JP2011111557A - Adhesive composition, circuit connecting material, connector and connection method of circuit member, and semiconductor device - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an adhesive composition with excellent low-temperature curability and storage stability, and a circuit connecting material using the same, and to provide a connector with excellent connection reliability, a connection method of a circuit member, and a semiconductor device. <P>SOLUTION: The adhesive composition includes (A) an alicyclic epoxy compound, (B) a cation generator, and (C1) a second cationically polymerizable compound having cationic polymerizability lower than that of the alicyclic epoxy compound. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to an adhesive composition, a circuit connection material, a connection body, a connection method of a circuit member, 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 of warping due to expansion differences. Therefore, a low temperature and short time connection condition is required. Furthermore, in order to reduce the cost, it is necessary to improve the throughput, and there is a demand for an adhesive capable of low temperature (100 to 170 ° C.), short time (within 10 seconds), in other words, low temperature rapid curing. .

  In order to achieve such low temperature rapid curing, a thermal latent catalyst having a low activation energy is used (see, for example, Patent Document 1). However, the adhesive in this case tends to decrease the storage stability near room temperature.

Japanese Patent No. 2706833

  The present invention has been made in view of the above circumstances, an adhesive composition excellent in low-temperature curability and storage stability, a circuit connection material using the same, and a connection body and a circuit excellent in connection reliability. It is an object to provide a method for connecting members and a semiconductor device.

  In order to solve the above-mentioned problems, the present inventors examined the use of a highly basic alicyclic epoxy compound in order to improve the low-temperature curability with a cationic curing type. During this examination, it was confirmed that practical storage stability could not be obtained depending on the type of the thermal cation generator. As a result of further investigation based on the above findings, the present inventors have found that a cation curable adhesive using a combination of an alicyclic epoxy compound and a specific cationic polymerizable compound is stored at 40 ° C. for 5 days. Even so, the present inventors have found that the circuit electrodes can be satisfactorily connected under mounting conditions such as 150 ° C. for 10 seconds and 130 ° C. for 10 seconds, and have completed the present invention.

  That is, the present invention contains (A) an alicyclic epoxy compound, (B) a cation generator, and (C1) a second cation polymerizable compound having lower cation polymerizability than the alicyclic epoxy compound. A first adhesive composition is provided.

  Here, the low cationic polymerizability means that the reaction rate is low in the polymerization reaction using the (B) cation generator.

  According to the first adhesive composition of the present invention, by having the above configuration, low temperature curability and storage stability can be achieved at a high level, and when used for connecting circuit members, Thus, a connection body having excellent connection reliability can be obtained. The present inventors consider that the cationic species at the polymerization terminal is stabilized when the C1 component is bonded to the polymerization terminal, and the subsequent growth reaction rate is appropriately reduced.

  The present invention also provides a second adhesive composition containing (A) an alicyclic epoxy compound, (B) a cation generator, and (C2) a glycidyl ether compound.

  According to the second adhesive composition of the present invention, by having the above configuration, low temperature curability and storage stability can be achieved at a high level, and when used for connecting circuit members, Thus, a connection body having excellent connection reliability can be obtained. The present inventors consider that the cationic species at the polymerization end is stabilized when the C2 component is bonded to the polymerization end, and the subsequent growth reaction rate is appropriately reduced.

  In the first and second adhesive compositions of the present invention, the cation generator is preferably a phosphate or borate that does not contain a toxic antimony atom.

  Furthermore, the cation generator is preferably sulfonium hexafluorophosphate, sulfonium tetrafluoroborate or sulfonium tetrakis (pentafluorophenyl) borate.

  Moreover, it is preferable that a cation generator does not contain antimony from a viewpoint of an environment or a health and safety aspect.

  Moreover, it is preferable that the 1st and 2nd adhesive composition of this invention contains 0.1-30 volume% of electroconductive particles with respect to the whole 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 is also composed of the first or second adhesive composition of the present invention, and is used for bonding circuit members to each other and electrically connecting circuit electrodes of each circuit member. Provide material.

  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. Provided is a connection body including a connection portion that bonds the circuit members to each other so as to be connected. The connection body of the present invention can be manufactured under heating conditions at a low temperature in a short time because the connection portion is made of a cured product of the circuit connection material of the present invention, and has excellent productivity and connection reliability. Can be. Therefore, the connection body of the present invention has little variation in quality and can exhibit sufficiently stable characteristics.

