JP6024235B2 - Adhesive composition and circuit connection structure - Google Patents

Adhesive composition and circuit connection structure Download PDF

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JP6024235B2
JP6024235B2 JP2012139896A JP2012139896A JP6024235B2 JP 6024235 B2 JP6024235 B2 JP 6024235B2 JP 2012139896 A JP2012139896 A JP 2012139896A JP 2012139896 A JP2012139896 A JP 2012139896A JP 6024235 B2 JP6024235 B2 JP 6024235B2
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adhesive composition
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formula
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resin
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JP2013064104A (en
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直 工藤
直 工藤
将司 大越
将司 大越
増田 克之
克之 増田
有福 征宏
征宏 有福
藤縄 貢
貢 藤縄
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日立化成株式会社
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Description

  The present invention relates to an adhesive composition and a circuit connection structure.

  2. Description of the Related Art Various adhesive compositions have been conventionally used in semiconductor elements and liquid crystal display elements for the purpose of bonding various members in the elements. The properties required for the adhesive composition are diverse, including adhesiveness, heat resistance, reliability in a high temperature and high humidity state, and the like.

In addition, the adherend used for bonding has various surface states such as printed wiring boards, organic base materials such as polyimide, metals such as copper and aluminum, ITO, IZO, SiN, and SiO 2. The base material which has is used. Therefore, the adhesive composition requires a molecular design that matches each adherend (for example, Patent Documents 1 to 3).

  On the other hand, the shape of the adhesive composition is a paste in which the adhesive composition is diluted with an organic solvent, or the adhesive composition is applied on a support (PET (polyethylene terephthalate) film, etc.) using a coating apparatus. There are film-like ones prepared by applying and drying with hot air for a predetermined time. Among these, film adhesives are preferred because they are easy to handle and can be easily connected.

  For the purpose of avoiding contact with oxygen and moisture in the air, the film adhesive composition is stored with its surface covered with PET or the like (hereinafter, this PET film covering the surface is referred to as “cover PET film”). . At this time, a release agent such as silicone is applied (release treatment) to the surface of the cover PET (the surface in contact with the adhesive) to prevent the adhesive composition from being transferred to the cover PET during storage. Often doing.

  Recently, in the manufacture of circuit connection structures or semiconductor devices using film adhesives, there is a need to improve throughput in order to reduce costs, and a shorter time (eg, heating at 70 ° C. for 2 seconds or less). There is a need for an adhesive composition that can be transferred from a support to a circuit member.

  In order to overcome this problem, there is an example of a film-like circuit connecting material that exhibits good transferability by using, for example, a resin having piperazine as a skeleton (for example, Patent Document 4).

Japanese Patent Laid-Open No. 1-113480 International Publication No. 98/44067 Pamphlet JP 2002-203427 A JP 2011-116937 A

  However, the polyimide resin obtained in Patent Document 4 has a very high melt viscosity of the resin itself, and the circuit connection material using the resin may not have sufficient fluidity depending on the connection substrate used. Therefore, particularly when using a thin circuit member, when connecting at a low pressure of, for example, 1 MPa for the purpose of preventing damage, the resin between the counter electrodes may not be sufficiently removed and a satisfactory electrical connection may not be obtained.

  Further, it is possible to improve the fluidity of the adhesive by lowering the Tg and molecular weight of the resin, but in this case, sufficient connection reliability is often not obtained.

  The present invention has been made in view of the above-described problems of the prior art, and uses an adhesive composition capable of maintaining sufficient connection reliability even during low-pressure connection, and the adhesive composition. An object is to provide a circuit connection structure.

  The present invention relates to an adhesive composition comprising a resin having a repeating unit represented by the following formula (1) and / or a repeating unit represented by the following formula (2), and conductive particles.

  In formula (1), R represents a diamine or diisocyanate residue, and m represents an integer of 1 to 30.

  In formula (2), R represents a diamine or diisocyanate residue, and m represents an integer of 1 to 30.

  According to the adhesive composition having such a configuration, it is possible to provide an adhesive composition capable of maintaining sufficient connection reliability even during low-pressure connection. Moreover, since this adhesive composition contains electroconductive particle, it can provide electroconductivity or anisotropic conductivity to an adhesive composition, and circuit components which have a circuit electrode are used for adhesive composition. It can be suitably used depending on the connection application. Moreover, the connection resistance between the circuit electrodes electrically connected through the adhesive composition can be sufficiently reduced.

  Here, the repeating unit represented by the formula (1) and / or the repeating unit represented by the formula (2) has a tetracarboxylic dianhydride having a siloxane skeleton represented by the following general formula (3). It is preferable that it is obtained from.

  In formula (3), m shows the integer of 1-30.

  The present invention also provides a pair of circuit members disposed opposite to each other, and the circuit members provided between the pair of circuit members so that the circuit electrodes of the pair of circuit members are electrically connected to each other. A circuit connection structure, wherein the connection member is a cured product of the adhesive composition of the present invention. Here, it is preferable that one of the pair of circuit members has a glass substrate and the other has a flexible substrate.

  Such a circuit connection structure has sufficient connection reliability because the connection member that connects the pair of circuit members is made of the cured product of the adhesive composition of the present invention.

  ADVANTAGE OF THE INVENTION According to this invention, the adhesive composition which can maintain sufficient connection reliability also at the time of a low voltage | pressure connection, and the circuit connection structure using this adhesive composition can be provided. Further, such an adhesive composition can be transferred to a circuit member in a shorter time than before and has a sufficiently long pot life.

It is a schematic cross section which shows one Embodiment of the film adhesive which consists of an adhesive composition of this invention. It is a schematic cross section which shows suitable one Embodiment of the circuit connection structure connected with the adhesive composition of this invention. It is process drawing which shows one Embodiment which manufactures a circuit connection structure with the adhesive composition of this invention with a schematic sectional drawing. It is a model top view of the circuit member to connect.

  Hereinafter, preferred embodiments of the present invention will be described in detail with reference to the drawings as the case may be. In the drawings, the same or corresponding parts are denoted by the same reference numerals, and redundant description is omitted. In the present invention, (meth) acrylic acid means acrylic acid or methacrylic acid corresponding thereto, (meth) acrylate means acrylate or methacrylate corresponding thereto, and (meth) acryloyl group means acryloyl group or Means a methacryloyl group;

  The resin according to this embodiment is a polymer having a repeating unit represented by the following formula (1) and / or a repeating unit represented by the following formula (2). Resins composed mainly of repeating units of formula (1) are generally referred to as polyimide resins. Resins composed mainly of repeating units of formula (2) are generally referred to as polyamic acid resins. In the present specification, a polymer having a repeating unit represented by the formula (1) and / or a repeating unit represented by the formula (2) is referred to as a “polyimide resin”.

  In formula (1) and (2), R shows the residue of the diamine or diisocyanate used for the synthesis | combination of a polyimide-type resin, and m shows the integer of 1-30. Preferably, all of the silicon atoms directly bonded to the norbornane ring are arranged in an exo configuration with respect to the norbornane ring, and all of the imide rings bonded to the norbornane ring are arranged in an exo configuration with respect to the norbornane ring. A plurality of R in the same molecule may be the same or different. R may be a residue having a structure corresponding to a portion obtained by removing an amino group or an isocyanate group from a diamine or diisocyanate described later. m is preferably 1 to 20, and more preferably 1 to 10.

The polyimide resin having a siloxane skeleton represented by the formula (1) can be synthesized, for example, by reacting a tetracarboxylic dianhydride having a siloxane skeleton represented by the following formula (3) with a diamine, followed by dehydration and ring closure. . The polyamic acid resin having a siloxane skeleton represented by the formula (2) can be synthesized by, for example, reacting a tetracarboxylic dianhydride having a siloxane skeleton represented by the following formula (3) with a diamine.

  In formula (3), m shows the integer of 1-30.

  It is preferable that all of the acid dianhydride as a raw material of the polyimide resin is a tetracarboxylic dianhydride represented by the formula (3), but the tetracarboxylic dianhydride represented by the formula (3) and other One or more tetracarboxylic dianhydrides can be used in combination. Thus, by using together the tetracarboxylic dianhydride shown by Formula (3) and other tetracarboxylic dianhydrides, the effect that resin physical properties, such as desirable Tg and an elasticity modulus, can be controlled, is acquired.

