JP2012177038A - Epoxy resin composition - Google Patents
Epoxy resin composition Download PDFInfo
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- JP2012177038A JP2012177038A JP2011040714A JP2011040714A JP2012177038A JP 2012177038 A JP2012177038 A JP 2012177038A JP 2011040714 A JP2011040714 A JP 2011040714A JP 2011040714 A JP2011040714 A JP 2011040714A JP 2012177038 A JP2012177038 A JP 2012177038A
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- epoxy resin
- skeleton
- resin composition
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- containing phenol
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- 229920000647 polyepoxide Polymers 0.000 title claims abstract description 58
- 239000003822 epoxy resin Substances 0.000 title claims abstract description 57
- 239000000203 mixture Substances 0.000 title claims abstract description 20
- -1 phenol compound Chemical class 0.000 claims abstract description 29
- 150000008065 acid anhydrides Chemical class 0.000 claims abstract description 25
- 239000004593 Epoxy Substances 0.000 claims abstract description 17
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 17
- 239000011574 phosphorus Substances 0.000 claims abstract description 16
- 230000001588 bifunctional effect Effects 0.000 claims abstract description 14
- 125000003983 fluorenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3CC12)* 0.000 claims abstract description 14
- 238000007142 ring opening reaction Methods 0.000 claims abstract description 12
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 10
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims abstract description 9
- 125000003118 aryl group Chemical group 0.000 claims description 17
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 14
- 239000007795 chemical reaction product Substances 0.000 claims description 8
- 150000001875 compounds Chemical class 0.000 claims description 8
- 230000003287 optical effect Effects 0.000 claims description 7
- 239000000047 product Substances 0.000 claims description 5
- 239000004065 semiconductor Substances 0.000 claims description 5
- 230000001681 protective effect Effects 0.000 claims description 4
- 239000000758 substrate Substances 0.000 claims description 3
- 238000007789 sealing Methods 0.000 claims 1
- 238000004383 yellowing Methods 0.000 abstract description 10
- 239000002305 electric material Substances 0.000 abstract 1
- 150000003017 phosphorus Chemical class 0.000 abstract 1
- 230000015572 biosynthetic process Effects 0.000 description 8
- 238000003786 synthesis reaction Methods 0.000 description 8
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 7
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 6
- 229920005989 resin Polymers 0.000 description 6
- 239000011347 resin Substances 0.000 description 6
- 238000002834 transmittance Methods 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 5
- 239000011342 resin composition Substances 0.000 description 5
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 4
- 238000002845 discoloration Methods 0.000 description 4
- 239000012776 electronic material Substances 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- 125000004432 carbon atom Chemical group C* 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- KMRIWYPVRWEWRG-UHFFFAOYSA-N 2-(6-oxobenzo[c][2,1]benzoxaphosphinin-6-yl)benzene-1,4-diol Chemical compound OC1=CC=C(O)C(P2(=O)C3=CC=CC=C3C3=CC=CC=C3O2)=C1 KMRIWYPVRWEWRG-UHFFFAOYSA-N 0.000 description 2
- NUDSREQIJYWLRA-UHFFFAOYSA-N 4-[9-(4-hydroxy-3-methylphenyl)fluoren-9-yl]-2-methylphenol Chemical compound C1=C(O)C(C)=CC(C2(C3=CC=CC=C3C3=CC=CC=C32)C=2C=C(C)C(O)=CC=2)=C1 NUDSREQIJYWLRA-UHFFFAOYSA-N 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
- NIHNNTQXNPWCJQ-UHFFFAOYSA-N fluorene Chemical compound C1=CC=C2CC3=CC=CC=C3C2=C1 NIHNNTQXNPWCJQ-UHFFFAOYSA-N 0.000 description 2
- 230000009477 glass transition Effects 0.000 description 2
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 150000002989 phenols Chemical class 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- MUTGBJKUEZFXGO-OLQVQODUSA-N (3as,7ar)-3a,4,5,6,7,7a-hexahydro-2-benzofuran-1,3-dione Chemical compound C1CCC[C@@H]2C(=O)OC(=O)[C@@H]21 MUTGBJKUEZFXGO-OLQVQODUSA-N 0.000 description 1
- 0 *c1cc(C2(c3ccccc3-c3c2cccc3)c(cc2*)cc(*)c2O)cc(*)c1O Chemical compound *c1cc(C2(c3ccccc3-c3c2cccc3)c(cc2*)cc(*)c2O)cc(*)c1O 0.000 description 1
- PMUPSYZVABJEKC-UHFFFAOYSA-N 1-methylcyclohexane-1,2-dicarboxylic acid Chemical compound OC(=O)C1(C)CCCCC1C(O)=O PMUPSYZVABJEKC-UHFFFAOYSA-N 0.000 description 1
- TUPXQRMDEWSUSH-UHFFFAOYSA-N 1-phenyl-9h-fluoren-2-ol Chemical compound OC1=CC=C2C3=CC=CC=C3CC2=C1C1=CC=CC=C1 TUPXQRMDEWSUSH-UHFFFAOYSA-N 0.000 description 1
- LLOXZCFOAUCDAE-UHFFFAOYSA-N 2-diphenylphosphorylbenzene-1,4-diol Chemical compound OC1=CC=C(O)C(P(=O)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 LLOXZCFOAUCDAE-UHFFFAOYSA-N 0.000 description 1
- ODGCZQFTJDEYNI-UHFFFAOYSA-N 2-methylcyclohex-3-ene-1,2-dicarboxylic acid Chemical compound OC(=O)C1(C)C=CCCC1C(O)=O ODGCZQFTJDEYNI-UHFFFAOYSA-N 0.000 description 1
