WO2011108588A1 - Curable resin composition and cured article thereof - Google Patents
Curable resin composition and cured article thereof Download PDFInfo
- Publication number
- WO2011108588A1 WO2011108588A1 PCT/JP2011/054767 JP2011054767W WO2011108588A1 WO 2011108588 A1 WO2011108588 A1 WO 2011108588A1 JP 2011054767 W JP2011054767 W JP 2011054767W WO 2011108588 A1 WO2011108588 A1 WO 2011108588A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- group
- resin composition
- curable resin
- epoxy resin
- alicyclic epoxy
- Prior art date
Links
- 239000011342 resin composition Substances 0.000 title claims abstract description 105
- 239000003822 epoxy resin Substances 0.000 claims abstract description 130
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 130
- 229920001296 polysiloxane Polymers 0.000 claims abstract description 79
- 125000002723 alicyclic group Chemical group 0.000 claims abstract description 74
- 150000008065 acid anhydrides Chemical class 0.000 claims abstract description 39
- 239000004065 semiconductor Substances 0.000 claims abstract description 34
- -1 saturated aliphatic cyclic acid anhydride Chemical class 0.000 claims description 123
- 150000001875 compounds Chemical class 0.000 claims description 51
- 239000000203 mixture Substances 0.000 claims description 47
- 230000003287 optical effect Effects 0.000 claims description 44
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims description 37
- 239000004593 Epoxy Substances 0.000 claims description 25
- 125000004432 carbon atom Chemical group C* 0.000 claims description 19
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 15
- 238000007789 sealing Methods 0.000 claims description 11
- 150000005846 sugar alcohols Polymers 0.000 claims description 8
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 claims description 6
- 238000005538 encapsulation Methods 0.000 claims description 4
- 235000010290 biphenyl Nutrition 0.000 claims description 3
- 239000004305 biphenyl Substances 0.000 claims description 3
- 125000006267 biphenyl group Chemical group 0.000 claims description 2
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- 238000006467 substitution reaction Methods 0.000 claims 2
- 229920005989 resin Polymers 0.000 abstract description 30
- 239000011347 resin Substances 0.000 abstract description 30
- 230000006866 deterioration Effects 0.000 abstract description 5
- 239000012776 electronic material Substances 0.000 abstract description 5
- 230000000704 physical effect Effects 0.000 abstract description 3
- 239000000565 sealant Substances 0.000 abstract description 3
- 238000001723 curing Methods 0.000 description 77
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 70
- 238000006243 chemical reaction Methods 0.000 description 63
- 239000000047 product Substances 0.000 description 63
- 238000004519 manufacturing process Methods 0.000 description 58
- 239000000463 material Substances 0.000 description 52
- 239000003795 chemical substances by application Substances 0.000 description 40
- 239000003566 sealing material Substances 0.000 description 38
- 238000012360 testing method Methods 0.000 description 36
- 229920002545 silicone oil Polymers 0.000 description 35
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 35
- 230000001070 adhesive effect Effects 0.000 description 29
- 238000005227 gel permeation chromatography Methods 0.000 description 29
- 230000015572 biosynthetic process Effects 0.000 description 28
- 238000000034 method Methods 0.000 description 28
- 239000002904 solvent Substances 0.000 description 27
- 238000003786 synthesis reaction Methods 0.000 description 27
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 25
- 239000000243 solution Substances 0.000 description 24
- 239000000853 adhesive Substances 0.000 description 23
- 125000003545 alkoxy group Chemical group 0.000 description 23
- 229910019142 PO4 Inorganic materials 0.000 description 20
- 239000003054 catalyst Substances 0.000 description 20
- 239000010408 film Substances 0.000 description 20
- 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 20
- 238000002156 mixing Methods 0.000 description 20
- 235000021317 phosphate Nutrition 0.000 description 20
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 19
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 19
- 238000010992 reflux Methods 0.000 description 19
- 229910052725 zinc Inorganic materials 0.000 description 19
- 239000011701 zinc Substances 0.000 description 19
- 239000010452 phosphate Substances 0.000 description 18
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 17
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 17
- 230000000052 comparative effect Effects 0.000 description 17
- 239000000758 substrate Substances 0.000 description 17
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 16
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 16
- 229910052698 phosphorus Inorganic materials 0.000 description 16
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Natural products OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 15
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 15
- 150000002148 esters Chemical class 0.000 description 15
- 239000011521 glass Substances 0.000 description 15
- 239000007788 liquid Substances 0.000 description 15
- 239000011574 phosphorus Substances 0.000 description 15
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 14
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 14
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 14
- 239000007789 gas Substances 0.000 description 14
- 239000000126 substance Substances 0.000 description 14
- 125000003700 epoxy group Chemical group 0.000 description 13
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 13
- 239000012321 sodium triacetoxyborohydride Substances 0.000 description 13
- 150000003751 zinc Chemical class 0.000 description 13
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 12
- 238000005259 measurement Methods 0.000 description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 11
- 238000010438 heat treatment Methods 0.000 description 11
- 229910052757 nitrogen Inorganic materials 0.000 description 11
- 239000002253 acid Substances 0.000 description 10
- 150000001412 amines Chemical class 0.000 description 10
- 125000005372 silanol group Chemical group 0.000 description 10
- 238000005406 washing Methods 0.000 description 10
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 9
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 9
- 239000000654 additive Substances 0.000 description 9
- 238000006482 condensation reaction Methods 0.000 description 9
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 9
- 238000000605 extraction Methods 0.000 description 9
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 9
- VYKXQOYUCMREIS-UHFFFAOYSA-N methylhexahydrophthalic anhydride Chemical compound C1CCCC2C(=O)OC(=O)C21C VYKXQOYUCMREIS-UHFFFAOYSA-N 0.000 description 9
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 9
- 230000035699 permeability Effects 0.000 description 9
- 230000001681 protective effect Effects 0.000 description 9
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 8
- 239000003963 antioxidant agent Substances 0.000 description 8
- 230000003078 antioxidant effect Effects 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 8
- 239000004611 light stabiliser Substances 0.000 description 8
- 150000002989 phenols Chemical class 0.000 description 8
- FWHUTKPMCKSUCV-UHFFFAOYSA-N 1,3-dioxo-3a,4,5,6,7,7a-hexahydro-2-benzofuran-5-carboxylic acid Chemical compound C1C(C(=O)O)CCC2C(=O)OC(=O)C12 FWHUTKPMCKSUCV-UHFFFAOYSA-N 0.000 description 7
- 239000003463 adsorbent Substances 0.000 description 7
- 150000001298 alcohols Chemical class 0.000 description 7
- 238000005260 corrosion Methods 0.000 description 7
- 238000004821 distillation Methods 0.000 description 7
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 7
- 239000012044 organic layer Substances 0.000 description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 6
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 6
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 6
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 6
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 6
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 6
- 125000000217 alkyl group Chemical group 0.000 description 6
- 230000007797 corrosion Effects 0.000 description 6
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical group [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 6
- 239000010410 layer Substances 0.000 description 6
- 229910000403 monosodium phosphate Inorganic materials 0.000 description 6
- 235000019799 monosodium phosphate Nutrition 0.000 description 6
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 6
- 239000002245 particle Substances 0.000 description 6
- 239000012945 sealing adhesive Substances 0.000 description 6
