TWI491638B - 熱硬化型組成物 - Google Patents
熱硬化型組成物 Download PDFInfo
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- TWI491638B TWI491638B TW099139298A TW99139298A TWI491638B TW I491638 B TWI491638 B TW I491638B TW 099139298 A TW099139298 A TW 099139298A TW 99139298 A TW99139298 A TW 99139298A TW I491638 B TWI491638 B TW I491638B
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- epoxy resin
- thermosetting composition
- bisphenol
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- 239000000203 mixture Substances 0.000 title claims description 57
- 229920001187 thermosetting polymer Polymers 0.000 title claims description 48
- 239000003822 epoxy resin Substances 0.000 claims description 23
- 229920000647 polyepoxide Polymers 0.000 claims description 23
- 229920005989 resin Polymers 0.000 claims description 20
- 239000011347 resin Substances 0.000 claims description 20
- 239000004841 bisphenol A epoxy resin Substances 0.000 claims description 13
- 239000004014 plasticizer Substances 0.000 claims description 12
- -1 aromatic primary amine Chemical class 0.000 claims description 10
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 claims description 9
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 claims description 8
- 239000004848 polyfunctional curative Substances 0.000 claims description 7
- 239000004593 Epoxy Substances 0.000 claims description 6
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 6
- 239000004842 bisphenol F epoxy resin Substances 0.000 claims description 5
- 239000007822 coupling agent Substances 0.000 claims description 5
- 239000004843 novolac epoxy resin Substances 0.000 claims description 5
- LSAMTNWZBYOWMZ-UHFFFAOYSA-N 4-methylaniline;trifluoroborane Chemical compound FB(F)F.CC1=CC=C(N)C=C1 LSAMTNWZBYOWMZ-UHFFFAOYSA-N 0.000 claims description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 4
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 claims description 4
- JDVIRCVIXCMTPU-UHFFFAOYSA-N ethanamine;trifluoroborane Chemical compound CCN.FB(F)F JDVIRCVIXCMTPU-UHFFFAOYSA-N 0.000 claims description 4
- 239000000945 filler Substances 0.000 claims description 4
- 239000004850 liquid epoxy resins (LERs) Substances 0.000 claims description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 3
- FPAFDBFIGPHWGO-UHFFFAOYSA-N dioxosilane;oxomagnesium;hydrate Chemical compound O.[Mg]=O.[Mg]=O.[Mg]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O FPAFDBFIGPHWGO-UHFFFAOYSA-N 0.000 claims description 3
