WO2019194041A1 - Sheet-shaped epoxy resin composition and cured product thereof, and sheet for sealing - Google Patents
Sheet-shaped epoxy resin composition and cured product thereof, and sheet for sealing Download PDFInfo
- Publication number
- WO2019194041A1 WO2019194041A1 PCT/JP2019/013183 JP2019013183W WO2019194041A1 WO 2019194041 A1 WO2019194041 A1 WO 2019194041A1 JP 2019013183 W JP2019013183 W JP 2019013183W WO 2019194041 A1 WO2019194041 A1 WO 2019194041A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- epoxy resin
- sheet
- resin composition
- epoxy
- sealing
- Prior art date
Links
- 239000003822 epoxy resin Substances 0.000 title claims abstract description 198
- 229920000647 polyepoxide Polymers 0.000 title claims abstract description 198
- 239000000203 mixture Substances 0.000 title claims abstract description 133
- 238000007789 sealing Methods 0.000 title claims description 50
- 239000004593 Epoxy Substances 0.000 claims abstract description 60
- 150000001875 compounds Chemical class 0.000 claims abstract description 36
- 239000003505 polymerization initiator Substances 0.000 claims abstract description 33
- 238000010538 cationic polymerization reaction Methods 0.000 claims abstract description 32
- 238000003860 storage Methods 0.000 claims abstract description 29
- 125000003118 aryl group Chemical group 0.000 claims abstract description 8
- 125000004923 naphthylmethyl group Chemical group C1(=CC=CC2=CC=CC=C12)C* 0.000 claims abstract description 5
- 238000002844 melting Methods 0.000 claims description 25
- 230000008018 melting Effects 0.000 claims description 25
- 238000006243 chemical reaction Methods 0.000 claims description 18
- 238000002834 transmittance Methods 0.000 claims description 16
- 230000020169 heat generation Effects 0.000 claims description 12
- 230000008859 change Effects 0.000 claims description 10
- 230000001681 protective effect Effects 0.000 claims description 8
- 125000000217 alkyl group Chemical group 0.000 claims description 6
- 125000004432 carbon atom Chemical group C* 0.000 claims description 6
- 125000004178 (C1-C4) alkyl group Chemical group 0.000 abstract 2
- 238000012360 testing method Methods 0.000 description 29
- 238000005259 measurement Methods 0.000 description 22
- 239000011521 glass Substances 0.000 description 17
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 15
- 239000000463 material Substances 0.000 description 14
- 239000000126 substance Substances 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 13
- 238000000034 method Methods 0.000 description 13
- 230000004888 barrier function Effects 0.000 description 12
- 239000007789 gas Substances 0.000 description 12
- 238000005401 electroluminescence Methods 0.000 description 11
- 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 10
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 10
- 238000001035 drying Methods 0.000 description 9
- 229920005989 resin Polymers 0.000 description 9
- 239000011347 resin Substances 0.000 description 9
- 239000002966 varnish Substances 0.000 description 9
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 8
- 229920003986 novolac Polymers 0.000 description 8
- 239000003566 sealing material Substances 0.000 description 8
- 238000010438 heat treatment Methods 0.000 description 7
- 239000002904 solvent Substances 0.000 description 7
- 238000000576 coating method Methods 0.000 description 6
- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical group C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-N 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 5
- 125000003700 epoxy group Chemical group 0.000 description 5
- -1 ethylene glycol monoalkyl ether Chemical class 0.000 description 5
- 229930185605 Bisphenol Natural products 0.000 description 4
- 239000000853 adhesive Substances 0.000 description 4
- 230000001070 adhesive effect Effects 0.000 description 4
- 229910052782 aluminium Inorganic materials 0.000 description 4
- 235000010290 biphenyl Nutrition 0.000 description 4
- 239000004305 biphenyl Substances 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 4
- 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 4
- 239000007788 liquid Substances 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 239000003381 stabilizer Substances 0.000 description 4
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 3
- 239000000945 filler Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- 239000003607 modifier Substances 0.000 description 3
- 229920000139 polyethylene terephthalate Polymers 0.000 description 3
- 239000005020 polyethylene terephthalate Substances 0.000 description 3
- 239000011342 resin composition Substances 0.000 description 3
- 230000000630 rising effect Effects 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 238000012546 transfer Methods 0.000 description 3
- 229920002799 BoPET Polymers 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- 239000006087 Silane Coupling Agent Substances 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 125000002777 acetyl group Chemical group [H]C([H])([H])C(*)=O 0.000 description 2
- 125000002723 alicyclic group Chemical group 0.000 description 2
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical compound [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 2
- 150000001450 anions Chemical group 0.000 description 2
- 229910052787 antimony Inorganic materials 0.000 description 2
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 2
- 150000001642 boronic acid derivatives Chemical class 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 238000005227 gel permeation chromatography Methods 0.000 description 2
- 239000004973 liquid crystal related substance Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 229920000515 polycarbonate Polymers 0.000 description 2
- 239000004417 polycarbonate Substances 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 description 2
- 239000008096 xylene Substances 0.000 description 2
- 0 *[S+](*)c(cc1)ccc1O Chemical compound *[S+](*)c(cc1)ccc1O 0.000 description 1
- HCNHNBLSNVSJTJ-UHFFFAOYSA-N 1,1-Bis(4-hydroxyphenyl)ethane Chemical compound C=1C=C(O)C=CC=1C(C)C1=CC=C(O)C=C1 HCNHNBLSNVSJTJ-UHFFFAOYSA-N 0.000 description 1
- CYSGHNMQYZDMIA-UHFFFAOYSA-N 1,3-Dimethyl-2-imidazolidinon Chemical compound CN1CCN(C)C1=O CYSGHNMQYZDMIA-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical compound CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 description 1
- KJCVRFUGPWSIIH-UHFFFAOYSA-N 1-naphthol Chemical compound C1=CC=C2C(O)=CC=CC2=C1 KJCVRFUGPWSIIH-UHFFFAOYSA-N 0.000 description 1
- CQOZJDNCADWEKH-UHFFFAOYSA-N 2-[3,3-bis(2-hydroxyphenyl)propyl]phenol Chemical compound OC1=CC=CC=C1CCC(C=1C(=CC=CC=1)O)C1=CC=CC=C1O CQOZJDNCADWEKH-UHFFFAOYSA-N 0.000 description 1
- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 description 1
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical compound C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 description 1
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 1
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 1
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000004962 Polyamide-imide Substances 0.000 description 1
- 239000005062 Polybutadiene Substances 0.000 description 1
- 229920001030 Polyethylene Glycol 4000 Polymers 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 229910018286 SbF 6 Inorganic materials 0.000 description 1
- 208000034189 Sclerosis Diseases 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 239000003242 anti bacterial agent Substances 0.000 description 1
- 230000003712 anti-aging effect Effects 0.000 description 1
- 239000003849 aromatic solvent Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 239000012461 cellulose resin Substances 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- 229930003836 cresol Natural products 0.000 description 1
- 150000001925 cycloalkenes Chemical class 0.000 description 1
- 150000001983 dialkylethers Chemical class 0.000 description 1
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 1
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 1
- 238000007602 hot air drying Methods 0.000 description 1
- 125000004464 hydroxyphenyl group Chemical group 0.000 description 1
- 150000002460 imidazoles Chemical class 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 238000007733 ion plating Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000005453 ketone based solvent Substances 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 238000001579 optical reflectometry Methods 0.000 description 1
- 125000003566 oxetanyl group Chemical group 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 238000005240 physical vapour deposition Methods 0.000 description 1
- 238000005268 plasma chemical vapour deposition Methods 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 229920001084 poly(chloroprene) Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920002312 polyamide-imide Polymers 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229940057838 polyethylene glycol 4000 Drugs 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920001021 polysulfide Polymers 0.000 description 1
- 239000005077 polysulfide Substances 0.000 description 1
- 150000008117 polysulfides Polymers 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000003755 preservative agent Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 238000007650 screen-printing Methods 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 229920000468 styrene butadiene styrene block copolymer Polymers 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-O sulfonium group Chemical group [SH3+] RWSOTUBLDIXVET-UHFFFAOYSA-O 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 238000001771 vacuum deposition Methods 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K59/00—Integrated devices, or assemblies of multiple devices, comprising at least one organic light-emitting element covered by group H10K50/00
- H10K59/80—Constructional details
- H10K59/87—Passivation; Containers; Encapsulations
- H10K59/871—Self-supporting sealing arrangements
- H10K59/8722—Peripheral sealing arrangements, e.g. adhesives, sealants
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/68—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the catalysts used
- C08G59/687—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the catalysts used containing sulfur
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
- C08G59/22—Di-epoxy compounds
- C08G59/24—Di-epoxy compounds carbocyclic
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/68—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the catalysts used
-
- 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
-
- G—PHYSICS
- G09—EDUCATION; CRYPTOGRAPHY; DISPLAY; ADVERTISING; SEALS
- G09F—DISPLAYING; ADVERTISING; SIGNS; LABELS OR NAME-PLATES; SEALS
- G09F9/00—Indicating arrangements for variable information in which the information is built-up on a support by selection or combination of individual elements
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
- H05B33/00—Electroluminescent light sources
- H05B33/02—Details
- H05B33/04—Sealing arrangements, e.g. against humidity
-
- 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
Definitions
- the present invention relates to a sheet-like epoxy resin composition, a cured product thereof, and a sealing sheet.
- Organic EL (Electro-Luminescence) elements have recently been widely used in displays and lighting devices because of their low power consumption. Since organic EL elements are easily deteriorated by moisture and oxygen in the air, they are generally used after being sealed with a sealing material or the like.
- a sheet-like resin composition containing an epoxy resin has been proposed as a sealing sheet for sealing an organic EL element.
- a low molecular weight epoxy resin, a high molecular weight epoxy resin, and a latent imidazole series A sheet-like epoxy resin composition containing a compound and a silane coupling agent has been proposed (for example, Patent Document 1 and Patent Document 2).
- Patent Document 3 a composition containing dicyclopentadienediol diglycidyl ether, a compound having an oxetane ring, and a photocationic polymerization initiator has been proposed ( Patent Document 3).
- a sealing sheet such as an organic EL element is usually used after being in close contact with a display element and then curing the sealing sheet.
- a sealing sheet such as an organic EL element is usually used after being in close contact with a display element and then curing the sealing sheet.
- the temperature at which the sealing sheet is cured is too high, there is a problem that the organic EL element is affected by the heat at the time of curing or the productivity of the display device is reduced.
- the sealing sheet when the curability of the sealing sheet is too high, the sealing sheet is cured during storage of the sealing sheet, which causes a problem that the sealing element cannot be sufficiently bonded.
- the sealing sheet needs to be processed into a sheet shape or set in an apparatus for bonding to a display element, and the exposure time to the manufacturing environment temperature is longer than that of a liquid sealing material. Therefore, higher storage stability is required as compared with a liquid sealing material.
- an object is to provide a sheet-like epoxy resin composition that can be cured at a relatively low temperature and that is excellent in storage stability.
- the first of the present invention relates to the following sheet-like epoxy resin composition.
- A an epoxy compound represented by the following general formula (1)
- B an epoxy resin having an aromatic ring and having a weight average molecular weight of 3000 to 100,000
- C And a cationic polymerization initiator represented by formula (2), wherein the content of the epoxy resin (B) is 45% by mass or more.
- R 1 represents an alkyl group having 1 to 4 carbon atoms or a naphthylmethyl group
- R 2 represents an alkyl group having 1 to 4 carbon atoms
- the second aspect of the present invention relates to the following sealing sheet and cured product.
- a sealing sheet comprising a layer made of the sheet-like epoxy resin composition according to any one of [1] to [5].
- the sealing sheet according to [6] having a protective film on at least one surface of the layer made of the sheet-like epoxy resin composition.
- the sealing sheet according to [6] or [7] which is used for surface sealing of the display element.
- the sheet-like epoxy resin composition of the present invention can be cured at a relatively low temperature, while having high storage stability. Therefore, it is suitable for a sealing material for sealing various display elements.
- Sheet-like epoxy resin composition of the present invention is used for, for example, a sealing sheet (surface sealing sheet), a transparent coating sheet, and the like, and particularly a sealing sheet (surface sealing sheet). ).
- a sheet-like epoxy resin composition is used for the sheet
- seat for transparent coatings means the material for which the transparency which fills between image display apparatuses, such as board
- the sheet-like epoxy resin composition for surface-sealing display elements, etc. can be softened at a relatively low temperature so as not to affect the display elements, and can be cured at a relatively low temperature. It is required to be. On the other hand, the sheet-like epoxy resin composition is also required to be difficult to be deformed or cured before being attached to the display element, that is, storage stability. However, the conventional sheet-like epoxy resin composition has a problem that it is difficult to achieve both good curability and storage stability before bonding.
- the present inventors have intensively studied (A) an epoxy compound having a specific structure, (B) an epoxy resin having an aromatic ring and a weight average molecular weight of 3000 to 100,000, C) By combining with a cationic polymerization initiator having a specific structure, it can be bonded to a display element at an appropriate temperature (for example, about 60 ° C.), and further relatively low temperature (for example, 90 ° C. or lower). ) And the storage stability before bonding to the display element was found to be very good.
- the sheet-like epoxy resin composition of the present invention combines these is considered as follows. Since a certain amount of the (B) epoxy resin is contained in the sheet-like epoxy resin composition, the sheet-like epoxy resin composition is hardly softened or melted during storage, and the shape can be maintained. In addition, when only (B) an epoxy resin is used, the curing temperature tends to be high, but since (A) an epoxy compound is included, the epoxy group tends to react even at a relatively low temperature (eg, 90 ° C. or less). The curability of the sheet-like epoxy resin composition is improved.
- Epoxy compound (A) is a compound having a structure represented by the following general formula (1) and has a dicyclopentadiene skeleton.
- the bonding position of the group bonded to the dicyclopentadiene skeleton is not particularly limited.
- the sheet-like epoxy resin composition only one type of compound having a structure represented by the following general formula (1) may be included, or two or more types may be included.
- the above (A) epoxy compound is liquid at 23 ° C. Since the (A) epoxy compound has a dicyclopentadiene structure, the reactivity of the epoxy group is likely to be good, and as described above, the sheet-like epoxy resin composition is easily cured even at a relatively low temperature.
- the epoxy compound may be prepared by a known method, but may be a commercially available product.
- Examples of commercially available epoxy compounds include EP-4088L and EP-4088S manufactured by ADEKA.
- the amount of the (A) epoxy compound contained in 100 parts by mass of the sheet-like epoxy resin composition is preferably 10 to 50 parts by mass, more preferably 10 to 40 parts by mass, More preferably, it is 30 parts by mass.
- the amount of the (A) epoxy compound is 10 parts by mass or more, the (A) epoxy compound and the (B) epoxy resin are likely to react at 90 ° C. or less, and the curability of the sheet-like epoxy resin composition is good. Prone.
- the amount of (A) the epoxy compound is 50 parts by mass or less, the amount of (B) the epoxy resin is relatively sufficient, and the storage stability of the sheet-like epoxy resin composition is likely to be increased.
- Epoxy resin (B)
- the epoxy resin is not particularly limited as long as it has at least one aromatic ring and one epoxy group in the molecule and has a weight average molecular weight of 3000 to 100,000.
- the sheet-like epoxy resin composition may contain only one type of (B) epoxy resin, or may contain two or more types.
- the epoxy resin composition is usually solid at normal temperature (23 ° C.).
- the weight average molecular weight of the epoxy resin is preferably 6000 to 60000, and more preferably 7000 to 40000. When the molecular weight of the (B) epoxy resin is 3000 or more, the (B) epoxy resin tends to be solid at room temperature. On the other hand, when the weight average molecular weight of the (B) epoxy resin is 1000000 or less, the fluidity of the sheet-like epoxy resin composition can be improved when the sheet-like epoxy resin composition is bonded to a display element or the like. It becomes easy to adhere to an element or the like.
- the said weight average molecular weight is a polystyrene conversion value measured by gel permeation chromatography (GPC).
- the epoxy equivalent of the (B) epoxy resin is preferably 900 g / eq or more and 20000 g / eq or less, and more preferably 1000 g / eq or more and 200000 g / eq or less.
- the epoxy equivalent of the epoxy resin is 900 g / eq or more, the tackiness at room temperature of the sheet-like epoxy resin composition is reduced. As a result, the handleability when the sheet-shaped epoxy resin composition is bonded to the display element is likely to be good, and the sheet-like epoxy resin composition is easily bonded accurately on the display element.
- the epoxy equivalent of the (B) epoxy resin is preferably 20000 g / eq or less.
- the epoxy equivalent of an epoxy resin is the said range, the melting temperature of a sheet-like epoxy resin composition will become a moderate range, and it will become possible to bond together with a display element at desired temperature.
- the said (B) epoxy resin contains a some epoxy resin, it is preferable that the epoxy equivalent of each epoxy resin is the said range.
- the epoxy resin may contain one or more epoxy groups in the molecule, but preferably contains a plurality of epoxy groups so as to satisfy the above-mentioned epoxy equivalent. Moreover, (B) epoxy resin should just contain one or more aromatic rings in a molecule
- epoxy resins include bisphenol A type, bisphenol F type, bisphenol E type, bisphenol S type, bisphenol AD type, and mixed types thereof, such as bisphenol type epoxy resins; diphenyl ether type epoxy resins; phenol novolac type, Cresol novolak type, biphenyl novolak type, bisphenol novolak type, naphthol novolak type, trisphenol novolak type, dicyclopentadiene novolak type, etc. novolac type epoxy resin; biphenyl type epoxy resin; naphthyl type epoxy resin; triphenolmethane type, triphenol Ethane type, triphenolalkane type epoxy resin such as triphenolpropane type; and the like.
- the epoxy resin is preferably a bisphenol type epoxy resin or a biphenyl type epoxy resin among the above.
- the amount of the bisphenol F skeleton in the epoxy resin increases, the softening point of the (B) epoxy resin tends to decrease. Therefore, when the melting temperature of the sheet-like epoxy resin composition is set to a relatively high temperature, it is preferable to use an epoxy resin having a small bisphenol F skeleton.
- the amount of (B) epoxy resin contained in 100 parts by mass of the sheet-like epoxy resin composition is 45 parts by mass or more, preferably 50 to 85 parts by mass, and more preferably 60 to 75 parts by mass. .
- (B) When the amount of the epoxy resin is 50 parts by mass or more, the storage stability of the sheet-like epoxy resin composition is likely to be increased, and further, the bonding temperature of the sheet-like epoxy resin composition is likely to be within an appropriate range. .
