CN117659667A - Thermosetting resin composition, anisotropic conductive film, and connection structure - Google Patents
Thermosetting resin composition, anisotropic conductive film, and connection structure Download PDFInfo
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- CN117659667A CN117659667A CN202311623638.6A CN202311623638A CN117659667A CN 117659667 A CN117659667 A CN 117659667A CN 202311623638 A CN202311623638 A CN 202311623638A CN 117659667 A CN117659667 A CN 117659667A
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- resin composition
- thermosetting resin
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- 239000011342 resin composition Substances 0.000 title claims abstract description 47
- 229920001187 thermosetting polymer Polymers 0.000 title claims abstract description 43
- 239000002245 particle Substances 0.000 claims abstract description 33
- UFERIGCCDYCZLN-UHFFFAOYSA-N 3a,4,7,7a-tetrahydro-1h-indene Chemical compound C1C=CCC2CC=CC21 UFERIGCCDYCZLN-UHFFFAOYSA-N 0.000 claims abstract description 29
- -1 quaternary ammonium salt compound Chemical class 0.000 claims abstract description 28
- 229920005989 resin Polymers 0.000 claims abstract description 27
- 239000011347 resin Substances 0.000 claims abstract description 27
- 239000000654 additive Substances 0.000 claims abstract description 22
- 230000000996 additive effect Effects 0.000 claims abstract description 22
- 239000003999 initiator Substances 0.000 claims abstract description 5
- 239000003822 epoxy resin Substances 0.000 claims description 35
- 229920000647 polyepoxide Polymers 0.000 claims description 35
- 238000001723 curing Methods 0.000 claims description 27
- 239000013034 phenoxy resin Substances 0.000 claims description 25
- 229920006287 phenoxy resin Polymers 0.000 claims description 25
- LWNGJAHMBMVCJR-UHFFFAOYSA-N (2,3,4,5,6-pentafluorophenoxy)boronic acid Chemical compound OB(O)OC1=C(F)C(F)=C(F)C(F)=C1F LWNGJAHMBMVCJR-UHFFFAOYSA-N 0.000 claims description 16
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 claims description 12
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 8
- 239000007787 solid Substances 0.000 claims description 8
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 7
- 229910052760 oxygen Inorganic materials 0.000 claims description 7
- 239000001301 oxygen Substances 0.000 claims description 7
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 claims description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 6
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 6
- 239000000539 dimer Substances 0.000 claims description 6
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 claims description 6
- 238000013007 heat curing Methods 0.000 claims description 5
- NQEJEMZJOBCYOD-UHFFFAOYSA-N (4-methoxyphenyl)methyl-dimethyl-phenylazanium Chemical compound C1=CC(OC)=CC=C1C[N+](C)(C)C1=CC=CC=C1 NQEJEMZJOBCYOD-UHFFFAOYSA-N 0.000 claims description 4
- 229930185605 Bisphenol Natural products 0.000 claims description 4
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 claims description 4
- 150000001450 anions Chemical class 0.000 claims description 4
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 3
- GMXOYEFGMAXIIU-UHFFFAOYSA-N C[N+](CC1=CC(=C(C=C1)C)C)(C1=CC=CC=C1)C Chemical compound C[N+](CC1=CC(=C(C=C1)C)C)(C1=CC=CC=C1)C GMXOYEFGMAXIIU-UHFFFAOYSA-N 0.000 claims description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 3
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 3
- 239000004305 biphenyl Substances 0.000 claims description 3
- 235000010290 biphenyl Nutrition 0.000 claims description 3
- 229910052796 boron Inorganic materials 0.000 claims description 3
- 229910017052 cobalt Inorganic materials 0.000 claims description 3
- 239000010941 cobalt Substances 0.000 claims description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 3
- 229910052802 copper Inorganic materials 0.000 claims description 3
- 239000010949 copper Substances 0.000 claims description 3
- HYVNJCOHGOONJK-UHFFFAOYSA-N dibenzyl-methyl-phenylazanium Chemical compound C=1C=CC=CC=1C[N+](C=1C=CC=CC=1)(C)CC1=CC=CC=C1 HYVNJCOHGOONJK-UHFFFAOYSA-N 0.000 claims description 3
- ONRGBXGMVZEZLY-UHFFFAOYSA-N dimethyl-[(4-methylphenyl)methyl]-phenylazanium Chemical compound C1=CC(C)=CC=C1C[N+](C)(C)C1=CC=CC=C1 ONRGBXGMVZEZLY-UHFFFAOYSA-N 0.000 claims description 3
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 3
- 229910052737 gold Inorganic materials 0.000 claims description 3
- 239000010931 gold Substances 0.000 claims description 3
- 229910052759 nickel Inorganic materials 0.000 claims description 3
- 229920003986 novolac Polymers 0.000 claims description 3
- 229910052763 palladium Inorganic materials 0.000 claims description 3
- 125000001453 quaternary ammonium group Chemical group 0.000 claims description 3
- 150000003839 salts Chemical class 0.000 claims description 3
- 229910052709 silver Inorganic materials 0.000 claims description 3
- 239000004332 silver Substances 0.000 claims description 3
- 229910000679 solder Inorganic materials 0.000 claims description 3
- HMKGBOLFVMRQRP-UHFFFAOYSA-N tribenzyl(phenyl)azanium Chemical compound C=1C=CC=CC=1C[N+](C=1C=CC=CC=1)(CC=1C=CC=CC=1)CC1=CC=CC=C1 HMKGBOLFVMRQRP-UHFFFAOYSA-N 0.000 claims description 3
- 239000000758 substrate Substances 0.000 description 26
- 238000003860 storage Methods 0.000 description 19
- 239000012790 adhesive layer Substances 0.000 description 13
- 238000000034 method Methods 0.000 description 13
- 239000011521 glass Substances 0.000 description 11
- 125000002723 alicyclic group Chemical group 0.000 description 9
- 239000003795 chemical substances by application Substances 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 9
- 239000000463 material Substances 0.000 description 9
- 239000002253 acid Substances 0.000 description 7
- 150000001875 compounds Chemical class 0.000 description 7
- 238000005259 measurement Methods 0.000 description 7
- 238000002156 mixing Methods 0.000 description 7
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 239000000853 adhesive Substances 0.000 description 5
- 230000001070 adhesive effect Effects 0.000 description 5
- 125000002091 cationic group Chemical group 0.000 description 5
- 230000020169 heat generation Effects 0.000 description 5
- 150000003856 quaternary ammonium compounds Chemical class 0.000 description 5
