JP2020041045A - Adhesive composition - Google Patents
Adhesive composition Download PDFInfo
- Publication number
- JP2020041045A JP2020041045A JP2018168973A JP2018168973A JP2020041045A JP 2020041045 A JP2020041045 A JP 2020041045A JP 2018168973 A JP2018168973 A JP 2018168973A JP 2018168973 A JP2018168973 A JP 2018168973A JP 2020041045 A JP2020041045 A JP 2020041045A
- Authority
- JP
- Japan
- Prior art keywords
- adhesive composition
- component
- film
- electronic component
- elastomer
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 230000001070 adhesive effect Effects 0.000 title claims abstract description 96
- 239000000853 adhesive Substances 0.000 title claims abstract description 94
- 239000000203 mixture Substances 0.000 title claims abstract description 76
- 229920001971 elastomer Polymers 0.000 claims abstract description 45
- 239000000806 elastomer Substances 0.000 claims abstract description 41
- -1 oxetane compound Chemical class 0.000 claims abstract description 29
- 150000001875 compounds Chemical class 0.000 claims abstract description 27
- 239000004593 Epoxy Substances 0.000 claims abstract description 26
- 125000002723 alicyclic group Chemical group 0.000 claims abstract description 23
- 238000010538 cationic polymerization reaction Methods 0.000 claims abstract description 16
- 239000002253 acid Substances 0.000 claims abstract description 15
- 239000003505 polymerization initiator Substances 0.000 claims abstract description 15
- 150000003242 quaternary ammonium salts Chemical class 0.000 claims abstract description 12
- 125000001453 quaternary ammonium group Chemical group 0.000 claims abstract description 5
- 239000002245 particle Substances 0.000 claims description 50
- 238000004519 manufacturing process Methods 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 8
- 229920006287 phenoxy resin Polymers 0.000 claims description 7
- 239000013034 phenoxy resin Substances 0.000 claims description 7
- 229920000800 acrylic rubber Polymers 0.000 claims description 6
- 229920000058 polyacrylate Polymers 0.000 claims description 6
- BIDWUUDRRVHZLQ-UHFFFAOYSA-N 3-ethyl-3-(2-ethylhexoxymethyl)oxetane Chemical compound CCCCC(CC)COCC1(CC)COC1 BIDWUUDRRVHZLQ-UHFFFAOYSA-N 0.000 claims description 3
- 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 2
- WBIQQQGBSDOWNP-UHFFFAOYSA-N 2-dodecylbenzenesulfonic acid Chemical compound CCCCCCCCCCCCC1=CC=CC=C1S(O)(=O)=O WBIQQQGBSDOWNP-UHFFFAOYSA-N 0.000 claims description 2
- DCOXQQBTTNZJBI-UHFFFAOYSA-N 3-ethyl-3-[[4-[4-[(3-ethyloxetan-3-yl)methoxymethyl]phenyl]phenyl]methoxymethyl]oxetane Chemical group C=1C=C(C=2C=CC(COCC3(CC)COC3)=CC=2)C=CC=1COCC1(CC)COC1 DCOXQQBTTNZJBI-UHFFFAOYSA-N 0.000 claims description 2
- 125000003118 aryl group Chemical group 0.000 claims description 2
- 150000001768 cations Chemical class 0.000 claims description 2
- 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 2
- JGTNAGYHADQMCM-UHFFFAOYSA-N perfluorobutanesulfonic acid Chemical compound OS(=O)(=O)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F JGTNAGYHADQMCM-UHFFFAOYSA-N 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims description 2
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims description 2
- ITMCEJHCFYSIIV-UHFFFAOYSA-N triflic acid Chemical compound OS(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-N 0.000 claims description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims 1
- 125000000217 alkyl group Chemical group 0.000 claims 1
- 150000001450 anions Chemical class 0.000 claims 1
- 229910052799 carbon Inorganic materials 0.000 claims 1
- 125000004122 cyclic group Chemical group 0.000 claims 1
- 238000003860 storage Methods 0.000 abstract description 28
- 125000002091 cationic group Chemical group 0.000 abstract description 10
- 239000000470 constituent Substances 0.000 abstract 7
- 239000010408 film Substances 0.000 description 53
- 239000000758 substrate Substances 0.000 description 36
- 239000010410 layer Substances 0.000 description 17
- 239000011521 glass Substances 0.000 description 12
- 229920005989 resin Polymers 0.000 description 12
- 239000011347 resin Substances 0.000 description 12
- 238000012360 testing method Methods 0.000 description 11
- 238000006243 chemical reaction Methods 0.000 description 10
- 238000011156 evaluation Methods 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 9
- 239000004033 plastic Substances 0.000 description 9
- 229920003023 plastic Polymers 0.000 description 9
- 238000005259 measurement Methods 0.000 description 8
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 5
- 239000000919 ceramic Substances 0.000 description 5
- 239000003822 epoxy resin Substances 0.000 description 5
- 229920000647 polyepoxide Polymers 0.000 description 5
- 229920000642 polymer Polymers 0.000 description 5
- 239000002313 adhesive film Substances 0.000 description 4
- 238000002788 crimping Methods 0.000 description 4
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 230000009257 reactivity Effects 0.000 description 4
- 239000005060 rubber Substances 0.000 description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 230000006866 deterioration Effects 0.000 description 3
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical class C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 230000000977 initiatory effect Effects 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 239000000178 monomer Substances 0.000 description 3
- 150000002921 oxetanes Chemical class 0.000 description 3
- 229920002857 polybutadiene Polymers 0.000 description 3
- 229920000139 polyethylene terephthalate Polymers 0.000 description 3
- 239000005020 polyethylene terephthalate Substances 0.000 description 3
- 239000007870 radical polymerization initiator Substances 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- 239000002356 single layer Substances 0.000 description 3
- 239000010409 thin film Substances 0.000 description 3
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 2
- 244000043261 Hevea brasiliensis Species 0.000 description 2
- 229920000459 Nitrile rubber Polymers 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- 239000005062 Polybutadiene Substances 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 238000005452 bending Methods 0.000 description 2
- 235000010290 biphenyl Nutrition 0.000 description 2
- 239000004305 biphenyl Substances 0.000 description 2
- 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 description 2
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000013329 compounding Methods 0.000 description 2
- 238000007906 compression Methods 0.000 description 2
- 239000004020 conductor Substances 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 230000005489 elastic deformation Effects 0.000 description 2
- 125000003700 epoxy group Chemical group 0.000 description 2
- 230000001747 exhibiting effect Effects 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- 229920003049 isoprene rubber Polymers 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 125000004184 methoxymethyl group Chemical group [H]C([H])([H])OC([H])([H])* 0.000 description 2
- 229920003052 natural elastomer Polymers 0.000 description 2
- 229920001194 natural rubber Polymers 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 229920001084 poly(chloroprene) Polymers 0.000 description 2
- 229920001721 polyimide Polymers 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 229920000468 styrene butadiene styrene block copolymer Polymers 0.000 description 2
- UNMJLQGKEDTEKJ-UHFFFAOYSA-N (3-ethyloxetan-3-yl)methanol Chemical compound CCC1(CO)COC1 UNMJLQGKEDTEKJ-UHFFFAOYSA-N 0.000 description 1
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 description 1
- HFCUBKYHMMPGBY-UHFFFAOYSA-N 2-methoxyethyl prop-2-enoate Chemical compound COCCOC(=O)C=C HFCUBKYHMMPGBY-UHFFFAOYSA-N 0.000 description 1
- VSKJLJHPAFKHBX-UHFFFAOYSA-N 2-methylbuta-1,3-diene;styrene Chemical compound CC(=C)C=C.C=CC1=CC=CC=C1.C=CC1=CC=CC=C1 VSKJLJHPAFKHBX-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical class S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 1
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000001588 bifunctional effect Effects 0.000 description 1
- FACXGONDLDSNOE-UHFFFAOYSA-N buta-1,3-diene;styrene Chemical compound C=CC=C.C=CC1=CC=CC=C1.C=CC1=CC=CC=C1 FACXGONDLDSNOE-UHFFFAOYSA-N 0.000 description 1
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000007771 core particle Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 125000006165 cyclic alkyl group Chemical group 0.000 description 1
- WDNQRCVBPNOTNV-UHFFFAOYSA-N dinonylnaphthylsulfonic acid Chemical compound C1=CC=C2C(S(O)(=O)=O)=C(CCCCCCCCC)C(CCCCCCCCC)=CC2=C1 WDNQRCVBPNOTNV-UHFFFAOYSA-N 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 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 1
- 238000010438 heat treatment Methods 0.000 description 1
- BDVZHDCXCXJPSO-UHFFFAOYSA-N indium(3+) oxygen(2-) titanium(4+) Chemical compound [O-2].[Ti+4].[In+3] BDVZHDCXCXJPSO-UHFFFAOYSA-N 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000002923 metal particle Substances 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229920003986 novolac Polymers 0.000 description 1
- 150000001451 organic peroxides Chemical class 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 229920006122 polyamide resin 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
- 238000002360 preparation method Methods 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 229910000679 solder Inorganic materials 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
- 229920006337 unsaturated polyester resin Polymers 0.000 description 1
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
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/04—Non-macromolecular additives inorganic
-
- 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
- C09J11/06—Non-macromolecular additives organic
-
- 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
- C09J11/08—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
- C09J119/00—Adhesives based on rubbers, not provided for in groups C09J107/00 - C09J117/00
-
- 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
- C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
- C09J133/04—Homopolymers or copolymers of esters
-
- 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
- C09J171/00—Adhesives based on polyethers obtained by reactions forming an ether link in the main chain; Adhesives based on derivatives of such polymers
- C09J171/08—Polyethers derived from hydroxy compounds or from their metallic derivatives
- C09J171/10—Polyethers derived from hydroxy compounds or from their metallic derivatives from phenols
-
- 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
-
- 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
- H01B1/22—Conductive material dispersed in non-conductive organic material the conductive material comprising metals or alloys
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B5/00—Non-insulated conductors or conductive bodies characterised by their form
- H01B5/16—Non-insulated conductors or conductive bodies characterised by their form comprising conductive material in insulating or poorly conductive material, e.g. conductive rubber
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Dispersion Chemistry (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Adhesives Or Adhesive Processes (AREA)
- Non-Insulated Conductors (AREA)
- Conductive Materials (AREA)
Abstract
Description
本発明は、異方性導電フィルムに好ましく適用可能な接着剤組成物に関する。 The present invention relates to an adhesive composition preferably applicable to an anisotropic conductive film.