  The present invention also includes the above-described circuit connection material interposed between a pair of circuit members arranged opposite to each other, and the whole is heated and pressurized to be formed of a cured product of the circuit connection material described above, between the pair of circuit members. Forming a connection part that bonds the circuit members to each other so that the circuit electrodes of the respective circuit members are electrically connected to each other, thereby obtaining a connection body including a pair of circuit members and the connection part. Provided is a method for connecting circuit members.

  The present invention also includes a semiconductor element, a substrate on which the semiconductor element is mounted, a semiconductor element connection member provided between the semiconductor element and the substrate, and electrically connecting the semiconductor element and the substrate. Provided is a semiconductor device which is a cured product of the above circuit connection material.

  Since the semiconductor device and the substrate are electrically connected by the cured product of the circuit connection material of the present invention, the semiconductor device of the present invention has little variation in quality, excellent connection reliability, and sufficiently stable characteristics. Can be shown.

  ADVANTAGE OF THE INVENTION According to this invention, the adhesive composition excellent in low-temperature curability and storage stability can be provided. Moreover, according to this invention, the connection body excellent in connection reliability, the connection method of a circuit member, and a semiconductor device can be provided.

It is a fragmentary sectional view showing one embodiment of a connection object of circuit members concerning the present invention. (A)-(c) is a series of process drawings which connect a circuit member, respectively. It is a fragmentary sectional view showing one embodiment of a semiconductor device of the present invention.

  Hereinafter, preferred embodiments of the present invention will be described in detail with reference to the accompanying drawings. In the description of the drawings, the same elements are denoted by the same reference numerals, and redundant description is omitted. For the convenience of illustration, the dimensional ratios in the drawings do not necessarily match those described.

  The adhesive composition according to the first embodiment of the present invention includes (A) an alicyclic epoxy compound, (B) a cation generator, and (C1) a cationic polymerization lower than that of the alicyclic epoxy compound. 2 cationically polymerizable compounds.

  The adhesive composition according to the second embodiment of the present invention contains (A) an alicyclic epoxy compound, (B) a cation generator, and (C2) a glycidyl ether compound.

  (A) An alicyclic epoxy compound should just be hardened | cured by the cation seed | species generate | occur | produced by heating from the (B) cation generator. Among them, an alicyclic epoxy compound having two or more epoxy groups is preferable because the crosslink density when cured is increased. Furthermore, the alicyclic epoxy compound which has 2-6 epoxy groups in a molecule | numerator is excellent in sclerosis | hardenability, and is especially preferable.

  Examples of (A) cycloaliphatic epoxy compounds include cyclohexene oxide and cyclopentene oxide-containing compounds obtained by oxidizing cyclohexene and cyclopentene ring-containing compounds. More specifically, for example, 2- (3,4-epoxy (Cyclohexyl-5,5-spiro-3,4-epoxy) cyclohexane-metadioxane, 3,4-epoxy-1-methylcyclohexyl-3,4-epoxy-1-methylhexanecarboxylate, 3,4-epoxy-3 -Methylcyclohexylmethyl-3,4-epoxy-3-methylcyclohexanecarboxylate, 3,4-epoxy-5-methylcyclohexylmethyl-3,4-epoxy-5-methylcyclohexanecarboxylate, 3,4-epoxy-6 -Methyl cyclohexyl carboxylate 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, 6-methyl-3,4-epoxycyclohexylmethyl-6-methyl-3,4-epoxycyclohexanecarboxylate, ethylene bis (3,4 Epoxycyclohexanecarboxylate), dicyclopentadiene diepoxide, bis (3,4-epoxycyclohexylmethyl) adipate, methylenebis (3,4-epoxycyclohexane) and the like. These can be used alone or in combination of two or more.

(A) As for the epoxy equivalent of an alicyclic epoxy compound, 43-1000 are preferable, 50-800 are more preferable, 73-600 are especially preferable. When the epoxy equivalent is less than 43 or more than 1000, the adhesion strength between the electrodes tends to be lowered when the electrodes described later are connected. As these alicyclic epoxy 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 preventing corrosion.

  (A) It is preferable to set it as 10-90 mass% with respect to the whole adhesive composition, and, as for content of an alicyclic epoxy 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) Although a well-known thing can be used as a cation generator without a restriction | limiting in particular, It is preferable that it is a compound which generate | occur | produces a cation seed | species by heating at 40-180 degreeC.

