WO2009093467A1 - エポキシ重合性組成物、それを含むシール材組成物 - Google Patents
エポキシ重合性組成物、それを含むシール材組成物 Download PDFInfo
- Publication number
- WO2009093467A1 WO2009093467A1 PCT/JP2009/000264 JP2009000264W WO2009093467A1 WO 2009093467 A1 WO2009093467 A1 WO 2009093467A1 JP 2009000264 W JP2009000264 W JP 2009000264W WO 2009093467 A1 WO2009093467 A1 WO 2009093467A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- epoxy
- compound
- polymerizable composition
- thiol
- cured product
- Prior art date
Links
- 239000004593 Epoxy Substances 0.000 title claims abstract description 251
- 239000000203 mixture Substances 0.000 title claims abstract description 193
- 239000003566 sealing material Substances 0.000 title claims description 26
- 239000002131 composite material Substances 0.000 title 1
- 150000001875 compounds Chemical class 0.000 claims abstract description 150
- -1 thiol compound Chemical class 0.000 claims abstract description 81
- 125000003396 thiol group Chemical group [H]S* 0.000 claims abstract description 41
- 238000007789 sealing Methods 0.000 claims description 70
- NIHNNTQXNPWCJQ-UHFFFAOYSA-N fluorene Chemical compound C1=CC=C2CC3=CC=CC=C3C2=C1 NIHNNTQXNPWCJQ-UHFFFAOYSA-N 0.000 claims description 69
- 239000000758 substrate Substances 0.000 claims description 36
- 230000003287 optical effect Effects 0.000 claims description 30
- 229910052717 sulfur Inorganic materials 0.000 claims description 29
- 239000011593 sulfur Substances 0.000 claims description 25
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 24
- 125000003700 epoxy group Chemical group 0.000 claims description 24
- 239000000463 material Substances 0.000 claims description 23
- 229920005989 resin Polymers 0.000 claims description 19
- 239000011347 resin Substances 0.000 claims description 19
- 230000035699 permeability Effects 0.000 claims description 16
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 15
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 claims description 14
- 229930185605 Bisphenol Natural products 0.000 claims description 12
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 12
- 125000004432 carbon atom Chemical group C* 0.000 claims description 9
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 9
- 238000010438 heat treatment Methods 0.000 claims description 8
- 125000000217 alkyl group Chemical group 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 7
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 4
- 125000004434 sulfur atom Chemical group 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 238000006116 polymerization reaction Methods 0.000 claims description 3
- 238000000034 method Methods 0.000 description 28
- 150000003573 thiols Chemical class 0.000 description 17
- 230000000052 comparative effect Effects 0.000 description 16
- 239000011342 resin composition Substances 0.000 description 14
- 229920000647 polyepoxide Polymers 0.000 description 11
- 238000006243 chemical reaction Methods 0.000 description 10
- 239000003822 epoxy resin Substances 0.000 description 9
- 125000003983 fluorenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3CC12)* 0.000 description 9
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 8
- 239000000853 adhesive Substances 0.000 description 8
- 230000001070 adhesive effect Effects 0.000 description 8
- 238000004132 cross linking Methods 0.000 description 8
- 238000000605 extraction Methods 0.000 description 7
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 238000002834 transmittance Methods 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 5
- 239000000945 filler Substances 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 239000003607 modifier Substances 0.000 description 5
- 230000005484 gravity Effects 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 230000000704 physical effect Effects 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 230000009257 reactivity Effects 0.000 description 4
- 239000003381 stabilizer Substances 0.000 description 4
- 125000001424 substituent group Chemical group 0.000 description 4
- 238000006467 substitution reaction Methods 0.000 description 4
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 4
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 3
- 239000000306 component Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 230000001771 impaired effect Effects 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- FDJWTMYNYYJBAT-UHFFFAOYSA-N 1,3,3-tris(sulfanylmethylsulfanyl)propylsulfanylmethanethiol Chemical compound SCSC(SCS)CC(SCS)SCS FDJWTMYNYYJBAT-UHFFFAOYSA-N 0.000 description 2
- XYXBMCIMPXOBLB-UHFFFAOYSA-N 3,4,5-tris(dimethylamino)-2-methylphenol Chemical compound CN(C)C1=CC(O)=C(C)C(N(C)C)=C1N(C)C XYXBMCIMPXOBLB-UHFFFAOYSA-N 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 239000010408 film Substances 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000001879 gelation Methods 0.000 description 2
- 230000009477 glass transition Effects 0.000 description 2
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 2
- 125000000654 isopropylidene group Chemical group C(C)(C)=* 0.000 description 2
- 239000004973 liquid crystal related substance Substances 0.000 description 2
- 238000004949 mass spectrometry Methods 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 2
- 230000002093 peripheral effect Effects 0.000 description 2
- 229920001228 polyisocyanate Polymers 0.000 description 2
- 239000005056 polyisocyanate Substances 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 150000004756 silanes Chemical class 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 150000003463 sulfur Chemical class 0.000 description 2
- WYYQKWASBLTRIW-UHFFFAOYSA-N 2-trimethoxysilylbenzoic acid Chemical compound CO[Si](OC)(OC)C1=CC=CC=C1C(O)=O WYYQKWASBLTRIW-UHFFFAOYSA-N 0.000 description 1
- XDLMVUHYZWKMMD-UHFFFAOYSA-N 3-trimethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C(C)=C XDLMVUHYZWKMMD-UHFFFAOYSA-N 0.000 description 1
- ULKLGIFJWFIQFF-UHFFFAOYSA-N 5K8XI641G3 Chemical compound CCC1=NC=C(C)N1 ULKLGIFJWFIQFF-UHFFFAOYSA-N 0.000 description 1
- 0 CC1(C=CC=CC11)c2cccc*2C11c2ccccc2*C(C=CC)=C1C=C Chemical compound CC1(C=CC=CC11)c2cccc*2C11c2ccccc2*C(C=CC)=C1C=C 0.000 description 1
- 239000002879 Lewis base Substances 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-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
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 229910052581 Si3N4 Inorganic materials 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- NOZAQBYNLKNDRT-UHFFFAOYSA-N [diacetyloxy(ethenyl)silyl] acetate Chemical compound CC(=O)O[Si](OC(C)=O)(OC(C)=O)C=C NOZAQBYNLKNDRT-UHFFFAOYSA-N 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 239000003242 anti bacterial agent Substances 0.000 description 1
- 230000003712 anti-aging effect Effects 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000012461 cellulose resin Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 description 1
- 125000001153 fluoro group Chemical class F* 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 150000002460 imidazoles Chemical class 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000013307 optical fiber Substances 0.000 description 1
- 239000012788 optical film Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 239000004038 photonic crystal Substances 0.000 description 1
- 239000004014 plasticizer 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
- 229920001155 polypropylene 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
- 239000003755 preservative agent Substances 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 238000007650 screen-printing Methods 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 125000006850 spacer group Chemical group 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229920000468 styrene butadiene styrene block copolymer Polymers 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- FRGPKMWIYVTFIQ-UHFFFAOYSA-N triethoxy(3-isocyanatopropyl)silane Chemical compound CCO[Si](OCC)(OCC)CCCN=C=O FRGPKMWIYVTFIQ-UHFFFAOYSA-N 0.000 description 1
- DQZNLOXENNXVAD-UHFFFAOYSA-N trimethoxy-[2-(7-oxabicyclo[4.1.0]heptan-4-yl)ethyl]silane Chemical compound C1C(CC[Si](OC)(OC)OC)CCC2OC21 DQZNLOXENNXVAD-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Images
Classifications
-
- 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
- C08G59/32—Epoxy compounds containing three or more epoxy groups
- C08G59/38—Epoxy compounds containing three or more epoxy groups together with di-epoxy compounds
-
- 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
- C08G59/20—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
- C08G59/226—Mixtures of di-epoxy compounds
-
- 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
- C08G59/40—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 curing agents used
- C08G59/4007—Curing agents not provided for by the groups C08G59/42 - C08G59/66
- C08G59/4064—Curing agents not provided for by the groups C08G59/42 - C08G59/66 sulfur containing compounds
-
- 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
- C08G59/40—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 curing agents used
- C08G59/66—Mercaptans
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B69/00—Dyes not provided for by a single group of this subclass
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J163/00—Adhesives based on epoxy resins; Adhesives based on derivatives of epoxy resins
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K3/00—Materials not provided for elsewhere
- C09K3/10—Materials in mouldable or extrudable form for sealing or packing joints or covers
-
- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
- G02F1/1333—Constructional arrangements; Manufacturing methods
- G02F1/1339—Gaskets; Spacers; Sealing of cells
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/02—Applications for biomedical use
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2666/00—Composition of polymers characterized by a further compound in the blend, being organic macromolecular compounds, natural resins, waxes or and bituminous materials, non-macromolecular organic substances, inorganic substances or characterized by their function in the composition
- C08L2666/02—Organic macromolecular compounds, natural resins, waxes or and bituminous materials
- C08L2666/14—Macromolecular compounds according to C08L59/00 - C08L87/00; Derivatives thereof
- C08L2666/22—Macromolecular compounds not provided for in C08L2666/16 - C08L2666/20
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K2102/00—Constructional details relating to the organic devices covered by this subclass
- H10K2102/301—Details of OLEDs
- H10K2102/302—Details of OLEDs of OLED structures
- H10K2102/3023—Direction of light emission
- H10K2102/3026—Top emission
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K50/00—Organic light-emitting devices
- H10K50/80—Constructional details
- H10K50/84—Passivation; Containers; Encapsulations
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K50/00—Organic light-emitting devices
- H10K50/80—Constructional details
- H10K50/84—Passivation; Containers; Encapsulations
- H10K50/842—Containers
- H10K50/8426—Peripheral sealing arrangements, e.g. adhesives, sealants
-
- 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
Definitions
- the present invention relates to an epoxy polymerizable composition, a transparent resin for optical materials and a sealing material composition containing the same, and an optical device having a sealing member made of a cured product thereof.
