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 PDFInfo
- 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
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- circuit
- adhesive composition
- meth
- epoxy resin
- adhesive
- Prior art date
Links
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J163/00—Adhesives based on epoxy resins; Adhesives based on derivatives of epoxy resins
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J9/00—Adhesives characterised by their physical nature or the effects produced, e.g. glue sticks
- C09J9/02—Electrically-conducting adhesives
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J201/00—Adhesives based on unspecified macromolecular compounds
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/20—Conductive material dispersed in non-conductive organic material
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01R—ELECTRICALLY-CONDUCTIVE CONNECTIONS; STRUCTURAL ASSOCIATIONS OF A PLURALITY OF MUTUALLY-INSULATED ELECTRICAL CONNECTING ELEMENTS; COUPLING DEVICES; CURRENT COLLECTORS
- H01R11/00—Individual 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
- H01R11/01—Individual 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
Description
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.
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.
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.
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.
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.
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.
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.
・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.
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.
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.
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.
Claims (8)
- (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. - 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.
- (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.
- (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. - 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.
- 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. - 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. - 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.
Priority Applications (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
PCT/JP2015/075253 WO2017037951A1 (en) | 2015-09-04 | 2015-09-04 | Adhesive composition, anisotropically electroconductive adhesive composition, circuit connecting material, and connected object |
KR1020187008753A KR102376223B1 (en) | 2015-09-04 | 2015-09-04 | Adhesive composition, anisotropically conductive adhesive composition, circuit connection material and connection body |
CN201580082812.8A CN107922817B (en) | 2015-09-04 | 2015-09-04 | Adhesive composition, anisotropic conductive adhesive composition, circuit connecting material, and connected body |
JP2017537184A JP6631631B2 (en) | 2015-09-04 | 2015-09-04 | Adhesive composition, anisotropic conductive adhesive composition, circuit connection material and connection body |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
PCT/JP2015/075253 WO2017037951A1 (en) | 2015-09-04 | 2015-09-04 | Adhesive composition, anisotropically electroconductive adhesive composition, circuit connecting material, and connected object |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2017037951A1 true WO2017037951A1 (en) | 2017-03-09 |
Family
ID=58186871
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/JP2015/075253 WO2017037951A1 (en) | 2015-09-04 | 2015-09-04 | Adhesive composition, anisotropically electroconductive adhesive composition, circuit connecting material, and connected object |
Country Status (4)
Country | Link |
---|---|
JP (1) | JP6631631B2 (en) |
KR (1) | KR102376223B1 (en) |
CN (1) | CN107922817B (en) |
WO (1) | WO2017037951A1 (en) |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
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 |
Family Cites Families (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2610900B2 (en) | 1987-10-27 | 1997-05-14 | ソニーケミカル 株式会社 | Thermosetting anisotropic conductive adhesive sheet and method for producing the same |
DE69836078T2 (en) | 1997-03-31 | 2007-05-10 | Hitachi Chemical Co., Ltd. | MATERIAL FOR CONNECTING PCB AND METHOD FOR CONNECTING SWITCHING CONNECTIONS |
US6225408B1 (en) * | 1998-06-12 | 2001-05-01 | Lord Corporation | Adhesive formulations |
CN108676520A (en) | 2011-09-06 | 2018-10-19 | 日立化成株式会社 | Anisotropically conducting adhesive, the application of adhesive composite and connector |
-
2015
- 2015-09-04 JP JP2017537184A patent/JP6631631B2/en active Active
- 2015-09-04 KR KR1020187008753A patent/KR102376223B1/en active IP Right Grant
- 2015-09-04 WO PCT/JP2015/075253 patent/WO2017037951A1/en active Application Filing
- 2015-09-04 CN CN201580082812.8A patent/CN107922817B/en active Active
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
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 |
Also Published As
Publication number | Publication date |
---|---|
JPWO2017037951A1 (en) | 2018-07-26 |
CN107922817B (en) | 2021-05-28 |
CN107922817A (en) | 2018-04-17 |
KR102376223B1 (en) | 2022-03-17 |
KR20180050336A (en) | 2018-05-14 |
JP6631631B2 (en) | 2020-01-15 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
JP5867508B2 (en) | Circuit connection material and connection body | |
JP6090311B2 (en) | Circuit connection material, circuit connection structure and adhesive film | |
JP6307966B2 (en) | Adhesive composition, anisotropic conductive adhesive composition, circuit connection material and connector | |
KR102478959B1 (en) | Adhesive composition and connected structure | |
JP6417675B2 (en) | Adhesive composition and connector | |
JP2018184607A (en) | Adhesive composition and connection body | |
JP2013227420A (en) | Circuit connection material, circuit connection structure, adhesion film and wound body | |
JP6645499B2 (en) | Adhesive composition and connector | |
TWI811185B (en) | Adhesive composition and structure | |
CN108350320B (en) | Adhesive composition and structure | |
WO2017037951A1 (en) | Adhesive composition, anisotropically electroconductive adhesive composition, circuit connecting material, and connected object | |
WO2023228729A1 (en) | Adhesive composition, circuit connection material, and connection body | |
TWI690580B (en) | Adhesive composition, anisotropic conductive adhesive composition, circuit connecting material and connector | |
WO2018070208A1 (en) | Connection structure, circuit connection member, and adhesive composition | |
TWI685554B (en) | Adhesive composition and connector | |
WO2022186016A1 (en) | Bonding film for circuit connection and connected body | |
TWI570208B (en) | Circuit connecting material and connection body |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 15903070 Country of ref document: EP Kind code of ref document: A1 |
|
ENP | Entry into the national phase |
Ref document number: 2017537184 Country of ref document: JP Kind code of ref document: A |
|
NENP | Non-entry into the national phase |
Ref country code: DE |
|
ENP | Entry into the national phase |
Ref document number: 20187008753 Country of ref document: KR Kind code of ref document: A |
|
122 | Ep: pct application non-entry in european phase |
Ref document number: 15903070 Country of ref document: EP Kind code of ref document: A1 |