- 239000004593 Epoxy Substances 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 239000007822 coupling agent Substances 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 125000003454 indenyl group Chemical group C1(C=CC2=CC=CC=C12)* 0.000 description 4
- 239000011256 inorganic filler Substances 0.000 description 4
- 229910003475 inorganic filler Inorganic materials 0.000 description 4
- 238000004806 packaging method and process Methods 0.000 description 4
- 230000009257 reactivity Effects 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical class S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- 150000001768 cations Chemical class 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000010410 layer Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 239000007800 oxidant agent Substances 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 238000010538 cationic polymerization reaction Methods 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 2
- 150000002484 inorganic compounds Chemical class 0.000 description 2
- 229910010272 inorganic material Inorganic materials 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 150000002894 organic compounds Chemical class 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 229920001721 polyimide Polymers 0.000 description 2
- 239000003505 polymerization initiator Substances 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 229920000098 polyolefin Polymers 0.000 description 2
- 230000001737 promoting effect Effects 0.000 description 2
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 230000003746 surface roughness Effects 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 238000001029 thermal curing Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 229920002799 BoPET Polymers 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- SCKXCAADGDQQCS-UHFFFAOYSA-N Performic acid Chemical compound OOC=O SCKXCAADGDQQCS-UHFFFAOYSA-N 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 150000004292 cyclic ethers Chemical class 0.000 description 1
- 238000004807 desolvation Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical class C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 238000006735 epoxidation reaction Methods 0.000 description 1
- 150000002118 epoxides Chemical class 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 150000002596 lactones Chemical class 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 150000001451 organic peroxides Chemical class 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229920006122 polyamide resin Polymers 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 239000009719 polyimide resin Substances 0.000 description 1
- 229920005672 polyolefin resin Polymers 0.000 description 1
- 229920005749 polyurethane resin Polymers 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000011885 synergistic combination Substances 0.000 description 1
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 1
- 229920006337 unsaturated polyester resin Polymers 0.000 description 1
- JLQFVGYYVXALAG-CFEVTAHFSA-N yasmin 28 Chemical compound OC1=CC=C2[C@H]3CC[C@](C)([C@](CC4)(O)C#C)[C@@H]4[C@@H]3CCC2=C1.C([C@]12[C@H]3C[C@H]3[C@H]3[C@H]4[C@@H]([C@]5(CCC(=O)C=C5[C@@H]5C[C@@H]54)C)CC[C@@]31C)CC(=O)O2 JLQFVGYYVXALAG-CFEVTAHFSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
- C08L71/08—Polyethers derived from hydroxy compounds or from their metallic derivatives
- C08L71/10—Polyethers derived from hydroxy compounds or from their metallic derivatives from phenols
- C08L71/12—Polyphenylene oxides
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B3/00—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties
- H01B3/18—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances
- H01B3/30—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes
- H01B3/40—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes epoxy resins
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2363/00—Characterised by the use of epoxy resins; Derivatives of epoxy resins
- C08J2363/02—Polyglycidyl ethers of bis-phenols
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2371/00—Characterised by the use of polyethers obtained by reactions forming an ether link in the main chain; Derivatives of such polymers
- C08J2371/08—Polyethers derived from hydroxy compounds or from their metallic derivatives
- C08J2371/10—Polyethers derived from hydroxy compounds or from their metallic derivatives from phenols
- C08J2371/12—Polyphenylene oxides
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2463/00—Characterised by the use of epoxy resins; Derivatives of epoxy resins
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Physics & Mathematics (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Materials Engineering (AREA)
- Non-Insulated Conductors (AREA)
Abstract
The present disclosure provides a thermosetting resin composition, an anisotropic conductive film, and a connection structure. The heat-curable resin composition of the present disclosure includes the following components: (A) A cationically polymerizable resin comprising tetrahydroindene diepoxide in an amount of 5 to 50% by weight of the thermosetting resin composition; (B) A thermal acid-generating initiator comprising a quaternary ammonium salt compound, the content of the quaternary ammonium salt compound accounting for 0.05-30 wt% of the cation-polymerizable resin; (C) A film-forming additive component, the film-forming additive componentThe content thereof is 20 to 70% by weight of the thermosetting resin composition; (D) Conductive particles, the content of which is 20-100000/mm 2 A conductive film.
Description
Technical Field
The present disclosure relates to the field of adhesive connection of electronic components, and more particularly, to a thermosetting resin composition, an anisotropic conductive film, and a connection structure.
Technical Field
In the fields of semiconductors, flat panel displays, and the like, anisotropic conductive films are widely used for fixing electronic components or for circuit connection because of their advantages such as directional conductive properties. For example, in the fields of chip packaging (COG) in which an IC chip is directly mounted on a glass substrate, packaging (FOG) of a flexible circuit board, and the like.
