WO2017037951A1 - Adhesive composition, anisotropically electroconductive adhesive composition, circuit connecting material, and connected object - Google Patents

Adhesive composition, anisotropically electroconductive adhesive composition, circuit connecting material, and connected object Download PDF

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Publication number
WO2017037951A1
WO2017037951A1 PCT/JP2015/075253 JP2015075253W WO2017037951A1 WO 2017037951 A1 WO2017037951 A1 WO 2017037951A1 JP 2015075253 W JP2015075253 W JP 2015075253W WO 2017037951 A1 WO2017037951 A1 WO 2017037951A1
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WIPO (PCT)
Prior art keywords
circuit
adhesive composition
meth
epoxy resin
adhesive
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PCT/JP2015/075253
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French (fr)
Japanese (ja)
Inventor
直 工藤
藤縄 貢
暁黎 杜
伊藤 彰浩
智樹 森尻
Original Assignee
日立化成株式会社
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Application filed by 日立化成株式会社 filed Critical 日立化成株式会社
Priority to PCT/JP2015/075253 priority Critical patent/WO2017037951A1/en
Priority to KR1020187008753A priority patent/KR102376223B1/en
Priority to CN201580082812.8A priority patent/CN107922817B/en
Priority to JP2017537184A priority patent/JP6631631B2/en
Publication of WO2017037951A1 publication Critical patent/WO2017037951A1/en

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    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09JADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J163/00Adhesives based on epoxy resins; Adhesives based on derivatives of epoxy resins
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09JADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J9/00Adhesives characterised by their physical nature or the effects produced, e.g. glue sticks
    • C09J9/02Electrically-conducting adhesives
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09JADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02Non-macromolecular additives
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09JADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J201/00Adhesives based on unspecified macromolecular compounds
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01BCABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/20Conductive material dispersed in non-conductive organic material
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01RELECTRICALLY-CONDUCTIVE CONNECTIONS; STRUCTURAL ASSOCIATIONS OF A PLURALITY OF MUTUALLY-INSULATED ELECTRICAL CONNECTING ELEMENTS; COUPLING DEVICES; CURRENT COLLECTORS
    • H01R11/00Individual connecting elements providing two or more spaced connecting locations for conductive members which are, or may be, thereby interconnected, e.g. end pieces for wires or cables supported by the wire or cable and having means for facilitating electrical connection to some other wire, terminal, or conductive member, blocks of binding posts
    • H01R11/01Individual connecting elements providing two or more spaced connecting locations for conductive members which are, or may be, thereby interconnected, e.g. end pieces for wires or cables supported by the wire or cable and having means for facilitating electrical connection to some other wire, terminal, or conductive member, blocks of binding posts characterised by the form or arrangement of the conductive interconnection between the connecting locations

Definitions

  • the present invention relates to an adhesive composition, an anisotropic conductive adhesive composition, a circuit connection material, and a connection body.
  • various adhesive compositions are conventionally used as a circuit connection material for the purpose of bonding various members in the element.
  • the adhesive composition is required to have various properties such as adhesiveness, heat resistance, reliability in a high temperature and high humidity state, and the like.
  • the adherends to be bonded are various surfaces formed from various materials such as printed wiring boards, organic materials such as polyimide films, metals such as copper and aluminum, and metal compounds such as ITO, SiN and SiO 2. Have Therefore, the adhesive composition is designed according to each adherend.
  • thermosetting resin composition containing a thermosetting resin such as an epoxy resin having high adhesion and high reliability is known (for example, Patent Document 1). reference).
  • Such an adhesive composition generally contains an epoxy resin, a curing agent such as a phenol resin that reacts with the epoxy resin, and a thermal latent catalyst that promotes the reaction between the epoxy resin and the curing agent.
  • the thermal latent catalyst is an important factor that determines the curing temperature and the curing rate. For this reason, various compounds are used as thermal latent catalysts from the viewpoint of storage stability at room temperature and curing rate during heating.
  • This adhesive composition is generally cured by heating at a temperature of 170 to 250 ° C. for 1 to 3 hours to exhibit a desired adhesive property.
  • radical curable adhesive containing a (meth) acrylate derivative and a peroxide has attracted attention (see, for example, Patent Document 2).
  • the radical curable adhesive is advantageous in terms of short-time curing because radicals which are reactive active species are rich in reactivity.
  • Patent Document 3 discloses a radical curable adhesive containing a (meth) acrylate compound having an epoxy group in the molecule.
  • thermosetting resin composition In order to achieve low temperature rapid curing of the adhesive composition, for example, in the above thermosetting resin composition, a thermal latent catalyst having a low activation energy may be used. It is very difficult to maintain storage stability.
  • radical curing type adhesives can achieve low temperature rapid curing relatively easily.
  • a connection body obtained using a radical curable adhesive is exposed to a high-temperature and high-humidity environment, the interface between the circuit member and the adhesive often peels off and bubbles are often generated.
  • the radical curable adhesive tends to cause large curing shrinkage as compared with an adhesive containing an epoxy resin.
  • Patent Document 3 discloses a radical curable adhesive containing a (meth) acrylate compound having an epoxy group in the molecule.
  • this adhesive for example, in connection conditions at a low temperature of 140 ° C.
  • the adhesiveness to the adherend was insufficient, and the generation of bubbles due to peeling of the interface between the circuit member and the adhesive could not be completely suppressed after the high temperature and high humidity test.
  • the present invention has been made in view of the above-mentioned problems of the prior art. Even though it is a radical curable adhesive, it can be used even at low temperature (for example, 140 ° C. or less) and for a short time (for example, 5 seconds or less). It is an object of the present invention to provide an adhesive composition that can maintain sufficient adhesive strength and connection reliability and can suppress peeling from an adherend under high temperature and high humidity conditions.
  • the present invention includes (a) a thermoplastic resin, (b) a radical polymerizable compound, (c) a radical polymerization initiator, and (d) an epoxy resin having no (meth) acryloyloxy group,
  • An adhesive composition substantially free from the cationic polymerization curing agent is provided. According to such an adhesive composition, sufficient adhesive strength and connection reliability are maintained even under low temperature (for example, 140 ° C. or less) and short time (for example, 5 seconds or less) connection conditions, and high temperature and high humidity conditions. It becomes possible to suppress peeling from the adherend.
  • the epoxy resin preferably has a biphenyl skeleton. By including an epoxy resin having such a skeleton, the above-described effects are further increased.
  • the adhesive composition of the present invention may further contain (e) conductive particles.
  • the adhesive composition can be imparted with conductivity or anisotropic conductivity, so that the adhesive composition can be more suitably used as a circuit connection material.
  • the connection resistance between the circuit electrodes electrically connected via the adhesive composition can be more easily reduced.
  • the present invention also includes (a) a thermoplastic resin, (b) a radically polymerizable compound, (c) a radical polymerization initiator, (d) an epoxy resin having no (meth) acryloyloxy group, and (e) a conductive material.
  • a thermoplastic resin e.g., polyethylene glycol dimethacrylate copolymer
  • a radical polymerization initiator e.g., a radical polymerization initiator
  • an epoxy resin having no (meth) acryloyloxy group e.
  • An anisotropic conductive adhesive composition containing particles and substantially free of an epoxy resin cationic polymerization curing agent is provided.
  • the epoxy resin preferably has a biphenyl skeleton.
  • the present invention also includes the above-described adhesive composition or anisotropic conductive adhesive composition, and circuit members having circuit electrodes are electrically connected to each other.
  • the circuit connection material used for bonding is provided.
  • the present invention also includes a first circuit member having a first circuit electrode formed on the main surface of the first circuit board, and a second circuit electrode formed on the main surface of the second circuit board.
  • a second circuit member disposed so that the second circuit electrode and the first circuit electrode face each other; and the first circuit member provided between the first circuit member and the second circuit member.
  • a connection member that electrically connects the second circuit member, and the connection member is a cured product of the adhesive composition or the anisotropic conductive adhesive composition of the present invention.
  • one of the first circuit board and the second circuit board is a glass substrate.
  • connection member that electrically connects the first circuit member and the second circuit member is a cured product of the adhesive composition or anisotropic conductive adhesive composition of the present invention. Therefore, sufficient adhesive strength and connection reliability are maintained, and peeling of the adhesive is sufficiently suppressed under high temperature and high humidity conditions.
  • the present invention although it is a radical curable adhesive, sufficient adhesive strength and connection reliability are maintained even at low temperature (for example, 140 ° C. or lower) and for a short time (for example, 5 seconds or shorter).
  • An adhesive composition capable of suppressing peeling from an adherend under high temperature and high humidity conditions can be provided.
  • (meth) acrylic acid means acrylic acid or methacrylic acid corresponding to it.
  • the adhesive composition according to this embodiment contains (a) a thermoplastic resin, (b) a radical polymerizable compound, (c) a radical polymerization initiator, and (d) an epoxy resin having no (meth) acryloyloxy group. To do.
  • the adhesive composition does not substantially contain an epoxy resin cationic polymerization curing agent.
  • the fact that the cation polymerization curing agent of the epoxy resin is not substantially contained means that the content of the cation polymerization curing agent of the epoxy resin is 1 with respect to 100 parts by mass of the total amount of the component (a) and the component (b). Although it is less than 5 parts by mass, it is preferably less than 1.0 part by mass, more preferably less than 0.5 part by mass, and it does not contain an epoxy resin cationic polymerization curing agent. preferable.
  • An epoxy resin cationic polymerization curing agent is a Bronsted acid, a Lewis acid, and a compound capable of generating these acids by energy such as heat and light.
  • Examples of the cationic polymerization curing agent for the epoxy resin include onium salts.
  • thermoplastic resin (a) examples include one or more selected from polyimide resin, polyamide resin, phenoxy resin, poly (meth) acrylic resin, polyester resin, polyurethane resin, polyester urethane resin, and polyvinyl butyral resin. These resins are mentioned.
  • the lower limit of the weight average molecular weight of the thermoplastic resin may be 5000 or more, or 10,000 or more. There exists a tendency for the adhesive strength of an adhesive composition to improve that the weight average molecular weight of a thermoplastic resin is 5000 or more.
  • the upper limit of the weight average molecular weight of the thermoplastic resin may be 400000 or less, 200000 or less, or 150,000 or less. If the weight average molecular weight of the thermoplastic resin is 400000 or less, good compatibility with other components tends to be easily obtained, and the fluidity of the adhesive tends to be easily obtained.
  • the weight average molecular weight of the thermoplastic resin is preferably from 5,000 to 400,000, more preferably from 5,000 to 200,000, particularly preferably from 10,000 to 150,000.
  • thermoplastic resin a rubber component can also be used for the purpose of stress relaxation and adhesion improvement.
  • the content of the thermoplastic resin is preferably 20 to 80 parts by mass, more preferably 30 to 70 parts by mass with respect to 100 parts by mass of the total amount of the components (a) and (b). More preferably, it is ⁇ 65 parts by mass. If the content of the thermoplastic resin is 20 parts by mass or more, the adhesive strength tends to be improved or the film formability of the adhesive composition tends to be improved, and if it is 80 parts by mass or less, the adhesive It tends to be easy to obtain fluidity.
  • the adhesive composition according to the present embodiment may contain any (b) radical polymerizable compound.
  • the radical polymerizable compound may be, for example, any of the monomer and oligomer of the compound described later, or may be a combination of both.
  • one or more polyfunctional (meth) acrylate compounds having two or more (meth) acryloyloxy groups are preferable.
  • examples of such (meth) acrylate compounds include epoxy (meth) acrylate, urethane (meth) acrylate, polyether (meth) acrylate, polyester (meth) acrylate, trimethylolpropane tri (meth) acrylate, and polyethylene glycol diester.
  • Polyalkylene glycol di (meth) acrylate such as (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, neopentyl glycol di (meth) acrylate, dipentaerythritol hexa (meth) Examples include acrylate, isocyanuric acid-modified bifunctional (meth) acrylate, and isocyanuric acid-modified trifunctional (meth) acrylate.
  • Examples of the epoxy (meth) acrylate include, for example, an epoxy (meth) acrylate obtained by adding (meth) acrylic acid to two glycidyl groups of bisphenol fluorenediglycidyl ether and ethylene glycol in two glycidyl groups of bisphenol fluorenediglycidyl ether. And / or the compound which introduce
  • the adhesive composition may contain a monofunctional (meth) acrylate compound as the (b) radical polymerizable compound for the purpose of controlling fluidity.
  • monofunctional (meth) acrylate compounds include pentaerythritol (meth) acrylate, 2-cyanoethyl (meth) acrylate, cyclohexyl (meth) acrylate, dicyclopentenyl (meth) acrylate, and dicyclopentenyloxyethyl (meth).
  • the adhesive composition contains a compound having a radical polymerizable functional group such as an allyl group, a maleimide group, and a vinyl group as the (b) radical polymerizable compound for the purpose of improving the crosslinking rate. Also good.
  • the adhesive composition preferably contains a radical polymerizable compound having a phosphate group as the (b) radical polymerizable compound for the purpose of improving the adhesive strength.
  • a radical polymerizable compound having a phosphate group as the (b) radical polymerizable compound for the purpose of improving the adhesive strength.
  • examples of the radically polymerizable compound having a phosphoric acid group include compounds represented by the following formula (1), (2) or (3).
  • R 5 represents a hydrogen atom or a methyl group
  • R 6 represents a (meth) acryloyloxy group
  • w and x each independently represents an integer of 1 to 8.
  • a plurality of R 5 , R 6 , w and x in the same molecule may be the same or different.
  • R 7 represents a (meth) acryloyloxy group
  • y and z each independently represents an integer of 1 to 8.
  • a plurality of R 7 , y and z in the same molecule may be the same or different.
  • R 8 represents a hydrogen atom or a methyl group
  • R 9 represents a (meth) acryloyloxy group
  • b and c each independently represent an integer of 1 to 8.
  • a plurality of R 8 and b in the same molecule may be the same or different.
  • radical polymerizable compound having a phosphoric acid group examples include acid phosphooxyethyl (meth) acrylate, acid phosphooxypropyl (meth) acrylate, acid phosphooxypolyoxyethylene glycol mono (meth) acrylate, and acid phosphooxypolyoxy.
  • Propylene glycol mono (meth) acrylate, 2,2'-di (meth) acryloyloxydiethyl phosphate, EO (ethylene oxide) modified di (meth) acrylate, phosphoric acid modified epoxy (meth) acrylate and vinyl phosphate Can be mentioned. These compounds can be used individually by 1 type or in combination of 2 or more types.
  • the content of the radically polymerizable compound having a phosphoric acid group is preferably 0.1 to 15 parts by mass with respect to 100 parts by mass of the total amount of the components (a) and (b), and 0.5 to 10 More preferably, it is more preferably 1 to 5 parts by mass. If the content of the radically polymerizable compound having a phosphoric acid group is 0.1 parts by mass or more, high adhesive strength tends to be obtained, and if it is 15 parts by mass or less, It is difficult to cause deterioration in physical properties, and the effect of improving reliability is good.
  • the total content of the (b) radical polymerizable compound contained in the adhesive composition is preferably 20 to 80 parts by mass with respect to 100 parts by mass of the total amount of the components (a) and (b). More preferably, it is ⁇ 70 parts by mass, and still more preferably 35-65 parts by mass. If the total content is 20 parts by mass or more, the heat resistance tends to be improved, and if it is 80 parts by mass or less, the effect of suppressing peeling after leaving in a high temperature and high humidity environment tends to increase.
  • the radical polymerization initiator can be arbitrarily selected from compounds such as peroxides and azo compounds. From the viewpoint 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 preferred. “1 minute half-life temperature” refers to a temperature at which the half-life of the peroxide is 1 minute. “Half-life” refers to the time taken for the concentration of a compound to decrease to half of its initial value at a given temperature.
  • radical polymerization initiator examples include 1,1,3,3-tetramethylbutylperoxyneodecanoate, di (4-tert-butylcyclohexyl) peroxydicarbonate, di (2-ethylhexyl) peroxydi Carbonate, cumylperoxyneodecanoate, 1,1,3,3-tetramethylbutylperoxyneodecanoate, dilauroyl peroxide, 1-cyclohexyl-1-methylethylperoxyneodecanoate, t- Hexyl peroxyneodecanoate, t-butyl peroxyneodecanoate, t-butyl peroxypivalate, 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate, 2,5 -Dimethyl-2,5-di (2-ethylhexanoylperoxy) hexane, t-hexyl
  • the content of the radical polymerization initiator is preferably 1 to 15 parts by mass and more preferably 2.5 to 10 parts by mass with respect to 100 parts by mass of the total amount of the components (a) and (b).
  • the amount is preferably 3 to 8 parts by mass.
  • Examples of the epoxy resin having no (meth) acryloyloxy group include 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, and bisphenol.
  • an aromatic polycyclic epoxy resin and an epoxy resin having a biphenyl skeleton are preferable, and an epoxy resin having a biphenyl skeleton is more preferable.
  • These can be used individually by 1 type or in combination of 2 or more types.
  • the lower limit of the molecular weight of the epoxy resin having no (meth) acryloyloxy group may be 250 or more, 300 or more, or 350 or more.
