JP5561199B2 - Adhesive composition, circuit connection material, connection body, method for manufacturing the same, and semiconductor device - Google Patents

Description

  The present invention relates to an adhesive composition, a circuit connection material, a connection body, a manufacturing method thereof, and a semiconductor device.

  In the fields of semiconductors and liquid crystal displays, various adhesives are used for fixing electronic components and connecting circuits. For example, for the connection between the liquid crystal display and the TCP, the connection between the FPC and the TCP, and the connection between the FPC and the printed wiring board, anisotropic conductivity in which conductive particles are dispersed in an adhesive composition as a circuit connection material. Adhesive is used. Recently, even when a semiconductor silicon chip is mounted on a substrate, so-called COG is performed in which the semiconductor silicon chip is directly mounted on the substrate instead of the conventional wire bond, and an anisotropic conductive adhesive or the like is also applied here. ing. In these fields, along with the increase in density and definition of electronic circuits, high adhesive strength and reliability are required for adhesives.

  In recent years, in the field of precision electronic equipment, the density of circuits has been further increased, and the electrode width and the electrode interval have become extremely narrow. For this reason, the connection conditions (170 ° C. or higher) of circuit connection materials using conventional epoxy resin systems have problems such as wiring dropping, peeling, and misalignment. In COG, the heat generated between the chip and the substrate is further increased. There has been a problem that warpage due to expansion difference, and chip and substrate peeling due to warpage remarkably occur. Therefore, there is a demand for an adhesive that can be connected at a low temperature for a short time and that can provide a higher adhesive force.

  As a means for achieving high adhesion strength, an adhesive composition in which a cationic polymerization type is combined with an oxetane compound that has less curing shrinkage than a glycidyl ether type epoxy and a thermal latent cation generator is used (for example, (See Patent Document 1).

JP 2001-072957 A

  However, in the system using the oxetane compound disclosed in Patent Document 1, the low-temperature short-time curability and storage stability of the adhesive composition are not sufficient.

  The present invention has been made in view of the above circumstances, and can achieve both a low-temperature short-time curability and storage stability, and can realize a circuit connection material excellent in connection reliability. It is an object to provide an object, a circuit connection material using the same, a connection body, a manufacturing method thereof, and a semiconductor device.

  In order to solve the above-mentioned problems, the present inventors have made various studies, and an adhesive composition comprising a combination of an oxetane compound and an epoxy compound and a specific heat-latent cation generator has been cured and stored at a low temperature for a short time. The inventors have found that it is possible to achieve both stability and good connection reliability and good adhesive force, and have completed the present invention.

  That is, this invention provides the adhesive composition containing an oxetane compound, an epoxy compound, and the sulfonium salt type | mold thermal latent cation generator shown by following General formula (1).

一般式（１）中、Ｒ^１及びＲ^２はそれぞれ独立に、炭素数が１〜４の炭化水素基を示し、Ｒ^１及びＲ^２は互いに結合して環を形成していてもよく、Ｒ^３及びＲ^４はそれぞれ独立に、水素原子、炭素数が１〜１０の脂肪族炭化水素基、又は、芳香族炭化水素基を示し、Ｘ⁻は、テトラフルオロホウ酸イオン、ヘキサフルオロリン酸イオン、ヘキサフルオロアンチモン酸イオン、又は、テトラキスペンタフルオロフェニルホウ酸イオンを示す。

In general formula (1), R ¹ and R ² each independently represent a hydrocarbon group having 1 to 4 carbon atoms, and R ¹ and R ² may be bonded to each other to form a ring; ³ and R ⁴ each independently represent a hydrogen atom, an aliphatic hydrocarbon group having 1 to 10 carbon atoms, or an aromatic hydrocarbon group, and X ⁻ represents a tetrafluoroborate ion or a hexafluorophosphate ion. , Hexafluoroantimonate ion or tetrakispentafluorophenylborate ion.

  Since the adhesive composition of the present invention has the above-described configuration, it is possible to realize a circuit connection material excellent in connection reliability that achieves both low-temperature short-time curability and storage stability.

  The adhesive composition of the present invention can contain conductive particles in a proportion of 0.1 to 30% by volume with respect to the total amount of the adhesive composition. In this case, when the adhesive composition is used as a circuit connection material, it becomes easy to connect the circuit electrodes with a low connection resistance while preventing a short circuit of the circuit.

  The present invention also comprises a circuit connecting material comprising the adhesive composition of the present invention, interposed between opposing circuit electrodes, and used for pressurizing the circuit electrodes and electrically connecting the electrodes in the pressurizing direction. I will provide a.

  The circuit connection material of the present invention can exhibit sufficient adhesive force under low temperature and short time connection conditions while having sufficient storage stability. Thereby, the connection body excellent in connection reliability can be obtained.

  The present invention also includes a pair of circuit members arranged opposite to each other and a cured product of the circuit connection material of the present invention, and the circuit electrodes interposed between the pair of circuit members are electrically connected to each other. A connection body including a connection portion for bonding circuit members together is provided.

  The present invention also includes a circuit connection material of the present invention interposed between a pair of circuit members arranged opposite to each other, and the whole is heated and pressurized to form a cured product of the circuit connection material. A connection body that obtains a connection body having a pair of circuit members and a connection portion by forming a connection portion that bonds the circuit members to each other so that circuit electrodes of each circuit member are electrically connected to each other. A manufacturing method is provided.

  The present invention also includes a semiconductor element, a substrate on which the semiconductor element is mounted, and a semiconductor element connection member that bonds the semiconductor element and the substrate so that the semiconductor element and the substrate are electrically connected to each other. Provides a semiconductor device which is a cured product of the circuit connection material of the present invention.

  According to the present invention, an adhesive composition that can achieve both low-temperature short-time curability and storage stability, and can realize a circuit connection material having excellent connection reliability, and a circuit connection material using the same A connection body, a manufacturing method thereof, and a semiconductor device can be provided.

It is a fragmentary sectional view showing one embodiment of a connection object concerning the present invention. (A)-(c) is a series of process drawing which connects a circuit member and obtains a connection body, respectively. It is a fragmentary sectional view showing one embodiment of a semiconductor device of the present invention.

  The adhesive composition of the present invention contains (A) an oxetane compound, (B) an epoxy compound, and (C) a sulfonium salt type heat latent cation generator represented by the following general formula (1).

一般式（１）中、Ｒ^１及びＲ^２はそれぞれ独立に、炭素数が１〜４の炭化水素基を示し、Ｒ^１及びＲ^２は互いに結合して環を形成していてもよく、Ｒ^３及びＲ^４はそれぞれ独立に、水素原子、炭素数が１〜１０の脂肪族炭化水素基、又は、芳香族炭化水素基を示し、Ｘ⁻は、テトラフルオロホウ酸イオン、ヘキサフルオロリン酸イオン、ヘキサフルオロアンチモン酸イオン、又は、テトラキスペンタフルオロフェニルホウ酸イオンを示す。

In general formula (1), R ¹ and R ² each independently represent a hydrocarbon group having 1 to 4 carbon atoms, and R ¹ and R ² may be bonded to each other to form a ring; ³ and R ⁴ each independently represent a hydrogen atom, an aliphatic hydrocarbon group having 1 to 10 carbon atoms, or an aromatic hydrocarbon group, and X ⁻ represents a tetrafluoroborate ion or a hexafluorophosphate ion. , Hexafluoroantimonate ion or tetrakispentafluorophenylborate ion.