  Examples of the tetracarboxylic dianhydride that can be used in combination with the tetracarboxylic dianhydride having a siloxane skeleton represented by the formula (3) include 1,2- (ethylene) bis (trimellitic anhydride), 1,3- ( Trimethylene) bis (trimellitic anhydride), 1,4- (tetramethylene) bis (trimellitic anhydride), 1,5- (pentamethylene) bis (trimellitic anhydride), 1,6- (hexamethylene) bis (trimellitate) Anhydride), 1,7- (heptamethylene) bis (trimellitic anhydride), 1,8- (octamethylene) bis (trimellitic anhydride), 1,9- (nonamethylene) bis (trimellitic anhydride), 1, 10- (Decamethylene) bis (trimellitate anhydride), 1,12- (dodecamethylene) bis (trimellitate anhydride) 1,16- (hexadecamethylene) bis (trimellitate anhydride), 1,18- (octadecamethylene) bis (trimellitate anhydride), pyromellitic dianhydride, 3,4,3 ', 4'- Biphenyltetracarboxylic dianhydride, 2,3,2 ′, 3′-biphenyltetracarboxylic dianhydride, 2,2-bis (3,4-dicarboxyphenyl) propane dianhydride, 2,2-bis (2,3-dicarboxyphenyl) propane dianhydride, 1,1-bis (2,3-dicarboxyphenyl) ethane dianhydride, 1,1-bis (3,4-dicarboxyphenyl) ethane dianhydride Bis (2,3-dicarboxyphenyl) methane dianhydride, bis (3,4-dicarboxyphenyl) methane dianhydride, bis (3,4-dicarboxyphenyl) sulfone dianhydride, , 4,9,10-perylenetetracarboxylic dianhydride, bis (3,4-dicarboxyphenyl) ether dianhydride, benzene-1,2,3,4-tetracarboxylic dianhydride, 3,4 , 3 ′, 4′-benzophenone tetracarboxylic dianhydride, 2,3,2 ′, 3′-benzophenone tetracarboxylic dianhydride, 3,3,3 ′, 4′-benzophenone tetracarboxylic dianhydride 1,2,5,6-naphthalenetetracarboxylic dianhydride, 1,8,4,5-naphthalenetetracarboxylic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, , 2,4,5-naphthalenetetracarboxylic dianhydride, 2,6-dichloronaphthalene-1,8,4,5-tetracarboxylic dianhydride, 2,7-dichloronaphthalene-1,8,4 5-tetraca Rubonic acid dianhydride, 2,3,6,7-tetrachloronaphthalene-1,8,4,5-tetracarboxylic dianhydride, phenanthrene-1,10,8,9-tetracarboxylic dianhydride, Pyrazine-2,3,5,6-tetracarboxylic dianhydride, thiophene-2,3,5,6-tetracarboxylic dianhydride, 2,3,3 ′, 4′-biphenyltetracarboxylic dianhydride Bis (3,4-dicarboxyphenyl) dimethylsilane dianhydride, bis (3,4-dicarboxyphenyl) methylphenylsilane dianhydride, bis (3,4-dicarboxyphenyl) diphenylsilane dianhydride 1,4-bis (3,4-dicarboxyphenyldimethylsilyl) benzene dianhydride, 1,3-bis (3,4-dicarboxyphenyl) -1,1,3,3-tetramethyldisic Hexane dianhydride, p-phenylenebis (trimellitic anhydride), ethylenetetracarboxylic dianhydride, 1,2,3,4-butanetetracarboxylic dianhydride, decahydronaphthalene-1,4,5,8 -Tetracarboxylic dianhydride, 4,8-dimethyl-1,2,3,5,6,7-hexahydronaphthalene-1,2,5,6-tetracarboxylic dianhydride, cyclopentane-1, 2,3,4-tetracarboxylic dianhydride, pyrrolidine-2,3,4,5-tetracarboxylic dianhydride, 1,2,3,4-cyclobutanetetracarboxylic dianhydride, bis (exo- Bicyclo [2,2,1] heptane-2,3-dicarboxylic dianhydride), bicyclo- [2,2,2] -oct-7-ene-2,3,5,6-tetracarboxylic dianhydride Product, 4,4′-bis (3 4-Dicarboxyphenoxy) diphenyl sulfide dianhydride, 5- (2,5-dioxotetrahydrofuryl) -3-methyl-3-cyclohexene-1,2-dicarboxylic dianhydride, tetrahydrofuran-2,3,4 , 5-tetracarboxylic dianhydride, 4,4 ′-(4,4′-isopropylidenediphenoxy) bis (phthalic dianhydride), 2,2-bis (3,4-dicarboxyphenyl) hexa Fluoropropane dianhydride (also known as “4,4′-hexafluoropropylidene acid dianhydride”), 2,2, -bis [4- (3,4-dicarboxyphenyl) phenyl] hexafluoropropane dianhydride Etc. can be illustrated. One or two or more of the above tetracarboxylic dianhydrides can be used in combination.

  Although the ratio of the compound of Formula (3) among tetracarboxylic dianhydrides made to react with diamine does not receive a restriction | limiting in particular, 50 mass% or more is preferable and 75% mass or more is more preferable. When the proportion of the tetracarboxylic dianhydride of the formula (3) is less than 50% by mass, the effect of increasing fluidity tends to be small.

Examples of diamines that can be used for synthesizing polyimide resins include o-phenylenediamine, m-phenylenediamine, p-phenylenediamine, 3,3′-diaminodiphenyl ether, 3,4′-diaminodiphenyl ether, 4,4′-diaminodiphenyl ether, 3,3′-diaminodiphenylmethane, 3,4′-diaminodiphenylmethane, 4,4′-diaminodiphenylmethane, bis (4-amino-3,5-dimethylphenyl) methane, bis (4 -Amino-3,5-diisopropylphenyl) methane, 3,3'-diaminodiphenyl sulfone, 3,4'-diaminodiphenyl sulfone, 4,4'-diaminodiphenyl sulfone, 3,3'-diaminodiphenyl sulfide, 3, 4'-diaminodiphenylsulfi 4,4′-diaminodiphenyl sulfide, 3,3′-diaminodiphenyl ketone, 3,4′-diaminodiphenyl ketone, 4,4′-diaminodiphenyl ketone, 2,2-bis (3-aminophenyl) propane, 2,2 ′-(3,4′-diaminodiphenyl) propane, 2,2-bis (4-aminophenyl) propane, 1,3-bis (3-aminophenoxy) benzene, 1,4-bis (3- Aminophenoxy) benzene, 1,4-bis (4-aminophenoxy) benzene, 3,3 ′-(1,4-phenylenebis (1-methylethylidene)) bisaniline, 3,4 ′-(1,4-phenylene) Bis (1-methylethylidene)) bisaniline, 4,4 ′-(1,4-phenylenebis (1-methylethylidene)) bisaniline, 2,2-bis (4- (3-amino) Nophenoxy) phenyl) propane, 2,2-bis (4- (4-aminophenoxy) phenyl) propane, bis (4- (3-aminophenoxy) phenyl) sulfide, bis (4- (4-aminophenoxy) phenyl ) Sulfide, bis (4- (3-aminophenoxy) phenyl) sulfone, bis (4- (4-aminophenoxy) phenyl) sulfone, aromatic diamines such as 3,5-diaminobenzoic acid, 1,2-diaminoethane 1,3-diaminopropane, 1,4-diaminobutane, 1,5-diaminopentane, 1,6-diaminohexane, 1,7-diaminoheptane, 1,8-diaminooctane, 1,9-diaminononane, , 10-diaminodecane, 1,11-diaminoundecane, 1,12-diaminododecane, 1,2-diaminocycl Hexane, or diamino polysiloxane, and the like represented by the following general formula (6). In Formula (6), n is preferably 1 to 15, more preferably 1 to 10.

  Furthermore, the diamine is, for example, 1,3-bis (aminomethyl) cyclohexane, aliphatic diamine such as polyoxyalkylene diamine manufactured by Mitsui Chemicals Fine Co., Ltd. [trade names: Jeffamine D-230, D-400, D- 2000, D-4000, ED-600, ED-900, ED-2001, EDR-148, etc.], 3,3′-diaminodiphenyldifluoromethane, 3,4′-diaminodiphenyldifluoromethane, 4,4′-diamino Diphenyldifluoromethane, 2,2-bis (3-aminophenyl) hexafluoropropane, 2,2- (3,4'-diaminodiphenyl) hexafluoropropane, 2,2-bis (4-aminophenyl) hexafluoropropane 2,2-bis (4- (3-aminophenoxy) phenyl) hexafluoro Propane, 2,2-bis (4- (4-aminophenoxy) phenyl) hexafluoropropane and the like. Among the above diamines, one kind can be used alone, or two or more kinds can be mixed and used.

  By using the polyimide resin according to this embodiment alone as an adhesive, sufficient adhesion, heat resistance, and fluidity to various substrates are given. By comprising, sufficient fluidity | liquidity and adhesiveness can be given to an adhesive composition.

  The weight average molecular weight of the polyimide resin is not particularly limited, but a general weight average molecular weight is preferably 5000 to 250,000, and more preferably 10,000 to 150,000. If the weight average molecular weight is less than 5,000, the film-forming property tends to be lowered when a film-like adhesive is used, and if it exceeds 250,000, the compatibility with other components tends to be poor.