  • the upper limit of the molecular weight of the epoxy resin having no (meth) acryloyloxy group may be 5000 or less, 3000 or less, or 1000 or less.
  • the molecular weight of the epoxy resin having no (meth) acryloyloxy group is preferably 250 to 5000, more preferably 300 to 3000, and further preferably 350 to 1000.
  • the lower limit value of the epoxy equivalent of the epoxy resin having no (meth) acryloyloxy group may be 100 or more, 150 or more, or 180 or more. If the epoxy equivalent is 100 or more, the connection reliability of the adhesive composition tends to be further improved.
  • the upper limit of the epoxy equivalent of an epoxy resin having no (meth) acryloyloxy group may be 300 or less, 275 or less, or 270 or less. There exists a tendency for the adhesiveness with respect to glass to increase that an epoxy equivalent is 300 or less. From the above viewpoint, the epoxy equivalent of the epoxy resin having no (meth) acryloyloxy group is preferably 100 to 300, more preferably 150 to 275, and still more preferably 180 to 270.
  • the lower limit of the content of the epoxy resin having no (meth) acryloyloxy group may be 1 part by mass or more with respect to 100 parts by mass of the total amount of the components (a) and (b), and 2.5 masses. Or 3 parts by mass or more. If the content is 1 part by mass or more, the effect of the present invention tends to be easily obtained at a higher level.
  • the upper limit of the content of the epoxy resin having no (meth) acryloyloxy group may be 15 parts by mass or less with respect to 100 parts by mass of the total amount of the component (a) and the component (b), and 10 masses. Or less. When the content is 15 parts by mass or less, radical polymerization tends to be difficult to inhibit when used under low temperature and short time conditions.
  • the content of the epoxy resin having no (meth) acryloyloxy group is preferably 1 to 15 parts by mass with respect to 100 parts by mass as the total of the components (a) and (b). More preferably, it is 5 to 10 parts by mass, and further preferably 3 to 10 parts by mass.
  • the adhesive composition according to this embodiment may contain a silane coupling agent.
  • the silane coupling agent is preferably a compound represented by the following formula (4).
  • R 1 , R 2 and R 3 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 is shown. At least one of R 1 , R 2 and R 3 is an alkoxy group.
  • R 4 is a (meth) acryloyl group, a (meth) acryloyloxy group, a vinyl group, an isocyanate group, an imidazole group, a mercapto group, an amino group optionally substituted with an aminoalkyl group, a methylamino group, a dimethylamino group, A benzylamino group, a phenylamino group, a cyclohexylamino group, a morpholino group, a piperazino group, a ureido group, a glycidyl group or a glycidoxy group; a represents an integer of 0 to 10.
  • silane coupling agent of the formula (4) examples include vinyltrimethoxysilane, vinyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3- (meth) Acryloxypropylmethyldimethoxysilane, 3- (meth) acryloxypropyltrimethoxysilane, 3- (meth) acryloxypropylmethyldiethoxysilane, 3- (meth) acryloxypropyltriethoxysilane, N-2- (amino Ethyl) -3-aminopropylmethyldimethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, 3-mercaptopropyltrimethoxysilane and 3-isocyanatopropyltriethoxysilane. That. These compounds can be used individually by 1 type or in combination of
  • the content of the silane coupling agent is preferably 0.1 to 10 parts by mass and preferably 0.25 to 5 parts by mass with respect to 100 parts by mass of the total amount of the components (a) and (b). Is more preferable. If the content of the silane coupling agent is 0.1 parts by mass or more, the effect of suppressing the separation of the interface between the circuit member and the circuit connecting material and the generation of bubbles tends to increase. When the content is 10 parts by mass or less, the pot life of the adhesive composition tends to be long.
  • a silane coupling agent has radically polymerizable functional groups, such as an acryloyl group (acryloyloxy group), it shall be contained in (b) component as a radically polymerizable compound.
  • the adhesive composition according to this embodiment may further contain (e) conductive particles.
  • the adhesive composition containing conductive particles can be particularly suitably used as an anisotropic conductive adhesive composition.
  • the conductive particles include metal particles such as Au, Ag, Pd, Ni, Cu, and solder, and carbon particles.
  • the conductive particles are composite particles having core particles made of a non-conductive material such as glass, ceramic, and plastic, and conductive layers such as metal, metal particles, and carbon that coat the core particles. May be.
  • the metal particles may be copper particles and particles having a silver layer covering the copper particles.
  • the core particle of the composite particle is preferably a plastic particle.
  • the composite particles having the plastic particles as the core particles have a deformability that is deformed by heating and pressurization. Therefore, when the circuit members are bonded to each other, the contact area between the circuit electrodes of the circuit members and the conductive particles Can be increased. Therefore, according to the adhesive composition containing these composite particles as conductive particles, a connection body that is more excellent in terms of connection reliability can be obtained.
  • the adhesive composition may contain insulating coated conductive particles having the conductive particles and an insulating layer or insulating particles covering at least a part of the surface of the conductive particles.
  • the insulating layer can be provided by a method such as hybridization.
  • the insulating layer or the insulating particles are formed from an insulating material such as a polymer resin.
  • the average particle diameter of the conductive particles is preferably 1 to 18 ⁇ m from the viewpoint of obtaining good dispersibility and conductivity.
  • the content of the conductive particles is preferably 0.1 to 30% by volume, more preferably 0.1 to 10% by volume, based on the total volume of the adhesive composition, and 0.5 to More preferably, it is 7.5 volume%. If content of electroconductive particle is 0.1 volume% or more, there exists a tendency for electroconductivity to improve. There exists a tendency for it to become difficult to produce the short circuit between circuit electrodes as content of electroconductive particle is 30 volume% or less. Content (volume%) of electroconductive particle is determined based on the volume in 23 degreeC of each component which comprises the adhesive composition before hardening. The volume of each component can be determined by converting mass to volume using specific gravity. 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. The increased volume can be obtained as the volume of the component.
  • an appropriate solvent water, alcohol, etc.
  • the adhesive composition may contain insulating organic or inorganic fine particles in addition to the conductive particles.
  • the inorganic fine particles include metal fine particles such as silica fine particles, alumina fine particles, silica-alumina fine particles, titania fine particles, zirconia fine particles, and nitride fine particles.
  • 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 fine particles may have a uniform structure or a core-shell type structure.
  • the content of the organic fine particles and the inorganic fine particles is preferably 5 to 30 parts by mass, and preferably 7.5 to 20 parts by mass with respect to 100 parts by mass of the total amount of the components (a) and (b). More preferred. If the content of the organic fine particles and the inorganic fine particles is 5 parts by mass or more, it tends to be relatively easy to maintain the electrical connection between the opposing electrodes, and if it is 30 parts by mass or less, the adhesive composition There is a tendency for the fluidity of things to improve.
  • the adhesive composition may contain various additives.
  • the adhesive composition according to the present embodiment can be used as a paste adhesive when it is liquid at normal temperature (25 ° C.). When the adhesive composition is solid at normal temperature, it may be used by heating, or it may be used by pasting it by adding a solvent.
  • the solvent used for pasting is not particularly limited as long as it has substantially no reactivity with the adhesive composition (including additives) and can sufficiently dissolve the adhesive composition. Not.
  • the adhesive composition according to the present embodiment can be formed into a film and used as a film adhesive.
  • a film adhesive is obtained by applying a solution obtained by adding a solvent or the like to an adhesive composition as necessary on a peelable support such as a fluororesin film, a polyethylene terephthalate film, or a release paper. It can be obtained by a method of removing a solvent or the like.
  • a film adhesive is more convenient in terms of handling and the like.
  • FIG. 1 is a schematic cross-sectional view showing an embodiment of a film adhesive comprising the adhesive composition according to the present embodiment.
  • a laminated film 100 shown in FIG. 1 includes a support 8 and a film adhesive 40 laminated on the support 8 in a peelable manner.
  • the film adhesive 40 is composed of an insulating adhesive layer 5 and conductive particles 7 dispersed in the insulating adhesive layer 5.
  • the insulating adhesive layer 5 is comprised from components other than electroconductive particle among the above-mentioned adhesive compositions. According to this film adhesive, it is easy to handle, can be easily installed on the adherend, and can be easily connected.
  • the film adhesive may have a multilayer structure composed of two or more layers. When the film adhesive contains conductive particles, the film adhesive can be suitably used as an anisotropic conductive film.
  • the adherends can usually be bonded together 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 to 120 seconds.
  • the adherends are sufficiently bonded to each other even when heated and pressed for a short time of 5 seconds under conditions of 140 ° C. and 1 MPa. It is possible.
  • the adhesive composition and film adhesive according to this embodiment can be used as an adhesive for different types of adherends having different thermal expansion coefficients.
  • the adhesive composition and the film-like adhesive according to the present embodiment include an anisotropic conductive adhesive, a circuit connecting material such as a silver paste and a silver film, an elastomer for CSP, an underfill material for CSP, It can be used as a semiconductor element adhesive material such as LOC tape.
  • the circuit connection material according to the present embodiment contains the above-described adhesive composition or anisotropic conductive adhesive composition.
  • Such a circuit connection material can be used for bonding circuit members having circuit electrodes so that the circuit electrodes of the respective circuit members are electrically connected to each other.
  • connection body using the film adhesive according to the present embodiment as an anisotropic conductive film, connecting circuit members having circuit electrodes formed on the main surface of the circuit board and the circuit board as adherends, An example of manufacturing the connection body will be described.
  • FIG. 2 is a schematic cross-sectional view showing an embodiment of a connection body including a connection member made of a cured product of the adhesive composition according to this embodiment.
  • the connection body 1 shown in FIG. 2 includes a first circuit member 20 and a second circuit member 30 that are arranged to face each other.
  • a connecting member 10 is provided between the first circuit member 20 and the second circuit member 30 to bond and connect 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 first circuit board 21.
  • An insulating layer may be formed on the main surface 21 a of the first circuit board 21.
  • 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.
  • An insulating layer may also be formed on the main surface 31 a of the second circuit board 31.
  • the first circuit member 20 and the second circuit member 30 are not particularly limited as long as they have circuit electrodes that require electrical connection.
  • a substrate made of an inorganic material such as a semiconductor, glass or ceramic
  • a substrate made of an organic material such as polyimide or polycarbonate
  • an inorganic material such as glass / epoxy
  • an organic material such as polyimide or polycarbonate
  • an inorganic material such as glass / epoxy
  • an organic material are used.
  • the first circuit board 21 may be a glass substrate
  • the second circuit board 31 may be a flexible substrate (preferably a resin film such as a polyimide film).
  • circuit members to be connected include glass or plastic substrates, printed wiring boards, ceramic wiring boards, flexible wiring boards on which electrodes such as ITO (indium tin oxide) films are formed, which are used in liquid crystal displays. And a semiconductor silicon chip. These are used in combination as necessary.
  • a member having a surface formed from an organic material such as a printed wiring board and a polyimide film
  • a metal such as copper or aluminum, ITO, silicon nitride
  • connection body obtained by connecting them is a solar cell, It is a solar cell module provided with a tab wire and a connecting member (cured product of the adhesive composition) for bonding them.
  • the connecting member 10 is made of a cured product of the adhesive composition according to the present embodiment.
  • the connecting member 10 contains an insulating layer 11 and conductive particles 7 dispersed in the insulating layer 11.
  • the electroconductive particle 7 is arrange
  • the connection member does not contain conductive particles, the first circuit electrode 22 and the second circuit electrode 32 come into contact with each other to be electrically connected.
  • connection member 10 is formed of a cured product of the adhesive composition according to this embodiment, the bonding strength of the connection member 10 to the first circuit member 20 and the second circuit member 30 is sufficiently high. Therefore, even after a reliability test (high temperature and high humidity test), it is possible to sufficiently suppress a decrease in adhesive strength and an increase in connection resistance.
  • connection body 1 includes, for example, a step of disposing a pair of circuit members having circuit electrodes disposed opposite to each other with a film adhesive made of an adhesive composition interposed therebetween, a pair of circuit members, and a film adhesive A step of bonding a pair of circuit members via a cured product of the adhesive composition (main connection step) by heating and curing the agent while pressing in the thickness direction of the film adhesive. Can be manufactured.
  • FIG. 3 is a process diagram showing a schematic cross-sectional view of one embodiment for producing a connection body using the adhesive composition according to the present embodiment.
  • the film adhesive 40 is placed on the main surface of the first circuit member 20 on the first circuit electrode 22 side.
  • the laminate of the film adhesive and the support is a circuit member in such a direction that the film adhesive 40 is positioned on the first circuit member 20 side. It is put on.
  • the film adhesive 40 is easy to handle because it is in the form of a film. For this reason, the film adhesive 40 can be easily interposed between the first circuit member 20 and the second circuit member 30, and the connection between the first circuit member 20 and the second circuit member 30 is possible. Work can be done easily.
  • the film adhesive 40 is the above-described adhesive composition (circuit connection material) formed in a film shape, and includes the conductive particles 7 and the insulating adhesive layer 5. Even when the adhesive composition does not contain conductive particles, it can be used as a circuit connection material for electrical connection by directly connecting the circuit electrodes.
  • the circuit connection material that does not contain conductive particles is sometimes called NCF (Non-Conductive-FILM) or NCP (Non-Conductive-Paste).
  • NCF Non-Conductive-FILM
  • NCP Non-Conductive-Paste
  • ACF isotropic Conductive FILM
  • ACP Analogenotropic Conductive Paste
  • the thickness of the film adhesive 40 is preferably 10 to 50 ⁇ m. If the thickness of the film adhesive 40 is 10 ⁇ m or more, the space between the first circuit electrode 22 and the second circuit electrode 32 tends to be easily filled with the adhesive. If the thickness of the film adhesive is 50 ⁇ m or less, the adhesive composition between the first circuit electrode 22 and the second circuit electrode 32 can be sufficiently eliminated, and the first circuit electrode 22 and the second circuit electrode The conduction between the two circuit electrodes 32 can be easily ensured.
  • the film adhesive 40 is temporarily connected to the first circuit member 20 (FIG. 3). (See (b) of). At this time, you may pressurize, heating. However, the heating temperature is set to a temperature sufficiently lower than the temperature at which the adhesive composition in the film adhesive 40 is not cured, that is, the temperature at which the radical polymerization initiator rapidly generates radicals.
  • the second circuit member 30 is placed on the film adhesive 40 in such a direction that the second circuit electrode is positioned on the first circuit member 20 side.
  • the second circuit member 30 is placed on the film adhesive 40 after the support is peeled off.
  • the film adhesive 40 is heated while applying pressures A and B in the thickness direction.
  • the heating temperature at this time is set to a temperature at which the radical polymerization initiator sufficiently generates radicals.
  • radicals are generated from the radical polymerization initiator, and polymerization of the radical polymerizable compound is started.
  • the connection shown in FIG. 2 is obtained by this connection.
  • the insulating adhesive is cured to form the insulating layer 11 in a state where the distance between the first circuit electrode 22 and the second circuit electrode 32 is sufficiently small. .
  • the first circuit member 20 and the second circuit member 30 are firmly connected via the connection member 10 including the insulating layer 11.
  • connection is preferably performed under the conditions of a heating temperature of 100 to 250 ° C., a pressure of 0.1 to 10 MPa, and a pressurization time of 0.5 to 120 seconds. These conditions are appropriately selected depending on the intended use, the adhesive composition, and the circuit member. According to the adhesive composition according to this embodiment, a connection body having sufficient reliability can be obtained even under a low temperature condition such as 140 ° C. or lower. After the connection, post-curing may be performed as necessary.
  • the reaction was continued for 15 hours after completion of the dropping, and when the NCO content was confirmed to be 0.2% by mass using an automatic potentiometric titrator (trade name AT-510, manufactured by Kyoto Electronics Industry Co., Ltd.) And urethane acrylate was obtained.
  • an automatic potentiometric titrator trade name AT-510, manufactured by Kyoto Electronics Industry Co., Ltd.
  • urethane acrylate was obtained.
  • the weight average molecular weight of urethane acrylate was 8500 (standard polystyrene conversion value).
  • the analysis by GPC was performed under the same conditions as the analysis of the weight average molecular weight of the polyurethane resin described above.
  • the reaction solution was returned to room temperature, and 300 parts by mass of benzene was added to dissolve the product. Subsequently, an aqueous sodium carbonate solution and distilled water were added thereto in this order, and the solution was washed three times. Thereafter, benzene was sufficiently distilled off to obtain a crude product.
  • a crude product was analyzed by liquid phase chromatography, in addition to the acrylate compound having one epoxy group as the target compound, a bifunctional acrylate compound having no epoxy group and the raw material bisphenol F type epoxy resin were crude products. It was found to be included. Therefore, the crude product was purified to obtain acrylate compound A having an epoxy group and an acryloyloxy group one by one and a bisphenol F type basic skeleton.
  • a flexible circuit board having 2200 copper circuits having a line width of 75 ⁇ m, a pitch of 150 ⁇ m and a thickness of 18 ⁇ m, a glass substrate and a thickness of 0 formed on the glass substrate
  • An ITO substrate (thickness 1.1 mm, surface resistance 20 ⁇ / ⁇ ) having a thin layer of 2 ⁇ m indium oxide (ITO) was connected.