- Organic EL displays are expected as next-generation displays or lighting devices because of their low power consumption and low viewing angle dependency.
- the organic EL element has a problem that it is easily degraded by moisture and oxygen in the atmosphere. Therefore, the organic EL element is used after being sealed with a seal member.
- the method for sealing the organic EL element includes a method called “frame sealing” and a method called “surface sealing”.
- Frame sealing is a method in which a peripheral portion of a sealing cap is sealed with a sealing member in a structure in which a sealing cap is disposed on an organic EL element disposed on a substrate (Patent Document 1, etc.) See).
- the sealing cap is a plate-like member made of stainless steel or glass processed into a certain shape. Since this process requires a lot of labor, the method is not sufficiently productive.
- the sealing cap since a space is generated between the sealing cap and the organic EL element, the sealing cap is easily bent. Therefore, there is a problem that it is difficult to apply to the manufacture of a large organic EL panel.
- Surface sealing which is a method that can solve this problem, is a structure in which a sealing plate is arranged on an organic EL element arranged on a substrate, between the sealing plate and the substrate, and an organic EL element.
- a space existing between the sealing plate and the sealing plate is filled with a sealing material composition and sealed (see Patent Document 2).
- Patent Document 2 since it is not necessary to process the sealing cap, there is an advantage that the sealing plate is not bent because the productivity is excellent and there is no space inside the sealing plate.
- the sealing member for surface sealing is disposed in the space formed between the organic EL element and the sealing plate, it needs to have a high refractive index (small difference in refractive index from the transparent cathode electrode). (Especially elements with a top emission structure). This is because if the refractive index of the sealing member is low, total reflection occurs between the cathode electrode and the sealing member, and the extraction efficiency of light emission from the organic EL element decreases.
- a sealing material composition for producing a surface-sealing seal member is also required to have a low curing shrinkage rate. This is because if the cure shrinkage rate is high, a fine gap is formed between the sealing member, which is a cured product, and the substrate due to internal stress, adhesive strength is lowered, and moisture permeability resistance is further lowered.
- a sealing material composition for producing a surface-sealing seal member is required to be liquid at a temperature near room temperature. If the sealing material composition is not liquid at a temperature near room temperature, workability is poor, and it is necessary to heat and seal the sealing material composition when sealing the organic EL element. In that case, since heat distortion of the display member occurs, it may not be sufficiently sealed. Further, when the sealing material composition is heated, the curing reaction proceeds and the viscosity tends to become unstable.
- an epoxy resin composition suitable for optical use for example, an epoxy resin composition containing an epoxy resin having a fluorene skeleton and an acid anhydride has been proposed (see Patent Document 3). Since this epoxy resin composition includes an epoxy resin having a fluorene skeleton in the molecular structure, the cured product is said to have excellent heat resistance and high transparency. Moreover, from the composition of the epoxy resin composition, the cured product is considered to have a high refractive index of about 1.63. However, this epoxy resin composition has a high softening point and is solid at room temperature. For this reason, when using this epoxy resin composition as a sealing material composition, there existed a problem that workability
- a photocurable adhesive composition suitable for bonding optical parts a photocurable adhesive composition containing a thiol compound and an epoxy compound has been proposed (see Patent Document 4). Since this photocurable adhesive composition contains a large amount of elemental sulfur, the cured product is said to have a high refractive index. In addition, the photocurable adhesive composition does not have a rigid molecular structure like a fluorene skeleton, and thus has a low softening point and excellent workability at room temperature, but has a problem of low heat resistance. .
- a sulfur-containing urethane resin containing a polyisocyanate compound and a thiol compound has been proposed as a resin suitable for lens applications (see Patent Document 5, etc.). Since this sulfur-containing urethane resin contains a large amount of sulfur element, the cured product has a high refractive index and is said to have a certain heat resistance by containing a polyisocyanate compound. Furthermore, since this sulfur-containing urethane resin has a low softening point, it is said that it is excellent in workability
- Patent Document 6 Japanese Patent Laid-Open No. 11-45778 JP 2001-357773 A JP-A-2005-41925 JP 2004-35857 A JP-A-2-270869 Japanese Patent Laid-Open No. 10-60397
- a sealing member of a surface-sealing type organic EL element (particularly an organic EL element having a top emission structure) is required to have a high refractive index and high heat resistance.
- the resin composition for producing the seal member is required to have low curing shrinkage and high workability.
- a seal member that sufficiently satisfies these performances or a resin composition for producing the seal member has not been proposed.
- the present invention is a resin composition having low curing shrinkage and high workability, and a cured product having a high refractive index and high heat resistance; It is an object of the present invention to provide a composition having a high refractive index as a cured resin composition.
- the sealing member for sealing elements of optical equipment and precision equipment particularly the sealing member of the surface sealing type organic EL element (particularly the organic EL element having a top emission structure) has a high refractive index, Low moisture permeability is required.
- a seal member that sufficiently satisfies this performance and a resin composition for producing the seal member have not been proposed.
- the present invention is a composition having a low moisture permeability, a cured product having a high refractive index and a high heat resistance; in particular, a composition in which the cured product has a low moisture permeability and a high refractive index. The purpose is to provide.
- the first of the present invention relates to an epoxy polymerizable composition shown below, a transparent resin for optical materials containing the same, or a cured product thereof.
- R 4 each independently represents an alkyl group having 1 to 5 carbon atoms; n represents each independently an integer of 0 to 3; m represents each independently an integer of 1 to 3; p represents each independently an integer of 0 to 4; q represents each independently an integer of 0 to 4] [Wherein Y represents a single bond, an oxygen atom or a sulfur atom; R 1 to R 4 , m, n, p, and q are defined in the same manner as in the general formula (1)] (A3) 30 An epoxy polymerizable composition comprising an epoxy compound having a softening point of 0 ° C. or less and (B1) a thiol compound having two or more thiol groups in one molecule.
- a transparent resin for optical materials comprising the epoxy polymerizable composition according to any one of [1] to [7].
- [9] A sealing material composition comprising the epoxy polymerizable composition according to any one of [1] to [7].
- [10] A cured product obtained by curing the transparent resin for optical materials according to [8]. [11] The cured product according to [10], wherein the refractive index is 1.64 or more. [12] The step of heating and mixing the (A2) fluorene type epoxy compound and the (A3) epoxy compound, and the mixture of the epoxy compound obtained in the step and the (B1) thiol compound are mixed at 30 ° C. or less. A process for producing an epoxy polymerizable composition according to any one of [1] to [7].
- the second of the present invention relates to the following epoxy polymerizable composition, a transparent resin for optical materials containing the same, or a cured product thereof.
- (A1) An epoxy compound having two or more epoxy groups in one molecule, (B2) a thiol compound having four or more thiol groups in one molecule, and (C) a curing accelerator.
- An epoxy polymerizable composition comprising.
- (B2) The epoxy polymerizable composition according to [13], further comprising (D) a silane coupling agent.
- the epoxy polymerizable composition according to any one of [13] to [15], wherein the (A1) epoxy compound is a fluorene type epoxy compound.
- the content of the component (A1) is 100 to 300 parts by mass and the content of the component (C) is 0.02 to 40 parts by mass with respect to 100 parts by mass of the component (B2).
- the content of the component (D) is 0.02 to 40 parts by mass, and the molar ratio of the epoxy group to the thiol group is 1: 0.9 to 1.1.
- the epoxy polymerizable composition according to any one of the above.
- [21] A cured product obtained by curing the transparent resin for optical materials according to [19].
- [22] The cured product according to [21], which has a refractive index of 1.64 or more.
- the third of the present invention relates to the following optical device and organic EL panel.
- An optical device comprising the cured product according to any one of [10], [11] and [21] to [23].
- An organic EL panel including a sealing member filled in a space formed therebetween, wherein the sealing member is any one of [10], [11], and [21] to [23]
- the epoxy polymerizable composition provided by the present invention has low cure shrinkage and high workability. Further, when an optical device, particularly an organic EL element having a top emission structure, is sealed using the epoxy polymerizable composition, the light extraction efficiency can be increased. In addition, when an organic EL device having a top emission structure is sealed using the epoxy polymerizable composition provided by the present invention, not only the light extraction efficiency can be improved, but also the penetration of moisture into the device can be suppressed. .
- Epoxy polymerizable composition The cured product of the epoxy polymerizable composition of the present invention is preferably transparent.
- transparent may be at least transparent enough to be used as a sealing member or an optical material through which light from an optical device passes.
- the epoxy polymerizable composition of the present invention contains (A) an epoxy compound, (B) a thiol compound, and, if necessary, other optional components (for example, (C) a curing accelerator).
- the epoxy polymerizable composition of the present invention is roughly classified into two.
- the first epoxy polymerizable composition of the present invention has high workability at room temperature and gives a cured product having a high refractive index.
- the first epoxy polymerizable composition comprises (A2) a fluorene type epoxy compound represented by the general formula (1) or (2), (A3) an epoxy compound having a softening point of 30 ° C. or less, and (B1) And a thiol compound having two or more thiol groups in one molecule.