- UHESRSKEBRADOO-UHFFFAOYSA-N ethyl carbamate;prop-2-enoic acid Chemical compound OC(=O)C=C.CCOC(N)=O UHESRSKEBRADOO-UHFFFAOYSA-N 0.000 claims description 3
- 125000000524 functional group Chemical group 0.000 claims description 3
- 239000001301 oxygen Substances 0.000 claims description 3
- 229910052760 oxygen Inorganic materials 0.000 claims description 3
- 239000013034 phenoxy resin Substances 0.000 claims description 3
- 229920006287 phenoxy resin Polymers 0.000 claims description 3
- 229920000728 polyester Polymers 0.000 claims description 3
- 150000003141 primary amines Chemical class 0.000 claims description 3
- 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 claims description 2
- YBRVSVVVWCFQMG-UHFFFAOYSA-N 4,4'-diaminodiphenylmethane Chemical compound C1=CC(N)=CC=C1CC1=CC=C(N)C=C1 YBRVSVVVWCFQMG-UHFFFAOYSA-N 0.000 claims description 2
- HLBLWEWZXPIGSM-UHFFFAOYSA-N 4-Aminophenyl ether Chemical compound C1=CC(N)=CC=C1OC1=CC=C(N)C=C1 HLBLWEWZXPIGSM-UHFFFAOYSA-N 0.000 claims description 2
- BZIVKXRNXXPVJD-UHFFFAOYSA-N 4-[3-(4-aminophenoxy)phenoxy]aniline Chemical compound NC1=CC=C(OC2=CC(=CC=C2)OC2=CC=C(C=C2)N)C=C1.NC1=CC=C(OC2=CC(=CC=C2)OC2=CC=C(C=C2)N)C=C1 BZIVKXRNXXPVJD-UHFFFAOYSA-N 0.000 claims description 2
- 229910015900 BF3 Inorganic materials 0.000 claims description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 2
- 125000002723 alicyclic group Chemical group 0.000 claims description 2
- 239000004844 aliphatic epoxy resin Substances 0.000 claims description 2
- 125000001931 aliphatic group Chemical group 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- 239000004927 clay Substances 0.000 claims description 2
- 229930003836 cresol Natural products 0.000 claims description 2
- OTARVPUIYXHRRB-UHFFFAOYSA-N diethoxy-methyl-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CCO[Si](C)(OCC)CCCOCC1CO1 OTARVPUIYXHRRB-UHFFFAOYSA-N 0.000 claims description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical class OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 claims description 2
- 235000012239 silicon dioxide Nutrition 0.000 claims description 2
- 239000000377 silicon dioxide Substances 0.000 claims description 2
- 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 claims description 2
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 claims description 2