- PFANXOISJYKQRP-UHFFFAOYSA-N 2-tert-butyl-4-[1-(5-tert-butyl-4-hydroxy-2-methylphenyl)butyl]-5-methylphenol Chemical compound C=1C(C(C)(C)C)=C(O)C=C(C)C=1C(CCC)C1=CC(C(C)(C)C)=C(O)C=C1C PFANXOISJYKQRP-UHFFFAOYSA-N 0.000 description 1
- IKEHOXWJQXIQAG-UHFFFAOYSA-N 2-tert-butyl-4-methylphenol Chemical compound CC1=CC=C(O)C(C(C)(C)C)=C1 IKEHOXWJQXIQAG-UHFFFAOYSA-N 0.000 description 1
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical compound C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 description 1
- PPODUESPZXFNMJ-UHFFFAOYSA-N 4-(4-hydroxyphenyl)-2,3-dimethylphenol Chemical compound C1=C(O)C(C)=C(C)C(C=2C=CC(O)=CC=2)=C1 PPODUESPZXFNMJ-UHFFFAOYSA-N 0.000 description 1
- WXQZLPFNTPKVJM-UHFFFAOYSA-N 4-[(4-hydroxycyclohexyl)methyl]cyclohexan-1-ol Chemical compound C1CC(O)CCC1CC1CCC(O)CC1 WXQZLPFNTPKVJM-UHFFFAOYSA-N 0.000 description 1
- ODJUOZPKKHIEOZ-UHFFFAOYSA-N 4-[2-(4-hydroxy-3,5-dimethylphenyl)propan-2-yl]-2,6-dimethylphenol Chemical compound CC1=C(O)C(C)=CC(C(C)(C)C=2C=C(C)C(O)=C(C)C=2)=C1 ODJUOZPKKHIEOZ-UHFFFAOYSA-N 0.000 description 1
- CDBAMNGURPMUTG-UHFFFAOYSA-N 4-[2-(4-hydroxycyclohexyl)propan-2-yl]cyclohexan-1-ol Chemical compound C1CC(O)CCC1C(C)(C)C1CCC(O)CC1 CDBAMNGURPMUTG-UHFFFAOYSA-N 0.000 description 1
- RPJFWRZEEKJTGN-UHFFFAOYSA-N 4-[2-(4-hydroxyphenyl)propan-2-yl]-2,6-dimethylphenol Chemical compound CC1=C(O)C(C)=CC(C(C)(C)C=2C=CC(O)=CC=2)=C1 RPJFWRZEEKJTGN-UHFFFAOYSA-N 0.000 description 1
- GCKIRZYWQROFEJ-UHFFFAOYSA-N 4-[2-[4-[1,1-bis(4-hydroxyphenyl)ethyl]phenyl]propyl]phenol Chemical compound C=1C=C(C(C)(C=2C=CC(O)=CC=2)C=2C=CC(O)=CC=2)C=CC=1C(C)CC1=CC=C(O)C=C1 GCKIRZYWQROFEJ-UHFFFAOYSA-N 0.000 description 1
- SUBDBMMJDZJVOS-UHFFFAOYSA-N 5-methoxy-2-{[(4-methoxy-3,5-dimethylpyridin-2-yl)methyl]sulfinyl}-1H-benzimidazole Chemical compound N=1C2=CC(OC)=CC=C2NC=1S(=O)CC1=NC=C(C)C(OC)=C1C SUBDBMMJDZJVOS-UHFFFAOYSA-N 0.000 description 1
- 229930185605 Bisphenol Natural products 0.000 description 1
- LCFVJGUPQDGYKZ-UHFFFAOYSA-N Bisphenol A diglycidyl ether Chemical compound C=1C=C(OCC2OC2)C=CC=1C(C)(C)C(C=C1)=CC=C1OCC1CO1 LCFVJGUPQDGYKZ-UHFFFAOYSA-N 0.000 description 1
- BVGRERKNAONPKU-UHFFFAOYSA-N CC1=C(C(=C(C(=C1O)C)C)C1=CC=C(C=C1)O)C.CC=1C(=C(C(=C(C1)C1=CC=CC=C1)C)C)C Chemical compound CC1=C(C(=C(C(=C1O)C)C)C1=CC=C(C=C1)O)C.CC=1C(=C(C(=C(C1)C1=CC=CC=C1)C)C)C BVGRERKNAONPKU-UHFFFAOYSA-N 0.000 description 1
- YIMQCDZDWXUDCA-UHFFFAOYSA-N [4-(hydroxymethyl)cyclohexyl]methanol Chemical compound OCC1CCC(CO)CC1 YIMQCDZDWXUDCA-UHFFFAOYSA-N 0.000 description 1
- 125000004018 acid anhydride group Chemical group 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 125000002723 alicyclic group Chemical group 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 125000000732 arylene group Chemical group 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- VCCBEIPGXKNHFW-UHFFFAOYSA-N biphenyl-4,4'-diol Chemical compound C1=CC(O)=CC=C1C1=CC=C(O)C=C1 VCCBEIPGXKNHFW-UHFFFAOYSA-N 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- BTANRVKWQNVYAZ-UHFFFAOYSA-N butan-2-ol Chemical compound CCC(C)O BTANRVKWQNVYAZ-UHFFFAOYSA-N 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000010538 cationic polymerization reaction Methods 0.000 description 1
- 238000005253 cladding Methods 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- IFDVQVHZEKPUSC-UHFFFAOYSA-N cyclohex-3-ene-1,2-dicarboxylic acid Chemical compound OC(=O)C1CCC=CC1C(O)=O IFDVQVHZEKPUSC-UHFFFAOYSA-N 0.000 description 1
- QSAWQNUELGIYBC-UHFFFAOYSA-N cyclohexane-1,2-dicarboxylic acid Chemical compound OC(=O)C1CCCCC1C(O)=O QSAWQNUELGIYBC-UHFFFAOYSA-N 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 1
- MUTGBJKUEZFXGO-UHFFFAOYSA-N hexahydrophthalic anhydride Chemical compound C1CCCC2C(=O)OC(=O)C21 MUTGBJKUEZFXGO-UHFFFAOYSA-N 0.000 description 1
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 1
- 150000002430 hydrocarbons Chemical group 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 238000007648 laser printing Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 125000004437 phosphorous atom Chemical group 0.000 description 1
- 150000003018 phosphorus compounds Chemical class 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- JIYNFFGKZCOPKN-UHFFFAOYSA-N sbb061129 Chemical compound O=C1OC(=O)C2C1C1C=C(C)C2C1 JIYNFFGKZCOPKN-UHFFFAOYSA-N 0.000 description 1
- 239000003566 sealing material Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 125000002298 terpene group Chemical group 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- UFDHBDMSHIXOKF-UHFFFAOYSA-N tetrahydrophthalic acid Natural products OC(=O)C1=C(C(O)=O)CCCC1 UFDHBDMSHIXOKF-UHFFFAOYSA-N 0.000 description 1
- 238000012719 thermal polymerization Methods 0.000 description 1
- XZZNDPSIHUTMOC-UHFFFAOYSA-N triphenyl phosphate Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)(=O)OC1=CC=CC=C1 XZZNDPSIHUTMOC-UHFFFAOYSA-N 0.000 description 1
Abstract
Description
本発明はエポキシ樹脂の特定の骨格を導入することで熱時変色を抑えることが出来、電子材料用途で特に高温に曝される部位に使用されるエポキシ樹脂硬化物を提供することに関する。 The present invention relates to providing a cured epoxy resin that can suppress thermal discoloration by introducing a specific skeleton of an epoxy resin and is used in a part exposed to a high temperature particularly in an electronic material application.