- Fluorene type epoxy compound can increase the refractive index of the cured product of the resin composition containing the fluorene type epoxy compound. Moreover, since fluorene is a rigid aromatic group, the cured product of the resin composition containing a fluorene type epoxy compound is considered to have high heat resistance.
- the softening point of the fluorene type epoxy compound is preferably 50 ° C. to 200 ° C., and more preferably 80 ° C. to 160 ° C. This is for improving the workability of the composition of the present invention and enhancing the heat resistance of the cured product.
- the fluorene type epoxy compound is represented by the general formula (1) or (2).
- R 1 in the general formula (1) independently represents a hydrogen atom or a methyl group, and is preferably a hydrogen atom in order to increase the reactivity of the epoxy group. “Independently” means that two or more R 1 present in a compound may be the same or different (the same applies hereinafter).
- R 2 in the general formula (1) is independently a hydrogen atom or a methyl group, but R 2 is preferably a hydrogen atom because of excellent reactivity of the epoxy group.
- N in the general formula (1) represents the number of repeating alkylene ether units.
- n is each independently an integer of 0 to 3. Since the softening point of a compound falls, so that n is large, workability
- m represents the number of substitutions of the epoxy group-containing substituent, and each independently represents an integer of 1 to 3.
- the “epoxy group-containing substituent” means a substituent containing an epoxy group that is substituted on a benzene ring.
- m is preferably 1.
- P in the general formula (1) represents the number of substitutions of R 3 and is independently an integer of 0 to 4.
- p is preferably 0 or 1, and more preferably 0.
- R 3 in the general formula (1) independently represents an alkyl group having 1 to 5 carbon atoms. When the number of carbon atoms is large, the softening point is lowered and the workability is improved. However, since the heat resistance and refractive index of the cured product may be too low, R 3 is preferably a methyl group.
- Q in the general formula (1) represents the number of substitutions of R 4 and is each independently an integer of 0 to 4.
- q is preferably 0 or 1, and more preferably 0.
- R 4 in the general formula (1) independently represents an alkyl group having 1 to 5 carbon atoms. When the number of carbon atoms is large, the softening point is lowered and the workability is improved. However, since the heat resistance and refractive index of the cured product may be too low, R 4 is preferably a methyl group.
- Y in the general formula (2) represents a single bond, an oxygen atom or a sulfur atom.
- R 1 to R 4 , m, n, p, and q in the general formula (2) are defined in the same manner as in the general formula (1).
- the compound represented by the general formula (2) has a rigid molecular structure as compared with the molecular structure of the compound represented by the general formula (1). Therefore, the heat resistance of the cured product of the compound represented by the general formula (2) is increased. In particular, when Y is a single bond, the heat resistance of the cured product is significantly improved, but the softening point becomes too high and workability may be reduced. On the other hand, when Y is an oxygen atom or a sulfur atom, the above balance is excellent.
- the fluorene type epoxy compound can be obtained, for example, by reacting phenol having a fluorene skeleton with epichlorohydrin (also referred to as “3-chloro-1,2-epoxypropane”) by a known method.
- epichlorohydrin also referred to as “3-chloro-1,2-epoxypropane”
- a desired epoxy compound can be synthesized by appropriately selecting the structure of a phenol having epichlorohydrin and a fluorene skeleton.
- R 1 in the general formula (1) can be appropriately changed by using an epichlorohydrin derivative instead of epichlorohydrin as a raw material.
- an epichlorohydrin derivative having a methyl group substituted at the 2-position of 3-chloro-1,2-epoxypropane is used as a raw material
- a fluorene type epoxy compound in which R 1 in the general formula (1) is a methyl group can be synthesized. .
- Phenol having a fluorene skeleton can be synthesized according to the method described in JP-A-2001-206862. If a phenol skeleton having a fluorene skeleton is selected, m, R 3 and p in the general formula (1) can be appropriately changed.
- A3 Epoxy compound having a softening point of 30 ° C. or lower An epoxy compound having a softening point of 30 ° C. or lower (preferably 25 ° C. or lower) can further improve the workability of the epoxy polymerizable composition.
- the softening point is measured by the ring and ball method (according to JIS K7234).
- the epoxy compound having a softening point of 30 ° C. or lower is not particularly limited, but may be a bisphenol type epoxy compound.
- the bisphenol type epoxy compound preferably has two or more epoxy groups in the molecule.
- a cured product of the resin composition containing such a compound has a high crosslinking density and excellent heat resistance.
- the bisphenol type epoxy compound is more preferably a compound represented by the following general formula (3).
- X represents a single bond, a methylene group, an isopropylidene group, —S—, or —SO 2 —.
- a bisphenol F type epoxy compound or a bisphenol A type epoxy compound in which X is a methylene group or an isopropylidene group is a liquid at room temperature. Therefore, since it is easy to dissolve a fluorene type epoxy compound, it is preferable to use it mixed with a fluorene type epoxy compound. In particular, a bisphenol F type epoxy compound is preferable.
- p is the number of substitutions of the substituent R 10 and is an integer of 0 to 4. From the viewpoint of heat resistance and moisture permeability resistance, p is preferably 0.
- Each R 10 is independently an alkyl group having 1 to 5 carbon atoms, preferably a methyl group.
- the bisphenol type epoxy compound can be synthesized by a reaction between bisphenol and epichlorohydrin.
- the structure of the bisphenol-type epoxy compound to be synthesized can be adjusted by appropriately changing the structure of the bisphenol used as a raw material.
- the thiol compound has two or more thiol groups in one molecule.
- the (B1) thiol compound can act as a curing agent for (A2) a fluorene type epoxy compound and (A3) an epoxy compound having a softening point of 30 ° C. or less.
- the thiol group of (B1) thiol compound reacts with the epoxy group of (A2) fluorene type epoxy compound, or (A3) the epoxy group of an epoxy compound having a softening point of 30 ° C. or lower.
- a cured product excellent in heat resistance, adhesive strength, and the like can be obtained by crosslinking reaction with each other.
- the compound having two or more thiol groups in one molecule is not particularly limited.
- the number of thiol groups is large, the cross-linked density of a cured product of the resulting epoxy compound (hereinafter also simply referred to as “cured product”) is improved, so that the heat resistance of the cured product is improved.
- the number of thiol groups is too large, the thiol groups are close to each other in the molecule of the thiol compound and steric hindrance is likely to occur, and the reactivity with the epoxy group is lowered.
- cured material will fall.
- the content of thiol groups in the molecule is represented by thiol equivalent (g / eq).
- the thiol equivalent of the thiol compound is 80 to 100 g / eq, preferably 85 to 95 g / eq, more preferably 86 to 92 g / eq.
- the thiol equivalent is a value obtained by dividing the molecular weight of (B1) thiol compound by the number of thiol groups contained in the molecule.
- the thiol equivalent is less than 80 g / eq, the distance between the cross-linking points of the cured product is shortened, so that the reactivity with the epoxy group is lowered and the conversion rate may not be increased.
- the thiol equivalent exceeds 100 g / eq, the distance between the crosslinking points of the cured product becomes too long, and the heat resistance of the cured product may be reduced.
- the thiol compound containing sulfur element in the molecule increases the refractive index of the cured product of the epoxy polymerizable composition. Therefore, the sulfur content of the (B1) thiol compound in the epoxy polymerizable composition is 50 to 80%, preferably 60 to 75%.
- the sulfur content is determined from the ratio of each element obtained by mass spectrometry of the thiol compound (the ratio of sulfur element to all elements). When the sulfur content is less than 50%, the refractive index of the cured product of the resin composition containing the sulfur content may not be sufficiently increased.
- the cured product of the resin composition containing the thiol compound since many thiol compounds having a sulfur content exceeding 80% contain an SS bond in the molecule, the cured product of the resin composition containing the thiol compound generates radicals or has chemical stability. May be inferior.
- the molecular weight of the thiol compound is preferably 140 to 500. (B1) If the molecular weight of the thiol compound is high, the viscosity may be too high or uniform curing may not be achieved. The molecular weight may be obtained by mass spectrometry.
- the thiol compound is not particularly limited as long as the thiol equivalent and the sulfur content are within the above ranges.
- Specific examples of (B1) thiol compounds include compounds represented by the following formulas (4), (5) and (6).
- the compounds represented by the formulas (4), (5) and (6) can be synthesized by known methods, but are also commercially available.
- the thiol equivalent of the compound of formula (4) is 87 g / eq and the sulfur content is 62%; the thiol equivalent of the compound of formula (5) is 91 g / eq and the sulfur content is 61%;
- the compound has a thiol equivalent of 89 g / eq and a sulfur content of 72%.
- the first epoxy polymerizable composition 20 to 100 parts by mass (preferably 20 to 70 parts by mass) of (A3) an epoxy compound having a softening point of 30 ° C. or lower with respect to 100 parts by mass of (A2) fluorene type epoxy compound. Part).
- (A2) Fluorene type epoxy compounds are often solid at room temperature, and (A3) epoxy compounds having a softening point of 30 ° C. or lower are often liquid at room temperature.
- the viscosity of the epoxy polymerizable composition is adjusted to an appropriate range (specifically, 0.1 to 100 Pa ⁇ s).