  From the viewpoint of environment and safety and health, the cation generator is preferably a phosphate or borate that does not contain antimony, and onium salts such as aromatic sulfonium salts, aliphatic sulfonium salts, aromatic iodonium salts, and the like. Metal arene complexes can also be used. Among these, sulfonium hexafluorophosphate, sulfonium tetrafluoroborate, or sulfonium tetrakis (pentafluorophenyl) boric acid, since it has better low-temperature curability and storage stability. Salts are preferred, and in particular, those having hexafluorophosphate, tetrafluoroborate, tetrakis (pentafluorophenyl) borate, etc. as the counter anion when forming the salt are preferably used in terms of reactivity. Among these, a sulfonium salt such as an aromatic sulfonium salt or an aliphatic sulfonium salt is preferable because of high generation efficiency of cationic species. From the viewpoint of imparting practical storage stability, an alkenyl group, an allyl group or a derivative thereof is preferably bonded to a sulfur atom. From the same viewpoint, it is particularly preferable to use an aliphatic sulfonium hexafluorophosphate having a structure in which an aromatic substituent is not bonded to a sulfur atom.

  Examples of the cation generator include 2-butenyldimethylsulfonium tetrakis (pentafluorophenyl) borate, 2-butenyldimethylsulfonium tetrafluoroborate, 2-butenyldimethylsulfonium hexafluorophosphate, 2-butenyltetramethylenesulfonium tetrakis (pentafluorophenyl) borate, 2-butenyltetramethylenesulfonium tetrafluoroborate, 2-butenyltetramethylenesulfonium hexafluorophosphate, 3-methyl-2-but Tenenyldimethylsulfonium tetrakis (pentafluorophenyl) borate, 3-methyl-2-butenyldimethylsulfonium tetrafluoroborate, 3-methyl-2-butenyldimethylsulfonium Safluorophosphate, 3-methyl-2-butenyltetramethylenesulfonium tetrakis (pentafluorophenyl) borate, 3-methyl-2-butenyltetramethylenesulfonium tetrafluoroborate, 3-methyl-2-butenyl Tetramethylenesulfonium hexafluorophosphate, 4-hydroxyphenylcinnamylmethylsulfonium tetrakis (pentafluorophenyl) borate, 4-hydroxyphenylcinnamylmethylsulfonium tetrafluoroborate, 4-hydroxyphenylcinnamylmethylsulfo Nium hexafluorophosphate, α-naphthylmethyltetramethylenesulfonium tetrakis (pentafluorophenyl) borate, α-naphthylmethyltetramethylenesulfonate Mutetrafluoroborate, α-naphthylmethyltetramethylenesulfonium hexafluorophosphate, cinnamyldimethylsulfonium tetrakis (pentafluorophenyl) borate, cinnamyldimethylsulfonium tetrafluoroborate, cinnamyldimethylsulfonium hexafluoro Phosphate, cinnamyl tetramethylene phonium tetrakis (pentafluorophenyl) borate, cinnamyl tetramethylene phonium tetrafluoroborate, cinnamyl tetramethylene phonium hexafluorophosphate, biphenylmethyldimethylsulfonium tetrakis (pentafluorophenyl) borate, Biphenylmethyldimethylsulfonium tetrafluoroborate, biphenylmethyldimethyls Rufonium hexafluorophosphate, biphenylmethyltetramethylenesulfonium tetrakis (pentafluorophenyl) borate, biphenylmethyltetramethylenesulfonium tetrafluoroborate, biphenylmethyltetramethylenesulfonium hexafluorophosphate, phenylmethyldimethylsulfonium tetrakis (Pentafluorophenyl) borate, phenylmethyldimethylsulfonium tetrafluoroborate, phenylmethyldimethylsulfonium hexafluorophosphate, phenylmethyltetramethylenesulfonium tetrakis (pentafluorophenyl) borate, phenylmethyltetramethylenesulfonium tetra Fluoroborate, phenylmethyltetramethylenesulfo Um hexafluorophosphate, fluorenylmethyldimethylsulfonium tetrakis (pentafluorophenyl) borate, fluorenylmethyldimethylsulfonium tetrafluoroborate, fluorenylmethyldimethylsulfonium hexafluorophosphate, fluorenylmethyltetra Examples include methylenesulfonium tetrakis (pentafluorophenyl) borate, fluorenylmethyltetramethylenesulfonium tetrafluoroborate, fluorenylmethyltetramethylenesulfonium hexafluorophosphate, and the like. These can be used alone or in combination of two or more.