特許文献１では樹脂自体に着色剤を添加し、レーザー印字の際にかかる熱により印字をはっきりさせるとあるが、エポキシ樹脂の改良による根本的な変色防止が望まれていた。 In Patent Document 1, a colorant is added to the resin itself, and printing is clarified by heat applied at the time of laser printing. However, it has been desired to fundamentally prevent discoloration by improving the epoxy resin.
特許文献２、３では特定のエポキシ樹脂を用い、テルペン骨格を硬化剤に導入することにより、耐熱性、密着性、熱時黄変性などが改良できるとある。しかし、硬化剤、エポキシ樹脂ともに特定の骨格を必須とするものであり、硬化促進剤についても限定されるものであった。 In Patent Documents 2 and 3, a specific epoxy resin is used and a terpene skeleton is introduced into a curing agent, thereby improving heat resistance, adhesion, hot yellowing, and the like. However, both the curing agent and the epoxy resin require a specific skeleton, and the curing accelerator is also limited.
特許文献４ではガラスとの密着性が良く、高い透明性、耐熱信頼性（熱変色耐性、耐熱収縮性）を有する光学部品用樹脂組成物が示されているが、特定の光酸発生剤を用いることにより着色を抑えるものである。 Patent Document 4 discloses a resin composition for optical parts that has good adhesion to glass, high transparency, and high heat resistance (thermal discoloration resistance, heat shrinkage resistance). A specific photoacid generator is used. By using it, coloring is suppressed.
また、特許文献４にはフルオレン骨格を有するエポキシ樹脂を含有すると高屈折率（１．５８以上）にすることが可能になり、また十分なガラス転移温度が得られるようになるとの記載があるが、その導入方法は樹脂ブレンドを行った後にカチオン重合による硬化により高屈折率とするものであり、酸無水物など公知慣用のエポキシ樹脂硬化剤を使用する場合の熱重合には向かない組成となっている。 Further, Patent Document 4 describes that when an epoxy resin having a fluorene skeleton is contained, a high refractive index (1.58 or more) can be obtained, and a sufficient glass transition temperature can be obtained. The introduction method is to make the refractive index high by curing by cationic polymerization after resin blending, and the composition is not suitable for thermal polymerization in the case of using a known and usual epoxy resin curing agent such as acid anhydride. ing.
従来からの要求性能である可視光透過性を満足しつつ高耐熱耐黄変性に優れた封止材および保護膜形成用組成物を提供できる電子材料用エポキシ樹脂硬化物を提供することにある。 An object of the present invention is to provide an epoxy resin cured product for an electronic material that can provide a sealing material and a composition for forming a protective film that are excellent in high heat resistance and yellowing resistance while satisfying the visible light transmittance that is a required performance from the past.
また、光導波路などのように屈折率を調節することが重要な用途の場合、コアとクラッドでのエポキシ樹脂の組成を変化させることで屈折率を調整でき、更にコア/クラッド間での熱時接着力を保持できるエポキシ樹脂組成物を提供することにある。 In applications where it is important to adjust the refractive index, such as in optical waveguides, the refractive index can be adjusted by changing the composition of the epoxy resin in the core and the cladding. An object of the present invention is to provide an epoxy resin composition that can maintain adhesive strength.
本発明者は前記した課題を解決すべく鋭意研究を重ねた結果、特定の骨格を含有させるエポキシ樹脂を使用することにより可視光透過率を満足しつつ、高耐熱黄変性に効果のある成分を加えることを見いだし、反応性に関してはエポキシ樹脂の末端はビスフェノールＡ（ＢＰＡ）型のジグリシジルエーテルとなるように工夫することにより、硬化性はＢＰＡ型エポキシ樹脂と同等でありながら可視光透過率を満足しつつ、高耐熱黄変性に優れるエポキシ樹脂（Ｄ）と酸無水物硬化剤を使用することにより目的を達成できることを見いだし、本発明を完成したものである。 As a result of intensive studies to solve the above-mentioned problems, the present inventor has found an effective component for high heat yellowing while satisfying visible light transmittance by using an epoxy resin containing a specific skeleton. As for the reactivity, the end of the epoxy resin is devised so as to be bisphenol A (BPA) type diglycidyl ether, and the visible light transmittance is improved while the curability is equivalent to the BPA type epoxy resin. The present invention has been completed by finding that the object can be achieved by using an epoxy resin (D) and an acid anhydride curing agent excellent in high heat-resistant yellowing while being satisfied.