- the content of the thiol compound is preferably determined by the molar ratio between the thiol group contained in the composition and the epoxy group. This is because it acts as a curing agent for the epoxy compound. That is, when an thiol group is excessively contained in the epoxy polymerizable composition, a thiol group that cannot react with the epoxy group remains in the cured product. For this reason, when the sealing member is used, the member to be sealed may be contaminated. On the other hand, when the thiol group is too small, the crosslinking density cannot be sufficiently increased, and the heat resistance of the obtained cured product may be lowered.
- composition ratio of (A2), (A3) and (B1) in the composition is not limited to these.
- the hardening accelerator may be contained in the 1st epoxy polymerizable composition.
- Examples of the curing accelerator include imidazole compounds and amine compounds. Examples of the imidazole compound include 2-ethyl-4-methylimidazole, and examples of the amine compound include trisdimethylaminomethylphenol.
- the curing accelerator may be a Lewis base compound.
- the content of the (C) curing accelerator in the first epoxy polymerizable composition is based on 100 parts by mass of the total amount of (A2) a fluorene type epoxy compound and (A3) an epoxy compound having a softening point of 30 ° C. or less.
- the amount is preferably 0.1 to 5 parts by mass. This is because the epoxy polymerizable composition has an excellent balance between curability and storage stability.
- the (D) silane coupling agent may be contained in the first epoxy polymerizable composition.
- the epoxy polymerizable composition containing a silane coupling agent has high adhesion to the substrate when it is used as a sealing material composition for organic EL.
- Examples of silane coupling agents include silane compounds having reactive groups such as epoxy groups, carboxyl groups, methacryloyl groups, and isocyanate groups.
- silane compounds include trimethoxysilylbenzoic acid, ⁇ -methacryloxypropyltrimethoxysilane, vinyltriacetoxysilane, vinyltrimethoxysilane, ⁇ -isocyanatopropyltriethoxysilane, ⁇ -glycidoxypropyltrimethoxy.
- Silane, ⁇ - (3,4-epoxycyclohexyl) ethyltrimethoxysilane and the like are included.
- the silane coupling agent may be a single type or a combination of two or more types.
- the content of the (D) silane coupling agent in the first epoxy polymerizable composition is preferably 0.05 to 30 parts by mass with respect to 100 parts by mass of the epoxy polymerizable composition, and 0.3 to The amount is more preferably 20 parts by mass, and further preferably 0.1 to 10 parts by mass.
- the first epoxy polymerizable composition may further contain optional components such as other resin components, fillers, modifiers, stabilizers and the like as long as the effects of the present invention are not impaired. it can.
- other resin components include polyamide, polyamideimide, polyurethane, polybutadiene, polychloroprene, polyether, polyester, styrene-butadiene-styrene block copolymer, petroleum resin, xylene resin, ketone resin, cellulose resin, fluorine series Oligomer, silicon oligomer and polysulfide oligomer are included. These 1 type can be contained individually or in combination of multiple types.
- the filler examples include glass beads, styrene polymer particles, methacrylate polymer particles, ethylene polymer particles, and propylene polymer particles.
- the filler may be a combination of a plurality of types.
- modifiers include polymerization initiation aids, anti-aging agents, leveling agents, wettability improvers, surfactants, plasticizers, and the like. You may use these in combination of multiple types.
- stabilizer include ultraviolet absorbers, preservatives, and antibacterial agents.
- the modifier may be a combination of a plurality of types.
- the first epoxy polymerizable composition can be quickly cured. This is to improve workability when sealing a sealing material such as an organic EL element. “Cure quickly” means, for example, curing within 120 minutes under heating conditions ( ⁇ 100 ° C.).
- Whether or not the epoxy polymerizable composition is cured may be determined by confirming with a finger whether the cured product is cured on a hot plate and gelled. Whether the epoxy polymerizable composition is cured may be determined from the conversion rate of the epoxy group. The conversion rate of the epoxy group can be calculated from the calorific value of the uncured exothermic peak by thermally analyzing the epoxy polymerizable composition before and after the curing reaction by DSC. It is easier to check whether or not gelation has occurred by finger touch.
- the curability of the first epoxy polymerizable composition is, for example, a composition ratio of (A2) a fluorene type epoxy compound and (A3) a mixture of epoxy compounds having a softening point of 30 ° C. or less, and (B1) a thiol compound, It is controlled by adjusting the content of the (C) curing accelerator as necessary.
- the viscosity of the first epoxy polymerizable composition at 25 ° C. is preferably 0.1 to 100 Pa ⁇ s, preferably 0.2 to 70 Pa ⁇ s, and 0.5 to 40 Pa ⁇ s. More preferably, it is 1 to 10 Pa ⁇ s.
- An epoxy polymerizable composition having a viscosity in this range is excellent in workability.
- the viscosity is measured with an E-type viscometer (RC-500 manufactured by Toki Sangyo Co., Ltd.) at a measurement temperature of 25 ° C.
- the first epoxy polymerizable composition preferably has a small curing shrinkage.
- the cure shrinkage is preferably 10% or less, and more preferably 8% or less.
- the curing shrinkage rate can be determined by applying the specific gravity of the composition before curing and the specific gravity of the cured product after curing to the following formula.
- the refractive index of the cured product of the first epoxy polymerizable composition is preferably more than 1.60, and more preferably 1.64 or more.
- the refractive index refers to a value measured with sodium D line (589 nm). Although the refractive index can be measured by a known method, it can generally be measured by a critical angle method using an Abbe refractometer.
- the extraction efficiency of light emitted from the organic EL element is enhanced. That is, in the organic EL element having the top emission structure, a transparent cathode electrode layer such as ITO is disposed on the organic EL layer. Since the refractive index of ITO is about 1.8, if the refractive index of the seal member disposed on the cathode electrode layer is too low, the extraction efficiency of light emitted from the organic EL element is lowered.
- the cured product of the epoxy polymerizable composition is preferably transparent in the visible light region. Transparency can be evaluated by light transmittance using an ultraviolet / visible spectrophotometer.
- the light transmittance of the cured product of the present invention is more preferably 90% or more at 450 nm. This is for improving the display properties when used as a sealing member of an optical device (including an organic EL element).
- the first epoxy polymerizable composition contains (A3) an epoxy compound having a softening point of 30 ° C. or lower. Therefore, a mixture of (A2) a fluorene type epoxy compound (having a relatively high softening point) and (A3) an epoxy compound having a softening point of 30 ° C. or lower is uniform with each other without impairing fluidity even at 30 ° C. or lower. Can dissolve. Moreover, since an epoxy compound and a thiol compound can be mixed even at 30 ° C. or lower, a curing reaction does not occur, and workability at room temperature is excellent.
- the second epoxy polymerizable composition of the present invention can be a cured product having a particularly high refractive index and low moisture permeability.
- the second epoxy polymerizable composition includes (A1) an epoxy compound having two or more epoxy groups in the molecule, (B2) a thiol compound having four or more thiol groups in the molecule, and (C) curing.
- An accelerator but may contain other optional components. Examples of the optional component include the aforementioned (D) silane coupling agent.
- (A1) Epoxy Compound The (A1) epoxy compound contained in the second epoxy polymerizable composition has two or more epoxy groups in one molecule.
- the (A1) epoxy compound is crosslinked and cured by the (B2) thiol compound.
- a part or all of the epoxy compound may be (A2) a fluorene type epoxy compound containing a fluorene skeleton in its molecular structure.
- (A2) fluorene type epoxy compounds include the compounds represented by the aforementioned general formulas (1) and (2).
- the part or all of the (A1) epoxy compound contained in the second epoxy polymerizable composition may be (A3) an epoxy compound having a softening point of 30 ° C. or lower (preferably 25 ° C. or lower).
- (A3) Examples of the epoxy compound having a softening point of 30 ° C. or lower (preferably 25 ° C. or lower) include the bisphenol type epoxy compound represented by the general formula (3).
- the second epoxy polymerizable composition preferably contains an epoxy compound having a softening point of 30 ° C. or less for obtaining fluidity at room temperature.
- the (B2) thiol compound contained in the second epoxy polymerizable composition has four or more thiol groups in one molecule.
- the (B2) thiol compound can act as a curing agent for the (A1) epoxy compound. That is, the thiol group of the (B2) thiol compound reacts with the epoxy group of the (A1) epoxy compound, thereby cross-linking the (A1) epoxy compounds to obtain a cured product having excellent heat resistance and adhesive strength. be able to.
- (B2) thiol compound contains four or more thiol groups in one molecule, the crosslinking density of the cured product of the epoxy resin is increased and the moisture permeability is decreased.
- the thiol equivalent of the thiol compound is 80 to 100 g / eq, preferably 85 to 95 g / eq, and more preferably 86 to 92 g / eq.
- the molecular weight of the (B2) thiol compound is preferably 140 to 500 as described above.
- the (B2) thiol compound examples include the compounds represented by the above formulas (5) and (6).
- the (B2) thiol compound may have 5 or more thiol groups.
- the (C) curing accelerator contained in the second epoxy polymerizable composition has a function of adjusting the balance between curability and storage stability of the epoxy polymerizable composition.
- Examples of the (C) curing accelerator include those similar to the (C) curing accelerator as described above.
- the second epoxy polymerizable composition may contain (D) a silane coupling agent.
- Examples of (D) silane coupling agents include those similar to (D) silane coupling agents similar to those described above.
- the content of the (A1) epoxy compound in the second epoxy polymerizable composition is preferably 100 to 300 parts by mass with respect to 100 parts by mass of (B2) thiol compound.
- the second epoxy polymerizable composition comprises (A3) softening at 30 ° C. or less of 20 to 100 parts by mass (preferably 20 to 70 parts by mass) with respect to 100 parts by mass of (A2) fluorene type epoxy compound. It is preferable that the epoxy compound which has a point is included. This is for appropriately adjusting the viscosity of the epoxy polymerizable composition.