ＩＣチップをガラス基板に異方性導電フィルムを用いて実装（即ち、ＣＯＧ実装）する場合、ＩＣチップに対する熱衝撃を緩和し、実装の生産性を向上させるために、低温速硬化性を示す異方性導電フィルムを使用することが求められている。従来、このような異方性導電フィルムの重合系として、汎用のグリシジルエーテル型化合物よりもカチオン重合反応性の高い脂環式エポキシ化合物に低極性オキセタン化合物を併用したカチオン重合性成分に、酸素による重合阻害がなく、暗反応性を示すカチオン重合開始剤として、熱によりプロトンを発生する第４級アンモニウム塩系熱酸発生剤を使用することが提案されている（特許文献１）。 When an IC chip is mounted on a glass substrate using an anisotropic conductive film (that is, COG mounting), in order to reduce thermal shock to the IC chip and to improve mounting productivity, a different type that exhibits low-temperature rapid curing properties. It is required to use an isotropic conductive film. Conventionally, as a polymerization system of such anisotropic conductive film, a cationic polymerizable component obtained by using a low-polarity oxetane compound in combination with an alicyclic epoxy compound having a higher cationic polymerization reactivity than a general-purpose glycidyl ether type compound, using oxygen. It has been proposed to use a quaternary ammonium salt-based thermal acid generator that generates a proton by heat as a cationic polymerization initiator having no polymerization inhibition and exhibiting dark reactivity (Patent Document 1).
しかしながら、特許文献１に開示された異方性導電フィルムは、ＣＯＧ実装の場合には、良好な接着強度と、実用的な保管ライフと、良好な導通特性とを実現しているが、フレキシブル回路基板（ＦＰＣ）をガラス基板やプラスチック基板に実装（ＦＯＧ実装やＦＯＰ実装）する場合には、実装後にＦＰＣに対して曲げ応力や引張り応力、剪断応力あるいは剥離応力等がかかるため、実用的な接着強度が得られにくくなることが懸念されている。更に、ＣＯＦ実装でも同様に導通抵抗値などの導通特性の低下や保管ライフ特性の低下という問題の発生が懸念されている。また、高価な低極性オキセタン化合物の使用を抑制もしくは省略できるようにすることも求められている。 However, the anisotropic conductive film disclosed in Patent Document 1 achieves good adhesive strength, practical storage life, and good conduction characteristics in the case of COG mounting. When a substrate (FPC) is mounted on a glass substrate or a plastic substrate (FOG mounting or FOP mounting), a bending stress, a tensile stress, a shearing stress, a peeling stress, or the like is applied to the FPC after the mounting, so that practical bonding is performed. There is a concern that it will be difficult to obtain strength. Further, there is a concern that the problem of deterioration of conduction characteristics such as conduction resistance value and deterioration of storage life characteristics may also occur in COF mounting. There is also a need to be able to suppress or omit the use of expensive low-polar oxetane compounds.
本発明の課題は、脂環式エポキシ化合物等のカチオン重合性成分と第４級アンモニウム塩系熱酸発生剤とを使用するカチオン重合性の接着剤組成物、中でも異方性導電接着剤について、ＣＯＧ実装だけでなくＦＯＧ実装やＦＯＰ実装においても実用的な低温速硬化性と導通特性と保管ライフ特性と接着特性とを実現できるようにすることである。 An object of the present invention is to provide a cationically polymerizable adhesive composition using a cationically polymerizable component such as an alicyclic epoxy compound and a quaternary ammonium salt-based thermal acid generator, especially an anisotropic conductive adhesive. It is an object of the present invention to realize practical low-temperature quick-curing properties, conduction properties, storage life properties, and adhesive properties that are practical not only in COG mounting but also in FOG mounting and FOP mounting.
本発明者は、脂環式エポキシ化合物に代表されるカチオン重合性成分と、カチオン重合開始剤として４級アンモニウム塩系熱酸発生剤と、成膜用成分とを含有する接着剤組成物に、エラストマーを配合し、しかも、カチオン重合性成分、エラストマー及び成膜用成分の含有量をそれぞれ所定範囲に調整することにより、本発明の課題を解決できることを見出し、本発明を完成させるに至った。 The present inventor has proposed a cationic polymerizable component represented by an alicyclic epoxy compound, a quaternary ammonium salt-based thermal acid generator as a cationic polymerization initiator, and an adhesive composition containing a film-forming component. The inventors have found that the problems of the present invention can be solved by blending an elastomer and adjusting the contents of the cationically polymerizable component, the elastomer, and the component for forming a film to respective predetermined ranges, thereby completing the present invention.
即ち、本発明は、カチオン重合性成分とカチオン重合開始剤とエラストマーと成膜用成分とを含有する接着剤組成物であって、
カチオン重合性成分が、脂環式エポキシ化合物又は低極性オキセタン化合物であり、
カチオン重合開始剤が、第４級アンモニウム塩系熱酸発生剤であり、
カチオン重合性成分の含有量が、カチオン重合性成分とエラストマーと成膜用成分との合計質量の１０〜４０質量％であり、
エラストマーの含有量が、カチオン重合性成分とエラストマーと成膜用成分との合計質量の１０〜４０質量％であり、そして
成膜用成分の含有量が、カチオン重合性成分とエラストマーと成膜用成分との合計質量の４０〜８０質量％である接着剤組成物を提供する。
That is, the present invention is an adhesive composition containing a cationically polymerizable component, a cationic polymerization initiator, an elastomer, and a film-forming component,
The cationically polymerizable component is an alicyclic epoxy compound or a low-polarity oxetane compound,
The cationic polymerization initiator is a quaternary ammonium salt-based thermal acid generator,
The content of the cationically polymerizable component is 10 to 40% by mass of the total mass of the cationically polymerizable component, the elastomer, and the film-forming component,
The content of the elastomer is 10 to 40% by mass of the total mass of the cationically polymerizable component, the elastomer, and the film forming component, and the content of the film forming component is the cationically polymerizable component, the elastomer, and the film forming component. An adhesive composition is provided which is 40 to 80% by mass of the total mass with the components.
また、本発明の接着剤組成物は、導電粒子を含有しているか否かに関わらず、ＦＰＣ、ＩＣチップ、ＩＣモジュールなどの第１電子部品と、プラスチック基板、ガラス基板、リジッド基板、セラミック基板、ＦＰＣなどの第２電子部品とを接続、好ましくは電気的に接続する際に（特に異方性導電接続する際に）適用することができる。特にＦＰＣが使われている接続構造体に好ましく適用することができ、ＦＰＣが第１電子部品に使われている接続構造体により好ましく適用することができる。従って、本発明は、上述の接着剤組成物で、第１電子部品と第２電子部品とが接続、好ましくは電気的に接続（好ましくは異方性導電接続）されている接続構造体、及びその製造方法も提供する。 In addition, the adhesive composition of the present invention includes a first electronic component such as an FPC, an IC chip, an IC module, a plastic substrate, a glass substrate, a rigid substrate, and a ceramic substrate regardless of whether or not the adhesive composition contains conductive particles. , FPC and the like, and can be applied when connecting, preferably electrically (especially when performing anisotropic conductive connection). In particular, the present invention can be preferably applied to a connection structure using an FPC, and the FPC can be preferably applied to a connection structure using a first electronic component. Therefore, the present invention provides a connection structure in which the first electronic component and the second electronic component are connected, preferably electrically connected (preferably anisotropic conductive connection), with the above-mentioned adhesive composition, and A method for its manufacture is also provided.
本発明の接着剤組成物においては、脂環式エポキシ化合物に代表されるカチオン重合性成分と、カチオン重合開始剤として４級アンモニウム塩系熱酸発生剤と、成膜用成分とに、更にエラストマーを配合し、しかも、カチオン重合性成分、エラストマー及び成膜用成分の含有量をそれぞれ所定範囲に調整する。このため、本発明の接着剤組成物は、異方性導電接続用の導電粒子を含有している場合には、従前と同様の低温速硬化性と、導通特性と、保管ライフ特性とを担保しながらも、ＦＯＧ実装やＦＯＰ実装においても実用的な接着強度を実現することができる。 In the adhesive composition of the present invention, a cationically polymerizable component represented by an alicyclic epoxy compound, a quaternary ammonium salt-based thermal acid generator as a cationic polymerization initiator, a film-forming component, and an elastomer And the contents of the cationically polymerizable component, the elastomer, and the component for film formation are each adjusted to a predetermined range. For this reason, when the adhesive composition of the present invention contains conductive particles for anisotropic conductive connection, it ensures the same low-temperature fast-curing property, conductive property, and storage life property as before. However, practical bonding strength can be realized even in FOG mounting or FOP mounting.
以下、本発明の一例を、詳細に説明する。 Hereinafter, an example of the present invention will be described in detail.
＜接着剤組成物＞
本発明の接着剤組成物は、カチオン重合性成分とカチオン重合開始剤とエラストマーと成膜用成分とを含有する。以下、これらの成分について詳細に説明する。なお、本発明の接着剤組成物は、液状接着剤、ペースト状接着剤、フィルム状接着剤、ペレット状接着剤等の種々の形態を取ることができる。中でも、好ましいフィルム状接着剤として、異方性導電フィルムを例示することができる。
<Adhesive composition>
The adhesive composition of the present invention contains a cationically polymerizable component, a cationic polymerization initiator, an elastomer, and a film-forming component. Hereinafter, these components will be described in detail. The adhesive composition of the present invention can take various forms such as a liquid adhesive, a paste adhesive, a film adhesive, and a pellet adhesive. Among them, an anisotropic conductive film can be exemplified as a preferable film adhesive.
