoxycyclohexyl-5,5-spiro-3,4-epoxy)cyclohexane-m-dioxane, 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-methylepoxycarboxylate, 3 , 4-epoxy-6-methyl epoxycarboxylate, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, 6-methyl-3 , 4-epoxycyclohexylmethyl-6-methyl-3,4-epoxycyclohexylcarboxylate, ethyl bis(3,4-epoxycyclohexanecarboxylate), ring Dicyclopentadiene oxide, bis(3,4-epoxycyclohexylmethyl) adipate, methylene bis(3,4-epoxycyclohexane), and the like. These may be used alone or in combination of two or more.

The propylene oxide compound of the component (C) is as long as it is in the molecule A propylene oxide compound having an oxacyclobutane group and hardened by irradiation or heating of active rays in the presence or absence of a hardener. Among them, a compound having two or more propylene oxide rings is preferred because the crosslinking density at the time of curing is increased. Further, an aliphatic or alicyclic compound having 2 to 6 propylene oxide rings in the molecule and having 1 to 6 hydroxyl groups is preferred from the viewpoint of excellent curability.

The propylene oxide compound may, for example, be a compound represented by the following general formula (V).

In the formula, R ⁹ represents a hydrogen atom, a fluorine atom or a monovalent hydrocarbon group, R ¹⁰ represents a hydrogen atom, an alkyl group or an aryl group, and n represents an integer of 1 to 4. However, when R ¹⁰ is a hydrogen atom, n is 1. n is an integer of 2 or more, bonded to an oxygen atom of a plurality of R ¹⁰ may be bonded to each other to the same junction of the carbon atoms of R ^10, R may be bonded to a different carbon atom of the ^10.

More specifically, the propylene oxide compound may, for example, be 1,4-bis[(3-oxocyclobutane-n-butoxy)methyl]benzene or 4,4'-bis[(3-oxygen). Cyclobutane-n-butoxy)methyl]biphenyl, 3-ethyl-3{[(3-ethylepoxypropan-3-yl)methoxy]methyl} propylene oxide , 3-ethyl-3-hydroxymethyl propylene oxide, 2-ethylhexyl propylene oxide, and the like.

a vinyl ether compound of the component (C), as long as it is in the molecule A compound having a vinyl ether group and hardened by irradiation or heating of active light in the presence or absence of a hardener. Among them, those having two or more epoxy groups in one molecule are preferred because the crosslinking density at the time of hardening is increased.

The vinyl ether compound is exemplified by the compound represented by the following general formula (VI).

In the formula, R ¹¹ represents an alkyl group or an aryl group, and n represents an integer of 1 to 4. n is an integer of 2 or more, the oxygen atom bonded to the plurality of R ¹¹ may be bonded to each other to the same junction of the carbon atoms of R ^11, R may also be bonded to different carbon atoms of ^1-11.

More specifically, the vinyl ether compound may, for example, be 1,4-butanediol divinyl ether, cyclohexane dimethanol divinyl ether, diethylene glycol divinyl ether or triethylene glycol divinyl ether.

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

The adhesive composition of the present embodiment can be hardened by heating Chemical. The heating temperature is preferably from 40 to 180 ° C, more preferably from 50 to 150 ° C, and the heating time is preferably from 0.1 second to 10 hours, more preferably from 1 second to 1 hour. When the heating temperature is less than 40 ° C, the curing rate is slow, and when it exceeds 180 ° C, an undesired side reaction occurs, and the connection reliability is lowered. In addition, if the heating time is less than 0.1 second, the curing reaction may not proceed. If the curing time exceeds 10 hours, the productivity of the cured product may be lowered, and undesired side reactions may occur, and the connection reliability may be lowered.

The adhesive composition of the present embodiment contains the above-described initiator system of the present embodiment. In other words, when the adhesive composition of the present embodiment is heated and cured, the onium salt compound of the component (A) is induced from the radical generated by the radical polymerization initiator of the component (B). Therefore, the adhesive composition of the present embodiment preferably contains no radical scavenger. Further, the content of the radically polymerizable vinyl compound is preferably from 0 to 10% by mass based on the total amount of the adhesive composition, preferably from 0 to 5% by mass, more preferably from 0 to 3% by mass. 0 to 1% by mass is more preferable, and 0% by mass is particularly preferable.