- the content of the (C) curing accelerator in the second epoxy polymerizable composition is preferably 0.02 to 40 parts by mass with respect to 100 parts by mass of (B2) thiol compound. Further, the amount is preferably 0.1 to 5 parts by mass with respect to 100 parts by mass in total of (B2) thiol compound and (A1) epoxy compound.
- the content of (D) the silane coupling agent in the second epoxy polymerizable composition is preferably 0.02 to 40 parts by mass with respect to 100 parts by mass of (B2) thiol compound.
- the content of (D) the silane coupling agent is preferably 0.05 to 30 parts by mass and preferably 0.1 to 20 parts by mass with respect to 100 parts by mass of (B2) thiol compound. More preferably, it is 0.3 to 10 parts by mass.
- the second epoxy polymerizable composition may further contain optional components such as other resin components, fillers, modifiers, stabilizers and the like as long as the effects of the present invention are not impaired. it can. Specific examples of other resin components, fillers, modifiers, stabilizers, and the like and the content in the epoxy polymerizable composition are the same as described above.
- the second epoxy polymerizable composition can be quickly cured as described above.
- the curability of the second epoxy polymerizable composition is controlled, for example, by adjusting the composition ratio of (A1) epoxy compound and (B2) thiol compound and (C) the content of the curing accelerator. .
- the viscosity of the second epoxy polymerizable composition at 25 ° C. is preferably 0.1 to 100 Pa ⁇ s.
- the curability and viscosity of the second epoxy polymerizable composition can be measured in the same manner as described above.
- the cured product of the second epoxy polymerizable composition preferably has a high refractive index exceeding 1.60 (preferably 1.64 or more), as described above. Further, the cured product preferably has a high light transmittance of 90% or more at 450 nm, as described above. Further, the curing shrinkage rate of the cured product is preferably 10% or less, more preferably 8% or less, as described above. The refractive index, light transmittance and cure shrinkage of the cured product can be measured in the same manner as described above.
- the cured product of the thickness of 100 [mu] m, JIS Z0208 60 ° C. conforming to moisture permeability in 90% RH is preferably not more than 20g / m 2 / 24h, more preferably at most 15g / m 2 / 24h.
- the second epoxy polymerizable composition contains a thiol compound having four or more thiol groups in one molecule. For this reason, a hardened
- the epoxy polymerizable composition of the present invention can be produced by any method as long as the effects of the invention are not impaired.
- the epoxy polymerizable composition includes 1) a step of preparing (A) an epoxy compound, 2) a step of mixing (A) the epoxy compound and (B) a thiol compound at a temperature at which no curing reaction occurs, It is manufactured by the method containing. Mixing includes a method in which these components are charged into a flask and agitated, and a method in which the components are kneaded with three rolls.
- the epoxy polymerizable composition containing (C) a curing accelerator, or (E) other optional component is, after 2) step, 3) (C) a step of mixing with a curing accelerator, or 4) (E) other optional. And a step of mixing with the components.
- step 1) when (A) the epoxy compound contains a large amount of an epoxy compound having a high softening point (for example, a fluorene type epoxy compound having a softening point of 50 ° C. or higher), the epoxy compound is heated under a heating condition (for example, 60 ° C. or higher). It is preferable to mix the compounds.
- an epoxy compound having a high softening point for example, a fluorene type epoxy compound having a softening point of 50 ° C. or higher
- the epoxy compound is heated under a heating condition (for example, 60 ° C. or higher). It is preferable to mix the compounds.
- step 2) (A) epoxy compound and (B) thiol compound are mixed, for example, under non-heating conditions (30 ° C. or lower), and (A) epoxy compound and (B) thiol compound curing reaction. It is preferable to suppress the progress (gelation, etc.) of (C) It is preferable that a hardening accelerator is similarly mixed at 30 degrees C or less.
- the (A) epoxy compound contains (A3) an epoxy compound having a softening point of 30 ° C. or lower because it is easy to mix with the (B) thiol compound under non-heating conditions.
- the epoxy polymerizable composition of this invention can be used as a sealing member especially by hardening
- the seal member include organic EL panels, liquid crystal displays, LEDs, seal members for electronic paper use; solar cells, seal members for CCD use, and the like.
- the optical material include an optical adhesive, an optical film, a hologram material, a photonic crystal, a diffraction grating, a prism, a refractive index distribution lens, an optical fiber, and an optical waveguide film.
- the epoxy polymerizable composition of the present invention is preferably used as, for example, a sealing material composition (or a transparent resin composition for optical materials) that serves as a sealing member of a light emitting device (in particular, an organic EL device having a top emission structure).
- the sealing material composition of the present invention is useful as a composition for producing a sealing member of an organic EL element having a top emission structure. That is, the organic EL panel of the present invention is interposed between the display substrate on which the organic EL element is disposed, the counter substrate paired with the display substrate, the display substrate and the counter substrate, and seals the organic EL element. And a sealing member.
- a sealing member that exists on the peripheral edge of the counter substrate is referred to as a frame-sealed organic EL panel.
- a sealing member filled in a space formed between an organic EL element and a counter substrate is called a surface-sealing type organic EL panel. Since the cured product has a high refractive index, the sealing material composition of the present invention is particularly suitable for producing a surface-sealing type sealing member of an organic EL panel having a top emission structure.
- FIG. 1 is a cross-sectional view schematically showing a surface-sealing type organic EL element having a top emission structure.
- 1 is a sealing member; 20 is an organic EL layer; 21 is a cathode transparent electrode layer (made of ITO, IZO, etc.); 22 is an anode reflective electrode layer (made of aluminum, silver, etc.) 30 is a display substrate; 31 is a counter substrate (sealing plate).
- the substrate is usually made of glass.
- the sealing member 1 in FIG. 1 is a cured product of the above-described sealing material composition.
- the cathode transparent electrode layer 21 may be made of silicon oxide, silicon nitride, or the like and covered with a protective film.
- organic EL panel using a cured product of the sealing material composition of the present invention as a sealing member can be produced by any method.
- the organic EL panel of the present invention is paired on 1) a step of applying a sealing material composition to a display substrate on which organic EL elements are arranged, and 2) on a display substrate on which the sealing material composition is applied. It can be manufactured by a method including a step of obtaining a laminate by superimposing a counter substrate (sealing plate), and a step of curing a sealing material composition of the obtained laminate. Each step may be performed according to a known method. Examples of the method of applying the sealing material composition include screen printing and a method using a dispenser. The curing step is preferably performed at 25 to 100 ° C. for 0.1 to 2 hours.
- the organic EL panel of the present invention is 1) a step of obtaining a laminate in which a display substrate on which organic EL elements are arranged and a counter substrate (sealing plate) paired with the substrate are overlapped with a spacer. It may be produced by a method including 2) a step of filling a sealing material composition between the display substrate and the counter substrate of the obtained laminate, and 3) a step of curing the filled sealing material composition.
- the compound is represented by the following formula (7).
- the softening point of the compound was 91.5 ° C., and the epoxy value was 3.89 eq / kg (epoxy equivalent 257 g / eq).
- Bisphenol type epoxy compound YL-983U (manufactured by Japan Epoxy Resin Co., Ltd.)
- the compound is a bisphenol F type epoxy compound.
- the compound was liquid at room temperature and the epoxy equivalent was 169 g / eq.
- 1,1,3,3-tetrakis (mercaptomethylthio) propane (Mitsui Chemicals)
- the compound represented by the following formula (6) is described in Japanese Patent No. 399427.
- the molecular weight of the compound is 356. Since the compound has four thiol groups in the molecule, the thiol equivalent is 89.0 g / eq.
- the sulfur content of the compound is 71.9%.
- FSH (Mitsui Chemicals)
- the compound represented by the following formula (5) is described in Japanese Patent No. 3444682.
- the molecular weight of the compound is 366. Since the compound has four thiol groups in the molecule, the thiol equivalent is 91.5 g / eq.
- the sulfur content of the compound is 61.2%.
- Curing accelerator 2E4MZ (2-ethyl-4-4methylimidazole) (manufactured by Shikoku Chemicals) JER Cure 3010 (Trisdimethylaminomethylphenol) (Japan Epoxy Resin Co., Ltd.)
- Example 1 50 parts by mass of YL-983U and 50 parts by mass of PG-100 were charged into the flask and mixed while heating. To this, 44.2 parts by mass of the compound represented by formula (4) (hereinafter referred to as “GST”) was added and mixed at room temperature, and 2.0 parts by mass of 2E4MZ was added and stirred at room temperature. Thus, an epoxy polymerizable composition was obtained.
- GST the compound represented by formula (4)
- Example 2 The composition ratio (weight ratio) as shown in Table 1 was mixed under the same conditions as in Example 1 to obtain an epoxy polymerizable composition.
- Example 6 the ratio of epoxy equivalent to thiol equivalent in the epoxy polymerizable composition was 1: 0.8, and in Example 7, it was 1: 1.2.
- Solubility A case where the epoxy polymerizable composition was a transparent and uniform solution was visually evaluated as ⁇ , and a case where it was not transparent (such as cloudy) was evaluated as ⁇ .
- the epoxy polymerizable composition was poured into a mold and heated at 80 ° C. for 2 hours to obtain a cured product having a thickness of 0.2 mm.