  • the connection was made by heating and pressurizing at 140 ° C. and 1 MPa for 5 seconds using a thermocompression bonding apparatus (heating method: constant heat type, manufactured by Toray Engineering Co., Ltd.).
  • a connection body in which the FPC and the ITO substrate were connected by a cured product of a film adhesive over a width of 1.5 mm was produced.
  • a SiN substrate (thickness 0.7 mm) having a glass substrate and a thin layer of 0.2 ⁇ m silicon nitride (SiN) formed on the glass substrate is used at 140 ° C. and 3 MPa.
  • a connection body between the FPC and the SiN substrate was produced by heating and pressurizing for 5 seconds.
  • connection resistance connection resistance
  • adhesive strength was measured by a 90-degree peeling method according to JIS-Z0237.
  • Tensilon UTM-4 manufactured by Toyo Baldwin Co., Ltd., trade name, peel strength 50 mm / min, 25 ° C. was used as an adhesive strength measuring device.
  • the connection resistance and the adhesive strength were measured for the connection body immediately after the connection and after being kept in a constant temperature and humidity chamber at 85 ° C. and 85% RH for 250 hours. The evaluation results are shown in Table 3.
  • connection resistance 5 ⁇ or less
  • adhesive strength 8 N / cm
  • Comparative Example 1 containing no epoxy resin and Comparative Example 2 containing 1 part by mass or more of the cationic polymerization curing agent of epoxy resin, the adhesive strength after the high-temperature and high-humidity test is sufficient as compared with each Example. Furthermore, when a SiN substrate was used, the occurrence of peeling was observed after the high-temperature and high-humidity test, and practical problems were also observed in the connection appearance.
  • SYMBOLS 1 Connection body, 5 ... Insulating adhesive layer, 7 ... Conductive particle, 8 ... Support body, 10 ... Connection member, 11 ... Insulating layer, 20 ... First circuit member, 21 ... First circuit board, 21a ... main surface, 22 ... first circuit electrode, 30 ... second circuit member, 31 ... second circuit board, 31a ... main surface, 32 ... second circuit electrode, 40 ... film adhesive, 100 ... Laminated film.

Abstract

The present invention relates to an adhesive composition which comprises (a) a thermoplastic resin, (b) a radical-polymerizable compound, (c) a free-radical polymerization initiator, and (d) an epoxy resin containing no (meth)acryloyloxy group and which contains substantially no cationic polymerization hardener for the epoxy resin.

Description

接着剤組成物、異方導電性接着剤組成物、回路接続材料及び接続体Adhesive composition, anisotropic conductive adhesive composition, circuit connection material and connector
 本発明は、接着剤組成物、異方導電性接着剤組成物、回路接続材料及び接続体に関する。 The present invention relates to an adhesive composition, an anisotropic conductive adhesive composition, a circuit connection material, and a connection body.
 半導体素子又は液晶表示素子において、素子中の種々の部材を結合させる目的で従来から種々の接着剤組成物が回路接続材料として使用されている。この接着剤組成物には、接着性をはじめとして、耐熱性、高温高湿状態における信頼性等の多様な特性が要求される。 In a semiconductor element or a liquid crystal display element, various adhesive compositions are conventionally used as a circuit connection material for the purpose of bonding various members in the element. The adhesive composition is required to have various properties such as adhesiveness, heat resistance, reliability in a high temperature and high humidity state, and the like.
 接着される被着体は、プリント配線板、ポリイミドフィルム等の有機材料、銅、アルミニウム等の金属、ITO、SiN、SiO等の金属化合物のように、種々の材料から形成された多様な表面を有する。そのため、接着剤組成物は、各被着体に合わせて設計される。 The adherends to be bonded are various surfaces formed from various materials such as printed wiring boards, organic materials such as polyimide films, metals such as copper and aluminum, and metal compounds such as ITO, SiN and SiO 2. Have Therefore, the adhesive composition is designed according to each adherend.
 半導体素子又は液晶表示素子用の接着剤組成物として、高接着性且つ高信頼性を示すエポキシ樹脂等の熱硬化性樹脂を含む熱硬化性樹脂組成物が知られている(例えば、特許文献1参照)。かかる接着剤組成物は、一般に、エポキシ樹脂、エポキシ樹脂と反応するフェノール樹脂等の硬化剤、及びエポキシ樹脂と硬化剤との反応を促進する熱潜在性触媒を含有する。このうち、熱潜在性触媒は、硬化温度及び硬化速度を決定する重要な因子である。そのため、熱潜在性触媒として、室温での貯蔵安定性、及び加熱時の硬化速度の観点から種々の化合物が用いられている。この接着剤組成物は、一般に170~250℃の温度で1~3時間加熱することにより硬化して所望の接着性を発揮する。 As an adhesive composition for a semiconductor element or a liquid crystal display element, a thermosetting resin composition containing a thermosetting resin such as an epoxy resin having high adhesion and high reliability is known (for example, Patent Document 1). reference). Such an adhesive composition generally contains an epoxy resin, a curing agent such as a phenol resin that reacts with the epoxy resin, and a thermal latent catalyst that promotes the reaction between the epoxy resin and the curing agent. Among these, the thermal latent catalyst is an important factor that determines the curing temperature and the curing rate. For this reason, various compounds are used as thermal latent catalysts from the viewpoint of storage stability at room temperature and curing rate during heating. This adhesive composition is generally cured by heating at a temperature of 170 to 250 ° C. for 1 to 3 hours to exhibit a desired adhesive property.
 また、(メタ)アクリレート誘導体と過酸化物とを含む、ラジカル硬化型接着剤が注目されている(例えば、特許文献2参照)。ラジカル硬化型接着剤は、反応活性種であるラジカルが反応性に富むため、短時間硬化の点で有利である。 Also, a radical curable adhesive containing a (meth) acrylate derivative and a peroxide has attracted attention (see, for example, Patent Document 2). The radical curable adhesive is advantageous in terms of short-time curing because radicals which are reactive active species are rich in reactivity.
 また、特許文献3には、分子内にエポキシ基を有する(メタ)アクリレート化合物を含有するラジカル硬化型接着剤が開示されている。 Patent Document 3 discloses a radical curable adhesive containing a (meth) acrylate compound having an epoxy group in the molecule.
特開平1-113480号公報Japanese Patent Laid-Open No. 1-113480 国際公開第98/44067号International Publication No. 98/44067 国際公開第2013/035164号International Publication No. 2013/035164
 最近の半導体素子の高集積化及び液晶素子の高精細化に伴い、素子間及び配線間ピッチが狭小化しており、回路接続のための硬化時の加熱が、周辺部材に悪影響を及ぼす可能性が高くなってきている。 With the recent high integration of semiconductor elements and high definition of liquid crystal elements, the pitch between elements and wirings is becoming narrower, and heating during curing for circuit connection may adversely affect peripheral members. It's getting higher.
 さらに、低コスト化のためには、スループットを向上させる必要性があり、より低温且つ短時間で硬化する接着剤組成物、換言すれば、「低温速硬化」の接着剤組成物の開発が要求されている。 Furthermore, in order to reduce costs, it is necessary to improve throughput, and it is necessary to develop an adhesive composition that cures at a lower temperature and in a shorter time, in other words, an adhesive composition that is "low temperature fast cure". Has been.
 接着剤組成物の低温速硬化を達成するために、例えば、上記熱硬化性樹脂組成物において、活性化エネルギーの低い熱潜在性触媒が使用されることもあるが、この場合、室温付近での貯蔵安定性を維持することが非常に難しい。 In order to achieve low temperature rapid curing of the adhesive composition, for example, in the above thermosetting resin composition, a thermal latent catalyst having a low activation energy may be used. It is very difficult to maintain storage stability.
 これに対しラジカル硬化型接着剤は、比較的容易に低温速硬化を達成することができる。しかし、ラジカル硬化型接着剤を用いて得た接続体は、高温高湿環境に曝されると、回路部材と接着剤との界面が剥離して、気泡が生じてしまうことが多い。その原因の一つとして、ラジカル硬化型接着剤が、エポキシ樹脂を含む接着剤と比較して大きな硬化収縮を生じる傾向があることが考えられる。 In contrast, radical curing type adhesives can achieve low temperature rapid curing relatively easily. However, when a connection body obtained using a radical curable adhesive is exposed to a high-temperature and high-humidity environment, the interface between the circuit member and the adhesive often peels off and bubbles are often generated. As one of the causes, it is conceivable that the radical curable adhesive tends to cause large curing shrinkage as compared with an adhesive containing an epoxy resin.
 上記ラジカル硬化型接着剤において、(メタ)アクリレート誘導体の配合量を少なくすると、回路部材と接着剤との界面の剥離をある程度抑制することができる。しかしこの場合、接着強度及び接続信頼性が低下する傾向がある。さらに、低圧条件での回路接続は、特に薄い回路部材を接続するときに、回路部材の破損を防止するために必要とされるが、例えば、1MPaのような低圧条件で回路接続を行う場合、対向する電極間の樹脂が充分に排除され難いために、従来のラジカル硬化型接着剤では満足な電気的接続が得られないことがある。 In the above radical curable adhesive, if the amount of the (meth) acrylate derivative is reduced, peeling of the interface between the circuit member and the adhesive can be suppressed to some extent. However, in this case, the adhesive strength and connection reliability tend to decrease. Furthermore, circuit connection under low pressure conditions is necessary to prevent damage to circuit members, particularly when connecting thin circuit members. For example, when circuit connection is performed under low pressure conditions such as 1 MPa, Since the resin between the electrodes facing each other is not sufficiently removed, a conventional radical curable adhesive may not provide a satisfactory electrical connection.
 一方、エポキシ樹脂とラジカル重合性化合物とを併用すると、ラジカル重合が阻害されるため、短時間硬化が困難となる。 On the other hand, when an epoxy resin and a radically polymerizable compound are used in combination, radical polymerization is inhibited, so that it is difficult to cure for a short time.
 特許文献3では、分子内にエポキシ基を有する(メタ)アクリレート化合物を含有するラジカル硬化型接着剤が開示されているが、この接着剤をもってしても、例えば140℃といった低温での接続条件においては、被着体に対する密着性が不充分となり、高温高湿試験後において回路部材と接着剤との界面の剥離による気泡の発生を完全に抑制することができなかった。 Patent Document 3 discloses a radical curable adhesive containing a (meth) acrylate compound having an epoxy group in the molecule. However, even with this adhesive, for example, in connection conditions at a low temperature of 140 ° C. The adhesiveness to the adherend was insufficient, and the generation of bubbles due to peeling of the interface between the circuit member and the adhesive could not be completely suppressed after the high temperature and high humidity test.
 本発明は、上記従来技術の有する課題に鑑みてなされたものであり、ラジカル硬化型接着剤でありながら、低温(例えば、140℃以下)且つ短時間(例えば、5秒以下)の接続条件でも充分な接着強度及び接続信頼性を維持し、しかも高温高湿条件において被着体との剥離を抑制することが可能な接着剤組成物を提供することを目的とする。 The present invention has been made in view of the above-mentioned problems of the prior art. Even though it is a radical curable adhesive, it can be used even at low temperature (for example, 140 ° C. or less) and for a short time (for example, 5 seconds or less). It is an object of the present invention to provide an adhesive composition that can maintain sufficient adhesive strength and connection reliability and can suppress peeling from an adherend under high temperature and high humidity conditions.
 本発明は、(a)熱可塑性樹脂、(b)ラジカル重合性化合物、(c)ラジカル重合開始剤、及び、(d)(メタ)アクリロイルオキシ基を有しないエポキシ樹脂、を含有し、エポキシ樹脂のカチオン重合硬化剤を実質的に含有しない、接着剤組成物を提供する。このような接着剤組成物によれば、低温(例えば、140℃以下)且つ短時間(例えば、5秒以下)の接続条件でも充分な接着強度及び接続信頼性を維持し、しかも高温高湿条件において被着体との剥離を抑制することが可能となる。 The present invention includes (a) a thermoplastic resin, (b) a radical polymerizable compound, (c) a radical polymerization initiator, and (d) an epoxy resin having no (meth) acryloyloxy group, An adhesive composition substantially free from the cationic polymerization curing agent is provided. According to such an adhesive composition, sufficient adhesive strength and connection reliability are maintained even under low temperature (for example, 140 ° C. or less) and short time (for example, 5 seconds or less) connection conditions, and high temperature and high humidity conditions. It becomes possible to suppress peeling from the adherend.
 エポキシ樹脂はビフェニル骨格を有することが好ましい。このような骨格を有するエポキシ樹脂を含有することにより、上述した効果がより大きくなる。 The epoxy resin preferably has a biphenyl skeleton. By including an epoxy resin having such a skeleton, the above-described effects are further increased.
 本発明の接着剤組成物は、(e)導電性粒子を更に含有していてもよい。導電性粒子を更に含有することにより、接着剤組成物に導電性又は異方導電性を付与することができるため、接着剤組成物を回路接続材料としてより好適に使用することができる。また、当該接着剤組成物を介して電気的に接続した回路電極間の接続抵抗を、より容易に低減することができる。 The adhesive composition of the present invention may further contain (e) conductive particles. By further containing conductive particles, the adhesive composition can be imparted with conductivity or anisotropic conductivity, so that the adhesive composition can be more suitably used as a circuit connection material. Moreover, the connection resistance between the circuit electrodes electrically connected via the adhesive composition can be more easily reduced.
 本発明はまた、(a)熱可塑性樹脂、(b)ラジカル重合性化合物、(c)ラジカル重合開始剤、(d)(メタ)アクリロイルオキシ基を有しないエポキシ樹脂、及び、(e)導電性粒子、を含有し、エポキシ樹脂のカチオン重合硬化剤を実質的に含有しない、異方導電性接着剤組成物を提供する。ここで、上記エポキシ樹脂は、ビフェニル骨格を有することが好ましい。 The present invention also includes (a) a thermoplastic resin, (b) a radically polymerizable compound, (c) a radical polymerization initiator, (d) an epoxy resin having no (meth) acryloyloxy group, and (e) a conductive material. An anisotropic conductive adhesive composition containing particles and substantially free of an epoxy resin cationic polymerization curing agent is provided. Here, the epoxy resin preferably has a biphenyl skeleton.
 本発明はまた、上述した接着剤組成物、又は異方導電性接着剤組成物を含有し、回路電極を有する回路部材同士を、それぞれの回路部材が有する回路電極同士が電気的に接続されるように接着するために用いられる回路接続材料を提供する。 The present invention also includes the above-described adhesive composition or anisotropic conductive adhesive composition, and circuit members having circuit electrodes are electrically connected to each other. The circuit connection material used for bonding is provided.
 本発明はまた、第一の回路基板の主面上に第一の回路電極が形成された第一の回路部材と、第二の回路基板の主面上に第二の回路電極が形成され、第二の回路電極と第一の回路電極とが対向するように配置された第二の回路部材と、第一の回路部材と第二の回路部材との間に設けられ、第一の回路部材と第二の回路部材とを電気的に接続する接続部材と、を備え、当該接続部材が、本発明の接着剤組成物又は異方導電性接着剤組成物の硬化物である、接続体を提供する。また、ここで、上記第一の回路基板及び第二の回路基板のうちの一方がガラス基板であることが好ましい。 The present invention also includes a first circuit member having a first circuit electrode formed on the main surface of the first circuit board, and a second circuit electrode formed on the main surface of the second circuit board. A second circuit member disposed so that the second circuit electrode and the first circuit electrode face each other; and the first circuit member provided between the first circuit member and the second circuit member. And a connection member that electrically connects the second circuit member, and the connection member is a cured product of the adhesive composition or the anisotropic conductive adhesive composition of the present invention. provide. Here, it is preferable that one of the first circuit board and the second circuit board is a glass substrate.
 本発明に係る接続体は、第一の回路部材と第二の回路部材とを電気的に接続する接続部材が、上記本発明の接着剤組成物又は異方導電性接着剤組成物の硬化物により構成されているため、充分な接着強度及び接続信頼性を維持し、しかも高温高湿条件において接着剤の剥離が充分に抑制される。 In the connection body according to the present invention, the connection member that electrically connects the first circuit member and the second circuit member is a cured product of the adhesive composition or anisotropic conductive adhesive composition of the present invention. Therefore, sufficient adhesive strength and connection reliability are maintained, and peeling of the adhesive is sufficiently suppressed under high temperature and high humidity conditions.
 本発明によれば、ラジカル硬化型接着剤でありながら、低温(例えば、140℃以下)且つ短時間(例えば、5秒以下)の接続条件でも充分な接着強度及び接続信頼性を維持し、しかも高温高湿条件において被着体との剥離を抑制することが可能な接着剤組成物を提供することができる。 According to the present invention, although it is a radical curable adhesive, sufficient adhesive strength and connection reliability are maintained even at low temperature (for example, 140 ° C. or lower) and for a short time (for example, 5 seconds or shorter). An adhesive composition capable of suppressing peeling from an adherend under high temperature and high humidity conditions can be provided.