Conventionally, an anisotropic conductive film is mainly produced by using an epoxy curing composition of an anionic curing agent or a cationic curing agent as an adhesive layer and dispersing conductive particles therein. As electronic components become smaller, more dense, and more refined, electrode widths and electrode spacings become narrower, and IC chips and glass substrates become very thin. The thermal compression bonding during connection causes problems such as burning of components, and misalignment of circuit wiring after packaging due to thermal expansion difference between opposing circuit boards. In particular, in COG packaging, there is a problem that display unevenness occurs on a display due to warpage of a substrate caused by curing shrinkage of an anisotropic conductive film or a difference in thermal expansion between an IC chip and a glass substrate. In addition, in terms of production costs, in order to reduce costs and improve production efficiency, it is required that the adhesive layer material for preparing the anisotropic conductive film be capable of completing curing at a lower temperature (for example, 140 to 150 ℃) and in a shorter time (for example, within 5 seconds).
In recent years, in order to achieve storage stability and low-temperature rapid curability of an adhesive layer material of an anisotropic conductive film, a cationic curing system capable of being cured at a low temperature has been mainly developed. As compared with the general-purpose glycidyl ether compounds, alicyclic epoxy compounds having higher cationic polymerization reactivity and no oxygen inhibition of polymerization reaction are used as polymerization initiators having dark reactivity, and sulfonium salt type thermal acid initiators generating protons by heat are proposed. Such an anisotropic conductive film containing an alicyclic epoxy compound and a sulfonium salt type thermal acid initiator exhibits a curing temperature at a relatively low temperature (for example, about 100 ℃).
However, there is a problem that polymerization starts even at a temperature of about 40 to 60 ℃, and the adhesive may be cured during storage, resulting in low storage stability. On the other hand, when a polymerization initiator having a lower reactivity (for example, an iodinated salt compound) is used, although the storage stability of the anisotropic conductive film is ensured, it is difficult to cure the adhesive layer material of the anisotropic conductive film under the condition of a lower temperature (for example, 140 to 150 ℃) and a shorter time (for example, within 5 seconds).
In view of the foregoing, there is also a need to provide an adhesive material which is excellent in storage stability, can be cured at a relatively low temperature and in a relatively short time, and which enables the connection reliability of the produced anisotropic conductive film to be good.
Disclosure of Invention
In view of the above, in order to overcome at least one of the above-mentioned and other drawbacks of the prior art, the present disclosure proposes a thermosetting resin composition which has storage stability and can be cured at a low temperature and in a short time by using tetrahydroindene diepoxide and a quaternary ammonium salt compound in a film-forming additive component thereof, and which is successfully manufactured into an anisotropic conductive film having good connection reliability. .
In addition, the present disclosure proposes a connection structure that anisotropically connects a first electronic component and a second electronic component by an anisotropically conductive film after curing, realizes a stable connection state under low stress, and reduces warpage of a substrate.
In order to achieve the above object, in one aspect of the present disclosure, there is provided a thermosetting resin composition suitable for heat curing to prepare an anisotropic conductive film, the composition comprising:
(A) A cationically polymerizable resin comprising tetrahydroindene diepoxide, wherein the content of the tetrahydroindene diepoxide is 5 to 50% by weight of the thermosetting resin composition;
(B) A thermal acid generator comprising a quaternary ammonium compound, wherein the content of the quaternary ammonium compound is 0.05-30% by weight of the cation polymerizable resin;
(C) A film-forming additive component, wherein the content of the film-forming additive component is 20 to 70 wt% of the thermosetting resin composition;
(D) Conductive particles, the content of which is 20-100000/mm 2 A conductive film.
According to an embodiment of the present disclosure, the tetrahydroindene diepoxide is contained in an amount of 10 to 40 wt% based on the above thermosetting resin composition.
According to an embodiment of the present disclosure, the quaternary ammonium salt compound is a salt composed of a quaternary ammonium cation and a borate-based anion.
According to an embodiment of the present disclosure, the quaternary ammonium salt compound is at least one selected from the group consisting of dimethylphenyl (4-methoxybenzyl) ammonium tetrakis (pentafluorophenyl) borate, dimethylphenyl (4-methylbenzyl) ammonium hexafluorotetrakis (pentafluorophenyl) borate, methylphenyl dibenzylammonium tetrakis (pentafluorophenyl) borate, phenyltribenzylammonium tetrakis (pentafluorophenyl) borate, dimethylphenyl (3, 4-dimethylbenzyl) ammonium tetrakis (pentafluorophenyl) borate, and N, N-diethyl-N-benzylaniline boron tetrafluoride.
According to an embodiment of the present disclosure, the content of the quaternary ammonium salt compound is 2 to 15wt% of the above-described cationically polymerizable resin.
According to an embodiment of the present disclosure, the content of the film-forming additive component is 30 to 60% by weight of the thermosetting resin composition.
According to embodiments of the present disclosure, the film-forming additive component includes an epoxy resin or a phenoxy resin that is solid at ambient temperature.
According to an embodiment of the present disclosure, the epoxy resin is at least one selected from a bisphenol type epoxy resin, a novolac type epoxy resin, a naphthalene type epoxy resin, and a biphenyl type epoxy resin.
According to an embodiment of the present disclosure, the above-mentioned phenoxy resin is selected from at least one of fluorene-type phenoxy resin, bisphenol-type phenoxy resin, novolac-type phenoxy resin, naphthalene-type phenoxy resin, biphenyl-type phenoxy resin.
According to an embodiment of the present disclosure, the conductive particles are selected from at least one of nickel, cobalt, silver, copper, gold, palladium, solder, metallized resin particles.
According to an embodiment of the present disclosure, the content of the conductive particles is 200 to 70000 pieces/mm 2 A conductive film.
According to an embodiment of the present disclosure, the cationically polymerizable resin further includes a dimer oxygen dicyclohexyl group, the content of the dimer oxygen dicyclohexyl group being 0 to 50% by weight of the cationically polymerizable resin.