- C Cationic polymerization initiator
- the cationic polymerization initiator is a compound represented by the following general formula (2). Only 1 type (C) cationic polymerization initiator may be contained in the sheet-like epoxy resin composition, and 2 or more types may be contained.
- R 1 represents an alkyl group having 1 to 4 carbon atoms or a naphthylmethyl group, and a naphthylmethyl group is particularly preferable.
- R 2 represents an alkyl group having 1 to 4 carbon atoms, and a methyl group is particularly preferable.
- (C) the cationic polymerization initiator is particularly preferably a compound represented by the following formula (2a).
- the cationic polymerization initiator may be prepared by a known method or may be a commercially available product. Examples of commercially available products include trade name SI-60 manufactured by Sanshin Chemical Industry Co., Ltd.
- the amount of the cationic polymerization initiator (C) contained in 100 parts by mass of the sheet-like epoxy resin composition is preferably 1 to 10 parts by mass, more preferably 2 to 8 parts by mass. More preferably, it is a part.
- (C) When the amount of the cationic polymerization initiator is 1 part by mass or more, the curability of the sheet-like epoxy resin composition tends to be good. On the other hand, when the amount of (C) the cationic polymerization initiator is 10 parts by mass or less, the storage stability of the sheet-like epoxy resin composition is likely to be increased.
- Examples of other components include other resins, fillers, modifiers, stabilizers, and the like.
- Examples of other resins include (A) epoxy compound and (B) epoxy resin not corresponding to epoxy resin, polyamide, polyamideimide, polyurethane, polybutadiene, polychloroprene, polyether, polyester, styrene-butadiene-styrene block Copolymers, xylene resins, ketone resins, cellulose resins, fluorine-based oligomers, silicon-based oligomers, polysulfide-based oligomers and the like are included.
- the sheet-like epoxy resin composition may contain only one kind or two or more kinds.
- the filler examples include glass beads, styrene polymer particles, methacrylate polymer particles, ethylene polymer particles, propylene polymer particles, and the like.
- the sheet-like epoxy resin composition may contain only one type of filler, or may contain two or more types.
- the modifier include a polymerization initiator, an anti-aging agent, a leveling agent, a wettability improver, a surfactant, a plasticizer, a solvent, a silane coupling agent, and the like.
- a polymerization initiator an anti-aging agent, a leveling agent, a wettability improver, a surfactant, a plasticizer, a solvent, a silane coupling agent, and the like.
- One of these modifiers may be included, or two or more thereof may be included.
- the sheet-like epoxy resin composition may contain only one kind or two or more kinds.
- the above-mentioned sheet-like epoxy resin composition can be manufactured by arbitrary methods, unless the effect of this invention is impaired.
- the sheet-like epoxy resin composition of the present invention is prepared by, for example, dissolving a resin composition containing (A) an epoxy compound, (B) an epoxy resin, and (C) a cationic polymerization initiator in various solvents at 30 ° C. or lower.
- the varnish can be applied to the base material in the form of a sheet and dried.
- solvents examples include aromatic solvents such as toluene and xylene; ketone solvents such as acetone, methyl ethyl ketone, and methyl isobutyl ketone; ethers, dibutyl ether, tetrahydrofuran, dioxane, ethylene glycol monoalkyl ether, ethylene glycol dialkyl ether Ethers such as propylene glycol or dialkyl ether; aprotic polar solvents such as N-methylpyrrolidone, dimethylimidazolidinone and dimethylformaldehyde; esters such as ethyl acetate and butyl acetate.
- aromatic solvents such as toluene and xylene
- ketone solvents such as acetone, methyl ethyl ketone, and methyl isobutyl ketone
- ethers dibutyl ether, tetrahydrofuran, dioxane,
- the (A) epoxy compound, (B) epoxy resin, (C) cationic polymerization initiator, and solvent may be mixed at one time. After the (B) epoxy resin or the like is dissolved in the solvent, other components are mixed. May be added. Examples of the mixing method include a known stirring method and a kneading method using three rolls.
- the varnish application method is not particularly limited, and examples thereof include screen printing, dispenser application, various roll methods, and the like. Moreover, it does not restrict
- the drying temperature and drying time of the varnish are the temperature and time at which (A) the epoxy compound and (B) the epoxy resin are not cured.
- the drying temperature is 20 to 100 ° C.
- the drying time can be about 1 minute to 3 hours, for example.
- the drying method is not particularly limited, and examples thereof include hot air drying and vacuum drying.
- the thickness of the sheet-like epoxy resin composition is appropriately selected depending on the application, but is, for example, 1 to 100 ⁇ m when used as a sealing material for display elements. It is preferably 5 to 50 ⁇ m, more preferably 10 to 30 ⁇ m.
- the melting temperature of the sheet-like epoxy resin composition is preferably 35 ° C. or more and 60 ° C. or less, and is 40 to 56 ° C. when the tackiness at the time of working the sheet-like epoxy resin composition is lowered. Is preferred.
- the sheet-like epoxy resin composition and the display element are bonded together, the sheet-like epoxy resin composition is softened (melted) so that a gap with the display element is hardly generated and can be adhered.
- the melting temperature of the sheet-like epoxy resin composition is 60 ° C. or less, the sheet-like epoxy resin composition can be bonded to the display element at a relatively low temperature (60 ° C. or less).
- the melting temperature of the sheet-like epoxy resin composition is 35 ° C.
- the tackiness at the time of working the sheet-like epoxy resin composition is low, and the workability tends to be good. Further, when the sheet-like epoxy resin composition is stored, the sheet-like epoxy resin composition is hardly deformed, and the shape can be maintained.
- the melting temperature can be measured as follows.
- the sheet-like epoxy resin composition is cut into a length of about 30 mm and a width of about 5 mm to produce a strip-shaped test piece.
- the test piece is brought into close contact with a glass plate heated on a hot plate. Thereafter, the test piece is gradually peeled from the glass plate in the 180 ° direction.
- This operation is started at a preset temperature of 40 ° C. of the hot plate, and each time the set temperature is raised by 1 ° C., a strip-shaped test piece is newly prepared and repeated, and the adhesive peelability of the layer made of the sheet-like epoxy resin composition at the time of peeling
- the temperature at which becomes the largest is the melting temperature. However, at 40 ° C., those having already high adhesive peelability are measured for melting temperature from 25 ° C.
- the melting temperature of the sheet-like epoxy resin composition after being stored at 40 ° C. for 17 hours is preferably within the range of the melting temperature ⁇ 10 ° C. of the sheet-like epoxy resin composition before storage, and within ⁇ 5 ° C. More preferably.
- the said temperature change becomes a parameter
- index of the storage stability of a sheet-like epoxy resin composition if a temperature change is 10 degrees C or less, it can be said that it is hard to produce a curing reaction etc. at the time of storage.
- the melting temperature of the sheet-like epoxy resin composition changes greatly during storage, it becomes necessary to change the temperature, pressure, etc. when the sheet-like epoxy resin composition is bonded to a display element or the like in accordance with the change.
- the heat generation starting temperature measured by a differential scanning calorimeter (DSC) of the sheet-like epoxy resin composition is preferably 60 ° C. or higher and 90 ° C. or lower, and more preferably 65 to 85 ° C.
- the exothermic start temperature is 60 ° C. or higher
- the (A) epoxy compound or the (B) epoxy resin is difficult to cure at the time of molding the sheet-like epoxy resin composition, at the time of storing the sheet-like epoxy resin composition, Storage stability is improved.
- the heat generation starting temperature is 90 ° C. or lower, the sheet-like epoxy resin composition can be cured at 90 ° C. or lower, and the display element and the like are hardly affected.
- the heat generation start temperature can be measured by the following method.
- the epoxy reaction rate when the sheet-like epoxy resin composition is heated at 85 ° C. for 50 minutes is preferably 80% or more, and more preferably 85% or more.
- the said epoxy reaction rate is a parameter
- the said epoxy reaction rate is 80% or more, it can be said that a sheet-like epoxy resin composition can fully be hardened even at 90 degrees C or less.
- the light transmittance at a wavelength of 550 nm is preferably 90% or more, more preferably 95% or more. Preferably, it is 97% or more.
- the sheet-shaped epoxy resin composition can be used for applications requiring light transmittance.
- the light transmittance of the cured product of the sheet-like epoxy resin composition can be measured by the following procedure.
- a laminate comprising a base film and a sheet-like epoxy resin composition having a thickness of 20 ⁇ m prepared on the base film is cut into a length of about 60 mm and a width of about 40 mm to obtain a test piece.
- Bubbles entered into the glass plate No. 3 made by Matsunami Glass, thickness 0.3 mm, 70 mm ⁇ 50 mm
- a hot plate heated to 70 ° C. of the layer made of the sheet-like epoxy resin composition of this test piece. Transfer and stick together with a roll.
- the test piece is removed from the hot plate and allowed to cool for 3 minutes.
- the base film is peeled off, and the sheet-like epoxy resin composition on the glass plate is heated in an oven at 85 ° C. for 50 minutes to obtain a cured product.
- the light transmittance at a wavelength of 550 nm of the glass plate on which the cured product of the sheet-like epoxy resin composition is formed is measured using an ultraviolet-visible light spectrophotometer (Shimadzu Corporation UV-2550). In the measurement, the light transmittance of the glass plate alone is used as the baseline. In addition, you may perform the measurement of the transmittance
- the sealing sheet of the present invention includes a layer made of the above-described sheet-like epoxy resin composition.
- the sealing sheet of the present invention is a laminate of a base film, the above-described sheet-shaped epoxy resin composition disposed on the base film, and a protective film disposed on the sheet-shaped epoxy resin composition. It can be a body or the like.
- the base film or the protective film examples include known release films. These films are preferably films having moisture barrier properties and gas barrier properties, such as polyethylene terephthalate films. Although depending on the film material, the thickness of the base film can be set to about 50 ⁇ m from the viewpoint of followability to a sealing material such as an organic EL element.
- the protective film is preferably laminated on a layer made of a sheet-like epoxy resin composition. Lamination can be performed at about 70 ° C. using a laminator, for example. The thickness of the protective film can also be about 20 to 40 ⁇ m depending on the film material.
- the sealing sheet of the present invention may further include a gas barrier layer depending on the application.
- the gas barrier layer is a layer that suppresses permeation of moisture and gas.
- Such a gas barrier layer can be disposed adjacent to the sheet-like epoxy resin composition, for example.
- the gas barrier layer examples include metals such as Al, Cr, Ni, Cu, Zn, Si, Fe, Ti, Ag, Au, and Co; oxides of these metals; nitrides of these metals; Oxynitrides; resins such as polyethylene terephthalate and polycarbonate are included.
- the gas barrier layer may be composed of one kind of material or may be composed of two or more kinds of materials.
- the gas barrier layer is preferably a layer having high light reflectance
- the gas barrier layer can be a layer made of, for example, Al or Cu.
- the gas barrier layer is preferably a light-transmitting layer.
- the layer can be a layer made of, for example, polyethylene terephthalate or polycarbonate.
- the thickness of the gas barrier layer can be about 10 to 3000 ⁇ m.
- the method for forming the gas barrier layer is not particularly limited, and examples of the dry process include various PVD methods such as vacuum deposition, sputtering, and ion plating; and CVD methods such as plasma CVD. Examples of the wet process include a plating method and a coating method.
- the sealing sheet of the present invention is used after a layer made of a sheet-like epoxy resin composition is brought into close contact with a desired material to be sealed and then a layer made of the sheet-like epoxy resin composition is cured.
- the material to be sealed which is an object to be sealed, is not particularly limited, and examples thereof include an organic EL element, a liquid crystal element, and an LED element.
- Epoxy compound EP-4088L manufactured by ADEKA dicyclopendiene type epoxy compound represented by the following general formula: epoxy equivalent 165 g / eq
- Epoxy resin jER4005P bisphenol F type epoxy resin manufactured by Mitsubishi Chemical Corporation, epoxy equivalent 950 g / eq, Mw 7582 YX6954B35: Biphenyl type epoxy resin manufactured by Mitsubishi Chemical Corporation, epoxy equivalent 10,000 g / eq, Mw36691 -JER4275: Mitsubishi Chemical Corporation bisphenol A / bisphenol F type epoxy resin, epoxy equivalent 8,400 g / eq, Mw58287
- Example 1 30 parts by mass of EP-4088L, 50 parts by mass of jER4005P, and 20 parts by mass (in terms of solid content) of YX6954B35 were added to the flask, and 100 parts by mass of methyl ethyl ketone was added thereto and stirred and dissolved at room temperature. To this solution, 2.5 parts by weight of cationic polymerization initiator SI-60 and 1 part by weight of KBM-403 were added and stirred at room temperature to prepare a varnish.
- the prepared varnish was coated with an applicator using a coating machine on a base film (release-treated PET film A53 (manufactured by Teijin Film Solutions Co., Ltd.) thickness 50 ⁇ m) so that the thickness after drying was about 20 ⁇ m.
- This film was dried in a 90 ° C. inert oven for 3 minutes, and the MEK in the varnish coating film was removed by drying to form a layer made of a sheet-like epoxy resin composition on the base film.
- the protective film Release processing PET film A31 (made by Teijin Film Solutions) thickness 38 micrometers
- the protective film was peeled off as appropriate, and the surface of the layer made of the sheet-like epoxy resin composition was exposed for use.
- Examples 2 to 10 and Comparative Examples 1 to 10 Varnishes were prepared in the same manner as in Example 1 with the composition ratios (mass ratios) shown in Tables 1 and 2. This was coated and dried to obtain a sealing sheet having a layer made of a sheet-like epoxy resin composition.
- Epoxy reaction rate at a curing temperature of 85 ° C. (%) A measurement sample was prepared in the same manner as the uncured product. Curing was performed in an oven set to 85 ° C. in advance, and a measurement sample was taken out 50 minutes after the sample was put in. Then, the calorific value of the cured product was specified by DSC at a heating rate of 5 ° C./min and a measurement temperature range of 20 ° C. to 300 ° C. And the epoxy reaction rate (%) in the curing temperature of 85 degreeC was calculated
- required from the measured calorific value from the formula shown below. Reaction rate (%) (Heat generation amount of uncured product ⁇ Heat generation amount after curing) / Heat generation amount of uncured product ⁇ 100
- the sealing sheet obtained in the example or the comparative example was cut into a length of about 150 mm and a width of about 40 mm to obtain a strip-shaped test piece.
- the layer made of the sheet-like epoxy resin composition of the test piece was transferred and pasted onto a glass plate heated on a hot plate heated to 70 ° C. with a roll so as not to contain bubbles.
- the test piece was removed from the hot plate and allowed to cool for 3 minutes. Thereafter, the base film was peeled off, and the transferability was evaluated as follows.
- ⁇ Resin layer transferred to the entire glass surface
- ⁇ Resin layer remaining on the substrate side
- ⁇ The resin layer does not adhere to the glass
- seat for sealing obtained by the Example or the comparative example was cut out to about 60 mm in length, and about 40 mm in width, and the test piece was obtained. Bubbles entered into the glass plate (No. 3 made by Matsunami Glass, thickness 0.3 mm, 70 mm ⁇ 50 mm) heated on a hot plate heated to 70 ° C. of the layer made of the sheet-like epoxy resin composition of this test piece. It was transferred by a roll and pasted together. The test piece was removed from the hot plate and allowed to cool for 3 minutes. Thereafter, the base film was peeled off, and the sheet-like epoxy resin composition on the glass plate was heated in an oven at 85 ° C.
- the light transmittance at a wavelength of 550 nm of the glass plate on which the cured product of the sheet-like epoxy resin composition was formed was measured using an ultraviolet-visible light spectrophotometer (Shimadzu Corporation UV-2550). In the measurement, the light transmittance of the glass plate alone was taken as the baseline.
- Comparative Example 1 that does not include an epoxy compound having an alicyclic structure, the epoxy reaction rate at a curing temperature of 85 ° C. is less than 80%, and the curing reaction is sufficiently performed when the temperature for curing is low. I could not proceed.
- SI-300 an acetyl group is bonded to a phenyl group and an anion is PF 6 —
- a heating test at 40 ° C. for 17 hours holding The later melting temperature exceeded 80 ° C.
- the change in melting temperature before and after the heating test was 10 ° C. or more, and it can be said that the storage stability was poor.
- the transferability after the heating test could not be bonded to the glass.
- SI-B2A (when an acetyl group is bonded to a phenyl group and an anion is B (C 6 F 5 ) 4 — ) (Comparative Example 8) is also obtained by simply forming into a sheet shape. It has hardened. The reactivity of the cationic polymerization initiator was too high, and the storage stability was poor. Moreover, since it was not able to transfer at 70 degreeC, the light transmittance after hardening was not able to be measured.
- SI-B7 or SI-80 other than the structure specified in the present invention was used as the cationic polymerization initiator (Comparative Examples 9 and 10), although the storage stability was good, it was at 85 ° C. The epoxy reaction rate of was low and could not be cured sufficiently at 85 ° C.
- the sealing material for display elements of the present invention can be cured at a relatively low temperature, and further has excellent storage stability. Therefore, the present invention can be applied to sealing various display elements.
Abstract
The problem addressed is to provide a sheet-shaped epoxy resin composition capable of curing at relatively low temperature and also having excellent storage stability. A sheet-shaped epoxy resin composition that solves the above problem includes (A) an epoxy compound represented by general formula (1), (B) an epoxy resin having an aromatic ring and a weight-average molecular weight of 3,000-100,000, and (C) a cationic polymerization initiator represented by general formula (2); and the content of the (B) epoxy resin is 45 mass% or higher. (In general formula (2), R1 represents a C1-4 alkyl group or a naphthylmethyl group, and R2 represents a C1-4 alkyl group)
Description
本発明は、シート状エポキシ樹脂組成物およびその硬化物、ならびに封止用シートに関する。
The present invention relates to a sheet-like epoxy resin composition, a cured product thereof, and a sealing sheet.
有機ＥＬ（Ｅｌｅｃｔｒｏ－Ｌｕｍｉｎｅｓｃｅｎｃｅ）素子は、消費電力が少ないことから、近年、ディスプレイや照明装置などに多く用いられている。有機ＥＬ素子は、大気中の水分や酸素によって劣化しやすいことから、封止材等によって封止して使用することが一般的である。
Organic EL (Electro-Luminescence) elements have recently been widely used in displays and lighting devices because of their low power consumption. Since organic EL elements are easily deteriorated by moisture and oxygen in the air, they are generally used after being sealed with a sealing material or the like.