本発明の要旨は、エポキシ当量が５００〜１，０００ｇ/eqであるエポキシ樹脂（Ｄ）と硬化剤として酸無水物を含有するエポキシ樹脂組成物であって、該エポキシ樹脂（Ｄ）は分子構造中に、（Ａ）２官能芳香族エポキシ類の骨格、（Ｂ）リン含有フェノール化合物の骨格及び/又はフルオレン環含有フェノール骨格、及び（Ｃ）酸無水物の開環反応を由来とする骨格を有することを特徴とするエポキシ樹脂組成物である。そして、エポキシ樹脂（Ｄ）に含有される各骨格の割合は、（Ｂ）リン含有フェノール化合物の骨格及び/又はフルオレン環含有フェノール骨格は、（Ａ）２官能芳香族エポキシ類１モルに対してリン含有フェノール化合物及び/又はフルオレン環含有フェノールを０．２モル〜０．７モル反応して得るものであり、（Ｃ）酸無水物の開環反応を由来とする骨格は、（Ａ）２官能芳香族エポキシ類１モルに対して酸無水物の開環反応物を０．２モル〜０．７モル反応して得ることを特徴とする上記記載のエポキシ樹脂組成物である。
そして、本発明は上記記載の樹脂組成物を硬化させて得られる硬化物、上記記載の樹脂組成物を用いて得られるカラーフィルター用保護膜、上記記載の樹脂組成物を用いて得られる光半導体用封止材、上記記載の樹脂組成物を用いて得られる光半導体用基板及び光半導体基板用表面保護膜である。
The gist of the present invention is an epoxy resin composition containing an epoxy resin (D) having an epoxy equivalent of 500 to 1,000 g / eq and an acid anhydride as a curing agent, wherein the epoxy resin (D) has a molecular structure. (A) a skeleton of a bifunctional aromatic epoxy, (B) a skeleton of a phosphorus-containing phenol compound and / or a fluorene ring-containing phenol skeleton, and (C) a skeleton derived from a ring-opening reaction of an acid anhydride. It is an epoxy resin composition characterized by having. The ratio of each skeleton contained in the epoxy resin (D) is as follows: (B) the skeleton of the phosphorus-containing phenol compound and / or the fluorene ring-containing phenol skeleton is (A) 1 mol of the bifunctional aromatic epoxy. A skeleton derived from a ring-opening reaction of (C) acid anhydride is obtained by reacting 0.2 to 0.7 mol of a phosphorus-containing phenol compound and / or a fluorene ring-containing phenol. The epoxy resin composition as described above, which is obtained by reacting 0.2 mol to 0.7 mol of an acid anhydride ring-opening reaction product with respect to 1 mol of a functional aromatic epoxy.
And this invention is the hardened | cured material obtained by hardening the said resin composition, the protective film for color filters obtained using the said resin composition, The optical semiconductor obtained using the said resin composition And a surface protective film for an optical semiconductor substrate obtained using the resin composition described above.
本発明で用いるエポキシ樹脂（Ｄ）は通常使用されている硬化剤である酸無水物を使用することにより、透明性、耐熱信頼性（高耐熱黄変性）の問題を解決することができる。さらには上記性能を維持しつつも屈折率を調整することが出来る。 The epoxy resin (D) used in the present invention can solve the problems of transparency and heat resistance reliability (high heat yellowing) by using an acid anhydride which is a commonly used curing agent. Furthermore, the refractive index can be adjusted while maintaining the above performance.
以下、本発明の実施の形態について、詳細に説明する。 Hereinafter, embodiments of the present invention will be described in detail.
本発明において、特に電子材料用途で用いられ、高温に曝される部位に使用されるエポキシ樹脂硬化物を提供できるエポキシ樹脂（Ｄ）は、分子構造中に、（Ａ）２官能芳香族エポキシ樹脂類の骨格、（Ｂ）リン含有フェノール化合物の骨格及び／又はフルオレン環含有フェノール化合物骨格を代表とする耐熱性を付与することの出来る剛直骨格を有する構造であり、且つ（Ｃ）酸無水物の開環反応を由来とする骨格を含有させることにより、屈折率を調節しながらも透明性、耐熱信頼性（熱変色耐性）を発現し、性能を維持できることを特徴とする。エポキシ樹脂（Ｄ）を得る方法としては、予め過剰モルの（Ｃ）酸無水物と過小モルの水酸基含有化合物とを反応させ、エステル結合とカルボキシル基を有する反応物を生成させ、（Ａ）２官能芳香族エポキシ樹脂類および剛直骨格を含有する（Ｂ）リン含有フェノール化合物及び／又はフルオレン環含有フェノール化合物を加えて再び反応させることにより得ることができる。酸無水物の開環反応物のモル数は、反応に用いた酸無水物のモル数に等しい数値を示す。また、（Ｃ）酸無水物と水酸基含有化合物との反応においては、（Ｃ）酸無水物を完全に開環させ、未反応酸無水物として残存させないことが必要であり、さらに水酸基含有化合物が単独で残らないことが必要である。 In the present invention, an epoxy resin (D) that can be used for an electronic material application and can provide a cured epoxy resin used in a portion exposed to a high temperature has (A) a bifunctional aromatic epoxy resin in its molecular structure. A structure having a rigid skeleton capable of imparting heat resistance typified by a skeleton of a kind, (B) a skeleton of a phosphorus-containing phenol compound and / or a fluorene ring-containing phenol compound skeleton, and (C) an acid anhydride By containing a skeleton derived from a ring-opening reaction, transparency and heat reliability (thermal discoloration resistance) can be expressed and the performance can be maintained while adjusting the refractive index. As a method for obtaining the epoxy resin (D), an excess molar amount of (C) acid anhydride and a minimal molar amount of a hydroxyl group-containing compound are reacted in advance to produce a reaction product having an ester bond and a carboxyl group, and (A) 2 It can be obtained by adding a functional aromatic epoxy resin and a (B) phosphorus-containing phenol compound and / or a fluorene ring-containing phenol compound containing a rigid skeleton and reacting again. The number of moles of the ring opening reaction product of the acid anhydride is a value equal to the number of moles of the acid anhydride used in the reaction. In the reaction of (C) the acid anhydride and the hydroxyl group-containing compound, it is necessary that the (C) acid anhydride is completely ring-opened and does not remain as an unreacted acid anhydride. It is necessary not to remain alone.