（カチオン重合性成分）
カチオン重合性成分は、接着剤組成物を硬化させる成分であり、エポキシ化合物として汎用のグリシジルエーテル型エポキシ化合物よりも高い反応性を有する脂環式エポキシ化合物又は低極性オキセタン化合物のいずれかを少なくとも含有している。これらは併用することもできる。好ましくは、カチオン重合性成分として脂環式エポキシ化合物だけを使用する。
(Cationically polymerizable component)
The cationically polymerizable component is a component that cures the adhesive composition, and contains at least either an alicyclic epoxy compound or a low-polarity oxetane compound having higher reactivity than a general-purpose glycidyl ether type epoxy compound as an epoxy compound. are doing. These can be used in combination. Preferably, only alicyclic epoxy compounds are used as cationically polymerizable components.
カチオン重合性成分の含有量は、良好な低温速硬化性を実現するために、カチオン重合性成分とエラストマーと成膜用成分との合計質量の１０質量％以上、好ましくは１５質量％以上であり、相対的にエラストマーの含有量を一定以上に保持して良好な接着性を実現するために、カチオン重合性成分とエラストマーと成膜用成分との合計質量の４０質量％以下、好ましくは３５質量％以下である。 The content of the cationically polymerizable component is 10% by mass or more, preferably 15% by mass or more of the total mass of the cationically polymerizable component, the elastomer, and the film-forming component in order to realize good low-temperature rapid curability. In order to relatively maintain the content of the elastomer at a certain level or more and achieve good adhesiveness, the total mass of the cationically polymerizable component, the elastomer and the film-forming component is 40% by mass or less, preferably 35% by mass. % Or less.
（脂環式エポキシ化合物）
脂環式エポキシ化合物を使用する理由は、汎用のグリシジルエーテル型エポキシ化合物よりも高いその反応性を利用して、異方性導電フィルムに良好な低温速硬化性を付与するためである。このような脂環式エポキシ化合物としては、分子内に２つ以上のエポキシ基を有するものが好ましく挙げられる。これらは液状であっても、固体状であってもよい。具体的には、ジグリシジルヘキサヒドロビスフェノールＡ、３，４−エポキシシクロヘキセニルメチル−３′，４′−エポキシシクロヘキセンカルボキシレート、ジエポキシビシクロヘキシル等を挙げることができる。なかでも、硬化物の光透過性を確保でき、速硬化性にも優れている点から、ジグリシジルヘキサヒドロビスフェノールＡ、特にジエポキシビシクロヘキシルを好ましく使用することができる。
(Alicyclic epoxy compound)
The reason for using an alicyclic epoxy compound is to provide good low-temperature quick-curing properties to the anisotropic conductive film by utilizing its higher reactivity than general-purpose glycidyl ether type epoxy compounds. As such an alicyclic epoxy compound, a compound having two or more epoxy groups in a molecule is preferable. These may be liquid or solid. Specific examples include diglycidyl hexahydrobisphenol A, 3,4-epoxycyclohexenylmethyl-3 ', 4'-epoxycyclohexenecarboxylate, diepoxybicyclohexyl, and the like. Among them, diglycidyl hexahydrobisphenol A, particularly diepoxybicyclohexyl, can be preferably used because the light transmittance of the cured product can be ensured and the rapid curing property is excellent.
（低極性オキセタン化合物）
本発明においては、脂環式エポキシ化合物に代えて、又は脂環式エポキシ化合物と共に低極性オキセタン化合物を併用することができる。低極性オキセタン化合物は、双極子モーメントが３．０ｄ以下のオキセタン化合物であり、表面張力が比較的低く、異方性導電フィルムの膜に良好なレベリング性を付与することができ、結果的に異方性導電フィルムの保管ライフを向上させることが可能となる。なお、低極性オキセタン化合物をカチオン重合性成分として使用した場合には、脂環式エポキシ化合物を使用した場合に比べ、異方性導電フィルムの示差走査熱量計（ＤＳＣ）で測定される反応開始温度が高くなる傾向があるが、実用的な低温速硬化性の範囲である。このような低極性オキセタン化合物としては、３−エチル−３−（２−エチルヘキシロキシメチル）オキセタン、３−エチル−３−ヒドロキシメチルオキセタン、ジ［１−エチル（３−オキセタニル）］メチルエーテル、４，４′−ビス[（３−エチル−３−オキセタニル）メトキシメチル]ビフェニル等が挙げられる。なかでも、表面張力が低く、濡れ性に優れることから、３−エチル−３−（２−エチルヘキシロキシメチル）オキセタン、特に４，４′−ビス[（３−エチル−３−オキセタニル）メトキシメチル]ビフェニルが好ましい。
(Low polarity oxetane compound)
In the present invention, a low-polarity oxetane compound can be used in combination with the alicyclic epoxy compound or together with the alicyclic epoxy compound. The low-polarity oxetane compound is an oxetane compound having a dipole moment of 3.0 d or less, has a relatively low surface tension, and can impart a good leveling property to the film of the anisotropic conductive film. The storage life of the isotropic conductive film can be improved. When a low-polarity oxetane compound was used as the cationically polymerizable component, the reaction initiation temperature measured by a differential scanning calorimeter (DSC) of an anisotropic conductive film was higher than when an alicyclic epoxy compound was used. Is in the range of practical low-temperature quick-curing properties. Examples of such low-polarity oxetane compounds include 3-ethyl-3- (2-ethylhexyloxymethyl) oxetane, 3-ethyl-3-hydroxymethyloxetane, di [1-ethyl (3-oxetanyl)] methyl ether, 4,4'-bis [(3-ethyl-3-oxetanyl) methoxymethyl] biphenyl and the like. Among them, 3-ethyl-3- (2-ethylhexyloxymethyl) oxetane, especially 4,4'-bis [(3-ethyl-3-oxetanyl) methoxymethyl, because of its low surface tension and excellent wettability ] Biphenyl is preferred.
カチオン重合性成分として、脂環式エポキシ化合物と低極性オキセタン化合物とを併用した場合、それらの配合割合（脂環式エポキシ化合物：低極性オキセタン化合物）は、質量基準で好ましくは２５：７５〜６０：４０、より好ましくは４５：５５〜６０：４０、特に好ましくは５０：５０〜５５：４５である。この範囲よりも低極性オキセタン化合物の配合量が増加すると、反応開始温度を上昇させる傾向があり、逆に減少すると保管ライフが低下する傾向がある。従って、脂環式エポキシ化合物と低極性オキセタン化合物との配合割合を調整することにより、異方性導電フィルムの反応開始温度、更には反応終了温度とをコントロールすることが可能となり、更に、反応時の昇温速度等を調整することにより、反応時間をコントロールすることも可能となる。 When an alicyclic epoxy compound and a low-polarity oxetane compound are used in combination as the cationic polymerizable component, the mixing ratio (alicyclic epoxy compound: low-polarity oxetane compound) is preferably 25:75 to 60 on a mass basis. : 40, more preferably 45:55 to 60:40, particularly preferably 50:50 to 55:45. When the amount of the oxetane compound having a lower polarity than the above range is increased, the reaction initiation temperature tends to increase, and when it decreases, the storage life tends to decrease. Therefore, by adjusting the mixing ratio of the alicyclic epoxy compound and the low-polarity oxetane compound, it becomes possible to control the reaction start temperature of the anisotropic conductive film, and furthermore, the reaction end temperature. The reaction time can be controlled by adjusting the rate of temperature rise of the reaction.
（カチオン重合開始剤）
本発明の接着剤組成物は、カチオン重合開始剤として、スルホニウム塩系熱酸発生剤ではなく第４級アンモニウム塩系熱酸発生剤を含有する。保管ライフを向上させるためである。ここで、「保管ライフ」とは、接着剤組成物を保管した際に、その特性が実用上問題が生じない期間を意味する。このような第４級アンモニウム塩系熱酸発生剤としては、第４級アンモニウムカチオンと、６フッ化アンチモン酸アニオン、６フッ化リン酸アニオン、トリフルオロメタンスルホン酸アニオン、パーフルオロブタンスルホン酸アニオン、ジノニルナフタレンスルホン酸アニオン、ｐ−トルエンスルホン酸アニオン、ドデシルベンゼンスルホン酸アニオン、またはテトラキス（ペンタフルオロフェニル）ボレートアニオンとの塩等を挙げることができる。また、第４級アンモニウムカチオンとしては、[ＮＲ１Ｒ２Ｒ３Ｒ４]＋で表されるカチオンを挙げることができる。ここで、Ｒ１、Ｒ２、Ｒ３及びＲ４は、直鎖、分岐鎖または環状の炭素数１〜１２のアルキル基またはアリール基であり、それぞれ水酸基、ハロゲン、アルコキシル基、アミノ基、エステル基等を有していてもよい。
(Cation polymerization initiator)
The adhesive composition of the present invention contains not a sulfonium salt-based thermal acid generator but a quaternary ammonium salt-based thermal acid generator as a cationic polymerization initiator. This is to improve the storage life. Here, the “storage life” means a period during which the properties of the adhesive composition do not cause practical problems when stored. Examples of such a quaternary ammonium salt-based thermal acid generator include a quaternary ammonium cation, a hexafluoroantimonate anion, a hexafluorophosphate anion, a trifluoromethanesulfonic acid anion, a perfluorobutanesulfonic acid anion, Examples thereof include a salt with a dinonylnaphthalenesulfonic acid anion, a p-toluenesulfonic acid anion, a dodecylbenzenesulfonic acid anion, or a tetrakis (pentafluorophenyl) borate anion. Examples of the quaternary ammonium cation include a cation represented by [NR 1 R 2 R 3 R 4 ] + . Here, R 1 , R 2 , R 3 and R 4 are a linear, branched or cyclic alkyl or aryl group having 1 to 12 carbon atoms, each of which is hydroxyl, halogen, alkoxyl, amino or ester. It may have a group or the like.