従来、有機ＥＬ素子を封止するための封止用シートとして、エポキシ樹脂を含むシート状樹脂組成物が提案されており、例えば、低分子量エポキシ樹脂と、高分子量エポキシ樹脂と、潜在性イミダゾール系化合物と、シランカップリング剤と、を含むシート状エポキシ樹脂組成物が提案されている（例えば、特許文献１および特許文献２）。
Conventionally, a sheet-like resin composition containing an epoxy resin has been proposed as a sealing sheet for sealing an organic EL element. For example, a low molecular weight epoxy resin, a high molecular weight epoxy resin, and a latent imidazole series A sheet-like epoxy resin composition containing a compound and a silane coupling agent has been proposed (for example, Patent Document 1 and Patent Document 2).
一方、各種表示素子を封止するための液状のシール材として、ジシクロペンタジエンジオールジグリシジルエーテルと、オキセタン環を有する化合物と、光カチオン重合開始剤と、を含む組成物が提案されている（特許文献３）。
On the other hand, as a liquid sealing material for sealing various display elements, a composition containing dicyclopentadienediol diglycidyl ether, a compound having an oxetane ring, and a photocationic polymerization initiator has been proposed ( Patent Document 3).
ここで、有機ＥＬ素子等の封止用シートは通常、表示素子と密着させた後、当該封止用シートを硬化させて用いられる。しかしながら、封止用シートを硬化させる際の温度が高すぎると、硬化時の熱によって有機ＥＬ素子が影響を受けてしまったり、表示装置の生産性が低下する、との課題が生じる。
Here, a sealing sheet such as an organic EL element is usually used after being in close contact with a display element and then curing the sealing sheet. However, when the temperature at which the sealing sheet is cured is too high, there is a problem that the organic EL element is affected by the heat at the time of curing or the productivity of the display device is reduced.
一方で、封止用シートの硬化性が高すぎると、封止用シートの保管時に、封止用シートが硬化してしまい、表示素子と十分に貼り合わせることができない、という課題が生じる。また特に、封止用シートは、シート状に加工したり、表示素子に貼り合わせるための装置にセットしたりする必要があり、液状の封止材より製造環境温度に晒される時間が長い。そのため、液状の封止材と比較して、より高い保存安定性が求められる。しかしながら、従来の封止用シートでは良好な硬化性と、高い保存安定性との両立が難しく、これらの要求を同時に満たすシート状の樹脂組成物は得られていないのが実状であった。
On the other hand, when the curability of the sealing sheet is too high, the sealing sheet is cured during storage of the sealing sheet, which causes a problem that the sealing element cannot be sufficiently bonded. In particular, the sealing sheet needs to be processed into a sheet shape or set in an apparatus for bonding to a display element, and the exposure time to the manufacturing environment temperature is longer than that of a liquid sealing material. Therefore, higher storage stability is required as compared with a liquid sealing material. However, it has been difficult for conventional sealing sheets to achieve both good curability and high storage stability, and a sheet-like resin composition that satisfies these requirements has not been obtained.
本発明は、このような課題を鑑みてなされたものである。具体的には、比較的低温で硬化が可能であり、さらには保存安定性に優れるシート状エポキシ樹脂組成物の提供を目的とする。
The present invention has been made in view of such problems. Specifically, an object is to provide a sheet-like epoxy resin composition that can be cured at a relatively low temperature and that is excellent in storage stability.
すなわち、本発明の第１は、以下のシート状エポキシ樹脂組成物に関する。
［１］（Ａ）下記一般式（１）で表されるエポキシ系化合物と、（Ｂ）芳香環を有し、かつ重量平均分子量が３０００～１０００００である、エポキシ樹脂と、（Ｃ）下記一般式（２）で表されるカチオン重合開始剤と、を含み、前記（Ｂ）エポキシ樹脂の含有量が４５質量％以上である、シート状エポキシ樹脂組成物。
（一般式（２）中、Ｒ１は炭素数１～４のアルキル基またはナフチルメチル基を表し、
Ｒ２は炭素数１～４のアルキル基を表す） That is, the first of the present invention relates to the following sheet-like epoxy resin composition.
[1] (A) an epoxy compound represented by the following general formula (1), (B) an epoxy resin having an aromatic ring and having a weight average molecular weight of 3000 to 100,000, and (C) And a cationic polymerization initiator represented by formula (2), wherein the content of the epoxy resin (B) is 45% by mass or more.
(In the general formula (2), R 1 represents an alkyl group having 1 to 4 carbon atoms or a naphthylmethyl group,
R 2 represents an alkyl group having 1 to 4 carbon atoms)
［１］（Ａ）下記一般式（１）で表されるエポキシ系化合物と、（Ｂ）芳香環を有し、かつ重量平均分子量が３０００～１０００００である、エポキシ樹脂と、（Ｃ）下記一般式（２）で表されるカチオン重合開始剤と、を含み、前記（Ｂ）エポキシ樹脂の含有量が４５質量％以上である、シート状エポキシ樹脂組成物。
Ｒ２は炭素数１～４のアルキル基を表す） That is, the first of the present invention relates to the following sheet-like epoxy resin composition.
[1] (A) an epoxy compound represented by the following general formula (1), (B) an epoxy resin having an aromatic ring and having a weight average molecular weight of 3000 to 100,000, and (C) And a cationic polymerization initiator represented by formula (2), wherein the content of the epoxy resin (B) is 45% by mass or more.
R 2 represents an alkyl group having 1 to 4 carbon atoms)
［２］前記（Ｂ）エポキシ樹脂のエポキシ当量が９００ｇ／ｅｑ以上である、［１］に記載のシート状エポキシ樹脂組成物。
［３］示差走査熱量計により測定される発熱開始温度が、６０℃以上９０℃以下であり、かつ８５℃で５０分加熱したときのエポキシ反応率が８０％以上である、［１］または［２］に記載のシート状エポキシ樹脂組成物。 [2] The sheet-like epoxy resin composition according to [1], wherein the epoxy equivalent of the (B) epoxy resin is 900 g / eq or more.
[3] The heat generation start temperature measured by a differential scanning calorimeter is 60 ° C. or higher and 90 ° C. or lower, and the epoxy reaction rate when heated at 85 ° C. for 50 minutes is 80% or higher. 2] The sheet-like epoxy resin composition according to [2].
［３］示差走査熱量計により測定される発熱開始温度が、６０℃以上９０℃以下であり、かつ８５℃で５０分加熱したときのエポキシ反応率が８０％以上である、［１］または［２］に記載のシート状エポキシ樹脂組成物。 [2] The sheet-like epoxy resin composition according to [1], wherein the epoxy equivalent of the (B) epoxy resin is 900 g / eq or more.
[3] The heat generation start temperature measured by a differential scanning calorimeter is 60 ° C. or higher and 90 ° C. or lower, and the epoxy reaction rate when heated at 85 ° C. for 50 minutes is 80% or higher. 2] The sheet-like epoxy resin composition according to [2].
［４］溶融温度が３５℃以上６０℃以下であり、かつ４０℃で１７時間保存後の溶融温度の変化が１０℃以内である、［１］～［３］のいずれかに記載のシート状エポキシ樹脂組成物。
［５］厚さ２０μｍのシート状エポキシ樹脂組成物を８５℃で５０分間硬化させたときの、波長５５０ｎｍの光の透過率が、９０％以上である、［１］～［４］のいずれかに記載のシート状エポキシ樹脂組成物。 [4] The sheet form according to any one of [1] to [3], wherein the melting temperature is 35 ° C. or more and 60 ° C. or less and the change in melting temperature after storage at 40 ° C. for 17 hours is within 10 ° C. Epoxy resin composition.
[5] Any of [1] to [4], wherein the transmittance of light having a wavelength of 550 nm is 90% or more when a sheet-like epoxy resin composition having a thickness of 20 μm is cured at 85 ° C. for 50 minutes. The sheet-like epoxy resin composition described in 1.
［５］厚さ２０μｍのシート状エポキシ樹脂組成物を８５℃で５０分間硬化させたときの、波長５５０ｎｍの光の透過率が、９０％以上である、［１］～［４］のいずれかに記載のシート状エポキシ樹脂組成物。 [4] The sheet form according to any one of [1] to [3], wherein the melting temperature is 35 ° C. or more and 60 ° C. or less and the change in melting temperature after storage at 40 ° C. for 17 hours is within 10 ° C. Epoxy resin composition.
[5] Any of [1] to [4], wherein the transmittance of light having a wavelength of 550 nm is 90% or more when a sheet-like epoxy resin composition having a thickness of 20 μm is cured at 85 ° C. for 50 minutes. The sheet-like epoxy resin composition described in 1.
また、本発明の第２は、以下の封止用シートおよび硬化物に関する。
［６］上記［１］～［５］のいずれかに記載のシート状エポキシ樹脂組成物からなる層を含む、封止用シート。
［７］前記シート状エポキシ樹脂組成物からなる層の少なくとも一方の面に、保護フィルムを有する、［６］に記載の封止用シート。
［８］表示素子の面封止に用いられる、［６］または［７］に記載の封止用シート。
［９］前記表示素子が有機ＥＬ素子である、［８］に記載の封止用シート。
［１０］上記［１］～［５］のいずれかに記載のシート状エポキシ樹脂組成物の硬化物。 The second aspect of the present invention relates to the following sealing sheet and cured product.
[6] A sealing sheet comprising a layer made of the sheet-like epoxy resin composition according to any one of [1] to [5].
[7] The sealing sheet according to [6], having a protective film on at least one surface of the layer made of the sheet-like epoxy resin composition.
[8] The sealing sheet according to [6] or [7], which is used for surface sealing of the display element.
[9] The sealing sheet according to [8], wherein the display element is an organic EL element.
[10] A cured product of the sheet-like epoxy resin composition according to any one of [1] to [5].
［６］上記［１］～［５］のいずれかに記載のシート状エポキシ樹脂組成物からなる層を含む、封止用シート。
［７］前記シート状エポキシ樹脂組成物からなる層の少なくとも一方の面に、保護フィルムを有する、［６］に記載の封止用シート。
［８］表示素子の面封止に用いられる、［６］または［７］に記載の封止用シート。
［９］前記表示素子が有機ＥＬ素子である、［８］に記載の封止用シート。
［１０］上記［１］～［５］のいずれかに記載のシート状エポキシ樹脂組成物の硬化物。 The second aspect of the present invention relates to the following sealing sheet and cured product.
[6] A sealing sheet comprising a layer made of the sheet-like epoxy resin composition according to any one of [1] to [5].
[7] The sealing sheet according to [6], having a protective film on at least one surface of the layer made of the sheet-like epoxy resin composition.
[8] The sealing sheet according to [6] or [7], which is used for surface sealing of the display element.
[9] The sealing sheet according to [8], wherein the display element is an organic EL element.
[10] A cured product of the sheet-like epoxy resin composition according to any one of [1] to [5].
本発明のシート状エポキシ樹脂組成物は、比較的低温で硬化が可能であり、その一方で高い保存安定性を有する。したがって、各種表示素子を封止するための封止材等に好適である。
The sheet-like epoxy resin composition of the present invention can be cured at a relatively low temperature, while having high storage stability. Therefore, it is suitable for a sealing material for sealing various display elements.
１．シート状エポキシ樹脂組成物
本発明のシート状エポキシ樹脂組成物は、例えば封止用シート（面封止用シート）、透明コート用シートなどに用いられ、特に封止用シート（面封止用シート）に好適に用いられる。以下、シート状エポキシ樹脂組成物が封止用シート（面封止用シート）に用いられる場合を例に説明する。なお、透明コート用シートとは、例えば、などの基板と液晶パネル等の画像表示装置の間を埋める透明性が要求される材料のことをいう。 1. Sheet-like epoxy resin composition The sheet-like epoxy resin composition of the present invention is used for, for example, a sealing sheet (surface sealing sheet), a transparent coating sheet, and the like, and particularly a sealing sheet (surface sealing sheet). ). Hereinafter, the case where a sheet-like epoxy resin composition is used for the sheet | seat for sealing (sheet for surface sealing) is demonstrated to an example. In addition, the sheet | seat for transparent coatings means the material for which the transparency which fills between image display apparatuses, such as board | substrates, such as a liquid crystal panel, is requested | required.
本発明のシート状エポキシ樹脂組成物は、例えば封止用シート（面封止用シート）、透明コート用シートなどに用いられ、特に封止用シート（面封止用シート）に好適に用いられる。以下、シート状エポキシ樹脂組成物が封止用シート（面封止用シート）に用いられる場合を例に説明する。なお、透明コート用シートとは、例えば、などの基板と液晶パネル等の画像表示装置の間を埋める透明性が要求される材料のことをいう。 1. Sheet-like epoxy resin composition The sheet-like epoxy resin composition of the present invention is used for, for example, a sealing sheet (surface sealing sheet), a transparent coating sheet, and the like, and particularly a sealing sheet (surface sealing sheet). ). Hereinafter, the case where a sheet-like epoxy resin composition is used for the sheet | seat for sealing (sheet for surface sealing) is demonstrated to an example. In addition, the sheet | seat for transparent coatings means the material for which the transparency which fills between image display apparatuses, such as board | substrates, such as a liquid crystal panel, is requested | required.
表示素子等を面封止するためのシート状エポキシ樹脂組成物には、表示素子に影響を及ぼさないよう、比較的低温で軟化して表示素子と密着したり、比較的低い温度で硬化が可能であることが求められる。一方で、シート状エポキシ樹脂組成物には、表示素子に貼り合わせる前には変形したり硬化したりし難いこと、すなわち保存安定性も求められる。しかしながら、従来のシート状エポキシ樹脂組成物では、良好な硬化性と、貼り合わせ前の保存安定性との両立が難しい、との課題があった。
The sheet-like epoxy resin composition for surface-sealing display elements, etc. can be softened at a relatively low temperature so as not to affect the display elements, and can be cured at a relatively low temperature. It is required to be. On the other hand, the sheet-like epoxy resin composition is also required to be difficult to be deformed or cured before being attached to the display element, that is, storage stability. However, the conventional sheet-like epoxy resin composition has a problem that it is difficult to achieve both good curability and storage stability before bonding.
これに対し、本発明者らの鋭意検討によって、（Ａ）特定の構造を有するエポキシ系化合物と、（Ｂ）芳香環を有し、かつ重量平均分子量が３０００～１０００００であるエポキシ樹脂と、（Ｃ）特定の構造を有するカチオン重合開始剤と、を組み合わせることで、適度な温度（例えば６０℃程度）で表示素子との貼り合わせが可能であること、さらには比較的低温（例えば９０℃以下）で硬化可能であること、表示素子との貼り合わせ前の保存安定性が非常に良好であることが見出された。
In contrast, the present inventors have intensively studied (A) an epoxy compound having a specific structure, (B) an epoxy resin having an aromatic ring and a weight average molecular weight of 3000 to 100,000, C) By combining with a cationic polymerization initiator having a specific structure, it can be bonded to a display element at an appropriate temperature (for example, about 60 ° C.), and further relatively low temperature (for example, 90 ° C. or lower). ) And the storage stability before bonding to the display element was found to be very good.
本発明のシート状エポキシ樹脂組成物が、これらを兼ね備える理由は、以下のように考えられる。シート状エポキシ樹脂組成物に（Ｂ）エポキシ樹脂が一定量含まれるため、保存時にはシート状エポキシ樹脂組成物が過度に軟化したり溶融したりし難く、その形状を保持することが可能となる。また（Ｂ）エポキシ樹脂のみであると、硬化温度が高くなりやすいが、（Ａ）エポキシ系化合物が共に含まれているため、比較的低温（例えば９０℃以下）でもエポキシ基が反応しやすくなり、シート状エポキシ樹脂組成物の硬化性が良好になる。
The reason why the sheet-like epoxy resin composition of the present invention combines these is considered as follows. Since a certain amount of the (B) epoxy resin is contained in the sheet-like epoxy resin composition, the sheet-like epoxy resin composition is hardly softened or melted during storage, and the shape can be maintained. In addition, when only (B) an epoxy resin is used, the curing temperature tends to be high, but since (A) an epoxy compound is included, the epoxy group tends to react even at a relatively low temperature (eg, 90 ° C. or less). The curability of the sheet-like epoxy resin composition is improved.
また、（Ｃ）特定の構造を有するカチオン重合開始剤が、上記（Ａ）エポキシ系化合物および（Ｂ）エポキシ樹脂と組み合わされているため、室温等では（Ａ）エポキシ系化合物や（Ｂ）エポキシ樹脂の硬化反応が促進され難く、シート状エポキシ樹脂組成物の保存安定性が良好になる。一方で、（Ｃ）カチオン重合開始剤は、９０℃以下で活性化するため、シート状エポキシ樹脂組成物を比較的低温でも硬化させることが可能となる。以下、本発明のシート状エポキシ樹脂組成物に含まれる各成分について、詳しく説明する。
In addition, since (C) a cationic polymerization initiator having a specific structure is combined with the above (A) epoxy compound and (B) epoxy resin, at room temperature or the like, (A) an epoxy compound or (B) epoxy The curing reaction of the resin is hardly promoted, and the storage stability of the sheet-like epoxy resin composition is improved. On the other hand, since the (C) cationic polymerization initiator is activated at 90 ° C. or lower, the sheet-like epoxy resin composition can be cured even at a relatively low temperature. Hereinafter, each component contained in the sheet-like epoxy resin composition of the present invention will be described in detail.
（Ａ）エポキシ系化合物
（Ａ）エポキシ系化合物は、下記一般式（１）で表される構造を有する化合物であり、ジシクロペンタジエン骨格を有する。ここで、ジシクロペンタジエン骨格に結合する基の結合位置は、特に制限されない。シート状エポキシ樹脂組成物には、下記一般式（１）で表される構造の化合物が１種のみ含まれていてもよく、２種以上含まれていてもよい。
(A) Epoxy compound (A) The epoxy compound is a compound having a structure represented by the following general formula (1) and has a dicyclopentadiene skeleton. Here, the bonding position of the group bonded to the dicyclopentadiene skeleton is not particularly limited. In the sheet-like epoxy resin composition, only one type of compound having a structure represented by the following general formula (1) may be included, or two or more types may be included.
（Ａ）エポキシ系化合物は、下記一般式（１）で表される構造を有する化合物であり、ジシクロペンタジエン骨格を有する。ここで、ジシクロペンタジエン骨格に結合する基の結合位置は、特に制限されない。シート状エポキシ樹脂組成物には、下記一般式（１）で表される構造の化合物が１種のみ含まれていてもよく、２種以上含まれていてもよい。
上記（Ａ）エポキシ系化合物は、２３℃で液状である。上記（Ａ）エポキシ系化合物がジシクロペンタジエン構造を有するため、エポキシ基の反応性が良好になりやすく、上述のように、シート状エポキシ樹脂組成物が比較的低温でも硬化しやすくなる。
The above (A) epoxy compound is liquid at 23 ° C. Since the (A) epoxy compound has a dicyclopentadiene structure, the reactivity of the epoxy group is likely to be good, and as described above, the sheet-like epoxy resin composition is easily cured even at a relatively low temperature.