  Examples of the conductive particles contained in the adhesive composition of the present embodiment include metal particles such as Au, Ag, Ni, Cu, and solder, and carbon particles. Further, the conductive particles may be a non-conductive glass, ceramic, plastic or the like as a core, and the core is covered with the metal, metal particles, carbon or the like. Moreover, as electroconductive particle, the metal particle | grains which consist of copper may coat | cover silver. When these conductive particles are used, the circuit connection structure is more excellent in connection reliability by increasing the contact area between the conductive particles and the electrodes when connecting circuit members because they are deformable by heating and pressing. The body is obtained. In addition, the conductive particles include those in which the surface of the conductive particles is coated with insulating particles, or those in which an insulating layer made of an insulating material is provided on the surface of the conductive particles by a method such as hybridization. It can also be used. By using such conductive particles, short circuit due to contact between adjacent conductive particles is less likely to occur.

  In addition, it is preferable that the conductive particles have a nucleus-side protrusion formed on the surface of the core of the nucleus, since the connection reliability is further improved. Such a nucleus can be formed by adsorbing a plurality of nucleus-side projections having a smaller diameter than the nucleus in the surface of the nucleus. The average particle size of such conductive particles is the particle size of the entire conductive particles including the protrusions.

  The average particle diameter of the conductive particles is preferably 1 to 10 μm from the viewpoint of obtaining good dispersibility and conductivity. When the average particle size is less than 1 μm, sufficient electrical connection of the circuit cannot be obtained, and when it exceeds 10 μm, there is a tendency that the conductive particles are not sufficiently dispersed and aggregate.

  On the other hand, the height of the protrusion is preferably 50 to 500 nm, and more preferably 75 to 300 nm or less. Moreover, it is preferable that the distance between adjacent protrusion parts is 1000 nm or less, and it is more preferable that it is 500 nm or less. When the height of the protrusion is lower than 50 nm, or when the distance between adjacent protrusions is larger than 1000 nm, the effect of the protrusion on the electrical connection tends to fade. For example, when connecting a pair of circuit members (first and second circuit members) arranged opposite to each other and the height of the protrusion is larger than 500 nm, the conductive particles and the first and second circuit members Since the contact area with the electrode portion is reduced, the connection resistance value tends to increase. In addition, the height H of the protrusion part of electroconductive particle and the distance between adjacent protrusion parts can be measured with an electron microscope.

  In addition, the fine particles with the surface of these conductive particles coated with a polymer resin or the like suppress short circuit due to contact between particles when the amount of the conductive particles is increased, and provide insulation between circuit electrodes. Can be improved. 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.

  Since the adhesive composition of this embodiment contains such conductive particles, it can be suitably used as an anisotropic conductive adhesive composition.

  The content of the conductive particles is preferably 0.1 to 30% by volume, and more preferably 0.1 to 10% by volume based on the total volume of the adhesive composition. When this content is less than 0.1% by volume, the conductivity tends to be inferior, and when it exceeds 30% by volume, a short circuit between circuit electrodes tends to occur. In addition, content of electroconductive particle is determined based on the volume of each component of the adhesive composition before hardening at 23 degreeC. In addition, the volume of each component can be calculated | required by converting mass into a volume using specific gravity. Also, put an appropriate solvent (water, alcohol, etc.) that can wet the component well without dissolving or swelling the component whose volume is to be measured. It is also possible to obtain the volume increased by charging as the volume of the component.

  The adhesive composition of the present embodiment may contain other components as long as it has the polyimide resin. From the viewpoint of obtaining good transferability and sufficient fluidity, the polyimide resin is It is preferably 1 to 60% by mass, more preferably 2.5 to 50% by mass, based on the total amount of the adhesive composition. If the content is less than 1% by mass, the transferability to the circuit member tends to deteriorate, and if it exceeds 60% by mass, the fluidity may decrease.

  The adhesive composition of the present embodiment further includes a radical polymerizable substance, a composition containing an epoxy resin and a latent curing agent for the epoxy resin (hereinafter referred to as “first composition”), heating, and the like. It is preferably a mixed composition with a composition containing a curing agent that generates free radicals (hereinafter referred to as “second composition”), or with the first composition and the second composition. Thereby, adhesive strength can be improved more and the stable performance can be maintained even after a reliability test.

  The epoxy resin contained in the first composition is bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, bisphenol A novolac type epoxy resin, bisphenol. Examples thereof include F novolac type epoxy resins, alicyclic epoxy resins, glycidyl ester type epoxy resins, glycidyl amine type epoxy resins, hydantoin type epoxy resins, isocyanurate type epoxy resins, and aliphatic chain epoxy resins. These epoxy resins may be halogenated or hydrogenated. Two or more of these epoxy resins may be used in combination.

  The latent curing agent contained in the first composition is not particularly limited as long as it can cure the epoxy resin. Examples of such latent curing agents include anionic polymerizable catalyst-type curing agents and cationic polymerizable agents. Catalyst-type curing agents, polyaddition-type curing agents, and the like. These can be used individually by 1 type or in mixture of 2 or more types. Of these, anionic or cationic polymerizable catalyst-type curing agents are preferred because they are excellent in rapid curability and do not require chemical equivalent considerations.

  Examples of the anionic or cationic polymerizable catalyst-type curing agent include imidazole, hydrazide, boron trifluoride-amine complex, sulfonium salt, amine imide, diaminomaleonitrile, melamine and derivatives thereof, polyamine salt, dicyandiamide and the like. These modifications can also be used. Examples of the polyaddition type curing agent include polyamines, polymercaptans, polyphenols, and acid anhydrides.

  When a tertiary amine or imidazole is blended as an anionic polymerization type catalyst curing agent, the epoxy resin is cured by heating at a medium temperature of about 160 ° C. to 200 ° C. for several tens of seconds to several hours. For this reason, the pot life is relatively long, which is preferable. As the cationic polymerization type catalyst-type curing agent, for example, a photosensitive onium salt (an aromatic diazonium salt, an aromatic sulfonium salt or the like is mainly used) that cures an epoxy resin by irradiation with energy rays is preferable. In addition to irradiation with energy rays, there are aliphatic sulfonium salts and the like that are activated by heating to cure the epoxy resin. This type of curing agent is preferable because it has a feature of fast curing.

  When these latent hardeners are coated with polymer materials such as polyurethane or polyester, metal thin films such as nickel or copper, and inorganic materials such as calcium silicate, the pot life is extended. This is preferable because it is possible.

  The radically polymerizable substance contained in the second composition can be any known one without particular limitation. In addition, the radical polymerizable compound can be used in either a monomer or oligomer state, and the monomer and oligomer may be mixed and used.

  Specifically, epoxy (meth) acrylate oligomer, urethane (meth) acrylate oligomer, polyether (meth) acrylate oligomer, oligomer such as polyester (meth) acrylate oligomer, trimethylolpropane tri (meth) acrylate, polyethylene glycol di ( (Meth) acrylate, polyalkylene glycol di (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, neopentyl glycol di (meth) acrylate, dipentaerythritol hexa (meth) acrylate, Glyci of isocyanuric acid modified bifunctional (meth) acrylate, isocyanuric acid modified trifunctional (meth) acrylate, bisphenol fluorenediglycidyl ether Such as epoxy (meth) acrylate with (meth) acrylic acid added to the thiol group, compounds with (meth) acryloyloxy group introduced into the compound with ethylene glycol or propylene glycol added to the glycidyl group of bisphenol fluorenediglycidyl ether, etc. Examples include polyfunctional (meth) acrylates. These compounds can be used individually by 1 type or in mixture of 2 or more types.

  In addition to the radical polymerizable substance, pentaerythritol (meth) acrylate, 2-cyanoethyl (meth) acrylate, cyclohexyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, 2- (2-ethoxyethoxy) ethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, n-hexyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, hydroxypropyl (Meth) acrylate, isobornyl (meth) acrylate, isodecyl (meth) acrylate, isooctyl (meth) acrylate, n-lauryl (meth) acrylate, 2-methoxyethyl (meth) acrylate 2-phenoxyethyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, 2- (meth) acryloyloxyethyl phosphate, N, N-dimethylaminoethyl (meth) acrylate, N, N-dimethylaminopropyl (meth) ) Acrylate, (meth) acryloylmorpholine, etc. may be used in combination. These compounds can be used individually by 1 type or in mixture of 2 or more types.

  The adhesive composition of the present embodiment preferably contains at least one compound having two or more (meth) acryloyl groups in the molecule as the radical polymerizable compound.