本実施形態に係る接着剤組成物からなるフィルム状接着剤の一実施形態を示す模式断面図である。It is a schematic cross section which shows one Embodiment of the film adhesive which consists of an adhesive composition which concerns on this embodiment. 本実施形態に係る接着剤組成物の硬化物からなる接続部材を備える接続体の一実施形態を示す模式断面図である。It is a schematic cross section which shows one Embodiment of a connection body provided with the connection member which consists of hardened | cured material of the adhesive composition which concerns on this embodiment. 本実施形態に係る接着剤組成物により接続体を製造する一実施形態を概略断面図により示す工程図である。It is process drawing which shows one Embodiment which manufactures a connection body with the adhesive composition which concerns on this embodiment with a schematic sectional drawing.
 以下、場合により図面を参照しつつ、本発明の好適な実施形態について詳細に説明する。ただし、本発明は以下の実施形態に限定されない。図面中、同一又は相当部分には同一符号を付し、重複する説明は適宜省略する。また、本明細書において、(メタ)アクリル酸はアクリル酸又はそれに対応するメタクリル酸を意味する。(メタ)アクリレート等の他の類似表現についても同様である。 Hereinafter, preferred embodiments of the present invention will be described in detail with reference to the drawings as the case may be. However, the present invention is not limited to the following embodiments. In the drawings, the same or corresponding parts are denoted by the same reference numerals, and repeated description will be omitted as appropriate. Moreover, in this specification, (meth) acrylic acid means acrylic acid or methacrylic acid corresponding to it. The same applies to other similar expressions such as (meth) acrylate.
 本実施形態に係る接着剤組成物は、(a)熱可塑性樹脂、(b)ラジカル重合性化合物、(c)ラジカル重合開始剤及び(d)(メタ)アクリロイルオキシ基を有しないエポキシ樹脂を含有する。 The adhesive composition according to this embodiment contains (a) a thermoplastic resin, (b) a radical polymerizable compound, (c) a radical polymerization initiator, and (d) an epoxy resin having no (meth) acryloyloxy group. To do.
 上記接着剤組成物は、エポキシ樹脂のカチオン重合硬化剤を実質的に含有しないことが好ましい。ここで、エポキシ樹脂のカチオン重合硬化剤を実質的に含有しないとは、エポキシ樹脂のカチオン重合硬化剤の含有量が、(a)成分及び(b)成分の総量100質量部に対して、1.5質量部未満であることを示すが、1.0質量部未満であることが好ましく、0.5質量部未満であることがより好ましく、エポキシ樹脂のカチオン重合硬化剤を含有しないことが更に好ましい。 It is preferable that the adhesive composition does not substantially contain an epoxy resin cationic polymerization curing agent. Here, the fact that the cation polymerization curing agent of the epoxy resin is not substantially contained means that the content of the cation polymerization curing agent of the epoxy resin is 1 with respect to 100 parts by mass of the total amount of the component (a) and the component (b). Although it is less than 5 parts by mass, it is preferably less than 1.0 part by mass, more preferably less than 0.5 part by mass, and it does not contain an epoxy resin cationic polymerization curing agent. preferable.
 エポキシ樹脂のカチオン重合硬化剤とは、ブレンステッド酸、ルイス酸、及び熱、光等のエネルギーによってこれらの酸を発生させることができる化合物である。エポキシ樹脂のカチオン重合硬化剤としては、例えば、オニウム塩等が挙げられる。 An epoxy resin cationic polymerization curing agent is a Bronsted acid, a Lewis acid, and a compound capable of generating these acids by energy such as heat and light. Examples of the cationic polymerization curing agent for the epoxy resin include onium salts.
 上記(a)熱可塑性樹脂としては、例えば、ポリイミド樹脂、ポリアミド樹脂、フェノキシ樹脂、ポリ(メタ)アクリル樹脂、ポリエステル樹脂、ポリウレタン樹脂、ポリエステルウレタン樹脂及びポリビニルブチラール樹脂から選ばれる1種又は2種以上の樹脂が挙げられる。 Examples of the thermoplastic resin (a) include one or more selected from polyimide resin, polyamide resin, phenoxy resin, poly (meth) acrylic resin, polyester resin, polyurethane resin, polyester urethane resin, and polyvinyl butyral resin. These resins are mentioned.
 熱可塑性樹脂の重量平均分子量の下限値は、5000以上であってもよく、10000以上であってもよい。熱可塑性樹脂の重量平均分子量が5000以上であると、接着剤組成物の接着強度が向上する傾向がある。一方、熱可塑性樹脂の重量平均分子量の上限値は、400000以下であってもよく、200000以下であってもよく、150000以下であってもよい。熱可塑性樹脂の重量平均分子量が400000以下であれば、他の成分との良好な相溶性が得られやすい傾向があり、接着剤の流動性が得られやすい傾向がある。熱可塑性樹脂の重量平均分子量は、5000~400000が好ましく、5000~200000がより好ましく、10000~150000が特に好ましい。 The lower limit of the weight average molecular weight of the thermoplastic resin may be 5000 or more, or 10,000 or more. There exists a tendency for the adhesive strength of an adhesive composition to improve that the weight average molecular weight of a thermoplastic resin is 5000 or more. On the other hand, the upper limit of the weight average molecular weight of the thermoplastic resin may be 400000 or less, 200000 or less, or 150,000 or less. If the weight average molecular weight of the thermoplastic resin is 400000 or less, good compatibility with other components tends to be easily obtained, and the fluidity of the adhesive tends to be easily obtained. The weight average molecular weight of the thermoplastic resin is preferably from 5,000 to 400,000, more preferably from 5,000 to 200,000, particularly preferably from 10,000 to 150,000.
 熱可塑性樹脂として、応力緩和及び接着性向上を目的として、ゴム成分を用いることもできる。 As the thermoplastic resin, a rubber component can also be used for the purpose of stress relaxation and adhesion improvement.
 熱可塑性樹脂の含有量は、(a)成分及び(b)成分の総量100質量部に対して、20~80質量部であることが好ましく、30~70質量部であることがより好ましく、35~65質量部であることが更に好ましい。熱可塑性樹脂の含有量が20質量部以上であれば、接着強度が向上したり、接着剤組成物のフィルム形成性が向上したりしやすい傾向があり、80質量部以下であると、接着剤の流動性が得られやすい傾向がある。 The content of the thermoplastic resin is preferably 20 to 80 parts by mass, more preferably 30 to 70 parts by mass with respect to 100 parts by mass of the total amount of the components (a) and (b). More preferably, it is ˜65 parts by mass. If the content of the thermoplastic resin is 20 parts by mass or more, the adhesive strength tends to be improved or the film formability of the adhesive composition tends to be improved, and if it is 80 parts by mass or less, the adhesive It tends to be easy to obtain fluidity.
 本実施形態に係る接着剤組成物は、(b)ラジカル重合性化合物として任意のものを含んでいてもよい。当該ラジカル重合性化合物は、例えば後述する化合物のモノマー及びオリゴマーのいずれであってもよいし、両者を併用したものであってもよい。 The adhesive composition according to the present embodiment may contain any (b) radical polymerizable compound. The radical polymerizable compound may be, for example, any of the monomer and oligomer of the compound described later, or may be a combination of both.
 上記化合物としては、2つ以上の(メタ)アクリロイルオキシ基を有する1種又は2種以上の多官能の(メタ)アクリレート化合物が好ましい。このような(メタ)アクリレート化合物としては、例えば、エポキシ(メタ)アクリレート、ウレタン(メタ)アクリレート、ポリエーテル(メタ)アクリレート、ポリエステル(メタ)アクリレート、トリメチロールプロパントリ(メタ)アクリレート、ポリエチレングリコールジ(メタ)アクリレート等のポリアルキレングリコールジ(メタ)アクリレート、ジシクロペンテニル(メタ)アクリレート、ジシクロペンテニロキシエチル(メタ)アクリレート、ネオペンチルグリコールジ(メタ)アクリレート、ジペンタエリスリトールヘキサ(メタ)アクリレート、イソシアヌル酸変性2官能(メタ)アクリレート及びイソシアヌル酸変性3官能(メタ)アクリレートが挙げられる。上記エポキシ(メタ)アクリレートとしては、例えば、ビスフェノールフルオレンジグリシジルエーテルの2つのグリシジル基に(メタ)アクリル酸を付加させたエポキシ(メタ)アクリレート並びにビスフェノールフルオレンジグリシジルエーテルの2つのグリシジル基にエチレングリコール及び/又はプロピレングリコールを付加させた化合物に(メタ)アクリロイルオキシ基を導入した化合物が挙げられる。これらの化合物は、1種を単独で又は2種以上を組み合わせて使用することができる。 As the above compound, one or more polyfunctional (meth) acrylate compounds having two or more (meth) acryloyloxy groups are preferable. Examples of such (meth) acrylate compounds include epoxy (meth) acrylate, urethane (meth) acrylate, polyether (meth) acrylate, polyester (meth) acrylate, trimethylolpropane tri (meth) acrylate, and polyethylene glycol diester. Polyalkylene glycol di (meth) acrylate such as (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, neopentyl glycol di (meth) acrylate, dipentaerythritol hexa (meth) Examples include acrylate, isocyanuric acid-modified bifunctional (meth) acrylate, and isocyanuric acid-modified trifunctional (meth) acrylate. Examples of the epoxy (meth) acrylate include, for example, an epoxy (meth) acrylate obtained by adding (meth) acrylic acid to two glycidyl groups of bisphenol fluorenediglycidyl ether and ethylene glycol in two glycidyl groups of bisphenol fluorenediglycidyl ether. And / or the compound which introduce | transduced the (meth) acryloyloxy group to the compound which added propylene glycol is mentioned. These compounds can be used individually by 1 type or in combination of 2 or more types.
 また、接着剤組成物は、流動性の調節等を目的として、(b)ラジカル重合性化合物として、単官能(メタ)アクリレート化合物を含んでいてもよい。単官能(メタ)アクリレート化合物としては、例えば、ペンタエリスリトール(メタ)アクリレート、2-シアノエチル(メタ)アクリレート、シクロヘキシル(メタ)アクリレート、ジシクロペンテニル(メタ)アクリレート、ジシクロペンテニロキシエチル(メタ)アクリレート、2-(2-エトキシエトキシ)エチル(メタ)アクリレート、2-エトキシエチル(メタ)アクリレート、2-エチルヘキシル(メタ)アクリレート、n-ヘキシル(メタ)アクリレート、2-ヒドロキシエチル(メタ)アクリレート、ヒドロキシプロピル(メタ)アクリレート、イソボルニル(メタ)アクリレート、イソデシル(メタ)アクリレート、イソオクチル(メタ)アクリレート、n-ラウリル(メタ)アクリレート、2-メトキシエチル(メタ)アクリレート、2-フェノキシエチル(メタ)アクリレート、テトラヒドロフルフリール(メタ)アクリレート、2-(メタ)アクリロイロキシエチルホスフェート、N,N-ジメチルアミノエチル(メタ)アクリレート、N,N-ジメチルアミノプロピル(メタ)アクリレート、複数のグリシジル基を有するエポキシ樹脂のグリシジル基の一つを(メタ)アクリル酸と反応させることで得られるグリシジル基含有(メタ)アクリレート及び(メタ)アクリロイルモルホリンが挙げられる。これらの化合物は、1種を単独で又は2種以上を組み合わせて使用することができる。 Further, the adhesive composition may contain a monofunctional (meth) acrylate compound as the (b) radical polymerizable compound for the purpose of controlling fluidity. Examples of monofunctional (meth) acrylate compounds include pentaerythritol (meth) acrylate, 2-cyanoethyl (meth) acrylate, cyclohexyl (meth) acrylate, dicyclopentenyl (meth) acrylate, and 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, glycidyl group-containing (meth) acrylate and (meth) acryloylmorpholine obtained by reacting one of the glycidyl groups of an epoxy resin having a plurality of glycidyl groups with (meth) acrylic acid. These compounds can be used individually by 1 type or in combination of 2 or more types.
 更に、接着剤組成物は、橋架け率の向上等を目的として、(b)ラジカル重合性化合物として、アリル基、マレイミド基、ビニル基等のラジカル重合性の官能基を有する化合物を含んでいてもよい。 Furthermore, the adhesive composition contains a compound having a radical polymerizable functional group such as an allyl group, a maleimide group, and a vinyl group as the (b) radical polymerizable compound for the purpose of improving the crosslinking rate. Also good.
 接着剤組成物は、接着強度の向上を目的として、(b)ラジカル重合性化合物として、リン酸基を有するラジカル重合性化合物を含有することが好ましい。リン酸基を有するラジカル重合性化合物としては、例えば、下記式(1)、(2)又は(3)で表される化合物が挙げられる。 The adhesive composition preferably contains a radical polymerizable compound having a phosphate group as the (b) radical polymerizable compound for the purpose of improving the adhesive strength. Examples of the radically polymerizable compound having a phosphoric acid group include compounds represented by the following formula (1), (2) or (3).
Figure JPOXMLDOC01-appb-C000001
 式(1)中、Rは水素原子又はメチル基を示し、Rは(メタ)アクリロイルオキシ基を示し、w及びxはそれぞれ独立に1~8の整数を示す。なお、同一分子中の複数のR、R、w及びxは、それぞれ同一でも異なっていてもよい。
Figure JPOXMLDOC01-appb-C000001
In formula (1), R 5 represents a hydrogen atom or a methyl group, R 6 represents a (meth) acryloyloxy group, and w and x each independently represents an integer of 1 to 8. A plurality of R 5 , R 6 , w and x in the same molecule may be the same or different.
Figure JPOXMLDOC01-appb-C000002
 式(2)中、Rは(メタ)アクリロイルオキシ基を示し、y及びzはそれぞれ独立に1~8の整数を示す。同一分子中の複数のR、y及びzは、それぞれ同一でも異なっていてもよい。
Figure JPOXMLDOC01-appb-C000002
In the formula (2), R 7 represents a (meth) acryloyloxy group, and y and z each independently represents an integer of 1 to 8. A plurality of R 7 , y and z in the same molecule may be the same or different.
Figure JPOXMLDOC01-appb-C000003
 式(3)中、Rは水素原子又はメチル基を示し、Rは(メタ)アクリロイルオキシ基を示し、b及びcはそれぞれ独立に1~8の整数を示す。同一分子中の複数のR及びbは同一でも異なっていてもよい。
Figure JPOXMLDOC01-appb-C000003
In the formula (3), R 8 represents a hydrogen atom or a methyl group, R 9 represents a (meth) acryloyloxy group, and b and c each independently represent an integer of 1 to 8. A plurality of R 8 and b in the same molecule may be the same or different.
 リン酸基を有するラジカル重合性化合物としては、例えば、アシッドホスホオキシエチル(メタ)アクリレート、アシッドホスホオキシプロピル(メタ)アクリレート、アシッドホスホオキシポリオキシエチレングリコールモノ(メタ)アクリレート、アシッドホスホオキシポリオキシプロピレングリコールモノ(メタ)アクリレート、2,2’-ジ(メタ)アクリロイロキシジエチルホスフェート、EO(エチレンオキサイド)変性リン酸ジ(メタ)アクリレート、リン酸変性エポキシ(メタ)アクリレート及びリン酸ビニルが挙げられる。これらの化合物は、1種を単独で又は2種以上を組み合わせて使用することができる。 Examples of the radical polymerizable compound having a phosphoric acid group include acid phosphooxyethyl (meth) acrylate, acid phosphooxypropyl (meth) acrylate, acid phosphooxypolyoxyethylene glycol mono (meth) acrylate, and acid phosphooxypolyoxy. Propylene glycol mono (meth) acrylate, 2,2'-di (meth) acryloyloxydiethyl phosphate, EO (ethylene oxide) modified di (meth) acrylate, phosphoric acid modified epoxy (meth) acrylate and vinyl phosphate Can be mentioned. These compounds can be used individually by 1 type or in combination of 2 or more types.
 リン酸基を有するラジカル重合性化合物の含有量は、(a)成分及び(b)成分の総量100質量部に対して、0.1~15質量部であることが好ましく、0.5~10質量部であることがより好ましく、1~5質量部であることが更に好ましい。リン酸基を有するラジカル重合性化合物の含有量が0.1質量部以上であれば、高い接着強度が得られやすい傾向があり、15質量部以下であると、硬化後の接着剤組成物の物性低下が生じにくく、信頼性向上の効果が良好となる。 The content of the radically polymerizable compound having a phosphoric acid group is preferably 0.1 to 15 parts by mass with respect to 100 parts by mass of the total amount of the components (a) and (b), and 0.5 to 10 More preferably, it is more preferably 1 to 5 parts by mass. If the content of the radically polymerizable compound having a phosphoric acid group is 0.1 parts by mass or more, high adhesive strength tends to be obtained, and if it is 15 parts by mass or less, It is difficult to cause deterioration in physical properties, and the effect of improving reliability is good.
 接着剤組成物に含まれる(b)ラジカル重合性化合物の総含有量は、(a)成分及び(b)成分の総量100質量部に対して、20~80質量部であることが好ましく、30~70質量部であることがより好ましく、35~65質量部であることが更に好ましい。この総含有量が20質量部以上であれば、耐熱性が向上する傾向があり、80質量部以下であると、高温高湿環境に放置後の剥離抑制の効果が大きくなる傾向がある。 The total content of the (b) radical polymerizable compound contained in the adhesive composition is preferably 20 to 80 parts by mass with respect to 100 parts by mass of the total amount of the components (a) and (b). More preferably, it is ˜70 parts by mass, and still more preferably 35-65 parts by mass. If the total content is 20 parts by mass or more, the heat resistance tends to be improved, and if it is 80 parts by mass or less, the effect of suppressing peeling after leaving in a high temperature and high humidity environment tends to increase.