- the refractive index of the cured product was measured using a refractometer (multi-wavelength Abbe refractometer DR-M4 manufactured by Atago Co., Ltd.). The measurement was performed using sodium D line (589 nm), and the refractive index of the cured product was used.
- Light transmittance The light transmittance at 450 nm of the cured product prepared as described above was measured using an ultraviolet / visible spectrophotometer (MULTISPEC-1500 manufactured by Shimadzu Corporation).
- Moisture permeability As described above, a cured product having a thickness of 100 ⁇ m was prepared, and the moisture permeability under conditions of 60 ° C. and 90% RH was measured according to JIS Z0208.
- Table 1 in FIG. 2 shows the evaluation results of the epoxy polymerizable compositions of Examples 1 to 8 and their cured products.
- the evaluation results of the epoxy polymerizable compositions of Comparative Examples 1 to 4 and their cured products are shown in Table 2 of FIG.
- the cured products of Examples 1 to 8 (cured products of the first epoxy polymerizable composition of the present invention) have a high refractive index of 1.64 or more, heat resistance, and low curing shrinkage. The property is also good. Furthermore, since the epoxy polymerizable compositions of Examples 1 to 8 have a viscosity in an appropriate range at room temperature, they have good solubility and excellent curability. In particular, it can be seen that the epoxy polymerizable compositions of Examples 1, 3, and 6 to 8 have an appropriate viscosity, and the cured product has an extremely high refractive index of 1.65 or more.
- the refractive index of the cured product of Comparative Example 2 is about 1.63. Moreover, since the composition of Comparative Example 1 did not contain a curing accelerator, it could not be cured. Since the compositions of Comparative Examples 3 and 4 did not contain a bisphenol type epoxy compound, the viscosity at room temperature was high, the solubility was low, and the curability and the like could not be evaluated.
- Example 9 The flask was charged with 128 parts by mass of YL-983U and 86 parts by mass of PG-100, and mixed for 1 hour while heating at 90 to 100 ° C. 100 parts by weight of 1,1,3,3-tetrakis (mercaptomethylthio) propane was added and mixed for 1 hour at room temperature. Further, 0.5 parts by mass of 2E4MZ was added and stirred at room temperature for 5 minutes to obtain an epoxy polymerizable composition.
- Example 10 to 12 Under the same composition ratio (weight ratio) as shown in Table 1, under the same conditions as in Example 9, (A1) an epoxy compound was mixed, and (B2) a thiol compound having four thiol groups in the molecule was added. Then, (C) a curing accelerator was added to obtain an epoxy polymerizable composition.
- the cured products of Examples 9-12 are suppressed in moisture permeability 12 ⁇ 18g / m 2 / 24h .
- the cured product of Comparative Example 5 and Example 1 described above has higher moisture permeability than the cured products of Examples 9-12. This is considered to be due to the number of thiol groups contained in the molecule of the thiol compound. That is, since there are many thiol groups contained in the thiol compound, it is considered that the crosslink density of the cured product was increased and the moisture permeability could be lowered.
- the refractive index of the cured product obtained in Examples 9, 11, and 12 was 1.66, whereas the refractive index of the cured product obtained in Example 10 was 1.64.
- cured material can be raised by using the epoxy compound which has a fluorene skeleton.
- the cured product of the first epoxy polymerizable composition of the present invention is used as a sealing member for an organic EL element, particularly a surface sealing type sealing member for an organic EL element having a top emission structure, the light extraction efficiency is improved. . Furthermore, since the first epoxy polymerizable composition of the present invention has good workability, the productivity of the organic EL panel can be improved. If the cured product of the second epoxy polymerizable composition of the present invention is used as a surface-sealing type sealing member for an organic EL element having a top emission structure in particular, the transmission of moisture and the like is reduced and the light extraction efficiency is improved. To do.
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Abstract
Description
[1] (A2)下記一般式(1)または(2)で表されるフルオレン型エポキシ化合物と、
[2] E型粘度計で測定された、25℃での粘度が0.1~100Pa・sである、[1]に記載のエポキシ重合性組成物。
[3] 前記(B1)チオール化合物のチオール当量が、80~100g/eqであり、かつ、前記(B1)チオール化合物の硫黄含有率が、50~80%である、[1]または[2]に記載のエポキシ重合性組成物。
[4] 前記(B1)チオール化合物のチオール当量が、85~95g/eqであり、かつ、前記硫黄含有率が、60~75%である、[1]~[3]のいずれかに記載のエポキシ重合性組成物。
[5] 前記(A3)エポキシ化合物が、ビスフェノール型エポキシ化合物である、[1]~[4]のいずれかに記載のエポキシ重合性組成物。
[6] 前記(A2)成分100質量部に対して、前記(A3)成分の含有量が、20~70質量部である、[1]~[5]のいずれかに記載のエポキシ重合性組成物。
[7] 前記(B1)チオール化合物の分子量が、140~500である、[1]~[6]のいずれかに記載のエポキシ重合性組成物。
[8] [1]~[7]のいずれかに記載のエポキシ重合性組成物を含む、光学材料用透明樹脂。
[9] [1]~[7]のいずれかに記載のエポキシ重合性組成物からなる、シール材組成物。
[11] 屈折率が1.64以上である、[10]に記載の硬化物。
[12] 前記(A2)フルオレン型エポキシ化合物と前記(A3)エポキシ化合物とを加熱混合する工程と、前記工程で得られたエポキシ化合物の混合物と前記(B1)チオール化合物とを30℃以下で混合する工程と、を含む、[1]~[7]のいずれかに記載のエポキシ重合性組成物の製造方法。