- SCPYDCQAZCOKTP-UHFFFAOYSA-N silanol Chemical compound [SiH3]O SCPYDCQAZCOKTP-UHFFFAOYSA-N 0.000 description 6
- 229910052709 silver Inorganic materials 0.000 description 6
- 239000004332 silver Substances 0.000 description 6
- AJPJDKMHJJGVTQ-UHFFFAOYSA-M sodium dihydrogen phosphate Chemical compound [Na+].OP(O)([O-])=O AJPJDKMHJJGVTQ-UHFFFAOYSA-M 0.000 description 6
- 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 6
- 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 5
- RGAHHPQKNPTZEY-UHFFFAOYSA-N 2-ethyl-4-methylhexane-1,1-diol Chemical compound CCC(C)CC(CC)C(O)O RGAHHPQKNPTZEY-UHFFFAOYSA-N 0.000 description 5
- 229910002012 Aerosil® Inorganic materials 0.000 description 5
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 5
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 5
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 5
- 238000000576 coating method Methods 0.000 description 5
- 238000009833 condensation Methods 0.000 description 5
- 230000005494 condensation Effects 0.000 description 5
- 239000012153 distilled water Substances 0.000 description 5
- 239000011256 inorganic filler Substances 0.000 description 5
- 229910003475 inorganic filler Inorganic materials 0.000 description 5
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 5
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 5
- OTLDLKLSNZMTTA-UHFFFAOYSA-N octahydro-1h-4,7-methanoindene-1,5-diyldimethanol Chemical compound C1C2C3C(CO)CCC3C1C(CO)C2 OTLDLKLSNZMTTA-UHFFFAOYSA-N 0.000 description 5
- 238000005580 one pot reaction Methods 0.000 description 5
- 239000012074 organic phase Substances 0.000 description 5
- 230000002093 peripheral effect Effects 0.000 description 5
- 229920003216 poly(methylphenylsiloxane) Polymers 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- 230000002829 reductive effect Effects 0.000 description 5
- 150000003839 salts Chemical class 0.000 description 5
- 238000002834 transmittance Methods 0.000 description 5
- LTVUCOSIZFEASK-MPXCPUAZSA-N (3ar,4s,7r,7as)-3a-methyl-3a,4,7,7a-tetrahydro-4,7-methano-2-benzofuran-1,3-dione Chemical compound C([C@H]1C=C2)[C@H]2[C@H]2[C@]1(C)C(=O)OC2=O LTVUCOSIZFEASK-MPXCPUAZSA-N 0.000 description 4
- ICKWICRCANNIBI-UHFFFAOYSA-N 2,4-di-tert-butylphenol Chemical compound CC(C)(C)C1=CC=C(O)C(C(C)(C)C)=C1 ICKWICRCANNIBI-UHFFFAOYSA-N 0.000 description 4
- JECYUBVRTQDVAT-UHFFFAOYSA-N 2-acetylphenol Chemical compound CC(=O)C1=CC=CC=C1O JECYUBVRTQDVAT-UHFFFAOYSA-N 0.000 description 4
- 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 4
- RGHHSNMVTDWUBI-UHFFFAOYSA-N 4-hydroxybenzaldehyde Chemical compound OC1=CC=C(C=O)C=C1 RGHHSNMVTDWUBI-UHFFFAOYSA-N 0.000 description 4
- MWSKJDNQKGCKPA-UHFFFAOYSA-N 6-methyl-3a,4,5,7a-tetrahydro-2-benzofuran-1,3-dione Chemical compound C1CC(C)=CC2C(=O)OC(=O)C12 MWSKJDNQKGCKPA-UHFFFAOYSA-N 0.000 description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 4
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 4
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 4
- 125000003118 aryl group Chemical group 0.000 description 4
- 239000002585 base Substances 0.000 description 4
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 description 4
- IIWFPIKUKKAYDT-UHFFFAOYSA-N bicyclo[2.2.1]hept-2-ene-3,4-diol Chemical compound C1CC2(O)C(O)=CC1C2 IIWFPIKUKKAYDT-UHFFFAOYSA-N 0.000 description 4
- 239000011230 binding agent Substances 0.000 description 4
- IMHDGJOMLMDPJN-UHFFFAOYSA-N biphenyl-2,2'-diol Chemical compound OC1=CC=CC=C1C1=CC=CC=C1O IMHDGJOMLMDPJN-UHFFFAOYSA-N 0.000 description 4
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 4
- 238000005266 casting Methods 0.000 description 4
- 239000008393 encapsulating agent Substances 0.000 description 4
- LZCLXQDLBQLTDK-UHFFFAOYSA-N ethyl 2-hydroxypropanoate Chemical compound CCOC(=O)C(C)O LZCLXQDLBQLTDK-UHFFFAOYSA-N 0.000 description 4
- HYBBIBNJHNGZAN-UHFFFAOYSA-N furfural Chemical compound O=CC1=CC=CO1 HYBBIBNJHNGZAN-UHFFFAOYSA-N 0.000 description 4
- 150000007529 inorganic bases Chemical class 0.000 description 4
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 4
- 239000004973 liquid crystal related substance Substances 0.000 description 4
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 4
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 4
- NXPPAOGUKPJVDI-UHFFFAOYSA-N naphthalene-1,2-diol Chemical compound C1=CC=CC2=C(O)C(O)=CC=C21 NXPPAOGUKPJVDI-UHFFFAOYSA-N 0.000 description 4
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 4
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 4
- 238000004382 potting Methods 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 229920002050 silicone resin Polymers 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 125000001424 substituent group Chemical group 0.000 description 4
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 description 4
- KNDQHSIWLOJIGP-UMRXKNAASA-N (3ar,4s,7r,7as)-rel-3a,4,7,7a-tetrahydro-4,7-methanoisobenzofuran-1,3-dione Chemical compound O=C1OC(=O)[C@@H]2[C@H]1[C@]1([H])C=C[C@@]2([H])C1 KNDQHSIWLOJIGP-UMRXKNAASA-N 0.000 description 3
- OVGRCEFMXPHEBL-UHFFFAOYSA-N 1-ethenoxypropane Chemical group CCCOC=C OVGRCEFMXPHEBL-UHFFFAOYSA-N 0.000 description 3
- DSKYSDCYIODJPC-UHFFFAOYSA-N 2-butyl-2-ethylpropane-1,3-diol Chemical compound CCCCC(CC)(CO)CO DSKYSDCYIODJPC-UHFFFAOYSA-N 0.000 description 3
- QCBSYPYHCJMQGB-UHFFFAOYSA-N 2-ethyl-1,3,5-triazine Chemical compound CCC1=NC=NC=N1 QCBSYPYHCJMQGB-UHFFFAOYSA-N 0.000 description 3
- LQOPXMZSGSTGMF-UHFFFAOYSA-N 6004-79-1 Chemical compound C1CC2C3C(=O)OC(=O)C3C1C2 LQOPXMZSGSTGMF-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- 229910052684 Cerium Inorganic materials 0.000 description 3
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 description 3
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 3
- 239000004952 Polyamide Chemical class 0.000 description 3
- 239000004793 Polystyrene Substances 0.000 description 3
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 description 3
- 230000002411 adverse Effects 0.000 description 3
- 125000003342 alkenyl group Chemical group 0.000 description 3
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- 150000002736 metal compounds Chemical class 0.000 description 1
- RTWNYYOXLSILQN-UHFFFAOYSA-N methanediamine Chemical compound NCN RTWNYYOXLSILQN-UHFFFAOYSA-N 0.000 description 1
- GQKZBCPTCWJTAS-UHFFFAOYSA-N methoxymethylbenzene Chemical compound COCC1=CC=CC=C1 GQKZBCPTCWJTAS-UHFFFAOYSA-N 0.000 description 1
- QLPMKRZYJPNIRP-UHFFFAOYSA-M methyl(trioctyl)azanium;bromide Chemical compound [Br-].CCCCCCCC[N+](C)(CCCCCCCC)CCCCCCCC QLPMKRZYJPNIRP-UHFFFAOYSA-M 0.000 description 1
- XKBGEWXEAPTVCK-UHFFFAOYSA-M methyltrioctylammonium chloride Chemical compound [Cl-].CCCCCCCC[N+](C)(CCCCCCCC)CCCCCCCC XKBGEWXEAPTVCK-UHFFFAOYSA-M 0.000 description 1
- 239000003094 microcapsule Substances 0.000 description 1
- 238000001393 microlithography Methods 0.000 description 1
- 229910003465 moissanite Inorganic materials 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- ORECYURYFJYPKY-UHFFFAOYSA-N n,n'-bis(2,2,6,6-tetramethylpiperidin-4-yl)hexane-1,6-diamine;2,4,6-trichloro-1,3,5-triazine;2,4,4-trimethylpentan-2-amine Chemical compound CC(C)(C)CC(C)(C)N.ClC1=NC(Cl)=NC(Cl)=N1.C1C(C)(C)NC(C)(C)CC1NCCCCCCNC1CC(C)(C)NC(C)(C)C1 ORECYURYFJYPKY-UHFFFAOYSA-N 0.000 description 1
- WQEPLUUGTLDZJY-UHFFFAOYSA-N n-Pentadecanoic acid Natural products CCCCCCCCCCCCCCC(O)=O WQEPLUUGTLDZJY-UHFFFAOYSA-N 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- FDAKZQLBIFPGSV-UHFFFAOYSA-N n-butyl-2,2,6,6-tetramethylpiperidin-4-amine Chemical compound CCCCNC1CC(C)(C)NC(C)(C)C1 FDAKZQLBIFPGSV-UHFFFAOYSA-N 0.000 description 1
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 1
- KYTZHLUVELPASH-UHFFFAOYSA-N naphthalene-1,2-dicarboxylic acid Chemical compound C1=CC=CC2=C(C(O)=O)C(C(=O)O)=CC=C21 KYTZHLUVELPASH-UHFFFAOYSA-N 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000003199 nucleic acid amplification method Methods 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 125000003261 o-tolyl group Chemical group [H]C1=C([H])C(*)=C(C([H])=C1[H])C([H])([H])[H] 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- WWZKQHOCKIZLMA-UHFFFAOYSA-N octanoic acid Chemical compound CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-N 0.000 description 1
- MBAUOPQYSQVYJV-UHFFFAOYSA-N octyl 3-[4-hydroxy-3,5-di(propan-2-yl)phenyl]propanoate Chemical compound OC1=C(C=C(C=C1C(C)C)CCC(=O)OCCCCCCCC)C(C)C MBAUOPQYSQVYJV-UHFFFAOYSA-N 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 230000005693 optoelectronics Effects 0.000 description 1
- 125000000962 organic group Chemical group 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 125000001037 p-tolyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)C([H])([H])[H] 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 125000000913 palmityl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 230000036961 partial effect Effects 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 125000004817 pentamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- 125000002255 pentenyl group Chemical group C(=CCCC)* 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- VGPSLAHKKFPLBQ-UHFFFAOYSA-N phosphane;tris(2-methylphenyl)phosphane Chemical class P.CC1=CC=CC=C1P(C=1C(=CC=CC=1)C)C1=CC=CC=C1C VGPSLAHKKFPLBQ-UHFFFAOYSA-N 0.000 description 1