 (c)ラジカル重合開始剤は、過酸化物及びアゾ化合物等の化合物から任意に選択することができる。安定性、反応性及び相溶性の観点から、1分間半減期温度が90~175℃で、且つ分子量が180~1000の過酸化物が好ましい。「1分間半減期温度」とは、過酸化物の半減期が1分である温度をいう。「半減期」とは、所定の温度において化合物の濃度が初期値の半分に減少するまでの時間をいう。 (C) The radical polymerization initiator can be arbitrarily selected from compounds such as peroxides and azo compounds. From the viewpoint 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 preferred. “1 minute half-life temperature” refers to a temperature at which the half-life of the peroxide is 1 minute. “Half-life” refers to the time taken for the concentration of a compound to decrease to half of its initial value at a given temperature.
 ラジカル重合開始剤としては、例えば、1,1,3,3-テトラメチルブチルパーオキシネオデカノエート、ジ(4-t-ブチルシクロヘキシル)パーオキシジカーボネート、ジ(2-エチルヘキシル)パーオキシジカーボネート、クミルパーオキシネオデカノエート、1,1,3,3-テトラメチルブチルパーオキシネオデカノエート、ジラウロイルパーオキサイド、1-シクロヘキシル-1-メチルエチルパーオキシネオデカノエート、t-ヘキシルパーオキシネオデカノエート、t-ブチルパーオキシネオデカノエート、t-ブチルパーオキシピバレート、1,1,3,3-テトラメチルブチルパーオキシ-2-エチルヘキサノエート、2,5-ジメチル-2,5-ジ(2-エチルヘキサノイルパーオキシ)ヘキサン、t-ヘキシルパーオキシ-2-エチルヘキサノエート、t-ブチルパーオキシ-2-エチルヘキサノエート、t-ブチルパーオキシネオヘプタノエート、t-アミルパーオキシ-2-エチルヘキサノエート、ジ-t-ブチルパーオキシヘキサヒドロテレフタレート、t-アミルパーオキシ-3,5,5-トリメチルヘキサノエート、3-ヒドロキシ-1,1-ジメチルブチルパーオキシネオデカノエート、1,1,3,3-テトラメチルブチルパーオキシ-2-エチルヘキサノエート、t-アミルパーオキシネオデカノエート、t-アミルパーオキシ-2-エチルヘキサノエート、3-メチルベンゾイルパーオキサイド、4-メチルベンゾイルパーオキサイド、ジ(3-メチルベンゾイル)パーオキサイド、ジベンゾイルパーオキサイド、ジ(4-メチルベンゾイル)パーオキサイド、2,2’-アゾビス-2,4-ジメチルバレロニトリル、1,1’-アゾビス(1-アセトキシ-1-フェニルエタン)、2,2’-アゾビスイソブチロニトリル、2,2’-アゾビス(2-メチルブチロニトリル)、ジメチル-2,2’-アゾビスイソブチロニトリル、4,4’-アゾビス(4-シアノバレリン酸)、1,1’-アゾビス(1-シクロヘキサンカルボニトリル)、t-ヘキシルパーオキシイソプロピルモノカーボネート、t-ブチルパーオキシマレイン酸、t-ブチルパーオキシ-3,5,5-トリメチルヘキサノエート、t-ブチルパーオキシラウレート、2,5-ジメチル-2,5-ジ(3-メチルベンゾイルパーオキシ)ヘキサン、t-ブチルパーオキシ-2-エチルヘキシルモノカーボネート、t-ヘキシルパーオキシベンゾエート、2,5-ジメチル-2,5-ジ(ベンゾイルパーオキシ)ヘキサン、t-ブチルパーオキシベンゾエート、ジブチルパーオキシトリメチルアジペート、t-アミルパーオキシノルマルオクトエート、t-アミルパーオキシイソノナノエート及びt-アミルパーオキシベンゾエートから選ばれる1以上の化合物である。 Examples of the radical polymerization initiator include 1,1,3,3-tetramethylbutylperoxyneodecanoate, di (4-tert-butylcyclohexyl) peroxydicarbonate, di (2-ethylhexyl) peroxydi Carbonate, cumylperoxyneodecanoate, 1,1,3,3-tetramethylbutylperoxyneodecanoate, dilauroyl peroxide, 1-cyclohexyl-1-methylethylperoxyneodecanoate, t- Hexyl peroxyneodecanoate, t-butyl peroxyneodecanoate, t-butyl peroxypivalate, 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate, 2,5 -Dimethyl-2,5-di (2-ethylhexanoylperoxy) hexane, t-hexyl -Oxy-2-ethylhexanoate, t-butylperoxy-2-ethylhexanoate, t-butylperoxyneoheptanoate, t-amylperoxy-2-ethylhexanoate, di-t-butyl Peroxyhexahydroterephthalate, t-amylperoxy-3,5,5-trimethylhexanoate, 3-hydroxy-1,1-dimethylbutylperoxyneodecanoate, 1,1,3,3-tetramethyl Butylperoxy-2-ethylhexanoate, t-amylperoxyneodecanoate, t-amylperoxy-2-ethylhexanoate, 3-methylbenzoyl peroxide, 4-methylbenzoyl peroxide, di ( 3-methylbenzoyl) peroxide, dibenzoyl peroxide, di (4-methyl) Nzoyl) peroxide, 2,2'-azobis-2,4-dimethylvaleronitrile, 1,1'-azobis (1-acetoxy-1-phenylethane), 2,2'-azobisisobutyronitrile, , 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-trimethylhexanoate, t-butylperoxylaurate, 2,5 -Dimethyl-2,5-di (3-methylbenzoylperoxy) hexane, t-butylperoxy-2-ethylhexyl monocar Bonate, t-hexylperoxybenzoate, 2,5-dimethyl-2,5-di (benzoylperoxy) hexane, t-butylperoxybenzoate, dibutylperoxytrimethyladipate, t-amylperoxynormal octoate, t -One or more compounds selected from amyl peroxyisononanoate and t-amyl peroxybenzoate.
 ラジカル重合開始剤の含有量は、(a)成分及び(b)成分の総量100質量部に対して、1~15質量部であることが好ましく、2.5~10質量部であることがより好ましく、3~8質量部であることが更に好ましい。 The content of the radical polymerization initiator is preferably 1 to 15 parts by mass and more preferably 2.5 to 10 parts by mass with respect to 100 parts by mass of the total amount of the components (a) and (b). The amount is preferably 3 to 8 parts by mass.
 (d)(メタ)アクリロイルオキシ基を有しないエポキシ樹脂としては、例えば、ビスフェノールA型エポキシ樹脂、ビスフェノールF型エポキシ樹脂、ビスフェノールS型エポキシ樹脂、フェノールノボラック型エポキシ樹脂、クレゾールノボラック型エポキシ樹脂、ビスフェノールAノボラック型エポキシ樹脂、ビスフェノールFノボラック型エポキシ樹脂、脂環式エポキシ樹脂、グリシジルエステル型エポキシ樹脂、グリシジルアミン型エポキシ樹脂、ヒダントイン型エポキシ樹脂、イソシアヌレート型エポキシ樹脂、芳香族多環式エポキシ樹脂、脂肪族鎖状エポキシ樹脂、脂肪族多環式エポキシ樹脂、ビフェニル骨格を有するエポキシ樹脂等が挙げられる。これらのエポキシ樹脂は、ハロゲン化されていてもよく、水素添加されていてもよい。これらの中で、接続信頼性がより向上する観点から、芳香族多環式エポキシ樹脂及びビフェニル骨格を有するエポキシ樹脂が好ましく、ビフェニル骨格を有するエポキシ樹脂がより好ましい。これらは1種を単独で又は2種以上を組み合わせて用いることができる。 (D) Examples of the epoxy resin having no (meth) acryloyloxy group include 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, and bisphenol. A novolac type epoxy resin, bisphenol F novolac type epoxy resin, alicyclic epoxy resin, glycidyl ester type epoxy resin, glycidyl amine type epoxy resin, hydantoin type epoxy resin, isocyanurate type epoxy resin, aromatic polycyclic epoxy resin, Examples include aliphatic chain epoxy resins, aliphatic polycyclic epoxy resins, and epoxy resins having a biphenyl skeleton. These epoxy resins may be halogenated or hydrogenated. Among these, from the viewpoint of improving connection reliability, an aromatic polycyclic epoxy resin and an epoxy resin having a biphenyl skeleton are preferable, and an epoxy resin having a biphenyl skeleton is more preferable. These can be used individually by 1 type or in combination of 2 or more types.
 (メタ)アクリロイルオキシ基を有しないエポキシ樹脂の分子量の下限値は、250以上であってもよく、300以上であってもよく、350以上であってもよい。分子量が250以上であれば、接着剤組成物をフィルム状接着剤として用いた場合に、乾燥工程でエポキシ樹脂が揮発するおそれが少ない。一方、(メタ)アクリロイルオキシ基を有しないエポキシ樹脂の分子量の上限値は、5000以下であってもよく、3000以下であってもよく、1000以下であってもよい。分子量が5000以下であると、接着剤の流動性が充分に得られやすい傾向がある。上記の観点から、(メタ)アクリロイルオキシ基を有しないエポキシ樹脂の分子量は、250~5000であることが好ましく、300~3000であることがより好ましく、350~1000であることが更に好ましい。 The lower limit of the molecular weight of the epoxy resin having no (meth) acryloyloxy group may be 250 or more, 300 or more, or 350 or more. When the molecular weight is 250 or more, when the adhesive composition is used as a film adhesive, there is little possibility that the epoxy resin volatilizes in the drying step. On the other hand, the upper limit of the molecular weight of the epoxy resin having no (meth) acryloyloxy group may be 5000 or less, 3000 or less, or 1000 or less. When the molecular weight is 5000 or less, the fluidity of the adhesive tends to be sufficiently obtained. From the above viewpoint, the molecular weight of the epoxy resin having no (meth) acryloyloxy group is preferably 250 to 5000, more preferably 300 to 3000, and further preferably 350 to 1000.
 (メタ)アクリロイルオキシ基を有しないエポキシ樹脂のエポキシ当量の下限値は、100以上であってもよく、150以上であってもよく、180以上であってもよい。エポキシ当量が100以上であれば、接着剤組成物の接続信頼性がより向上する傾向がある。一方、(メタ)アクリロイルオキシ基を有しないエポキシ樹脂のエポキシ当量の上限値は、300以下であってもよく、275以下であってもよく、270以下であってもよい。エポキシ当量が300以下であると、ガラスに対する密着性がより増加する傾向がある。上記の観点から、(メタ)アクリロイルオキシ基を有しないエポキシ樹脂のエポキシ当量は、100~300であることが好ましく、150~275であることがより好ましく、180~270であることが更に好ましい。 The lower limit value of the epoxy equivalent of the epoxy resin having no (meth) acryloyloxy group may be 100 or more, 150 or more, or 180 or more. If the epoxy equivalent is 100 or more, the connection reliability of the adhesive composition tends to be further improved. On the other hand, the upper limit of the epoxy equivalent of an epoxy resin having no (meth) acryloyloxy group may be 300 or less, 275 or less, or 270 or less. There exists a tendency for the adhesiveness with respect to glass to increase that an epoxy equivalent is 300 or less. From the above viewpoint, the epoxy equivalent of the epoxy resin having no (meth) acryloyloxy group is preferably 100 to 300, more preferably 150 to 275, and still more preferably 180 to 270.
 (メタ)アクリロイルオキシ基を有しないエポキシ樹脂の含有量の下限値は、(a)成分及び(b)成分の総量100質量部に対し、1質量部以上であってもよく、2.5質量部以上であってもよく、3質量部以上であってもよい。含有量が1質量部以上であれば、本発明の効果がより高いレベルで得られやすくなる傾向がある。一方、(メタ)アクリロイルオキシ基を有しないエポキシ樹脂の含有量の上限値は、(a)成分及び(b)成分の総量100質量部に対し、15質量部以下であってもよく、10質量部以下であってもよい。含有量が15質量部以下であると、低温短時間条件において使用した場合にラジカル重合が阻害されにくくなる傾向がある。上記の観点から、(メタ)アクリロイルオキシ基を有しないエポキシ樹脂の含有量は、(a)成分及び(b)成分の総量100質量部に対し、1~15質量部であることが好ましく、2.5~10質量部であることがより好ましく、3~10質量部であることが更に好ましい。 The lower limit of the content of the epoxy resin having no (meth) acryloyloxy group may be 1 part by mass or more with respect to 100 parts by mass of the total amount of the components (a) and (b), and 2.5 masses. Or 3 parts by mass or more. If the content is 1 part by mass or more, the effect of the present invention tends to be easily obtained at a higher level. On the other hand, the upper limit of the content of the epoxy resin having no (meth) acryloyloxy group may be 15 parts by mass or less with respect to 100 parts by mass of the total amount of the component (a) and the component (b), and 10 masses. Or less. When the content is 15 parts by mass or less, radical polymerization tends to be difficult to inhibit when used under low temperature and short time conditions. From the above viewpoint, the content of the epoxy resin having no (meth) acryloyloxy group is preferably 1 to 15 parts by mass with respect to 100 parts by mass as the total of the components (a) and (b). More preferably, it is 5 to 10 parts by mass, and further preferably 3 to 10 parts by mass.
 本実施形態に係る接着剤組成物は、シランカップリング剤を含有していてもよい。シランカップリング剤は、好ましくは、下記式(4)で表される化合物である。 The adhesive composition according to this embodiment may contain a silane coupling agent. The silane coupling agent is preferably a compound represented by the following formula (4).
Figure JPOXMLDOC01-appb-C000004
 式(4)中、R、R及びRはそれぞれ独立に、水素原子、炭素数1~5のアルキル基、炭素数1~5のアルコキシ基、炭素数1~5のアルコキシカルボニル基又はアリール基を示す。R、R及びRのうち少なくとも1つはアルコキシ基である。Rは(メタ)アクリロイル基、(メタ)アクリロイルオキシ基、ビニル基、イソシアナート基、イミダゾール基、メルカプト基、アミノアルキル基で置換されていてもよいアミノ基、メチルアミノ基、ジメチルアミノ基、ベンジルアミノ基、フェニルアミノ基、シクロヘキシルアミノ基、モルホリノ基、ピペラジノ基、ウレイド基、グリシジル基又はグリシドキシ基を示す。aは0~10の整数を示す。
Figure JPOXMLDOC01-appb-C000004
In the formula (4), R 1 , R 2 and R 3 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 is shown. At least one of R 1 , R 2 and R 3 is an alkoxy group. R 4 is a (meth) acryloyl group, a (meth) acryloyloxy group, a vinyl group, an isocyanate group, an imidazole group, a mercapto group, an amino group optionally substituted with an aminoalkyl group, a methylamino group, a dimethylamino group, A benzylamino group, a phenylamino group, a cyclohexylamino group, a morpholino group, a piperazino group, a ureido group, a glycidyl group or a glycidoxy group; a represents an integer of 0 to 10.
 式(4)のシランカップリング剤としては、例えば、ビニルトリメトキシシラン、ビニルトリエトキシシラン、3-グリシドキシプロピルトリメトキシシラン、3-グリシドキシプロピルメチルジエトキシシラン、3-(メタ)アクリロキシプロピルメチルジメトキシシラン、3-(メタ)アクリロキシプロピルトリメトキシシラン、3-(メタ)アクリロキシプロピルメチルジエトキシシラン、3-(メタ)アクリロキシプロピルトリエトキシシラン、N-2-(アミノエチル)-3-アミノプロピルメチルジメトキシシラン、N-フェニル-3-アミノプロピルトリメトキシシラン、3-ウレイドプロピルトリエトキシシラン、3-メルカプトプロピルトリメトキシシラン及び3-イソシアネートプロピルトリエトキシシランが挙げられる。これらの化合物は、1種を単独で又は2種以上を組み合わせて使用することができる。 Examples of the silane coupling agent of the formula (4) include vinyltrimethoxysilane, vinyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3- (meth) Acryloxypropylmethyldimethoxysilane, 3- (meth) acryloxypropyltrimethoxysilane, 3- (meth) acryloxypropylmethyldiethoxysilane, 3- (meth) acryloxypropyltriethoxysilane, N-2- (amino Ethyl) -3-aminopropylmethyldimethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, 3-mercaptopropyltrimethoxysilane and 3-isocyanatopropyltriethoxysilane. That. These compounds can be used individually by 1 type or in combination of 2 or more types.