  Furthermore, the adhesive composition of the present embodiment has a functional group that is polymerized by an active radical such as an allyl group, a maleimide group, and a vinyl group in addition to the compound having the (meth) acryloyl group as a radical polymerizable compound. You may add a compound suitably. Specifically, N-vinylimidazole, N-vinylpyridine, N-vinylpyrrolidone, N-vinylformamide, N-vinylcaprolactam, 4,4′-vinylidenebis (N, N-dimethylaniline), N-vinylacetamide N, N-dimethylacrylamide, N-isopropylacrylamide, N, N-diethylacrylamide, methylolacrylamide, 4,4'-diphenylmethane bismaleimide, 3,3'-dimethyl-5,5'-4,4'-diphenylmethane Examples thereof include bismaleimide and 1,6-bismaleimide- (2,2,4-trimethyl) hexane.

  Moreover, it is preferable to use together the radical polymerizable substance which has the phosphate ester structure represented by following formula (20)-(22) with the said radical polymerizable substance. In this case, since the adhesive strength to the surface of an inorganic material such as metal is improved, it is suitable for bonding circuit electrodes.


In formula (20), R 4 represents a (meth) acryloyloxy group, R 5 represents a hydrogen atom or a methyl group, and w and x each independently represents an integer of 1 to 8. In the formula, R 4 s , R 5 s , w s, and x s may be the same or different.


In formula (21), R 6 represents a (meth) acryloyloxy group, and y and z each independently represents an integer of 1 to 8. In the formula, R 6 s , y s, and z s may be the same or different.


In Formula (22), R 7 represents a (meth) acryloyloxy group, R 8 represents a hydrogen atom or a methyl group, and a and b each independently represent an integer of 1 to 8.

  Other specific examples include acid phosphooxyethyl methacrylate, acid phosphooxyethyl acrylate, acid phosphooxypropyl methacrylate, acid phosphooxypolyoxyethylene glycol monomethacrylate, acid phosphooxypolyoxypropylene glycol monomethacrylate, 2,2′-di. (Meth) acryloyloxydiethyl phosphate, EO-modified phosphoric acid dimethacrylate, phosphoric acid-modified epoxy acrylate, vinyl phosphate and the like.

  Moreover, the radically polymerizable substance which has a phosphate ester structure is obtained also by making phosphoric anhydride and 2-hydroxyethyl (meth) acrylate react. Specific examples include mono (2-methacryloyloxyethyl) acid phosphate and di (2-methacryloyloxyethyl) acid phosphate. These may be used alone or in combination of two or more compounds.

  The content of the radical polymerizable substance having a phosphate ester structure is preferably 0.01 to 50 parts by mass with respect to a total of 100 parts by mass of the radical polymerizable substance and the film forming material to be blended as necessary. 0.5-5 mass parts is more preferable.

  The curing agent that generates free radicals upon heating (radical polymerization initiator) contained in the second composition is a curing agent that decomposes by heating to generate free radicals, and is a conventionally known peroxide. And known compounds such as azo compounds can be used. However, from the viewpoints of stability, reactivity, and compatibility, a peroxide having a one-minute half-life temperature of 90 to 175 ° C. and a molecular weight of 180 to 1000 is preferable. Here, “one-minute half-life temperature” refers to the temperature at which the half-life is 1 minute, and “half-life” refers to the time until the concentration of the compound decreases to half of the initial value.

  Specific examples of radical polymerization initiators include 1,1,3,3-tetramethylbutylperoxyneodecanoate, di (4-t-butylcyclohexyl) peroxydicarbonate, and di (2-ethylhexyl) peroxy. Dicarbonate, cumylperoxyneodecanoate, dilauroyl peroxide, 1-cyclohexyl-1-methylethylperoxyneodecanoate, t-hexylperoxyneodecanoate, t-butylperoxyneodecanoate , T-butylperoxypivalate, 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate, 2,5-dimethyl-2,5-di (2-ethylhexanoylperoxy) Hexane, t-hexylperoxy-2-ethylhexanoate, t-butylperoxy-2- Tylhexanoate, t-butylperoxyneoheptanoate, t-amylperoxy-2-ethylhexanoate, di-t-butylperoxyhexahydroterephthalate, t-amylperoxy-3,5,5 -Trimethylhexanoate, 3-hydroxy-1,1-dimethylbutylperoxyneodecanoate, t-amylperoxyneodecanoate, t-amylperoxy-2-ethylhexanoate, 3-methylbenzoyl Peroxide, 4-methylbenzoyl peroxide, di (3-methylbenzoyl) peroxide, dibenzoyl peroxide, di (4-methylbenzoyl) peroxide, 2,2′-azobis-2,4-dimethylvaleronitrile, 1,1′-azobis (1-acetoxy-1-phenylethane) 2,2′-azobisisobutyronitrile, 2,2′-azobis (2-methylbutyronitrile), dimethyl-2,2′-azobisisobutyronitrile, 4,4′-azobis (4- Cyanovaleric acid), 1,1′-azobis (1-cyclohexanecarbonitrile), t-hexylperoxyisopropyl monocarbonate, t-butylperoxymaleic acid, t-butylperoxy-3,5,5-trimethylhexano Ate, t-butyl peroxylaurate, 2,5-dimethyl-2,5-di (3-methylbenzoylperoxy) hexane, t-butylperoxy-2-ethylhexyl monocarbonate, t-hexyl peroxybenzoate, 2,5-dimethyl-2,5-di (benzoylperoxy) hexane, t-butylperoxybenzoe And dibutyl peroxytrimethyl adipate, t-amyl peroxy normal octoate, t-amyl peroxy isononanoate, t-amyl peroxybenzoate and the like. These compounds may be used alone or in combination of two or more compounds.

  Moreover, the compound which generate | occur | produces a radical by light irradiation with a wavelength of 150-750 nm can be used as a radical polymerization initiator. Such compounds include, for example, Photoinitiation, Photopolymerization, and Photocuring, J. Mol. -P. The α-acetaminophenone derivatives and phosphine oxide derivatives described in Fouassier, Hanser Publishers (1995), p17 to p35 are more preferable because of their high sensitivity to light irradiation. These compounds may be used alone or in combination with the above peroxides or azo compounds.

  Further, in order to suppress corrosion of the connection terminals of the circuit member, the amount of chlorine ions or organic acid contained in the radical polymerization initiator is preferably 5000 ppm or less, and further, less organic acid is generated after thermal decomposition. Those are more preferred. Moreover, since the stability of the produced adhesive composition is improved, it is preferable to use a radical polymerization initiator having a mass retention of 20% by mass or more after being left open at room temperature and normal pressure for 24 hours.

  A stabilizer may be added to the second composition in order to control the curing rate and impart storage stability. Such stabilizers include quinone derivatives such as benzoquinone and hydroquinone, phenol derivatives such as 4-methoxyphenol and 4-t-butylcatechol, 2,2,6,6-tetramethylpiperidine-1-oxyl and 4 Aminoxyl derivatives such as -hydroxy-2,2,6,6-tetramethylpiperidine-1-oxyl, and hindered amine derivatives such as tetramethylpiperidyl methacrylate are preferred.

  The addition amount of the stabilizer is preferably 0.01 to 15% by mass, and more preferably 0.1 to 10% by mass based on the total amount of the adhesive composition. When the addition amount is less than 0.01% by mass, the addition effect tends to be insufficient, and when it exceeds 15 parts by mass, the polymerization reaction tends to be inhibited.

  The adhesive composition according to the present embodiment may further contain a thermoplastic resin other than the above polyimide resin. The other thermoplastic resin is, for example, one or more selected from the group consisting of phenoxy resin, polyester resin, polyurethane resin, polyester urethane resin, butyral resin, and acrylic resin. By combining these thermoplastic resins and polyimide resins, the Tg, adhesiveness, and heat resistance of the adhesive can be adjusted.

  The thermoplastic resin may contain a siloxane bond or a fluorine substituent. These can be suitably used as long as the resins to be mixed are completely compatible with each other or microphase separation occurs and becomes cloudy.

  The weight average molecular weight of the thermoplastic resin is preferably 5,000 to 200,000, and more preferably 10,000 to 150,000. If the weight average molecular weight is less than 5,000, the film formability tends to decrease, and if it exceeds 200,000, the compatibility with other components tends to deteriorate.

  The content of the thermoplastic resin is preferably 15 to 70% by mass, more preferably 20 to 60% by mass, based on the total amount of the adhesive, with respect to the total mass of the polyimide resin. When the content of the thermoplastic resin is less than 15% by mass, the film formability tends to decrease, and when it is more than 70% by mass, it tends to be difficult to ensure sufficient fluidity.

  Adhesive aids such as coupling agents represented by alkoxysilane derivatives and silazane derivatives, adhesion improvers, and leveling agents may be appropriately added to the adhesive composition of the present embodiment. Specifically, a compound represented by the following general formula (23) is preferable as such an adhesion assistant. These adhesion assistants can be used alone or in combination of two or more.