In another aspect of the present disclosure, there is provided an anisotropic conductive film made by thermally curing the above-mentioned thermal curing type resin composition;
according to embodiments of the present disclosure, the heat curing temperature is 140 to 160 ℃ and the curing time is within 5 seconds.
In still another aspect of the present disclosure, there is provided a connection structure in which the first electronic component and the second electronic component are anisotropically connected by using the above anisotropic conductive film.
The thermosetting resin composition provided by the present disclosure can be cured at a lower temperature (for example) and in a shorter time by adding tetrahydroindene diepoxide and quaternary ammonium salt compound to film-forming additive components, and by the synergistic combination of both; meanwhile, due to the existence of a rigid indene skeleton, the curing shrinkage is small, the glass transition temperature (Tg) is high, the storage stability is improved, and meanwhile, the low-temperature rapid curing is realized.
The connection state of the connection structure body after solidification is stable under low stress, the warping of the substrate can be reduced, and the connection reliability is greatly improved.
Detailed Description
For the purposes of promoting an understanding of the principles and advantages of the disclosure, reference will now be made in detail to the embodiments. However, the present disclosure is not limited to the following embodiments.
The terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the disclosure. The terms "comprises," "comprising," and/or the like, as used herein, specify the presence of stated features, steps, operations, and/or components, but do not preclude the presence or addition of one or more other features, steps, operations, or components. All terms (including technical and scientific terms) used herein have the same meaning as commonly understood by one of ordinary skill in the art unless otherwise defined. It should be noted that the terms used herein should be construed to have meanings consistent with the context of the present specification and should not be construed in an idealized or overly formal manner.
In the course of realizing the present disclosure, it was found that a cationic curing system using a tetrahydroindene diepoxide and a quaternary ammonium salt compound in a film-forming additive component of a thermosetting resin composition, the indene skeleton in the tetrahydroindene diepoxide had no steric hindrance and the curing shrinkage was very small. Further, the cured product Tg is high due to the rigid skeleton. Therefore, the connection reliability of the anisotropic conductive film obtained by thermally curing the composition can be improved, while the storage stability and the curing at a lower temperature in a shorter time can be achieved. In contrast, the anisotropic conductive film can provide a connection structure with high connection reliability, which can suppress warpage of the substrate as much as possible under relatively low stress.
In one aspect of the present disclosure, the thermosetting resin composition of the present disclosure is mainly composed of tetrahydroindene diepoxide, quaternary ammonium salt compound, film-forming additive component, and conductive particles as essential components. More specifically, provided is a thermosetting resin composition suitable for thermosetting to prepare an anisotropic conductive film, the composition comprising the following components:
(A) The cation polymerizable resin includes tetrahydroindene diepoxide, and the content of the tetrahydroindene diepoxide is 5 to 50% by weight of the thermosetting resin composition, and may be, for example, 5% by weight, 10% by weight, 20% by weight, 30% by weight, 40% by weight, 50% by weight, or the like;
(B) The thermal acid generator includes quaternary ammonium salt compound, wherein the content of the quaternary ammonium salt compound is 0.05-30 wt% of the cation polymerizable resin, for example, 0.05 wt%, 1wt%, 10wt%, 15wt%, 20wt%, 35 wt%, 30wt%, etc.;
(C) The content of the film-forming additive component is 20 to 70 wt% of the thermosetting resin composition, and may be, for example, 20wt%, 30wt%, 40 wt%, 50 wt%, 60 wt%, 70 wt%, etc.;
(D) Conductive particles, the content of which is 20-100000/mm 2 The conductive film may be 20 pieces/mm, for example 2 50 pieces/mm 2 80 pieces/mm 2 100 pieces/mm 2 、1000Individual/mm 2 10000 pieces/mm 2 100000/mm 2 Etc.
According to embodiments of the present disclosure, a cationic curing system employing tetrahydroindene diepoxide and a quaternary ammonium compound in a film-forming additive component, in combination, can be sufficiently cured at a relatively low temperature (e.g., 140-160 ℃) and for a relatively short period of time (e.g., within 5 seconds). The cured product has the characteristics of high Tg and small curing shrinkage rate compared with other alicyclic epoxy resin because of the rigid indene skeleton without three-dimensional obstacle, so that each conductive film containing conductive particles formed by the cured product shows a stable connection state under low stress, and the warping of a substrate can be reduced to the greatest extent.
According to an embodiment of the present disclosure, a cationically polymerizable resin used in the present disclosure refers to a resin or a resin monomer having at least one cationically polymerizable functional group, which may be exemplified by: cyclic ethers, cyclic imines, lactones, and the like. Examples of the cationically polymerizable resin include not only tetrahydroindene diepoxide monomers but also other epoxy resins.
Further in the case of using other epoxy resins in combination according to the embodiments of the present disclosure, an epoxy resin having the same reactivity as tetrahydroindene diepoxide as much as possible may be selected, for example, an alicyclic epoxy resin or the like may be used, with use of a dimeric oxy dicyclohexyl group being preferred.
According to an embodiment of the present disclosure, the cationically polymerizable resin further includes a dimer oxygen dicyclohexyl group, and the content of the dimer oxygen dicyclohexyl group is 0 to 50% by weight of the cationically polymerizable resin, and may be, for example, 0% by weight, 10% by weight, 20% by weight, 30% by weight, 40% by weight, 50% by weight, or the like.
According to the embodiments of the present disclosure, tetrahydroindene diepoxide is an alicyclic epoxy resin having an indene skeleton, and can be prepared by a conventionally known method. For example, a tetrahydroindene diepoxide (a compound represented by the following formula (T)) is produced by epoxidizing a corresponding cyclic polyolefin compound (a compound represented by the following formula (I)) with an oxidizing agent.
Examples of the oxidizing agent include hydrogen peroxide, aliphatic percarboxylic acid, and organic peroxide. The amount of the oxidizing agent to be used is 1 equivalent or more, preferably 1 to 2 equivalents, to the unsaturated bond of the cyclic polyolefin compound.