  The content of the cation generator which is (B) phosphate or borate is preferably 0.05 to 30 parts by mass with respect to 100 parts by mass of (A) alicyclic epoxy compound, 0.1 It is more preferable to set it as -15 mass parts. 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.

  (B) The cation generator can be contained alone or in combination of two or more. In the adhesive composition of this embodiment, 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 epoxy 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.

  (C1) As the second cationic polymerizable compound having a lower cationic polymerizable than the alicyclic epoxy compound, for example, bisphenol type epoxy resin derived from epichlorohydrin and bisphenol A, bisphenol F or the like, polyglycidyl ether, poly Glycidyl ester, aromatic epoxy compound, cresol novolak type epoxy resin, novolak type epoxy compound such as phenol novolak type epoxy resin, glycidyl amine type epoxy compound, glycidyl ester type epoxy compound, biphenyl diglycidyl ether, triglycidyl isocyanurate, polyglycidyl Examples thereof include a copolymer of methacrylate, glycidyl methacrylate and a vinyl monomer copolymerizable therewith. 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. Among these, the use of a glycidyl ether compound is preferable from the viewpoint of achieving both low-temperature curability and a stabilizing action.

  Whether or not the second cationic polymerizable compound is lower in cationic polymerization than the alicyclic epoxy compound can be confirmed by the following method. That is, in differential scanning calorimetry of the mixture with the cationic polymerization initiator, it can be seen that the exothermic peak is observed at a lower temperature than when alicyclic epoxy is used.

  As the (C2) glycidyl ether compound contained in the adhesive composition according to the second embodiment, the above glycidyl ether compound can be used.

  The content of the component (C1) according to the first embodiment and the content of the component (C1) according to the second embodiment are preferably 1 to 50% by mass with respect to the entire adhesive composition, More preferably, the content is 30% by mass. When the content is less than 5% by mass, only an adhesive composition having a poor stabilizing action can be obtained. On the other hand, when the content exceeds 50% by mass, the curing reaction becomes insufficient, and the resistance value of the connected body. Becomes higher.

  The adhesive composition of the present embodiment is preferably one that can be cured by heat treatment. Curing here means that the conversion rate of the epoxy group is 70% or more. The temperature of the heating treatment 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.

  The adhesive composition of this embodiment 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.

  To the adhesive composition of the present embodiment, a metal hydroxide or a metal oxide can be added and mixed for the purpose of preventing corrosion of the adherend. 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.

  The compounding amount of the metal hydroxide or metal oxide compounded in the adhesive composition of the present embodiment is preferably 0.1 to 60 parts by mass with respect to 100 parts by mass of the (A) alicyclic epoxy compound. 1 to 30 parts by mass is more preferable. 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 this embodiment, a chain ether compound or a cyclic ether compound can be added and mixed for the purpose of controlling the curing behavior of the (A) alicyclic epoxy compound. The chain ether compound or the cyclic ether compound is not particularly limited as long as it has two or more ether groups in one molecule, and a known one can be used. Examples of such compounds include polyethylene glycols such as diethylene glycol, triethylene glycol, and tetraethylene glycol, derivatives obtained by functionalizing the terminal hydroxyl groups with ether bonds or ester bonds, and simple substances such as ethylene oxide, propylene oxide, and cyclohexene oxide. Polymer of functional epoxy, cross-linked polyfunctional epoxy, polymer of monofunctional or polyfunctional oxetane, polymer of monofunctional or polyfunctional tetrahydrofuran, 12-crown-4-ether, 14-crown- 4-ether, 15-crown-5-ether, 18-crown-6-ether, 21-crown-7-ether, 24-crown-8-ether, 30-crown-7-ether, benzo-18-crown- 6-ether, dibenzo 18-crown-6-ether, tribenzo-18-crown-6-ether, cyclized polyethylene glycols, cyclized like polymers of monofunctional epoxy such as ethylene oxide or propylene oxide or cyclohexene oxide. These can be used individually by 1 type or in mixture of 2 or more types.

  From the viewpoint of reaction control ability, a cyclic ether compound is particularly preferable. 12-crown-4-ether, 14-crown-4-ether, 15-crown-5-ether, 18-crown-6-ether, 21-crown- 7-ether, 24-crown-8-ether, 30-crown-7-ether, benzo-18-crown-6-ether, dibenzo-18-crown-6-ether, tribenzo-18-crown-6-ether Is preferred.