 シランカップリング剤の含有量は、(a)成分及び(b)成分の総量100質量部に対して、0.1~10質量部であることが好ましく、0.25~5質量部であることがより好ましい。シランカップリング剤の含有量が0.1質量部以上であれば、回路部材と回路接続材料の界面の剥離、及び気泡の発生を抑制する効果がより大きくなる傾向があり、シランカップリング剤の含有量が10質量部以下であると、接着剤組成物のポットライフが長くなる傾向がある。
 なお、シランカップリング剤がアクリロイル基(アクリロイルオキシ基)等のラジカル重合性官能基を有する場合には、ラジカル重合性化合物として(b)成分に含まれるものとする。
The content of the silane coupling agent is preferably 0.1 to 10 parts by mass and preferably 0.25 to 5 parts by mass with respect to 100 parts by mass of the total amount of the components (a) and (b). Is more preferable. If the content of the silane coupling agent is 0.1 parts by mass or more, the effect of suppressing the separation of the interface between the circuit member and the circuit connecting material and the generation of bubbles tends to increase. When the content is 10 parts by mass or less, the pot life of the adhesive composition tends to be long.
In addition, when a silane coupling agent has radically polymerizable functional groups, such as an acryloyl group (acryloyloxy group), it shall be contained in (b) component as a radically polymerizable compound.
 本実施形態に係る接着剤組成物は、(e)導電性粒子を更に含有していてもよい。導電性粒子を含有する接着剤組成物は、異方導電性接着剤組成物として特に好適に用いることができる。 The adhesive composition according to this embodiment may further contain (e) conductive particles. The adhesive composition containing conductive particles can be particularly suitably used as an anisotropic conductive adhesive composition.
 導電性粒子としては、例えば、Au、Ag、Pd、Ni、Cu、はんだ等の金属粒子、カーボン粒子などが挙げられる。また、導電性粒子は、ガラス、セラミック、プラスチック等の非導電性材料からなる核体粒子と、該核体粒子を被覆する金属、金属粒子、カーボン等の導電層と、を有する複合粒子であってもよい。金属粒子は、銅粒子及び該銅粒子を被覆する銀層を有する粒子であってもよい。複合粒子の核体粒子は、好ましくはプラスチック粒子である。 Examples of the conductive particles include metal particles such as Au, Ag, Pd, Ni, Cu, and solder, and carbon particles. The conductive particles are composite particles having core particles made of a non-conductive material such as glass, ceramic, and plastic, and conductive layers such as metal, metal particles, and carbon that coat the core particles. May be. The metal particles may be copper particles and particles having a silver layer covering the copper particles. The core particle of the composite particle is preferably a plastic particle.
 上記プラスチック粒子を核体粒子とする複合粒子は、加熱及び加圧によって変形する変形性を有するので、回路部材同士を接着する際に、該回路部材が有する回路電極と導電性粒子との接触面積を増加させることができる。そのため、これらの複合粒子を導電性粒子として含有する接着剤組成物によれば、接続信頼性の点でより一層優れる接続体が得られる。 The composite particles having the plastic particles as the core particles have a deformability that is deformed by heating and pressurization. Therefore, when the circuit members are bonded to each other, the contact area between the circuit electrodes of the circuit members and the conductive particles Can be increased. Therefore, according to the adhesive composition containing these composite particles as conductive particles, a connection body that is more excellent in terms of connection reliability can be obtained.
 上記導電性粒子と、その表面の少なくとも一部を被覆する絶縁層又は絶縁性粒子とを有する絶縁被覆導電性粒子を、接着剤組成物が含有していてもよい。絶縁層は、ハイブリダイゼーション等の方法により設けることができる。絶縁層又は絶縁性粒子は、高分子樹脂等の絶縁性材料から形成される。このような絶縁被覆導電性粒子を用いることで、隣接する導電性粒子同士による短絡が生じにくくなる。 The adhesive composition may contain insulating coated conductive particles having the conductive particles and an insulating layer or insulating particles covering at least a part of the surface of the conductive particles. The insulating layer can be provided by a method such as hybridization. The insulating layer or the insulating particles are formed from an insulating material such as a polymer resin. By using such insulating coating conductive particles, short circuit between adjacent conductive particles is less likely to occur.
 導電性粒子の平均粒径は、良好な分散性及び導電性を得る観点から、1~18μmであることが好ましい。 The average particle diameter of the conductive particles is preferably 1 to 18 μm from the viewpoint of obtaining good dispersibility and conductivity.
 導電性粒子の含有量は、接着剤組成物の全体積を基準として、0.1~30体積%であることが好ましく、0.1~10体積%であることがより好ましく、0.5~7.5体積%であることが更に好ましい。導電性粒子の含有量が0.1体積%以上であれば、導電性が向上する傾向がある。導電性粒子の含有量が30体積%以下であると、回路電極間の短絡が生じにくくなるという傾向がある。導電性粒子の含有量(体積%)は、硬化前の接着剤組成物を構成する各成分の23℃での体積に基づいて決定される。各成分の体積は、比重を利用して質量を体積に換算することで求めることができる。体積を測定しようとする成分を溶解したり膨潤させたりせず、その成分をよくぬらすことができる適当な溶媒(水、アルコール等)をメスシリンダー等に入れ、そこへ測定対象の成分を導入して増加した体積をその成分の体積として求めることもできる。 The content of the conductive particles is preferably 0.1 to 30% by volume, more preferably 0.1 to 10% by volume, based on the total volume of the adhesive composition, and 0.5 to More preferably, it is 7.5 volume%. If content of electroconductive particle is 0.1 volume% or more, there exists a tendency for electroconductivity to improve. There exists a tendency for it to become difficult to produce the short circuit between circuit electrodes as content of electroconductive particle is 30 volume% or less. Content (volume%) of electroconductive particle is determined based on the volume in 23 degreeC of each component which comprises the adhesive composition before hardening. The volume of each component can be determined by converting mass to volume using specific gravity. 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. The increased volume can be obtained as the volume of the component.
 接着剤組成物は、導電性粒子の他に、絶縁性の有機又は無機微粒子を含有していてもよい。無機微粒子としては、例えば、シリカ微粒子、アルミナ微粒子、シリカ-アルミナ微粒子、チタニア微粒子、ジルコニア微粒子等の金属酸化物微粒子の他、窒化物微粒子などが挙げられる。有機微粒子としては、例えば、シリコーン微粒子、メタクリレート-ブタジエン-スチレン微粒子、アクリル-シリコーン微粒子、ポリアミド微粒子、ポリイミド微粒子等が挙げられる。これらの微粒子は、均一な構造を有していてもよいし、コア-シェル型構造を有していてもよい。 The adhesive composition may contain insulating organic or inorganic fine particles in addition to the conductive particles. Examples of the inorganic fine particles include metal fine particles such as silica fine particles, alumina fine particles, silica-alumina fine particles, titania fine particles, zirconia fine particles, and nitride fine particles. 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 fine particles may have a uniform structure or a core-shell type structure.
 有機微粒子及び無機微粒子の含有量は、(a)成分及び(b)成分の総量100質量部に対して、5~30質量部であることが好ましく、7.5~20質量部であることがより好ましい。有機微粒子及び無機微粒子の含有量が5質量部以上であれば、相対する電極間の電気的接続を維持することが比較的容易になる傾向があり、30質量部以下であると、接着剤組成物の流動性が向上する傾向がある。
 接着剤組成物は、各種添加剤を含有してもよい。
The content of the organic fine particles and the inorganic fine particles is preferably 5 to 30 parts by mass, and preferably 7.5 to 20 parts by mass with respect to 100 parts by mass of the total amount of the components (a) and (b). More preferred. If the content of the organic fine particles and the inorganic fine particles is 5 parts by mass or more, it tends to be relatively easy to maintain the electrical connection between the opposing electrodes, and if it is 30 parts by mass or less, the adhesive composition There is a tendency for the fluidity of things to improve.
The adhesive composition may contain various additives.
 本実施形態に係る接着剤組成物は、常温(25℃)で液状である場合は、ペースト状接着剤として使用することができる。接着剤組成物が常温で固体である場合には、加熱して使用してもよいし、溶剤を加えることによりペースト化して使用してもよい。ペースト化のために使用する溶剤は、接着剤組成物(添加剤も含む。)との反応性を実質的に有さず、且つ接着剤組成物を充分に溶解可能なものであれば特に制限されない。 The adhesive composition according to the present embodiment can be used as a paste adhesive when it is liquid at normal temperature (25 ° C.). When the adhesive composition is solid at normal temperature, it may be used by heating, or it may be used by pasting it by adding a solvent. The solvent used for pasting is not particularly limited as long as it has substantially no reactivity with the adhesive composition (including additives) and can sufficiently dissolve the adhesive composition. Not.
 本実施形態に係る接着剤組成物は、フィルム状に成形して、フィルム状接着剤として用いることもできる。フィルム状接着剤は、例えば、接着剤組成物に必要に応じて溶剤等を加えるなどして得られた溶液を、フッ素樹脂フィルム、ポリエチレンテレフタレートフィルム、離型紙等の剥離性支持体上に塗布し、溶剤等を除去する方法により得ることができる。フィルム状接着剤は、取り扱い等の点から一層便利である。 The adhesive composition according to the present embodiment can be formed into a film and used as a film adhesive. For example, a film adhesive is obtained by applying a solution obtained by adding a solvent or the like to an adhesive composition as necessary on a peelable support such as a fluororesin film, a polyethylene terephthalate film, or a release paper. It can be obtained by a method of removing a solvent or the like. A film adhesive is more convenient in terms of handling and the like.
 図1は、本実施形態に係る接着剤組成物からなるフィルム状接着剤の一実施形態を示す模式断面図である。図1に示す積層フィルム100は、支持体8と、支持体8上に剥離可能に積層されたフィルム状接着剤40とを備える。フィルム状接着剤40は、絶縁性接着剤層5と、絶縁性接着剤層5中に分散した導電性粒子7とから構成される。絶縁性接着剤層5は、上述の接着剤組成物のうち導電性粒子以外の成分から構成される。このフィルム状接着剤によれば、取り扱いが容易であり、被着体へ容易に設置することができ、接続作業を容易に行うことができる。フィルム状接着剤は、2種以上の層からなる多層構成を有していてもよい。フィルム状接着剤が導電性粒子を含有する場合、フィルム状接着剤を異方導電性フィルムとして好適に用いることができる。 FIG. 1 is a schematic cross-sectional view showing an embodiment of a film adhesive comprising the adhesive composition according to the present embodiment. A laminated film 100 shown in FIG. 1 includes a support 8 and a film adhesive 40 laminated on the support 8 in a peelable manner. The film adhesive 40 is composed of an insulating adhesive layer 5 and conductive particles 7 dispersed in the insulating adhesive layer 5. The insulating adhesive layer 5 is comprised from components other than electroconductive particle among the above-mentioned adhesive compositions. According to this film adhesive, it is easy to handle, can be easily installed on the adherend, and can be easily connected. The film adhesive may have a multilayer structure composed of two or more layers. When the film adhesive contains conductive particles, the film adhesive can be suitably used as an anisotropic conductive film.
 本実施形態に係る接着剤組成物及びフィルム状接着剤によれば、通常、加熱及び加圧を併用して被着体同士を接着させることができる。加熱温度は、好ましくは100~250℃である。圧力は、被着体に損傷を与えない範囲であれば特に制限されないが、一般的には0.1~10MPaであることが好ましい。これらの加熱及び加圧は、0.5~120秒間の範囲で行うことが好ましい。本実施形態に係る接着剤組成物及びフィルム状接着剤によれば、例えば、140℃、1MPa程度の条件にて、5秒間の短時間の加熱及び加圧でも被着体同士を充分に接着させることが可能である。 According to the adhesive composition and the film adhesive according to the present embodiment, the adherends can usually be bonded together 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 to 120 seconds. According to the adhesive composition and the film-like adhesive according to the present embodiment, for example, the adherends are sufficiently bonded to each other even when heated and pressed for a short time of 5 seconds under conditions of 140 ° C. and 1 MPa. It is possible.
 本実施形態に係る接着剤組成物及びフィルム状接着剤は、熱膨張係数の異なる異種の被着体の接着剤として使用することができる。具体的には、本実施形態に係る接着剤組成物及びフィルム状接着剤は、異方導電接着剤の他、銀ペースト、銀フィルム等の回路接続材料、CSP用エラストマー、CSP用アンダーフィル材、LOCテープ等の半導体素子接着材料として使用することができる。 The adhesive composition and film adhesive according to this embodiment can be used as an adhesive for different types of adherends having different thermal expansion coefficients. Specifically, the adhesive composition and the film-like adhesive according to the present embodiment include an anisotropic conductive adhesive, a circuit connecting material such as a silver paste and a silver film, an elastomer for CSP, an underfill material for CSP, It can be used as a semiconductor element adhesive material such as LOC tape.
 本実施形態に係る回路接続材料は、上述した接着剤組成物、又は異方導電性接着剤組成物を含有する。このような回路接続材料は、回路電極を有する回路部材同士を、それぞれの回路部材が有する回路電極同士が電気的に接続されるように接着するために用いることができる。 The circuit connection material according to the present embodiment contains the above-described adhesive composition or anisotropic conductive adhesive composition. Such a circuit connection material can be used for bonding circuit members having circuit electrodes so that the circuit electrodes of the respective circuit members are electrically connected to each other.
 以下、本実施形態に係るフィルム状接着剤を異方導電性フィルムとして使用して、回路基板及び回路基板の主面上に形成された回路電極を有する回路部材同士を被着体として接続し、接続体を製造する一例について説明する。 Hereinafter, using the film adhesive according to the present embodiment as an anisotropic conductive film, connecting circuit members having circuit electrodes formed on the main surface of the circuit board and the circuit board as adherends, An example of manufacturing the connection body will be described.
 図2は、本実施形態に係る接着剤組成物の硬化物からなる接続部材を備える接続体の一実施形態を示す模式断面図である。図2に示す接続体1は、対向配置された第一の回路部材20及び第二の回路部材30を備えている。第一の回路部材20と第二の回路部材30との間には、これらを接着及び接続する接続部材10が設けられている。 FIG. 2 is a schematic cross-sectional view showing an embodiment of a connection body including a connection member made of a cured product of the adhesive composition according to this embodiment. The connection body 1 shown in FIG. 2 includes a first circuit member 20 and a second circuit member 30 that are arranged to face each other. A connecting member 10 is provided between the first circuit member 20 and the second circuit member 30 to bond and connect them.
 第一の回路部材20は、第一の回路基板21と、第一の回路基板21の主面21a上に形成された第一の回路電極22とを備える。第一の回路基板21の主面21a上には、絶縁層が形成されていてもよい。 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 first circuit board 21. An insulating layer may be formed on the main surface 21 a of the first circuit board 21.
 第二の回路部材30は、第二の回路基板31と、第二の回路基板31の主面31a上に形成された第二の回路電極32とを備える。第二の回路基板31の主面31a上にも、絶縁層が形成されていてもよい。 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. An insulating layer may also be formed on the main surface 31 a of the second circuit board 31.
 第一の回路部材20及び第二の回路部材30は、電気的接続を必要とする回路電極を有するものであれば特に制限はない。第一の回路基板21及び第二の回路基板31としては、例えば、半導体、ガラス、セラミック等の無機材料の基板、ポリイミド、ポリカーボネート等の有機材料の基板、ガラス/エポキシ等の無機物と有機物とを含む基板が挙げられる。第一の回路基板21がガラス基板であり、第二の回路基板31がフレキシブル基板(好ましくは、ポリイミドフィルム等の樹脂フィルム)であってもよい。 The first circuit member 20 and the second circuit member 30 are not particularly limited as long as they have circuit electrodes that require electrical connection. As the first circuit board 21 and the second circuit board 31, for example, a substrate made of an inorganic material such as a semiconductor, glass or ceramic, a substrate made of an organic material such as polyimide or polycarbonate, an inorganic material such as glass / epoxy, and an organic material are used. A substrate containing. The first circuit board 21 may be a glass substrate, and the second circuit board 31 may be a flexible substrate (preferably a resin film such as a polyimide film).
 接続される回路部材の具体例としては、液晶ディスプレイに用いられている、ITO(indium tin oxide)膜等の電極が形成されているガラス又はプラスチック基板、プリント配線板、セラミック配線板、フレキシブル配線板、半導体シリコンチップ等が挙げられる。これらは必要に応じて組み合わせて使用される。このように、本実施形態に係る接着剤組成物によれば、プリント配線板及びポリイミドフィルム等の有機材料から形成された表面を有する部材の他、銅、アルミニウム等の金属、ITO、窒化ケイ素(SiN)、二酸化ケイ素(SiO)などの無機材料から形成された表面を有する部材のように、多種多様な表面状態を有する回路部材を接着するために用いることができる。 Specific examples of circuit members to be connected include glass or plastic substrates, printed wiring boards, ceramic wiring boards, flexible wiring boards on which electrodes such as ITO (indium tin oxide) films are formed, which are used in liquid crystal displays. And a semiconductor silicon chip. These are used in combination as necessary. Thus, according to the adhesive composition according to the present embodiment, in addition to a member having a surface formed from an organic material such as a printed wiring board and a polyimide film, a metal such as copper or aluminum, ITO, silicon nitride ( It can be used for bonding circuit members having a wide variety of surface states, such as members having a surface formed of an inorganic material such as SiN x ) or silicon dioxide (SiO 2 ).