The epoxidation reaction is preferably carried out in a solvent, and examples of the solvent used include aliphatic hydrocarbons such as hexane and cyclohexane, aromatic hydrocarbons such as toluene, esters such as ethyl acetate and methyl acetate, and the like.
The reaction temperature is preferably 20 to 70℃and may be, for example, 20℃30℃40℃50℃60℃70 ℃. The reaction time is in the range of 1 to 100 hours depending on the reaction scale and the like, and may be, for example, 1 hour, 10 hours, 20 hours, 30 hours, 50 hours, 70 hours, 90 hours, 100 hours and the like.
After the completion of the reaction, the target tetrahydroindene diepoxide can be obtained by, for example, a method of precipitation of a poor solvent, a method of adding an epoxide into hot water with stirring and distilling off the solvent, a direct desolvation method, or the like. There are 4 stereoisomers based on a stereo configuration of 2 epoxy rings in tetrahydroindene diepoxide, but the ratio thereof has little influence on the characteristics of the anisotropic conductive film of the present disclosure.
According to the embodiments of the present disclosure, the tetrahydroindene diepoxide is contained in an amount of 10 to 40 wt% of the thermosetting resin composition.
According to the embodiments of the present disclosure, if the content of tetrahydroindene diepoxide is too small, the intended effect cannot be achieved, and if the content is too large, the film properties cannot be maintained.
According to embodiments of the present disclosure, the quaternary ammonium salt compound may be a salt composed of a quaternary ammonium cation and a borate-based anion;
the quaternary ammonium salt compound is used as a thermal acid initiator for curing an epoxy resin such as tetrahydroindene diepoxide, and can act on the cured resin at a relatively low temperature in a short time to improve the storage stability. The borate-based anion is preferably BF 4 -or (BX) 4 ) -wherein X represents phenyl substituted with at least 2 or more fluoro or trifluoromethyl groups.
Preferably, the quaternary ammonium salt compound is at least one selected from the group consisting of dimethylphenyl (4-methoxybenzyl) ammonium tetrakis (pentafluorophenyl) borate, dimethylphenyl (4-methylbenzyl) ammonium hexafluorotetrakis (pentafluorophenyl) borate, methylphenyl dibenzylammonium tetrakis (pentafluorophenyl) borate, phenyltribenzylammonium tetrakis (pentafluorophenyl) borate, dimethylphenyl (3, 4-dimethylbenzyl) ammonium tetrakis (pentafluorophenyl) borate, and N, N-diethyl-N-benzylaniline boron tetrafluoride.
According to an embodiment of the present disclosure, the content of the quaternary ammonium compound is 2 to 15wt% of the cationic polymerizable resin, and may be, for example, 2wt%, 5wt%, 8wt%, 10wt%, 13 wt%, 15wt%, or the like. The content of the quaternary ammonium compound is within this range, and the anisotropic conductive film obtained therefrom is excellent in low-temperature and short-time curability and storage stability.
According to the embodiment of the present disclosure, the film-forming additive component is a component for forming the anisotropic conductive film, and a solid epoxy resin or a phenoxy resin is used as an essential component at normal temperature, and may be used alone or in combination.
According to the embodiments of the present disclosure, the film forming property, the workability, and the connection reliability of the solid epoxy resin and the phenoxy resin at normal temperature are excellent, the cationic polymerization reaction is not hindered, and the curing reaction can be completed at a low temperature and in a short time. In addition, even after the reliability test under the high-temperature and high-humidity environment, the occurrence of peeling of the connection portion of the connection structure can be significantly suppressed.
According to an embodiment of the present disclosure, as the epoxy resin in a solid state at normal temperature, for example, at least one of bisphenol type epoxy resin, novolac type epoxy resin, naphthalene type epoxy resin, biphenyl type epoxy resin may be cited. Bisphenol type epoxy resin is preferably used from the viewpoint of film formability or processability.
Examples of the phenoxy resin in a solid state at ordinary temperature include at least one of fluorene-type phenoxy resin, bisphenol-type phenoxy resin, novolak-type phenoxy resin, naphthalene-type phenoxy resin, and biphenyl-type phenoxy resin.
According to embodiments of the present disclosure, further, the following film-forming auxiliary ingredients may also be used: unsaturated polyester resins, saturated polyester resins, polyurethane resins, butadiene resins, polyimide resins, polyamide resins, polyolefin resins, and the like.
According to the embodiment of the present disclosure, the content of the film-forming additive component is preferably 30 to 60 wt% based on the thermosetting resin composition, and may be, for example, 30wt%, 35 wt%, 40 wt%, 45 wt%, 50 wt%, 55 wt%, 60 wt%, or the like.
According to the embodiment of the present disclosure, the film forming additive component can sufficiently exhibit its film forming ability within this range.
According to an embodiment of the present disclosure, the conductive particles may be selected from at least one of nickel, cobalt, silver, copper, gold, palladium, solder, metallized resin particles, for example;
preferably, the content of the conductive particles is 200 to 70000 pieces/mm 2 The conductive film may be 200 pieces/mm, for example 2 500 pieces/mm 2 1000 pieces/mm 2 5000 pieces/mm 2 10000 pieces/mm 2 30000 pieces/mm 2 50000 pieces/mm 2 70000 pieces/mm 2 Etc. The measurement of this content can be counted by observation with an optical microscope.
According to the embodiment of the present disclosure, the average particle diameter of the conductive particles should be able to cope with the deviation in the wiring height. In order to suppress an increase in on-resistance and suppress occurrence of short-circuiting, the average particle diameter of the conductive particles is preferably 2.5 μm to 30 μm, more preferably 3 μm to 20 μm. The particle size of the conductive particles can be measured by a general particle size distribution measuring apparatus, and the average particle size thereof can also be measured by a particle size distribution measuring apparatus.