上記（ Ａ ）２官能芳香族エポキシ樹脂類のエポキシ樹脂としては、２官能芳香族フェノールをグリシジルエーテル化物である２官能芳香族エポキシ樹脂であり、２官能芳香族フェノールとしてはビスフェノールＡ（ＢＰＡ）、ビスフェノールＦ、ビスフェノールＳ、４，４’−ビフェノール、テトラメチルビスフェノールＡ、ジメチルビスフェノールＡ、テトラメチルビスフェノールＦ、ジメチルビスフェノールＦ、テトラメチルビスフェノールＳ、ジメチルビスフェノールＳ、ビフェニル、テトラメチルビフェニルテトラメチル−４，４’−ビフェノール、ジメチル−４，４’−ビフェノール、１−（４−ヒドロキシフェニル）−２−［４−（１，１−ビス−（４−ヒドロキシフェニル）エチル）フェニル］プロパン、２，２’−メチレン−ビス（４−メチル−６−ｔｅｒｔ−ブチルフェノール）、４，４’−ブチリデン−ビス（３−メチル−６−ｔｅｒｔ−ブチルフェノール）、トリスヒドロキシフェニルメタン、レゾルシノール、ハイドロキノン、１，１−ジ−４−ヒドロキシフェニルフルオレン等の２官能芳香族フェノールが挙げられる。これらは単独であるいは２種以上あわせて用いられる。 The epoxy resin of the (A) bifunctional aromatic epoxy resin is a bifunctional aromatic epoxy resin that is a glycidyl etherified product of a difunctional aromatic phenol, and the bifunctional aromatic phenol is bisphenol A (BPA), Bisphenol F, bisphenol S, 4,4′-biphenol, tetramethyl bisphenol A, dimethyl bisphenol A, tetramethyl bisphenol F, dimethyl bisphenol F, tetramethyl bisphenol S, dimethyl bisphenol S, biphenyl, tetramethylbiphenyl tetramethyl-4, 4′-biphenol, dimethyl-4,4′-biphenol, 1- (4-hydroxyphenyl) -2- [4- (1,1-bis- (4-hydroxyphenyl) ethyl) phenyl] propane, 2,2 '-Methyl -Bis (4-methyl-6-tert-butylphenol), 4,4'-butylidene-bis (3-methyl-6-tert-butylphenol), trishydroxyphenylmethane, resorcinol, hydroquinone, 1,1-di-4 -Bifunctional aromatic phenols such as hydroxyphenylfluorene. These may be used alone or in combination of two or more.
上記（ Ｂ ）成分のリン含有フェノール化合物としては、一般式（１）に示される化合物である。 The phosphorus-containing phenol compound as the component (B) is a compound represented by the general formula (1).
この化合物に該当する具体的な例として、例えば、１０−（２，５−ジヒドロキシフェニル）−１０Ｈ−９−オキサ−１０−ホスファフェナントレン−１０−オキシド（三光株式会社製 商品名ＨＣＡ−ＨＱ）、１０−（１，４−ジオキシナフタレン）−１０Ｈ−９−オキサ−１０−ホスファフェナントレン−１０−オキシド、ジフェニルホスフィニルヒドロキノン（北興化学工業株式会社製 商品名ＰＰＱ）、ジフェニルホスフェニル−１，４−ジオキシナフタリン、１，４−シクロオクチレンホスフィニル−１，４−フェニルジオール（日本化学工業株式会社製 商品名ＣＰＨＯ−ＨＱ）、１，５−シクロオクチレンホスフィニル−１，４−フェニルジオール（日本化学工業株式会社製 商品名ＣＰＨＯ−ＨＱ）等のリン含有フェノール類を挙げる事ができるが、これらに限定されるものではない。
また、これらのリン含有フェノール化合物は２種類以上を併用して使用する事もできる。これらリン化合物のうち一般式（１）で示されるＡがベンゼン環であるものが硬化物の色の面から特に好ましい。
As a specific example corresponding to this compound, for example, 10- (2,5-dihydroxyphenyl) -10H-9-oxa-10-phosphaphenanthrene-10-oxide (trade name HCA-HQ manufactured by Sanko Co., Ltd.) 10- (1,4-dioxynaphthalene) -10H-9-oxa-10-phosphaphenanthrene-10-oxide, diphenylphosphinylhydroquinone (trade name PPQ, manufactured by Hokuko Chemical Co., Ltd.), diphenylphosphenyl- 1,4-dioxynaphthalene, 1,4-cyclooctylenephosphinyl-1,4-phenyldiol (trade name CPHO-HQ, manufactured by Nippon Chemical Industry Co., Ltd.), 1,5-cyclooctylenephosphinyl- Phosphorus-containing phenols such as 1,4-phenyldiol (trade name CPHO-HQ manufactured by Nippon Chemical Industry Co., Ltd.) However, it is not limited to these.
These phosphorus-containing phenol compounds can be used in combination of two or more. Among these phosphorus compounds, those in which A represented by the general formula (1) is a benzene ring are particularly preferred from the viewpoint of the color of the cured product.