  (A) The oxetane compound should just be hardened | cured by the cation seed | species generate | occur | produced by heating from the (C) cation generator. The adhesive composition of the present invention preferably contains an oxetane compound having 1 to 4 oxetane rings in the molecule from the viewpoint that cracks are unlikely to occur after curing.

  Examples of the oxetane compound having one oxetane ring include a compound represented by the following general formula (2).

In the general formula (2), R ⁵ represents a hydrogen atom, a methyl group, an ethyl group, a propyl group or a butyl group, such as an alkyl group having 1 to 6 carbon atoms, a fluoroalkyl group having 1 to 6 carbon atoms, or an allyl group. An aryl group, a furyl group or a thienyl group. R ⁶ is an alkyl group having 1 to 6 carbon atoms such as methyl group, ethyl group, propyl group or butyl group, 1-propenyl group, 2-propenyl group, 2-methyl-1-propenyl group, 2-methyl- Such as 2-propenyl group, 1-butenyl group, 2-butenyl group or 3-butenyl group, alkenyl group having 2 to 6 carbon atoms, phenyl group, benzyl group, fluorobenzyl group, methoxybenzyl group, phenoxyethyl group, etc. A group having an aromatic ring, an alkylcarbonyl group having 2 to 6 carbon atoms such as an ethylcarbonyl group, a propylcarbonyl group or a butylcarbonyl group, an alkylcarbonyl group having 2 to 6 carbon atoms such as an ethoxycarbonyl group, a propoxycarbonyl group or a butoxycarbonyl group; Alkoxycarbonyl group, ethylcarbamoyl group, propylcarbamoyl group, butylcarbamoyl group or Is an N-alkylcarbamoyl group having 2 to 6 carbon atoms such as a pentylcarbamoyl group.

  Examples of the compound having two oxetane rings include a compound represented by the following general formula (3).

In General Formula (3), R ⁵ is the same group as that in General Formula (2). R ⁷ is, for example, a linear or branched alkylene group such as an ethylene group, a propylene group or a butylene group, or a linear or branched poly (alkyleneoxy) such as a poly (ethyleneoxy) group or a poly (propyleneoxy) group. ) Group, propenylene group, methylpropenylene group or butenylene group or other linear or branched unsaturated hydrocarbon group, carbonyl group, alkylene group containing carbonyl group, alkylene group containing carboxyl group or alkylene group containing carbamoyl group Etc.

R ⁷ may be a polyvalent group selected from the groups represented by the following general formulas (4) to (16). Among these, the group represented by the formula (11) is preferable from the viewpoint of curability and peeling prevention.

In the general formula (4), R ⁸ is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms such as a methyl group, an ethyl group, a propyl group or a butyl group, a methoxy group, an ethoxy group, a propoxy group or a butoxy group. An alkoxy group having 1 to 4 carbon atoms, a halogen atom such as a chlorine atom or a bromine atom, a nitro group, a cyano group, a mercapto group, a lower alkyl carboxyl group, a carboxyl group, or a carbamoyl group.

In the general formula (5), R ⁹ is an oxygen atom, a sulfur atom, a methylene group, an amino group, a sulfonyl group, a bis (trifluoromethyl) methylene group, or a dimethylmethylene group.

In the general formula (6), R ¹⁰ represents a hydrogen atom, a methyl group, an ethyl group, a propyl group, a butyl group or the like, an alkyl group having 1 to 4 carbon atoms, a methoxy group, an ethoxy group, a propoxy group, or a butoxy group. An alkoxy group having 1 to 4 carbon atoms, a halogen atom such as a chlorine atom or a bromine atom, a nitro group, a cyano group, a mercapto group, a lower alkyl carboxyl group, a carboxyl group, or a carbamoyl group.

In the general formula (7), R ¹¹ is an oxygen atom, a sulfur atom, a methylene group, an amino group, a sulfonyl group, a bis (trifluoromethyl) methylene group, a dimethylmethylene group, a phenylmethylmethylene group, or a biphenylmethylene group. .

In General Formula (8) and General Formula (9), R ¹² represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms such as a methyl group, an ethyl group, a propyl group, or a butyl group, a methoxy group, an ethoxy group, or a propoxy group. Or a C 1-4 alkoxy group such as a butoxy group, a halogen atom such as a chlorine atom or a bromine atom, a nitro group, a cyano group, a mercapto group, a lower alkyl carboxyl group, a carboxyl group or a carbamoyl group. Further, R ¹² may be substituted at 2 to 4 positions of the naphthalene ring.

Preferred examples of the compound having two oxetane rings other than the compounds described above include compounds represented by the following general formula (17). In the general formula (17), R ⁵ is the same group as that in the general formula (2).

  Examples of the compound having 3 to 4 oxetane rings include a compound represented by the following general formula (18).

In the general formula (18), R ⁵ is the same group as in the general formula (2), and m is 3 or 4. R ¹³ is, for example, a branched alkylene group having 1 to 12 carbon atoms such as groups represented by the following general formula (19), formula (20) and formula (21), or a group represented by the following general formula (22). Branched poly (alkyleneoxy) groups such as

一般式（１９）において、Ｒ^１４はメチル基、エチル基又はプロピル基等の低級アルキル基である。

In the general formula (19), R ¹⁴ is a lower alkyl group such as a methyl group, an ethyl group, or a propyl group.

一般式（２２）において、ｎは１〜１０の整数である。

In General formula (22), n is an integer of 1-10.

  Preferable specific examples of the oxetane compound used in the present invention include the following compounds.

  In addition to these, compounds having 1 to 4 oxetane rings having a relatively high molecular weight of about 1,000 to 5,000 are also included. Furthermore, as a polymer containing oxetane, a polymer having an oxetane ring in the side chain can be used similarly. In the present invention, one oxetane compound can be used alone, or two or more oxetane compounds can be used in combination.

(A) The oxetane equivalent of the oxetane compound is preferably 43 to 1000, more preferably 50 to 800, and particularly preferably 73 to 600. When the oxetane equivalent is less than 43 or more than 1000, the adhesion strength between the electrodes tends to be reduced when the electrodes described later are connected. For these oxetane compounds, it is preferable to use a high-purity product in which impurity ions (Na ⁺ , Cl ^{− and the} like), hydrolyzable chlorine and the like are reduced to 300 ppm or less, from the viewpoint of corrosion prevention.