- 125000004437 phosphorous atom Chemical group 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- JSSXHAMIXJGYCS-UHFFFAOYSA-N piperazin-4-ium-2-carboxylate Chemical compound OC(=O)C1CNCCN1 JSSXHAMIXJGYCS-UHFFFAOYSA-N 0.000 description 1
- 125000003386 piperidinyl group Chemical group 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 229920001467 poly(styrenesulfonates) Polymers 0.000 description 1
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 description 1
- 238000012643 polycondensation polymerization Methods 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 239000009719 polyimide resin Substances 0.000 description 1
- 229920006324 polyoxymethylene Polymers 0.000 description 1
- 150000008442 polyphenolic compounds Chemical class 0.000 description 1
- 235000013824 polyphenols Nutrition 0.000 description 1
- 229920000137 polyphosphoric acid Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 125000004368 propenyl group Chemical group C(=CC)* 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 239000003223 protective agent Substances 0.000 description 1
- 239000011253 protective coating Substances 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000002310 reflectometry Methods 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 238000012552 review Methods 0.000 description 1
- 229910052594 sapphire Inorganic materials 0.000 description 1
- 239000010980 sapphire Substances 0.000 description 1
- 238000007650 screen-printing Methods 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Inorganic materials [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 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
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 239000001488 sodium phosphate Substances 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 239000003760 tallow Substances 0.000 description 1
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 description 1
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
- BRKFQVAOMSWFDU-UHFFFAOYSA-M tetraphenylphosphanium;bromide Chemical compound [Br-].C1=CC=CC=C1[P+](C=1C=CC=CC=1)(C=1C=CC=CC=1)C1=CC=CC=C1 BRKFQVAOMSWFDU-UHFFFAOYSA-M 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- AYEKOFBPNLCAJY-UHFFFAOYSA-O thiamine pyrophosphate Chemical compound CC1=C(CCOP(O)(=O)OP(O)(O)=O)SC=[N+]1CC1=CN=C(C)N=C1N AYEKOFBPNLCAJY-UHFFFAOYSA-O 0.000 description 1
- 239000013008 thixotropic agent Substances 0.000 description 1
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 1
- 238000005809 transesterification reaction Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- STCOOQWBFONSKY-UHFFFAOYSA-N tributyl phosphate Chemical compound CCCCOP(=O)(OCCCC)OCCCC STCOOQWBFONSKY-UHFFFAOYSA-N 0.000 description 1
- CPUDPFPXCZDNGI-UHFFFAOYSA-N triethoxy(methyl)silane Chemical compound CCO[Si](C)(OCC)OCC CPUDPFPXCZDNGI-UHFFFAOYSA-N 0.000 description 1
- JCVQKRGIASEUKR-UHFFFAOYSA-N triethoxy(phenyl)silane Chemical compound CCO[Si](OCC)(OCC)C1=CC=CC=C1 JCVQKRGIASEUKR-UHFFFAOYSA-N 0.000 description 1
- UDUKMRHNZZLJRB-UHFFFAOYSA-N triethoxy-[2-(7-oxabicyclo[4.1.0]heptan-4-yl)ethyl]silane Chemical compound C1C(CC[Si](OCC)(OCC)OCC)CCC2OC21 UDUKMRHNZZLJRB-UHFFFAOYSA-N 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
- AAAQKTZKLRYKHR-UHFFFAOYSA-N triphenylmethane Chemical compound C1=CC=CC=C1C(C=1C=CC=CC=1)C1=CC=CC=C1 AAAQKTZKLRYKHR-UHFFFAOYSA-N 0.000 description 1
- DCAFJGSRSBLEPX-UHFFFAOYSA-N tris(2,3-dibutylphenyl) phosphite Chemical compound CCCCC1=CC=CC(OP(OC=2C(=C(CCCC)C=CC=2)CCCC)OC=2C(=C(CCCC)C=CC=2)CCCC)=C1CCCC DCAFJGSRSBLEPX-UHFFFAOYSA-N 0.000 description 1
- OOZKMYBQDPXENQ-UHFFFAOYSA-N tris(2,3-diethylphenyl) phosphite Chemical compound CCC1=CC=CC(OP(OC=2C(=C(CC)C=CC=2)CC)OC=2C(=C(CC)C=CC=2)CC)=C1CC OOZKMYBQDPXENQ-UHFFFAOYSA-N 0.000 description 1
- WTLBZVNBAKMVDP-UHFFFAOYSA-N tris(2-butoxyethyl) phosphate Chemical compound CCCCOCCOP(=O)(OCCOCCCC)OCCOCCCC WTLBZVNBAKMVDP-UHFFFAOYSA-N 0.000 description 1
- QFGXDXGDZKTYFD-UHFFFAOYSA-N tris[2,3-di(propan-2-yl)phenyl] phosphite Chemical compound CC(C)C1=CC=CC(OP(OC=2C(=C(C(C)C)C=CC=2)C(C)C)OC=2C(=C(C(C)C)C=CC=2)C(C)C)=C1C(C)C QFGXDXGDZKTYFD-UHFFFAOYSA-N 0.000 description 1
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 1
- 229910000406 trisodium phosphate Inorganic materials 0.000 description 1
- 235000019801 trisodium phosphate Nutrition 0.000 description 1
- 238000009281 ultraviolet germicidal irradiation Methods 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 238000013191 viscoelastic testing Methods 0.000 description 1
- 125000005023 xylyl group Chemical group 0.000 description 1
- 239000011667 zinc carbonate Substances 0.000 description 1
- 235000004416 zinc carbonate Nutrition 0.000 description 1
- 229910000010 zinc carbonate Inorganic materials 0.000 description 1
- UGZADUVQMDAIAO-UHFFFAOYSA-L zinc hydroxide Chemical compound [OH-].[OH-].[Zn+2] UGZADUVQMDAIAO-UHFFFAOYSA-L 0.000 description 1
- 229910021511 zinc hydroxide Inorganic materials 0.000 description 1
- 229940007718 zinc hydroxide Drugs 0.000 description 1
- 229940105125 zinc myristate Drugs 0.000 description 1
- IFNXAMCERSVZCV-UHFFFAOYSA-L zinc;2-ethylhexanoate Chemical compound [Zn+2].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O IFNXAMCERSVZCV-UHFFFAOYSA-L 0.000 description 1
- MFXMOUUKFMDYLM-UHFFFAOYSA-L zinc;dihydrogen phosphate Chemical compound [Zn+2].OP(O)([O-])=O.OP(O)([O-])=O MFXMOUUKFMDYLM-UHFFFAOYSA-L 0.000 description 1
- IJQXGKBNDNQWAT-UHFFFAOYSA-L zinc;docosanoate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCCCCCC([O-])=O IJQXGKBNDNQWAT-UHFFFAOYSA-L 0.000 description 1
- GBFLQPIIIRJQLU-UHFFFAOYSA-L zinc;tetradecanoate Chemical compound [Zn+2].CCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCC([O-])=O GBFLQPIIIRJQLU-UHFFFAOYSA-L 0.000 description 1
- 229910052845 zircon Inorganic materials 0.000 description 1
- GFQYVLUOOAAOGM-UHFFFAOYSA-N zirconium(iv) silicate Chemical compound [Zr+4].[O-][Si]([O-])([O-])[O-] GFQYVLUOOAAOGM-UHFFFAOYSA-N 0.000 description 1
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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L23/00—Details of semiconductor or other solid state devices
- H01L23/28—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection
- H01L23/29—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection characterised by the material, e.g. carbon
- H01L23/293—Organic, e.g. plastic
- H01L23/296—Organo-silicon 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
- C08G59/30—Di-epoxy compounds containing atoms other than carbon, hydrogen, oxygen and nitrogen
- C08G59/306—Di-epoxy compounds containing atoms other than carbon, hydrogen, oxygen and nitrogen containing silicon
-
- 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
- C08G59/42—Polycarboxylic acids; Anhydrides, halides or low molecular weight esters thereof
- C08G59/4215—Polycarboxylic acids; Anhydrides, halides or low molecular weight esters thereof cycloaliphatic
-
- 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
- C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
- C08L83/04—Polysiloxanes
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L23/00—Details of semiconductor or other solid state devices
- H01L23/28—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection
- H01L23/29—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection characterised by the material, e.g. carbon
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
- H01L2924/0001—Technical content checked by a classifier
- H01L2924/0002—Not covered by any one of groups H01L24/00, H01L24/00 and H01L2224/00
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L33/00—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L33/48—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor body packages
- H01L33/52—Encapsulations
- H01L33/56—Materials, e.g. epoxy or silicone resin
Definitions
- Patent Document 4 an epoxy resin having an organopolysiloxane structure having a high crosslinking density (containing silicon atoms having three bonded oxygen atoms in a proportion exceeding 40 mol% per all silicon atoms). Attempts have been made to use alicyclic epoxy resins in combination. However, the composition described in Patent Document 4 has a high crosslinking density of the organopolysiloxane and a high content of the alicyclic epoxy resin, so that the cured product becomes too hard although it has excellent adhesion. It has been found that stress is easily applied to the chip when the LED is sealed. Further, it has been found that this causes a problem that illuminance deterioration during lighting is severe.