（Ａ）エポキシ系化合物は、公知の方法で調製したものであってもよいが、市販品であってもよい。（Ａ）エポキシ系化合物の市販品の例には、ＡＤＥＫＡ社製ＥＰ－４０８８Ｌ、ＥＰ－４０８８Ｓ等が含まれる。
(A) The epoxy compound may be prepared by a known method, but may be a commercially available product. (A) Examples of commercially available epoxy compounds include EP-4088L and EP-4088S manufactured by ADEKA.
ここで、シート状エポキシ樹脂組成物１００質量部に含まれる（Ａ）エポキシ系化合物の量は、１０～５０質量部であることが好ましく、１０～４０質量部であることがより好ましく、１５～３０質量部であることがさらに好ましい。（Ａ）エポキシ系化合物の量が１０質量部以上であると、９０℃以下で（Ａ）エポキシ化合物および（Ｂ）エポキシ樹脂が反応しやすくなり、シート状エポキシ樹脂組成物の硬化性が良好になりやすい。一方、（Ａ）エポキシ系化合物の量が５０質量部以下であると、相対的に（Ｂ）エポキシ樹脂の量が十分になりやすく、シート状エポキシ樹脂組成物の保存安定性が高まりやすくなる。
Here, the amount of the (A) epoxy compound contained in 100 parts by mass of the sheet-like epoxy resin composition is preferably 10 to 50 parts by mass, more preferably 10 to 40 parts by mass, More preferably, it is 30 parts by mass. When the amount of the (A) epoxy compound is 10 parts by mass or more, the (A) epoxy compound and the (B) epoxy resin are likely to react at 90 ° C. or less, and the curability of the sheet-like epoxy resin composition is good. Prone. On the other hand, when the amount of (A) the epoxy compound is 50 parts by mass or less, the amount of (B) the epoxy resin is relatively sufficient, and the storage stability of the sheet-like epoxy resin composition is likely to be increased.
（Ｂ）エポキシ樹脂
（Ｂ）エポキシ樹脂は、分子内に芳香環およびエポキシ基をそれぞれ１つ以上有し、かつ重量平均分子量が３０００～１０００００である樹脂であれば特に制限されない。シート状エポキシ樹脂組成物には、（Ｂ）エポキシ樹脂が１種のみ含まれていてもよく、２種以上含まれていてもよい。 (B) Epoxy resin (B) The epoxy resin is not particularly limited as long as it has at least one aromatic ring and one epoxy group in the molecule and has a weight average molecular weight of 3000 to 100,000. The sheet-like epoxy resin composition may contain only one type of (B) epoxy resin, or may contain two or more types.
（Ｂ）エポキシ樹脂は、分子内に芳香環およびエポキシ基をそれぞれ１つ以上有し、かつ重量平均分子量が３０００～１０００００である樹脂であれば特に制限されない。シート状エポキシ樹脂組成物には、（Ｂ）エポキシ樹脂が１種のみ含まれていてもよく、２種以上含まれていてもよい。 (B) Epoxy resin (B) The epoxy resin is not particularly limited as long as it has at least one aromatic ring and one epoxy group in the molecule and has a weight average molecular weight of 3000 to 100,000. The sheet-like epoxy resin composition may contain only one type of (B) epoxy resin, or may contain two or more types.
（Ｂ）エポキシ樹脂組成物は、通常、常温（２３℃）で固形である。（Ｂ）エポキシ樹脂の重量平均分子量は、６０００～６００００であることが好ましく、７０００～４００００であることがより好ましい。（Ｂ）エポキシ樹脂の分子量が３０００以上であると、（Ｂ）エポキシ樹脂が常温で固形になりやすい。一方、（Ｂ）エポキシ樹脂の重量平均分子量が１００００００以下であると、シート状エポキシ樹脂組成物を表示素子等と貼り合わせる際に、シート状エポキシ樹脂組成物の流動性を高めることができ、表示素子等と密着させやすくなる。上記重量平均分子量は、ゲルパーミエーションクロマトグラフィー（ＧＰＣ）により測定される、ポリスチレン換算値である。
(B) The epoxy resin composition is usually solid at normal temperature (23 ° C.). (B) The weight average molecular weight of the epoxy resin is preferably 6000 to 60000, and more preferably 7000 to 40000. When the molecular weight of the (B) epoxy resin is 3000 or more, the (B) epoxy resin tends to be solid at room temperature. On the other hand, when the weight average molecular weight of the (B) epoxy resin is 1000000 or less, the fluidity of the sheet-like epoxy resin composition can be improved when the sheet-like epoxy resin composition is bonded to a display element or the like. It becomes easy to adhere to an element or the like. The said weight average molecular weight is a polystyrene conversion value measured by gel permeation chromatography (GPC).
また、（Ｂ）エポキシ樹脂のエポキシ当量は、９００ｇ／ｅｑ以上２００００ｇ／ｅｑ以下であることが好ましく、１０００ｇ／ｅｑ以上２０００００ｇ／ｅｑ以下であることがより好ましい。エポキシ樹脂のエポキシ当量が９００ｇ／ｅｑ以上であると、シート状エポキシ樹脂組成物の常温でのタック性が小さくなる。その結果、シート状エポキシ樹脂組成物を表示素子と貼り合わせる際のハンドリング性が良好になりやすく、表示素子上に正確に貼り合わせやすくなる。一方、（Ｂ）エポキシ樹脂のエポキシ当量が過度に大きくなると、シート状エポキシ樹脂組成物作製時に、溶剤への溶解性が低下したり、（Ａ）エポキシ系化合物との相溶性が悪くなったりする等という課題が生じることがある。そこで、（Ｂ）エポキシ樹脂のエポキシ当量は２００００ｇ／ｅｑ以下であることが好ましい。（Ｂ）エポキシ樹脂のエポキシ当量が上記範囲であると、シート状エポキシ樹脂組成物の溶融温度が適度な範囲となり、所望の温度で表示素子と貼り合わせることが可能となる。なお、上記（Ｂ）エポキシ樹脂に、複数のエポキシ樹脂が含まれる場合、各エポキシ樹脂のエポキシ当量が上記範囲であることが好ましい。
In addition, the epoxy equivalent of the (B) epoxy resin is preferably 900 g / eq or more and 20000 g / eq or less, and more preferably 1000 g / eq or more and 200000 g / eq or less. When the epoxy equivalent of the epoxy resin is 900 g / eq or more, the tackiness at room temperature of the sheet-like epoxy resin composition is reduced. As a result, the handleability when the sheet-shaped epoxy resin composition is bonded to the display element is likely to be good, and the sheet-like epoxy resin composition is easily bonded accurately on the display element. On the other hand, when the epoxy equivalent of the (B) epoxy resin becomes excessively large, the solubility in a solvent is reduced during the preparation of the sheet-like epoxy resin composition, or the compatibility with the (A) epoxy compound is deteriorated. Etc. may arise. Therefore, the epoxy equivalent of the (B) epoxy resin is preferably 20000 g / eq or less. (B) When the epoxy equivalent of an epoxy resin is the said range, the melting temperature of a sheet-like epoxy resin composition will become a moderate range, and it will become possible to bond together with a display element at desired temperature. In addition, when the said (B) epoxy resin contains a some epoxy resin, it is preferable that the epoxy equivalent of each epoxy resin is the said range.
（Ｂ）エポキシ樹脂は、分子中にエポキシ基を１つ以上含んでいればよいが、上述のエポキシ当量を満たすように、複数のエポキシ基を含むことが好ましい。また、（Ｂ）エポキシ樹脂は、分子中に芳香環を１つ以上含んでいればよく、芳香環の数は特に限定されない。
(B) The epoxy resin may contain one or more epoxy groups in the molecule, but preferably contains a plurality of epoxy groups so as to satisfy the above-mentioned epoxy equivalent. Moreover, (B) epoxy resin should just contain one or more aromatic rings in a molecule | numerator, and the number of aromatic rings is not specifically limited.
（Ｂ）エポキシ樹脂の例にはビスフェノールＡ型、ビスフェノールＦ型、ビスフェノールＥ型、ビスフェノールＳ型、ビスフェノールＡＤ型、またはこれらの混合型等のビスフェノール型エポキシ樹脂；ジフェニルエーテル型エポキシ樹脂；フェノールノボラック型、クレゾールノボラック型、ビフェニルノボラック型、ビスフェノールノボラック型、ナフトールノボラック型、トリスフェノールノボラック型、ジシクロペンタジエンノボラック型等のノボラック型エポキシ樹脂；ビフェニル型エポキシ樹脂；ナフチル型エポキシ樹脂；トリフェノールメタン型、トリフェノールエタン型、トリフェノールプロパン型等のトリフェノールアルカン型エポキシ樹脂；等が含まれる。
(B) Examples of epoxy resins include bisphenol A type, bisphenol F type, bisphenol E type, bisphenol S type, bisphenol AD type, and mixed types thereof, such as bisphenol type epoxy resins; diphenyl ether type epoxy resins; phenol novolac type, Cresol novolak type, biphenyl novolak type, bisphenol novolak type, naphthol novolak type, trisphenol novolak type, dicyclopentadiene novolak type, etc. novolac type epoxy resin; biphenyl type epoxy resin; naphthyl type epoxy resin; triphenolmethane type, triphenol Ethane type, triphenolalkane type epoxy resin such as triphenolpropane type; and the like.
（Ｂ）エポキシ樹脂は、上記の中でもビスフェノール型エポキシ樹脂、またはビフェニル型エポキシ樹脂が好ましい。ただし、エポキシ樹脂中のビスフェノールＦ骨格の量が多くなると、（Ｂ）エポキシ樹脂の軟化点が低下する傾向にある。したがって、シート状エポキシ樹脂組成物の溶融温度を比較的高い温度とする場合には、ビスフェノールＦ骨格の少ないエポキシ樹脂とすることが好ましい。
(B) The epoxy resin is preferably a bisphenol type epoxy resin or a biphenyl type epoxy resin among the above. However, when the amount of the bisphenol F skeleton in the epoxy resin increases, the softening point of the (B) epoxy resin tends to decrease. Therefore, when the melting temperature of the sheet-like epoxy resin composition is set to a relatively high temperature, it is preferable to use an epoxy resin having a small bisphenol F skeleton.
シート状エポキシ樹脂組成物１００質量部に含まれる（Ｂ）エポキシ樹脂の量は、４５質量部以上であり、５０～８５質量部であることが好ましく、６０～７５質量部であることがより好ましい。（Ｂ）エポキシ樹脂の量が５０質量部以上であると、シート状エポキシ樹脂組成物の保存安定性が高まりやすく、さらにはシート状エポキシ樹脂組成物の貼り合わせ温度が適度な範囲に収まりやすくなる。
The amount of (B) epoxy resin contained in 100 parts by mass of the sheet-like epoxy resin composition is 45 parts by mass or more, preferably 50 to 85 parts by mass, and more preferably 60 to 75 parts by mass. . (B) When the amount of the epoxy resin is 50 parts by mass or more, the storage stability of the sheet-like epoxy resin composition is likely to be increased, and further, the bonding temperature of the sheet-like epoxy resin composition is likely to be within an appropriate range. .
（Ｃ）カチオン重合開始剤
（Ｃ）カチオン重合開始剤は、下記一般式（２）で表される化合物である。シート状エポキシ樹脂組成物に（Ｃ）カチオン重合開始剤は１種のみ含まれていてもよく、２種以上含まれていてもよい。
上記一般式（２）中、Ｒ１は炭素数１～４のアルキル基またはナフチルメチル基を表し、ナフチルメチル基が特に好ましい。一方、Ｒ２は炭素数１～４のアルキル基を表し、メチル基が特に好ましい。
(C) Cationic polymerization initiator (C) The cationic polymerization initiator is a compound represented by the following general formula (2). Only 1 type (C) cationic polymerization initiator may be contained in the sheet-like epoxy resin composition, and 2 or more types may be contained.
In the general formula (2), R 1 represents an alkyl group having 1 to 4 carbon atoms or a naphthylmethyl group, and a naphthylmethyl group is particularly preferable. On the other hand, R 2 represents an alkyl group having 1 to 4 carbon atoms, and a methyl group is particularly preferable.
（Ｃ）カチオン重合開始剤は、下記一般式（２）で表される化合物である。シート状エポキシ樹脂組成物に（Ｃ）カチオン重合開始剤は１種のみ含まれていてもよく、２種以上含まれていてもよい。
すなわち、（Ｃ）カチオン重合開始剤は、特に下記式（２ａ）で表される化合物であることが好ましい。
That is, (C) the cationic polymerization initiator is particularly preferably a compound represented by the following formula (2a).
上記一般式（２）（もしくは式（２ａ））で表されるように、スルホニウムに結合する基がヒドロキシフェニル基であると、シート状エポキシ樹脂組成物の硬化速度が過度に高まらず、シート状エポキシ樹脂組成物の保存安定性が高まる。また、上記（Ｃ）カチオン重合開始剤のアニオンが、ＳｂＦ６
－であると、比較的低温でシート状エポキシ樹脂組成物を硬化させることが可能となる。
As represented by the above general formula (2) (or formula (2a)), when the group bonded to sulfonium is a hydroxyphenyl group, the curing rate of the sheet-shaped epoxy resin composition is not excessively increased, and the sheet shape The storage stability of the epoxy resin composition is increased. Further, above (C) anionic cationic polymerization initiator, SbF 6 - When a, it is possible to relatively curing a sheet-like epoxy resin composition at a low temperature.
（Ｃ）カチオン重合開始剤は、公知の方法で調製したものであってもよく、市販品であってもよい。市販品の例には、三新化学工業社製 商品名ＳＩ－６０等が含まれる。
(C) The cationic polymerization initiator may be prepared by a known method or may be a commercially available product. Examples of commercially available products include trade name SI-60 manufactured by Sanshin Chemical Industry Co., Ltd.
シート状エポキシ樹脂組成物１００質量部に含まれる（Ｃ）カチオン重合開始剤の量は、１～１０質量部であることが好ましく、２～８質量部であることがより好ましく、２～５質量部であることがさらに好ましい。（Ｃ）カチオン重合開始剤の量が１質量部以上であると、シート状エポキシ樹脂組成物の硬化性が良好になりやすい。一方、（Ｃ）カチオン重合開始剤の量が１０質量部以下であると、シート状エポキシ樹脂組成物の保存安定性が高まりやすくなる。
The amount of the cationic polymerization initiator (C) contained in 100 parts by mass of the sheet-like epoxy resin composition is preferably 1 to 10 parts by mass, more preferably 2 to 8 parts by mass. More preferably, it is a part. (C) When the amount of the cationic polymerization initiator is 1 part by mass or more, the curability of the sheet-like epoxy resin composition tends to be good. On the other hand, when the amount of (C) the cationic polymerization initiator is 10 parts by mass or less, the storage stability of the sheet-like epoxy resin composition is likely to be increased.
（Ｄ）その他の成分
シート状エポキシ樹脂組成物には、本発明の効果を大きくは損なわない範囲において、上述の（Ａ）エポキシ系化合物、（Ｂ）エポキシ樹脂、および（Ｃ）カチオン重合開始剤以外の成分が含まれていてもよい。 (D) Other components In the sheet-like epoxy resin composition, the above-mentioned (A) epoxy compound, (B) epoxy resin, and (C) cationic polymerization initiator are within the range not greatly impairing the effects of the present invention. Other components may be included.
シート状エポキシ樹脂組成物には、本発明の効果を大きくは損なわない範囲において、上述の（Ａ）エポキシ系化合物、（Ｂ）エポキシ樹脂、および（Ｃ）カチオン重合開始剤以外の成分が含まれていてもよい。 (D) Other components In the sheet-like epoxy resin composition, the above-mentioned (A) epoxy compound, (B) epoxy resin, and (C) cationic polymerization initiator are within the range not greatly impairing the effects of the present invention. Other components may be included.
その他の成分の例には、その他の樹脂や、充填材、改質剤、安定剤等が含まれる。
その他の樹脂の例には、上記（Ａ）エポキシ化合物および（Ｂ）エポキシ樹脂に相当しないエポキシ樹脂や、ポリアミド、ポリアミドイミド、ポリウレタン、ポリブタジエン、ポリクロロプレン、ポリエーテル、ポリエステル、スチレン－ブタジエン－スチレンブロック共重合体、キシレン樹脂、ケトン樹脂、セルロース樹脂、フッ素系オリゴマー、シリコン系オリゴマー、ポリスルフィド系オリゴマー等が含まれる。シート状エポキシ樹脂組成物には、これらが１種のみ含まれていてもよく、２種以上含まれていてもよい。 Examples of other components include other resins, fillers, modifiers, stabilizers, and the like.
Examples of other resins include (A) epoxy compound and (B) epoxy resin not corresponding to epoxy resin, polyamide, polyamideimide, polyurethane, polybutadiene, polychloroprene, polyether, polyester, styrene-butadiene-styrene block Copolymers, xylene resins, ketone resins, cellulose resins, fluorine-based oligomers, silicon-based oligomers, polysulfide-based oligomers and the like are included. The sheet-like epoxy resin composition may contain only one kind or two or more kinds.
その他の樹脂の例には、上記（Ａ）エポキシ化合物および（Ｂ）エポキシ樹脂に相当しないエポキシ樹脂や、ポリアミド、ポリアミドイミド、ポリウレタン、ポリブタジエン、ポリクロロプレン、ポリエーテル、ポリエステル、スチレン－ブタジエン－スチレンブロック共重合体、キシレン樹脂、ケトン樹脂、セルロース樹脂、フッ素系オリゴマー、シリコン系オリゴマー、ポリスルフィド系オリゴマー等が含まれる。シート状エポキシ樹脂組成物には、これらが１種のみ含まれていてもよく、２種以上含まれていてもよい。 Examples of other components include other resins, fillers, modifiers, stabilizers, and the like.
Examples of other resins include (A) epoxy compound and (B) epoxy resin not corresponding to epoxy resin, polyamide, polyamideimide, polyurethane, polybutadiene, polychloroprene, polyether, polyester, styrene-butadiene-styrene block Copolymers, xylene resins, ketone resins, cellulose resins, fluorine-based oligomers, silicon-based oligomers, polysulfide-based oligomers and the like are included. The sheet-like epoxy resin composition may contain only one kind or two or more kinds.