The adhesive composition of the present embodiment may further contain conductive particles. Examples of the conductive particles include metal particles such as Au, Ag, Ni, Cu, and solder, or carbon. Further, it is also possible to use a non-conductive glass, ceramic, plastic or the like as a core, and to coat the metal, metal particles or carbon on the core. When the conductive particles are made of plastic and are coated with the above metal, metal particles or carbon or hot molten metal particles on the core, Since it has deformability by heat and pressure, it is preferable because the contact area with the electrode at the time of connection increases and the reliability is improved. In addition, the fine particles coated with the polymer resin or the like on the surface of the conductive particles can suppress the shortcoming caused by the contact of the particles when the amount of the conductive particles increases, and the insulation between the electrode circuits can be improved. It is suitable to use it alone or in combination with conductive particles.

The average particle diameter of the conductive particles is preferably from 1 to 18 μm from the viewpoint of improving dispersibility and conductivity. The content ratio of the conductive particles in the adhesive composition of the present embodiment is not particularly limited, and 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. . When the content ratio of the conductive particles is less than 0.1% by volume, the conductivity tends to be poor, and if it exceeds 30% by volume, the circuit may be short-circuited. In addition, "% by volume" is determined based on the volume of 23 ° C of each component before curing, and the volume of each component can be calculated by converting the specific gravity into mass. Further, it is also possible to put in a measuring cylinder or the like without dissolving or swelling the components, and to put this component into a suitable solvent (water, alcohol, etc.) which allows the component to be well wetted, and to increase the volume as its Find the volume.

The adhesive composition of the present embodiment may be added or mixed with an anticorrosive agent composed of a metal hydroxide or a metal oxide for the purpose of preventing corrosion of the adherend. Corrosion inhibitors are more specifically At least one selected from the group consisting of aluminum hydroxide, magnesium hydroxide, calcium hydroxide, cerium oxide, aluminum oxide, magnesium oxide, cerium oxide, tin oxide, titanium oxide, manganese oxide, and zirconium oxide is preferred. Further, from the viewpoints of dispersion of the adhesive composition, high adhesion of the adherend, and corrosion resistance of the adherend, when the anticorrosive agent is in the form of particles, the particle diameter is preferably 10 μm or less.

The content ratio of the anticorrosive agent in the adhesive composition of the present embodiment is preferably 0.1 to 60% by mass, more preferably 1 to 30% by mass based on the total amount of the component (A). When the content ratio of the anticorrosive agent is less than 0.1% by mass, the anticorrosive effect may not be sufficiently obtained. When the content is more than 60% by mass, the dispersibility may be lowered and the connection reliability of the adhesive composition may be lowered.

The adhesive composition of the present embodiment may further contain a chain ether compound or a cyclic ether compound. In particular, when the alicyclic epoxy compound is contained as the component (C), the hardening behavior of the alicyclic epoxy compound can be easily and surely controlled by further containing a chain or cyclic ether compound.

The chain or cyclic ether compound is one which has two or more ether bonds in one molecule. There is no particular limitation, and a known person can also be used. For example, a polyethylene glycol such as diethylene glycol, triethylene glycol or tetraethylene glycol of a chain ether compound may be mentioned; and terminal hydroxyl groups of polyethylene glycols may be ether-bonded or ester-bonded. Functionalized derivative; ethylene oxide, ring a polymer of a monofunctional epoxy compound such as oxypropane or cyclohexene oxide; a polymer of a polyfunctional epoxy compound; a polymer of a monofunctional or polyfunctional propylene oxide compound; a polymer of a monofunctional or polyfunctional tetrahydrofuran Wait. Further, examples of the cyclic ether compound include 12-crown-4-ether, 14-crown-4-ether, 15-crown-5-ether, 18-crown-6-ether, 21-crown-7-ether, and 24. - crown-8-ether, 30-crown-7-ether, benzo-18-crown-6-ether, dibenzo-18-crown-6-ether, tribenzo-18-crown-6-ether, a cyclized product of a polyethylene glycol or a cyclized product of a polymer of an epoxy compound. These may be used alone or in combination.