According to the embodiments of the present disclosure, depending on the type of circuit board to be connected, the components of the thermosetting resin composition may suitably contain an inorganic filler such as silica, a stress-relaxing agent such as a rubber component, or an additive such as a coupling agent or a leveling agent.
According to embodiments of the present disclosure, the inorganic filler may be used in an amount of 1 to 30wt%, for example, 1wt%, 5wt%, 15wt%, 20wt%, 25wt%, 30wt%, etc. The addition of the inorganic filler can reduce the thermal expansion coefficient and has a stabilizing effect on the connection state.
According to embodiments of the present disclosure, the stress-relieving agent may be used in an amount of 5 to 20wt%, for example, 5wt%, 8wt%, 10wt%, 15wt%, 20wt%, etc. The stress relieving agent can relieve shrinkage stress generated in the curing process, so that the connection state is stabilized.
According to an embodiment of the present disclosure, the coupling agent is a compound having both a portion reactive with an organic compound and a portion reactive with an inorganic compound, particularly a portion reactive with an organic compound is an epoxy group, a portion reactive with an inorganic compound is silane (silicon), and a silane coupling agent is preferably used. The amount of the coupling agent may be 0.01 to 5wt%, preferably 0.5 to 2.0wt%, for example, 0.5wt%, 1wt%, 2wt%, 4wt%, 5wt%, etc. Coupling agents may be used to improve adhesion to glass interfaces. Particularly, the glass interface peeling phenomenon can be prevented under the reliability of high temperature and high humidity.
According to embodiments of the present disclosure, the leveling agent may be used in an amount of 0.1 to 1.0wt%, for example, 0.1wt%, 0.3wt%, 0.6wt%, 0.8wt%, 1.0wt%, etc. The leveling agent has the effect of enabling the anisotropic conductive film to be peeled off from the release film more easily, and simultaneously, the leveling agent can enable the anisotropic conductive film to have a good pre-adhesion effect when being temporarily adhered to the circuit board.
In another aspect of the present disclosure, there is provided an anisotropic conductive film made by thermally curing the above-mentioned thermal curing type resin composition.
According to the embodiment of the disclosure, when the anisotropic conductive film is used for conductive connection of electronic components, the connection state after curing can be stable under low stress, and the warping of a substrate is reduced as far as possible.
According to an embodiment of the present disclosure, the heat curing temperature is preferably 140 to 160 ℃, and may be 140 ℃, 145 ℃, 150 ℃, 155 ℃, 160 ℃, or the like, and the curing time is preferably 5 seconds or less, and may be 1 second, 2 seconds, 3 seconds, 4 seconds, 5 seconds, or the like, for example.
According to an embodiment of the present disclosure, the anisotropic conductive film is produced by first uniformly dispersing an inorganic filler in an organic solvent such as toluene, then dissolving a film-forming additive component in the redispersion solution, and mixing and dispersing tetrahydroindene diepoxide, a quaternary ammonium salt compound and conductive particles therein to prepare a coating material, forming the coating material into a film by a known film-forming method, and then thermally curing the coating material.
According to the embodiment of the present disclosure, the anisotropic conductive film of the present disclosure may be a single layer or a double-layer structure of a layer containing conductive particles and a layer not containing conductive particles. By forming the bilayer structure, particle capturing efficiency at the time of connection can be improved, thereby reducing the amount of high-price conductive particles used and manufacturing cost.
According to the embodiment of the present disclosure, the film thickness of the anisotropic conductive film may be coated to be capable of sufficiently filling the thickness of the electrode portion of the circuit substrate, also depending on the size and number of the electrodes. Generally 3-10 mu mm thicker than the electrode height.
In still another aspect of the present disclosure, there is provided a connection structure in which the first electronic component and the second electronic component are anisotropically connected by using the above anisotropic conductive film.
According to an embodiment of the present disclosure, the first electronic component may be, for example, an electrode portion of the 1 st circuit substrate, and the second electronic component may be, for example, a connection portion of the 2 nd wired circuit substrate.
According to the embodiments of the present disclosure, further, the anisotropic conductive film can be preferably applied when anisotropically conductive connecting a 1 st circuit substrate such as an IC chip, COF, FPC, or the like with a 2 nd circuit substrate such as a glass circuit substrate, a plastic circuit substrate, a rigid circuit substrate, a ceramic circuit substrate, a polyimide circuit substrate, or the like. In addition, a known method can be used as a method for connecting electronic components of the anisotropic conductive film.
The proposal of the heat-curable resin composition, the anisotropic conductive film and the connection structure provides a method with excellent preservation stability and cost effectiveness for the research of the anisotropic conductive film, which has far-reaching significance for the development of adhesive materials in electronic products.
For the purposes of promoting an understanding of the principles and advantages of the disclosure, reference will now be made in detail to the embodiments. The test materials, reagents and the like used in the examples described below are commercially available unless otherwise specified. The examples are not intended to identify specific techniques or conditions, but are conventional and may be carried out according to techniques or conditions described in the literature in this field or according to product specifications.
Example 1: thermosetting resin composition
Tetrahydroindene diepoxide as component (a); a quaternary ammonium salt compound (product name CXC-1821, manufactured by King Industries Co., ltd.) was used as the component (B); a phenoxy resin (product name YP-50, manufactured by Nikki chemical materials Co., ltd.) was used as the component (C), and the mixing ratio of each component was shown in Table 1. Further, conductive particles (C) (trade name: ni-plated resin particles manufactured by Mircoparl, water chemical industry Co., ltd.) having an average particle diameter of 4 μm were used and mixed and dispersed to 60000 pieces/mm 2 A thermosetting resin composition, i.e., a binder composition, was obtained. Further, the adhesive composition was applied to a 50 μm thick release PET film using an applicator, and dried with hot air at 60℃for 5 minutes to obtain an adhesive layer having a thickness of 18. Mu.m. The mixing ratio of each component is shown in Table 1.