充填材の例には、ガラスビーズ、スチレン系ポリマー粒子、メタクリレート系ポリマー粒子、エチレン系ポリマー粒子、プロピレン系ポリマー粒子等が含まれる。シート状エポキシ樹脂組成物には、充填材が１種のみ含まれていてもよく、２種以上含まれていてもよい。
Examples of the filler include glass beads, styrene polymer particles, methacrylate polymer particles, ethylene polymer particles, propylene polymer particles, and the like. The sheet-like epoxy resin composition may contain only one type of filler, or may contain two or more types.
改質剤の具体例には、重合開始剤、老化防止剤、レベリング剤、濡れ性改良剤、界面活性剤、可塑剤、溶剤、シランカップリング剤等が含まれる。これらの改質剤は１種のみ含まれていてもよく、２種以上含まれていてもよい。
Specific examples of the modifier include a polymerization initiator, an anti-aging agent, a leveling agent, a wettability improver, a surfactant, a plasticizer, a solvent, a silane coupling agent, and the like. One of these modifiers may be included, or two or more thereof may be included.
一方、安定剤の具体例には、紫外線吸収剤、防腐剤、抗菌剤等が含まれる。シート状エポキシ樹脂組成物には、これらが１種のみ含まれていてもよく、２種以上含まれていてもよい。
On the other hand, specific examples of the stabilizer include ultraviolet absorbers, preservatives, antibacterial agents and the like. The sheet-like epoxy resin composition may contain only one kind or two or more kinds.
（Ｅ）シート状エポキシ樹脂組成物の製造方法
上述のシート状エポキシ樹脂組成物は、本発明の効果を損なわない限り、任意の方法で製造することができる。本発明のシート状エポキシ樹脂組成物は、例えば（Ａ）エポキシ系化合物、（Ｂ）エポキシ樹脂、および（Ｃ）カチオン重合開始剤を含む樹脂組成物を、各種溶剤等に３０℃以下で溶解させてワニスとし、これを基材上にシート状に塗布し、乾燥させることで作製することができる。 (E) Manufacturing method of sheet-like epoxy resin composition The above-mentioned sheet-like epoxy resin composition can be manufactured by arbitrary methods, unless the effect of this invention is impaired. The sheet-like epoxy resin composition of the present invention is prepared by, for example, dissolving a resin composition containing (A) an epoxy compound, (B) an epoxy resin, and (C) a cationic polymerization initiator in various solvents at 30 ° C. or lower. The varnish can be applied to the base material in the form of a sheet and dried.
上述のシート状エポキシ樹脂組成物は、本発明の効果を損なわない限り、任意の方法で製造することができる。本発明のシート状エポキシ樹脂組成物は、例えば（Ａ）エポキシ系化合物、（Ｂ）エポキシ樹脂、および（Ｃ）カチオン重合開始剤を含む樹脂組成物を、各種溶剤等に３０℃以下で溶解させてワニスとし、これを基材上にシート状に塗布し、乾燥させることで作製することができる。 (E) Manufacturing method of sheet-like epoxy resin composition The above-mentioned sheet-like epoxy resin composition can be manufactured by arbitrary methods, unless the effect of this invention is impaired. The sheet-like epoxy resin composition of the present invention is prepared by, for example, dissolving a resin composition containing (A) an epoxy compound, (B) an epoxy resin, and (C) a cationic polymerization initiator in various solvents at 30 ° C. or lower. The varnish can be applied to the base material in the form of a sheet and dried.
溶剤の例には、トルエン、キシレン等の芳香族溶剤；アセトン、メチルエチルケトン、メチルイソブチルケトン等のケトン系溶剤；エーテル、ジブチルエーテル、テトラヒドロフラン、ジオキサン、エチレングリコ－ルモノアルキルエーテル、エチレングリコ－ルジアルキルエーテル、プロピレングリコールまたはジアルキルエーテル等のエーテル類；Ｎ－メチルピロリドン、ジメチルイミダゾリジノン、ジメチルフォルムアルデヒド等の非プロトン性極性溶剤；酢酸エチル、酢酸ブチル等のエステル類等が含まれる。
Examples of solvents include aromatic solvents such as toluene and xylene; ketone solvents such as acetone, methyl ethyl ketone, and methyl isobutyl ketone; ethers, dibutyl ether, tetrahydrofuran, dioxane, ethylene glycol monoalkyl ether, ethylene glycol dialkyl ether Ethers such as propylene glycol or dialkyl ether; aprotic polar solvents such as N-methylpyrrolidone, dimethylimidazolidinone and dimethylformaldehyde; esters such as ethyl acetate and butyl acetate.
なお（Ａ）エポキシ系化合物、（Ｂ）エポキシ樹脂、（Ｃ）カチオン重合開始剤、および溶剤は一度に混合してもよく、溶剤に（Ｂ）エポキシ樹脂等を溶解させた後、他の成分を添加してもよい。混合方法の例には、公知の攪拌法や、三本ロールで混練する方法等が含まれる。
The (A) epoxy compound, (B) epoxy resin, (C) cationic polymerization initiator, and solvent may be mixed at one time. After the (B) epoxy resin or the like is dissolved in the solvent, other components are mixed. May be added. Examples of the mixing method include a known stirring method and a kneading method using three rolls.
また、ワニスの塗布方法は特に限定されず、その例には、スクリーン印刷や、ディスペンサー塗布、各種ロール法等が含まれる。また、ワニスを塗布する基材の種類に特に制限されず、公知の離型フィルム等とすることができる。また、ワニスの塗布厚みは、目的とするシート状エポキシ樹脂組成物の膜厚に応じて適宜選択され、乾燥後のシート状エポキシ樹脂組成物の膜厚に合わせて適宜選択される。
The varnish application method is not particularly limited, and examples thereof include screen printing, dispenser application, various roll methods, and the like. Moreover, it does not restrict | limit especially in the kind of base material which apply | coats a varnish, It can be set as a well-known release film. Moreover, the application | coating thickness of a varnish is suitably selected according to the film thickness of the target sheet-like epoxy resin composition, and is suitably selected according to the film thickness of the sheet-like epoxy resin composition after drying.
ワニスの乾燥温度および乾燥時間は、（Ａ）エポキシ系化合物および（Ｂ）エポキシ樹脂が硬化しない温度および時間とする。例えば乾燥温度は、２０～１００℃であり、乾燥時間は、例えば１分～３時間程度とすることができる。乾燥方法は、特に限定されず、例えば熱風乾燥、真空乾燥等がある。
The drying temperature and drying time of the varnish are the temperature and time at which (A) the epoxy compound and (B) the epoxy resin are not cured. For example, the drying temperature is 20 to 100 ° C., and the drying time can be about 1 minute to 3 hours, for example. The drying method is not particularly limited, and examples thereof include hot air drying and vacuum drying.
（Ｆ）シート状エポキシ樹脂組成物の物性等
シート状エポキシ樹脂組成物の厚みは、用途に応じて適宜選択されるが、例えば表示素子の封止材とする場合には、１～１００μｍであることが好ましく、５～５０μｍであることがより好ましく、１０～３０μｍであることがさらに好ましい。 (F) Physical Properties of Sheet-like Epoxy Resin Composition The thickness of the sheet-like epoxy resin composition is appropriately selected depending on the application, but is, for example, 1 to 100 μm when used as a sealing material for display elements. It is preferably 5 to 50 μm, more preferably 10 to 30 μm.
シート状エポキシ樹脂組成物の厚みは、用途に応じて適宜選択されるが、例えば表示素子の封止材とする場合には、１～１００μｍであることが好ましく、５～５０μｍであることがより好ましく、１０～３０μｍであることがさらに好ましい。 (F) Physical Properties of Sheet-like Epoxy Resin Composition The thickness of the sheet-like epoxy resin composition is appropriately selected depending on the application, but is, for example, 1 to 100 μm when used as a sealing material for display elements. It is preferably 5 to 50 μm, more preferably 10 to 30 μm.
シート状エポキシ樹脂組成物の溶融温度は、３５℃以上６０℃以下であることが好ましく、シート状エポキシ樹脂組成物の作業時のタック性をより低くする場合には、４０～５６℃であることが好ましい。シート状エポキシ樹脂組成物と表示素子とを貼り合わせる際、シート状エポキシ樹脂組成物を軟化（溶融）させることで、表示素子との隙間が生じ難く、密着させることが可能となる。シート状エポキシ樹脂組成物の溶融温度が６０℃以下であると、シート状エポキシ樹脂組成物を比較的低い温度（６０℃以下）で表示素子に貼り合わせることが可能となる。一方で、シート状エポキシ樹脂組成物の溶融温度が３５℃以上であると、シート状エポキシ樹脂組成物の作業時のタック性が低く、作業性が良好になりやすい。また、シート状エポキシ樹脂組成物の保存時等には、シート状エポキシ樹脂組成物が変形したりし難く、その形状を維持することが可能となる。
The melting temperature of the sheet-like epoxy resin composition is preferably 35 ° C. or more and 60 ° C. or less, and is 40 to 56 ° C. when the tackiness at the time of working the sheet-like epoxy resin composition is lowered. Is preferred. When the sheet-like epoxy resin composition and the display element are bonded together, the sheet-like epoxy resin composition is softened (melted) so that a gap with the display element is hardly generated and can be adhered. When the melting temperature of the sheet-like epoxy resin composition is 60 ° C. or less, the sheet-like epoxy resin composition can be bonded to the display element at a relatively low temperature (60 ° C. or less). On the other hand, when the melting temperature of the sheet-like epoxy resin composition is 35 ° C. or higher, the tackiness at the time of working the sheet-like epoxy resin composition is low, and the workability tends to be good. Further, when the sheet-like epoxy resin composition is stored, the sheet-like epoxy resin composition is hardly deformed, and the shape can be maintained.
溶融温度は、以下のように測定することができる。シート状エポキシ樹脂組成物を、長さ約３０ｍｍ、幅約５ｍｍに切り出して短冊状の試験片を作製する。この試験片を、ホットプレート上で加熱したガラス板上に密着させる。その後、当該試験片を１８０°方向へ徐々にガラス板から剥離する。この操作を、ホットプレートの設定温度４０℃から始め、設定温度を１℃上げる毎に短冊状の試験片を新たに用意して繰り返し、剥離時にシート状エポキシ樹脂組成物からなる層の粘着剥離性が最も大きくなる温度を、溶融温度とする。ただし４０℃で、すでに粘着剥離性の大きいものは２５℃より溶融温度の測定を実施する。
The melting temperature can be measured as follows. The sheet-like epoxy resin composition is cut into a length of about 30 mm and a width of about 5 mm to produce a strip-shaped test piece. The test piece is brought into close contact with a glass plate heated on a hot plate. Thereafter, the test piece is gradually peeled from the glass plate in the 180 ° direction. This operation is started at a preset temperature of 40 ° C. of the hot plate, and each time the set temperature is raised by 1 ° C., a strip-shaped test piece is newly prepared and repeated, and the adhesive peelability of the layer made of the sheet-like epoxy resin composition at the time of peeling The temperature at which becomes the largest is the melting temperature. However, at 40 ° C., those having already high adhesive peelability are measured for melting temperature from 25 ° C.
また、４０℃で１７時間保存した後のシート状エポキシ樹脂組成物の溶融温度は、保存前のシート状エポキシ樹脂組成物の溶融温度±１０℃の範囲に収まることが好ましく、±５℃以内であることがより好ましい。当該温度変化は、シート状エポキシ樹脂組成物の保存安定性の指標となり、温度変化が１０℃以下であれば、保存時に硬化反応等が生じ難いといえる。また、保存時にシート状エポキシ樹脂組成物の溶融温度が大きく変化すると、その変動に合わせてシート状エポキシ樹脂組成物を表示素子等に貼り合わせるときの温度や圧力等を変更する必要が生じる。これに対し、４０℃で１７時間保存した後の溶融温度変化が１０℃以内であれば、貼り合わせ時の条件を大きく変更する必要がなく、効率よく表示素子等の封止を行うことが可能となるという利点もある。
Further, the melting temperature of the sheet-like epoxy resin composition after being stored at 40 ° C. for 17 hours is preferably within the range of the melting temperature ± 10 ° C. of the sheet-like epoxy resin composition before storage, and within ± 5 ° C. More preferably. The said temperature change becomes a parameter | index of the storage stability of a sheet-like epoxy resin composition, and if a temperature change is 10 degrees C or less, it can be said that it is hard to produce a curing reaction etc. at the time of storage. Further, when the melting temperature of the sheet-like epoxy resin composition changes greatly during storage, it becomes necessary to change the temperature, pressure, etc. when the sheet-like epoxy resin composition is bonded to a display element or the like in accordance with the change. On the other hand, if the change in melting temperature after storage at 40 ° C. for 17 hours is within 10 ° C., it is not necessary to greatly change the conditions at the time of bonding, and it is possible to efficiently seal display elements and the like. There is also an advantage of becoming.
一方、シート状エポキシ樹脂組成物の示差走査作熱量計（ＤＳＣ）により測定される発熱開始温度は６０℃以上９０℃以下であることが好ましく、６５～８５℃であることがより好ましい。発熱開始温度が６０℃以上であると、シート状エポキシ樹脂組成物の成形時や、シート状エポキシ樹脂組成物の保存時等に（Ａ）エポキシ系化合物や（Ｂ）エポキシ樹脂が硬化し難く、保存安定性が良好となる。一方、発熱開始温度が９０℃以下であると、シート状エポキシ樹脂組成物を９０℃以下で硬化させることが可能となり、表示素子等に影響を及ぼし難くなる。上記発熱開始温度は、以下の方法で測定することができる。まず、シート状エポキシ樹脂組成物１０ｍｇを採取し、ＤＳＣ測定用アルミセルに詰め、測定試験サンプルを準備する。そして、当該測定試験サンプルについて、昇温速度５℃／分、測定温度範囲：２０℃～３００℃にて温度特性を測定することで、発熱開始温度を特定することができる。
On the other hand, the heat generation starting temperature measured by a differential scanning calorimeter (DSC) of the sheet-like epoxy resin composition is preferably 60 ° C. or higher and 90 ° C. or lower, and more preferably 65 to 85 ° C. When the exothermic start temperature is 60 ° C. or higher, the (A) epoxy compound or the (B) epoxy resin is difficult to cure at the time of molding the sheet-like epoxy resin composition, at the time of storing the sheet-like epoxy resin composition, Storage stability is improved. On the other hand, when the heat generation starting temperature is 90 ° C. or lower, the sheet-like epoxy resin composition can be cured at 90 ° C. or lower, and the display element and the like are hardly affected. The heat generation start temperature can be measured by the following method. First, 10 mg of a sheet-like epoxy resin composition is collected, packed in an aluminum cell for DSC measurement, and a measurement test sample is prepared. Then, by measuring the temperature characteristics of the measurement test sample at a temperature rising rate of 5 ° C./min and a measurement temperature range: 20 ° C. to 300 ° C., the heat generation start temperature can be specified.
一方、シート状エポキシ樹脂組成物を８５℃で５０分加熱したときのエポキシ反応率が８０％以上であることが好ましく、８５％以上であることがより好ましい。当該エポキシ反応率は、８５℃でシート状エポキシ樹脂組成物を硬化させたときの硬化性の指標であり、その値が高いほど、シート状エポキシ樹脂組成物が低温でも硬化しやすいことを表す。そして、上記エポキシ反応率が８０％以上であれば、シート状エポキシ樹脂組成物を９０℃以下でも、十分に硬化可能であるといえる。
On the other hand, the epoxy reaction rate when the sheet-like epoxy resin composition is heated at 85 ° C. for 50 minutes is preferably 80% or more, and more preferably 85% or more. The said epoxy reaction rate is a parameter | index of sclerosis | hardenability when a sheet-like epoxy resin composition is hardened at 85 degreeC, It represents that a sheet-like epoxy resin composition is easy to harden | cure at low temperature, so that the value is high. And if the said epoxy reaction rate is 80% or more, it can be said that a sheet-like epoxy resin composition can fully be hardened even at 90 degrees C or less.
上記エポキシ反応率は、以下のように測定することができる。まず、あらかじめ８５℃に設定したオーブン中にシート状エポキシ樹脂組成物（サンプル）を載置する。そして、サンプル投入から５０分後に測定サンプルを取り出す。そして、昇温速度５℃／分、測定温度範囲：２０℃～３００℃にてＤＳＣで硬化品の発熱量を特定する。そして、測定された発熱量および上述の未硬化の状態の発熱量に基づき、下記に示す式でエポキシ反応率を求める。
エポキシ反応率（％）＝（未硬化品の発熱量－硬化後の発熱量）／未硬化品の発熱量×１００ The epoxy reaction rate can be measured as follows. First, a sheet-like epoxy resin composition (sample) is placed in an oven set to 85 ° C. in advance. And a measurement sample is taken out 50 minutes after sample introduction. Then, the calorific value of the cured product is specified by DSC at a temperature rising rate of 5 ° C./min and a measurement temperature range of 20 ° C. to 300 ° C. And based on the measured calorific value and the above-mentioned uncured calorific value, the epoxy reaction rate is obtained by the following formula.
Epoxy reaction rate (%) = (heat value of uncured product−heat value after curing) / heat value of uncured product × 100
エポキシ反応率（％）＝（未硬化品の発熱量－硬化後の発熱量）／未硬化品の発熱量×１００ The epoxy reaction rate can be measured as follows. First, a sheet-like epoxy resin composition (sample) is placed in an oven set to 85 ° C. in advance. And a measurement sample is taken out 50 minutes after sample introduction. Then, the calorific value of the cured product is specified by DSC at a temperature rising rate of 5 ° C./min and a measurement temperature range of 20 ° C. to 300 ° C. And based on the measured calorific value and the above-mentioned uncured calorific value, the epoxy reaction rate is obtained by the following formula.
Epoxy reaction rate (%) = (heat value of uncured product−heat value after curing) / heat value of uncured product × 100
また、厚さ２０μｍのシート状エポキシ樹脂組成物を８５℃で５０分間硬化させたときの、波長５５０ｎｍの光の透過率が、９０％以上であることが好ましく、９５％以上であることがより好ましく、９７％以上であることがさらに好ましい。シート状エポキシ樹脂組成物の硬化物の光の透過率が９０％以上であると、シート状エポキシ樹脂組成物を、光透過性が要求される用途にも用いることが可能となる。
Further, when the sheet-shaped epoxy resin composition having a thickness of 20 μm is cured at 85 ° C. for 50 minutes, the light transmittance at a wavelength of 550 nm is preferably 90% or more, more preferably 95% or more. Preferably, it is 97% or more. When the light transmittance of the cured product of the sheet-shaped epoxy resin composition is 90% or more, the sheet-shaped epoxy resin composition can be used for applications requiring light transmittance.