Among the above, from the viewpoint of reaction regulation ability, a cyclic ether compound is preferred, and 12-crown-4-ether, 14-crown-4-ether, 15-crown-5-ether, 18-crown-6-ether are preferred. , 21-crown-7-ether, 24-crown-8-ether, 30-crown-7-ether, benzo-18-crown-6-ether, dibenzo-18-crown-6-ether, triphenyl And -18-crown-6-ether is more preferred.

The content of the chain or cyclic ether compound in the adhesive composition of the present embodiment is preferably 0.005 to 10 mol%, more preferably 0.01 to 5 mol%, based on the component (A). When the content of the chain or cyclic ether compound is less than 0.005 mol%, it is difficult to obtain high adhesive strength, and if it exceeds 20 mol%, curing is inhibited, resulting in a low crosslink density.

The adhesive composition of the present embodiment may contain various known additives as long as it does not impair the effects of the present invention. For example, inorganic fillers, reinforcing materials, colorants, stabilizers (heat stabilizers, weathering improvers, etc.), extenders, viscosity modifiers, terpene phenol copolymers, terpene resins, rosin derivatives, alicyclic rings Residual agent, flame retardant, ultraviolet absorber, anti-oxidant, anti-tarnishing agent, antibacterial agent, anti-mold agent, anti-aging agent, anti-static agent, plasticizer, slip agent, foaming Agent, release agent, etc.

Examples of the coloring agent include dyes such as direct dyes, acid dyes, basic dyes, and metal-salt dyes, inorganic pigments such as carbon black and mica, and coupled azo, condensed azo, lanthanide, and thioindole. An organic pigment such as a dioxazone or a phthalocyanine. Further, examples of the stabilizer include compounds such as hindered phenol-based, hydrazine-based, phosphorus-based, benzophenone-based, benzotriazole-based, and oxadiphenylanilide-based compounds. Further, examples of the inorganic filler include glass fiber, asbestos fiber, carbon fiber, cerium oxide fiber, alumina fiber, zirconia fiber, boron nitride fiber, tantalum nitride fiber, basic magnesium sulfate fiber, boron fiber, Inorganic and metal fibers of stainless steel fibers, aluminum, titanium, copper, bismuth, magnesium, etc., metal powders of copper, iron, nickel, zinc, tin, lead, stainless steel, aluminum, gold and silver, wood powder, aluminum silicate, Talc, clay, carbonate, sulfate, phosphate, borate, borosilicate, aluminosilicate, titanate, alkaline sulfate, alkaline carbonate and other alkaline salts, glass hollow spheres, A glass material such as glass cullet, tantalum carbide, aluminum nitride, mullite, cordierite, or the like.

The adhesive composition of the present embodiment is intended to be thickened or thinned, and may suitably contain various polymers. The polymer to be contained can be used without any limitation as long as it does not significantly impede the hardening of the component (C). As the polymer, phenoxy resin, polymethacrylate, polyacrylate, polyester, polyvinyl butyrate, SBS (styrene-butadiene-styrene block copolymer) can be used. And epoxy modified materials, SEBS (styrene-ethylene-butylene-styrene block copolymer) and modified substances thereof. These may be used alone or in combination of two or more types. Furthermore, such polymers may also contain a siloxane coupling or a fluorine substituent. These may be suitably used as an adhesive composition as long as they are completely compatible with the mixed resin or are in a state of being turbid by microphase separation. In particular, for the purpose of thin film formation, YP-50, YP-50S, YP-55U, YP-70, ZX-1356-2, FX-316, FX-293 containing phenoxy resin (Dongdu Huacheng) Company name), Denka Butyral 3000-1, 3000-2, 3000-4, 3000-K, 4000-2, 5000-A, 5000-D (Electrical Chemical Industry Co., Ltd.) A film-forming polymer such as a film is preferred.