Example 2: thermosetting resin composition
In comparison with example 1, the adhesive layer was obtained in the same manner as in example 1 except that the component (A) was changed to tetrahydroindene diepoxide and alicyclic epoxy resin (product name: CELLOXIDE 8000, manufactured by Kagaku Co., ltd.). The mixing ratio of each component is shown in Table 1.
Example 3: thermosetting resin composition
In comparison with example 1, the adhesive layer was obtained in the same manner as in example 1 except that the component (C) was changed to a solid epoxy resin (product name YD-020, manufactured by KUKDO CHEMICAL Co., ltd.). The mixing ratios of the components are shown in Table 1.
Comparative example 1
An adhesive layer was obtained in the same manner as in example 1 except that the component (A) was changed to an alicyclic epoxy resin (product name: CELLOXIDE 8000, manufactured by Kagaku Kogyo Co., ltd.). The mixing ratio of each component is shown in Table 1.
Comparative example 2
An adhesive layer was obtained in the same manner as in example 1 except that the component (B) was changed to a sulfonate compound (product name: SAN-Aid SI-60L, manufactured by Sanxinshi chemical Co., ltd.). The mixing ratio of each component is shown in Table 1.
The thermosetting resin compositions of examples 1 to 3 and comparative examples 1 to 2 were subjected to performance test by the following specific test methods:
1. differential Scanning Calorimeter (DSC) measurements
The adhesive layers obtained in each of the examples and comparative examples were measured using differential scanning calorimeter (DSC 250, manufactured by TA company). The sample amount is 5mg, the measurement temperature ranges from 50 ℃ to 250 ℃ and the heating rate is 10 ℃/min, and the heating start temperature, the heating end temperature and the heating value are tested. The results are shown in Table 1.
2. Evaluation of storage stability
The adhesive layers obtained in the examples and comparative examples were left to stand in a thermostatic device at 40℃for 24 hours. The adhesive layer after being left at 40℃was subjected to DSC measurement, and the storage stability was judged from the heat generation reduction rate. The decrease rate was less than 10% and was judged as "X" when 10% or more. The results are shown in Table 1.
Heat generation amount reduction ratio (%) = [ (heat generation amount before 40 ℃ placement-heat generation amount after 40 ℃ placement)/heat generation amount before 40 ℃ placement ]
Example 4: connection structure body
IC chips (outline: 1.6mm.times.15.1 mm, bump height: 12 μm), glass substrates (OA-10G manufactured by Japanese electric glass Co., ltd., outline: 40 mm.times.20 mm, thickness: 0.5mm, surface ITO (indium tin oxide) wiring pitch (wiring width: 22 μm, line width: 8 μm)), the adhesive layers obtained in each of examples and comparative examples were cut to a size of 2.times.20 mm, and bonded to the glass substrates, and the bonded substrates were heated and pressed at a bonding condition of 140℃and 160℃under a pressure and a time of 60MPa for 5 seconds, whereby the cured anisotropic conductive films were bonded to the IC chips and the glass substrates to obtain a bonded structure.
The connection structure of example 4 was subjected to performance test, and the specific test method is as follows:
1. measurement of connection resistance
The connection resistance after the connection of the connection structure was measured, and the connection resistance after the high-temperature and high-humidity environment exposure (85 ℃ C./85% RH/500 hours) was measured. The measurement was performed using a function checker (model: RM3545, manufactured by HIOKI Co.) and the resistance value when a current of 1mA was passed was measured by the 4-terminal method. The connection resistance value after the high-temperature and high-humidity exposure was determined to be equal to or smaller than 10Ω and equal to or greater than 10Ω was determined to be x. The results are shown in Table 1.
2. Evaluation of warpage
The measurement of the warp of the glass substrate side was performed on the connection structure connected at 160 ℃/60MPa/5 seconds. The surface roughness was measured by moving the contact pin on the back surface side of the glass substrate to which the IC chip was not connected, using a surface roughness measuring machine (trade name: SE500A, manufactured by Xiao ban research Co., ltd.). The results are shown in Table 1.
TABLE 1
CELLOXIDE 8000: alicyclic epoxy resin (structural name of dicyclohexyl)
The product is CXC-1821 quaternary ammonium salt (dimethyl phenyl (4-methoxybenzyl) ammonium tetra (pentafluorophenyl) borate)
SI-60L: sulfonium salt (methyl hexafluoroantimonate (4-hydroxyphenyl) benzyl sulfonium)
YP-50: phenoxy resin (bisphenol A type phenoxy resin)
The method comprises the following steps: epoxy resin (bisphenol A type epoxy resin)
As can be seen from table 1 above, the composition using tetrahydroindene diepoxide and quaternary ammonium salt in example 1 showed a reduction in heat generation of less than 10% after 24 hours of storage at 40 ℃, indicating good storage stability; in example 2, the other alicyclic epoxy resin was used as the cationically polymerizable resin, and this storage stability was maintained, and in example 3, the solid epoxy resin was used as the film-forming additive component, and this storage stability was also maintained. In comparative example 2, since the sulfonate compound was used as the thermal acid generator, the amount of heat generated after storage at 40℃for 24 hours was significantly reduced, and the storage stability was deteriorated.