第４級アンモニウム塩系熱酸発生剤の具体例としては、Ｋｉｎｇ Ｉｎｄｕｓｔｒｉｅｓ，Ｉｎｃ．製造のＣＸＣ−１６１２、ＣＸＣ−１７３３、ＣＸＣ−１７３８、ＴＡＧ−２６７８、ＣＸＣ−１６１４、ＴＡＧ−２６８９、ＴＡＧ−２６９０、ＴＡＧ−２７００、ＣＸＣ−１８０２−６０、ＣＸＣ−１８２１等が挙げられる。これらは、楠本化成（株）から入手可能である。 Specific examples of the quaternary ammonium salt-based thermal acid generator include King Industries, Inc. Manufactured CXC-1612, CXC-1733, CXC-1738, TAG-2678, CXC-1614, TAG-2689, TAG-2690, TAG-2700, CXC-1802-60, CXC-1821 and the like. These are available from Kusumoto Kasei.
カチオン重合開始剤の含有量は、良好な低温速硬化性を実現するために、カチオン重合性成分１００質量部に対して、好ましくは２質量部以上、より好ましくは５質量部以上であり、また、ライフの低下や端子や電極のマイグレーション（腐食）の悪化を抑制するために、好ましくは２０質量部以下、より好ましくは１０質量部以下である。 The content of the cationic polymerization initiator is preferably at least 2 parts by mass, more preferably at least 5 parts by mass, based on 100 parts by mass of the cationically polymerizable component, in order to achieve good low-temperature rapid curability. The amount is preferably 20 parts by mass or less, more preferably 10 parts by mass or less, in order to suppress a reduction in life and deterioration of migration (corrosion) of terminals and electrodes.
（エラストマー）
本発明の接着剤組成物は、良好な接着強度を実現するために、エラストマーを含有する。ここで、エラストマーとは、常温でゴム弾性を示す高分子である。具体的には、２０〜７０℃で１〜４０Ｍｐａのヤング率を示す高分子であり、熱硬化性であってもよいが、通常は熱可塑性である。また、本発明に適用可能なエラストマーは、好ましくは−１００〜０℃のガラス転位温度（Ｔｇ）と、好ましくは２００００〜２００００００の重量平均分子量を有する。
(Elastomer)
The adhesive composition of the present invention contains an elastomer in order to achieve good adhesive strength. Here, the elastomer is a polymer that exhibits rubber elasticity at room temperature. Specifically, it is a polymer showing a Young's modulus of 1 to 40 Mpa at 20 to 70 ° C., and may be thermosetting, but is usually thermoplastic. Further, the elastomer applicable to the present invention preferably has a glass transition temperature (Tg) of -100 to 0C and a weight average molecular weight of preferably 20,000 to 2,000,000.
このようなエラストマーの例としては、天然ゴム（ＮＲ）、イソプレンゴム（ＩＲ）、ブタジエンゴム（ＢＲ）、スチレンブタジエンゴム（ＳＢＲ）、スチレン−ブタジエン−スチレンゴム（ＳＢＳ）、スチレン−エチレン−ブチレン−スチレンゴム（ＳＥＢＳ）、スチレン−イソプレン−スチレンゴム（ＳＩＳ）、クロロプレンゴム（ＣＲ）、アクリロニトリルブタジエンゴム（ＮＢＲ）、アクリルゴム（ＡＣＭ）等が挙げられる。これらの中から、カチオン重合性成分の重合物に対して良好な相溶性を示すものを選択することが好ましい。カチオン重合性成分が脂環式エポキシ化合物又は低極性オキセタン化合物のいずれかを少なくとも含有していることから、ポリマー鎖にエステル結合が存在するアクリルゴムを好ましく使用できる。 Examples of such elastomers include natural rubber (NR), isoprene rubber (IR), butadiene rubber (BR), styrene butadiene rubber (SBR), styrene-butadiene-styrene rubber (SBS), styrene-ethylene-butylene- Examples include styrene rubber (SEBS), styrene-isoprene-styrene rubber (SIS), chloroprene rubber (CR), acrylonitrile butadiene rubber (NBR), and acrylic rubber (ACM). It is preferable to select, from these, those exhibiting good compatibility with the polymer of the cationically polymerizable component. Since the cationically polymerizable component contains at least either an alicyclic epoxy compound or a low-polar oxetane compound, an acrylic rubber having an ester bond in the polymer chain can be preferably used.
アクリルゴムとしては、水酸基、カルボキシル基、アミド基、エポキシ基等の種々の官能基を有していてもよい。中でも、本発明におけるカチオン重合性成分の重合物に対してより親和性を高めることが期待できる官能基として水酸基を有するアクリルゴムを好ましく使用することができる。例えば、ヒドロキシエチルアクリレート等とエチルアクリレート、ブチルアクリレート、メトキシエチルアクリレート等との共重合体を挙げることができる。 The acrylic rubber may have various functional groups such as a hydroxyl group, a carboxyl group, an amide group, and an epoxy group. Among them, an acrylic rubber having a hydroxyl group as a functional group that can be expected to further increase the affinity for the polymer of the cationically polymerizable component in the present invention can be preferably used. For example, a copolymer of hydroxyethyl acrylate and the like with ethyl acrylate, butyl acrylate, methoxyethyl acrylate and the like can be mentioned.
エラストマーの含有量は、接着剤組成物に対して良好な接着性を付与するために、カチオン重合性成分とエラストマーと成膜用成分との合計質量の１０質量％以上、好ましくは２０質量％以上であり、相対的にカチオン重合成分の含有量を一定以上に保持して良好な接着性を実現するために、カチオン重合性成分とエラストマーと成膜用成分との合計質量の４０質量％以下、好ましくは３０質量％以下である。 The content of the elastomer is 10% by mass or more, preferably 20% by mass or more of the total mass of the cationically polymerizable component, the elastomer and the film-forming component in order to impart good adhesiveness to the adhesive composition. In order to relatively maintain the content of the cationically polymerizable component at a certain level or more and achieve good adhesiveness, 40% by mass or less of the total mass of the cationically polymerizable component, the elastomer, and the film forming component, Preferably it is 30% by mass or less.
（成膜用成分）
成膜用成分は、接着剤組成物をフィルム化（膜状化）するために使用される成分であり、膜形成能を有する成分である。このような成膜用成分としては、フェノキシ樹脂、不飽和ポリエステル樹脂、飽和ポリエステル樹脂、ウレタン樹脂、ブタジエン樹脂、ポリイミド樹脂、ポリアミド樹脂、ポリオレフィン樹脂等を挙げることができ、これらの２種以上を併用することができる。これらの中でも、製膜性、加工性、接続信頼性の観点から、フェノキシ樹脂を好ましく使用することができる。
(Components for film formation)
The component for film formation is a component used for forming a film (forming a film) of the adhesive composition, and is a component having a film forming ability. Examples of such a film forming component include a phenoxy resin, an unsaturated polyester resin, a saturated polyester resin, a urethane resin, a butadiene resin, a polyimide resin, a polyamide resin, and a polyolefin resin. can do. Among these, a phenoxy resin can be preferably used from the viewpoints of film formability, workability, and connection reliability.
成膜用成分の含有量は、接着剤組成物に対して良好な成膜性を付与するために、カチオン重合性成分とエラストマーと成膜用成分との合計質量の４０質量％以上、好ましくは５０質量％以上であり、相対的にエラストマーの含有量を一定以上に保持して良好な接着性を実現するために、カチオン重合性成分とエラストマーと成膜用成分との合計質量の８０質量％以下、好ましくは７０質量％以下である。 The content of the film-forming component is 40% by mass or more of the total mass of the cationically polymerizable component, the elastomer, and the film-forming component in order to impart good film-forming properties to the adhesive composition. 50% by mass or more, and 80% by mass of the total mass of the cationically polymerizable component, the elastomer, and the film-forming component in order to relatively maintain the content of the elastomer at a certain level or more and achieve good adhesion. Or less, preferably 70% by mass or less.
（導電粒子）
本発明の接着剤組成物は、導電接続、好ましくは異方性導電接続を可能とするために、導電粒子を含有する。導電粒子としては、従来公知の導電フィルムや導電ペースト、あるいは異方性導電フィルムや異方性導電ペーストに用いられているものの中から適宜選択して使用することができる。例えばニッケル、コバルト、銀、銅、金、パラジウムなどの金属粒子、ハンダなどの合金粒子、金属被覆樹脂粒子などが挙げられる。２種以上を併用することもできる。
(Conductive particles)
The adhesive composition of the present invention contains conductive particles to enable conductive connection, preferably anisotropic conductive connection. The conductive particles can be appropriately selected from those used in conventionally known conductive films and conductive pastes, or those used in anisotropic conductive films and anisotropic conductive pastes. Examples include metal particles such as nickel, cobalt, silver, copper, gold, and palladium, alloy particles such as solder, and metal-coated resin particles. Two or more can be used in combination.
本発明の接着剤組成物中の導電粒子の存在態様としては、組成物をフィルムにした場合に平面視において、組成物中にランダムに分散している態様、組成物中で導電粒子が互いに離隔している態様、組成物フィルムに導電粒子が規則配列されている態様等が挙げられる（特開２０１６−０６６５７３、特開２０１６−１０３４７６等参照）。 The conductive particles in the adhesive composition of the present invention may be present in the form of a film, in which the conductive particles are randomly dispersed in the composition in plan view, and the conductive particles are separated from each other in the composition. And JP-A-2006-066573, JP-A-2006-103476, and the like.
導電粒子の平均粒径としては、特に制限は無く、目的に応じて適宜選択すればよいが、一例として１μｍ以上３０μｍ以下であってもよい。配線高さのばらつきに対応できるようにし、また、導通抵抗の上昇を抑制し、且つショートの発生を抑制するために、好ましくは２．５μｍ以上３０μｍ以下、より好ましくは３μｍ以上９μｍ以下である。導電粒子の粒径は、一般的な粒度分布測定装置により測定することができ、また、その平均粒径も粒度分布測定装置を用いて求めることができる。一例として、画像型粒度分布測定装置ＦＰＩＡ−３０００（マルバーン社）が挙げられる。 The average particle size of the conductive particles is not particularly limited and may be appropriately selected depending on the purpose. For example, the average particle size may be 1 μm or more and 30 μm or less. The thickness is preferably 2.5 μm or more and 30 μm or less, more preferably 3 μm or more and 9 μm or less in order to cope with variations in wiring height, to suppress an increase in conduction resistance, and to suppress occurrence of a short circuit. The particle size of the conductive particles can be measured with a general particle size distribution measuring device, and the average particle size can also be determined using a particle size distribution measuring device. As an example, an image-type particle size distribution measuring device FPIA-3000 (Malvern) can be mentioned.