 例えば、一方の回路部材が、フィンガー電極、バスバー電極等の電極を有する太陽電池セルであり、他方の回路部材がタブ線であるとき、これらを接続して得られる接続体は、太陽電池セル、タブ線及びこれらを接着する接続部材(接着剤組成物の硬化物)を備える太陽電池モジュールである。 For example, when one circuit member is a solar cell having electrodes such as finger electrodes and bus bar electrodes, and the other circuit member is a tab wire, the connection body obtained by connecting them is a solar cell, It is a solar cell module provided with a tab wire and a connecting member (cured product of the adhesive composition) for bonding them.
 接続部材10は、本実施形態に係る接着剤組成物の硬化物からなる。接続部材10は、絶縁層11及び絶縁層11中に分散した導電性粒子7を含有している。導電性粒子7は、対向する第一の回路電極22と第二の回路電極32との間のみならず、主面21a、31aの間にも配置されている。第一の回路電極22及び第二の回路電極32は、導電性粒子7を介して電気的に接続されているため、第一の回路電極22及び第二の回路電極32間の接続抵抗が充分に低減される。したがって、第一の回路電極22及び第二の回路電極32間の電流の流れを円滑にすることができ、回路の持つ機能を充分に発揮することができる。接続部材が導電性粒子を含有していない場合には、第一の回路電極22と第二の回路電極32とが接触することで、電気的に接続される。 The connecting member 10 is made of a cured product of the adhesive composition according to the present embodiment. The connecting member 10 contains an insulating layer 11 and conductive particles 7 dispersed in the insulating layer 11. The electroconductive particle 7 is arrange | positioned not only between the 1st circuit electrode 22 and the 2nd circuit electrode 32 which oppose but between the main surfaces 21a and 31a. Since the first circuit electrode 22 and the second circuit electrode 32 are electrically connected via the conductive particles 7, the connection resistance between the first circuit electrode 22 and the second circuit electrode 32 is sufficient. Reduced to 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 fully exhibited. When the connection member does not contain conductive particles, the first circuit electrode 22 and the second circuit electrode 32 come into contact with each other to be electrically connected.
 接続部材10が本実施形態に係る接着剤組成物の硬化物によって形成されていることから、第一の回路部材20及び第二の回路部材30に対する接続部材10の接着強度は充分に高い。そのため、信頼性試験(高温高湿試験)後においても接着強度の低下及び接続抵抗の増大を充分に抑制することができる。 Since the connection member 10 is formed of a cured product of the adhesive composition according to this embodiment, the bonding strength of the connection member 10 to the first circuit member 20 and the second circuit member 30 is sufficiently high. Therefore, even after a reliability test (high temperature and high humidity test), it is possible to sufficiently suppress a decrease in adhesive strength and an increase in connection resistance.
 接続体1は、例えば、回路電極を有し対向配置された一対の回路部材を、接着剤組成物からなるフィルム状接着剤を間に挟んで配置する工程と、一対の回路部材及びフィルム状接着剤を、フィルム状接着剤の厚み方向に加圧しながら加熱して硬化することにより、一対の回路部材を接着剤組成物の硬化物を介して接着する工程(本接続工程)と、を備える方法により、製造することができる。 The connection body 1 includes, for example, a step of disposing a pair of circuit members having circuit electrodes disposed opposite to each other with a film adhesive made of an adhesive composition interposed therebetween, a pair of circuit members, and a film adhesive A step of bonding a pair of circuit members via a cured product of the adhesive composition (main connection step) by heating and curing the agent while pressing in the thickness direction of the film adhesive. Can be manufactured.
 図3は、本実施形態に係る接着剤組成物により接続体を製造する一実施形態を概略断面図により示す工程図である。図3の(a)に示されるように、フィルム状接着剤40が、第一の回路部材20の第一の回路電極22側の主面上に載せられる。フィルム状接着剤40が上述の支持体上に設けられている場合、フィルム状接着剤40が第一の回路部材20側に位置する向きで、フィルム状接着剤及び支持体の積層体が回路部材に載せられる。フィルム状接着剤40は、フィルム状であることから取り扱いが容易である。このため、第一の回路部材20と第二の回路部材30との間にフィルム状接着剤40を容易に介在させることができ、第一の回路部材20と第二の回路部材30との接続作業を容易に行うことができる。 FIG. 3 is a process diagram showing a schematic cross-sectional view of one embodiment for producing a connection body using the adhesive composition according to the present embodiment. As shown in FIG. 3A, the film adhesive 40 is placed on the main surface of the first circuit member 20 on the first circuit electrode 22 side. When the film adhesive 40 is provided on the above-described support, the laminate of the film adhesive and the support is a circuit member in such a direction that the film adhesive 40 is positioned on the first circuit member 20 side. It is put on. The film adhesive 40 is easy to handle because it is in the form of a film. For this reason, the film adhesive 40 can be easily interposed between the first circuit member 20 and the second circuit member 30, and the connection between the first circuit member 20 and the second circuit member 30 is possible. Work can be done easily.
 フィルム状接着剤40は、フィルム状に形成された上述の接着剤組成物(回路接続材料)であり、導電性粒子7及び絶縁性接着剤層5を有する。接着剤組成物は、導電性粒子を含有しない場合も、回路電極同士を直接接続させることにより、電気的に接続するための回路接続材料として使用できる。導電性粒子を含有しない回路接続材料は、NCF(Non-Conductive-FILM)又はNCP(Non-Conductive-Paste)と呼ばれることもある。接着剤組成物が導電性粒子を有する場合、これを用いた回路接続材料は、ACF(Anisotropic Conductive FILM)又はACP(Anisotropic Conductive Paste)と呼ばれることもある。 The film adhesive 40 is the above-described adhesive composition (circuit connection material) formed in a film shape, and includes the conductive particles 7 and the insulating adhesive layer 5. Even when the adhesive composition does not contain conductive particles, it can be used as a circuit connection material for electrical connection by directly connecting the circuit electrodes. The circuit connection material that does not contain conductive particles is sometimes called NCF (Non-Conductive-FILM) or NCP (Non-Conductive-Paste). When the adhesive composition has conductive particles, a circuit connecting material using the conductive particles may be referred to as ACF (Anisotropic Conductive FILM) or ACP (Anisotropic Conductive Paste).
 フィルム状接着剤40の厚さは、10~50μmであることが好ましい。フィルム状接着剤40の厚さが10μm以上であれば、第一の回路電極22及び第二の回路電極32間が、接着剤により充填されやすくなる傾向がある。フィルム状接着剤の厚さが50μm以下であれば、第一の回路電極22及び第二の回路電極32間の接着剤組成物を充分に排除しきることができ、第一の回路電極22及び第二の回路電極32間の導通を容易に確保することができる。 The thickness of the film adhesive 40 is preferably 10 to 50 μm. If the thickness of the film adhesive 40 is 10 μm or more, the space between the first circuit electrode 22 and the second circuit electrode 32 tends to be easily filled with the adhesive. If the thickness of the film adhesive is 50 μm or less, the adhesive composition between the first circuit electrode 22 and the second circuit electrode 32 can be sufficiently eliminated, and the first circuit electrode 22 and the second circuit electrode The conduction between the two circuit electrodes 32 can be easily ensured.
 フィルム状接着剤40の厚み方向に、図3の(a)に示されるように圧力A、Bを加えることにより、フィルム状接着剤40が第一の回路部材20に仮接続される(図3の(b)を参照。)。このとき、加熱しながら加圧してもよい。ただし、加熱温度はフィルム状接着剤40中の接着剤組成物が硬化しない温度、すなわちラジカル重合開始剤がラジカルを急激に発生する温度よりも充分に低い温度に設定される。 By applying pressures A and B in the thickness direction of the film adhesive 40 as shown in FIG. 3A, the film adhesive 40 is temporarily connected to the first circuit member 20 (FIG. 3). (See (b) of). At this time, you may pressurize, heating. However, the heating temperature is set to a temperature sufficiently lower than the temperature at which the adhesive composition in the film adhesive 40 is not cured, that is, the temperature at which the radical polymerization initiator rapidly generates radicals.
 続いて、図3の(c)に示されるように、第二の回路部材30を、第二の回路電極が第一の回路部材20側に位置する向きでフィルム状接着剤40上に載せる。フィルム状接着剤40が支持体上に設けられている場合は、支持体を剥離してから第二の回路部材30をフィルム状接着剤40上に載せる。 Subsequently, as shown in FIG. 3C, the second circuit member 30 is placed on the film adhesive 40 in such a direction that the second circuit electrode is positioned on the first circuit member 20 side. In the case where the film adhesive 40 is provided on the support, the second circuit member 30 is placed on the film adhesive 40 after the support is peeled off.
 その後、フィルム状接着剤40を、その厚み方向に圧力A、Bを加えながら、加熱する。このときの加熱温度は、ラジカル重合開始剤がラジカルを充分に発生する温度に設定される。これにより、ラジカル重合開始剤からラジカルが発生し、ラジカル重合性化合物の重合が開始される。本接続により、図2に示す接続体が得られる。フィルム状接着剤40を加熱することにより、第一の回路電極22と第二の回路電極32との間の距離を充分に小さくした状態で絶縁性接着剤が硬化して絶縁層11を形成する。その結果、第一の回路部材20と第二の回路部材30とが、絶縁層11を含む接続部材10を介して強固に接続される。 Then, the film adhesive 40 is heated while applying pressures A and B in the thickness direction. The heating temperature at this time is set to a temperature at which the radical polymerization initiator sufficiently generates radicals. As a result, radicals are generated from the radical polymerization initiator, and polymerization of the radical polymerizable compound is started. The connection shown in FIG. 2 is obtained by this connection. By heating the film adhesive 40, the insulating adhesive is cured to form the insulating layer 11 in a state where the distance between the first circuit electrode 22 and the second circuit electrode 32 is sufficiently small. . As a result, the first circuit member 20 and the second circuit member 30 are firmly connected via the connection member 10 including the insulating layer 11.
 本接続は、加熱温度が100~250℃、圧力が0.1~10MPa、加圧時間が0.5~120秒の条件で行われることが好ましい。これらの条件は、使用する用途、接着剤組成物、回路部材によって適宜選択される。本実施形態に係る接着剤組成物によれば、140℃以下のような低温条件でも、充分な信頼性を有する接続体を得ることができる。本接続後、必要に応じて、後硬化を行ってもよい。 This connection is preferably performed under the conditions of a heating temperature of 100 to 250 ° C., a pressure of 0.1 to 10 MPa, and a pressurization time of 0.5 to 120 seconds. These conditions are appropriately selected depending on the intended use, the adhesive composition, and the circuit member. According to the adhesive composition according to this embodiment, a connection body having sufficient reliability can be obtained even under a low temperature condition such as 140 ° C. or lower. After the connection, post-curing may be performed as necessary.
 以下、実施例及び比較例を挙げて、本発明についてより具体的に説明する。ただし、本発明は以下の実施例に限定されるものではない。 Hereinafter, the present invention will be described more specifically with reference to examples and comparative examples. However, the present invention is not limited to the following examples.
<ポリウレタン樹脂の合成>
 還流冷却器、温度計及び撹拌機を備えたセパラブルフラスコに、エーテル結合を有するジオールであるポリプロピレングリコール(数平均分子量Mn=2000)1000質量部及び溶媒としてのメチルエチルケトン4000質量部を加え、40℃で30分間撹拌した。溶液を70℃まで昇温した後、触媒としてのジメチル錫ラウレート12.7mgを加えた。次いで、この溶液に対して、4,4’-ジフェニルメタンジイソシアネート125質量部をメチルエチルケトン125質量部に溶解して調製した溶液を、1時間かけて滴下した。その後、赤外分光光度計でNCOの吸収ピークが認められなくなるまでこの温度で撹拌を続けて、ポリウレタン樹脂のメチルエチルケトン溶液を得た。この溶液の固形分濃度(ポリウレタン樹脂の濃度)が30質量%となるように調整した。得られたポリウレタン樹脂の重量平均分子量は、GPC(ゲルパーミエーションクロマトグラフィー)による測定の結果、320000(標準ポリスチレン換算値)であった。以下にGPCの分析条件を表1に示す。
<Synthesis of polyurethane resin>
To a separable flask equipped with a reflux condenser, a thermometer and a stirrer was added 1000 parts by mass of polypropylene glycol (number average molecular weight Mn = 2000), which is a diol having an ether bond, and 4000 parts by mass of methyl ethyl ketone as a solvent, and 40 ° C. For 30 minutes. After heating the solution to 70 ° C., 12.7 mg of dimethyltin laurate as a catalyst was added. Next, a solution prepared by dissolving 125 parts by mass of 4,4′-diphenylmethane diisocyanate in 125 parts by mass of methyl ethyl ketone was added dropwise to this solution over 1 hour. Thereafter, stirring was continued at this temperature until an NCO absorption peak was not observed with an infrared spectrophotometer, to obtain a methyl ethyl ketone solution of a polyurethane resin. The solid content concentration (polyurethane resin concentration) of this solution was adjusted to 30% by mass. The weight average molecular weight of the obtained polyurethane resin was 320,000 (standard polystyrene conversion value) as a result of measurement by GPC (gel permeation chromatography). The GPC analysis conditions are shown in Table 1 below.
Figure JPOXMLDOC01-appb-T000005
Figure JPOXMLDOC01-appb-T000005
<ウレタンアクリレートの合成>
 温度計、撹拌機、不活性ガス導入口、及び還流冷却器を装着した2リットルの四つ口フラスコに、ポリカーボネートジオール(アルドリッチ社製、Mn=2000)4000質量部と、2-ヒドロキシエチルアクリレート238質量部と、ハイドロキノンモノメチルエーテル0.49質量部と、スズ系触媒4.9質量部とを仕込んで反応液を調製した。70℃に加熱した反応液に対して、イソホロンジイソシアネート(IPDI)666質量部を3時間かけて均一に滴下し、反応させた。滴下完了後、15時間反応を継続し、電位差自動滴定装置(商品名AT-510、京都電子工業株式会社製)にてNCO含有量が0.2質量%となったことを確認した時点で反応を終了し、ウレタンアクリレートを得た。GPCによる分析の結果、ウレタンアクリレートの重量平均分子量は8500(標準ポリスチレン換算値)であった。なお、GPCによる分析は前述のポリウレタン樹脂の重量平均分子量の分析と同様の条件で行った。
<Synthesis of urethane acrylate>
In a 2 liter four-necked flask equipped with a thermometer, stirrer, inert gas inlet, and reflux condenser, 4000 parts by mass of polycarbonate diol (manufactured by Aldrich, Mn = 2000) and 2-hydroxyethyl acrylate 238 A reaction solution was prepared by charging 0.47 parts by mass of hydroquinone monomethyl ether and 4.9 parts by mass of a tin-based catalyst. To the reaction liquid heated to 70 ° C., 666 parts by mass of isophorone diisocyanate (IPDI) was uniformly dropped over 3 hours to be reacted. The reaction was continued for 15 hours after completion of the dropping, and when the NCO content was confirmed to be 0.2% by mass using an automatic potentiometric titrator (trade name AT-510, manufactured by Kyoto Electronics Industry Co., Ltd.) And urethane acrylate was obtained. As a result of analysis by GPC, the weight average molecular weight of urethane acrylate was 8500 (standard polystyrene conversion value). The analysis by GPC was performed under the same conditions as the analysis of the weight average molecular weight of the polyurethane resin described above.
<エポキシ基を有するアクリレート化合物Aの合成>
 撹拌装置、還流冷却器及び温度計を装着した反応器に、ビスフェノールF型エポキシ樹脂(商品名JER806、三菱化学株式会社製:ビスフェノールFのジグリシジルエーテル、エポキシ当量165)330質量部と、アクリル酸72質量部(エポキシ樹脂中のエポキシ基2モルに対してアクリル酸1モルの比率)と、ベンジルトリエチルアンモニウムクロライド1質量部と、t-ブチルカテコール0.1質量部とを仕込んで反応液を調製した。反応液を100℃で3時間撹拌しながら、エポキシ基とアクリル酸との反応を進行させた。反応終了後、反応液を室温に戻してから、ベンゼン300質量部を添加して生成物を溶解させた。続いて、これに炭酸ナトリウム水溶液及び蒸留水をこの順に添加して、溶液を3回ずつ洗浄した。その後、ベンゼンを充分に蒸留除去して、粗生成物を得た。粗生成物を液相クロマトグラフィーにより分析したところ、目的化合物であるエポキシ基を1つ有するアクリレート化合物の他に、エポキシ基を有しない2官能アクリレート化合物及び原料のビスフェノールF型エポキシ樹脂が粗生成物に含まれることが分かった。そこで、粗生成物を精製して、エポキシ基及びアクリロイルオキシ基を一つずつ有し、ビスフェノールF型の基本骨格を有するアクリレート化合物Aを得た。
<Synthesis of acrylate compound A having an epoxy group>
In a reactor equipped with a stirrer, a reflux condenser and a thermometer, 330 parts by mass of bisphenol F type epoxy resin (trade name JER806, manufactured by Mitsubishi Chemical Corporation: diglycidyl ether of bisphenol F, epoxy equivalent 165), and acrylic acid Prepare a reaction solution by adding 72 parts by mass (ratio of 1 mol of acrylic acid to 2 mol of epoxy groups in the epoxy resin), 1 part by mass of benzyltriethylammonium chloride and 0.1 part by mass of t-butylcatechol. did. The reaction between the epoxy group and acrylic acid was allowed to proceed while stirring the reaction solution at 100 ° C. for 3 hours. After completion of the reaction, the reaction solution was returned to room temperature, and 300 parts by mass of benzene was added to dissolve the product. Subsequently, an aqueous sodium carbonate solution and distilled water were added thereto in this order, and the solution was washed three times. Thereafter, benzene was sufficiently distilled off to obtain a crude product. When the crude product was analyzed by liquid phase chromatography, in addition to the acrylate compound having one epoxy group as the target compound, a bifunctional acrylate compound having no epoxy group and the raw material bisphenol F type epoxy resin were crude products. It was found to be included. Therefore, the crude product was purified to obtain acrylate compound A having an epoxy group and an acryloyloxy group one by one and a bisphenol F type basic skeleton.