In example 4, the connection structure obtained by using the thermosetting resin compositions of examples 1 to 3 had a connection resistance value of less than 10Ω after exposure to high temperature and high humidity even when connected at a low temperature of 140 ℃, indicating that the connection state was stable and the warpage of the connection structure was small. The thermosetting resin composition of comparative example 1 was used to prepare a connection structure at a connection temperature of 140℃and, since tetrahydroindene diepoxide was not used, the resistance value was 10. OMEGA. Or more after 85℃to 85% RH/500 hours, and the connection state became unstable. The thermosetting resin composition of comparative example 2 was used, and although tetrahydroindene diepoxide was used, a sulfonate compound was used as a thermal acid generator; when the connection structure is produced at a connection temperature of 140℃and 160℃and the resistance value is 10. OMEGA. Or more after 85 ℃/85% RH/500 hours, the connection state becomes unstable.
As described above, the thermosetting resin composition of the present disclosure has excellent storage stability and can be cured at a relatively low temperature (for example, 140 to 150 ℃) in a short time (for example, within 5 seconds), so that the connection state of the cured anisotropic conductive film is stable under low stress, warpage of the substrate can be reduced as much as possible, and a connection structure having excellent connection reliability can be produced.
While the foregoing is directed to embodiments of the present disclosure, other and further details of the invention may be had by the present application, it is to be understood that the foregoing description is merely exemplary of the present disclosure and that no limitations are intended to the scope of the disclosure, except insofar as modifications, equivalents, improvements or modifications may be made without departing from the spirit and principles of the present disclosure.
Claims (10)
1. A thermosetting resin composition suitable for heat curing to produce an anisotropic conductive film, the composition comprising the following components:
(A) A cationically polymerizable resin comprising tetrahydroindene diepoxide in an amount of 5 to 50% by weight of the thermosetting resin composition;
(B) A thermal acid-generating initiator comprising a quaternary ammonium salt compound, the content of the quaternary ammonium salt compound accounting for 0.05-30 wt% of the cation-polymerizable resin;
(C) A film-forming additive component, wherein the content of the film-forming additive component is 20-70 wt% of the thermosetting resin composition;
(D) Conductive particles, the content of which is 20-100000/mm 2 A conductive film.
2. The thermosetting resin composition according to claim 1, wherein the tetrahydroindene diepoxide is present in an amount of 10 to 40% by weight of the thermosetting resin composition.
3. The thermosetting resin composition according to claim 1, wherein the quaternary ammonium salt compound is a salt composed of a quaternary ammonium cation and a borate-based anion;
preferably, the quaternary ammonium salt compound is at least one selected from the group consisting of dimethylphenyl (4-methoxybenzyl) ammonium tetrakis (pentafluorophenyl) borate, dimethylphenyl (4-methylbenzyl) ammonium hexafluorotetrakis (pentafluorophenyl) borate, methylphenyl dibenzylammonium tetrakis (pentafluorophenyl) borate, phenyltribenzylammonium tetrakis (pentafluorophenyl) borate, dimethylphenyl (3, 4-dimethylbenzyl) ammonium tetrakis (pentafluorophenyl) borate, and N, N-diethyl-N-benzylaniline boron tetrafluoride.
4. The thermosetting resin composition according to claim 1 or 3, wherein the content of the quaternary ammonium salt compound is 2 to 15% by weight of the cationically polymerizable resin.
5. The thermosetting resin composition according to claim 1, wherein the content of the film-forming additive component is 30 to 60% by weight of the thermosetting resin composition.
6. The thermosetting resin composition according to claim 1 or 5, wherein the film-forming additive component comprises an epoxy resin or a phenoxy resin in a solid state at ordinary temperature;
preferably, the epoxy resin is at least one selected from bisphenol type epoxy resin, novolac type epoxy resin, naphthalene type epoxy resin, biphenyl type epoxy resin;
preferably, the phenoxy resin is at least one selected from fluorene-type phenoxy resin, bisphenol-type phenoxy resin, novolac-type phenoxy resin, naphthalene-type phenoxy resin, and biphenyl-type phenoxy resin.
7. The thermosetting resin composition according to claim 1, wherein the conductive particles are at least one selected from nickel, cobalt, silver, copper, gold, palladium, solder, metallized resin particles;
preferably, the content of the conductive particles is 200 to 70000 pieces/mm 2 A conductive film.
8. The thermosetting resin composition according to claim 1, wherein the cationically polymerizable resin further comprises a dimer oxygen dicyclohexyl group, and the content of the dimer oxygen dicyclohexyl group is 0 to 50% by weight of the cationically polymerizable resin.
9. An anisotropic conductive film produced by thermally curing the thermally curable resin composition according to any one of claims 1 to 8;
preferably, the temperature of the heat curing is 140 to 160 ℃ and the curing time is less than 5 seconds.
10. A connection structure formed by anisotropically conductive connection of a first electronic component and a second electronic component using the anisotropic conductive film according to claim 9.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2012136577A (en) * | 2010-12-24 | 2012-07-19 | Nippon Zeon Co Ltd | Semiconductor-sealing material and semiconductor device |
| CN108602970A (en) * | 2016-02-22 | 2018-09-28 | 迪睿合株式会社 | Anisotropic conductive film |
| JP2019182964A (en) * | 2018-04-06 | 2019-10-24 | 株式会社スリーボンド | Cationic curable resin composition and cured article thereof |
| CN112566995A (en) * | 2018-09-10 | 2021-03-26 | 迪睿合株式会社 | Adhesive composition |
-
2023
- 2023-11-30 CN CN202311623638.6A patent/CN117659667B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2012136577A (en) * | 2010-12-24 | 2012-07-19 | Nippon Zeon Co Ltd | Semiconductor-sealing material and semiconductor device |
| CN108602970A (en) * | 2016-02-22 | 2018-09-28 | 迪睿合株式会社 | Anisotropic conductive film |
| JP2019182964A (en) * | 2018-04-06 | 2019-10-24 | 株式会社スリーボンド | Cationic curable resin composition and cured article thereof |
| CN112566995A (en) * | 2018-09-10 | 2021-03-26 | 迪睿合株式会社 | Adhesive composition |
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