  (A) It is preferable to set it as 10-90 mass% with respect to the whole adhesive composition, and, as for content of an oxetane compound, it is more preferable to set it as 25-75 mass%. When the content is less than 10% by mass, the physical properties (glass transition temperature, elastic modulus, etc.) of the cured product of the adhesive composition tend to decrease. On the other hand, when the content exceeds 90% by mass, curing shrinkage occurs. It tends to be too large and the adhesive strength tends to decrease.

  (B) As an epoxy compound, in order to obtain low-temperature curability and high adhesiveness, a glycidyl ether type epoxy resin or an alicyclic epoxy resin can be used.

  The glycidyl ether type epoxy resin only needs to be cured by a cation species generated by heating from a cation generator. Examples thereof include bisphenol type epoxy resins derived from epichlorohydrin and bisphenol A, bisphenol F, and the like, polyglycidyl ether, and biphenyl diglycidyl ether. Furthermore, resins in which various functional groups such as a carbonyl group, a carboxyl group, an amino group, a nitro group, a hydroxyl group, a sulfonyl group, and a halogen are substituted for these resins are also applicable. These can be used individually by 1 type or in combination of 2 or more type in order to obtain the adhesive composition which has a desired characteristic. In particular, a bisphenol A type epoxy resin is preferable from the viewpoint of increasing adhesive strength.

  The alicyclic epoxy resin only needs to be cured by a cation species generated by heating from a cation generator. Among these, alicyclic epoxy resins having two or more epoxy groups are preferable because the crosslink density when cured is increased. Furthermore, the alicyclic epoxy resin which has 2-6 epoxy groups in a molecule | numerator is excellent in sclerosis | hardenability, and is especially preferable.

  Examples of alicyclic epoxy resins include cyclohexene oxide and cyclopentene oxide-containing compounds obtained by oxidizing cyclohexene and cyclopentene ring-containing compounds. More specifically, for example, 2- (3,4-epoxycyclohexyl-5 , 5-spiro-3,4-epoxy) cyclohexane-metadioxane, 3,4-epoxy-1-methylcyclohexyl-3,4-epoxy-1-methylhexanecarboxylate, 3,4-epoxy-3-methylcyclohexyl Methyl-3,4-epoxy-3-methylcyclohexanecarboxylate, 3,4-epoxy-5-methylcyclohexylmethyl-3,4-epoxy-5-methylcyclohexanecarboxylate, 3,4-epoxy-6-methylsilane Chloexyl carboxylate, 3, -Epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, 6-methyl-3,4-epoxycyclohexylmethyl-6-methyl-3,4-epoxycyclohexanecarboxylate, ethylenebis (3,4-epoxycyclohexanecarboxylate ), Dicyclopentadiene diepoxide, bis (3,4-epoxycyclohexylmethyl) adipate, methylene bis (3,4-epoxycyclohexane) and the like. These can be used alone or in combination of two or more.

  (B) The content of the epoxy compound is preferably 1 to 50% by mass, and more preferably 5 to 30% by mass with respect to the entire adhesive composition. When the content is less than 5% by mass, the storage stability of the adhesive composition tends to be insufficient. On the other hand, when the content exceeds 50% by mass, the curing reaction becomes insufficient, and the resistance of the connection body. The value becomes higher.

  (C) As the cation generator, a sulfonium salt type heat latent cation generator represented by the following general formula (1) is used.

In General Formula (1), R ¹ and R ² each independently represent a hydrocarbon group having 1 to 4 carbon atoms, and R ¹ and R ² may be bonded to each other to form a ring. Examples of the hydrocarbon group having 1 to 4 carbon atoms include a methyl group, an ethyl group, a propyl group, and a butyl group. When R ¹ and R ² are bonded to each other to form a ring, examples thereof include a hydrocarbon group having 4 to 6 carbon atoms such as a tetramethylene group capable of forming a cyclic compound with a sulfur atom. From the viewpoint of imparting storage stability, R ¹ and R ² are preferably a methyl group, or R ¹ and R ² are preferably a tetramethylene group that is bonded to each other to form a ring with a sulfur atom.

In general formula (1), R ³ and R ⁴ each independently represent a hydrogen atom, an aliphatic hydrocarbon group having 1 to 10 carbon atoms, or an aromatic hydrocarbon group. Examples of the aromatic hydrocarbon group include a phenyl group and derivatives thereof. From the viewpoint of imparting storage stability, R ³ is preferably a hydrogen atom or a methyl group, and R ⁴ is preferably a methyl group or a phenyl group.

Further, in the general formula (1), X ^- represents a tetrafluoroborate ion, hexafluorophosphate ion, hexafluoroantimonate ion, or tetrakis pentafluorophenyl borate ion. These ions are the counter anions of the sulfonium cation and form the sulfonium salt of formula (1).

  Specific examples of the cation generator include cinnamyldimethylsulfonium hexafluoroantimonate, cinnamyltetramethylenesulfonium hexafluoroantimonate, 3-methyl-2-butenyldimethylsulfonium hexafluoroantimonate, and 3-methyl-2. -Butenyltetramethylenesulfonium hexafluoroantimonate can be preferably used. In the above, hexafluoroantimonate salt is taken as an example, but other hexafluorophosphate salts, tetrafluoroborate salts and tetrakispentafluorophenylborate salts can also be used.

  (C) The content of the cation generator is preferably 0.05 to 30 parts by mass and more preferably 0.1 to 15 parts by mass with respect to 100 parts by mass of the (A) oxetane compound. If this content is less than 0.05 parts by mass, curing tends to be insufficient, and if it exceeds 30 parts by mass, the compatibility tends to decrease.

  Additives can be added to the adhesive composition of the present invention for the purpose of controlling the curing behavior of the (A) oxetane compound. This additive efficiently captures cations generated from the cation generator, and specific examples include sulfonium salts having methyl sulfate ions, crown ethers, and sulfides.

  Examples of the sulfonium salt having methyl sulfate ion include benzyl-p-hydroxyphenylmethylsulfonium methylsulfate, benzyl-p-hydroxyphenylethylsulfonium sulfate, p-chlorobenzyl-4-hydroxyphenylmethylsulfonium methylsulfate, p-nitrobenzyl-4-hydroxyphenylmethylsulfonium sulfate, o-methylbenzyl-4-hydroxyphenylmethylsulfonium sulfate, m-methylbenzyl-4-hydroxyphenylmethylsulfonium sulfate, benzyl-4-methoxyphenylmethylsulfonium Sulfate, benzyl-3-methyl-4-hydroxyphenylmethylsulfonium sulfate, benzyl-3-methyl-4-hydroxy 5-tert-butylphenyl methyl sulfonium sulfate, dibenzyl-4-hydroxyphenyl sulfonium sulfate, alpha-naphthylmethyl-4-hydroxyphenyl methyl sulfonium sulfate, 4-hydroxyphenyl dimethyl methyl sulfate and the like. Among these, 4-hydroxyphenyldimethylsulfonium sulfate is preferable from the viewpoint of curing control ability.

  Examples of the crown ether 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 and the like.