- LEDs using silicone resins or silicone-modified epoxy resins are generally poor in gas permeability resistance. Therefore, when a silicone resin or a silicone-modified epoxy resin is used as the LED sealing material, coloring on the LED chip is not a problem, but there is a problem that internal components are deteriorated and coloring occurs. . In particular, when used in a living environment, various compounds are floating, and the penetration of such compounds into the interior triggers problems.
- Patent Documents 5 and 6 use techniques such as coating a gas permeation-resistant protective agent and coating a metal part with an inorganic material. In addition to an increase in productivity and productivity, there is a problem in that light extraction efficiency is deteriorated due to a difference in refractive index between the covering portion and the sealant.
- the present invention has been made in view of the above prior art, and the object thereof is a curable resin capable of providing a cured product satisfying various physical properties required as an electrical semiconductor material application, particularly as an optical semiconductor sealing material. It is to provide a composition, specifically, it has excellent curability, adhesiveness, light resistance, heat resistance and gas permeability resistance, and resin stress to a chip when used as an LED sealing material.
- An object of the present invention is to provide a curable resin composition that can provide a cured product that is low in illuminance and does not cause illuminance deterioration.
- (2) Contains an epoxycyclohexyl group-containing organopolysiloxane (A), an alicyclic epoxy resin (B) and an acid anhydride (C), and includes an epoxycyclohexyl group-containing organopolysiloxane (A) and an alicyclic epoxy resin ( A curable resin composition, wherein the amount of the alicyclic epoxy resin (B) in the total amount of B) is 2 to 40% by weight.
- the content of the alicyclic epoxy resin (B) in the total amount of the epoxycyclohexyl group-containing organopolysiloxane (A) and the alicyclic epoxy resin (B) is 10 ⁇ (epoxycyclohexyl group-containing organopolysiloxane ( The curable resin composition according to (1) or (2), wherein the weight average molecular weight of A) / (epoxy equivalent of epoxycyclohexyl group-containing organopolysiloxane (A)) is not more than wt%. (4) The curable resin composition according to any one of (1) to (3) above, further comprising a polyvalent carboxylic acid (D).
- the above polyvalent carboxylic acid (D) is a compound obtained by reacting a bi- to hexafunctional polyhydric alcohol having 5 or more carbon atoms with a saturated aliphatic cyclic acid anhydride.
- Curable resin composition as described in (4).
- the epoxysiloxane group-containing organopolysiloxane (A) is a chain-like silicone moiety comprising dimethyl-substituted, diphenyl-substituted or a mixture thereof, and a three-dimensional condensate moiety having an epoxycyclohexyl group (silsesquioxane moiety).
- the curable resin composition according to any one of the above (1) to (6) which is a block-type compound having: (8) A cured product obtained by curing the curable resin composition according to any one of (1) to (7) above.
- a curable resin composition for optical semiconductor encapsulation comprising the curable resin composition according to any one of (1) to (7) above.
- An optical semiconductor device obtained by curing and sealing with the curable resin composition for optical semiconductor encapsulation described in (9) above.
- the curable resin composition of the present invention is useful for electrical and electronic material applications, particularly as an optical semiconductor sealing material, and has excellent curability, adhesiveness, light resistance, heat resistance, and gas permeability resistance, and an LED sealing material.
- the resin When used as a hardened material, the resin has little resin stress on the chip and does not cause illuminance deterioration.
- the curable resin composition of the present invention contains an epoxycyclohexyl group-containing organopolysiloxane (A), an alicyclic epoxy resin (B), and an acid anhydride (C).
- the epoxycyclohexyl group-containing organopolysiloxane (A) is an epoxy resin having an epoxycyclohexyl group in at least its molecule, and is generally synthesized by a sol-gel reaction using trialkoxysilane having an epoxycyclohexyl group as a raw material. Can do.
- Japanese Unexamined Patent Publication No. 2004-256609 Japanese Unexamined Patent Publication No.
- the block type siloxane compound (A1) is produced using, for example, an alkoxysilane compound (a) represented by the general formula (1) and a silicone oil (b) represented by the general formula (2) as raw materials as described below. If necessary, the alkoxysilane compound (c) represented by the general formula (3) can be used as a raw material.
- the chain silicone part of the block type siloxane compound (A1) is formed from silicone oil (b), and the three-dimensional network silsesquioxane part is alkoxysilane (a) (and, if necessary, alkoxysilane (c )).
- each raw material will be described in detail.
- the alkoxysilane compound (a) is represented by the following formula (1).
- X in the general formula (1) is not particularly limited as long as it is an organic group having an epoxycyclohexyl group.
- ⁇ - (3,4-epoxycyclohexyl) ethyl group ⁇ - (3,4-epoxycyclohexyl) propyl group
- ⁇ - (3,4-epoxycyclohexyl) propyl group ⁇ - (3,4-epoxycyclohexyl) propyl group
- ⁇ - (3,4-epoxycyclohexyl) examples thereof include an alkyl group having 1 to 5 carbon atoms substituted with a cyclohexyl group having an epoxy group such as a butyl group.
- an alkyl group having 1 to 3 carbon atoms substituted with a cyclohexyl group having an epoxy group is preferable, and a ⁇ - (3,4-epoxycyclohexyl) ethyl group is particularly preferable.
- a plurality of R 2 may be the same or different and each represents a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms.
- R 2 is preferably a methyl group or an ethyl group, and particularly preferably a methyl group, from the viewpoint of reaction conditions such as compatibility and reactivity.
- alkoxysilane (a) examples include ⁇ - (3,4-epoxycyclohexyl) ethyltrimethoxysilane, ⁇ - (3,4-epoxycyclohexyl) ethyltriethoxysilane, and the like. 3,4-epoxycyclohexyl) ethyltrimethoxysilane is preferred.
- These alkoxysilane compounds (a) may be used independently, may use 2 or more types, and can also be used together with the alkoxysilane (c) mentioned later.