シート状エポキシ樹脂組成物の硬化物の光線透過率は、以下の手順で測定することができる。
基材フィルムと、当該基材フィルム上に作製された厚み２０μｍのシート状エポキシ樹脂組成物とからなる積層体を、長さ約６０ｍｍ、幅約４０ｍｍに切り出して試験片を得る。この試験片のシート状エポキシ樹脂組成物からなる層を、７０℃に加熱したホットプレート上で加熱したガラス板（松浪硝子製Ｎｏ.３、厚さ０．３ｍｍ、７０ｍｍ×５０ｍｍ）に気泡の入らぬようにロールにて転写して貼り合わせる。当該試験片をホットプレート上から外し、３分間放冷する。その後、基材フィルムを剥離して、ガラス板上のシート状エポキシ樹脂組成物をオーブンにて８５℃で５０分間加熱して、硬化物とする。シート状エポキシ樹脂組成物の硬化物が形成されたガラス板の、波長５５０ｎｍにおける光線透過率を、紫外可視光分光光度計（島津製作所 ＵＶ－２５５０）を用いて測定する。測定では、ガラス板単独の光線透過率をベースラインとする。なお、透過率の測定は、厚み２０μｍ以外のシート状エポキシ樹脂組成物を用いて行ってもよい。この場合、得られた透過率をシート状エポキシ樹脂組成物の厚みが２０μｍであるときの透過率に換算する。 The light transmittance of the cured product of the sheet-like epoxy resin composition can be measured by the following procedure.
A laminate comprising a base film and a sheet-like epoxy resin composition having a thickness of 20 μm prepared on the base film is cut into a length of about 60 mm and a width of about 40 mm to obtain a test piece. Bubbles entered into the glass plate (No. 3 made by Matsunami Glass, thickness 0.3 mm, 70 mm × 50 mm) heated on a hot plate heated to 70 ° C. of the layer made of the sheet-like epoxy resin composition of this test piece. Transfer and stick together with a roll. The test piece is removed from the hot plate and allowed to cool for 3 minutes. Thereafter, the base film is peeled off, and the sheet-like epoxy resin composition on the glass plate is heated in an oven at 85 ° C. for 50 minutes to obtain a cured product. The light transmittance at a wavelength of 550 nm of the glass plate on which the cured product of the sheet-like epoxy resin composition is formed is measured using an ultraviolet-visible light spectrophotometer (Shimadzu Corporation UV-2550). In the measurement, the light transmittance of the glass plate alone is used as the baseline. In addition, you may perform the measurement of the transmittance | permeability using sheet-like epoxy resin compositions other than 20 micrometers in thickness. In this case, the obtained transmittance is converted into the transmittance when the thickness of the sheet-like epoxy resin composition is 20 μm.
基材フィルムと、当該基材フィルム上に作製された厚み２０μｍのシート状エポキシ樹脂組成物とからなる積層体を、長さ約６０ｍｍ、幅約４０ｍｍに切り出して試験片を得る。この試験片のシート状エポキシ樹脂組成物からなる層を、７０℃に加熱したホットプレート上で加熱したガラス板（松浪硝子製Ｎｏ.３、厚さ０．３ｍｍ、７０ｍｍ×５０ｍｍ）に気泡の入らぬようにロールにて転写して貼り合わせる。当該試験片をホットプレート上から外し、３分間放冷する。その後、基材フィルムを剥離して、ガラス板上のシート状エポキシ樹脂組成物をオーブンにて８５℃で５０分間加熱して、硬化物とする。シート状エポキシ樹脂組成物の硬化物が形成されたガラス板の、波長５５０ｎｍにおける光線透過率を、紫外可視光分光光度計（島津製作所 ＵＶ－２５５０）を用いて測定する。測定では、ガラス板単独の光線透過率をベースラインとする。なお、透過率の測定は、厚み２０μｍ以外のシート状エポキシ樹脂組成物を用いて行ってもよい。この場合、得られた透過率をシート状エポキシ樹脂組成物の厚みが２０μｍであるときの透過率に換算する。 The light transmittance of the cured product of the sheet-like epoxy resin composition can be measured by the following procedure.
A laminate comprising a base film and a sheet-like epoxy resin composition having a thickness of 20 μm prepared on the base film is cut into a length of about 60 mm and a width of about 40 mm to obtain a test piece. Bubbles entered into the glass plate (No. 3 made by Matsunami Glass, thickness 0.3 mm, 70 mm × 50 mm) heated on a hot plate heated to 70 ° C. of the layer made of the sheet-like epoxy resin composition of this test piece. Transfer and stick together with a roll. The test piece is removed from the hot plate and allowed to cool for 3 minutes. Thereafter, the base film is peeled off, and the sheet-like epoxy resin composition on the glass plate is heated in an oven at 85 ° C. for 50 minutes to obtain a cured product. The light transmittance at a wavelength of 550 nm of the glass plate on which the cured product of the sheet-like epoxy resin composition is formed is measured using an ultraviolet-visible light spectrophotometer (Shimadzu Corporation UV-2550). In the measurement, the light transmittance of the glass plate alone is used as the baseline. In addition, you may perform the measurement of the transmittance | permeability using sheet-like epoxy resin compositions other than 20 micrometers in thickness. In this case, the obtained transmittance is converted into the transmittance when the thickness of the sheet-like epoxy resin composition is 20 μm.
２．封止用シート
本発明の封止用シートは、上述のシート状エポキシ樹脂組成物からなる層を含む。本発明の封止用シートは、基材フィルムと、当該基材フィルム上に配置された上述のシート状エポキシ樹脂組成物と、当該シート状エポキシ樹脂組成物上に配置された保護フィルムとの積層体等とすることができる。 2. Sealing Sheet The sealing sheet of the present invention includes a layer made of the above-described sheet-like epoxy resin composition. The sealing sheet of the present invention is a laminate of a base film, the above-described sheet-shaped epoxy resin composition disposed on the base film, and a protective film disposed on the sheet-shaped epoxy resin composition. It can be a body or the like.
本発明の封止用シートは、上述のシート状エポキシ樹脂組成物からなる層を含む。本発明の封止用シートは、基材フィルムと、当該基材フィルム上に配置された上述のシート状エポキシ樹脂組成物と、当該シート状エポキシ樹脂組成物上に配置された保護フィルムとの積層体等とすることができる。 2. Sealing Sheet The sealing sheet of the present invention includes a layer made of the above-described sheet-like epoxy resin composition. The sealing sheet of the present invention is a laminate of a base film, the above-described sheet-shaped epoxy resin composition disposed on the base film, and a protective film disposed on the sheet-shaped epoxy resin composition. It can be a body or the like.
基材フィルムまたは保護フィルムの例には、公知の離型フィルムが含まれる。これらのフィルムは水分バリア性やガスバリア性を有するフィルム等であることが好ましく、例えばポリエチレンテレフタレートフィルム等とすることができる。基材フィルムの厚さは、フィルム材質にもよるが、有機ＥＬ素子等の被封止材への追従性の観点から、５０μｍ程度とすることができる。一方、保護フィルムは、シート状エポキシ樹脂組成物からなる層上にラミネートされていることが好ましく、ラミネートは、例えばラミネーターを用いて７０℃程度で行うことができる。保護フィルムの厚さも、フィルム材質によるが、２０～４０μｍ程度とすることができる。
Examples of the base film or the protective film include known release films. These films are preferably films having moisture barrier properties and gas barrier properties, such as polyethylene terephthalate films. Although depending on the film material, the thickness of the base film can be set to about 50 μm from the viewpoint of followability to a sealing material such as an organic EL element. On the other hand, the protective film is preferably laminated on a layer made of a sheet-like epoxy resin composition. Lamination can be performed at about 70 ° C. using a laminator, for example. The thickness of the protective film can also be about 20 to 40 μm depending on the film material.
本発明の封止用シートは、用途に応じてガスバリア層をさらに含んでいてもよい。ガスバリア層は、水分やガスの透過を抑制する層である。このようなガスバリア層は、例えばシート状エポキシ樹脂組成物に隣接して配置すること等ができる。
The sealing sheet of the present invention may further include a gas barrier layer depending on the application. The gas barrier layer is a layer that suppresses permeation of moisture and gas. Such a gas barrier layer can be disposed adjacent to the sheet-like epoxy resin composition, for example.
ガスバリア層を構成する材料の例にはＡｌ、Ｃｒ、Ｎｉ、Ｃｕ、Ｚｎ、Ｓｉ、Ｆｅ、Ｔｉ、Ａｇ、Ａｕ、Ｃｏ等の金属；これら金属の酸化物；これら金属の窒化物；これら金属の酸化窒化物；ポリエチレンテレフタレートやポリカーボネート等の樹脂等が含まれる。ガスバリア層は、１種の材料で構成されてもよいし、２種以上の材料で構成されてもよい。なお、封止用シートに光反射性が要求される場合（例えば、ボトムエミッション方式の有機ＥＬ素子の封止等に用いられる場合）、ガスバリア層を光反射率の高い層とすることが好ましく、ガスバリア層は、例えばＡｌやＣｕ等からなる層とすることができる。一方、封止用シートに光透過性が要求される場合（例えばトップエミッション方式の有機ＥＬ素子等の封止に用いられる場合）、ガスバリア層を光透過性の高い層とすることが好ましく、ガスバリア層は、例えばポリエチレンテレフタレートやポリカーボネート等からなる層とすることができる。ガスバリア層の厚みは、１０～３０００μｍ程度とすることができる。
Examples of materials constituting the gas barrier layer include metals such as Al, Cr, Ni, Cu, Zn, Si, Fe, Ti, Ag, Au, and Co; oxides of these metals; nitrides of these metals; Oxynitrides; resins such as polyethylene terephthalate and polycarbonate are included. The gas barrier layer may be composed of one kind of material or may be composed of two or more kinds of materials. In addition, when light reflectivity is required for the sealing sheet (for example, when used for sealing a bottom emission type organic EL element), the gas barrier layer is preferably a layer having high light reflectance, The gas barrier layer can be a layer made of, for example, Al or Cu. On the other hand, when the light-transmitting property is required for the sealing sheet (for example, when used for sealing a top emission type organic EL element or the like), the gas barrier layer is preferably a light-transmitting layer. The layer can be a layer made of, for example, polyethylene terephthalate or polycarbonate. The thickness of the gas barrier layer can be about 10 to 3000 μm.
ガスバリア層の形成方法は、特に制限されず、ドライプロセスとしては、真空蒸着、スパッタリング、イオンプレーティング等の各種ＰＶＤ法；プラズマＣＶＤ等のＣＶＤ法等が含まれる。ウエットプロセスとしては、めっき法、塗布法等が含まれる。
The method for forming the gas barrier layer is not particularly limited, and examples of the dry process include various PVD methods such as vacuum deposition, sputtering, and ion plating; and CVD methods such as plasma CVD. Examples of the wet process include a plating method and a coating method.
本発明の封止用シートは、シート状エポキシ樹脂組成物からなる層を所望の被封止材と密着させた後、シート状エポキシ樹脂組成物からなる層を硬化させて用いられる。封止対象である被封止材は、特に限定されないが、例えば有機ＥＬ素子や、液晶素子、ＬＥＤ素子等が含まれる。
The sealing sheet of the present invention is used after a layer made of a sheet-like epoxy resin composition is brought into close contact with a desired material to be sealed and then a layer made of the sheet-like epoxy resin composition is cured. The material to be sealed, which is an object to be sealed, is not particularly limited, and examples thereof include an organic EL element, a liquid crystal element, and an LED element.
以下において、実施例を参照して本発明を説明する。実施例によって、本発明の範囲は限定して解釈されない。
Hereinafter, the present invention will be described with reference to examples. By way of example, the scope of the invention is not construed as limiting.
［材料］
実施例および比較例では、以下の材料を用いた。 [material]
In the examples and comparative examples, the following materials were used.
実施例および比較例では、以下の材料を用いた。 [material]
In the examples and comparative examples, the following materials were used.
（Ａ）エポキシ系化合物
・ＥＰ－４０８８Ｌ：ＡＤＥＫＡ社製 下記一般式で表されるジシクロペンジエン型エポキシ系化合物 エポキシ当量１６５ｇ／ｅｑ
(A) Epoxy compound
EP-4088L: manufactured by ADEKA dicyclopendiene type epoxy compound represented by the following general formula: epoxy equivalent 165 g / eq
・ＥＰ－４０８８Ｌ：ＡＤＥＫＡ社製 下記一般式で表されるジシクロペンジエン型エポキシ系化合物 エポキシ当量１６５ｇ／ｅｑ
EP-4088L: manufactured by ADEKA dicyclopendiene type epoxy compound represented by the following general formula: epoxy equivalent 165 g / eq
（Ｂ）エポキシ樹脂
・ｊＥＲ４００５Ｐ：三菱ケミカル社製 ビスフェノールＦ型エポキシ樹脂、エポキシ当量９５０ｇ／ｅｑ、Ｍｗ７５８２
・ＹＸ６９５４Ｂ３５：三菱ケミカル社製 ビフェニル型エポキシ樹脂、エポキシ当量１０，０００ｇ／ｅｑ、Ｍｗ３６６９１
・ｊＥＲ４２７５：三菱ケミカル社製 ビスフェノールＡ／ビスフェノールＦ型エポキシ樹脂、エポキシ当量８，４００ｇ／ｅｑ、Ｍｗ５８２８７ (B) Epoxy resin jER4005P: bisphenol F type epoxy resin manufactured by Mitsubishi Chemical Corporation, epoxy equivalent 950 g / eq, Mw 7582
YX6954B35: Biphenyl type epoxy resin manufactured by Mitsubishi Chemical Corporation, epoxy equivalent 10,000 g / eq, Mw36691
-JER4275: Mitsubishi Chemical Corporation bisphenol A / bisphenol F type epoxy resin, epoxy equivalent 8,400 g / eq, Mw58287
・ｊＥＲ４００５Ｐ：三菱ケミカル社製 ビスフェノールＦ型エポキシ樹脂、エポキシ当量９５０ｇ／ｅｑ、Ｍｗ７５８２
・ＹＸ６９５４Ｂ３５：三菱ケミカル社製 ビフェニル型エポキシ樹脂、エポキシ当量１０，０００ｇ／ｅｑ、Ｍｗ３６６９１
・ｊＥＲ４２７５：三菱ケミカル社製 ビスフェノールＡ／ビスフェノールＦ型エポキシ樹脂、エポキシ当量８，４００ｇ／ｅｑ、Ｍｗ５８２８７ (B) Epoxy resin jER4005P: bisphenol F type epoxy resin manufactured by Mitsubishi Chemical Corporation, epoxy equivalent 950 g / eq, Mw 7582
YX6954B35: Biphenyl type epoxy resin manufactured by Mitsubishi Chemical Corporation, epoxy equivalent 10,000 g / eq, Mw36691
-JER4275: Mitsubishi Chemical Corporation bisphenol A / bisphenol F type epoxy resin, epoxy equivalent 8,400 g / eq, Mw58287
（その他のエポキシ樹脂）
・ＹＬ－９８３Ｕ：三菱ケミカル社製 ビスフェノールＦ型エポキシ樹脂 エポキシ当量 １６５ｇ／ｅｑ、Ｍｗ３９８
・ＣＥＬ２０２１Ｐ：ダイセル化学社製 シクロアルケンオキサイド型エポキシ樹脂、エポキシ当量１２８ｇ／ｅｑ、Ｍｗ２５２
・ｊＥＲ１００１：三菱ケミカル社製 ビスフェノールＡ型エポキシ樹脂、エポキシ当量 ４５０ｇ／ｅｑ、Ｍｗ２３２２ (Other epoxy resins)
YL-983U: Bisphenol F type epoxy resin manufactured by Mitsubishi Chemical Corporation Epoxy equivalent 165 g / eq, Mw 398
-CEL2021P: Daicel Chemical Industries, Ltd. cycloalkene oxide type epoxy resin, epoxy equivalent 128g / eq, Mw252
JER1001: bisphenol A type epoxy resin manufactured by Mitsubishi Chemical Corporation, epoxy equivalent 450 g / eq, Mw 2322
・ＹＬ－９８３Ｕ：三菱ケミカル社製 ビスフェノールＦ型エポキシ樹脂 エポキシ当量 １６５ｇ／ｅｑ、Ｍｗ３９８
・ＣＥＬ２０２１Ｐ：ダイセル化学社製 シクロアルケンオキサイド型エポキシ樹脂、エポキシ当量１２８ｇ／ｅｑ、Ｍｗ２５２
・ｊＥＲ１００１：三菱ケミカル社製 ビスフェノールＡ型エポキシ樹脂、エポキシ当量 ４５０ｇ／ｅｑ、Ｍｗ２３２２ (Other epoxy resins)
YL-983U: Bisphenol F type epoxy resin manufactured by Mitsubishi Chemical Corporation Epoxy equivalent 165 g / eq, Mw 398
-CEL2021P: Daicel Chemical Industries, Ltd. cycloalkene oxide type epoxy resin, epoxy equivalent 128g / eq, Mw252
JER1001: bisphenol A type epoxy resin manufactured by Mitsubishi Chemical Corporation, epoxy equivalent 450 g / eq, Mw 2322
（Ｃ）カチオン重合開始剤
・ＳＩ－６０：三新化学工業社製 下記一般式（２ａ）で表される六フッ化アンチモン型カチオン重合開始剤
(C) Cationic polymerization initiator SI-60: manufactured by Sanshin Chemical Industry Co., Ltd. Antimony hexafluoride type cationic polymerization initiator represented by the following general formula (2a)
・ＳＩ－６０：三新化学工業社製 下記一般式（２ａ）で表される六フッ化アンチモン型カチオン重合開始剤
（その他のカチオン重合開始剤）
・ＳＩ－８０：三新化学工業社製 下記一般式（２ｂ）で表される六フッ化アンチモン型カチオン重合開始剤
・ＳＩ－３００：三新化学工業社製 下記一般式（２ｃ）で表される、六フッ化リン型カチオン重合開始剤
・ＳＩ－Ｂ２Ａ：三新化学工業社製 下記一般式（２ｄ）で表される、フッ化ボレート型カチオン重合開始剤
・ＳＩ－Ｂ７：三新化学工業社製 下記一般式（２ｅ）で表される、フッ化ボレート型カチオン重合開始剤
(Other cationic polymerization initiators)
SI-80: manufactured by Sanshin Chemical Industry Co., Ltd. Antimony hexafluoride type cationic polymerization initiator represented by the following general formula (2b)
SI-300: Sanshin Chemical Co., Ltd. Phosphorus hexafluoride type cationic polymerization initiator represented by the following general formula (2c)
SI-B2A: Sanshin Chemical Industry Co., Ltd. Fluorinated borate type cationic polymerization initiator represented by the following general formula (2d)
SI-B7: manufactured by Sanshin Chemical Industry Co., Ltd. Fluorinated borate type cationic polymerization initiator represented by the following general formula (2e)
・ＳＩ－８０：三新化学工業社製 下記一般式（２ｂ）で表される六フッ化アンチモン型カチオン重合開始剤
SI-80: manufactured by Sanshin Chemical Industry Co., Ltd. Antimony hexafluoride type cationic polymerization initiator represented by the following general formula (2b)
（Ｄ）安定剤
・ＳＩ助剤：三新化学工業社製 カチオン重合用ポットライフ安定剤
・ＰＥＧ４０００：ポリエチレングリコール４０００ 和光純薬工業社性 和光１級
・１，４－ＢＤ：１，４－ブタンジオール 和光純薬工業社製 和光特級 (D) Stabilizer ・ SI auxiliary agent: Pot life stabilizer for cation polymerization manufactured by Sanshin Chemical Industry Co., Ltd. ・ PEG4000: Polyethylene glycol 4000 Wako Pure Chemical Industries, Ltd. Wako first grade ・ 1,4-BD: 1,4-butane Diol Wako Pure Chemical Industries Wako Special Grade
・ＳＩ助剤：三新化学工業社製 カチオン重合用ポットライフ安定剤
・ＰＥＧ４０００：ポリエチレングリコール４０００ 和光純薬工業社性 和光１級
・１，４－ＢＤ：１，４－ブタンジオール 和光純薬工業社製 和光特級 (D) Stabilizer ・ SI auxiliary agent: Pot life stabilizer for cation polymerization manufactured by Sanshin Chemical Industry Co., Ltd. ・ PEG4000: Polyethylene glycol 4000 Wako Pure Chemical Industries, Ltd. Wako first grade ・ 1,4-BD: 1,4-butane Diol Wako Pure Chemical Industries Wako Special Grade
（Ｅ）カップリング剤
・ＫＢＭ－４０３：信越化学工業株式会社製 (E) Coupling agent • KBM-403: Shin-Etsu Chemical Co., Ltd.