  As the sulfides, any organic compound can be used as long as it is an alkyl sulfide or aryl sulfide containing one or more sulfide structures, and specifically, a chain having 2 to 40 carbon atoms such as dimethyl sulfide or diethyl sulfide. Alkyl sulfide compounds, tetrahydrothiophene, thiomorpholine, phenylmethyl sulfide, 4-hydroxyphenyl sulfide, 4-methoxycarbonyloxyphenyl methyl sulfide, diphenyl sulfide, diacetyl sulfide, benzyl methyl sulfide, benzyl sulfide, bis (4-hydroxy-3- Methylphenyl) sulfide, bis (4-hydroxyphenyl) sulfide, bis (benzoylmethyl) sulfide, di (α-phenylethyl) sulfide, diphenyle Sulfide, difurfuryl sulfide, furfuryl methyl sulfide, and the like methoxymethyl phenyl sulfide is.

  The use ratio of the additive is preferably 0.01 to 20 parts by mass, particularly preferably 0.1 to 10 parts by mass with respect to (C) the cation generator. When the amount of the additive used is large, a termination reaction is caused at the time of curing, resulting in a low crosslinking density, and there is a possibility that a satisfactory cured product cannot be obtained. Moreover, when there are few usage-amounts of an additive, the effect as an additive will not be acquired and the circuit connection material which has the outstanding pot life will not be obtained.

  In the adhesive composition of the present invention, a chain transfer agent can be used in appropriate combination in order to increase the cation generation efficiency of the cation generator and the reaction rate of the oxetane compound. The chain transfer agent is not particularly limited as long as it is a protic compound, and a known compound can be used. Specifically, cyclohexenediol, 2,3-butanediol, ethylene glycol, diethylene glycol, Alcohols such as triethylene glycol and derivatives thereof can be used.

  The adhesive composition of the present invention is preferably one that can be cured by heat treatment. Curing here means that the conversion of the oxetane group is 70% or more. The temperature of the heating treatment is preferably 40 ° C. to 180 ° C., more preferably 50 ° C. to 160 ° 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 less than 40 ° C, the curing rate is slow, and when it exceeds 180 ° C, unwanted side reactions tend to proceed. When the heating time is less than 0.1 seconds, the curing reaction does not proceed sufficiently, and when it exceeds 10 hours, the productivity of the cured product is lowered, and undesired side reactions are likely to proceed.

  The adhesive composition of the present invention can further contain conductive particles. Examples of the conductive particles include metal particles such as Au, Ag, Ni, Cu, and solder, and carbon particles. Further, the conductive particles may have non-conductive glass, ceramic, plastic, or the like as a core, and the core is coated with the metal, metal particles, carbon, or the like. When the conductive particles are made of plastic as a core and the core is coated with the above metal, metal particles, carbon, or the like, or a hot-melt metal particle, the circuit members are connected to each other because they are deformable by heating and pressing. In this case, the contact area between the conductive particles and the electrode is increased, which is preferable because the reliability is improved.

  In addition, fine particles with the surface of the conductive particles further coated with a polymer resin or the like suppress short-circuiting due to contact between particles when the amount of conductive particles is increased, and improve insulation between circuit electrodes. Can be preferably used. The particle | grains which coat | covered the surface of the electroconductive particle with polymeric resin etc. can be used individually or in mixture with another electroconductive particle.

  The average particle size of the conductive particles is preferably 1 to 18 μm from the viewpoint of dispersibility and conductivity. The blending amount of the conductive particles is preferably 0.1 to 30% by volume, and more preferably 0.1 to 10% by volume based on the entire adhesive composition. When the blending amount of the conductive particles is less than 0.1% by volume, the conductivity tends to be inferior, and when it exceeds 30% by volume, a short circuit tends to occur. In addition, although volume% is determined based on the volume of each component before 23 degreeC hardening, the volume of each component can be converted into a volume from a weight using specific gravity. In addition, do not dissolve or swell the component in a graduated cylinder, etc., but put in a suitable solvent (water, alcohol, etc.) that wets the component well. You can ask for it.

  For the purpose of preventing corrosion of the adherend, a metal hydroxide or a metal oxide can be added to and mixed with the adhesive composition of the present invention. Specifically, the metal hydroxide or metal oxide includes aluminum hydroxide, magnesium hydroxide, calcium hydroxide, silicon oxide, aluminum oxide, magnesium oxide, antimony oxide, tin oxide, titanium oxide, manganese oxide, and zirconium oxide. It is preferably at least one selected. Further, these particle diameters are preferably 10 μm or less from the viewpoint of dispersion in the adhesive composition, high adhesion to the adherend and ability to prevent corrosion of the adherend.

  It is preferable that the compounding quantity of the metal hydroxide or metal oxide in the adhesive composition of this embodiment shall be 0.1-60 mass parts with respect to 100 mass parts of (A) oxetane compounds, and 1-30 mass parts. More preferably. If the blending amount is less than 0.1 parts by mass, a sufficient corrosion prevention effect cannot be obtained, and if it exceeds 60 parts by mass, the dispersibility tends to deteriorate.

  In the adhesive composition of the present invention, various known additives such as inorganic fillers, reinforcing materials, colorants, stabilizers (thermal stabilizers, weather resistance improvement) are within the range that does not impair the effects of the invention. Agents), extenders, viscosity modifiers, terpene phenol copolymers, terpene resins, rosin derivatives, alicyclic hydrocarbon resins, tackifiers, flame retardants, ultraviolet absorbers, antioxidants, Anti-discoloring agents, antibacterial agents, antifungal agents, anti-aging agents, antistatic agents, plasticizers, lubricants, foaming agents, release agents and the like can be added and mixed. Examples of the colorant include direct dyes, acid dyes, basic dyes, metal complex dyes, inorganic pigments such as carbon black and mica, and coupling azo, condensed azo, anthraquinone, thioindigo, and dioxazone. And organic pigments such as phthalocyanine. Examples of the stabilizer include hindered phenol-based, hydrazine-based, phosphorus-based, benzophenone-based, benzotriazole-based, and oxalic acid anilide-based compounds. Furthermore, as the inorganic filler, glass fiber, asbestos fiber, carbon fiber, silica fiber, alumina fiber, zirconia fiber, boron nitride fiber, silicon nitride fiber, basic magnesium sulfate fiber, boron fiber, stainless steel fiber, aluminum Inorganic and metal fibers such as titanium, copper, brass, magnesium, etc., metal powders such as copper, iron, nickel, zinc, tin, lead, stainless steel, aluminum, gold and silver, wood powder, aluminum silicate, talc, clay, Carbonates, sulfates, phosphates, borates, borosilicates, aluminosilicates, titanates, basic sulfates, basic carbonates and other basic salts, glass hollow spheres, glass flakes, etc. Examples thereof include glass materials, silicon carbide, aluminum nitride, mullite, cordierite and the like.