  The content of the chain or cyclic ether compound in the adhesive composition of the present embodiment is preferably 0.05 to 20 chemical equivalents relative to (B) the cation generator, and 0.1 to 10 chemical equivalents. It is particularly preferable that When the content of the chain or cyclic ether compound is less than 0.05 chemical equivalent, it is difficult to obtain high adhesive strength. On the other hand, when the content exceeds 20 chemical equivalents, curing is prohibited, resulting in low crosslink density and There is a fear.

  The adhesive composition of the present embodiment has various known additives such as inorganic fillers, reinforcing materials, colorants, stabilizers (thermal stabilizers, weather resistance) as long as the effects of the invention are not impaired. Improvers, etc.), extenders, viscosity modifiers, terpene phenol copolymers, terpene resins, rosin derivatives, alicyclic hydrocarbon resins, tackifiers, flame retardants, UV absorbers, antioxidants Anti-discoloring agents, antibacterial agents, antifungal agents, anti-aging agents, antistatic agents, plasticizers, lubricants, foaming agents, mold 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 embodiment 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) alicyclic epoxy compound. Such polymers include polyimides, polyamides, 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 larger 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 in 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) alicyclic epoxy 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 this embodiment can be used in the form of a paste when it is liquid at room temperature. In the case of a solid at room temperature, it may be heated and used, or may be made into a paste using a solvent. The solvent that can be used is not particularly limited as long as it is not reactive with the adhesive composition and 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 embodiment 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 embodiment 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 of the present embodiment and the adhesive composition (anisotropic conductive film) containing conductive particles are present between opposing electrodes on the substrate, and are heated and pressed to contact the electrodes and the substrate. It can be used as a circuit connection material for obtaining adhesion between the electrodes and connecting 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.

(Circuit member connection)
Next, a preferred embodiment of the connection member for circuit members of the present invention will be described. FIG. 1 is a schematic cross-sectional view showing an embodiment of a connection member for circuit members according to the present invention. As shown in FIG. 1, the connection member 1 of the circuit member of the present embodiment includes a first circuit member 20 and a second circuit member 30 facing each other, and the first circuit member 20 and the second circuit member 30 are provided. Between these circuit members 30, a connecting portion 10 is provided for electrically connecting them. 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 the present 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 circuit member 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.

(Circuit member connection method)
Next, the above-described circuit member connection method will be described with reference to FIG.

  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. Even when the circuit connecting material does not contain the conductive particles 7, the circuit connecting material can be used for anisotropic conductive bonding as an insulating adhesive, and is sometimes called NCP (Non-Conductive Paste). Further, when the circuit connecting material contains the conductive particles 7, the circuit connecting material may be referred to as ACP (Anisotropic Conductive Paste).

  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 obtained. Is 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.

(Semiconductor device)
Next, an embodiment of the semiconductor device of this embodiment 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.

  Hereinafter, the contents of the present invention will be described more specifically with reference to examples and comparative examples. In addition, this invention is not limited to the following Example.

Example 1
As alicyclic epoxy compound, alicyclic epoxy resin Cexaloid GT401 (product name, manufactured by Daicel Chemical Industries, Ltd.) and (B) 3-methyl-2-butenyltetramethylenesulfonium hexafluorophosphate as cation generator Got ready. A phenoxy resin (YP-70, manufactured by Toto Kasei Co., Ltd., product name) was prepared as a binder. Moreover, the bis A type | mold glycidyl ether eposet BPA-328 (made by Nippon Shokubai Co., Ltd., product name) was prepared as a 2nd cationically polymerizable compound. Conductive particles having an average particle size of 3 μm and a specific gravity of 2.5, in which a nickel layer having a thickness of 0.2 μm is provided on the surface of particles having polystyrene as a core, and a metal having a thickness of 0.02 μm is provided outside the nickel layer. It was created.

  The above components other than the conductive particles were mixed at a solid weight ratio shown in Table 1, and 8 vol% of the above conductive particles were mixed and dispersed in this mixture to obtain an adhesive composition. This adhesive composition was applied to a PET resin film having a thickness of 40 μm using a coating apparatus, and a film-like circuit connecting material having an adhesive layer thickness of 20 μm was obtained by hot air drying at 70 ° C. for 5 minutes. This was used as the film-like circuit connecting material of Example 1.

(Example 2)
Example 2 was conducted in the same manner as in Example 1 except that cinnamyldimethylsulfonium hexafluorophosphate was used as a cation generator instead of 3-methyl-2-butenyltetramethylenesulfonium hexafluorophosphate. A film-like circuit connecting material was obtained.