- YGIHPJPEUFRZDN-UHFFFAOYSA-N 4-aminobenzenesulfonamide;aniline Chemical compound NC1=CC=CC=C1.NC1=CC=C(S(N)(=O)=O)C=C1 YGIHPJPEUFRZDN-UHFFFAOYSA-N 0.000 claims 1
- 229930185605 Bisphenol Natural products 0.000 claims 1
- WZKSXHQDXQKIQJ-UHFFFAOYSA-N F[C](F)F Chemical compound F[C](F)F WZKSXHQDXQKIQJ-UHFFFAOYSA-N 0.000 claims 1
- OAKJQQAXSVQMHS-UHFFFAOYSA-N hydrazine Substances NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 claims 1
- YRZFHTRSHNGOSR-UHFFFAOYSA-N phenylmethanamine;trifluoroborane Chemical compound FB(F)F.NCC1=CC=CC=C1 YRZFHTRSHNGOSR-UHFFFAOYSA-N 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 description 11
- 239000000758 substrate Substances 0.000 description 9
- MQJKPEGWNLWLTK-UHFFFAOYSA-N Dapsone Chemical compound C1=CC(N)=CC=C1S(=O)(=O)C1=CC=C(N)C=C1 MQJKPEGWNLWLTK-UHFFFAOYSA-N 0.000 description 8
- KUBDPQJOLOUJRM-UHFFFAOYSA-N 2-(chloromethyl)oxirane;4-[2-(4-hydroxyphenyl)propan-2-yl]phenol Chemical compound ClCC1CO1.C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 KUBDPQJOLOUJRM-UHFFFAOYSA-N 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- 239000011888 foil Substances 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 239000003921 oil Substances 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 3
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 238000004806 packaging method and process Methods 0.000 description 3
- 230000000704 physical effect Effects 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- FDDDEECHVMSUSB-UHFFFAOYSA-N sulfanilamide Chemical compound NC1=CC=C(S(N)(=O)=O)C=C1 FDDDEECHVMSUSB-UHFFFAOYSA-N 0.000 description 3
- 229940124530 sulfonamide Drugs 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- 230000004888 barrier function Effects 0.000 description 2
- WGQKYBSKWIADBV-UHFFFAOYSA-N benzylamine Chemical compound NCC1=CC=CC=C1 WGQKYBSKWIADBV-UHFFFAOYSA-N 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005538 encapsulation Methods 0.000 description 2
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 238000007719 peel strength test Methods 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
- AHDSRXYHVZECER-UHFFFAOYSA-N 2,4,6-tris[(dimethylamino)methyl]phenol Chemical compound CN(C)CC1=CC(CN(C)C)=C(O)C(CN(C)C)=C1 AHDSRXYHVZECER-UHFFFAOYSA-N 0.000 description 1
- ZRYCRPNCXLQHPN-UHFFFAOYSA-N 3-hydroxy-2-methylbenzaldehyde Chemical compound CC1=C(O)C=CC=C1C=O ZRYCRPNCXLQHPN-UHFFFAOYSA-N 0.000 description 1