  The adhesive composition of the present invention may be appropriately added with various polymers for the purpose of thickening and film formation described later. The polymer to be used can use a well-known polymer without a restriction | limiting especially if it does not inhibit hardening of (A) oxetane compound and (B) epoxy compound. Examples of such polymers include polyimide, polyamide, phenoxy resins, polymethacrylates, polyacrylates, polyimides, polyurethanes, polyesters, polyester urethanes, polyvinyl butyrals, SBS and its epoxy modified products, SEBS and its A modified body, NBR and its hydrogenated body, etc. can be used. These can be used alone or in admixture of two or more. Furthermore, these polymers may contain siloxane bonds and fluorine substituents. These can be suitably used as the adhesive composition as long as the resins to be mixed are completely compatible with each other or microphase separation occurs and the mixture becomes cloudy.

  The higher the molecular weight of the polymer, the easier it is to form a film, and the melt viscosity that affects the fluidity as an adhesive can be set over a wide range. The weight average molecular weight of the polymer is preferably from 5,000 to 150,000, particularly preferably from 10,000 to 80,000. If the weight average molecular weight of the polymer is less than 5,000, the film formability tends to be inferior, and if it exceeds 150,000, the compatibility with other components tends to be poor. As a compounding quantity of the said polymer, it is preferable to set it as 20-320 mass parts with respect to 100 mass parts of (A) oxetane compounds. When the blending amount of the polymer is less than 20 parts by mass or more than 320 parts by mass, fluidity and adhesiveness tend to decrease.

  The adhesive composition of the present invention can be used in the form of a paste when it is liquid at room temperature. In the case of a solid at room temperature, it may be heated and used, or may be made into a paste using a solvent. The solvent that can be used is not particularly limited as long as it is not reactive with the adhesive composition and additives, and exhibits sufficient solubility, but has a boiling point of 50 to 150 ° C. at normal pressure. Those are preferred. If the boiling point is less than 50 ° C., it may volatilize if left at room temperature, which limits the use in an open system. On the other hand, if the boiling point exceeds 150 ° C., it is difficult to volatilize the solvent, which may adversely affect the reliability after bonding.

  The adhesive composition of this invention can adhere | attach an adherend using heating and pressurization together. The heating temperature is preferably 50 to 190 ° C. The pressure is not particularly limited as long as it does not damage the adherend, but is generally preferably 0.1 to 30 MPa. These heating and pressurization are preferably performed in the range of 0.5 seconds to 120 seconds.

  The adhesive composition of the present invention can be used after it is formed into a film. This film adhesive is obtained by applying a mixed solution obtained by adding a solvent or the like to an adhesive composition on a peelable substrate such as a fluororesin film, a polyethylene terephthalate film, a release paper, or the like on a substrate such as a nonwoven fabric. It can be obtained by impregnating the mixed solution and placing it on a peelable substrate and removing the solvent and the like. Thus, when the adhesive composition is in the form of a film, the handleability is excellent and it is more convenient.

  Moreover, when a film is produced from the adhesive composition of the present invention containing conductive particles, an anisotropic conductive film can be obtained. For example, the anisotropic conductive film can be placed between opposing electrodes on the substrate and bonded to each other by heating and pressing, and can be electrically connected. Here, as the substrate on which the electrode is formed, an inorganic material such as a semiconductor, glass or ceramic, an organic material such as polyimide or polycarbonate, or a combination of these composites such as glass / epoxy can be applied.

  The adhesive composition of the present invention can be used as an adhesive for different types of adherends having different thermal expansion coefficients. Specifically, it is used as a semiconductor element adhesive material typified by anisotropic conductive adhesive, silver paste, silver film, etc., circuit connection material, CSP elastomer, CSP underfill material, LOC tape, etc. Can do.

  The adhesive composition according to the present invention and, for example, the adhesive composition according to the present invention containing conductive particles such as an anisotropic conductive film are present between opposing electrodes on a substrate and heated. By applying pressure, contact between both electrodes and adhesion between the substrates can be obtained and used as a circuit connection material for connection with the electrodes. Substrates for forming electrodes include inorganic materials such as semiconductors, glass and ceramics, polyimide substrates represented by TCP, FPC and COF, substrates having electrodes formed on films such as polycarbonate, polyester and polyethersulfone, and prints. Each combination of these composites such as a wiring board can be applied.

  Next, preferred embodiments of the connection body and the manufacturing method thereof according to the present invention will be described.

  FIG. 1 is a schematic cross-sectional view showing an embodiment of a connection body according to the present invention. As shown in FIG. 1, the connection body 1 of the present embodiment includes a first circuit member 20 and a second circuit member 30 that face each other, and the first circuit member 20 and the second circuit member. A connecting portion 10 for electrically connecting them to 30 is provided. The first circuit member 20 includes a first circuit board 21 and a first circuit electrode 22 formed on the main surface 21 a of the circuit board 21. Note that an insulating layer (not shown) may be formed on the main surface 21a of the circuit board 21 in some cases.

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

The first circuit member 20 and the second circuit member 30 are not particularly limited as long as electrodes that require electrical connection are formed. Specifically, glass or plastic substrates, printed wiring boards, ceramic wiring boards, flexible wiring boards, semiconductor silicon chips, etc., on which electrodes are formed of ITO (indium tin oxide) used for liquid crystal displays, etc. These can be used in combination as required. As described above, in this embodiment, a material made of an organic material such as a printed wiring board or polyimide, a metal such as copper or aluminum, or an inorganic material such as ITO, silicon nitride (SiN _x ), or silicon dioxide (SiO ₂ ) is used. As described above, circuit members having various surface states can be used.

  The connection portion 10 is formed of a cured product of a circuit connection material made of the adhesive composition according to the present invention, and contains an insulating substance 11 and conductive particles 7. The conductive particles 7 are disposed not only between the first circuit electrode 22 and the second circuit electrode 32 facing each other, but also between the main surfaces 21a and 31a. In the connection body 1 of the present embodiment, the first circuit electrode 22 and the second circuit electrode 32 are electrically connected via the conductive particles 7. For this reason, the connection resistance between the first circuit electrode 22 and the second circuit electrode 32 is sufficiently reduced. Therefore, the flow of current between the first circuit electrode 22 and the second circuit electrode 32 can be made smooth, and the functions of the circuit can be sufficiently exhibited. Moreover, it is also possible to show the anisotropy of electrical connection by setting the conductive particles 7 to the above-described mixing ratio.

  In addition, when the connection part 10 does not contain the electrically-conductive particle 7, they are made to contact directly so that a desired amount of electric current may flow between the 1st circuit electrode 22 and the 2nd circuit electrode 32? Alternatively, it is electrically connected by being close enough.

  Since the connection part 10 is comprised by the hardened | cured material of the circuit connection material which consists of the adhesive composition which concerns on the said invention, the adhesive strength of the connection part 10 with respect to the 1st circuit member 20 or the 2nd circuit member 30 Is sufficiently high, the connection resistance is sufficiently low, and this state can be maintained for a long period of time. Further, such connection can be achieved by heat treatment at a low temperature in a short time. Therefore, the long-term reliability of the electrical characteristics between the first circuit electrode 22 and the second circuit electrode 32 can be sufficiently increased.

  Next, the manufacturing method of the connection body mentioned above is demonstrated, referring FIG. 2 which is the process drawing.