In formula (23), R 9 , R 10 and R 11 are each independently a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, an alkoxycarbonyl group having 1 to 5 carbon atoms, Or an aryl group, and R 12 represents a (meth) acryloyl group, a vinyl group, an isocyanate group, an imidazole group, a mercapto group, an amino group, a methylamino group, a dimethylamino group, a benzylamino group, a phenylamino group, or a cyclohexylamino group. A group, a morpholino group, a piperazino group, a ureido group or a glycidyl group, and c represents an integer of 1 to 10.

  A rubber component may be added to the adhesive composition of the present embodiment for the purpose of stress relaxation and adhesive improvement. Specific examples of the rubber component include polyisoprene, polybutadiene, carboxyl-terminated polybutadiene, hydroxyl-terminated polybutadiene, 1,2-polybutadiene, carboxyl-terminated 1,2-polybutadiene, hydroxyl-terminated 1,2-polybutadiene, acrylic rubber, styrene- Butadiene rubber, hydroxyl-terminated styrene-butadiene rubber, acrylonitrile-butadiene rubber, carboxyl group, hydroxyl group, (meth) acryloyl group or morpholine group-containing acrylonitrile-butadiene rubber, carboxylated nitrile rubber, hydroxyl-terminated poly (oxypropylene) ), Alkoxysilyl group-terminated poly (oxypropylene), poly (oxytetramethylene) glycol, polyolefin glycol, poly-ε-caprolactone, and the like.

  The rubber component is preferably a rubber component containing a cyano group or a carboxyl group, which is a highly polar group, in the side chain or terminal from the viewpoint of improving adhesiveness. These compounds can be used individually by 1 type or in mixture of 2 or more types.

  In the present embodiment, known organic or inorganic fine particles that are not particularly limited can be used. Specific examples of inorganic fine particles include metal fine particles represented by silica fine particles, alumina fine particles, silica-alumina fine particles, titania fine particles, zirconia fine particles and the like, as well as nitride fine particles.

  Specific examples of the organic fine particles include silicone fine particles, methacrylate-butadiene-styrene fine particles, acryl-silicone fine particles, polyamide fine particles, and polyimide fine particles. These may have a uniform structure or a core-shell structure.

  The content of organic or inorganic fine particles used in the present embodiment is preferably in the range of 5 to 30% by mass, more preferably in the range of 10 to 20% by mass based on the total amount of the adhesive composition. If the blending amount of the inorganic fine particles is less than 5% by mass, the electrical connection between the opposing electrodes tends not to be maintained.

  The adhesive composition of the present embodiment is mixed with or without using the polyimide resin and a solvent capable of dissolving and dispersing the additive components such as the first composition, the second composition, and the stabilizer. Can be manufactured. The conductive particles may be added as appropriate during the dissolution / dispersion process.

  The adhesive composition of this embodiment can also be used in the form of a film. A solution prepared by adding a solvent or the like to the adhesive composition as necessary is applied to a peelable substrate such as a fluororesin film, a polyethylene terephthalate film, or a release paper, or a substrate such as a nonwoven fabric is impregnated with the solution. Can be used as a film after removing the solvent and the like. Use in the form of a film is more convenient from the viewpoint of handleability.

  FIG. 1 is a schematic cross-sectional view showing an embodiment of a film adhesive comprising the adhesive composition of the present invention. An adhesive sheet 100 shown in FIG. 1 includes a support substrate 8 and a film adhesive composition 40 that is detachably laminated on the support substrate 8. The film adhesive composition 40 includes an insulating adhesive component 5 and conductive particles 7 dispersed in the adhesive component 5.

  As long as the support base material 8 can maintain the adhesive composition in a film shape, the shape and material thereof are arbitrary. Specifically, a fluororesin film, a polyethylene terephthalate film (PET), a biaxially stretched polypropylene film (OPP), a nonwoven fabric, or the like can be used as a supporting substrate.

  According to this film adhesive composition 40, it is easy to handle, can be easily installed on the adherend, and can be easily connected. Moreover, the adhesive sheet 100 may have a multilayer structure including two or more types of layers. Moreover, since the film adhesive composition 40 contains the said electroconductive particle 7, it can be used suitably as an anisotropic conductive film.

  The film adhesive composition 40 of this embodiment can adhere | attach adherends normally using heating and pressurization together. The heating temperature is preferably 100 to 250 ° C. The pressure is not particularly limited as long as it does not damage the adherend, but it is generally preferably 0.1 to 10 MPa. These heating and pressurization are preferably performed in the range of 0.5 seconds to 120 seconds. According to the film-like adhesive composition 40 of the present embodiment, for example, adherends can be sufficiently bonded to each other even under short-time heating and pressurization for 15 seconds under conditions of 150 to 200 ° C. and 1 MPa. Is possible.

  Moreover, the film adhesive composition 40 of this 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.

  Hereinafter, an example in which the film-like adhesive composition 40 of the present embodiment is used as an anisotropic conductive film, and circuit members having circuit electrodes formed on the main surface of the circuit board are connected as adherends. explain. That is, an anisotropic conductive film is disposed between opposing circuit electrodes on a circuit board, and heated and pressed to perform electrical connection between opposing circuit electrodes and adhesion between circuit boards. Can be connected. Here, as a circuit board for forming a circuit electrode, a substrate made of an inorganic substance such as a semiconductor, glass or ceramic, a board made of an organic substance such as polyimide or polycarbonate, a board formed by combining an inorganic substance such as glass / epoxy and an organic substance, or the like. Can be used.

  FIG. 2 is a schematic cross-sectional view showing an embodiment of the circuit connection structure (circuit member connection structure) of the present invention. As shown in FIG. 2, the circuit member connection structure of the present embodiment includes a first circuit member 20 and a second circuit member 30 that are opposed to each other. A circuit connection member 10 is provided between the circuit member 30 and the circuit member 30.

  The first circuit member 20 includes a circuit board (first circuit board) 21 and a circuit electrode (first circuit electrode) 22 formed on the main surface 21 a of the circuit board 21. Note that an insulating layer may be formed on the main surface 21 a of the circuit board 21 in some cases.

  On the other hand, the second circuit member 30 includes a circuit board (second circuit board) 31 and a circuit electrode (second circuit electrode) 32 formed on the main surface 31 a of the circuit board 31. In addition, an insulating layer may be formed on the main surface 31a of the circuit board 31 in some cases.

The first and second circuit members 20 and 30 are not particularly limited as long as electrodes that require electrical connection are formed. Specific examples include glass or plastic substrates on which electrodes are formed of ITO or IZO used for liquid crystal displays, printed wiring boards, ceramic wiring boards, flexible wiring boards having flexible substrates, semiconductor silicon chips, and the like. These are used in combination as needed. As described above, in the present embodiment, materials such as printed wiring boards and polyimides, metals such as copper and aluminum, ITO (indium tin oxide), silicon nitride (SiN x ), silicon dioxide (SiO 2 ) are used. Circuit members having various surface states such as inorganic materials such as the above can be used.

  The circuit connection member 10 is made of a cured product of the film adhesive composition 40 of the present embodiment. The circuit connection member 10 contains an insulating material 11 and conductive particles 7. The conductive particles 7 are disposed not only between the circuit electrode 22 and the circuit electrode 32 facing each other but also between the main surfaces 21a and 31a. In the circuit member connection structure, the circuit electrodes 22 and 32 are electrically connected via the conductive particles 7. That is, the conductive particles 7 are in direct contact with both the circuit electrodes 22 and 32.

  Here, the electroconductive particle 7 is the electroconductive particle demonstrated previously, and the insulating substance 11 is the hardened | cured material of each insulating component which comprises the adhesive composition or film adhesive of this embodiment. is there.

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

  Since the circuit connection member 10 is composed of the adhesive composition of the present embodiment or the cured product of the film adhesive, the adhesion strength of the circuit connection member 10 to the circuit member 20 or 30 is sufficiently high, and the circuit connection member 10 is reliable. Stable performance (good adhesive strength and connection resistance) can be maintained even after the property test (high temperature and high humidity test).

  Next, an example of a method for manufacturing the circuit member connection structure described above will be described with reference to FIG. First, the first circuit member 20 and the film adhesive composition 40 described above are prepared (see FIG. 3A). The film adhesive composition 40 is formed by forming an adhesive composition (circuit connection material) into a film shape, and contains the conductive particles 7 and the adhesive component 5.

  The thickness of the film adhesive composition 40 is preferably 8 to 50 μm. If the thickness of the film adhesive composition 40 is less than 8 μm, the adhesive composition tends to be insufficiently filled between the circuit electrodes 22 and 32. On the other hand, when it exceeds 50 μm, the adhesive composition between the circuit electrodes 22 and 32 cannot be sufficiently removed, and it is difficult to ensure conduction between the circuit electrodes 22 and 32.