上記（ Ｂ ）成分のフルオレン環含有フェノール化合物としては一般式(２)に示される化合物であり、ビスフェノールフルオレン（ＢＰＦＬ）または、ビスクレゾールフルオレン（ＢＣＦＬ）が好ましい。 The fluorene ring-containing phenol compound of the component (B) is a compound represented by the general formula (2), and bisphenol fluorene (BPFL) or biscresol fluorene (BCFL) is preferable.
上記（ Ｃ ）酸無水物の開環反応を由来とする骨格とは、酸無水物基と水酸基含有化合物との反応により形成されたエステル結合（カルボニル基）および開環反応時に同時に形成されるカルボキシル基とエポキシ基との反応により形成されるエステル結合の両者を示すものである。酸無水物としては、メチルヘキサヒドロフタル酸、ヘキサヒドロフタル酸、メチルテトラヒドロフタル酸、テトラヒドロフタル酸、メチルナジック酸、フタル酸、イソフタル酸、テレフタル酸等の脂環族及び芳香族多価カルボン酸類の無水物が挙げられ、単独あるいは２種以上の混合物として使うことができる。
また、水酸基含有化合物としては２価アルコールに代表され、エチレングリコール、プロピレングリコール、ネオペンチルグリコール、１，６−ヘキサンジオール等の脂肪族グリコール類、２，２−ビス（４−ヒドロキシシクロヘキシル）プロパン（水添ビスフェノールＡ）、１，４シクロヘキサンジメタノール、ビス（４−ヒドロキシシクロヘキシル）メタン、スピログリコール、２−（５−エチル−５−ヒドロキシメチル−１，３−ジオキサン−２−イル）−２−メチルプロパン−１−オール等の脂環族グリコール類が挙げられ、単独あるいは２種以上の混合物として使うことができる。
The skeleton derived from the ring opening reaction of (C) acid anhydride is an ester bond (carbonyl group) formed by the reaction of an acid anhydride group and a hydroxyl group-containing compound and a carboxyl formed simultaneously during the ring opening reaction. It shows both ester bonds formed by the reaction of a group and an epoxy group. Examples of acid anhydrides include alicyclic and aromatic polycarboxylic acids such as methylhexahydrophthalic acid, hexahydrophthalic acid, methyltetrahydrophthalic acid, tetrahydrophthalic acid, methylnadic acid, phthalic acid, isophthalic acid, and terephthalic acid. Can be used alone or as a mixture of two or more.
Examples of the hydroxyl group-containing compound include dihydric alcohols, aliphatic glycols such as ethylene glycol, propylene glycol, neopentyl glycol, and 1,6-hexanediol, 2,2-bis (4-hydroxycyclohexyl) propane ( Hydrogenated bisphenol A), 1,4 cyclohexanedimethanol, bis (4-hydroxycyclohexyl) methane, spiroglycol, 2- (5-ethyl-5-hydroxymethyl-1,3-dioxan-2-yl) -2- Examples thereof include alicyclic glycols such as methylpropan-1-ol, which can be used alone or as a mixture of two or more.
（Ｂ）リン含有フェノール化合物及び／又はフルオレン環含有フェノール化合物は（Ａ）２官能芳香族エポキシ樹脂類１ｍｏｌに対して０．２ｍｏｌ〜０．７ｍｏｌ用いることができ、０．２ｍｏｌ以下では耐熱性に劣り、含有量を増やすことにより、屈折率および耐熱黄変性は高くなるが、０．７ｍｏｌ以上ではエポキシ樹脂（Ｄ）の軟化点が高くなり実用性に劣るものとなる。 (B) The phosphorus-containing phenol compound and / or the fluorene ring-containing phenol compound can be used in an amount of 0.2 mol to 0.7 mol with respect to 1 mol of the (A) bifunctional aromatic epoxy resin. Inferior, increasing the content increases the refractive index and heat-resistant yellowing, but if it is 0.7 mol or more, the softening point of the epoxy resin (D) increases and the practicality becomes inferior.
また、（Ｃ）酸無水物の開環反応物は２官能芳香族エポキシ樹脂類１ｍｏｌに対して０．２ｍｏｌ〜０．７ｍｏｌ用いることができ、この場合には含有量を増やすことにより、屈折率は小さくなる傾向となる。（Ｂ）リン含有フェノール化合物及び／又はフルオレン環含有フェノール化合物の含有量を（Ａ）２官能芳香族エポキシ樹脂類１ｍｏｌに対して０．２ｍｏｌ〜０．７ｍｏｌとすること、および（Ｃ）酸無水物の開環反応物を（Ａ）２官能芳香族エポキシ樹脂類１ｍｏｌに対して０．２ｍｏｌ〜０．７ｍｏｌとすることにより、高屈折率と高耐熱黄変性とを具備するエポキシ樹脂（Ｄ）を得ることができる。 In addition, the ring opening reaction product of (C) acid anhydride can be used in an amount of 0.2 mol to 0.7 mol with respect to 1 mol of the bifunctional aromatic epoxy resin. In this case, the refractive index is increased by increasing the content. Tends to be smaller. (B) The content of the phosphorus-containing phenol compound and / or the fluorene ring-containing phenol compound is 0.2 mol to 0.7 mol with respect to 1 mol of the bifunctional aromatic epoxy resin (A), and (C) acid anhydride The epoxy resin (D) having high refractive index and high heat-resistant yellowing property by setting the ring-opening reaction product of the product to 0.2 mol to 0.7 mol with respect to 1 mol of the bifunctional aromatic epoxy resin (A) Can be obtained.