- 238000003848 UV Light-Curing Methods 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000001723 curing Methods 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000005401 electroluminescence Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 239000012044 organic layer Substances 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- VXGDDOCDUQOYEZ-UHFFFAOYSA-N trifluoroborane Chemical compound FB(F)F.FB(F)F VXGDDOCDUQOYEZ-UHFFFAOYSA-N 0.000 description 1
Classifications
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- 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
- C08G59/182—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 using pre-adducts of epoxy compounds with curing agents
- C08G59/184—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 using pre-adducts of epoxy compounds with curing agents with amines
-
- 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
- C08G59/02—Polycondensates containing more than one epoxy group per molecule
- C08G59/04—Polycondensates containing more than one epoxy group per molecule of polyhydroxy compounds with epihalohydrins or precursors thereof
- C08G59/06—Polycondensates containing more than one epoxy group per molecule of polyhydroxy compounds with epihalohydrins or precursors thereof of polyhydric phenols
- C08G59/066—Polycondensates containing more than one epoxy group per molecule of polyhydroxy compounds with epihalohydrins or precursors thereof of polyhydric phenols with chain extension or advancing agents
-
- 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
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
-
- 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
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Epoxy Resins (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Description
本發明係有關於一種電子元件之封裝材料，且特別是有關於一種有機電激發光元件(organic electroluminescent device)封裝用之熱硬化型組成物(thermosetting composition)。
有機電激發光元件(organic electroluminescent device)因為輕薄、低消耗功率(low power consumption)、高反應速率(rapid response speed)、寬視角(wide viewing angle)等優點，已成為平面顯示器(flat display)的明日之星。
傳統的有機電激發光元件使用紫外光型環氧樹脂(UV light curing epoxy)，此類的樹脂較為硬脆，未來不適合於軟性基材(flexible substrate)的封裝。此外，使用紫外光型環氧樹脂進行整面型塗佈封裝(entire surface-coated sealing)時，紫外光的能量會造成元件中的有機材料劣化(degradation)，或者是硬化過程由於快速反應的應力(stress)變化造成陰極與有機層剝離(peeling)問題，或者是樹脂硬化不完全的問題。