When the molecular weight of the above polymer is large, film formability can be easily obtained, and the melt viscosity which affects the fluidity of the adhesive composition can be set widely. Although the weight average molecular weight of the above polymer is not particularly limited, it is preferably 5,000 to 150,000, and is 10,000 to 80,000. For better. When the weight average molecular weight is less than 5,000, the film formability tends to be poor, and if it exceeds 150,000, the compatibility with other components tends to be inferior.

The content of the polymer in the adhesive composition of the present embodiment is preferably 20 to 320% by mass, more preferably 50 to 150% by mass, based on 100 parts by mass of the component (C). When the content ratio of the polymer is less than 20% by mass or more than 320% by mass, the fluidity and adhesiveness of the adhesive composition tend to be lowered.

When the adhesive composition of the present embodiment is liquid at normal temperature, it can be used in the form of a paste. When it is a solid at room temperature, it can be gelatinized by using a solvent in addition to heating. The solvent which can be used is not particularly limited as long as it exhibits non-reactivity with the adhesive composition and the additive, and exhibits sufficient solubility, and it is preferably a boiling point of 50 to 150 ° C under normal pressure. In a solvent having a boiling point of less than 50 ° C, there is a volatilization when it is left at room temperature, and its use in an open system is limited. Further, in a solvent having a boiling point of more than 150 ° C, it is difficult to volatilize the solvent, which may adversely affect the reliability after adhesion.

The adhesive composition of the present embodiment can be adhered by heating and pressurization in combination. The heating temperature is not particularly limited, and a temperature of 50 to 190 ° C is preferred. The pressure is not particularly limited as long as it does not cause damage to the object to be attached, and is generally 0.1 to 30 MPa. good. It is preferred that the heating and pressurization be carried out in the range of from 0.5 second to 120 seconds.

The adhesive composition of the present embodiment can be used as an adhesive for an adherend of a different type of thermal expansion coefficient. Specifically, a semiconductor element adhesive material represented by a circuit connecting material represented by an anisotropic conductive adhesive, a silver paste, a silver film, or the like, an elastomer for CSP, a primer for CSP, a LOC tape, or the like can be used.

The method of connecting the anisotropic conductive film and the electrode produced by using the adhesive composition of the present embodiment and the conductive particles, for example, may be performed by heating and pressing an electrode having a different conductive film on the substrate. The method. In this way, adhesion between the contacts of the two electrodes and the substrate is obtained, and the connection to the electrodes can be performed. The substrate on which the electrode is formed can be applied to an inorganic material such as a semiconductor, a glass or a ceramic, a polyimide substrate represented by TCP or FPC or COF, and an electrode is formed on a film of polycarbonate, polyester, polyether or the like. Each combination of such a substrate, a printed circuit board, or the like.

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

[Examples]

Hereinafter, the present invention will be specifically described based on examples and comparative examples, but the present invention is not limited by the following examples. Moreover, in the following description, "DSC peak temperature" is a pointer to the ring The peak temperature in the differential scanning calorimetry of a mixture of oxypropyl ether type epoxy compounds.

(Example 1)

(A) component is Photoinitiator 2074 (Rhodia company name, 4-methylphenyl [4-(1-methylethyl) phenyl] quinone (pentafluorophenyl) borate, (B) component system Use Perhexa 25O (Nippon Oil Co., Ltd. product name, 2,5-dimethyl-2,5-di(ethylhexylperoxy)hexane, purity 50%, 1 minute half-life temperature 119 ° C), ( C) The epoxy propyl ether type epoxy compound YL980 (product name of Japan Epoxy Resin Co., Ltd., bisphenol F type epoxy resin) is used as the component. The binder is phenoxy resin (YP-70, Dongdu Huacheng ( In addition, a nickel layer having a thickness of 0.2 μm is provided on the surface of the particles having polystyrene as a core, and a metal having a thickness of 0.02 μm is provided on the outer side of the nickel layer to have an average particle diameter of 3 μm and a specific gravity of 2.5. The conductive particles are used.