  Next, the film adhesive composition 40 is placed on the surface of the first circuit member 20 on which the circuit electrodes 22 are formed. When the film adhesive composition 40 is adhered on the support, the film adhesive composition 40 side is directed to the first circuit member 20 so that the first circuit member 20 Put it on. At this time, the film adhesive composition 40 is in a film form and is easy to handle. For this reason, the film-like adhesive composition 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 Can be easily connected.

  And the film adhesive composition 40 is pressurized to the arrow A and B direction of Fig.3 (a), and the film adhesive composition 40 is temporarily connected to the 1st circuit member 20 (FIG.3 (b)). reference). At this time, you may pressurize, heating. However, the heating temperature is lower than the temperature at which the adhesive composition in the film adhesive composition 40 is not cured.

  Subsequently, as shown in FIG. 3C, the second circuit member 30 is placed on the film adhesive composition 40 so that the second circuit electrode faces the first circuit member 20. In addition, when the film adhesive composition 40 has adhered on the support body, after peeling a support body, the 2nd circuit member 30 is mounted on the film adhesive composition 40. FIG.

  And it heats through the 1st and 2nd circuit members 20 and 30 to the arrow A and B direction of FIG.3 (c), heating the film adhesive composition 40. FIG. The heating temperature at this time is set to a temperature at which the polymerization reaction can be started. In this way, the film-like adhesive composition 40 is cured to perform the main connection, and a circuit member connection structure as shown in FIG. 2 is obtained.

  Here, as described above, the connection conditions are preferably a heating temperature of 100 to 250 ° C., a pressure of 0.1 to 10 MPa, and a connection time of 0.5 seconds to 120 seconds. These conditions are appropriately selected depending on the application to be used, the adhesive composition, and the circuit member, and may be post-cured as necessary.

  By manufacturing the circuit member connection structure as described above, in the circuit member connection structure obtained, the conductive particles 7 can be brought into contact with both of the circuit electrodes 22 and 32 facing each other. , 32 can be sufficiently reduced.

  In addition, the adhesive component 5 is cured by the heating of the film-like adhesive composition 40 in a state where the distance between the circuit electrode 22 and the circuit electrode 32 is sufficiently small, so that the insulating material 11 is obtained. The member 20 and the second circuit member 30 are firmly connected via the circuit connection member 10. That is, in the circuit member connection structure obtained, since the circuit connection member 10 is made of a cured product of the adhesive composition of the present embodiment, the adhesion strength of the circuit connection member 10 to the circuit member 20 or 30 is high. While being sufficiently high, the connection resistance between the electrically connected circuit electrodes can be sufficiently reduced. Moreover, even when it is left for a long time in a high temperature and high humidity environment, it is possible to sufficiently suppress a decrease in adhesive strength and an increase in connection resistance.

  In addition, the pressure in the said pressurization is computable as a load per crimping | compression-bonding area. The crimping area referred to here is the area of the portion to be heated and pressed among the portions where the film adhesive composition 40 and the circuit electrodes 22 and 32 on the circuit boards 21 and 31 overlap.

  First, how to obtain the crimping area will be described. FIG. 4 is a schematic plan view of circuit members to be connected. As shown in FIG. 4A, a plurality of first circuit electrodes 22 are arranged in parallel on the main surface 21 a of the first circuit board 21. The first circuit electrodes 22 are arranged in parallel over the width x and have a length y per one. The first circuit board 21 is formed on the first circuit electrode 22 with the first After the film adhesive composition 40 is placed so as to cover the entire circuit electrode 22, it is used for connection with the second circuit board 31.

As shown in FIGS. 4B and 4C, the second circuit board 31 has a film shape so that the second circuit electrode provided on the main surface thereof faces the first circuit electrode 22. Place on the adhesive composition 40. In the region where the first and second circuit electrodes 22 and 32 overlap (hereinafter referred to as “electrode facing region”), when heating and pressurization is performed on all the portions (the region 50a in FIG. 4B) In the case of heating and pressurizing), the pressure-bonding area is obtained by the product of the width x and the length y 1 of the electrode facing region. On the other hand, when heating and pressing are performed on a part of the electrode facing portion (when the region 50b in FIG. 4C is heated and pressed), the crimping area is equal to the width x of the electrode facing region. The product of the length y 2 of the portion where the heating and pressurization is performed in the electrode facing region is obtained.

The pressure can be determined as follows. For example, it is assumed that a pressure load of 6 kgf is applied to a circuit board in which the width of the electrode facing region is 30 mm and the length in the direction perpendicular to the width is 2 mm.
When heating and pressurization is performed for all parts of the electrode facing region (in the case of FIG. 4B), the total area of the portion to be heated and pressed becomes equal to the area of the electrode facing region,
Pressure = is determined as applied load (kgf) / electrode facing region area xy 1 of (cm 2) = 6kgf / 0.6cm 2 = 10kgf / cm 2 (≒ 1.0MPa).

On the other hand, if the heating and pressurizing is performed for a part of the electrode facing region (the case of FIG. 4 (c)), for example, if y 2 is 1 mm, the pressure is
Pressure = Pressure load (kgf) / area of the portion where heat and pressure are applied in the electrode facing region xy 2 (cm 2 ) = 6 kgf / 0.3 cm 2 = 20 kgf / cm 2 (≈2.0 MPa) .

  Moreover, if the said relational expression is used, the pressurization load for achieving a target pressure on the contrary can also be calculated | required.

For example, in the circuit board and the circuit electrode having the above configuration, in order to set the pressure in the electrode facing region to 1.0 MPa (≈10 kgf / cm 2 ), the pressurizing load set in the pressurizing device is obtained by the following calculation. The pressure load may be applied to the corresponding pressure-bonding head.
In the case of FIG.
Target pressure = 1.0 MPa (10 kgf / cm 2 )
Total area of heated and pressurized parts (= area of electrode facing region) = xy 1 = 3.0 cm × 0.2 cm = 0.6 cm 2
Pressurization load = (total area of the part to be heated and pressurized) × (target pressure) = 0.6 cm 2 × 10 kgf / cm 2 = 6 kgf
Can be obtained as

On the other hand, in the case of FIG.
Target pressure = 1.0 MPa (10 kgf / cm 2 )
Total area of the portion to be heated and pressurized = xy 2 = 3.0 cm × 0.1 cm = 0.3 cm 2
Pressurization load = (total area of the part to be heated and pressurized) × (target pressure) = 0.3 cm 2 × 10 kgf / cm 2 = 3 kgf
Can be obtained as

For example, in the case of FIG. 4B, when there are a plurality of (for example, 10) connecting portions and each portion is pressurized simultaneously, the applied pressure is as follows.
Target pressure = 1.0 MPa (10 kgf / cm 2 )
Total area of parts to be heated and pressurized = xy 1 × 10 (pieces) = 3.0 cm × 0.2 cm × 10 = 6 cm 2
Pressurization load = (total area of the part to be heated and pressurized) × (target pressure) = 6 cm 2 × 10 kgf / cm 2 = 60 kgf

  Thus, in this embodiment, the pressure in circuit connection can be set while mutually converting the pressure (MPa) and the pressurizing load (kgf). Note that the circuit board may undergo thermal expansion during heating and pressurization, resulting in the occurrence of misalignment of the counter electrode, but in this embodiment, the pressure is calculated by performing the above case classification before heating and pressurization. The pressure when the positional deviation occurs is calculated by the same calculation method as that when no positional deviation occurs.

  The preferred embodiment of the present invention has been described above, but the present invention is not limited to the above embodiment. For example, the adhesive composition of the present invention can be used to connect a solar battery cell provided with electrodes such as finger electrodes and bus bar electrodes, and a tab wire. That is, the circuit connection structure of the present invention includes a solar battery cell and a tab wire so that the solar battery cell having an electrode, a tab wire, and the electrode and the tab wire are electrically connected in a state of facing each other. A solar cell module including a connection member to be bonded, the connection member being formed of a cured product of the adhesive composition.

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

<Synthesis of polyimide resin>
1. Synthesis of polyimide resin (PI-1) using acid dianhydride having siloxane skeleton represented by formula (3) Into a 300 mL separable flask equipped with a Dean-Stark reflux condenser, thermometer and stirrer, Acid dianhydride 5,5′-exo- (1,1,3,3,5,5,7,7,9,9-decamethylpentasiloxane-1,5-diyl) bisbicyclo [2.2 .1] 24.0 mmol of heptane-exo-2,3-dicarboxylic dianhydride, 24.0 mmol of 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, and N-methyl-2-pyrrolidone A reaction solution prepared by adding 140 g of (NMP) was stirred at room temperature (25 ° C.) for 30 minutes. Next, 21.0 mmol of 1,4-bisaminopropylpiperazine, which is a diamine, 21.0 mmol of 2,2-bis [4- (4-aminophenoxy) phenyl] hexafluoropropane, and 6.0 mmol of polyoxypropylenediamine were added. . Thereafter, the temperature of the reaction solution is raised to 180 ° C., and refluxed for 1 hour while removing the mixture of water and NMP with a Dean-Stark reflux condenser, and a polyimide resin having a siloxane skeleton represented by the formula (1) (hereinafter “PI”). -1 ")). The NMP solution of PI-1 was poured into water and the precipitate was collected. This precipitate was pulverized and dried to obtain solid PI-1. As a result of measurement by GPC, the weight average molecular weight of the obtained PI-1 was 51000 in terms of standard polystyrene. Moreover, it measured on the conditions of the temperature increase rate of 10 degree-C / min and the tension method using UBM company wide area dynamic viscoelasticity measuring apparatus E-4000, and measured the maximum value of tan-delta as a glass transition temperature. As a result of the measurement, the glass transition temperature was 118 ° C. PI-1 was dissolved in MEK (methyl ethyl ketone) to prepare a MEK solution having a concentration of 30% by mass.