  First, the first circuit member 20 and the film-like circuit connecting material 40 described above are prepared (see FIG. 2A). The film-like circuit connection material 40 is formed by forming the circuit connection material according to the present invention into a film shape as described above. The circuit connection material contains an adhesive component 5 and conductive particles 7. Here, the adhesive component according to the present invention described above is used for the adhesive component 5.

  The thickness of the film-like circuit connecting material 40 is preferably 10 to 50 μm. If the thickness of the film-like circuit connecting material 40 is less than 10 μm, the circuit connecting material tends to be insufficiently filled between the circuit electrodes 22 and 32. On the other hand, when the thickness exceeds 50 μm, the adhesive composition between the circuit electrodes 22 and 32 cannot be sufficiently removed, and it tends to be difficult to ensure conduction between the circuit electrodes 22 and 32.

  Next, the film-like circuit connecting material 40 is placed on the surface of the first circuit member 20 on which the circuit electrodes 22 are formed. When the film-like circuit connecting material 40 is attached on a support (not shown), the film-like circuit connecting material 40 side is directed to the first circuit member 20 so that the first circuit is connected. Place on member 20. At this time, the film-like circuit connecting material 40 is film-like and easy to handle. For this reason, the film-like circuit connecting material 40 can be easily interposed between the first circuit member 20 and the second circuit member 30, and the first circuit member 20 and the second circuit member 30 Connection work can be performed easily.

  And the film-form circuit connection material 40 is pressurized to the arrow A and B direction of Fig.2 (a), and the film-form circuit connection material 40 is temporarily connected to the 1st circuit member 20 (refer FIG.2 (b)). . At this time, you may pressurize, heating. However, the heating temperature is lower than the temperature at which the adhesive composition in the film-like circuit connecting material 40 is not cured.

  Subsequently, as shown in FIG. 2 (c), the second circuit member 30 is placed on the film-like circuit connection material 40 with the second circuit electrode facing the first circuit member 20. In addition, when the film-form circuit connection material 40 has adhered on the support body (not shown), after peeling a support body, the 2nd circuit member 30 is mounted on the film-form circuit connection material 40. FIG.

  And it heats through the 1st and 2nd circuit members 20 and 30 to the arrow A and B direction of FIG.2 (c), heating the film-form circuit connection material 40. FIG. The heating temperature at this time is a temperature at which the cation generator according to the present invention can generate cation species. Thereby, cation species are generated in the cation generator, and polymerization of the alicyclic epoxy compound is started. In this way, the film-like circuit connection material 40 is cured and the main connection is performed, and a circuit member connection body as shown in FIG. 1 is obtained.

  The heating temperature is preferably 40 ° C to 180 ° C, more preferably 50 ° C 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 less than 40 ° C, the curing rate is slow, and when it exceeds 180 ° C, unwanted side reactions tend to proceed. When the heating time is less than 0.1 seconds, the curing reaction does not proceed, and when it exceeds 10 hours, the productivity of the cured product is lowered, and undesired side reactions are likely to proceed.

  When the circuit member connection body is manufactured as described above, in the obtained circuit member connection body, the conductive particles 7 can be brought into contact with both the circuit electrodes 22 and 32 facing each other. The connection resistance between them can be sufficiently reduced. Further, since the connection portion can be formed by heating in a short time at a low temperature, the influence on the circuit member can be reduced.

  Further, by heating the film-like circuit connecting material 40, the adhesive component 5 is cured to become the insulating substance 11 in a state where the distance between the circuit electrode 22 and the circuit electrode 32 is sufficiently small, and the first circuit member is obtained. 20 and the second circuit member 30 are firmly connected via the connection portion 10. That is, in the obtained connection member of the circuit member, since the connection part 10 is composed of a cured product of the circuit connection material containing the adhesive composition, the adhesion strength of the connection part 10 to the circuit member 20 or 30 is high. It becomes sufficiently high and the connection resistance between the circuit electrodes 22 and 32 can be sufficiently reduced. Moreover, the connection body of this circuit member can maintain such a state over a long period of time. Therefore, the obtained connection member of the circuit members is sufficiently prevented from changing with time in the distance between the circuit electrodes 22 and 32 and is excellent in long-term reliability of the electrical characteristics between the circuit electrodes 22 and 32.

  Moreover, in the said embodiment, although the connection body of a circuit member is manufactured using the film-form circuit connection material 40, it replaces with the film-form circuit connection material 40, and uses the circuit connection material which is not formed in the film form. May be. Even in this case, if the circuit connection material is dissolved in a solvent and the solution is applied to either the first circuit member 20 or the second circuit member 30 and dried, the first and second circuit members 20 are used. , 30 can interpose a circuit connecting material.

  Further, instead of the conductive particles 7, other conductive materials may be used. Other conductive materials include particulate or short fiber carbon, metal wires such as Au-plated Ni wire, and the like.

  Next, an embodiment of a semiconductor device according to the present invention will be described. FIG. 3 is a schematic cross-sectional view showing an embodiment of the semiconductor device of the present invention. As shown in FIG. 3, the semiconductor device 2 of this embodiment includes a semiconductor element 50 and a substrate 60 that serves as a semiconductor support member, and these are electrically connected between the semiconductor element 50 and the substrate 60. A semiconductor element connection member 80 is provided to connect to the semiconductor device. The semiconductor element connection member 80 is stacked on the main surface 60 a of the substrate 60, and the semiconductor element 50 is further stacked on the semiconductor element connection member 80.

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

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

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

  In the case where the semiconductor element connecting member 80 does not contain the conductive particles 7, the semiconductor element 50 and the circuit pattern 61 are brought into direct contact with each other so that a desired amount of current flows or sufficiently close thereto. Connected to.

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

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

  EXAMPLES Hereinafter, although an Example and a comparative example demonstrate this invention further more concretely, this invention is not limited to a following example.

<Synthesis of sulfonium salt type heat latent cation generator>
(Synthesis Example 1)
Cinnamyl bromide (11.8 g, 60.0 mmol) and dimethyl sulfide (3.0 g, 63.0 mmol) were added to the screw vial, sealed, and stirred overnight at room temperature without solvent. Thereafter, unreacted dimethyl sulfide was distilled off under reduced pressure to obtain colorless solid cinnamyldimethylsulfonium bromide (15.6 g, yield 100%). Cinnamyldimethylsulfonium bromide (3.1 g, 12.0 mmol) was placed in an Erlenmeyer flask, and further ethyl acetate (24 mL) was added and dissolved. Then, sodium hexafluoroantimonate (3.4 g, 13.2 mmol) was dissolved in water (26 mL) and slowly dropped into the system. After stirring at room temperature for 2 hours, the organic layer was extracted with ethyl acetate (50 mL), further washed with water (50 mL × 3), and dried under reduced pressure to obtain cinnamyldimethylsulfonium hexafluoroantimonate as a pale yellow solid. (2.9 g, yield 58%).