（Ｂ）リン含有フェノール化合物の骨格及び／又はフルオレン環含有フェノール化合物と（Ｃ）酸無水物と水酸基との反応を由来とする骨格の成分をそれぞれ０．２ｍｏｌの配合量とした場合、エポキシ当量は５００ｇ／ｅｑ程度となり、この配合量を下回る場合は高屈折率と高耐熱黄変性の効果が見込めない。逆にエポキシ当量が１，０００ｇ／ｅｑを超える場合は得られるエポキシ樹脂の軟化点が高くなってしまい成形、塗工が困難となる。エポキシ樹脂（Ｄ）の好ましいエポキシ当量の範囲は５００ｇ／ｅｑ〜１，０００ｇ／ｅｑであり、より好ましくは８００ｇ／ｅｑ〜１，０００ｇ／ｅｑであり、更に好ましくは８５０ｇ／ｅｑ〜９５０ｇ／ｅｑである。 (B) When the amount of the skeleton component derived from the reaction between the skeleton of the phosphorus-containing phenol compound and / or the fluorene ring-containing phenol compound and (C) the acid anhydride and the hydroxyl group is 0.2 mol, epoxy equivalent Is about 500 g / eq, and if it is less than this amount, the effects of high refractive index and high heat-resistant yellowing cannot be expected. On the other hand, when the epoxy equivalent exceeds 1,000 g / eq, the softening point of the resulting epoxy resin becomes high, and molding and coating become difficult. The preferable epoxy equivalent range of the epoxy resin (D) is 500 g / eq to 1,000 g / eq, more preferably 800 g / eq to 1,000 g / eq, and still more preferably 850 g / eq to 950 g / eq. is there.
実施例及び比較例に基づき本発明を具体的に説明するが本発明の範囲がこれらの実施例に限定されるものではない。以下の合成例、実施例及び比較例に於いて、「部」は「重量部」を示す。さらに本発明では以下の試験方法を使用した。
エポキシ当量 ：ＪＩＳ Ｋ−７２３６により測定した。
軟化点：ＪＩＳ Ｋ−７２３４により測定した。
屈折率： ERMA社製アッベ屈折計ＥＲ−７ＭＷを使用し、シクロヘキサノンに固形分３０重量％となるように溶解し、測定を行い、計算により固形分１００％の屈折率を求めた。
Ｔｇ（ガラス転移温度） ：ＳＩＩ社製 ＥＸＴＥＲ ＤＳＣ６２００を使用して、２０℃から１０℃／分の昇温速度により測定した。
ΔＹＩ値（イエローインデックス）：東京電色社製測色色差計 TC-1500MC-88を使用して測定を行い、熱履歴を掛ける前のＹＩ値をブランクとして所定熱履歴後のＹＩ値との差を示した。
透過度：日本分光株式会社製 Ｖ−６５０を使用し、波長４５０ｎｍでの透過率を記載した。
The present invention will be specifically described based on Examples and Comparative Examples, but the scope of the present invention is not limited to these Examples. In the following synthesis examples, examples and comparative examples, “parts” means “parts by weight”. Furthermore, the following test method was used in the present invention.
Epoxy equivalent: Measured according to JIS K-7236.
Softening point: Measured according to JIS K-7234.
Refractive index: An Abbe refractometer ER-7MW manufactured by ERMA was used, dissolved in cyclohexanone so as to have a solid content of 30% by weight, measured, and a refractive index of 100% solid content was obtained by calculation.
Tg (glass transition temperature): Measured at 20 ° C. to 10 ° C./min temperature increase rate using EXTER DSC6200 manufactured by SII.
ΔYI value (Yellow index): Measured using a colorimetric color difference meter TC-1500MC-88 manufactured by Tokyo Denshoku Co., Ltd. The difference from the YI value after a predetermined thermal history with the YI value before applying the thermal history as a blank showed that.
Transmittance: V-650 manufactured by JASCO Corporation was used, and the transmittance at a wavelength of 450 nm was described.
合成例 １
攪拌機、温度計、窒素吹き込み管、及び冷却管を備えた反応装置にリカシッドＨＨ（ヘキサヒドロ無水フタル酸（ＨＨＰＡ）；新日本理化製）７５．３部とリカビノールＨＢ（水添ビスフェノールＡ（ＨＢＰＡ）；新日本理化製）３０．９部との混合物を窒素ガス雰囲気中で撹拌しながら１３０℃で２時間反応させて、次いでＹＤ−１２８（２，２−ビス（４−ヒドロキシフェニル）プロパンのジグリシジルエーテル；新日鐵化学製、エポキシ当量１８７ｇ／ｅｑ、粘度１３，０００ｍＰｓ・ｓ／２５℃）３７４部及び１０−（２，５−ジヒドロキシフェニル）−１０Ｈ−９−オキサ−１０−ホスファフェナントレン−１０−オキシド（三光株式会社製 商品名ＨＣＡ−ＨＱ、融点２５６℃、リン含有量９．６％、水酸基当量１６２ｇ／ｅｑ．）を１１１．４部及びトリフェニルフォスフェイト０．２重量部を仕込み１５０℃で４時間攪拌混合して軟化点１０７℃、エポキシ当量９０9ｇ／ｅｑの樹脂１を得た。
Synthesis example 1
In a reactor equipped with a stirrer, a thermometer, a nitrogen blowing tube, and a cooling tube, 75.3 parts of Ricacid HH (Hexahydrophthalic anhydride (HHPA); manufactured by Nippon Nippon Chemical Co., Ltd.) and Ricabinol HB (hydrogenated bisphenol A (HBPA)); Nihon Rika Co., Ltd.) 30.9 parts of the mixture were reacted in a nitrogen gas atmosphere with stirring at 130 ° C. for 2 hours, and then YD-128 (2,2-bis (4-hydroxyphenyl) propane diglycidyl Ether: Nippon Steel Chemical Co., Ltd., epoxy equivalent 187 g / eq, viscosity 13,000 mPs · s / 25 ° C.) 374 parts and 10- (2,5-dihydroxyphenyl) -10H-9-oxa-10-phosphaphenanthrene- 10-oxide (trade name HCA-HQ, manufactured by Sanko Co., Ltd., melting point 256 ° C., phosphorus content 9.6%, hydroxyl group equivalent 162 g / eq. 111.4 parts and 0.2 parts by weight of triphenyl phosphate were added and stirred and mixed at 150 ° C. for 4 hours to obtain Resin 1 having a softening point of 107 ° C. and an epoxy equivalent of 909 g / eq.