なお、導電粒子が金属被覆樹脂粒子である場合、樹脂コア粒子の粒子硬さ（２０％Ｋ値；圧縮弾性変形特性Ｋ２０）は、良好な接続信頼性を得るために、好ましくは１００〜１０００ｋｇｆ／ｍｍ２、より好ましくは２００〜５００ｋｇｆ／ｍｍ２である。圧縮弾性変形特性Ｋ２０は、例えば、微小圧縮試験機（ＭＣＴ−Ｗ２０１、（株）島津製作所製）を使用して測定温度２０℃で測定することができる。 When the conductive particles are metal-coated resin particles, the particle hardness (20% K value; compression elastic deformation characteristic K 20 ) of the resin core particles is preferably 100 to 1000 kgf in order to obtain good connection reliability. / Mm 2 , more preferably 200 to 500 kgf / mm 2 . Compressive elastic deformation characteristic K 20, for example, micro-compression tester (MCT-W201, (Ltd.) manufactured by Shimadzu Corporation) can be measured at a measurement temperature of 20 ° C. using.
本発明の接着剤組成物における導電粒子の存在量は、等方性導電接続あるいは異方性導電接続すべき端子の幅や面積、端子間距離等の接続レイアウトに応じて導電粒子捕捉効率の低下を抑制し、且つショートの発生を抑制することを考慮して決定することができる。異方性導電接続に適用する場合には、好ましくは１平方ｍｍ当たり５０個以上１０００００個以下、より好ましくは２００個以上７００００個以下である。この存在量の測定は材料の薄膜を公知の金属顕微鏡などの光学顕微鏡や電子顕微鏡等で観察することにより行うことができる。この薄膜の厚みは、接続に使用する際の厚みとして測定すればよい（市販のデジタルシックネスゲージ等で測定することができる）。なお、異方性導電接続前において、接着剤組成物中の導電粒子が光学顕微鏡等で観察し難い場合がある。そのような場合には、異方性導電接続後の接着剤組成物を観察してもよい。この場合には、接続前後の接着剤組成物の厚変化を考慮して存在量を割り出すことができる。 The amount of the conductive particles present in the adhesive composition of the present invention is reduced in the conductive particle capturing efficiency according to the connection layout such as the width and area of the terminal to be isotropically connected or the anisotropically conductive connection and the distance between the terminals. And the occurrence of a short circuit can be suppressed. When applied to anisotropic conductive connection, the number is preferably 50 or more and 100,000 or less per square mm, more preferably 200 or more and 70,000 or less. The measurement of the abundance can be performed by observing the thin film of the material with a known optical microscope such as a metal microscope or an electron microscope. The thickness of this thin film may be measured as a thickness when used for connection (can be measured with a commercially available digital thickness gauge or the like). Before the anisotropic conductive connection, the conductive particles in the adhesive composition may be difficult to observe with an optical microscope or the like. In such a case, the adhesive composition after the anisotropic conductive connection may be observed. In this case, the existing amount can be determined in consideration of the thickness change of the adhesive composition before and after connection.
なお、導電粒子の接着剤組成物中の存在量は質量基準で表すこともができる。異方性導電接続に適用する場合、その存在量は、接着剤組成物の全質量を１００質量部としたときに、その１００質量部中に好ましくは１質量部以上３０質量部以下、より好ましくは３質量部以上１０質量部以下となる量である。 In addition, the amount of the conductive particles present in the adhesive composition can be expressed on a mass basis. When applied to an anisotropic conductive connection, its abundance is preferably 1 part by mass or more and 30 parts by mass or less, more preferably 100 parts by mass, when the total mass of the adhesive composition is 100 parts by mass. Is an amount of 3 parts by mass or more and 10 parts by mass or less.
（その他の成分）
本発明の接着剤組成物は、必要に応じ、その他の硬化性樹脂としてビスフェノールＡ型エポキシ樹脂、ビスフェノールＦ型エポキシ樹脂、ノボラック型エポキシ樹脂、それらの変性エポキシ樹脂等の他のエポキシ樹脂、シランカップリング剤、充填剤、軟化剤、促進剤、老化防止剤、着色剤（顔料、染料）、有機溶剤、イオンキャッチャー剤などを含有することができる。また、必要に応じて、（メタ）アクリレート化合物とラジカル重合開始剤とを含有することができる。ここで、（メタ）アクリレート化合物としては、従来公知の（メタ）アクリレートモノマーを使用することができる。例えば、単官能（メタ）アクリレート系モノマー、二官能以上の多官能（メタ）アクリレート系モノマーを使用することができる。ここで、（メタ）アクリレートには、アクリレートとメタクリレートとが包含される。また、ラジカル重合開始剤としては、有機過酸化物、アゾビスイソブチロニトリル等の公知のラジカル重合開始剤を含有することができる。
(Other components)
The adhesive composition of the present invention may contain, if necessary, other epoxy resins such as bisphenol A type epoxy resin, bisphenol F type epoxy resin, novolak type epoxy resin, modified epoxy resin thereof, and silane cup as other curable resins. It may contain a ring agent, a filler, a softener, an accelerator, an antioxidant, a coloring agent (pigment, dye), an organic solvent, an ion catcher agent and the like. Further, if necessary, a (meth) acrylate compound and a radical polymerization initiator can be contained. Here, as the (meth) acrylate compound, a conventionally known (meth) acrylate monomer can be used. For example, a monofunctional (meth) acrylate monomer or a bifunctional or higher polyfunctional (meth) acrylate monomer can be used. Here, (meth) acrylate includes acrylate and methacrylate. The radical polymerization initiator may contain a known radical polymerization initiator such as an organic peroxide and azobisisobutyronitrile.
（接着剤組成物の調製）
本発明の接着剤組成物は、前述したカチオン重合性成分とカチオン重合開始剤とエラストマーと成膜用成分と（必要に応じて導電粒子と他の成分と）を、カチオン重合性成分の含有量、エラストマーの含有量及び成膜用成分の含有量が、カチオン重合性成分とエラストマーと成膜用成分との合計質量のそれぞれ１０〜４０質量％、１０〜４０質量％及び４０〜８０質量％となるような配合量で、必要に応じてトルエンなどの溶媒と共に均一に混合することにより調製することができる。
(Preparation of adhesive composition)
The adhesive composition of the present invention comprises the above-mentioned cationically polymerizable component, cationic polymerization initiator, elastomer, film-forming component (and, if necessary, conductive particles and other components), and the content of the cationically polymerizable component. The content of the elastomer and the content of the film-forming component are 10 to 40% by mass, 10 to 40% by mass, and 40 to 80% by mass, respectively, of the total mass of the cationically polymerizable component, the elastomer, and the film-forming component. It can be prepared by mixing uniformly with a solvent such as toluene, if necessary, in such an amount.
なお、接着剤組成物を異方性導電フィルムとして使用する場合には、導電粒子と溶剤とを含有させて調製した接着剤組成物（塗料）を、公知のフィルム化手法を利用してフィルム化することにより製造することができる。 When the adhesive composition is used as an anisotropic conductive film, the adhesive composition (paint) prepared by containing the conductive particles and the solvent is formed into a film by using a known film forming technique. Can be manufactured.
なお、このような異方性導電フィルムは単層であってもよいが、導電粒子を含有していない絶縁性樹脂層を積層してもよい。このような絶縁性樹脂層としては、導電粒子含有層よりも最低溶融粘度が低く、流動性が比較的低いものが好ましい。最低溶融粘度比は導電粒子含有層が、絶縁性樹脂層の２以上であれば好ましく、５以上であればより好ましく、８以上であれば更により好ましい。導電粒子含有層が比較的高粘度であれば、接続時に不要な導電粒子の流動が抑制され、捕捉性が高まり、ショートの抑制にもなる。この最低溶融粘度は、一例として回転式レオメータ（ＴＡ Ｉｎｓｔｒｕｍｅｎｔｓ社製）を用い、測定圧力５ｇで一定に保持し、直径８ｍｍの測定プレートを使用し求めることができ、より具体的には、温度範囲３０〜２００℃において、昇温速度１０℃／分、測定周波数１０Ｈｚ、前記測定プレートに対する荷重変動５ｇとすることにより求めることができる。その場合、異方性導電フィルムは、導電粒子含有層／絶縁性樹脂層の２層構成となる。必要に応じて３層以上としてもよい。このような絶縁性樹脂層は、基本的には本発明の接着剤組成物と同じ組成物から形成することができる。 Note that such an anisotropic conductive film may be a single layer, or may be an insulating resin layer containing no conductive particles. Such an insulating resin layer preferably has a lower minimum melt viscosity and a relatively lower fluidity than the conductive particle-containing layer. The minimum melt viscosity ratio is preferably 2 or more, more preferably 5 or more, and even more preferably 8 or more of the insulating resin layer of the conductive particle-containing layer. If the conductive particle-containing layer has a relatively high viscosity, the flow of unnecessary conductive particles at the time of connection is suppressed, the trapping property is enhanced, and the short circuit is suppressed. The minimum melt viscosity can be determined by using a rotary rheometer (manufactured by TA Instruments) as an example, using a measurement plate having a diameter of 8 mm, keeping the measurement pressure constant at 5 g, and more specifically, a temperature range. At a temperature of 30 to 200 ° C., the temperature can be determined at a rate of 10 ° C./min, a measurement frequency of 10 Hz, and a load variation of 5 g with respect to the measurement plate. In that case, the anisotropic conductive film has a two-layer structure of a conductive particle-containing layer / insulating resin layer. If necessary, three or more layers may be provided. Such an insulating resin layer can be basically formed from the same composition as the adhesive composition of the present invention.