- Silicone oil (b) is represented by the following formula (2)
- a plurality of R 3 may be the same or different from each other, and may be an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 14 carbon atoms, or an alkenyl having 2 to 10 carbon atoms. Indicates a group.
- m represents the number of repetitions.
- alkyl group having 1 to 10 carbon atoms examples include linear, branched or cyclic alkyl groups having 1 to 10 carbon atoms, such as a methyl group, an ethyl group, an n-propyl group, an i-propyl group, n-butyl group, i-butyl group, sec-butyl group, t-butyl group, n-pentyl group, i-pentyl group, amyl group, n-hexyl group, cyclopentyl group, cyclohexyl group, octyl group, 2-ethylhexyl Group, nonyl group, decyl group and the like.
- methyl group, ethyl group, cyclohexyl group and n-propyl group are preferable in consideration of light resistance.
- the aryl group having 6 to 14 carbon atoms include a phenyl group, an o-tolyl group, an m-tolyl group, a p-tolyl group, and a xylyl group.
- the alkenyl group having 2 to 10 carbon atoms include alkenyl groups such as vinyl group, 1-methylvinyl group, allyl group, propenyl group, butenyl group, pentenyl group and hexenyl group.
- R 3 is preferably a methyl group, a phenyl group, a cyclohexyl group or an n-propyl group from the viewpoints of light resistance and heat resistance, and particularly preferably a methyl group or a phenyl group.
- those having a phenyl group in at least a part of the substituents are particularly preferable from the viewpoint of compatibility.
- m represents an average value of 3 to 200, preferably 3 to 100, more preferably 3 to 50.
- m represents an average value of 3 to 200, preferably 3 to 100, more preferably 3 to 50.
- the weight average molecular weight (Mw) of the silicone oil (b) is preferably in the range of 300 to 18,000 (measured by gel permeation chromatography (GPC)).
- GPC gel permeation chromatography
- those having a molecular weight of 300 to 10,000 are preferable in consideration of the elastic modulus at a low temperature, and those having a molecular weight of 300 to 5,000 are more preferable in consideration of compatibility at the time of forming the composition. 1,000 is preferred.
- the weight average molecular weight is less than 300, the properties of the chain silicone portion of the characteristic segment are difficult to be obtained, and the properties as a block type may be impaired.
- the molecular weight exceeds 18,000 a severe layer separation structure is formed.
- the molecular weight of the silicone oil (b) can be calculated by polystyrene conversion and weight average molecular weight (Mw) measured under the following conditions using GPC.
- the kinematic viscosity of the silicone oil (b) is preferably in the range of 10 to 200 cSt, more preferably 30 to 90 cSt.
- the viscosity is less than 10 cSt, the viscosity of the block type siloxane compound (A1) becomes too low and may not be suitable as an optical semiconductor sealing agent.
- the viscosity exceeds 200 cSt, the viscosity of the block type siloxane compound (A1) Is unfavorable because it tends to cause an adverse effect on workability.
- preferable silicone oil (b) examples include the following product names.
- PRX413 and BY16-873 are manufactured by Toray Dow Corning Silicone
- X-21-5841 and KF-9701 are manufactured by Shin-Etsu Chemical
- XC96-723, TSR160, YR3370 and YF3800 are manufactured by Momentive.
- XF3905 YF3057, YF3807, YF3802, YF3897, YF3804, XF3905, manufactured by Gelest, DMS-S12, DMS-S14, DMS-S15, DMS-S21, DMS-S27, DMS-S31, DMS-S32, DMS -S33, DMS-S35, DMS-S42, DMS-S45, DMS-S51, PDS-0332, PDS-1615, PDS-9931 and the like.
- PRX413, BY16-873, X-21-5841, KF-9701, XC96-723, YF3800, YF3804, DMS-S12, DMS-S14, DMS-S15, DMS-S21 PDS-1615 is preferred.
- X-21-5841, XC96-723, YF3800, YF3804, DMS-S14, and PDS-1615 are particularly preferable from the viewpoint of molecular weight in order to give the silicone site flexibility.
- These silicone oils (b) may be used alone or in combination of two or more.
- the alkoxysilane (c) has a structure of the following formula (3).
- preferable alkoxysilane (c) include methyltrimethoxysilane, phenyltrimethoxysilane, methyltriethoxysilane, and phenyltriethoxysilane. Of these, methyltrimethoxysilane and phenyltrimethoxysilane are preferred.
- alkoxysilane (a) which is a silicon compound having an alkoxy group as production step (ii) (and alkoxysilane (c) added if necessary), and alkoxy of the silicone oil obtained in production step (i)
- a method for producing a block-type siloxane compound (A1) by passing water through the silane-modified product (d) and subjecting it to a hydrolytic condensation reaction between alkoxy groups.
- a production step (ii) an alkoxy group in the molecule is obtained by performing a hydrolysis-condensation reaction between alkoxy groups by adding water of alkoxysilane (a) (and alkoxysilane (c) added as necessary).
- silsesquioxane (e) which has this is performed. Then, through a reaction of silicone oil (b) and silsesquioxane (e) as a production step (i), a step of dealcoholization condensation reaction of the alkoxy group and silanol group remaining in the silsesquioxane structure, A method for producing a block-type siloxane compound (A1).
- a silicone oil is obtained by a dealcoholization condensation reaction between a silicone oil (b) having a silanol group at the terminal and an alkoxysilane (a) (and an alkoxysilane (c) added as necessary).
- the dealcohol condensation of the silicone oil (b) and the alkoxysilane (a) (and the alkoxysilane (c) added if necessary) is performed, and the terminal of the silicone oil is obtained.
- the body (d) is considered to exist in a structure represented by the following formula (4).
- R 2 , R 3 and m have the same meaning as described above, and R 6 represents X and / or R 4. )
- a second-stage reaction (production step (ii)) is performed in which water is added as it is to hydrolyze and condense alkoxy groups.
- the following reactions (I) to (III) occur.
- (I) A condensation reaction between alkoxy groups of the alkoxysilane (a) remaining in the system (and the alkoxysilane (c) added if necessary).
- (II) A condensation reaction between the alkoxy groups of the alkoxysilane-modified product (d) obtained in the production step (i) and the alkoxysilane (a) (and the alkoxysilane (c) added as necessary).
- the production of the block type siloxane compound (A1) can be carried out without a catalyst, but if it is no catalyst, the reaction proceeds slowly, and it is preferably carried out in the presence of a catalyst from the viewpoint of shortening the reaction time.
- a catalyst any compound that exhibits acidity or basicity can be used.
- the acidic catalyst include inorganic acids such as hydrochloric acid, sulfuric acid and nitric acid, and organic acids such as formic acid, acetic acid and oxalic acid.
- Examples of basic catalysts include sodium hydroxide, potassium hydroxide, lithium hydroxide, alkali metal hydroxides such as cesium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, etc.
- the catalyst As a method for adding the catalyst, it is added directly or used in a state dissolved in a soluble solvent or the like. Among them, it is preferable to add the catalyst in a state in which the catalyst is dissolved in advance in alcohols such as methanol, ethanol, propanol and butanol. At this time, adding as an aqueous solution using water or the like causes the condensation of the alkoxysilane (a) (and the alkoxysilane (c) to be added as necessary) unilaterally as described above, The silsesquioxane oligomer produced thereby and the silicone oil (b) may not be compatible with each other and may become cloudy.
- alcohols such as methanol, ethanol, propanol and butanol.
- the production of the block type siloxane compound (A1) can be carried out without solvent or in a solvent. Moreover, a solvent can also be added in the middle of a manufacturing process.
- the solvent for use is not particularly limited as long as it is a solvent that dissolves alkoxysilane (a), alkoxysilane (c), silicone oil (b), and alkoxysilane-modified product (d).
- reaction in alcohols is preferable from the viewpoint of reaction control, and methanol and ethanol are more preferable.
- the amount of solvent used is not particularly limited as long as the reaction proceeds smoothly, but alkoxysilane (a) (and alkoxysilane (c) added as necessary), a compound of silicone oil (b) Usually, about 0 to 900 parts by weight is used with respect to 100 parts by weight.
- the reaction temperature is usually 20 to 160 ° C., preferably 40 to 140 ° C., particularly preferably 50 to 150 ° C., depending on the amount of catalyst.
- the reaction time is usually 1 to 40 hours, preferably 5 to 30 hours, in each production step.
- the catalyst is removed by quenching and / or washing with water as necessary.
- a solvent that can be separated from water.