為了解決上述問題，有不少專利提出熱硬化型樹脂(thermosetting resin)。JP 10-135255提出熱硬化型樹脂，其以酸酐系(anhydride)作為硬化劑中，咪唑(imidazole)作為硬化促進劑(curing accelerating agent)，然而，此方法需要較高的硬化溫度。JP 2006-228708提出熱硬化型樹脂，其使用酸酐作為硬化劑，以2,4,6-三(二甲胺基甲基)苯酚(2,4,6-tris(dimethylaminomethyl)phenol)作為促進劑，然而，此成分需要在100℃1小時以上才能使樹脂反應完全。
因此，業界極需發展一種有機電激發光元件封裝用之熱硬化型組成物，此組成物不但不會對元件造成不良的影響，且適用於軟性基材。
本發明提供一種熱硬化型組成物，包括以下成分：(a)一寡聚合物，其中該寡聚合物係由液態環氧樹脂與具有4個反應氫原子之芳香族一級胺反應(aromatic primary amine)而得，該環氧樹脂與該一級胺之當量莫耳比為1:0.15~1:2.50，且該寡聚物佔該熱硬化型組成物為約1~35重量百分比；(b)一長分子鏈樹脂，其中該長分子鏈樹脂佔該熱硬化型組成物為約5~10重量百分比；(c)具有兩個或兩個以上官能基之一環氧樹脂，其中該環氧樹脂佔該熱硬化型組成物為約50~80重量百分比；以及(d)一可塑劑(plasticizer)，其中該可塑劑佔該熱硬化型組成物為約5~15重量百分比。
為讓本發明之上述和其他目的、特徵、和優點能更明顯易懂，下文特舉出較佳實施例，並配合所附圖式，作詳細說明如下：
本發明提供一種熱硬化型組成物，其成份中包括成分(a)寡聚物，此寡聚合物係由液態環氧樹脂與具有4個反應氫原子之芳香族一級胺反應(aromatic primary amine)而得，環氧樹脂與一級胺之當量莫耳比為1:0.15~1:2.50，且寡聚物佔熱硬化型組成物為約1~35重量百分比。
此外，本發明之熱硬化型組成物亦包括其他成份，如成分(b)長分子鏈樹脂，其中長分子鏈樹脂佔熱硬化型組成物為約5~10重量百分比；成分(c)具有兩個或兩個以上官能基之環氧樹脂，且環氧樹脂佔熱硬化型組成物為約50~80重量百分比；以及成分(d)可塑劑(plasticizer)，其中可塑劑佔熱硬化型組成物為約5~15重量百分比。
上述成分(a)中之液態環氧樹脂包括雙酚A系環氧樹脂(bisphenol A epoxy)、或雙酚F系(bisphenol F epoxy)環氧樹脂、或脂肪族環氧樹脂(aliphatic epoxy)、脂環族環氧樹脂(cycloaliphatic epoxy)或上述之衍生物。而成分(a)中之具有4個反應氫原子之芳香族一級胺包括4,4'-二氨基二苯碸(4,4'-Diaminodiphenyl sulfone)、氨基苯磺酰胺(4-Aminobenzenesulfonamide)、4,4'-二氨基二苯醚(4,4'-diaminodiphenyl ether)、1,3-雙(4'-氨基苯氧基)苯(4,4'-(1,3-Phenylenedioxy)dianiline)、4,4'-二氨基二苯甲烷(4,4'-Diaminodiphenyl methane)或上述之衍生物。
於一實施例中，使用雙酚A環氧樹脂與4,4'-二氨基二苯碸(4,4'-Diaminodiphenyl sulfone)於溫度為約100℃~150℃的條件下進行反應，可製得一寡聚物。於另一實施例中，使用雙酚A環氧樹脂與氨基苯磺酰胺(4-Aminobenzenesulfonamide)於溫度為約100℃~150℃的條件下進行反應，可製得另一寡聚物。
上述成分(b)之長分子鏈樹脂之平均分子量為約大於5萬，其包括苯氧樹脂(phenoxy resin)、雙酚A系環氧樹脂、或雙酚F系環氧樹脂、或雙酚A/雙酚F系環氧樹脂或上述之衍生物。
上述成分(c)之環氧樹脂包括甲酚醛(cresol novolac)環氧樹脂、或酚醛(phenol novolac)環氧樹脂、雙酚A系環氧樹脂、或雙酚F系環氧樹脂、脂肪族環氧樹脂、脂環族環氧樹脂或上述之衍生物。
上述成分(d)之可塑劑之室溫黏度為約20,000~52,000 cps，其包括聚氨酯丙烯酸酯寡聚物(urethane acrylate oligmer)、聚酯丙烯酸酯寡聚物(polyester acrylate oligmer)、丙烯酸寡聚物(acrylic oligmer)、鄰苯二甲酸酯類(phthalate esters)或上述之衍生物。
此處須注意的是，成分(a)作為熱硬化型組成物之剛性部分(rigidity)，可作為熱硬化劑，成分(b)與成分(c)作為熱硬化型組成物之主要基質(matrix)，再額外搭配添加成分(d)可塑劑，以增加熱硬化型組成物之附著力(adhesion)。
此外，本發明之熱硬化型組成物亦可加入其他添加劑，例如其他熱硬化劑、填充物或耦合劑。熱硬化劑包括三氟化硼乙胺(boron trifluoride monoethylamine)、三氟化硼甲苯胺(boron trifluoride p-toluidine)、三氟化硼二甲基苯胺(boron trifluoride p-toluidine)、三氟化硼苄胺(boron trifluoride benzyl amine)、或三氟化硼二甲基胺(boron trifluoride N,N-dimethyl amine)。
填充物之作用在於增加熱硬化型組成物之阻水氣、氧氣之效果，其包括二氧化矽(silicon dioxide)、滑石粉(talcum powder)、氧化鋁(aluminum oxide)、黏土(clay)。