[13] (A1)1分子内に2つ以上のエポキシ基を有するエポキシ化合物と、(B2)1分子内に4つ以上のチオール基を有するチオール化合物と、(C)硬化促進剤と、を含むエポキシ重合性組成物。
[14] (D)シランカップリング剤をさらに含む、[13]に記載のエポキシ重合性組成物。
[15] 前記(B2)チオール化合物のチオール当量が、80~100g/eqである、[13]または[14]に記載のエポキシ重合性組成物。
[16] 前記(A1)エポキシ化合物がフルオレン型エポキシ化合物である、[13]~[15]のいずれかに記載のエポキシ重合性組成物。
[17] 前記(B2)成分100質量部に対して、前記(A1)成分の含有量が100~300質量部であり、前記(C)成分の含有量が0.02~40質量部であり、前記(D)成分の含有量が0.02~40質量部であり、かつエポキシ基とチオール基のモル比が1:0.9~1.1である、[14]~[16]のいずれかに記載のエポキシ重合性組成物。
[18] 前記(B2)チオール化合物の分子量が、140~500である、[13]~[17]のいずれかに記載のエポキシ重合性組成物。
[19] [13]~[18]のいずれかに記載のエポキシ重合性組成物を含む光学材料用透明樹脂。
[20] [13]~[18]のいずれかに記載のエポキシ重合性組成物からなる、シール材組成物。
[22] 屈折率が1.64以上である、[21]に記載の硬化物。
[23] 厚み100μmの硬化物の、JIS Z0208に準拠した60℃、90%RHにおける透湿度が20g/m2/24h以下であり、かつ、前記(B2)チオール化合物の硫黄含有量が50~80%である、[21]または[22]に記載の硬化物。
[24] [10]、[11]および[21]~[23]のいずれかに記載の硬化物を含む光デバイス。
[25] 有機EL素子が配置された表示基板と、前記表示基板と対になる対向基板と、前記表示基板と前記対向基板との間に介在し、かつ前記有機EL素子と前記対向基板との間に形成される空間に充填されているシール部材と、を含む有機ELパネルであって、前記シール部材は、[10]、[11]および[21]~[23]のいずれかに記載の硬化物である、有機ELパネル。
[26] 有機EL素子はトップエミッション構造である、[25]に記載の有機ELパネル。
また、本発明により提供されるエポキシ重合性組成物を用いて、特にトップエミッション構造の有機EL素子を封止すると、光の取り出し効率を高めるだけでなく、素子内部への水分の透過を抑制できる。
1 シール部材
20 有機EL層
21 カソード透明電極層
22 アノード反射電極層
30 基板
31 封止板
本発明のエポキシ重合性組成物の硬化物は、透明となることが好ましい。透明とは、少なくとも光デバイスからの光が通過するシール部材や光学材料として用いられる程度に透明であればよい。本発明のエポキシ重合性組成物は、(A)エポキシ化合物と、(B)チオール化合物と、必要に応じて他の任意成分(例えば(C)硬化促進剤)と、を含む。本発明のエポキシ重合性組成物は、2つに大別される。
フルオレン型エポキシ化合物は、それを含む樹脂組成物の硬化物の屈折率を高めることができる。また、フルオレンは剛直な芳香族基であるため、フルオレン型エポキシ化合物を含む樹脂組成物の硬化物は、耐熱性が高くなると考えられる。
一般式(1)におけるnは、アルキレンエーテルユニットの繰り返し数を表す。nはそれぞれ独立して0~3の整数である。nが大きいほど化合物の軟化点が低下するので、後述するように、樹脂組成物としたときの作業性が向上する。しかし、nが大きすぎると、その硬化物の耐熱性が低下することがある。よってnは0または1であることが好ましい。
30℃以下(好ましくは25℃以下)の軟化点を有するエポキシ化合物は、エポキシ重合性組成物の作業性をさらに向上させうる。軟化点は環球法(JIS K7234に準拠)により測定される。
(B1)チオール化合物は、1分子内に2以上のチオール基を有することを特徴とする。(B1)チオール化合物は、(A2)フルオレン型エポキシ化合物および(A3)軟化点が30℃以下のエポキシ化合物の硬化剤として作用しうる。つまり(B1)チオール化合物のチオール基は、(A2)フルオレン型エポキシ化合物のエポキシ基、または、(A3)軟化点が30℃以下のエポキシ化合物のエポキシ基と反応することにより、これらのエポキシ化合物を互いに架橋反応させて、耐熱性や接着強度等に優れた硬化物とすることができる。
第1のエポキシ重合性組成物には、(C)硬化促進剤が含まれていてもよい。(C)硬化促進剤の例には、イミダゾール化合物やアミン化合物が含まれる。イミダゾール化合物の例には、2-エチル-4-メチルイミダゾールなどが含まれ、アミン化合物の例には、トリスジメチルアミノメチルフェノールなどが含まれる。(C)硬化促進剤は、ルイス塩基化合物であってもよい。
第1のエポキシ重合性組成物には、(D)シランカップリング剤が含まれていてもよい。(D)シランカップリング剤を含むエポキシ重合性組成物は、有機EL用シール材組成物としたときに基板との密着性が高い。(D)シランカップリング剤の例には、エポキシ基、カルボキシル基、メタクリロイル基、イソシアネート基などの反応性基を有するシラン化合物が含まれる。シラン化合物の具体例には、トリメトキシシリル安息香酸、γ-メタクリロキシプロピルトリメトキシシラン、ビニルトリアセトキシシラン、ビニルトリメトキシシラン、γ-イソシアナトプロピルトリエトキシシラン、γ-グリシドキシプロピルトリメトキシシラン、β-(3,4-エポキシシクロヘキシル)エチルトリメトキシシランなどが含まれる。シランカップリング剤は、1種単独であっても、2種以上の組み合わせであってもよい。
第1のエポキシ重合性組成物は、本発明の効果を損なわない範囲で、その他樹脂成分、充填剤、改質剤、安定剤などの任意成分をさらに含有することができる。
他の樹脂成分の例には、ポリアミド、ポリアミドイミド、ポリウレタン、ポリブタジェン、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、石油樹脂、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が含まれる。これらの1種単独を、または複数種の組み合わせを含有することができる。
第1のエポキシ重合性組成物は、速やかに硬化できることが好ましい。有機EL素子などの被封止材を封止するときの作業性を高めるためである。速やかに硬化できるとは、例えば、加熱条件下(~100℃)において、120分以内に硬化することをいう。
第1のエポキシ重合性組成物の硬化物の屈折率は、1.60を超えることが好ましく、1.64以上であることがより好ましい。屈折率は、ナトリウムD線(589nm)で測定した値をいう。屈折率は公知の方法で測定できるが、一般的にアッベ屈折率計による臨界角法で測定することができる。
第2のエポキシ重合性組成物に含まれる(A1)エポキシ化合物は、1分子内に2つ以上のエポキシ基を有する。(A1)エポキシ化合物は、(B2)チオール化合物によって架橋されて硬化する。
第2のエポキシ重合性組成物に含まれる(B2)チオール化合物は、1分子内に4つ以上のチオール基を有することを特徴とする。(B2)チオール化合物は、(A1)エポキシ化合物の硬化剤として作用しうる。つまり、(B2)チオール化合物のチオール基は、(A1)エポキシ化合物のエポキシ基と反応することにより、(A1)エポキシ化合物を互いに架橋させて、耐熱性や接着強度などに優れた硬化物とすることができる。また、(B2)チオール化合物は、1分子内に4つ以上のチオール基を含むことから、エポキシ樹脂の硬化物の架橋密度を高め、透湿度を低下させる。
第2のエポキシ重合性組成物に含まれる(C)硬化促進剤は、エポキシ重合性組成物の硬化性と保存安定性とのバランスを調整する機能を有する。(C)硬化促進剤の例には、前述と同様の(C)硬化促進剤と同様のものが含まれる。
第2のエポキシ重合性組成物には、(D)シランカップリング剤が含まれてもよい。(D)シランカップリング剤の例には、前述と同様の(D)シランカップリング剤と同様のものが含まれる。
第2のエポキシ重合性組成物は、本発明の効果を損なわない範囲で、その他樹脂成分、充填剤、改質剤、安定剤などの任意成分をさらに含有することができる。その他樹脂成分、充填剤、改質剤、安定剤などの具体例、およびエポキシ重合性組成物における含有量は、前述と同様である。
第2のエポキシ重合性組成物は、前述と同様に、速やかに硬化できることが好ましい。第2のエポキシ重合性組成物の硬化性は、例えば、(A1)エポキシ化合物と、(B2)チオール化合物との組成比や、(C)硬化促進剤の含有量を調節することによって制御される。
第2のエポキシ重合性組成物の硬化物は、前述と同様に、1.60を超える(好ましくは1.64以上の)高い屈折率を有することが好ましい。また硬化物は、前述と同様に、450nmにおいて90%以上の高い光線透過率を有することが好ましい。また硬化物の硬化収縮率は、前述と同様に、10%以下であることが好ましく、8%以下であることがより好ましい。硬化物の屈折率、光線透過率および硬化収縮率は、前述と同様に測定することができる。
本発明のエポキシ重合性組成物は、発明の効果を損なわない限り、任意の方法で製造されうる。例えば、エポキシ重合性組成物は、1)(A)エポキシ化合物を準備する工程と、2)(A)エポキシ化合物と(B)チオール化合物を、硬化反応が生じない温度下で混合する工程と、を含む方法で製造される。混合は、これらの成分をフラスコに装入して攪拌する方法や、三本ロールで混練する方法が含まれる。
本発明のエポキシ重合性組成物は、硬化されることにより、特にシール部材として用いられうる。さらに、光デバイスからの光が通過するシール部材または光学材料に適用されることが好ましい。シール部材の例には、有機ELパネル、液晶ディスプレイ、LED、電子ペーパー用途のシール部材;太陽電池、CCD用途のシール部材などが含まれる。光学材料の例には、光学接着剤、光学フィルム、ホログラム材料、フォトニック結晶、回折格子、プリズム、屈折率分布レンズ、光ファイバー、光導波路フィルム等が含まれる。
前記の通り、本発明のシール材組成物は、トップエミッション構造の有機EL素子のシール部材を作製するための組成物として有用である。つまり本発明の有機ELパネルは、有機EL素子が配置された表示基板と、表示基板と対になる対向基板と、表示基板と対向基板との間に介在し、前記有機EL素子を封止するシール部材とを有する。前述の通り、シール部材が、対向基板の周縁部に存在するものを枠封止型の有機ELパネルという。一方、シール部材が有機EL素子と対向基板との間に形成される空間に充填されているものを、面封止型の有機ELパネルという。本発明のシール材組成物は、その硬化物の屈折率が高いため、トップエミッション構造の有機ELパネルの、面封止型のシール部材の作製に特に適する。
フルオレン型エポキシ化合物
当該化合物は、下記式(7)で表される。当該化合物の軟化点は91.5℃であり、エポキシ価は3.89eq/kg(エポキシ当量257g/eq)であった。
当該化合物の軟化点は50℃であり、エポキシ価は3.26eq/kg(エポキシ当量307g/eq)であった。
YL-983U(ジャパンエポキシレジン社製)
当該化合物は、ビスフェノールF型エポキシ化合物である。当該化合物は室温で液体であり、エポキシ当量は169g/eqであった。
GST(三井化学株式会社製)
下記の式(4)で示される化合物であり、特許第2621991号公報に記載されている。当該化合物の分子量は260である。当該化合物は、分子内に3つのチオール基を有しているため、チオール当量は86.7g/eqである。当該化合物の硫黄含有率は61.5%である。
下記の式(6)で示される化合物であり、特許3995427号に記載されている。当該化合物の分子量は356である。当該化合物は、分子内に4つのチオール基を有しているため、チオール当量は89.0g/eqである。当該化合物の硫黄含有率は71.9%である。