- Preferred solvents include ketones such as methyl ethyl ketone, methyl isobutyl ketone and cyclopentanone, esters such as ethyl acetate, butyl acetate, ethyl lactate and isopropyl butanoate, hydrocarbons such as hexane, cyclohexane, toluene and xylene. Can be illustrated.
- the catalyst may be removed only by washing with water, but the reaction is carried out under acidic or basic conditions. It is preferable to remove the adsorbent by filtration after adsorbing the catalyst using Any compound that exhibits acidity or basicity can be used for the neutralization reaction.
- the compound exhibiting acidity include inorganic acids such as hydrochloric acid, sulfuric acid and nitric acid, and organic acids such as formic acid, acetic acid and oxalic acid.
- Examples of compounds showing basicity include alkali metal hydroxides such as sodium hydroxide, potassium hydroxide, lithium hydroxide and cesium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate.
- Inorganic bases such as alkali metal carbonates, phosphoric acid, sodium dihydrogen phosphate, disodium hydrogen phosphate, trisodium phosphate, phosphates such as polyphosphoric acid, sodium tripolyphosphate, ammonia, triethylamine, diethylenetriamine, n-butylamine, Organic bases such as dimethylaminoethanol, triethanolamine, and tetramethylammonium hydroxide can be used.
- inorganic bases or inorganic acids are preferable because they can be easily removed from the product, and phosphates that can more easily adjust the pH to near neutral are more preferable.
- adsorbent examples include activated clay, activated carbon, zeolite, inorganic / organic synthetic adsorbent, ion exchange resin, and the like, and specific examples include the following products.
- activated clay for example, Toshin Kasei Co., Ltd., activated clay SA35, SA1, T, R-15, E, Nikkanite G-36, G-153, G-168 are manufactured by Mizusawa Chemical Co., Ltd. Galeon Earth, Mizuka Ace, etc. are listed.
- a synthetic adsorbent for example, Kyoward 100, 200, 300, 400, 500, 600, 700, 1000, 2000 manufactured by Kyowa Chemical Co., Ltd., Amberlist 15JWET, 15DRY, manufactured by Rohm and Haas Co., Ltd. 16WET, 31WET, A21, Amberlite IRA400JCl, IRA403BLCl, IRA404JCl, Dow Chemical Co., Dowex 66, HCR-S, HCR-W2, MAC-3, and the like.
- the adsorbent is added to the reaction solution, followed by treatment such as stirring and heating to adsorb the catalyst, and then the adsorbent is filtered and the residue is washed with water to remove the catalyst and adsorbent.
- the molecular weight is the equivalent ratio of alkoxysilane (a) (and optionally added alkoxysilane (c)) to silicone oil (b), the molecular weight of silicone oil (b), the amount of water added during the reaction, The reaction time and reaction temperature can be adjusted.
- the weight average molecular weight is a polystyrene equivalent weight average molecular weight (Mw) measured using GPC (gel permeation chromatography) under the following conditions.
- the ratio of silicon atoms bonded to three oxygens derived from silsesquioxane in the block type siloxane compound (A1) to the total silicon atoms is preferably 8 to 30 mol%, more preferably 8 to 25 mol%.
- the ratio of silicon atoms bonded to three oxygens derived from silsesquioxane with respect to all silicon atoms is less than 8 mol%, the characteristics of the chain silicone sites appear and the cured product tends to be too soft. .
- it exceeds 30 mol% the characteristic of the silsesquioxane structure site
- the epoxycyclohexyl group-containing organopolysiloxane (A) and the block type siloxane compound (A1) in the present invention preferably include a phenyl skeleton in the structure.
- the phenyl skeleton is introduced into the block-type siloxane compound (A1), it is contained in at least one of silicone oil (b) and alkoxysilane (a) (and alkoxysilane (c) added if necessary). It only has to be.
- the strength and refractive index of the cured product are improved.
- the refractive index the light extraction efficiency is improved when used as an optical semiconductor sealing material.
- the phenyl skeleton also has an effect of filling a space between molecules and preventing gas permeation.
- epoxy resins include esterification reaction of cyclohexene carboxylic acid and alcohols or esterification reaction of cyclohexene methanol and carboxylic acids (Tetrahedron vol.36 p.2409 (1980), Tetrahedron Letter p.4475 (1980), etc.) Described), or Tyschenko reaction of cyclohexene aldehyde (method described in Japanese Patent Application Laid-Open No. 2003-170059, Japanese Patent Application Laid-Open No.
- Examples of carboxylic acids include, but are not limited to, oxalic acid, maleic acid, fumaric acid, phthalic acid, isophthalic acid, adipic acid, and cyclohexanedicarboxylic acid.
- the acetal compound by the acetal reaction of a cyclohexene aldehyde derivative and an alcohol form is mentioned.
- these epoxy resins include ERL-4221, UVR-6105, ERL-4299 (all trade names, all manufactured by Dow Chemical), Celoxide 2021P, Epolide GT401, EHPE3150, EHPE3150CE (all trade names, all Daicel) (Chemical Industry) and dicyclopentadiene diepoxide, and the like, but are not limited to these (Reference: Review Epoxy Resin Basic Edition I p76-85). These may be used alone or in combination of two or more.
- a compound having an epoxycyclohexane structure is also preferable from the viewpoint of improving gas permeability resistance.
- the epoxy equivalent (measured by the method described in JIS K-7236) of the alicyclic epoxy resin (B) is 100 to 500 g / eq. And preferably 100 to 300 g / eq. Are more preferred.
- the content of the alicyclic epoxy resin (B) is less than 1.5% by weight, the resulting cured product is brittle, has a high linear expansion coefficient, and has poor adhesion, and as an optical semiconductor sealing material Inferior to suitability.
- the content of the alicyclic epoxy resin (B) is more preferably 1.7 to 20% by weight, and particularly preferably 1.8 to 20% by weight. Further, when the content of the alicyclic epoxy resin is increased, the content of the alicyclic epoxy resin (B) is more preferably 5 to 20% by weight, particularly preferably 10 to 20% by weight.
- the quantity ratio can be determined by the epoxy equivalent of each other.
- the dispersibility of the epoxy group contained in the organopolysiloxane (A) it has been found that a cured product having a balance between hardness and flexibility and excellent light extraction efficiency can be obtained.
- the epoxy group dispersibility of the epoxycyclohexyl group-containing organopolysiloxane (A) refers to the weight average molecular weight of the epoxycyclohexyl group-containing organopolysiloxane (A) and the epoxycyclohexyl group-containing organopolysiloxane (A). It means a value divided by an epoxy equivalent (amount of resin containing 1 g equivalent of epoxy (unit: g / eq.)), Whereby the average of epoxy groups contained in one molecule of epoxycyclohexyl group-containing organopolysiloxane (A) The amount can be estimated.
- the flexibility derived from the chain silicone moiety is effectively expressed, the cured product has a better balance between hardness and flexibility, and has improved light extraction efficiency. It is possible to obtain According to the above formula, the greater the amount of epoxy groups per molecule, the greater the amount of alicyclic epoxy resin (B) introduced. On the other hand, the smaller the amount of epoxy groups per molecule, the smaller the amount of alicyclic epoxy resin (B) introduced.
- the ratio P calculated from the above formula is desirably 40 or less (that is, the maximum content of the alicyclic epoxy resin (B) is 40% by weight or less). However, the ratio P is an amount within the range of 1.5 to 40% by weight described above. Preferably, the alicyclic epoxy resin (B) is 1.5 to 20% by weight and the ratio P is 40 or less.
- the curable resin composition of the present invention contains an acid anhydride (C) as a curing agent.
- the acid anhydride (C) is excellent in transparency and is excellent in workability because it is liquid.
- Specific examples of acid anhydrides include phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, maleic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methyl nadic anhydride, nadic anhydride, hexahydrophthalic anhydride Acid, methylhexahydrophthalic anhydride, butanetetracarboxylic anhydride, bicyclo [2,2,1] heptane-2,3-dicarboxylic anhydride, methylbicyclo [2,2,1] heptane-2,3- And acid anhydrides such as dicarboxylic acid anhydride and cyclohexane-1,2,4-tricarboxylic acid-1,
- hexahydrophthalic anhydride methylhexahydrophthalic anhydride, cyclohexane-1,2,4-tricarboxylic acid- 1,2-anhydride is preferable, and methylhexahydrophthalic anhydride and cyclohexane-1,2,4-tricarboxylic acid-1,2-anhydride are particularly preferable.