耦合劑(coupling agent)之作用同樣是增加熱硬化型組成物之附著力，其中耦合劑包括3-甘油丙基三甲氧基矽烷(3-glycidoxypropyltrimethoxysilane)、2-(3,4-環氧基環己基)乙基三甲氧基矽烷(2-(3,4 epoxycyclohexyl)-ethyltrimethoxysilane)、3-甘油基丙基甲基二乙氧基矽烷(3-glycidoxypropylmethyl diethoxy silane)或3-甘油基丙基三乙氧基(3-glycidoxypropyltriethoxysilane)。
本發明之熱硬化型組成物之形成方法，係先將液態環氧樹脂與具有4個反應氫原子之芳香族一級胺進行反應，以合成寡聚物，再混合寡聚物、長分子鏈樹脂、具有兩個或兩個以上之環氧樹脂與可塑劑，於為約70-90℃的條件下反應約15~30分鐘，即可完成硬化反應，相較於先前技術(需大於100℃且需1小時以上，本發明之反應溫度較低，且反應時間較短。
本發明之熱硬化型組成物經由抗折測試(flexibility test)，實驗結果顯示此組成物可歷經3000次彎折而不會有明顯的裂痕，證明本發明之組成物具有良好的撓曲性(flexible ability)。另外，本發明之熱硬化型組成物經由抗撕強度測試(peel strength)，實驗結果顯示抗撕強度為約2.5~3.5公斤，代表本發明之熱硬化型組成物與基材之間具有優異的附著力，此組成物不僅可以應用於軟性基材之封裝，更可以應用在金屬薄片或玻璃基板的封裝。再者，本發明之熱硬化型組成物亦具有抑制暗點(dark spot)的產生且具有優異的阻氣能力。
【實施例】
(1) 寡聚物之合成
100份重量的液態雙酚A環氧樹脂(EPON 828)與35份重量的4,4'-二氨基二苯碸(4,4'-diaminodiphenyl sulfone;DDS)混合後(當量莫耳比為1:1.063)，置於130℃油浴器內反應約1小時，以完成EO-01寡聚合物。
100份重量的液態雙酚A環氧樹脂(EPON 828)與35份重量的對氨基苯磺酰胺(4-aminobenzenesulfonamide)混合後(當量莫耳比為1:1.533)，置於130℃油浴器內反應約1小時，以完成EO-02寡聚合物。
100份重量的液態雙酚A環氧樹脂(EPON 828)與5份重量的4,4'-二氨基二苯碸(4,4'-diaminodiphenyl sulfone;DDS)混合後(當量莫耳比為1:0.152)，置於130℃油浴器內反應約1小時，以完成EO-03寡聚合物。
100份重量的液態雙酚A環氧樹脂(EPON 828)與80份重量的4,4'-二氨基二苯碸(4,4'-diaminodiphenyl sulfone;DDS)混合後(當量莫耳比為1:2.429)，置於130℃油浴器內反應約1小時，以完成EO-04寡聚合物。
(2) 熱硬化型組成物之形成
將上述之寡聚物(EO-01、EO-02、EO-03、或EO-04)；長分子鏈樹脂(PKHH(苯氧基樹脂，phenoxy resin)、EPIKOTE 1256(bisphenol A type epoxy resin,Mw＞51,000)、EPIKOTE 4250(bisphenol A/F(50/50) type epoxy resin,Mw＞59,000))；具有兩個或兩個以上官能基之環氧樹脂(ECN 1299(甲基酚醛環氧樹脂，cresol formaldehyde novolac epoxy resin)、EPON 828(雙酚A環氧樹脂，bisphenol A epoxy resin))；可塑劑(CN997(urethane acrylate oligmer於25℃下的黏度為25,000 cps)、CN2200(polyester acrylate oligmer，於25℃下的黏度為52,000 cps)、DOUBLEMER 3710(acylic oligmer，於25℃下的黏度為52,000 cps)；以及有機溶劑丙二醇甲醚醋酸酯(propylene glycol mono-methyl ether acetate)於100~130℃進行融熔混合，接著降至室溫後額外再分別加入滑石粉與熱硬化劑(BF3-MEA，boron trifluoride monoethylamine，三氟化硼乙胺)，再經由三滾筒研磨，即可製得實施例1-實施例13
。
(3) 物理性質測量
(i) 抗折測試(flexibility test)：將組成物塗佈於60μm金屬箔上(4×4.5 cm2
)，先於烘箱70℃烘烤1小時，然後置於真空烘箱45℃烘烤15小時，再彎折3000次，以顯微鏡觀察直徑5公分範圍內的裂痕，其中⊕表示無裂痕，而×表示有裂痕。
(ii) 抗撕強度測試(peel strength test)：將組成物塗佈於金屬箔上(4×4.5 cm2
)，先於烘箱70℃烘烤1小時，再於真空烘箱45℃烘烤15小時，然後此封裝蓋先置放90℃環境5~15分鐘預反應，接著在60~90℃下與聚亞醯胺(PI)塑膠基材進行貼合，之後置於90℃環境30分鐘完成硬化反應，使用雙柱式拉力機(QC Teck)測試上述完成之樣品，當測試所得數值越高，表示附著力越好。
(iii) 水氣測試(WVTR test(water vapor transmission rate test))：將組成物塗佈於PET離型膜上(15×15 cm2
)，先於烘箱70℃烘烤1小時，再於真空烘箱45℃烘烤15小時，然後此封裝蓋先置放90℃環境30分鐘完成硬化反應，於40℃下，90%溼度的條件下使用水氣滲透儀測試上述完成之樣品，當測試所得數值越低，表示抗水氣效果越好。
(iv) 暗點測試：將組成物塗佈於金屬箔上(4×4.5 cm2
)，先於烘箱70℃烘烤1小時，再於真空烘箱45℃烘烤15小時，然後此封裝蓋先置放90℃環境5~15分鐘預反應，接著將此封裝蓋與已蒸鍍完成之有機電激發光元件(OLED)在60~90℃下進行壓合，之後置於90℃環境30分鐘完成硬化反應。