下記の式(5)で示される化合物であり、特許第3444682号公報に記載されている。当該化合物の分子量は366である。当該化合物は、分子内に4つのチオール基を有しているため、チオール当量は91.5g/eqである。当該化合物の硫黄含有率は61.2%である。
2E4MZ(2-エチル-4-4メチルイミダゾール)(四国化成社製)
JERキュア3010(トリスジメチルアミノメチルフェノール)(ジャパンエポキシレジン社製)
フラスコに、50質量部のYL-983Uと、50質量部のPG-100とを装入し、加温しながら混合した。これに44.2質量部の式(4)で表される化合物(以下、「GST」と記す)を添加して室温で混合し、2.0質量部の2E4MZを添加して室温で攪拌してエポキシ重合性組成物を得た。
表1に示される通りの組成比率(重量比)で、実施例1と同様の条件下で混合して、エポキシ重合性組成物を得た。実施例6では、エポキシ重合性組成物中のエポキシ当量とチオール当量の比率が1:0.8であり、実施例7では、1:1.2であった。
フラスコに、100質量部のYL-983Uと、51質量部のGSTとを装入し、室温で攪拌してエポキシ重合性組成物を得た。
比較例1で得たエポキシ重合性組成物に、実施例1と同様の条件下で、2質量部のJERキュア3010を混合してエポキシ重合性組成物を得た。
100質量部のPG100と、38質量部のGSTと、2質量部の2E4MZとを、実施例1と同様の条件下で混合してエポキシ重合性組成物を得た。
100質量部のEG210と、32質量部のGSTと、2質量部の2E4MZを、実施例1と同様の条件下で混合してエポキシ重合性組成物を得た。
エポキシ重合性組成物が、目視による観測で、透明で均一な溶液である場合を○、透明でない(白濁している等)場合を×と評価した。
エポキシ重合性組成物を室温(25℃)で放置し、一定時間経過後の組成物について指触にてゲルの状態を測定し、ゲル化するまでの時間(硬化時間)を求めた。同様にエポキシ重合性組成物を80℃に加熱し、80℃における硬化時間を測定した。これらの硬化時間が30分以内の場合を○、30分以上の場合を×と評価した。
E型粘度計(BROOKFIEL社製のデジタルレオメータ型式DII-III ULTRA)を用いて、25℃におけるエポキシ重合性組成物の粘度を測定した。
エポキシ重合性組成物を型に流し込み、80℃で2h加熱して厚み0.2mmの硬化物を得た。屈折率測定計(アタゴ社製の多波長アッベ屈折計DR-M4)を用いて当該硬化物の屈折率を測定した。測定はナトリウムD線(589nm)を用いて行い、硬化物の屈折率とした。
前記の通り調製された硬化物について、紫外/可視分光光度計(島津製作所製のMULTISPEC-1500)を用いて450nmにおける光線透過率を測定した。
前記の通り調製された硬化物について、TMA(セイコーインスツルメンツ社製のTMA/SS6000)を用いて、昇温速度5℃/分の条件で線膨張係数を測定し、その変曲点からTgを求めた。
前記の通り調製された硬化前の組成物の比重と、硬化後の硬化物の比重とを、下記式に当てはめることにより求めた。
前記の通りに厚み100μmの硬化物を調製して、JIS Z0208に準じて、60℃90%RH条件での透湿量を測定した。
フラスコに、128質量部のYL-983Uと、86質量部のPG-100とを装入し、90~100℃で加温しながら1時間混合した。100質量部の1,1,3,3-テトラキス(メルカプトメチルチオ)プロパンを添加し、室温で1時間混合した。さらに、0.5質量部の2E4MZを加え、室温で5分攪拌してエポキシ重合性組成物を得た。
表1に示される通りの組成比率(重量比)で、実施例9と同様の条件下で、(A1)エポキシ化合物を混合し、(B2)分子内に4つのチオール基を有するチオール化合物を添加および混合し、(C)硬化促進剤を加えて、エポキシ重合性組成物を得た。
表2に示される通りの組成比率(重量比)で、実施例9と同様の条件下で、(A1)エポキシ化合物を混合し、(B1)分子内に3つのチオール基を有するチオール化合物を添加および混合し、(C)硬化促進剤を加えて、エポキシ重合性組成物を得た。
本発明の第2のエポキシ重合性組成物の硬化物を、特にトップエミッション構造の有機EL素子の面封止型のシール部材とすれば、水分等の透過が少なく、かつ光の取り出し効率が向上する。
Claims (26)
- (A2)下記一般式(1)または一般式(2)で表されるフルオレン型エポキシ化合物と、
R2は、それぞれ独立に水素原子またはメチル基を表し;
R3は、それぞれ独立に炭素数が1~5のアルキル基を表し;
R4は、それぞれ独立に炭素数が1~5のアルキル基を表し;
nは、それぞれ独立に0~3の整数を表し;
mは、それぞれ独立に1~3の整数を表し;
pは、それぞれ独立に0~4の整数を表し;
qは、それぞれ独立に0~4の整数を表す]
R1~R4、m、n、p、およびqは、一般式(1)と同様に定義される]
(A3)30℃以下の軟化点を有するエポキシ化合物と、
(B1)1分子内に2つ以上のチオール基を有するチオール化合物と、を含む、エポキシ重合性組成物。 - E型粘度計で測定された、25℃での粘度が0.1~100Pa・sである、請求項1に記載のエポキシ重合性組成物。
- 前記(B1)チオール化合物のチオール当量が、80~100g/eqであり、かつ、
前記(B1)チオール化合物の硫黄含有率が、50~80%である、請求項1に記載のエポキシ重合性組成物。 - 前記(B1)チオール化合物のチオール当量が、85~95g/eqであり、かつ、
前記(B1)チオール化合物の硫黄含有率が、60~75%である、請求項1に記載のエポキシ重合性組成物。 - 前記(A3)エポキシ化合物が、ビスフェノール型エポキシ化合物である、請求項1に記載のエポキシ重合性組成物。
- 前記(A2)成分100質量部に対して、
前記(A3)成分の含有量が、20~70質量部である、請求項1に記載のエポキシ重合性組成物。 - 前記(B1)チオール化合物の分子量が、140~500である、請求項1に記載のエポキシ重合性組成物。
- 請求項1に記載のエポキシ重合性組成物を含む、光学材料用透明樹脂。
- 請求項1に記載のエポキシ重合性組成物からなる、シール材組成物。
- 請求項8に記載の光学材料用透明樹脂を硬化してなる、硬化物。
- 屈折率が1.64以上である、請求項10に記載の硬化物。
- 前記(A2)フルオレン型エポキシ化合物と前記(A3)エポキシ化合物とを加熱混合する工程と、
前記工程で得られたエポキシ化合物の混合物と、前記(B1)チオール化合物とを30℃以下で混合する工程と、
を含む、請求項1に記載のエポキシ重合性組成物の製造方法。 - (A1)1分子内に2つ以上のエポキシ基を有するエポキシ化合物と、
(B2)1分子内に4つ以上のチオール基を有するチオール化合物と、
(C)硬化促進剤と、
を含む、エポキシ重合性組成物。 - (D)シランカップリング剤をさらに含む、請求項13に記載のエポキシ重合性組成物。
- 前記(B2)チオール化合物のチオール当量が、80~100g/eqである、請求項13に記載のエポキシ重合性組成物。
- 前記(A1)エポキシ化合物がフルオレン型エポキシ化合物である、請求項13に記載のエポキシ重合性組成物。
- 前記(B2)成分100質量部に対して、
前記(A1)成分の含有量が、100~300質量部であり、
前記(C)成分の含有量が、0.02~40質量部であり、
前記(D)成分の含有量が、0.02~40質量部であり、かつ
エポキシ基とチオール基のモル比が1:0.9~1.1である、請求項14に記載のエポキシ重合性組成物。 - 前記(B2)チオール化合物の分子量が、140~500である、請求項13に記載のエポキシ重合性組成物。
- 請求項13に記載のエポキシ重合性組成物を含む、光学材料用透明樹脂。
- 請求項13に記載のエポキシ重合性組成物からなる、シール材組成物。
- 請求項19に記載の光学材料用透明樹脂を硬化してなる、硬化物。
- 屈折率が1.64以上である、請求項21に記載の硬化物。
- 厚み100μmの硬化物の、JIS Z0208に準拠した60℃、90%RHにおける透湿度が20g/m2/24h以下であり、かつ、
前記(B2)チオール化合物の硫黄含有量が50~80%である、請求項22に記載の硬化物。 - 請求項10または21に記載の硬化物を含む光デバイス。
- 有機EL素子が配置された表示基板と、
前記表示基板と対になる対向基板と、
前記表示基板と前記対向基板との間に介在し、かつ前記有機EL素子と前記対向基板との間に形成される空間に充填されているシール部材と、を含む有機ELパネルであって、
前記シール部材は、請求項11または22に記載の硬化物である、有機ELパネル。 - 有機EL素子はトップエミッション構造である、請求項25に記載の有機ELパネル。
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JP2013209437A (ja) * | 2012-03-30 | 2013-10-10 | Sumitomo Bakelite Co Ltd | 透明シートおよび電子部品用基板 |
JP2014063144A (ja) * | 2012-08-27 | 2014-04-10 | Asahi Glass Co Ltd | 光学フィルタおよび固体撮像装置 |
WO2018159564A1 (ja) * | 2017-02-28 | 2018-09-07 | 味の素株式会社 | 樹脂組成物 |
JPWO2018159564A1 (ja) * | 2017-02-28 | 2019-12-19 | 味の素株式会社 | 樹脂組成物 |
WO2018190347A1 (ja) * | 2017-04-13 | 2018-10-18 | Jnc株式会社 | 熱硬化性樹脂組成物、硬化膜、硬化膜付き基板、電子部品およびインクジェット用インク |
JP2020164562A (ja) * | 2019-03-28 | 2020-10-08 | 味の素株式会社 | 一液型樹脂組成物 |
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Also Published As
Publication number | Publication date |
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TW200940587A (en) | 2009-10-01 |
EP2236539B1 (en) | 2014-12-03 |
JPWO2009093467A1 (ja) | 2011-05-26 |
CN101910236B (zh) | 2014-04-16 |
CN103865034B (zh) | 2016-08-17 |
RU2444538C1 (ru) | 2012-03-10 |
TWI439482B (zh) | 2014-06-01 |
US8889803B2 (en) | 2014-11-18 |
EP2236539A1 (en) | 2010-10-06 |
HK1149284A1 (en) | 2011-09-30 |
CN103865034A (zh) | 2014-06-18 |
KR20120088859A (ko) | 2012-08-08 |
KR20100102642A (ko) | 2010-09-24 |
KR101258041B1 (ko) | 2013-04-24 |
JP5395677B2 (ja) | 2014-01-22 |
KR101220789B1 (ko) | 2013-01-11 |
EP2236539A4 (en) | 2012-11-28 |
CN101910236A (zh) | 2010-12-08 |
US20110001419A1 (en) | 2011-01-06 |
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