The components (A) to (C) were blended with the binder in the weight ratio shown in Table 1, and the conductive particles were dispersed and dispersed at 8 vol%, and coated on a PET resin film having a thickness of 40 μm using a coating device. The film was dried at 70 ° C and a hot air of 5 minutes to obtain a film-like adhesive composition having a thickness of the adhesive layer of 20 μm.

(Example 2)

In addition to the (B) component replacing Perhexa 250, Peroyl was used. A film-like adhesive composition was obtained in the same manner as in Example 1 except that L (Nippon Oil Co., Ltd. product name, diperoxylauric acid group, purity 98%, and 1-minute half-life temperature: 116 ° C). The mixing ratio of each component is shown in Table 1.

(Example 3)

In addition to the (C) component, the alicyclic epoxy compound EPOLEAD GT401 was used in place of YL980 (Daicel Chemical Industry Co., Ltd. product name, epoxidized butane tetracarboxylate-(3-cyclohexenyl) A film-like adhesive composition was obtained in the same manner as in Example 2 except that ε-caprolactone was modified. The mixing ratio of each component is shown in Table 1.

(Example 4)

The propylene oxide compound OXT-121 (product name, 1,4-bis[(3-oxocyclobutanyl-n-butoxy)) was used in addition to the (C) component in place of YL980. A film-like adhesive composition was obtained in the same manner as in Example 2 except for phenyl). The mixing ratio of each component is shown in Table 1.

(Example 5)

A film-like adhesive composition was obtained in the same manner as in Example 2 except that YL980 and a vinyl ether compound CHDVE (product name of Nippon Carbide Industrial Co., Ltd., cyclohexanedimethanol divinyl ether) were used in combination. The mixing ratio of each component is shown in Table 1. .

(Comparative Example 1)

A film-like adhesive composition was obtained in the same manner as in Example 2 except that the component (B) was not used. The mixing ratio of each component is shown in Table 2.

(Comparative Example 2)

In addition to the (C) component replacing YL980, an alicyclic epoxy compound EPOLEAD GT401 (product name of Daicel Chemical Industry Co., Ltd., bismuth oxyalkylene tetracarboxylate-(3-cyclohexenylmethyl) modification was used. A film-like adhesive composition was obtained in the same manner as in Comparative Example 1, except for ε-caprolactone. The mixing ratio of each component is shown in Table 2.

(Comparative Example 3)

The propylene oxide compound OXT-121 (product name, 1,4-bis[(3-oxocyclobutanyl-n-butoxy)) was used in addition to the (C) component in place of YL980. A film-like adhesive composition was obtained in the same manner as in Comparative Example 1, except for phenyl). The mixing ratio of each component is shown in Table 2.

(Comparative Example 4)

The same formula as in Comparative Example 1 except that YL980 and a vinyl ether compound CHDVE (product name of Nippon Carbide Industrial Co., Ltd., cyclohexane dimethanol divinyl ether) were used in combination with the component (C). The film obtained a film-like adhesive composition. The mixing ratio of each component is shown in Table 2.

(Comparative Example 5)

A film-like adhesive composition was obtained in the same manner as in Example 2 except that the component (A) was not used. The mixing ratio of each component is shown in Table 2.

(Comparative Example 6)

In addition to the (C) component replacing YL980, an alicyclic epoxy compound EPOLEAD GT401 (product name of Daicel Chemical Industry Co., Ltd., epoxidized butane tetracarboxylate-(3-cyclohexenylmethyl)) was used. A film-like adhesive composition was obtained in the same manner as in Comparative Example 5 except for ε-caprolactone. The mixing ratio of each component is shown in Table 2.

(Comparative Example 7)

The propylene oxide compound OXT-121 (product name, 1,4-bis[(3-oxocyclobutanyl-n-butoxy)) was used in addition to the (C) component in place of YL980. A film-like adhesive composition was obtained in the same manner as in Comparative Example 5 except for phenyl). The mixing ratio of each component is shown in Table 2.