<Production of film-like circuit connection material>
Example 1
As a polymer, a bisphenol A type phenoxy resin (product name: PKHC, manufactured by InChem (PKHC / methyl ethyl ketone = 40/60 parts by mass), a solution of 50 parts by mass (polymer component), and an oxetane compound of biphenylenebisoxetane (product name: OXBP, Ube) Kosan Co., Ltd.) 35 parts by mass, bisphenol A type epoxy resin (product name: Epicoat 828, manufactured by Mitsubishi Chemical Corporation) as an epoxy compound, 10 parts by mass, cinnamyl dimethylsulfonium hexafluoroantimonate as a thermal latent cation generator 5 parts by mass The resin solution was prepared by mixing 35 parts by mass of Ni-plated polystyrene particles (average particle size: 3 μm) as conductive particles, and this resin solution was applied to a PET film having one surface treated with a thickness of 50 μm using a coating apparatus, Dry with hot air at 70 ° C for 5 minutes As a result, a film-like circuit connecting material having an adhesive layer thickness of 20 μm was obtained, and the content of the conductive particles in the obtained film-like circuit connecting material was 5% by volume.

(Example 2)
As a polymer, a bisphenol A type phenoxy resin (product name: PKHC, manufactured by InChem (PKHC / methyl ethyl ketone = 40/60 parts by mass), a solution of 50 parts by mass (polymer component), and an oxetane compound of biphenylenebisoxetane (product name: OXBP, Ube) Kosan Co., Ltd.) 35 parts by mass, epoxy compound 3,4-epoxycyclohexenylmethyl-3 ′, 4′-epoxycyclohexenecarboxylate (product name: Celoxide 2021P, manufactured by Daicel Chemical Industries), 10 parts by mass, thermal latent cation 5 parts by mass of cinnamyldimethylsulfonium hexafluoroantimonate as a generator, 0.15 parts by mass of 4-hydroxyphenyldimethylsulfonium methylsulfate as an additive, Ni-plated polystyrene particles (average particle size as conductive particles) (μm) 35 parts by mass was mixed to obtain a resin solution, which was applied to a PET film having a 50 μm-thick surface treated with a coating apparatus and dried with hot air at 70 ° C. for 5 minutes to form an adhesive. A film-like circuit connecting material having a layer thickness of 20 μm was obtained, and the content of conductive particles in the obtained film-like circuit connecting material was 5% by volume.

(Example 3)
As a polymer, a bisphenol A type phenoxy resin (product name: PKHC, manufactured by InChem (PKHC / methyl ethyl ketone = 40/60 parts by mass), a solution of 50 parts by mass (polymer component), and an oxetane compound of biphenylenebisoxetane (product name: OXBP, Ube) Kosan Co., Ltd.) 35 parts by mass, epoxy compound 3,4-epoxycyclohexenylmethyl-3 ′, 4′-epoxycyclohexenecarboxylate (product name: Celoxide 2021P, manufactured by Daicel Chemical Industries), 10 parts by mass, thermal latent cation 5 parts by mass of cinnamyldimethylsulfonium hexafluoroantimonate as a generator, 0.15 parts by mass of 4-hydroxyphenyldimethylsulfonium methylsulfate as an additive, Ni-plated polystyrene particles (average particle size as conductive particles) (μm) 35 parts by mass was mixed to obtain a resin solution, which was applied to a PET film having a 50 μm-thick surface treated with a coating apparatus and dried with hot air at 70 ° C. for 5 minutes to form an adhesive. A film-like circuit connecting material having a layer thickness of 20 μm was obtained, and the content of conductive particles in the obtained film-like circuit connecting material was 5% by volume.

(Comparative Example 1)
As a polymer, a bisphenol A type phenoxy resin (product name: PKHC, manufactured by InChem (PKHC / methyl ethyl ketone = 40/60 parts by mass), a solution of 50 parts by mass (polymer component), and an oxetane compound of biphenylenebisoxetane (product name: OXBP, Ube) Kosan Co., Ltd.) 35 parts by mass, epoxy compound as bisphenol A type epoxy resin (product name: Epicoat 828, manufactured by Mitsubishi Chemical Corporation), 10 parts by mass, as thermal latent cation generator, 4-hydroxyphenylbenzylmethylsulfonium hexafluoroantimony 5 parts by weight of Nate and 35 parts by weight of Ni-plated polystyrene particles (average particle size: 3 μm) as conductive particles were mixed to obtain a resin solution, which was applied to a PET film having a surface treated on one side having a thickness of 50 μm using a coating apparatus. Apply and 5 minutes at 70 ° C The film-like circuit connecting material having an adhesive layer thickness of 20 μm was obtained by hot air drying, and the content of the conductive particles in the obtained film-like circuit connecting material was 5% by volume.

(Comparative Example 2)
As a polymer, a bisphenol A type phenoxy resin (product name: PKHC, manufactured by InChem (PKHC / methyl ethyl ketone = 40/60 parts by mass), a solution of 50 parts by mass (polymer component), and an oxetane compound of biphenylenebisoxetane (product name: OXBP, Ube) Kosan Co., Ltd.) 35 parts by mass, epoxy compound bisphenol A type epoxy resin (product name: Epicoat 828, manufactured by Mitsubishi Chemical Corporation) 10 parts by mass, thermal latent cation generator, 4-hydroxyphenyl-methyl-1-naphthyl 5 parts by mass of methylsulfonium hexafluoroantimonate, 0.15 parts by mass of 4-hydroxyphenyldimethylsulfonium methylsulfate as an additive, and 35 parts by mass of Ni-plated polystyrene particles (average particle size 3 μm) as conductive particles With solution The resin solution was applied to a PET film having a surface of 50 μm on one surface using a coating apparatus and dried with hot air at 70 ° C. for 5 minutes, whereby a film-like circuit connecting material having an adhesive layer thickness of 20 μm. In addition, the content of the conductive particles in the obtained film-like circuit connecting material was 5% by volume.

(Comparative Example 3)
As a polymer, a bisphenol A type phenoxy resin (product name: PKHC, manufactured by InChem (PKHC / methyl ethyl ketone = 40/60 parts by mass), a solution of 50 parts by mass (polymer component), and an oxetane compound of biphenylenebisoxetane (product name: OXBP, Ube) (Made by Kosan Co., Ltd.) 45 parts by mass, 5 parts by mass of cinnamyldimethylsulfonium hexafluoroantimonate as a thermal latent cation generator, and 35 parts by mass of Ni-plated polystyrene particles (average particle size 3 μm) as conductive particles This resin solution was applied to a PET film having a surface of 50 μm on one surface using a coating apparatus and dried with hot air at 70 ° C. for 5 minutes, whereby a film-like circuit connecting material having an adhesive layer thickness of 20 μm. The film-like circuit connecting material obtained was The content of Rushirubeden particles was 5% by volume.