將此OLED元件放置在高溫高濕60℃/90%溼度環境下120小時，觀察元件暗點產生情形：⊕表示暗點增加率<5%；Φ
表示暗點增加率<10%；×表示暗點增加率>10%。
表1顯示實施例1
~實施例13
之熱硬化型組成物各成分之組成與其物性結果。
註1：phr(parts per hundreds of resin)：每100單位樹脂中，某物質所添加的量。
由表1之數據可得知，熱硬化型組成物用於有機電激發光元件封止時，除了擁有優異的抑制暗點(Dark Spots)與阻氣能力之外，更有良好的撓曲性與基材附著力的表現。
表2顯示比較例1
~比較例4
之熱硬化型組成物各成分之組成與其物性結果。
由表2的數據可得知，當組成物僅有寡聚合物(EO-01 Oligmer)時，其對基材之附著力幾乎為零；而當組成物無寡聚合物存在時，其對基材的附著力低於2公斤重；再者是當組成物無可塑劑(CN997、CN2200或DOUBLEMER3710)時，其對基材的附著力低於1公斤重。另外，比較實施例中之組成皆無法有效抑制暗點的產生。
雖然本發明已以數個較佳實施例揭露如上，然其並非用以限定本發明，任何所屬技術領域中具有通常知識者，在不脫離本發明之精神和範圍內，當可作任意之更動與潤飾，因此本發明之保護範圍當視後附之申請專利範圍所界定者為準。
Claims (11)
- 一種熱硬化型組成物，包括以下成分：(a)一寡聚合物，其中該寡聚合物係由液態環氧樹脂與具有4個反應氫原子之芳香族一級胺反應(aromatic primary amine)而得，該環氧樹脂與該一級胺之當量莫耳比為1：0.15~1：2.50，且該寡聚物佔該熱硬化型組成物為約1~35重量百分比；(b)一平均分子量大於5萬之長分子鏈樹脂，其中該長分子鏈樹脂佔該熱硬化型組成物為約5~10重量百分比；(c)具有兩個或兩個以上官能基之一環氧樹脂，其中該環氧樹脂佔該熱硬化型組成物為約50~80重量百分比；以及(d)一可塑劑(plasticizer)，其中該可塑劑佔該熱硬化型組成物為約5~15重量百分比，其中該成分(d)中之可塑劑係聚氨酯丙烯酸酯寡聚物(urethane acrylate oligmer)、聚酯丙烯酸酯寡聚物(polyester acrylate oligmer)、或鄰苯二甲酸酯類(phthalate esters)。
- 如申請專利範圍第1項所述之熱硬化型組成物，其中成分(a)中之該液態環氧樹脂包括雙酚A系環氧樹脂(bisphenol A epoxy)、或雙酚F系(bisphenol F epoxy)環氧樹脂、或脂肪族環氧樹脂(aliphatic epoxy)、或脂環族環氧樹脂(cycloaliphatic epoxy)。
- 如申請專利範圍第1項所述之熱硬化型組成物，其中成分(a)中之該具有4個反應氫原子之芳香族一級胺包括4,4'-二氨基二苯碸(4,4'-Diaminodiphenyl sulfone)、氨基苯 磺酰胺(4-Aminobenzenesulfonamide)、4,4'-二氨基二苯醚(4,4'-diaminodiphenyl ether)、1,3-雙(4'-氨基苯氧基)苯(4,4'-(1,3-Phenylenedioxy)dianiline)、或4,4'-二氨基二苯甲烷(4,4'-Diaminodiphenyl methane)。
- 如申請專利範圍第1項所述之熱硬化型組成物，其中成分(b)中之該長分子鏈樹脂包括苯氧樹脂(phenoxy resin)、雙酚A系環氧樹脂、雙酚F系環氧樹脂、或雙酚A/雙酚F系環氧樹脂。
- 如申請專利範圍第1項所述之熱硬化型組成物，其中成分(c)中之該環氧樹脂包括甲酚醛(cresol novolac)環氧樹脂、或酚醛(phenol novolac)環氧樹脂、雙酚A系環氧樹脂、或雙酚F系環氧樹脂、脂肪族環氧樹脂、或脂環族環氧樹脂。
- 如申請專利範圍第1項所述之熱硬化型組成物，尚包括一熱硬化劑。
- 如申請專利範圍第6項所述之熱硬化型組成物，其中該熱硬化劑包括三氟化硼乙胺(boron trifluoride monoethylamine)、三氟化硼甲苯胺(boron trifluoride p-toluidine)、三氟化硼二甲基苯胺(boron trifluoride p-toluidine)、三氟化硼苄胺(boron trifluoride benzyl amine)、或三氟化硼二甲基胺(boron trifluoride N,N-dimethyl amine)。
- 如申請專利範圍第1項所述之熱硬化型組成物，尚包括一填充物(filler)。
- 如申請專利範圍第8項所述之熱硬化型組成物，其中該填充物包括二氧化矽(silicon dioxide)、滑石粉(talcum powder)、氧化鋁(aluminum oxide)、或黏土(clay)。
- 如申請專利範圍第1項所述之熱硬化型組成物，尚包括一耦合劑(coupling agent)。
- 如申請專利範圍第10項所述之熱硬化型組成物，其中該耦合劑包括3-甘油丙基三甲氧基矽烷(3-glycidoxypropyltrimethoxysilane)、2-(3,4-環氧基環己基)乙基三甲氧基矽烷(2-(3,4epoxycyclohexyl)-ethyltrimethoxysilane)、3-甘油基丙基甲基二乙氧基矽烷(3-glycidoxypropylmethyl diethoxy silane)、或3-甘油基丙基三乙氧基(3-glycidoxypropyltriethoxysilane)。
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