(Comparative Example 8)

A film-like adhesive composition was obtained in the same manner as in Comparative Example 5 except that the component (C) was used in combination with YL980 and a vinyl ether compound CHDVE (product name of Nippon Carbide Industries Co., Ltd.). Things. The mixing ratio of each component is shown in Table 2.

(Comparative Example 9)

In addition to the Photoinitiator 2074 of the component (A), San-Aid SI-60 (Sanshin Chemical Industry Co., Ltd. product name, 4-hydroxyphenylmethyl-α-naphthylmethyl hexafluoroantimonate) was used. A film-like adhesive composition was obtained in the same manner as in Example 2 except that the component (B) was not used. The mixing ratio of each component is shown in Table 2.

(Comparative Example 10)

In addition to the (C) component replacing YL980, an alicyclic epoxy compound EPOLEAD GT401 (product name of Daicel Chemical Industry Co., Ltd., epoxidized butane tetracarboxylate-(3-cyclohexenylmethyl)) was used. A film-like adhesive composition was obtained in the same manner as in Comparative Example 9 except for ε-caprolactone. The mixing ratio of each component is shown in Table 2.

(Comparative Example 11)

The propylene oxide compound OXT-121 (product name, 1,4-bis[(3-oxocyclobutanyl-n-butoxy)) was used in addition to the (C) component in place of YL980. A film-like adhesive composition was obtained in the same manner as in Comparative Example 9 except for phenyl). The mixing ratio of each component is shown in Table 2.

Also, in Tables 1 and 2, "PI2074" means Photoinitiator 2074. Further, the mixing ratio of each component means a part by mass.

[Differential scanning calorimetry]

Fig. 1 shows the results of differential scanning calorimetry of Examples 1, 2 and Comparative Example 1 using glycerol epoxide epoxy YL980 as component C, and Fig. 2 shows the implementation of GT401 using alicyclic epoxy as component C. The results of the differential scanning calorimetry of Example 3 and Comparative Example 2, FIG. 3 shows the results of the differential scanning calorimetry of Example 4 and Comparative Example 3 using OXT-121 of propylene oxide as component C, and FIG. 4 shows the use of the epoxy propyl group. The differential scanning calorimetry results of Example 5 and Comparative Example 4 of ether type epoxy YL980 and vinyl ether CHDVE as component C.

In Examples 1 to 5 containing a sulfonium salt compound and a radical polymerization initiator, heat generation peaks at around 100 ° C and at low temperatures were confirmed. In Example 2 using Peroyl L which was lower than the one minute half-life temperature of Example 1, a comparative heat peak was confirmed on the low temperature side. On the other hand, in Comparative Examples 1 to 4 which did not contain a radical polymerization initiator, the heat generation peak was relatively high.

[hardening rate measurement test]

The film-like adhesive compositions of Examples 1 to 5 and Comparative Examples 1 to 11 were heated and cured by heating on a hot plate at 110 to 160 ° C for 10 seconds. Based on the infrared absorption spectrum, the area of the signal intensity of the epoxy group, the oxocyclobutane group, and the vinyl group before heating and the area of the signal intensity after heating were determined as the hardening rate. The results of Examples 1 to 5 are shown in Fig. 5, the results of Comparative Examples 1 to 8 are shown in Fig. 6, and the results of Comparative Examples 9 to 11 are shown in Fig. 7.

In Examples 1 to 5 containing a phosphonium salt compound and a radical polymerization initiator, a high hardening rate was exhibited at a low temperature. On the other hand, in Comparative Examples 1 to 4 which did not contain a radical polymerization initiator, hardening was hardly performed at a low temperature. Further, in Comparative Examples 5 to 8 which did not contain the onium salt compound, the hardening did not proceed. That is, it can be understood that any of the sulfonium salt compound and the radical polymerization initiator is low in activity at a low temperature even when the activity is low with respect to the cationically polymerizable product. In Comparative Examples 9 to 11 in which the onium salt compound SI-60 which is not the component (A) of the present invention is used, even if no radical polymerization initiator is cured at a low temperature.