(Comparative Example 4)
As a polymer, bisphenol A type phenoxy resin (product name: PKHC, manufactured by InChem (PKHC / methyl ethyl ketone = 40/60 parts by mass), 50 parts by mass (polymer component), as an epoxy compound, bisphenol A type epoxy resin (product name: Epicoat) 828, manufactured by Mitsubishi Chemical Corporation), 45 parts by mass, 5 parts by mass of cinnamyldimethylsulfonium hexafluoroantimonate as a heat-latent cation generator, and 35 parts by mass of Ni-plated polystyrene particles (average particle size 3 μm) as conductive particles. The resin solution was applied to a PET film having a surface of 50 μm on one surface using a coating apparatus and dried with hot air at 70 ° C. for 5 minutes, whereby a film with an adhesive layer thickness of 20 μm was obtained. A circuit connection material was obtained, and the film-like circuit connection obtained was obtained. The content of the conductive particles in the material was 5% by volume.

<Measurement of reaction rate>
The film-like circuit connecting materials of Examples 1 to 3 and Comparative Examples 1 to 4 were heated at 160 ° C. for 5 seconds. Then, the infrared absorption spectrum of each film-form circuit connection material was measured, and the conversion rate of cyclic ether was computed. The results are shown in Table 1 as ◯ when the conversion rate of the cyclic ether is 80% or more and x when the conversion rate is less than 80%.

<Measurement of storage stability>
The film-like circuit connecting materials of Examples 1 to 3 and Comparative Examples 1 to 4 were left in a thermostatic device at 40 ° C. for 5 days. After standing, the infrared absorption spectrum of each film-like circuit connecting material was measured, and the conversion rate of the cyclic ether was calculated. The results are shown in Table 1, where the conversion rate of the cyclic ether is less than 5%, ◯ is 5% or more and less than 10%, and ◯ is 10% or more.

(Production of connected body)
Each of the film-like circuit connecting materials of Examples 1 to 3 and Comparative Examples 1 to 4 is a glass substrate (Corning # 1737, outer shape 38 mm × 28 mm, thickness 0.5 mm, and ITO wiring pattern (pattern width 50 μm, pitch) on the surface. Having a size of 2 × 20 mm from a PET resin film. Next, an IC chip (outer shape 1.7 mm × 17.2 mm, thickness 0.55 mm, bump size 50 μm × 50 μm, bump pitch 50 μm) was loaded at 160 ° C. for 5 seconds and 80 MPa (bump area conversion). It was mounted by heating and pressing.

(Measurement of adhesive strength)
The die shear strength test was done about the connection body connected using Examples 1-3 and the film-form circuit connection material of Comparative Examples 1-4. The results are shown in Table 1.

(Measurement of connection resistance)
About the connection body connected using Examples 1-3 and the film-form circuit connection material of Comparative Examples 1-4, the resistance value between adjacent circuits (The maximum value in 14 terminal measurement) was measured. In addition, the resistance value (maximum value among 14 terminals measured) after a high temperature and high humidity test in which a load was applied for 500 hours under the conditions of 500 hours, 85 ° C., and 85% RH was also measured. The results are shown in Table 1 where the resistance value is less than 1Ω, 未 満, less than 15Ω is ◯, 15Ω or more is x, and poor connection is xx.

  As shown in Table 1, the film-like circuit connecting materials obtained in Examples 1 to 3 have both low temperature rapid curability and storage stability, and also have good die shear strength and connection reliability, and high temperature and high humidity. Good connection reliability was obtained even after the test.

  As a cation generator, the film-like circuit connecting material of Comparative Example 1 blended with 4-hydroxyphenylbenzylmethylsulfonium hexafluoroantimonate has good storage stability but does not cure at 160 ° C. for 5 seconds, and as a cation generator. The film-like circuit connecting material of Comparative Example 2 containing 4-hydroxyphenyl-methyl-1-naphthylmethylsulfonium hexafluoroantimonate has high curability but deteriorates storage stability, and exhibits both curability and storage stability. It was difficult to achieve both.

  On the other hand, the film-like circuit connection material of Comparative Example 3 using only the oxetane compound as a monomer deteriorates the storage stability although the curability is good, and the film-like circuit connection of Comparative Example 4 using only an epoxy compound as the monomer. Although the material had good curability and storage stability, the connection reliability after the high-temperature and high-humidity test deteriorated.

  According to the present invention, by using a combination of an oxetane compound and an epoxy compound and using a cation generator having a specific structure, low-temperature fast curability, storage stability and connection reliability are good, and further, high die shear strength is achieved. It was confirmed that a film-like circuit connecting material that can be expressed was obtained.

DESCRIPTION OF SYMBOLS 1 ... Connection body, 2 ... Semiconductor device, 5 ... Adhesive component, 7 ... Conductive particle, 10 ... Connection part, 11 ... Insulating substance, 20 ... 1st circuit member, 21 ... 1st circuit board, 22 ... 1st circuit electrode, 30 ... 2nd circuit member, 31 ... 2nd circuit board, 32 ... 2nd circuit electrode, 40 ... film-like circuit connection material, 50 ... semiconductor element, 60 ... substrate, 61 ... circuit Pattern, 70... Sealing material, 80... Semiconductor element connecting member.

Claims (6)

An oxetane compound,
An epoxy compound,
A sulfonium salt type heat latent cation generator represented by the following general formula (1);
An adhesive composition containing

[In General Formula (1), R ¹ and R ² each independently represent a hydrocarbon group having 1 to 4 carbon atoms, and R ¹ and R ² may be bonded to each other to form a ring, R ³ and R ⁴ each independently represent a hydrogen atom, an aliphatic hydrocarbon group having 1 to 10 carbon atoms, or an aromatic hydrocarbon group, and X ⁻ represents a tetrafluoroborate ion, a hexafluorophosphate. An ion, a hexafluoroantimonate ion, or a tetrakispentafluorophenylborate ion; ]   The adhesive composition according to claim 1, comprising conductive particles in a proportion of 0.1 to 30% by volume with respect to the total amount of the adhesive composition.   A circuit connection comprising the adhesive composition according to claim 1, which is interposed between circuit electrodes facing each other, and is used to pressurize the circuit electrodes and electrically connect the electrodes in the pressurizing direction. material. A pair of circuit members disposed opposite to each other;
It consists of the hardened | cured material of the circuit connection material of Claim 3, and the said circuit members are adhere | attached so that it may interpose between said pair of circuit members and the circuit electrodes which each circuit member has may be electrically connected. A connection,
A connection body comprising:   The circuit connection material according to claim 3 is interposed between a pair of circuit members arranged opposite to each other, and the whole is heated and pressurized to be made of a cured product of the circuit connection material, between the pair of circuit members. A connection body including the pair of circuit members and the connection portion is obtained by forming a connection portion that bonds the circuit members so that the circuit electrodes of the respective circuit members that are interposed are electrically connected to each other. The manufacturing method of a connection body. A semiconductor element;
A substrate on which the semiconductor element is mounted;
A semiconductor element connecting member for bonding the semiconductor element and the substrate so that the semiconductor element and the substrate are electrically connected;
The said semiconductor element connection member is a semiconductor device which is the hardened | cured material of the circuit connection material of Claim 3.

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