・ＫＢＭ－４０３：信越化学工業株式会社製 (E) Coupling agent • KBM-403: Shin-Etsu Chemical Co., Ltd.
（Ｆ）溶剤
・メチルエチルケトン（ＭＥＫ） (F) Solvent ・ Methyl ethyl ketone (MEK)
・メチルエチルケトン（ＭＥＫ） (F) Solvent ・ Methyl ethyl ketone (MEK)
［実施例１］
フラスコに、３０質量部のＥＰ－４０８８Ｌと、５０質量部のｊＥＲ４００５Ｐと、２０質量部（固形分換算）のＹＸ６９５４Ｂ３５とを投入し、これに１００質量部のメチルエチルケトンを加え、室温で攪拌溶解した。この溶液に、２．５質量部のカチオン重合開始剤ＳＩ－６０と１質量部のＫＢＭ－４０３、とを添加して室温で攪拌し、ワニスを調製した。 [Example 1]
30 parts by mass of EP-4088L, 50 parts by mass of jER4005P, and 20 parts by mass (in terms of solid content) of YX6954B35 were added to the flask, and 100 parts by mass of methyl ethyl ketone was added thereto and stirred and dissolved at room temperature. To this solution, 2.5 parts by weight of cationic polymerization initiator SI-60 and 1 part by weight of KBM-403 were added and stirred at room temperature to prepare a varnish.
フラスコに、３０質量部のＥＰ－４０８８Ｌと、５０質量部のｊＥＲ４００５Ｐと、２０質量部（固形分換算）のＹＸ６９５４Ｂ３５とを投入し、これに１００質量部のメチルエチルケトンを加え、室温で攪拌溶解した。この溶液に、２．５質量部のカチオン重合開始剤ＳＩ－６０と１質量部のＫＢＭ－４０３、とを添加して室温で攪拌し、ワニスを調製した。 [Example 1]
30 parts by mass of EP-4088L, 50 parts by mass of jER4005P, and 20 parts by mass (in terms of solid content) of YX6954B35 were added to the flask, and 100 parts by mass of methyl ethyl ketone was added thereto and stirred and dissolved at room temperature. To this solution, 2.5 parts by weight of cationic polymerization initiator SI-60 and 1 part by weight of KBM-403 were added and stirred at room temperature to prepare a varnish.
調製したワニスを、塗工機を用いて、基材フィルム（離型処理ＰＥＴフィルム Ａ５３（帝人フィルムソリューション社製）厚み５０μｍ）に、乾燥後厚みが約２０μｍとなるようにアプリケーターで塗工した。このフィルムを９０℃イナートオーブン中で、３分間乾燥させて、ワニス塗工膜中のＭＥＫを乾燥除去して、基材フィルム上にシート状エポキシ樹脂組成物からなる層を形成した。さらに、シート状エポキシ樹脂組成物からなる層上に、保護フィルム（離型処理ＰＥＴフィルム Ａ３１（帝人フィルムソリューション社製）厚み３８μｍ）を７０℃で熱圧着し、封止用シートを得た。なお、保護フィルムは適宜剥がし、シート状エポキシ樹脂組成物からなる層の表面を露出させて使用した。
The prepared varnish was coated with an applicator using a coating machine on a base film (release-treated PET film A53 (manufactured by Teijin Film Solutions Co., Ltd.) thickness 50 μm) so that the thickness after drying was about 20 μm. This film was dried in a 90 ° C. inert oven for 3 minutes, and the MEK in the varnish coating film was removed by drying to form a layer made of a sheet-like epoxy resin composition on the base film. Furthermore, on the layer which consists of a sheet-like epoxy resin composition, the protective film (Release processing PET film A31 (made by Teijin Film Solutions) thickness 38 micrometers) was thermocompression bonded at 70 degreeC, and the sheet | seat for sealing was obtained. In addition, the protective film was peeled off as appropriate, and the surface of the layer made of the sheet-like epoxy resin composition was exposed for use.
［実施例２～１０、および比較例１～１０］
表１および表２に示す組成比率（質量比）で実施例１と同様にワニスを調製した。これを、塗工し乾燥させて、シート状エポキシ樹脂組成物からなる層を有する封止用シートを得た。 [Examples 2 to 10 and Comparative Examples 1 to 10]
Varnishes were prepared in the same manner as in Example 1 with the composition ratios (mass ratios) shown in Tables 1 and 2. This was coated and dried to obtain a sealing sheet having a layer made of a sheet-like epoxy resin composition.
表１および表２に示す組成比率（質量比）で実施例１と同様にワニスを調製した。これを、塗工し乾燥させて、シート状エポキシ樹脂組成物からなる層を有する封止用シートを得た。 [Examples 2 to 10 and Comparative Examples 1 to 10]
Varnishes were prepared in the same manner as in Example 1 with the composition ratios (mass ratios) shown in Tables 1 and 2. This was coated and dried to obtain a sealing sheet having a layer made of a sheet-like epoxy resin composition.
［評価］
実施例および比較例で得られたシート状エポキシ樹脂組成物からなる層の物性値を以下の方法で評価した。結果を表１および表２に示す。 [Evaluation]
The physical property values of the layers composed of the sheet-like epoxy resin compositions obtained in Examples and Comparative Examples were evaluated by the following methods. The results are shown in Tables 1 and 2.
実施例および比較例で得られたシート状エポキシ樹脂組成物からなる層の物性値を以下の方法で評価した。結果を表１および表２に示す。 [Evaluation]
The physical property values of the layers composed of the sheet-like epoxy resin compositions obtained in Examples and Comparative Examples were evaluated by the following methods. The results are shown in Tables 1 and 2.
（１）溶融温度
１）ブランク値測定（０時間）
実施例または比較例で得られた封止用シートを、長さ約３０ｍｍ、幅約５ｍｍに切り出して短冊状の試験片を得た。この試験片のシート状エポキシ樹脂組成物からなる層を、ホットプレート上で加熱したガラス板上に密着させた。その後、当該試験片を１８０°方向へ徐々にガラス板から剥離した。この操作を、ホットプレートの設定温度４０℃から始め、設定温度を１℃上げる毎に短冊状の試験片を新たに用意して繰り返し、剥離時にシート状エポキシ樹脂組成物からなる層の粘着剥離性が最も大きくなる温度を、溶融温度とした。ただし４０℃で、すでに粘着剥離性の大きいものは再度２５℃より溶融温度の測定を実施した。 (1) Melting temperature 1) Blank value measurement (0 hour)
The sealing sheet obtained in the example or the comparative example was cut into a length of about 30 mm and a width of about 5 mm to obtain a strip-shaped test piece. The layer which consists of a sheet-like epoxy resin composition of this test piece was stuck on the glass plate heated on the hotplate. Thereafter, the test piece was gradually peeled from the glass plate in the 180 ° direction. This operation is started at a preset temperature of 40 ° C. of the hot plate, and each time the set temperature is raised by 1 ° C., a strip-shaped test piece is newly prepared and repeated, and the adhesive peelability of the layer made of the sheet-like epoxy resin composition at the time of peeling The temperature at which the temperature became the largest was taken as the melting temperature. However, at 40 ° C., those having already large adhesive peelability were measured again at 25 ° C. for the melting temperature.
１）ブランク値測定（０時間）
実施例または比較例で得られた封止用シートを、長さ約３０ｍｍ、幅約５ｍｍに切り出して短冊状の試験片を得た。この試験片のシート状エポキシ樹脂組成物からなる層を、ホットプレート上で加熱したガラス板上に密着させた。その後、当該試験片を１８０°方向へ徐々にガラス板から剥離した。この操作を、ホットプレートの設定温度４０℃から始め、設定温度を１℃上げる毎に短冊状の試験片を新たに用意して繰り返し、剥離時にシート状エポキシ樹脂組成物からなる層の粘着剥離性が最も大きくなる温度を、溶融温度とした。ただし４０℃で、すでに粘着剥離性の大きいものは再度２５℃より溶融温度の測定を実施した。 (1) Melting temperature 1) Blank value measurement (0 hour)
The sealing sheet obtained in the example or the comparative example was cut into a length of about 30 mm and a width of about 5 mm to obtain a strip-shaped test piece. The layer which consists of a sheet-like epoxy resin composition of this test piece was stuck on the glass plate heated on the hotplate. Thereafter, the test piece was gradually peeled from the glass plate in the 180 ° direction. This operation is started at a preset temperature of 40 ° C. of the hot plate, and each time the set temperature is raised by 1 ° C., a strip-shaped test piece is newly prepared and repeated, and the adhesive peelability of the layer made of the sheet-like epoxy resin composition at the time of peeling The temperature at which the temperature became the largest was taken as the melting temperature. However, at 40 ° C., those having already large adhesive peelability were measured again at 25 ° C. for the melting temperature.
２）４０℃１７時間加熱後測定
実施例または比較例で得られた封止用シートを、長さ約３０ｍｍ、幅約５ｍｍに切り出して短冊状の試験片を得た。この試験片を、４０℃オーブン中で１７時間保存した。保存後の試験片のシート状エポキシ樹脂組成物からなる層の溶融温度を、上述のブランク値測定と同様にして測定した。ただし溶融温度の最大測定温度は硬化進行の影響を受けるため８０℃までとした。 2) Measurement after heating at 40 ° C. for 17 hours The sealing sheets obtained in the examples or comparative examples were cut into a length of about 30 mm and a width of about 5 mm to obtain strip-shaped test pieces. The specimen was stored in a 40 ° C. oven for 17 hours. The melting temperature of the layer made of the sheet-like epoxy resin composition of the test piece after storage was measured in the same manner as in the blank value measurement described above. However, the maximum measurement temperature of the melting temperature is up to 80 ° C. because it is affected by the progress of curing.
実施例または比較例で得られた封止用シートを、長さ約３０ｍｍ、幅約５ｍｍに切り出して短冊状の試験片を得た。この試験片を、４０℃オーブン中で１７時間保存した。保存後の試験片のシート状エポキシ樹脂組成物からなる層の溶融温度を、上述のブランク値測定と同様にして測定した。ただし溶融温度の最大測定温度は硬化進行の影響を受けるため８０℃までとした。 2) Measurement after heating at 40 ° C. for 17 hours The sealing sheets obtained in the examples or comparative examples were cut into a length of about 30 mm and a width of about 5 mm to obtain strip-shaped test pieces. The specimen was stored in a 40 ° C. oven for 17 hours. The melting temperature of the layer made of the sheet-like epoxy resin composition of the test piece after storage was measured in the same manner as in the blank value measurement described above. However, the maximum measurement temperature of the melting temperature is up to 80 ° C. because it is affected by the progress of curing.
（２）硬化性
１）未硬化品の発熱量測定および発熱開始温度測定
実施例または比較例で得られた封止用シートを、約５０ｍｍ角に切り出して試験片を得た。この試験片のシート状エポキシ樹脂層からなる層を、ピンセットにて基材より剥離して１０ｍｇを採取し、ＤＳＣ測定用アルミセルに詰め、測定試験サンプルを準備した。そして、昇温速度５℃／分、測定温度範囲：２０℃～３００℃にてＤＳＣで未硬化品の発熱開始温度および発熱量を特定した。 (2) Curability 1) Measurement of calorific value of uncured product and measurement of heat generation start temperature The sheet for sealing obtained in Examples or Comparative Examples was cut into approximately 50 mm squares to obtain test pieces. A layer made of the sheet-like epoxy resin layer of this test piece was peeled off from the base material with tweezers, 10 mg was collected, packed in an aluminum cell for DSC measurement, and a measurement test sample was prepared. Then, the heat generation start temperature and the heat generation amount of the uncured product were specified by DSC at a temperature rising rate of 5 ° C./min and a measurement temperature range: 20 ° C. to 300 ° C.
１）未硬化品の発熱量測定および発熱開始温度測定
実施例または比較例で得られた封止用シートを、約５０ｍｍ角に切り出して試験片を得た。この試験片のシート状エポキシ樹脂層からなる層を、ピンセットにて基材より剥離して１０ｍｇを採取し、ＤＳＣ測定用アルミセルに詰め、測定試験サンプルを準備した。そして、昇温速度５℃／分、測定温度範囲：２０℃～３００℃にてＤＳＣで未硬化品の発熱開始温度および発熱量を特定した。 (2) Curability 1) Measurement of calorific value of uncured product and measurement of heat generation start temperature The sheet for sealing obtained in Examples or Comparative Examples was cut into approximately 50 mm squares to obtain test pieces. A layer made of the sheet-like epoxy resin layer of this test piece was peeled off from the base material with tweezers, 10 mg was collected, packed in an aluminum cell for DSC measurement, and a measurement test sample was prepared. Then, the heat generation start temperature and the heat generation amount of the uncured product were specified by DSC at a temperature rising rate of 5 ° C./min and a measurement temperature range: 20 ° C. to 300 ° C.
２）硬化温度８５℃におけるエポキシ反応率（％）
未硬化品と同様にして測定サンプルを準備した。硬化はあらかじめ８５℃に設定したオーブン中で行い、サンプル投入から５０分後に測定サンプルを取り出した。そして、昇温速度５℃／分、測定温度範囲：２０℃～３００℃にてＤＳＣで硬化品の発熱量を特定した。そして、測定された発熱量から、下記に示す式より、硬化温度８５℃におけるエポキシ反応率（％）を求めた。
反応率（％）＝（未硬化品の発熱量－硬化後の発熱量）／未硬化品の発熱量×１００ 2) Epoxy reaction rate at a curing temperature of 85 ° C. (%)
A measurement sample was prepared in the same manner as the uncured product. Curing was performed in an oven set to 85 ° C. in advance, and a measurement sample was taken out 50 minutes after the sample was put in. Then, the calorific value of the cured product was specified by DSC at a heating rate of 5 ° C./min and a measurement temperature range of 20 ° C. to 300 ° C. And the epoxy reaction rate (%) in the curing temperature of 85 degreeC was calculated | required from the measured calorific value from the formula shown below.
Reaction rate (%) = (Heat generation amount of uncured product−Heat generation amount after curing) / Heat generation amount of uncured product × 100
未硬化品と同様にして測定サンプルを準備した。硬化はあらかじめ８５℃に設定したオーブン中で行い、サンプル投入から５０分後に測定サンプルを取り出した。そして、昇温速度５℃／分、測定温度範囲：２０℃～３００℃にてＤＳＣで硬化品の発熱量を特定した。そして、測定された発熱量から、下記に示す式より、硬化温度８５℃におけるエポキシ反応率（％）を求めた。
反応率（％）＝（未硬化品の発熱量－硬化後の発熱量）／未硬化品の発熱量×１００ 2) Epoxy reaction rate at a curing temperature of 85 ° C. (%)
A measurement sample was prepared in the same manner as the uncured product. Curing was performed in an oven set to 85 ° C. in advance, and a measurement sample was taken out 50 minutes after the sample was put in. Then, the calorific value of the cured product was specified by DSC at a heating rate of 5 ° C./min and a measurement temperature range of 20 ° C. to 300 ° C. And the epoxy reaction rate (%) in the curing temperature of 85 degreeC was calculated | required from the measured calorific value from the formula shown below.
Reaction rate (%) = (Heat generation amount of uncured product−Heat generation amount after curing) / Heat generation amount of uncured product × 100
（３）転写性評価
実施例または比較例で得られた封止用シートを、長さ約１５０ｍｍ、幅約４０ｍｍに切り出して短冊状の試験片を得た。この試験片のシート状エポキシ樹脂組成物からなる層を、７０℃に加熱したホットプレート上で加熱したガラス板上に気泡の入らぬようにロールにて転写して貼り合わせた。当該試験片をホットプレート上から外し、３分間放冷した。その後、基材フィルムを剥離して、転写性の評価を以下のように行った。
〇：樹脂層がガラス全面に転写
△：基材側に樹脂層の残りあり
×：樹脂層がガラスに密着せず (3) Transferability evaluation The sealing sheet obtained in the example or the comparative example was cut into a length of about 150 mm and a width of about 40 mm to obtain a strip-shaped test piece. The layer made of the sheet-like epoxy resin composition of the test piece was transferred and pasted onto a glass plate heated on a hot plate heated to 70 ° C. with a roll so as not to contain bubbles. The test piece was removed from the hot plate and allowed to cool for 3 minutes. Thereafter, the base film was peeled off, and the transferability was evaluated as follows.