2. Synthesis of polyimide resin (PI-2) using acid dianhydride having siloxane skeleton of formula (3) In the same apparatus as the synthesis of PI-1, acid dianhydride having siloxane skeleton 5,5′-exo- (1,1,3,3,5,5,7,7,9,9-decamethylpentasiloxane-1,5-diyl) bisbicyclo [2.2.1] heptane-exo-2,3-dicarboxylic acid 30.0 mmol of dianhydride, 30.0 mmol of 4,4′-hexafluoropropylidenebisphthalic acid dianhydride, 181 g of N-methyl-2-pyrrolidone, 26.25 mmol of 1,4-bisaminopropylpiperazine which is a diamine , 2,2-bis [4- (4-aminophenoxy) phenyl] hexafluoropropane 26.25 mmol and polyoxypropylenediamine 7.50 mmol were used. An NMP solution of a polyimide resin having a siloxane skeleton represented by the formula (1) (hereinafter referred to as “PI-2”) was obtained by the same procedure as PI-1. The NMP solution of PI-2 was poured into water, and the precipitate was collected. This precipitate was pulverized and dried to obtain solid PI-2. As a result of measurement by GPC, the weight average molecular weight of the obtained PI-2 was 44000 in terms of standard polystyrene. The glass transition temperature was 98 ° C. PI-2 was dissolved in MEK (methyl ethyl ketone) to prepare a MEK solution having a concentration of 30% by mass.

3. Synthesis of polyimide resin (PI-3) not using acid dianhydride having a siloxane skeleton In the same apparatus as the synthesis of PI-1, 4,2.0′-hexafluoropropylidenebisphthalic dianhydride, N-methyl-2-pyrrolidone (NMP) 100 g, diamine 1,4-bisaminopropylpiperazine 22.75 mmol, 2,2-bis [4- (4-aminophenoxy) phenyl] hexafluoropropane 22.75 mmol and An NMP solution of a polyimide resin not containing a siloxane skeleton (hereinafter referred to as “PI-3”) was obtained by the same procedure as PI-1 except that 6.5 mmol of polyoxypropylenediamine was used. An NMP solution of PI-3 was poured into water, and the precipitate was collected. This precipitate was pulverized and dried to obtain solid PI-3. As a result of measurement by GPC, the weight average molecular weight of the obtained PI-3 was 59000 in terms of standard polystyrene. The glass transition temperature was 196 ° C. PI-3 was dissolved in MEK (methyl ethyl ketone) to prepare a MEK solution having a concentration of 30% by mass.

4). Synthesis of polyimide resin (PI-4) having a siloxane skeleton different from that shown in formula (3) The same apparatus as the synthesis of PI-1 does not have the structure of general formula (1) but has a siloxane skeleton X-2-22290AS (trade name, manufactured by Shin-Etsu Chemical Co., Ltd.) 27.0 mmol which is an acid dianhydride, 27.0 mmol of 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, N-methyl-2- Using 120 g of pyrrolidone, 23.63 mmol of 1,4-bisaminopropylpiperazine as a diamine, 23.63 mmol of 2,2-bis [4- (4-aminophenoxy) phenyl] hexafluoropropane and 6.75 mmol of polyoxypropylenediamine The polyimide resin having a siloxane skeleton different from that shown in the formula (3) by the same procedure as PI-1. An NMP solution (hereinafter referred to as “PI-4”) was obtained. An NMP solution of PI-5 was poured into water, and the precipitate was collected. This precipitate was pulverized and dried to obtain solid PI-4. As a result of measurement by GPC, the weight average molecular weight of the obtained PI-4 was 53000 in terms of standard polystyrene. The glass transition temperature was 72 ° C. PI-4 was dissolved in MEK (methyl ethyl ketone) to prepare a MEK solution having a concentration of 30% by mass.

<Formulation of epoxy resin>
Further, a liquid curing agent containing a microcapsule type latent curing agent (a microencapsulated amine curing agent), a bisphenol F type epoxy resin, and a naphthalene type epoxy resin in a mass ratio of 34:49:17. A contained epoxy resin (epoxy equivalent: 202) was prepared.

<Synthesis of phenoxy resin>
A phenoxy resin was synthesized from a bisphenol A-type epoxy resin and a phenol compound having a fluorene ring structure in the molecule (4,4 ′-(9-fluorenylidene) -diphenyl), and this resin was combined with toluene / ethyl acetate = It melt | dissolved in the 50/50 mixed solvent, and was set as the solution of 40 mass% of solid content.

<Synthesis of acrylic rubber>
To a 2000 mL separable flask equipped with a reflux condenser, a thermometer, and a stirrer, 500 g of deionized water, 40 g of butyl acrylate, 30 g of ethyl acrylate, 30 g of acrylonitrile, and 3 g of glycidyl methacrylate were added and stirred for 1 hour at room temperature in a nitrogen stream. The mixture was heated to 70 ° C. and stirred as it was for 3 hours, further heated to 90 ° C. and stirred for 3 hours. The obtained solid was recovered, washed with water and dried to obtain acrylic rubber 2 having no piperazine skeleton. By dissolving in a mixed solvent of toluene / ethyl acetate = 50/50 by mass ratio, a solution of acrylic rubber 2 having a solid content of 15% by mass was obtained. The weight average molecular weight of the obtained acrylic rubber 2 was 800,000 as a result of measurement by GPC.

<Synthesis of urethane acrylate>
400 parts of polycaprolactone diol having a weight average molecular weight of 800, 131 parts of 2-hydroxypropyl acrylate, 0.5 parts of dibutyltin dilaurate as a catalyst, and 1.0 part of hydroquinone monomethyl ether as a polymerization inhibitor were heated to 50 ° C. with stirring. And mixed. Next, 222 parts of isophorone diisocyanate was added dropwise, and the mixture was further heated to 80 ° C. with stirring to conduct a urethanization reaction. After confirming that the reaction rate of the isocyanate group was 99% or more, the reaction temperature was lowered to obtain urethane acrylate having a weight average molecular weight of 8500.

<Preparation of conductive particles>
A layer made of nickel was provided on the surface of the polystyrene particles so as to have a thickness of 0.2 μm, and a layer made of gold was provided on the surface of the layer made of nickel so as to have a thickness of 0.04 μm. . Thus, conductive particles having an average particle diameter of 5 μm were produced.

<Examples and Comparative Examples>
Example 1
The said material was mix | blended in the ratio of polyimide resin PI-1 / acrylic rubber / hardening agent containing epoxy resin = 20g / 30g / 50g by solid content mass, and the adhesive composition containing liquid was produced. Conductive particles were dispersed by 3% by volume in this adhesive composition-containing liquid to prepare an adhesive composition-containing liquid.
And this adhesive composition containing liquid was apply | coated to the 50-micrometer-thick polyethylene terephthalate (PET) film which carried out the surface treatment (mold release process) on one side using a coating apparatus, and PET was carried out by hot-air drying for 70 degreeC for 3 minutes. A film adhesive composition (Example 1) having a thickness of 16 μm was obtained on the film.

(Example 2)
The said material was mix | blended in the ratio of polyimide resin PI-1 / phenoxy resin / acrylic rubber / curing agent containing epoxy resin = 10g / 20g / 20g / 50g by solid content mass, and the adhesive composition containing liquid was created. Otherwise in the same manner as in Example 1, a film adhesive composition (Example 2) was obtained.

(Example 3)
The above materials in terms of solid mass, polyimide resin PI-1 / urethane acrylate / phosphate ester acrylate / t-hexylperoxy 2-ethylhexanate (manufactured by NOF Corporation, trade name Percure HO) = 30 g / 70 g / 3g / 5g was blended to prepare an adhesive composition-containing liquid. Otherwise in the same manner as in Example 1, a film adhesive composition (Example 3) was obtained.