本発明の接着性組成物が異方性導電フィルムである場合、その層厚は使用目的等に応じて適宜設定することができ、好ましくは３〜５０μｍ厚、より好ましくは５〜２０μｍ厚である。これは導電粒子含有層のみからなる単層であっても、導電粒子含有層と絶縁性樹脂層を積層したものであっても全体の厚みを指す。導電粒子含有層と絶縁性樹脂層の厚みの比率は、使用目的に応じて適宜設定することができる。 When the adhesive composition of the present invention is an anisotropic conductive film, its layer thickness can be appropriately set according to the purpose of use and the like, and is preferably 3 to 50 μm, more preferably 5 to 20 μm. . This refers to the entire thickness of a single layer composed of only the conductive particle-containing layer or a laminate of the conductive particle-containing layer and the insulating resin layer. The ratio of the thickness of the conductive particle-containing layer to the thickness of the insulating resin layer can be appropriately set according to the purpose of use.
＜接続構造体＞
本発明の接着剤組成物は、導電粒子を含有しているか否かに関わらず、第１電子部品と第２電子部品とを接続、好ましくは電気的に接続する際に（特に異方性導電接続する際に）適用することができる。第１電子部品と第２電子部品とは、同種の電子部品でも互いに相違する電子部品でもよいが、第２電子部品として、第１電子部品と同程度もしくはより高い剛性を有する電子部品を選択することが好ましい。また、第１電子部品と第２電子部品とを圧着ツールと定盤との間に挟持して接続を行う際に圧着ツール側に第１電子部品を配置する場合には、第２電子部品としては定盤に載置し易い水平面を有する電子部品を選択することが好ましい。第１電子部品の例として、ＦＰＣ、ＩＣチップ、ＩＣモジュール等を挙げることができ、第２電子部品の例として、プラスチック基板、ガラス基板、リジッド基板、セラミック基板、ＦＰＣ等を挙げることができる。異方性導電接続の場合、第１電子部品としてＦＰＣを好ましく選択することができ、第１電子部品がＦＰＣで第２電子部品が比較的剛性のある基板となるプラスチック基板やガラス基板、リジット基板、セラミック基板の場合を特に好ましく選択することができる。更により好ましくは、第２電子部品である基板自体が前記のように剛性があり且つ形状変形し得る（わずかな反りが問題となり易い）性質を有するプラスチック基板やガラス基板を選択することができる（つまり、ＦＯＰやＦＯＧの場合である）。これは本発明の接着剤組成物が、異方性導電接続後に第１電子部品を屈曲させた状態で維持可能な配合から構成することが可能だからである。なお、このような本発明の接着剤組成物で、導電粒子を含有しているか否かに関わらず、第１電子部品と第２電子部品とが接続、好ましくは電気的に接続されている接続構造体、及び第１電子部品と第２電子部品とを接続、好ましくは電気的に接続する、接続構造体の製造方法も本発明の一部である。特に、導電粒子を含有する本発明の接着剤組成物を異方性導電接着剤（好ましくは異方性導電フィルム）として適用した場合、本発明は、そのような異方性導電接着剤で、第１電子部品と第２電子部品とが異方性導電接続されている接続構造体、及び第１電子部品と第２電子部品とを異方性導電接続する、接続構造体の製造方法も本発明の一部である。なお、本発明の接着剤組成物で、第１異方性導電接着剤組成物を用いた電子部品の接続方法としては、公知の手法を利用することができる。
<Connection structure>
The adhesive composition of the present invention can be used to connect the first electronic component and the second electronic component, preferably electrically, irrespective of whether the adhesive composition contains conductive particles (especially anisotropic conductive material). (When connecting). Although the first electronic component and the second electronic component may be the same type of electronic component or different electronic components, an electronic component having the same or higher rigidity as the first electronic component is selected as the second electronic component. Is preferred. In the case where the first electronic component and the second electronic component are sandwiched between the crimping tool and the platen for connection and the first electronic component is arranged on the crimping tool side, the second electronic component is used as the second electronic component. It is preferable to select an electronic component having a horizontal surface that can be easily mounted on the surface plate. Examples of the first electronic component include an FPC, an IC chip, an IC module, and the like, and examples of the second electronic component include a plastic substrate, a glass substrate, a rigid substrate, a ceramic substrate, and an FPC. In the case of anisotropic conductive connection, FPC can be preferably selected as the first electronic component, and a plastic substrate, a glass substrate, or a rigid substrate in which the first electronic component is an FPC and the second electronic component is a relatively rigid substrate. The case of a ceramic substrate can be particularly preferably selected. Still more preferably, a plastic substrate or a glass substrate having such a property that the substrate itself, which is the second electronic component, is rigid and capable of being deformed in shape as described above (a slight warpage tends to be a problem) can be selected ( That is, it is the case of FOP or FOG). This is because the adhesive composition of the present invention can be composed of a composition that can maintain the first electronic component in a bent state after the anisotropic conductive connection. Note that, in such an adhesive composition of the present invention, a connection in which the first electronic component and the second electronic component are connected, preferably electrically connected, regardless of whether or not the adhesive composition contains conductive particles. The structure and a method of manufacturing a connection structure for connecting, preferably electrically, the first electronic component and the second electronic component are also part of the invention. In particular, when the adhesive composition of the present invention containing conductive particles is applied as an anisotropic conductive adhesive (preferably an anisotropic conductive film), the present invention relates to such an anisotropic conductive adhesive. The present invention also provides a connection structure in which the first electronic component and the second electronic component are anisotropically conductively connected, and a method of manufacturing a connection structure in which the first electronic component and the second electronic component are anisotropically conductively connected. Part of the invention. As a method for connecting electronic components using the first anisotropic conductive adhesive composition in the adhesive composition of the present invention, a known method can be used.
以下、本発明を実施例により具体的に説明する。 Hereinafter, the present invention will be described specifically with reference to examples.
実施例１〜１１、比較例１〜７
表１の配合表に従って、脂環式エポキシ化合物としてジエポキシビシクロヘキシル（セロキサイド８０００、（株）ダイセル）、低極性オキセタン化合物として４，４′−ビス[（３−エチル−３−オキセタニル）メトキシメチル]ビフェニル（ＯＸＢＰ、宇部興産（株））、エラストマーとして水酸基含有アクリルゴム（ＳＧ−８０Ｈ、ナガセケムテックス（株））、熱カチオン重合開始剤（第４級アンモニウム塩系熱酸発生剤、商品名ＣＸＣ−１６１２、楠本化成（株））、フェノキシ樹脂（ＹＰ−５０、新日鉄住金化学（株））、および平均粒径４μｍの導電性粒子（Ｎｉ／Ａｕメッキ樹脂粒子、ＡＵＬ７０４、積水化学工業（株））を、固形分が５０質量％となるようにトルエンに添加し、接着剤組成物を調製した。
Examples 1 to 11, Comparative Examples 1 to 7
According to the composition table in Table 1, diepoxybicyclohexyl (Celoxide 8000, Daicel Co., Ltd.) as the alicyclic epoxy compound and 4,4'-bis [(3-ethyl-3-oxetanyl) methoxymethyl as the low-polar oxetane compound. ] Biphenyl (OXBP, Ube Industries, Ltd.), hydroxyl-containing acrylic rubber (SG-80H, Nagase ChemteX Corporation) as an elastomer, thermal cationic polymerization initiator (quaternary ammonium salt-based thermal acid generator, trade name) CXC-1612, Kusumoto Kasei Co., Ltd.), phenoxy resin (YP-50, Nippon Steel & Sumikin Chemical Co., Ltd.), and conductive particles having an average particle diameter of 4 μm (Ni / Au plated resin particles, AUL704, Sekisui Chemical Co., Ltd.) )) Was added to toluene so that the solid content was 50% by mass, to prepare an adhesive composition.
得られた接着剤組成物を、厚さ５０μｍのポリエチレンテレフタレート剥離フィルム（ＰＥＴ剥離フィルム）上に、乾燥厚が６μｍとなるよう塗布し、６０℃のオーブン中で５分間乾燥することにより、単層の異方性導電フィルムを形成した。 The resulting adhesive composition was applied on a 50 μm-thick polyethylene terephthalate release film (PET release film) to a dry thickness of 6 μm, and dried in an oven at 60 ° C. for 5 minutes to form a single layer. Was formed.
実施例１２〜１４
導電粒子を含有しない接着剤組成物の評価のために、実施例１、３及び５で調製した接着剤組成物から導電粒子を除くこと以外は、実施例１と同様の操作を繰り返すことにより、絶縁性の接着フィルムを作成した。
Examples 12 to 14
For the evaluation of the adhesive composition containing no conductive particles, except for removing the conductive particles from the adhesive composition prepared in Examples 1, 3 and 5, by repeating the same operation as in Example 1, An insulating adhesive film was prepared.
＜＜評価１＞＞
各実施例１〜１１及び比較例１〜７で得られた異方性導電フィルムを用いて以下に説明するように接続構造体を作成し、「接着強度」、「ＤＳＣ反応開始温度」、「保管ライフ」、「初期導通抵抗」及び「信頼性テスト後導通抵抗」をそれぞれ試験もしくは測定し、評価した。
<< Evaluation 1 >>
Using the anisotropic conductive films obtained in Examples 1 to 11 and Comparative Examples 1 to 7, a connection structure was prepared as described below, and “adhesion strength”, “DSC reaction start temperature”, “ "Storage life", "initial conduction resistance" and "conduction resistance after reliability test" were each tested or measured and evaluated.