◯: Resin layer transferred to the entire glass surface △: Resin layer remaining on the substrate side ×: The resin layer does not adhere to the glass
実施例または比較例で得られた封止用シートを、長さ約１５０ｍｍ、幅約４０ｍｍに切り出して短冊状の試験片を得た。この試験片のシート状エポキシ樹脂組成物からなる層を、７０℃に加熱したホットプレート上で加熱したガラス板上に気泡の入らぬようにロールにて転写して貼り合わせた。当該試験片をホットプレート上から外し、３分間放冷した。その後、基材フィルムを剥離して、転写性の評価を以下のように行った。
〇：樹脂層がガラス全面に転写
△：基材側に樹脂層の残りあり
×：樹脂層がガラスに密着せず (3) Transferability evaluation The sealing sheet obtained in the example or the comparative example was cut into a length of about 150 mm and a width of about 40 mm to obtain a strip-shaped test piece. The layer made of the sheet-like epoxy resin composition of the test piece was transferred and pasted onto a glass plate heated on a hot plate heated to 70 ° C. with a roll so as not to contain bubbles. The test piece was removed from the hot plate and allowed to cool for 3 minutes. Thereafter, the base film was peeled off, and the transferability was evaluated as follows.
◯: Resin layer transferred to the entire glass surface △: Resin layer remaining on the substrate side ×: The resin layer does not adhere to the glass
（４）硬化物の光線透過率の測定
実施例または比較例で得られた封止用シートを、長さ約６０ｍｍ、幅約４０ｍｍに切り出して試験片を得た。この試験片のシート状エポキシ樹脂組成物からなる層を、７０℃に加熱したホットプレート上で加熱したガラス板（松浪硝子製Ｎｏ.３、厚さ０．３ｍｍ、７０ｍｍ×５０ｍｍ）に気泡の入らぬようにロールにて転写して貼り合わせた。当該試験片をホットプレート上から外し、３分間放冷した。その後、基材フィルムを剥離して、ガラス板上のシート状エポキシ樹脂組成物をオーブンにて８５℃で５０分間加熱して、硬化物とした。シート状エポキシ樹脂組成物の硬化物が形成されたガラス板の、波長５５０ｎｍにおける光線透過率を、紫外可視光分光光度計（島津製作所 ＵＶ－２５５０）を用いて測定した。測定では、ガラス板単独の光線透過率をベースラインとした。 (4) Measurement of light transmittance of hardened | cured material The sheet | seat for sealing obtained by the Example or the comparative example was cut out to about 60 mm in length, and about 40 mm in width, and the test piece was obtained. Bubbles entered into the glass plate (No. 3 made by Matsunami Glass, thickness 0.3 mm, 70 mm × 50 mm) heated on a hot plate heated to 70 ° C. of the layer made of the sheet-like epoxy resin composition of this test piece. It was transferred by a roll and pasted together. The test piece was removed from the hot plate and allowed to cool for 3 minutes. Thereafter, the base film was peeled off, and the sheet-like epoxy resin composition on the glass plate was heated in an oven at 85 ° C. for 50 minutes to obtain a cured product. The light transmittance at a wavelength of 550 nm of the glass plate on which the cured product of the sheet-like epoxy resin composition was formed was measured using an ultraviolet-visible light spectrophotometer (Shimadzu Corporation UV-2550). In the measurement, the light transmittance of the glass plate alone was taken as the baseline.
実施例または比較例で得られた封止用シートを、長さ約６０ｍｍ、幅約４０ｍｍに切り出して試験片を得た。この試験片のシート状エポキシ樹脂組成物からなる層を、７０℃に加熱したホットプレート上で加熱したガラス板（松浪硝子製Ｎｏ.３、厚さ０．３ｍｍ、７０ｍｍ×５０ｍｍ）に気泡の入らぬようにロールにて転写して貼り合わせた。当該試験片をホットプレート上から外し、３分間放冷した。その後、基材フィルムを剥離して、ガラス板上のシート状エポキシ樹脂組成物をオーブンにて８５℃で５０分間加熱して、硬化物とした。シート状エポキシ樹脂組成物の硬化物が形成されたガラス板の、波長５５０ｎｍにおける光線透過率を、紫外可視光分光光度計（島津製作所 ＵＶ－２５５０）を用いて測定した。測定では、ガラス板単独の光線透過率をベースラインとした。 (4) Measurement of light transmittance of hardened | cured material The sheet | seat for sealing obtained by the Example or the comparative example was cut out to about 60 mm in length, and about 40 mm in width, and the test piece was obtained. Bubbles entered into the glass plate (No. 3 made by Matsunami Glass, thickness 0.3 mm, 70 mm × 50 mm) heated on a hot plate heated to 70 ° C. of the layer made of the sheet-like epoxy resin composition of this test piece. It was transferred by a roll and pasted together. The test piece was removed from the hot plate and allowed to cool for 3 minutes. Thereafter, the base film was peeled off, and the sheet-like epoxy resin composition on the glass plate was heated in an oven at 85 ° C. for 50 minutes to obtain a cured product. The light transmittance at a wavelength of 550 nm of the glass plate on which the cured product of the sheet-like epoxy resin composition was formed was measured using an ultraviolet-visible light spectrophotometer (Shimadzu Corporation UV-2550). In the measurement, the light transmittance of the glass plate alone was taken as the baseline.
表１に示されるように、（Ａ）所定の構造を有するエポキシ系化合物と、（Ｂ）芳香環を有し、かつ平均分子量が３０００～１０００００であるエポキシ樹脂と、（Ｃ）特定の構造を有するカチオン重合開始剤と、を含む実施例１～１０のエポキシ樹脂組成物によれば、加熱試験前と加熱試験後の溶融温度の変化が少なかった。これは、加熱試験によって影響を受け難く、保存安定性が優れていたといえる。またこれらは、８５℃でのエポキシ反応率も高く、いずれも９０℃以下で十分に硬化させることが可能であった。
As shown in Table 1, (A) an epoxy compound having a predetermined structure, (B) an epoxy resin having an aromatic ring and an average molecular weight of 3000 to 100,000, and (C) a specific structure According to the epoxy resin compositions of Examples 1 to 10 including the cationic polymerization initiator having, there was little change in the melting temperature before and after the heating test. This is hardly affected by the heating test and can be said to have excellent storage stability. These also had a high epoxy reaction rate at 85 ° C., and all of them could be sufficiently cured at 90 ° C. or less.
これに対し、脂環式構造を有するエポキシ系化合物を含まない比較例１では、硬化温度８５℃でのエポキシ反応率が８０％未満であり、硬化のための温度が低いと十分に硬化反応を進めることができなかった。
On the other hand, in Comparative Example 1 that does not include an epoxy compound having an alicyclic structure, the epoxy reaction rate at a curing temperature of 85 ° C. is less than 80%, and the curing reaction is sufficiently performed when the temperature for curing is low. I could not proceed.
また、脂環式構造を有するエポキシ系化合物を含んでいたとしても、本願の（Ａ）エポキシ系化合物のようにジシクロペンタジエン骨格を有さない場合には（比較例２）、シート状に成形しただけで硬化してしまった。その結果、溶融温度が８０℃を超えてしまい、発熱開始温度を測定できなかった。また、７０℃で転写できなかったため、硬化後の光線透過率を測定できなかった。
Moreover, even if it contains an epoxy compound having an alicyclic structure, when it does not have a dicyclopentadiene skeleton like (A) the epoxy compound of the present application (Comparative Example 2), it is molded into a sheet shape. It just hardened. As a result, the melting temperature exceeded 80 ° C., and the heat generation start temperature could not be measured. Moreover, since it was not able to transfer at 70 degreeC, the light transmittance after hardening was not able to be measured.
また、カチオン重合開始剤として、ＳＩ－３００（フェニル基にアセチル基が結合し、アニオンがＰＦ６
－である）を用いた場合（例えば比較例３～６）、４０℃１７時間保持の加熱試験後の溶融温度が８０℃を超えた。加熱試験前後での溶融温度の変化が１０℃以上であり、保存安定性が悪かったといえる。また、加熱試験後の転写性の評価でも、ガラスへ貼り合わせることができなかった。また、カチオン重合開始剤として、ＳＩ－Ｂ２Ａ（フェニル基にアセチル基が結合し、アニオンがＢ（Ｃ６Ｆ５）４
－である）場合（比較例８）も、シート状に成形しただけで硬化してしまった。カチオン重合開始剤の反応性が高すぎ、保存安定性が悪かった。また、７０℃で転写できなかったため、硬化後の光線透過率を測定できなかった。
Further, when SI-300 (an acetyl group is bonded to a phenyl group and an anion is PF 6 — ) is used as a cationic polymerization initiator (for example, Comparative Examples 3 to 6), a heating test at 40 ° C. for 17 hours holding The later melting temperature exceeded 80 ° C. The change in melting temperature before and after the heating test was 10 ° C. or more, and it can be said that the storage stability was poor. In addition, the transferability after the heating test could not be bonded to the glass. In addition, as a cationic polymerization initiator, SI-B2A (when an acetyl group is bonded to a phenyl group and an anion is B (C 6 F 5 ) 4 — ) (Comparative Example 8) is also obtained by simply forming into a sheet shape. It has hardened. The reactivity of the cationic polymerization initiator was too high, and the storage stability was poor. Moreover, since it was not able to transfer at 70 degreeC, the light transmittance after hardening was not able to be measured.
さらに、カチオン重合開始剤として、本発明で特定する構造以外のＳＩ－Ｂ７やＳＩ－８０を用いた場合（比較例９および１０）には、保存安定性は良好であったものの、８５℃でのエポキシ反応率が低く、８５℃で十分に硬化させることができなかった。
Further, when SI-B7 or SI-80 other than the structure specified in the present invention was used as the cationic polymerization initiator (Comparative Examples 9 and 10), although the storage stability was good, it was at 85 ° C. The epoxy reaction rate of was low and could not be cured sufficiently at 85 ° C.
本出願は、２０１８年４月２日出願の特願２０１８－０７０９６１号に基づく優先権を主張する。当該出願明細書に記載された内容は、すべて本願明細書に援用される。
This application claims priority based on Japanese Patent Application No. 2018-070961 filed on Apr. 2, 2018. All the contents described in the application specification are incorporated herein by reference.
本発明の表示素子用封止材は比較的低温で硬化が可能であり、さらには保存安定性に優れる。したがって、種々の表示素子の封止等に適用可能である。
The sealing material for display elements of the present invention can be cured at a relatively low temperature, and further has excellent storage stability. Therefore, the present invention can be applied to sealing various display elements.
The sealing material for display elements of the present invention can be cured at a relatively low temperature, and further has excellent storage stability. Therefore, the present invention can be applied to sealing various display elements.
Claims (10)
- （Ａ）下記一般式（１）で表されるエポキシ系化合物と、
（Ｃ）下記一般式（２）で表されるカチオン重合開始剤と、
Ｒ２は炭素数１～４のアルキル基を表す）
を含み、
前記（Ｂ）エポキシ樹脂の含有量が４５質量％以上である、
シート状エポキシ樹脂組成物。 (A) an epoxy compound represented by the following general formula (1);
(C) a cationic polymerization initiator represented by the following general formula (2);
R 2 represents an alkyl group having 1 to 4 carbon atoms)
Including
The content of the (B) epoxy resin is 45% by mass or more.
Sheet-like epoxy resin composition. - 前記（Ｂ）エポキシ樹脂のエポキシ当量が９００ｇ／ｅｑ以上である、
請求項１に記載のシート状エポキシ樹脂組成物。 The epoxy equivalent of the (B) epoxy resin is 900 g / eq or more,
The sheet-like epoxy resin composition according to claim 1. - 示差走査熱量計により測定される発熱開始温度が、６０℃以上９０℃以下であり、かつ８５℃で５０分加熱したときのエポキシ反応率が８０％以上である、
請求項１または２に記載のシート状エポキシ樹脂組成物。 The heat generation starting temperature measured by a differential scanning calorimeter is 60 ° C. or higher and 90 ° C. or lower, and the epoxy reaction rate when heated at 85 ° C. for 50 minutes is 80% or higher,
The sheet-like epoxy resin composition according to claim 1 or 2. - 溶融温度が３５℃以上６０℃以下であり、かつ
４０℃で１７時間保存後の溶融温度の変化が１０℃以内である、
請求項１～３のいずれか一項に記載のシート状エポキシ樹脂組成物。 The melting temperature is 35 ° C. or more and 60 ° C. or less, and the change in the melting temperature after storage at 40 ° C. for 17 hours is within 10 ° C.,
The sheet-like epoxy resin composition according to any one of claims 1 to 3. - 厚さ２０μｍのシート状エポキシ樹脂組成物を８５℃で５０分間硬化させたときの、波長５５０ｎｍの光の透過率が、９０％以上である、
請求項１～４のいずれか一項に記載のシート状エポキシ樹脂組成物。 When the sheet-shaped epoxy resin composition having a thickness of 20 μm is cured at 85 ° C. for 50 minutes, the light transmittance at a wavelength of 550 nm is 90% or more.
The sheet-like epoxy resin composition according to any one of claims 1 to 4. - 請求項１～５のいずれか一項に記載のシート状エポキシ樹脂組成物からなる層を含む、
封止用シート。 A layer comprising the sheet-like epoxy resin composition according to any one of claims 1 to 5,
Sealing sheet. - 前記シート状エポキシ樹脂組成物からなる層の少なくとも一方の面に、保護フィルムを有する、
請求項６に記載の封止用シート。 On at least one surface of the layer made of the sheet-like epoxy resin composition, a protective film is provided,
The sealing sheet according to claim 6. - 表示素子の面封止に用いられる、
請求項６または７に記載の封止用シート。 Used for surface sealing of display elements,
The sealing sheet according to claim 6 or 7. - 前記表示素子が有機ＥＬ素子である、
請求項８に記載の封止用シート。 The display element is an organic EL element;
The sealing sheet according to claim 8. - 請求項１～５のいずれか一項に記載のシート状エポキシ樹脂組成物の硬化物。
A cured product of the sheet-like epoxy resin composition according to any one of claims 1 to 5.
Priority Applications (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201980023888.1A CN111936543B (en) | 2018-04-02 | 2019-03-27 | Sheet-like epoxy resin composition, cured product thereof, and sealing sheet |
| KR1020207027243A KR102439370B1 (en) | 2018-04-02 | 2019-03-27 | Sheet-like epoxy resin composition and cured product thereof, and sheet for sealing |
| JP2020511716A JP7084472B2 (en) | 2018-04-02 | 2019-03-27 | Sheet-shaped epoxy resin composition and its cured product, and sealing sheet |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2018070961 | 2018-04-02 | ||
| JP2018-070961 | 2018-04-02 |
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| WO2019194041A1 true WO2019194041A1 (en) | 2019-10-10 |
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PCT/JP2019/013183 WO2019194041A1 (en) | 2018-04-02 | 2019-03-27 | Sheet-shaped epoxy resin composition and cured product thereof, and sheet for sealing |
Country Status (5)
| Country | Link |
|---|---|
| JP (1) | JP7084472B2 (en) |
| KR (1) | KR102439370B1 (en) |
| CN (1) | CN111936543B (en) |
| TW (1) | TW201942180A (en) |
| WO (1) | WO2019194041A1 (en) |
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| JP2013227420A (en) * | 2012-04-25 | 2013-11-07 | Hitachi Chemical Co Ltd | Circuit connection material, circuit connection structure, adhesion film and wound body |
| JP2014031465A (en) * | 2012-08-06 | 2014-02-20 | Dexerials Corp | Circuit connecting material |
| WO2015129670A1 (en) * | 2014-02-27 | 2015-09-03 | 積水化学工業株式会社 | Curable resin composition for sealing organic electroluminescent display element, curable resin sheet for sealing organic electroluminescent display element, and organic electroluminescent display element |
| JP2016179564A (en) * | 2015-03-23 | 2016-10-13 | 味の素株式会社 | Resin sheet |
| WO2017014037A1 (en) * | 2015-07-21 | 2017-01-26 | 古河電気工業株式会社 | Curable hygroscopic resin composition for sealing electronic device, resin cured product, and electronic device |
| WO2018235824A1 (en) * | 2017-06-23 | 2018-12-27 | 三井化学株式会社 | Image display device sealing material and image display device sealing sheet |
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| JP2003327951A (en) | 2002-05-10 | 2003-11-19 | Mitsui Chemicals Inc | Photo-setting resin composition for sealing material |
| JP4816863B2 (en) | 2004-12-22 | 2011-11-16 | 株式会社スリーボンド | Thermosetting composition for sealing organic EL elements |
| JP5288150B2 (en) | 2005-10-24 | 2013-09-11 | 株式会社スリーボンド | Thermosetting composition for sealing organic EL elements |
| WO2019065455A1 (en) * | 2017-09-29 | 2019-04-04 | 三井化学株式会社 | Image display device sealing material and image display device sealing sheet |
-
2019
- 2019-03-27 KR KR1020207027243A patent/KR102439370B1/en active IP Right Grant
- 2019-03-27 CN CN201980023888.1A patent/CN111936543B/en active Active
- 2019-03-27 WO PCT/JP2019/013183 patent/WO2019194041A1/en active Application Filing
- 2019-03-27 JP JP2020511716A patent/JP7084472B2/en active Active
- 2019-04-01 TW TW108111440A patent/TW201942180A/en unknown
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2013227420A (en) * | 2012-04-25 | 2013-11-07 | Hitachi Chemical Co Ltd | Circuit connection material, circuit connection structure, adhesion film and wound body |
| JP2014031465A (en) * | 2012-08-06 | 2014-02-20 | Dexerials Corp | Circuit connecting material |
| WO2015129670A1 (en) * | 2014-02-27 | 2015-09-03 | 積水化学工業株式会社 | Curable resin composition for sealing organic electroluminescent display element, curable resin sheet for sealing organic electroluminescent display element, and organic electroluminescent display element |
| JP2016179564A (en) * | 2015-03-23 | 2016-10-13 | 味の素株式会社 | Resin sheet |
| WO2017014037A1 (en) * | 2015-07-21 | 2017-01-26 | 古河電気工業株式会社 | Curable hygroscopic resin composition for sealing electronic device, resin cured product, and electronic device |
| WO2018235824A1 (en) * | 2017-06-23 | 2018-12-27 | 三井化学株式会社 | Image display device sealing material and image display device sealing sheet |
Also Published As
| Publication number | Publication date |
|---|---|
| TW201942180A (en) | 2019-11-01 |
| KR102439370B1 (en) | 2022-09-01 |
| KR20200125649A (en) | 2020-11-04 |
| JP7084472B2 (en) | 2022-06-14 |
| CN111936543A (en) | 2020-11-13 |
| CN111936543B (en) | 2023-06-30 |
| JPWO2019194041A1 (en) | 2021-02-12 |
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