Example 4
The above-mentioned material in solid mass, polyimide resin PI-1 / phenoxy resin / urethane acrylate / phosphate ester acrylate / t-hexylperoxy 2-ethylhexanate = 15 g / 15 g / 70 g / 3 g / 5 g It mix | blended and the adhesive composition containing liquid was created. Otherwise in the same manner as in Example 1, a film adhesive composition (Example 4) was obtained.

(Example 5)
The above-mentioned materials are blended at a solid content mass of polyimide resin PI-1 / phenoxy resin / acrylic rubber / curing agent-containing epoxy resin = 0.5 g / 29.5 g / 20 g / 50 g, and an adhesive composition-containing liquid is prepared. Created. Otherwise in the same manner as in Example 1, a film adhesive composition (Example 5) was obtained.

(Example 6)
The above materials were blended at a ratio of solid content mass of polyimide resin PI-2 / phenoxy resin / acrylic rubber / curing agent-containing epoxy resin = 10 g / 20 g / 20 g / 50 g to prepare an adhesive composition-containing liquid. Otherwise in the same manner as in Example 1, a film adhesive composition (Example 5) was obtained.

(Comparative Example 1)
The said material was mix | blended in the ratio of polyimide resin PI-3 / acrylic rubber / hardening agent containing epoxy resin = 30g / 20g / 50g by solid content mass, and the adhesive composition containing liquid was created. Otherwise in the same manner as in Example 1, a film adhesive composition (Comparative Example 1) was obtained.

(Comparative Example 2)
The said material was mix | blended in the ratio of polyimide resin PI-4 / acrylic rubber / hardening agent containing epoxy resin = 30g / 20g / 50g by solid content mass, and the adhesive composition containing liquid was created. Otherwise in the same manner as in Example 1, a film adhesive composition (Comparative Example 2) was obtained.

<Evaluation of transferability>
The film adhesive compositions obtained in Examples 1 to 6 and Comparative Examples 1 and 2 were transferred to a circuit member using a thermocompression bonding apparatus (heating method: constant heat type, manufactured by Toray Engineering Co., Ltd.). The test was conducted under two heating and pressing conditions of 1 MPa at a temperature of 70 ° C. for 2 seconds and 1 MPa at a temperature of 80 ° C. for 5 seconds. As the circuit member, glass (thickness 1.1 mm, surface resistance 20Ω / □) on which a thin layer of indium oxide (ITO) having a thickness of 0.2 μm was formed was used. As a result, since all the films produced this time contained a polyimide resin having a piperazine skeleton, the film could be transferred without any problems under any conditions.

  The film-like adhesive compositions obtained in Examples 1 to 6 and Comparative Examples 1 and 2 were used at a temperature of 70 ° C. using a thermocompression bonding apparatus (heating method: constant heat type, manufactured by Toray Engineering Co., Ltd.). The film was transferred to glass (thickness 1.1 mm, surface resistance 20Ω / □) on which a thin layer of indium oxide (ITO) having a thickness of 0.2 μm was formed at 1 MPa for 2 seconds. A flexible circuit board having 500 copper circuits having a line width of 25 μm, a pitch of 50 μm, and a thickness of 18 μm is 3 MPa at a temperature of 190 ° C. using a thermocompression bonding apparatus (heating method: constant heat type, manufactured by Toray Engineering Co., Ltd.). And heating and pressurizing for 15 seconds. Thereby, the connection body (circuit connection structure) which connected the FPC board | substrate and ITO board | substrate with the hardened | cured material of the film adhesive composition over width 2mm was produced. Further, thermocompression bonding was performed at 160 ° C. and 1 MPa for 10 seconds using the same FPC and ITO glass.

<Measurement of connection resistance and adhesive strength>
The resistance value (connection resistance) between adjacent circuits of the obtained connection body was measured with a multimeter. The resistance value was shown as an average of 37 resistances between adjacent circuits. Next, the adhesive strength of this connection body was measured by a 90-degree peeling method according to JIS-Z0237 and evaluated. Here, Tensilon UTM-4 (peeling speed 50 mm / min, 25 ° C.) manufactured by Toyo Baldwin Co., Ltd. was used as a measuring device for adhesive strength.

  Further, the obtained connection body was left in a high-temperature and high-humidity test apparatus having a temperature of 85 ° C. and a relative humidity of 85% RH for 250 hours, and then connection resistance and adhesive strength were measured in the same manner as described above.

  The above results are shown in Tables 1 and 2.

  As is apparent from the results shown in Table 2, Examples 1 to 6 showed good values for both connection resistance and adhesive strength in both 3 MPa and 1 MPa connections. On the other hand, in Comparative Example 1 and Comparative Example 2 using the polyimide resin having no siloxane skeleton represented by the formula (3), the connection resistance was high when connected at 1 MPa. In addition, the connection resistance after the high-temperature and high-humidity test increased significantly in the 1 MPa connection in Comparative Example 1 and in the 3 MPa and 1 MPa connections in Comparative Example 2.

  DESCRIPTION OF SYMBOLS 5 ... Adhesive component, 7 ... Electroconductive particle, 8 ... Support base material, 10 ... Circuit connection member, 11 ... Insulating substance, 20 ... 1st circuit member, 21 ... Circuit board (1st circuit board), 21a ... main surface, 22 ... circuit electrode (first circuit electrode), 30 ... second circuit member, 31 ... circuit board (second circuit board), 31a ... main surface, 32 ... circuit electrode (second electrode) Circuit electrode), 40 ... film adhesive composition, 50a, 50b ... heating and pressing region, 100 ... adhesive sheet.

Claims (6)

  1. It contains a resin having a repeating unit represented by the following formula (1) and / or a repeating unit represented by the following formula (2), conductive particles, an epoxy resin, and a latent curing agent for the epoxy resin. , Adhesive composition.

    [In Formula (1), R shows the residue of diamine or diisocyanate, several R in the same molecule | numerator may be same or different, and m shows the integer of 1-30. ]

    [In Formula (2), R shows the residue of diamine or diisocyanate, several R in the same molecule | numerator may be same or different, and m shows the integer of 1-30. ]
  2. Curing that generates a free radical by heating, a resin having a repeating unit represented by the following formula (1) and / or a resin having a repeating unit represented by the following formula (2), conductive particles, a radical polymerizable substance, and An adhesive composition comprising an agent.

    [In Formula (1), R shows the residue of diamine or diisocyanate, several R in the same molecule | numerator may be same or different, and m shows the integer of 1-30. ]

    [In Formula (2), R shows the residue of diamine or diisocyanate, several R in the same molecule | numerator may be same or different, and m shows the integer of 1-30. ]
  3. It consists of a resin having a repeating unit represented by the following formula (1) and / or a repeating unit represented by the following formula (2), conductive particles, and other thermoplastic resins and rubber components other than the resin. An adhesive composition comprising at least one selected from the group.

    [In Formula (1), R shows the residue of diamine or diisocyanate, several R in the same molecule | numerator may be same or different, and m shows the integer of 1-30. ]

    [In Formula (2), R shows the residue of diamine or diisocyanate, several R in the same molecule | numerator may be same or different, and m shows the integer of 1-30. ]
  4. The repeating unit represented by the formula (1) and / or the repeating unit represented by the formula (2) is obtained from a tetracarboxylic dianhydride having a siloxane skeleton represented by the following general formula (3). The adhesive composition as described in any one of Claims 1-3 which is what is obtained.

    [In Formula (3), m shows the integer of 1-30. ]
  5. A pair of circuit members disposed opposite to each other, a connection member provided between the pair of circuit members, and bonding the circuit members to each other so that circuit electrodes of the pair of circuit members are electrically connected; A circuit connection structure, wherein the connection member is a cured product of the adhesive composition according to any one of claims 1 to 4 .
  6. The circuit connection structure according to claim 5 , wherein one of the pair of circuit members has a glass substrate and the other has a flexible substrate.
JP2012139896A 2011-08-30 2012-06-21 Adhesive composition and circuit connection structure Active JP6024235B2 (en)

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JPH05320172A (en) * 1990-12-13 1993-12-03 Tonen Corp Disiloxanetetracarboxylic dianhydride and its production
JP2740064B2 (en) * 1991-10-14 1998-04-15 住友ベークライト株式会社 Thermocompression possible film adhesive
JP2740590B2 (en) * 1991-11-01 1998-04-15 住友ベークライト株式会社 Thermally crimpable conductive adhesive film
TW340132B (en) * 1994-10-20 1998-09-11 Ibm Structure for use as an electrical interconnection means and process for preparing the same
JP2005347273A (en) * 2005-06-06 2005-12-15 Hitachi Chem Co Ltd Thermally cross-linking type circuit-connecting material and method for producing circuit board by using the same
US8524921B2 (en) * 2009-02-18 2013-09-03 Hitachi Chemical Co., Ltd. Liquid tetracarboxylic dianhydrides and process for the preparation thereof

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