＜接続構造体の作成＞
テスト用ＦＰＣ（３８μｍ厚ポリイミドの片面に２００μｍピッチ（Ｌ／Ｓ＝１００μｍ／１００μｍ）で電極（８μｍ厚Ｃｕ／Ｓｎメッキ）が形成された印刷回路）と、片面にインジウムチタンオキサイド薄膜（１０Ω／□）が設けられた０．５ｍｍ厚のテスト用ガラス基板とを、それらの間に、剥離フィルムを取り去った実施例もしくは比較例で作成した異方性導電フィルム（２．０ｍｍ×５０．０ｍｍ短冊形状）を介して、１３０℃、３ＭＰａ、５秒（ツール幅：２．０ｍｍ）という条件で異方性導電接続し、接続構造体を得た。
<Create connection structure>
Test FPC (printed circuit having electrodes (8 μm thick Cu / Sn plating) formed at a pitch of 200 μm (L / S = 100 μm / 100 μm) on one side of 38 μm thick polyimide) and indium titanium oxide thin film (10 Ω / □ on one side) ) Provided with a 0.5 mm-thick test glass substrate, and an anisotropic conductive film (2.0 mm × 50.0 mm strip shape) prepared in the example or the comparative example in which the release film was removed between them. ), Anisotropic conductive connection was performed under the conditions of 130 ° C., 3 MPa, and 5 seconds (tool width: 2.0 mm) to obtain a connection structure.
＜接着強度＞
引張試験機（ＲＴＣ１２２５Ａ、ＡＭＤ社）に上記で得られた接続構造体のガラス基板を固定し、（長さ１ｃｍに切断した）テスト用ＦＰＣを、常温（２５℃）・５０ｍｍ／秒の速度で９０度方向に引き上げ、引き剥げに要した力を接着強度（Ｎ）とし、以下の基準で評価した。得られた結果を表１に示す。
<Adhesive strength>
The glass substrate of the connection structure obtained above was fixed to a tensile tester (RTC1225A, AMD), and the test FPC (cut to a length of 1 cm) was tested at room temperature (25 ° C.) at a speed of 50 mm / sec. The film was pulled up in the direction of 90 degrees, and the force required for peeling was defined as the adhesive strength (N), and evaluated according to the following criteria. Table 1 shows the obtained results.
（接着強度評価基準）
Ａ（非常に良好）：接着強度が１０Ｎ以上
Ｂ（良好） ：接着強度が５Ｎ以上１０Ｎ未満
Ｃ（不良） ：接着強度が５Ｎ未満
(Adhesion strength evaluation criteria)
A (very good): adhesive strength is 10 N or more B (good): adhesive strength is 5 N or more and less than 10 N C (poor): adhesive strength is less than 5 N
＜ＤＳＣ反応開始温度＞
異方性導電フィルムから切り出した５ｍｇのサンプルを、アルミＰＡＮ（ＴＡ Ｉｎｓｕｔｒｕｍｅｎｔｓ Ｉｎｃ．）に格納し、それをＤＳＣ測定装置（Ｑ２０００， ＴＡ Ｉｎｓｔｒｕｍｅｎｔｓ Ｉｎｃ．）にセットし、３０℃から２５０℃まで、１０℃／分の昇温速度で示差走査熱量計測定を行い、得られたＤＳＣチャートから発熱ピークの立ち上がり温度を反応開始温度として読み取った。得られた結果を表１に示す。反応開始温度が低いほど低温速硬化性が良好であることが意味する。実用的には反応開始温度が１００℃以下であることが望まれる。
<DSC reaction start temperature>
A sample of 5 mg cut out from the anisotropic conductive film was stored in an aluminum PAN (TA Instruments Inc.), which was set in a DSC measuring device (Q2000, TA Instruments Inc.), and was cooled from 30 ° C to 250 ° C. A differential scanning calorimeter measurement was performed at a heating rate of ° C./min, and the rising temperature of the exothermic peak was read as the reaction start temperature from the obtained DSC chart. Table 1 shows the obtained results. The lower the reaction initiation temperature, the better the low-temperature quick-curing property. Practically, it is desired that the reaction start temperature is 100 ° C. or lower.
＜保管ライフ＞
以下に説明するように保管ライフ１〜３の試験評価を行い、保管ライフ１については、１０日以上、保管ライフ２については７日以上、保管ライフ３について７日以上であることが望まれる。実用上、保管ライフ１〜３の少なくとも一つが満足されればよいが、二つが満足されることが好ましく、すべてが満足されることがより好ましい。なお、接着剤組成物の保管ライフの評価という観点からは、保管ライフ１（ＤＳＣピーク）が満足されることが望ましい。
<Storage life>
As described below, test evaluations of storage lives 1 to 3 are performed, and it is desired that storage life 1 is 10 days or more, storage life 2 is 7 days or more, and storage life 3 is 7 days or more. In practice, it is sufficient that at least one of the storage lives 1 to 3 is satisfied, but preferably two are satisfied, and more preferably all are satisfied. From the viewpoint of evaluating the storage life of the adhesive composition, it is desirable that storage life 1 (DSC peak) be satisfied.
＜保管ライフ１＞
ＰＥＴ剥離フィルムで裏打ちされている異方性導電フィルムを、湿度４０％、温度２５℃又は３０℃に設定されている恒温恒湿室に投入し、投入後２４時間毎にサンプリングを行った。サンプリングした異方性導電フィルムについて、前述した接続構造体の製造条件でサンプルを作成してＤＳＣ測定を行い、ピーク強度が恒温恒湿室に投入前の７０％以上を維持している日数を数え、維持できた日数を保管ライフとした。
<Storage life 1>
The anisotropic conductive film lined with the PET release film was placed in a constant temperature / humidity chamber set at a humidity of 40% and a temperature of 25 ° C. or 30 ° C., and sampling was performed every 24 hours after the introduction. With respect to the sampled anisotropic conductive film, a sample is prepared under the above-described manufacturing conditions of the connection structure and DSC measurement is performed, and the number of days in which the peak intensity is maintained at 70% or more before being put into the constant temperature and humidity chamber is counted. The number of days that could be maintained was defined as the storage life.
＜保管ライフ２＞
保管ライフ１と同様にサンプリングした異方性導電フィルムについて、前述したように導通抵抗値を測定し、５Ω未満を維持した日数を数え、維持できた日数を保管ライフとした。
<Storage life 2>
With respect to the anisotropic conductive film sampled in the same manner as in the case of the storage life 1, the conduction resistance was measured as described above, the number of days maintaining less than 5Ω was counted, and the number of days that could be maintained was defined as the storage life.
＜保管ライフ３＞
保管ライフ１と同様にサンプリングした異方性導電フィルムについて、前述したように接着強度を測定し、５Ｎ以上を維持した日数を数え、維持できた日数を保管ライフとした。
<Storage life 3>
With respect to the anisotropic conductive film sampled in the same manner as in the case of the storage life 1, the adhesive strength was measured as described above, and the number of days in which 5 N or more was maintained was counted.
＜初期導通抵抗、信頼性テスト後導通抵抗＞
接続構造体の作成直後の導通抵抗値（初期導通抵抗値）、並びに８５℃・８５％ＲＨ・５００時間の湿熱試験後の導通抵抗値（信頼性テスト後導通抵抗値）を、それぞれデジタルマルチメータ（デジタルマルチメータ７５５５、横河電機(株)）を用いて４端子法（１ｍＡ通電時）で測定し、以下の評価基準で評価した。得られた結果を表１に示す。
<Initial conduction resistance, conduction resistance after reliability test>
The conduction resistance value immediately after the connection structure was created (initial conduction resistance value) and the conduction resistance value after a moist heat test at 85 ° C./85% RH / 500 hours (conduction resistance value after reliability test) were measured by a digital multimeter. (Digital multimeter 7555, Yokogawa Electric Corporation) was used to measure by the four-terminal method (at the time of applying 1 mA), and evaluated according to the following evaluation criteria. Table 1 shows the obtained results.
（初期導通抵抗・信頼性テスト後導通抵抗値評価基準）
ＯＫ（良好）：初期導通抵抗値が２Ω未満、信頼性テスト後導通抵抗値が５Ω未満
ＮＧ（不良）：初期導通抵抗値が２Ω以上、信頼性テスト後導通抵抗値が５Ω以上
(Evaluation criteria for initial conduction resistance and conduction resistance after reliability test)
OK (good): initial conduction resistance value is less than 2Ω, conduction resistance value after reliability test is less than 5Ω NG (poor): initial conduction resistance value is 2Ω or more, conduction resistance value after reliability test is 5Ω or more
＜＜評価結果の考察１＞＞
表１の比較例１、実施例１〜５及び比較例２の結果から、カチオン重合性成分として脂環式エポキシ化合物もしくは低極性オキセタン化合物の好ましい配合量が、カチオン重合性成分とエラストマーと成膜用成分としてフェノキシ樹脂との合計質量の１０〜４０質量％であることがわかる。また、比較例３、４、実施例１、４、７−９及び比較例５の結果から、エラストマーの好ましい配合量が、カチオン重合性成分とエラストマーと成膜用成分としてフェノキシ樹脂との合計質量の１０〜４０質量％であることがわかる。更に、比較例６、実施例２、４、６、１０、１１及び比較例７の結果から、成膜用成分の含有量が、カチオン重合性成分とエラストマーと成膜用成分としてフェノキシ樹脂との合計質量の４０〜８０質量％であることがわかる。
<< Evaluation results 1 >>
From the results of Comparative Example 1, Examples 1 to 5 and Comparative Example 2 in Table 1, the preferred compounding amount of the alicyclic epoxy compound or the low-polar oxetane compound as the cationically polymerizable component is such that the film is formed with the cationically polymerizable component and the elastomer. It turns out that it is 10-40 mass% of the total mass with a phenoxy resin as a component for use. Also, from the results of Comparative Examples 3 and 4, Examples 1, 4, 7-9, and Comparative Example 5, the preferred compounding amount of the elastomer was the total mass of the cationically polymerizable component, the elastomer, and the phenoxy resin as the film-forming component. It can be seen that the content is 10 to 40% by mass. Furthermore, from the results of Comparative Example 6, Examples 2, 4, 6, 10, 11 and Comparative Example 7, the content of the film-forming component was lower than that of the cationic polymerizable component, the elastomer, and the phenoxy resin as the film-forming component. It turns out that it is 40-80 mass% of the total mass.