(Comparative Example 1)
A film-like circuit connection material of Comparative Example 1 was obtained in the same manner as Example 1 except that BPA-328 was not used.

(Comparative Example 2)
(A) In place of the alicyclic epoxy compound (GT401), the film-like circuit connection of Comparative Example 2 was performed in the same manner as in Example 1 except that glycidyl ether YL980 (product name, manufactured by Japan Epoxy Resin Co., Ltd.) was used. Obtained material.

[Create connection]
The film-like circuit connecting materials of Examples and Comparative Examples obtained as described above are respectively glass substrates (Corning # 1737, outer shape 38 mm × 28 mm, thickness 0.5 mm, ITO wiring pattern on the surface (pattern width 50 μm, pitch 50 μm) 2) having a size of 2 × 20 mm. Next, an IC chip (outer diameter 1.7 mm × 17.2 mm, thickness 0.55 mm, bump size 50 μm × 50 μm, bump pitch 50 μm) is 80 MPa (bumps) under the mounting conditions (temperature and time) shown in Table 2 (Area equivalent) Load was applied under heat and pressure.

[Evaluation of connection resistance]
The resistance value between adjacent circuits of this connection body (maximum value among 14 terminals measured) was measured. Moreover, the resistance value (maximum value among 14 terminals measured) after applying a load for 500 hours at 85 ° C. and 85% RH was also measured. These results are shown in Table 2.

  From the resistance measurement performed as described above, it was found that the connection bodies connected by the film-like circuit connection materials of Examples 1 and 2 and Comparative Example 1 showed a good connection resistance value of 10Ω or less.

[Measurement of storage stability]
The film-like circuit connecting materials of Examples 1 and 2 and Comparative Examples 1 and 2 were left in a thermostatic device at 40 ° C. for 5 days. After leaving, connection bodies were prepared using the respective film-like circuit connection materials, and the resistance was measured. Table 3 shows the measurement results.

  From the resistance measurement performed as described above, alicyclic epoxy GT401, 3-methyl-2-butenyltetramethylenesulfonium hexafluorophosphate, cinnamyldimethylsulfonium hexafluorophosphate, and glycidyl ether were used. A film-like circuit connection material using BPA-328 (Examples 1 and 2) is a connection body in which circuit members are connected at a low temperature in a short time and the connection resistance value is sufficiently small even after being left at 40 ° C. for 5 days. It turns out that it is obtained.

DESCRIPTION OF SYMBOLS 1 ... Connection body of circuit member, 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 ... Board | substrate, 61 ... Circuit pattern, 70 ... Sealing material, 80 ... Semiconductor element connection member.

Claims (10)

  An adhesive composition containing (A) an alicyclic epoxy compound, (B) a cation generator, and (C1) a second cation polymerizable compound having lower cation polymerizability than the alicyclic epoxy compound. object.   An adhesive composition containing (A) an alicyclic epoxy compound, (B) a cation generator, and (C2) a glycidyl ether compound.   The adhesive composition according to claim 1 or 2, wherein the cation generator is a phosphate or a borate.   The adhesive according to claim 1 or 2, wherein the cation generator is sulfonium hexafluorophosphate, sulfonium tetrafluoroborate, or sulfonium tetrakis (pentafluorophenyl) borate. Composition.   The adhesive composition according to any one of claims 1 to 4, wherein the cation generator is a compound containing no antimony.   The adhesive composition as described in any one of Claims 1-5 which contains 0.1-30 volume% of electroconductive particles with respect to the whole adhesive composition.   A circuit connection material comprising the adhesive composition according to any one of claims 1 to 6 and used for bonding circuit members to each other and electrically connecting circuit electrodes included in each circuit member. . A pair of circuit members disposed opposite to each other;
It consists of the hardened | cured material of the circuit connection material of Claim 7, and the said circuit members are adhere | attached so that the circuit electrodes which are interposed between the said pair of circuit members and each circuit member has may be electrically connected. A connection body comprising a connection portion.   The circuit connection material according to claim 7 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, and 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 connection method of a circuit member. A semiconductor element;
A substrate on which the semiconductor element is mounted;
A semiconductor element connecting member provided between the semiconductor element and the substrate and electrically connecting the semiconductor element and the substrate;
The semiconductor device is a semiconductor device, which is a cured product of the circuit connection material according to claim 7.

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