- the amount of the acid anhydride (C) used in the curable resin composition of the present invention is preferably 0.7 to 1.2 equivalents relative to 1 equivalent of the epoxy groups of all epoxy resins. When less than 0.7 equivalent or more than 1.2 equivalent with respect to 1 equivalent of epoxy group, curing may be incomplete and good cured properties may not be obtained. When used in combination with a curing agent such as a polyvalent carboxylic acid to be described later, the total amount of the curing agent used is preferably within the above range.
- the acid anhydride (C) is preferably used in combination with the polyvalent carboxylic acid (D) which is another curing agent, and the content when used in combination with the polyvalent carboxylic acid (D) described later is It is desirable to be determined by a ratio, and the range of the following formula is preferable.
- W1 / (W1 + W2) 0.05-0.70 (W1 represents a blended part by weight of the polyvalent carboxylic acid (D), and W2 represents a blended part by weight of the acid anhydride (C).)
- the range of W1 / (W1 + W2) is more preferably 0.05 to 0.60, still more preferably 0.10 to 0.55, and particularly preferably 0.15 to 0.4.
- the polyvalent carboxylic acid (D) used in the present invention is desirably a compound having at least two or more carboxyl groups and having an aliphatic hydrocarbon group as a main skeleton.
- the polyvalent carboxylic acid is not only a polyvalent carboxylic acid having a single structure, but also a mixture of a plurality of compounds having different substituent positions or different substituents, that is, a polyvalent carboxylic acid composition. In the present invention, they are collectively referred to as a polyvalent carboxylic acid.
- a bi- to hexa-functional carboxylic acid is particularly preferable, and a compound obtained by reacting a bi- to hexa-functional polyhydric alcohol having 5 or more carbon atoms with an acid anhydride is more preferable.
- the polycarboxylic acid whose said acid anhydride is a saturated aliphatic cyclic acid anhydride is preferable.
- the bi- to hexafunctional polyhydric alcohol is not particularly limited as long as it is a compound having an alcoholic hydroxyl group, but ethylene glycol, propylene glycol, 1,3-propanediol, 1,2-butanediol, 1,4-butanediol.
- 2-ethyl-2 -Branched chain structures such as butyl-1,3-propanediol, neopentyl glycol, 2,4-diethylpentanediol, 1,4-cyclohexanedimethanol, tricyclodecane dimethanol, norbornenediol, carbinol-modified silicone oil Or ring Concrete, more preferably polyhydric alcohols having a siloxane structure.
- carbinol-modified silicone oil is specifically the following formula (4A)
- R 8 represents an alkylene group having 1 to 10 carbon atoms
- R 7 represents a methyl group or a phenyl group
- p represents an average value of 1 to 100.
- a plurality of Q's represent at least one of a hydrogen atom, a methyl group and a carboxyl group.
- P is a chain-like, cyclic aliphatic group having 2 to 20 carbon atoms derived from the aforementioned polyhydric alcohol. .
- m is preferably from 1 to 7, particularly preferably from 2 to 6.
- the ratio of phosphorus atom to zinc atom is preferably 1.2 to 2.3, more preferably 1.3 to 2.0. . Particularly preferred is 1.4 to 1.9. That is, in a particularly preferred form, the amount of phosphate ester (or phosphate derived from phosphate ester) is 2.0 moles or less per mole of zinc ion, and not a simple ionic structure, some molecules are ion-bonded (or arranged). Those having a structure related by coordinate bond are preferred.
- Such a zinc salt and / or zinc complex can also be obtained, for example, by the technique described in Japanese Patent Publication No. 2003-51495.
- the content of the zinc salt and / or the zinc complex (E) is zinc relative to the total amount of the epoxycyclohexyl group-containing organopolysiloxane (A) and the alicyclic epoxy resin (B).
- the salt and / or zinc complex (E) is 0.01 to 8% by weight, more preferably 0.05 to 5% by weight, and further 0.1 to 4% by weight. Further, it is particularly preferably 0.1 to 2% by weight.
- the curable resin composition of the present invention when used in an optical material, particularly an optical semiconductor encapsulant, it contains a hindered amine compound as a light stabilizer and a phosphorus compound as an antioxidant as particularly preferable components. That is preferred.
- the light stabilizer is used in an amount of 0.005 to 5 by weight with respect to the total amount of the epoxycyclohexyl group-containing organopolysiloxane (A) and the alicyclic epoxy resin (B). % By weight, more preferably 0.01 to 4% by weight, and 0.1 to 2% by weight.
- the phosphorus compound is used in an amount of 0.005 to 5 by weight with respect to the total amount of the epoxycyclohexyl group-containing organopolysiloxane (A) and the alicyclic epoxy resin (B). % By weight, more preferably 0.01 to 4% by weight, and 0.1 to 2% by weight.
- the curable resin composition of the present invention includes an epoxycyclohexyl group-containing organopolysiloxane (A) and an alicyclic epoxy resin (B) as an epoxy resin, and an acid anhydride (C) and a polyvalent carboxylic acid (D) as a curing agent. It is preferable to contain.
- the curable resin composition of the present invention comprises an epoxycyclohexyl group-containing organopolysiloxane (A) and an alicyclic epoxy resin (B) as an epoxy resin, and an acid anhydride (C) and a polyvalent carboxylic acid (as a curing agent). D) It is preferable to contain a zinc salt and / or a zinc complex (E) as an additive.
- the curable resin composition of the present invention preferably contains a hindered amine light stabilizer and a phosphorus-containing antioxidant as additives. These can be used in combination with other epoxy resins, curing agents and various additives described below.
- epoxy resin component other epoxy resins that can be used in combination with the epoxycyclohexyl group-containing organopolysiloxane (A) and the alicyclic epoxy resin (B) include novolac type epoxy resins, bisphenol A type epoxy resins, biphenyl type epoxy resins, A triphenylmethane type epoxy resin, a phenol aralkyl type epoxy resin, etc. are mentioned.
- curing agents that can be used include amines and polyamide compounds (diaminodiphenylmethane, diethylenetriamine, triethylenetetramine, diaminodiphenylsulfone, isophoronediamine, dicyandiamide, polyamide resin synthesized from ethylenediamine and dimer of linolenic acid, etc.) , Reaction product of acid anhydride and silicone alcohol (phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, maleic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methyl nadic anhydride, anhydrous Nadic acid, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, butanetetracarboxylic anhydride, bicyclo [2,2,1] heptane-2,3-dicarboxylic anhydride, methylbicyclo [2,2,2,
- the curable resin composition of the present invention may contain various additives and auxiliary materials as listed below.
- the curable resin composition of the present invention may contain a phosphorus-containing compound as a flame retardant component.
- the phosphorus-containing compound may be a reactive type or an additive type.
- a binder resin can be blended with the curable resin composition of the present invention as required.
- the binder resin include butyral resins, acetal resins, acrylic resins, epoxy-nylon resins, NBR-phenol resins, epoxy-NBR resins, polyamide resins, polyimide resins, and silicone resins.
- the blending amount of the binder resin is preferably in a range that does not impair the flame retardancy and heat resistance of the cured product, and is usually 0.1% relative to 100 parts by weight of the epoxy resin component and the curing agent component contained in the curable resin composition. 05 to 50 parts by weight, preferably 0.05 to 20 parts by weight are used as necessary.
- a silane coupling agent a release agent such as stearic acid, palmitic acid, zinc stearate, and calcium stearate, various compounding agents such as pigments, and various thermosetting resins are added to the curable resin composition of the present invention. can do.
- the particle size of the inorganic filler used is transparent by using a nano-order level filler. It is possible to supplement the mechanical strength and the like without hindering.
- the addition amount thereof is 1 to 80 parts by weight, preferably 5 parts per 100 parts by weight of the organic component such as epoxycyclohexyl group-containing organopolysiloxane (A). ⁇ 60 parts by weight is preferred.
- silica fine powder also called Aerosil or Aerosol
- a thixotropic agent can be added.
- silica fine powder include Aerosil 50, Aerosil 90, Aerosil 130, Aerosil 200, Aerosil 300, Aerosil 380, Aerosil OX50, Aerosil TT600, Aerosil R972, Aerosil R974, AerosilR202, AerosilR202, AerosilR202 Aerosil R805, RY200, RX200 (made by Nippon Aerosil Co., Ltd.), etc. are mentioned.