<導電性粒子の作製>
 ポリスチレン粒子の表面に、厚さ0.2μmのニッケル層を形成し、更にこのニッケル層の外側に、厚さ0.04μmの金層を形成させた。こうして平均粒径4μmの導電性粒子を作製した。
<Preparation of conductive particles>
A nickel layer having a thickness of 0.2 μm was formed on the surface of the polystyrene particles, and a gold layer having a thickness of 0.04 μm was further formed outside the nickel layer. Thus, conductive particles having an average particle diameter of 4 μm were produced.
<フィルム状接着剤の作製>
 表2に示す原料を、表2に示す質量比で混合した。そこに上記導電性粒子を1.5体積%の割合で分散させて、フィルム状接着剤を形成するための塗工液を得た。この塗工液を厚み50μmのポリエチレンテレフタレート(PET)フィルムに塗工装置を用いて塗布した。塗膜を70℃で10分間熱風乾燥して、厚み18μmのフィルム状接着剤を形成させた。
<Production of film adhesive>
The raw materials shown in Table 2 were mixed at the mass ratio shown in Table 2. The said electroconductive particle was disperse | distributed in the ratio of 1.5 volume% there, and the coating liquid for forming a film adhesive was obtained. This coating solution was applied to a polyethylene terephthalate (PET) film having a thickness of 50 μm using a coating apparatus. The coating film was dried with hot air at 70 ° C. for 10 minutes to form a film adhesive having a thickness of 18 μm.
 表2に示す各数値は、固形分の質量部を示す。また、表2に記載した各原料の具体的物質は、以下に示すとおりである。
・ポリウレタン樹脂、ウレタンアクリレート及びエポキシ基を有するアクリレート化合物A:上述のとおり合成したもの、
・フェノキシ樹脂:PKHC(ユニオンカーバイド社製、商品名:平均分子量45000)40gをメチルエチルケトン60gに溶解して調製した40質量%の溶液、
・エポキシ樹脂A:YX4000(三菱化学株式会社製、商品名:分子量384、エポキシ当量192、ビフェニル型エポキシ樹脂)、
・エポキシ樹脂B:YX7399(三菱化学株式会社製、商品名:分子量528、エポキシ当量264、ビフェニル型エポキシ樹脂)、
・エポキシ樹脂C:JER806(三菱化学株式会社製、商品名:分子量330、エポキシ当量165、ビスフェノールF型エポキシ樹脂)、
・リン酸エステル:2-メタクリロイルオキシエチルアシッドフォスフェート(商品名ライトエステルP-2M、共栄社化学株式会社製)、
・シランカップリング剤:3-メタクリロキシプロピルトリメトキシシラン(商品名KBM-503、信越化学工業株式会社製)、
・過酸化物:ラウロイルパーオキサイド(商品名パーロイルL、日油株式会社製:分子量398.6)、
・エポキシ樹脂のカチオン重合硬化剤:脂肪族スルホニウム塩系潜在性カチオン重合硬化剤(商品名アデカオプトマーCP-66、株式会社ADEKA製)
・無機微粒子:シリカ粒子(商品名R104、日本アエロジル株式会社製)10gをトルエン45g及び酢酸エチル45gの混合溶媒に分散させて調製した10質量%の分散液。
Each numerical value shown in Table 2 indicates a mass part of solid content. Moreover, the specific substance of each raw material described in Table 2 is as shown below.
-Polyurethane resin, urethane acrylate and acrylate compound A having an epoxy group: synthesized as described above,
-Phenoxy resin: 40% by mass solution prepared by dissolving 40 g of PKHC (manufactured by Union Carbide, trade name: average molecular weight 45000) in 60 g of methyl ethyl ketone,
Epoxy resin A: YX4000 (manufactured by Mitsubishi Chemical Corporation, trade name: molecular weight 384, epoxy equivalent 192, biphenyl type epoxy resin),
Epoxy resin B: YX7399 (manufactured by Mitsubishi Chemical Corporation, trade name: molecular weight 528, epoxy equivalent 264, biphenyl type epoxy resin),
Epoxy resin C: JER806 (manufactured by Mitsubishi Chemical Corporation, trade name: molecular weight 330, epoxy equivalent 165, bisphenol F type epoxy resin),
・ Phosphate ester: 2-methacryloyloxyethyl acid phosphate (trade name Light Ester P-2M, manufactured by Kyoeisha Chemical Co., Ltd.)
Silane coupling agent: 3-methacryloxypropyltrimethoxysilane (trade name KBM-503, manufactured by Shin-Etsu Chemical Co., Ltd.)
Peroxide: Lauroyl peroxide (trade name Parroyl L, manufactured by NOF Corporation: molecular weight 398.6),
・ Cationic polymerization curing agent for epoxy resin: aliphatic sulfonium salt-based latent cationic polymerization curing agent (trade name Adekaoptomer CP-66, manufactured by ADEKA Corporation)
Inorganic fine particles: A 10% by mass dispersion prepared by dispersing 10 g of silica particles (trade name R104, manufactured by Nippon Aerosil Co., Ltd.) in a mixed solvent of 45 g of toluene and 45 g of ethyl acetate.
Figure JPOXMLDOC01-appb-T000006
Figure JPOXMLDOC01-appb-T000006
<接続体の作製>
 上記フィルム状接着剤を回路接続材料として用い、ライン幅75μm、ピッチ150μm及び厚さ18μmの銅回路を2200本有するフレキシブル回路板(FPC)と、ガラス基板及びガラス基板上に形成された厚さ0.2μmの酸化インジウム(ITO)の薄層を有するITO基板(厚さ1.1mm、表面抵抗20Ω/□)とを接続した。接続は、熱圧着装置(加熱方式:コンスタントヒート型、東レエンジニアリング株式会社製)を用い、140℃、1MPaで5秒間の加熱及び加圧により行った。これにより、幅1.5mmにわたりFPCとITO基板とがフィルム状接着剤の硬化物により接続された接続体を作製した。
<Production of connected body>
Using the film adhesive as a circuit connecting material, a flexible circuit board (FPC) having 2200 copper circuits having a line width of 75 μm, a pitch of 150 μm and a thickness of 18 μm, a glass substrate and a thickness of 0 formed on the glass substrate An ITO substrate (thickness 1.1 mm, surface resistance 20Ω / □) having a thin layer of 2 μm indium oxide (ITO) was connected. The connection was made by heating and pressurizing at 140 ° C. and 1 MPa for 5 seconds using a thermocompression bonding apparatus (heating method: constant heat type, manufactured by Toray Engineering Co., Ltd.). As a result, a connection body in which the FPC and the ITO substrate were connected by a cured product of a film adhesive over a width of 1.5 mm was produced.
 また、ITO基板に代えて、ガラス基板及びガラス基板上に形成された0.2μmの窒化ケイ素(SiN)の薄層を有するSiN基板(厚さ0.7mm)を用いて、140℃、3MPaで5秒間の加熱及び加圧により、FPCとSiN基板との接続体を作製した。 Further, instead of the ITO substrate, a SiN substrate (thickness 0.7 mm) having a glass substrate and a thin layer of 0.2 μm silicon nitride (SiN) formed on the glass substrate is used at 140 ° C. and 3 MPa. A connection body between the FPC and the SiN substrate was produced by heating and pressurizing for 5 seconds.
<接続抵抗、接着強度の測定>
 得られたFPCとITO基板との接続体の隣接回路間の抵抗値(接続抵抗)を、マルチメーターで測定した。抵抗値は、隣接回路間の抵抗37点の平均で示した。また、この接続体の接着強度を、JIS-Z0237に準じて90度剥離法で測定した。接着強度の測定装置として、テンシロンUTM-4(東洋ボールドウィン株式会社製、商品名、剥離強度50mm/min、25℃)を使用した。接続抵抗及び接着強度は、接続直後及び85℃、85%RHの恒温恒湿槽中に250時間保持後の接続体について測定した。評価結果を表3に示す。
<Measurement of connection resistance and adhesive strength>
The resistance value (connection resistance) between adjacent circuits of the connection body of the obtained FPC and ITO substrate was measured with a multimeter. The resistance value is shown as an average of 37 resistances between adjacent circuits. Further, the adhesive strength of this connection body was measured by a 90-degree peeling method according to JIS-Z0237. Tensilon UTM-4 (manufactured by Toyo Baldwin Co., Ltd., trade name, peel strength 50 mm / min, 25 ° C.) was used as an adhesive strength measuring device. The connection resistance and the adhesive strength were measured for the connection body immediately after the connection and after being kept in a constant temperature and humidity chamber at 85 ° C. and 85% RH for 250 hours. The evaluation results are shown in Table 3.
<接続体外観観察>
 顕微鏡(商品名ECLIPSE L200、株式会社ニコン製)を用いてITO基板及びSiN基板の接続体について、高温高湿試験後の回路接続材料の硬化物とFPCとの界面、及び硬化物とガラスとの界面における剥離の有無を調べた。剥離がない場合を「A」、剥離が実用上問題ない程度にわずかに認められる場合を「B」、剥離が実用上問題ある程度に認められる場合を「C」と判定した。評価結果を表3に示す。評価が「A」又は「B」であれば、剥離が実用上問題ない範囲のものということができる。
<Appearance of connected body appearance>
Using a microscope (trade name ECLIPSE L200, manufactured by Nikon Corporation) for the connection of the ITO substrate and the SiN substrate, the interface between the cured product and FPC of the circuit connection material after the high-temperature and high-humidity test, and the cured product and glass The presence or absence of peeling at the interface was examined. The case where there was no peeling was determined as “A”, the case where peeling was slightly recognized to the extent that there was no practical problem, and “B”, and the case where peeling was recognized to some extent in practical use was determined as “C”. The evaluation results are shown in Table 3. If the evaluation is “A” or “B”, it can be said that peeling does not cause any practical problem.
Figure JPOXMLDOC01-appb-T000007
Figure JPOXMLDOC01-appb-T000007
 各実施例のフィルム状接着剤によれば、低温且つ短時間の硬化条件によって、接続直後及び高温高湿試験後のいずれの場合も、良好な接続抵抗(5Ω以下)及び接着強度(8N/cm以上)を示すことが確認され、接続外観も実用上問題がない程度に良好であった。 According to the film-like adhesive of each example, good connection resistance (5Ω or less) and adhesive strength (8 N / cm), both in the case immediately after the connection and after the high-temperature and high-humidity test, depending on the curing conditions at low temperature for a short time. The connection appearance was also good enough to have no practical problem.
 これに対し、エポキシ樹脂を含有しない比較例1及びエポキシ樹脂のカチオン重合硬化剤を1質量部以上含有する比較例2では、各実施例と比較して高温高湿試験後における接着強度が充分でなく、更に、SiN基板を用いた場合において、高温高湿試験後に剥離の発生が認められ、接続外観においても実用上問題が認められた。 On the other hand, in Comparative Example 1 containing no epoxy resin and Comparative Example 2 containing 1 part by mass or more of the cationic polymerization curing agent of epoxy resin, the adhesive strength after the high-temperature and high-humidity test is sufficient as compared with each Example. Furthermore, when a SiN substrate was used, the occurrence of peeling was observed after the high-temperature and high-humidity test, and practical problems were also observed in the connection appearance.
 1…接続体、5…絶縁性接着剤層、7…導電性粒子、8…支持体、10…接続部材、11…絶縁層、20…第一の回路部材、21…第一の回路基板、21a…主面、22…第一の回路電極、30…第二の回路部材、31…第二の回路基板、31a…主面、32…第二の回路電極、40…フィルム状接着剤、100…積層フィルム。 DESCRIPTION OF SYMBOLS 1 ... Connection body, 5 ... Insulating adhesive layer, 7 ... Conductive particle, 8 ... Support body, 10 ... Connection member, 11 ... Insulating layer, 20 ... First circuit member, 21 ... First circuit board, 21a ... main surface, 22 ... first circuit electrode, 30 ... second circuit member, 31 ... second circuit board, 31a ... main surface, 32 ... second circuit electrode, 40 ... film adhesive, 100 ... Laminated film.

Claims (8)

  1.  (a)熱可塑性樹脂、
     (b)ラジカル重合性化合物、
     (c)ラジカル重合開始剤、及び、
     (d)(メタ)アクリロイルオキシ基を有しないエポキシ樹脂、
    を含有し、エポキシ樹脂のカチオン重合硬化剤を実質的に含有しない、接着剤組成物。
    (A) a thermoplastic resin,
    (B) a radically polymerizable compound,
    (C) a radical polymerization initiator, and
    (D) an epoxy resin having no (meth) acryloyloxy group,
    An adhesive composition containing substantially no epoxy resin cationic polymerization curing agent.
  2.  前記エポキシ樹脂がビフェニル骨格を有する、請求項1に記載の接着剤組成物。 The adhesive composition according to claim 1, wherein the epoxy resin has a biphenyl skeleton.
  3.  (e)導電性粒子を更に含有する、請求項1又は2に記載の接着剤組成物。 (E) The adhesive composition according to claim 1 or 2, further comprising conductive particles.
  4.  (a)熱可塑性樹脂、
     (b)ラジカル重合性化合物、
     (c)ラジカル重合開始剤、
     (d)(メタ)アクリロイルオキシ基を有しないエポキシ樹脂、及び、
     (e)導電性粒子、
    を含有し、エポキシ樹脂のカチオン重合硬化剤を実質的に含有しない、異方導電性接着剤組成物。
    (A) a thermoplastic resin,
    (B) a radically polymerizable compound,
    (C) a radical polymerization initiator,
    (D) an epoxy resin having no (meth) acryloyloxy group, and
    (E) conductive particles,
    An anisotropic conductive adhesive composition that contains substantially no cationic polymerization curing agent for epoxy resin.
  5.  前記エポキシ樹脂がビフェニル骨格を有する、請求項4に記載の異方導電性接着剤組成物。 The anisotropic conductive adhesive composition according to claim 4, wherein the epoxy resin has a biphenyl skeleton.
  6.  請求項1~3のいずれか一項に記載の接着剤組成物、又は請求項4若しくは5に記載の異方導電性接着剤組成物を含有し、
     回路電極を有する回路部材同士を、それぞれの回路部材が有する回路電極同士が電気的に接続されるように接着するために用いられる回路接続材料。
    Containing the adhesive composition according to any one of claims 1 to 3, or the anisotropic conductive adhesive composition according to claim 4 or 5,
    A circuit connecting material used for bonding circuit members having circuit electrodes to each other so that the circuit electrodes of the respective circuit members are electrically connected.
  7.  第一の回路基板の主面上に第一の回路電極が形成された第一の回路部材と、
     第二の回路基板の主面上に第二の回路電極が形成され、前記第二の回路電極と前記第一の回路電極とが対向するように配置された第二の回路部材と、
     前記第一の回路部材と前記第二の回路部材との間に設けられ、前記第一の回路部材と前記第二の回路部材とを電気的に接続する接続部材と、を備え、
     前記接続部材が、請求項1~3のいずれか一項に記載の接着剤組成物、又は請求項4若しくは5に記載の異方導電性接着剤組成物の硬化物である、接続体。
    A first circuit member having a first circuit electrode formed on the main surface of the first circuit board;
    A second circuit member formed on the main surface of the second circuit board, wherein the second circuit electrode is disposed so that the second circuit electrode and the first circuit electrode face each other;
    A connection member provided between the first circuit member and the second circuit member, and electrically connecting the first circuit member and the second circuit member;
    A connection body, wherein the connection member is the adhesive composition according to any one of claims 1 to 3 or the cured product of the anisotropic conductive adhesive composition according to claim 4 or 5.
  8.  前記第一の回路基板及び前記第二の回路基板のうちの一方がガラス基板である、請求項7に記載の接続体。 The connection body according to claim 7, wherein one of the first circuit board and the second circuit board is a glass substrate.
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JPH10168412A (en) * 1996-12-10 1998-06-23 Sumitomo Bakelite Co Ltd Anisotropically conductive adhesive
JP2013138013A (en) * 2009-11-16 2013-07-11 Hitachi Chemical Co Ltd Circuit connection material and connection structure of circuit member using the same
JP2015183118A (en) * 2014-03-25 2015-10-22 日立化成株式会社 Adhesive composition, anisotropic conductive adhesive composition, circuit connecting material, and connected body

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