＜＜評価２＞＞
実施例１２〜１４で得られた、導電粒子を含有しない各接着フィルムを用いて、＜＜評価１＞＞と同様の条件で接続構造体を作成し、更に「接着強度」を測定し、評価したところ、実施例１２及び１４の接着フィルムを使用して作成した接続構造体における接着強度は５Ｎ以上（Ｂ評価）であり、実施例１３の接着フィルムを使用して作成した接続構造体における接着強度は１０Ｎ以上（Ａ評価）であった。いずれも、実用上問題のない接着強度であった。
<< Evaluation 2 >>
Using each adhesive film containing no conductive particles obtained in Examples 12 to 14, a connection structure was prepared under the same conditions as in << Evaluation 1 >>, and the "adhesive strength" was further measured and evaluated. As a result, the bonding strength of the connection structure prepared using the adhesive films of Examples 12 and 14 was 5 N or more (B evaluation), and the bonding strength of the connection structure prepared using the adhesive film of Example 13 was evaluated. The strength was 10 N or more (A rating). In each case, there was no practical problem.
本発明の接着剤組成物は、ＣＯＧ実装だけでなくＦＯＧ実装やＦＯＰ実装においても実用的な低温速硬化性と導通特性と保管ライフ特性と接着特性とを実現できるので、産業上有用である。 INDUSTRIAL APPLICABILITY The adhesive composition of the present invention is industrially useful because it can realize practical low-temperature quick-curing properties, conduction properties, storage life properties, and adhesive properties not only in COG mounting but also in FOG mounting and FOP mounting.
しかしながら、特許文献１に開示された異方性導電フィルムは、ＣＯＧ実装の場合には、良好な接着強度と、実用的な保管ライフ特性と、良好な導通特性とを実現しているが、フレキシブル回路基板（ＦＰＣ）をガラス基板やプラスチック基板に実装（ＦＯＧ実装やＦＯＰ実装）する場合には、実装後にＦＰＣに対して曲げ応力や引張り応力、剪断応力あるいは剥離応力等がかかるため、実用的な接着強度が得られにくくなることが懸念されているだけでなく、導通抵抗値などの導通特性の低下や保管ライフ特性の低下という問題の発生も懸念されている。また、異方性導電フィルムにおいて、高価な低極性オキセタン化合物の使用を抑制もしくは省略できるようにすることも求められている。 However, the anisotropic conductive film disclosed in Patent Document 1 achieves good adhesive strength, practical storage life characteristics , and good conduction characteristics in the case of COG mounting, but is flexible. When a circuit board (FPC) is mounted on a glass substrate or a plastic substrate (FOG mounting or FOP mounting), a bending stress, a tensile stress, a shear stress, a peeling stress, or the like is applied to the FPC after the mounting, so that it is practical. not only the adhesive strength is difficult to obtain is concerned, the problem occurred that reduction of the reduction and storage life properties of conduction characteristics, such as conduction resistance is also a concern. It is also required that anisotropic conductive films can suppress or omit the use of expensive low-polarity oxetane compounds.
＜接続構造体＞
本発明の接着剤組成物は、導電粒子を含有しているか否かに関わらず、第１電子部品と第２電子部品とを接続、好ましくは電気的に接続する際に（特に異方性導電接続する際に）適用することができる。第１電子部品と第２電子部品とは、同種の電子部品でも互いに相違する電子部品でもよいが、第２電子部品として、第１電子部品と同程度もしくはより高い剛性を有する電子部品を選択することが好ましい。また、第１電子部品と第２電子部品とを圧着ツールと定盤との間に挟持して接続を行う際に圧着ツール側に第１電子部品を配置する場合には、第２電子部品としては定盤に載置し易い水平面を有する電子部品を選択することが好ましい。第１電子部品の例として、ＦＰＣ、ＩＣチップ、ＩＣモジュール等を挙げることができ、第２電子部品の例として、プラスチック基板、ガラス基板、リジッド基板、セラミック基板、ＦＰＣ等を挙げることができる。異方性導電接続の場合、第１電子部品としてＦＰＣを好ましく選択することができ、第１電子部品がＦＰＣで第２電子部品が比較的剛性のある基板となるプラスチック基板やガラス基板、リジット基板、セラミック基板の場合を特に好ましく選択することができる。更により好ましくは、第２電子部品である基板自体が前記のように剛性があり且つ形状変形し得る（わずかな反りが問題となり易い）性質を有するプラスチック基板やガラス基板を選択することができる（つまり、ＦＯＰやＦＯＧの場合である）。これは本発明の接着剤組成物が、異方性導電接続後に第１電子部品を屈曲させた状態で維持可能な配合から構成することが可能だからである。なお、このような本発明の接着剤組成物で、導電粒子を含有しているか否かに関わらず、第１電子部品と第２電子部品とが接続、好ましくは電気的に接続されている接続構造体、及び第１電子部品と第２電子部品とを接続、好ましくは電気的に接続する、接続構造体の製造方法も本発明の一部である。特に、導電粒子を含有する本発明の接着剤組成物を異方性導電接着剤（好ましくは異方性導電フィルム）として適用した場合、本発明は、そのような異方性導電接着剤で、第１電子部品と第２電子部品とが異方性導電接続されている接続構造体、及び第１電子部品と第２電子部品とを異方性導電接続する、接続構造体の製造方法も本発明の一部である。なお、本発明の接着剤組成物を用いた電子部品の接続方法としては、公知の手法を利用することができる。
<Connection structure>
The adhesive composition of the present invention can be used to connect the first electronic component and the second electronic component, preferably electrically, irrespective of whether the adhesive composition contains conductive particles (especially anisotropic conductive material). (When connecting). Although the first electronic component and the second electronic component may be the same type of electronic component or different electronic components, an electronic component having the same or higher rigidity as the first electronic component is selected as the second electronic component. Is preferred. In the case where the first electronic component and the second electronic component are sandwiched between the crimping tool and the platen for connection and the first electronic component is arranged on the crimping tool side, the second electronic component is used as the second electronic component. It is preferable to select an electronic component having a horizontal surface that can be easily mounted on the surface plate. Examples of the first electronic component include an FPC, an IC chip, an IC module, and the like, and examples of the second electronic component include a plastic substrate, a glass substrate, a rigid substrate, a ceramic substrate, and an FPC. In the case of anisotropic conductive connection, FPC can be preferably selected as the first electronic component, and a plastic substrate, a glass substrate, or a rigid substrate in which the first electronic component is an FPC and the second electronic component is a relatively rigid substrate. The case of a ceramic substrate can be particularly preferably selected. Still more preferably, a plastic substrate or a glass substrate having such a property that the substrate itself, which is the second electronic component, is rigid and capable of being deformed in shape as described above (a slight warpage tends to be a problem) can be selected ( That is, it is the case of FOP or FOG). This is because the adhesive composition of the present invention can be composed of a composition that can maintain the first electronic component in a bent state after the anisotropic conductive connection. Note that, in such an adhesive composition of the present invention, a connection in which the first electronic component and the second electronic component are connected, preferably electrically connected, regardless of whether or not the adhesive composition contains conductive particles. The structure and a method of manufacturing a connection structure for connecting, preferably electrically, the first electronic component and the second electronic component are also part of the invention. In particular, when the adhesive composition of the present invention containing conductive particles is applied as an anisotropic conductive adhesive (preferably an anisotropic conductive film), the present invention relates to such an anisotropic conductive adhesive. The present invention also provides a connection structure in which the first electronic component and the second electronic component are anisotropically conductively connected, and a method of manufacturing a connection structure in which the first electronic component and the second electronic component are anisotropically conductively connected. Part of the invention. In addition, as a method for connecting electronic components using the adhesive composition of the present invention, a known method can be used.
Claims (11)
カチオン重合性成分が、脂環式エポキシ化合物又は低極性オキセタン化合物であり、
カチオン重合開始剤が、第４級アンモニウム塩系熱酸発生剤であり、
カチオン重合性成分の含有量が、カチオン重合性成分とエラストマーと成膜用成分との合計質量の１０〜４０質量％であり、
エラストマーの含有量が、カチオン重合性成分とエラストマーと成膜用成分との合計質量の１０〜４０質量％であり、そして
成膜用成分の含有量が、カチオン重合性成分とエラストマーと成膜用成分との合計質量の４０〜８０質量％である接着剤組成物。 An adhesive composition containing a cationically polymerizable component, a cationic polymerization initiator, an elastomer, and a film-forming component,
The cationically polymerizable component is an alicyclic epoxy compound or a low-polarity oxetane compound,
The cationic polymerization initiator is a quaternary ammonium salt-based thermal acid generator,
The content of the cationically polymerizable component is 10 to 40% by mass of the total mass of the cationically polymerizable component, the elastomer, and the film-forming component,
The content of the elastomer is 10 to 40% by mass of the total mass of the cationically polymerizable component, the elastomer, and the film forming component, and the content of the film forming component is the cationically polymerizable component, the elastomer, and the film forming component. An adhesive composition which is 40 to 80% by mass of the total mass of the components.
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| CN201980055667.2A CN112566995A (en) | 2018-09-10 | 2019-09-03 | Adhesive composition |
| PCT/JP2019/034517 WO2020054495A1 (en) | 2018-09-10 | 2019-09-03 | Adhesive composition |
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| WO2022255012A1 (en) * | 2021-06-03 | 2022-12-08 | デクセリアルズ株式会社 | Adhesive agent composition, adhesive film, connected structure, and method for manufacturing connected structure |
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| CN115029089B (en) * | 2022-06-06 | 2023-06-06 | 韦尔通科技股份有限公司 | high-Tg, high-adhesion and aging-resistant epoxy adhesive composition, and preparation method and application thereof |
| JP2023052255A (en) * | 2022-08-23 | 2023-04-11 | サンアプロ株式会社 | Acid generator, curable composition comprising the acid generator, and cured product thereof |
| CN117659667A (en) * | 2023-11-30 | 2024-03-08 | 常州德创高新材料科技有限公司 | Thermosetting resin composition, anisotropic conductive film, and connection structure |
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