[Save stability test]

The film-like adhesive compositions of Examples 1 to 5 and Comparative Examples 1 to 11 were placed in a thermostat at 40 ° C for 1 to 5 days. According to the infrared absorption spectrum, the hardening rate after standing was determined. The results of Examples 1 to 5 are shown in Figure 8, and the results of Comparative Examples 1 to 8 are shown in Figure 9, which will be compared. The results of Examples 9 to 11 are shown in Fig. 10.

In Examples 1 to 5, hardening hardly proceeded and the stability was good. Further, in the hardening rate measurement test, Comparative Examples 5 to 8 which were not cured were hardly hardened. On the other hand, in Comparative Examples 9 to 11, the hardening was progressing slowly, and the storage stability was low.

From the above, it is apparent that a combination of the onium salt compound of the component (A), the radical polymerization initiator of the component (B), and the cationically polymerizable component of the component (C) can be used to form a low-temperature rapid hardenability and A system of excellent effects that preserves stability while coexisting.

[Production of connector]

Each of the film-like adhesive compositions of Examples 1 to 5 and Comparative Examples 1 to 11 was transferred from a PET resin film to a glass substrate at a size of 2 × 20 mm (Corning #1737, outer shape: 38 mm × 28 mm, thickness: 0.5 mm, The surface has an ITO (Indium Tin Oxide) wiring pattern (pattern width 50 μm, pitch 50 μm). The IC wafer (outer shape: 1.7 mm × 17.2 mm, thickness: 0.55 mm, size of protrusion 50 μm × 50 μm, pitch of protrusions 50 μm) was set as shown in Table 3 (temperature and time), and negatively 80 MPa (projection area) Conversion) The load is heated and pressurized and mounted. Further, the film-like adhesive composition after the storage stability test was also similarly mounted.

[Evaluation of connection resistance]

Measuring the electricity between adjacent circuits of the connector produced as described above Resistance (maximum value in the 14-terminal measurement). The results obtained are shown in Table 3.

When the film-like adhesive compositions of Examples 1 to 5 were used, good values of less than 5 Ω were simultaneously displayed before and after the storage stability test. When the film-like adhesive compositions of Comparative Examples 1 to 8 were used, they could not be joined. Further, when the film-like adhesive compositions of Comparative Examples 9 to 11 were used, they were unable to be joined after the storage stability test.

Claims (10)

An adhesive composition comprising (A) an onium salt compound represented by the following general formula (I), (B) a radical polymerization initiator, (C) a cationically polymerizable substance, and a (D) film. The adhesive composition of the polymer is based on the total amount of the above-mentioned adhesive composition, and the content of the radically polymerizable vinyl compound contained in the adhesive composition is 0% by mass, R ¹ - I ⁺ -R ² Y ^- (I) wherein R ¹ and R ² each independently represent a substituted or unsubstituted aryl group, and Y ^- represents an anionic residue. The requested item 1 of the adhesive composition, wherein the Y ^- is ^{_{SbF 6 -, [P (R}} 6) a (F) 6-a] - ( wherein, R ⁶ represents a hydrogen atom of at least part of fluorine atoms Substituted alkyl, a represents an integer from 0 to 5; when a is an integer of 2 or more, the plural R ⁶ may be the same or different from each other), B(C ₆ F ₅ ) ₄ ^- or C(CF ₃ SO ₂ ) ₃ ^- . The adhesive composition of claim 1 or 2, wherein the aforementioned radical polymerization initiator is an organic peroxide. The adhesive composition of claim 3, wherein the organic peroxide has a one minute half-life temperature of from 80 to 170 °C. The adhesive composition of claim 1 or 2, wherein the foregoing The cationically polymerizable substance contains at least one compound selected from the group consisting of an epoxy compound, an oxetane compound, and a vinyl ether compound. An adhesive composition according to claim 1 or 2, which further contains (E) conductive particles. The adhesive composition of claim 6, which is anisotropically conductive. The adhesive composition of claim 1 or 2, which is used as an adhesive composition for circuit connection. The adhesive composition of claim 1 or 2 which is hardened by heating. A film-like adhesive composition obtained by forming the adhesive composition according to any one of claims 1 to 9 into a film form.