合成例 ２−１６
実施例１で使用した装置を用い、表１に記載の割合で合成例１と同様の条件及び操作によって合成を行い、それぞれ樹脂２〜１４を得た。なお、合成例１１で使用したエポキシ樹脂ＹＤＦ−１７０は、２，２−ビス（４−ヒドロキシフェニル）メタンのジグリシジルエーテル（新日鐵化学製、エポキシ当量１７０ｇ／ｅｑ、粘度３，５００ｍＰｓ・ｓ／２５℃）である。
Synthesis Example 2-16
Using the apparatus used in Example 1, synthesis was performed under the same conditions and operations as in Synthesis Example 1 at the ratios shown in Table 1, and Resins 2 to 14 were obtained, respectively. The epoxy resin YDF-170 used in Synthesis Example 11 is diglycidyl ether of 2,2-bis (4-hydroxyphenyl) methane (manufactured by Nippon Steel Chemical Co., Ltd., epoxy equivalent 170 g / eq, viscosity 3,500 mPs · s). / 25 ° C).
実施例１
合成例１で得られた硬化剤として樹脂１を１００部と硬化剤としてリカシッドＨＨを１３部と溶剤であるテトラヒドロフラン７５部に溶解した後、硬化触媒としてヒシコーリンＰＸ−４ＥＴ（日本化学工業株式会社製 有機ホスホニウム塩化合物）０．２５部を混合し、０．２ｍｍ厚のガラス板に乾燥後フィルムとして１００μｍとなるように塗布し、１００℃の熱風循環オーブンに２時間により乾燥させた後に、１４０℃の熱風循環オーブンで１０時間硬化させ、ガラス板付きの試験片を得た。得られたガラス板付きの試験片をそのまま利用してΔＹＩ値と透過度を測定した。その結果を表２に示した。
Example 1
After dissolving 100 parts of resin 1 as a curing agent obtained in Synthesis Example 1 and 13 parts of liquid HH as a curing agent and 75 parts of tetrahydrofuran as a solvent, Hishicolin PX-4ET (manufactured by Nippon Chemical Industry Co., Ltd.) as a curing catalyst (Organic phosphonium salt compound) 0.25 part was mixed, applied to a 0.2 mm-thick glass plate to a film thickness of 100 μm after drying, dried in a hot air circulating oven at 100 ° C. for 2 hours, and then 140 ° C. Was cured for 10 hours in a hot air circulating oven to obtain a test piece with a glass plate. The obtained specimen with glass plate was used as it was, and the ΔYI value and the transmittance were measured. The results are shown in Table 2.
実施例２〜実施例９及び比較例１〜７
合成例２〜１６で得られた樹脂２〜１６を用い、実施例１と同様の硬化条件により試験片を作成し、評価を行った。その結果を表２に示した。
Examples 2 to 9 and Comparative Examples 1 to 7
Using the resins 2 to 16 obtained in Synthesis Examples 2 to 16, test pieces were prepared under the same curing conditions as in Example 1 and evaluated. The results are shown in Table 2.
本発明は、高温に曝される部位に使用される透明性、耐熱信頼性（高耐熱黄変性）を発現し、性能を維持できることを特徴としたエポキシ樹脂硬化物を提供し、特に電子材料用途に利用することが出来る。また、低軟化点であるエポキシ樹脂（Ｄ）を用いることによって、成形性、塗工性に優れるエポキシ樹脂組成物とすることができる。 The present invention provides a cured epoxy resin characterized in that it exhibits transparency and heat resistance reliability (high heat yellowing) used in parts exposed to high temperatures, and can maintain performance, particularly for electronic materials. Can be used. Moreover, it can be set as the epoxy resin composition excellent in a moldability and coating property by using the epoxy resin (D) which is a low softening point.
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| JP2015178592A (en) * | 2014-02-27 | 2015-10-08 | 新日鉄住金化学株式会社 | Method for producing fluorene skeleton-containing epoxy resin, epoxy resin composition, and cured product |
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| CN104725600A (en) * | 2013-12-19 | 2015-06-24 | 新日铁住金化学株式会社 | The optical epoxy resin composition and cured product thereof |
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| KR102261966B1 (en) * | 2013-12-19 | 2021-06-07 | 닛테츠 케미컬 앤드 머티리얼 가부시키가이샤 | The optical epoxy resin composition and cured product thereof |
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| KR20150101932A (en) | 2014-02-27 | 2015-09-04 | 신닛테츠 수미킨 가가쿠 가부시키가이샤 | Method for producing fluorene skeleton-containing epoxy resin, epoxy resin composition, and cured product thereof |
| JP2015178592A (en) * | 2014-02-27 | 2015-10-08 | 新日鉄住金化学株式会社 | Method for producing fluorene skeleton-containing epoxy resin, epoxy resin composition, and cured product |
| TWI654216B (en) | 2014-02-27 | 2019-03-21 | 日商日鐵化學材料股份有限公司 | Epoxy resin having fluorene skeleton and method for producing the same, epoxy resin composition and application thereof, and cured object |
| KR102289998B1 (en) * | 2014-02-27 | 2021-08-13 | 닛테츠 케미컬 앤드 머티리얼 가부시키가이샤 | Method for producing fluorene skeleton-containing epoxy resin, epoxy resin composition, and cured product thereof |
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