- TINUVIN 328, TINUVIN 234, TINUVIN 326, TINUVIN 120, TINUVIN 477, TINUVIN 479, CHIMASSORB 2020FDL, CHIMASSORB 119FL, and the like are manufactured by Ciba Specialty Chemicals.
- the obtained curable resin composition of the present invention When the obtained curable resin composition of the present invention is in a liquid state, potting, casting, impregnating the base material, pouring the curable resin composition into a mold, casting, and curing by heating Let Further, when the obtained curable resin composition of the present invention is solid, it is molded using a cast after casting or a transfer molding machine, and further cured by heating. In addition, what is necessary is just to add and mix the hardening accelerator, an amine compound, a phosphorus containing compound, a phenol compound, binder resin, an inorganic filler, etc. which are arbitrary components at the said mixing process. The curing temperature and time are 80 to 200 ° C. and 2 to 10 hours.
- the curable resin composition of the present invention is dissolved in a solvent such as toluene, xylene, acetone, methyl ethyl ketone, methyl isobutyl ketone, dimethylformamide, dimethylacetamide, N-methylpyrrolidone, etc. to obtain a curable resin composition varnish, glass fiber,
- a prepreg obtained by impregnating a base material such as carbon fiber, polyester fiber, polyamide fiber, alumina fiber, paper, etc. and heat-dried is subjected to hot press molding to obtain a cured product of the curable resin composition of the present invention. can do.
- the curable resin composition of the present invention is used as a sealing material for an optical semiconductor such as a high-intensity white LED, or a die bond material, an epoxy resin, a curing agent, a coupling agent, an antioxidant, a light stabilizer, etc.
- An epoxy resin composition is prepared by thoroughly mixing the additives, and is used as a sealing material or for both a die bond material and a sealing material.
- a mixing method a kneader, a three-roll, a universal mixer, a planetary mixer, a homomixer, a homodisper, a bead mill or the like is used to mix at room temperature or warm.
- the curable resin composition of the present invention is applied by dispenser, potting, or screen printing, and then heated by placing the semiconductor chip thereon. Curing can be performed to bond the semiconductor chip.
- methods such as hot air circulation, infrared rays and high frequency can be used.
- the curable resin composition of the present invention can be used for general applications in which curable resins such as epoxy resins are used.
- curable resins such as epoxy resins
- adhesives examples include civil engineering, architectural, automotive, general office and medical adhesives, as well as electronic material adhesives.
- adhesives for electronic materials include interlayer adhesives for multilayer substrates such as build-up substrates, die bonding agents, semiconductor adhesives such as underfills, BGA reinforcing underfills, anisotropic conductive films ( ACF) and an adhesive for mounting such as anisotropic conductive paste (ACP).
- sealing agents potting, dipping, transfer mold sealing for capacitors, transistors, diodes, light-emitting diodes, ICs, LSIs, potting sealings for ICs, LSIs such as COB, COF, TAB, flip chip
- underfill for QFP, BGA, CSP, etc., and sealing can be used.
- the cured product obtained in the present invention can be used for various applications including optical component materials.
- the optical material refers to general materials used for applications that allow light such as visible light, infrared light, ultraviolet light, X-rays, and lasers to pass through the material. More specifically, in addition to LED sealing materials such as lamp type and SMD type, the following may be mentioned. It is a peripheral material for liquid crystal display devices such as a substrate material, a light guide plate, a prism sheet, a deflection plate, a retardation plate, a viewing angle correction film, an adhesive, and a film for a liquid crystal such as a polarizer protective film in the liquid crystal display field.
- color PDP plasma display
- antireflection films antireflection films
- optical correction films housing materials
- front glass protective films front glass replacement materials
- adhesives and LED displays that are expected as next-generation flat panel displays
- LED molding materials LED sealing materials, front glass protective films, front glass substitute materials, adhesives, and substrate materials for plasma addressed liquid crystal (PALC) displays, light guide plates, prism sheets, deflection plates , Phase difference plate, viewing angle correction film, adhesive, polarizer protective film, front glass protective film in organic EL (electroluminescence) display, front glass substitute material, adhesive, and various in field emission display (FED) Film substrate
- PLC plasma addressed liquid crystal
- VD video disc
- CD / CD-ROM CD-R / RW
- DVD-R / DVD-RAM MO / MD
- PD phase change disc
- disc substrate materials for optical cards Pickup lenses, protective films, sealing materials, adhesives and the like.
- optical equipment field they are still camera lens materials, finder prisms, target prisms, finder covers, and light receiving sensor parts. It is also a photographic lens and viewfinder for video cameras.
- optical components they are fiber materials, lenses, waveguides, element sealing materials, adhesives and the like around optical switches in optical communication systems.
- optical passive components and optical circuit components there are lenses, waveguides, LED sealing materials, CCD sealing materials, adhesives, and the like.
- OEIC optoelectronic integrated circuit
- automotive lamp reflectors In the field of automobiles and transport equipment, automotive lamp reflectors, bearing retainers, gear parts, anti-corrosion coatings, switch parts, headlamps, engine internal parts, electrical parts, various interior and exterior parts, drive engines, brake oil tanks, and automotive defenses Rusted steel plate, interior panel, interior material, wire harness for protection / bundling, fuel hose, automobile lamp, glass substitute.
- it is a multilayer glass for railway vehicles.
- they are toughness imparting agents for aircraft structural materials, engine peripheral members, protective / bundling wire harnesses, and corrosion-resistant coatings.
- it In the construction field, it is interior / processing materials, electrical covers, sheets, glass interlayers, glass substitutes, and solar cell peripheral materials. For agriculture, it is a house covering film.
- optical / electronic functional organic materials include organic EL element peripheral materials, organic photorefractive elements, optical amplification elements that are light-to-light conversion devices, optical arithmetic elements, substrate materials around organic solar cells, fiber materials, elements Sealing material, adhesive and the like.
- each physical property value in an Example was measured with the following method.
- GPC gel permeation chromatography
- Various conditions of GPC Manufacturer Shimadzu Corporation Column: Guard column SHODEX GPC LF-G LF-804 (3) Flow rate: 1.0 ml / min. Column temperature: 40 ° C
- Solvent THF (tetrahydrofuran)
- Detector RI (differential refraction detector)
- Epoxy equivalent Measured by the method described in JIS K-7236.
- the epoxy equivalent of the obtained compound (S-1) was 605 g / eq.
- the weight average molecular weight was 2120, and the appearance was a colorless and transparent liquid resin.
- the value of the ratio P was 35, and the ratio of silicon atoms bonded to three oxygens derived from silsesquioxane to all silicon atoms was about 18 mol%.
- the epoxy equivalent of the obtained compound (S-3) was 636 g / eq.
- the weight average molecular weight was 2090, and the appearance was a colorless and transparent liquid resin.
- the value of the ratio P was 33, and the ratio of silicon atoms bonded to three oxygens derived from silsesquioxane to all silicon atoms was about 17 mol%.
- the curing condition is 140 ° C. ⁇ 5 hours after 110 ° C. ⁇ 2 hours of preliminary curing.
- the curing agent composition (H-1) obtained in Synthesis Example 6 was synthesized.
- Curing agent composition (H-2) obtained in Example 7 phosphate ester zinc complex (C-2) as curing accelerator, hindered amine (L-1) as light stabilizer, antioxidant (O-1
- the curable resin compositions of Examples 4 to 6 and Comparative Example 5 were obtained by blending at a blending ratio (parts by weight) shown in Table 3 below and defoaming for 20 minutes. Furthermore, the obtained curable resin composition was cured in the following manner, and the transmittance and light resistance were evaluated.
- the curable resin composition of the present invention exhibited high illuminance retention even in an accelerated test in which an excessive current was passed at high temperature and high humidity, and had high characteristics as an LED.
- the curable resin compositions of Examples 9 to 11 and Comparative Examples 6 and 7 were obtained by blending at a blending ratio (parts by weight) shown in Table 5 below and performing defoaming for 20 minutes. It was.
- the curable resin compositions of the examples do not discolor the lead frame silver plating as compared with the curable resin compositions of the comparative examples (containing a polysiloxane compound and an acid anhydride). It was found that it was excellent in long-term corrosion gas resistance.
- Synthesis example B To a flask equipped with a stirrer, a reflux condenser, a stirrer, and a Dean-Stark tube, while purging with nitrogen, 150 parts of toluene and 2,4-diethyl-1,5-pentanediol (Kyowa Hakko Chemical Co., Ltd. Kyowa All PD9) ) 80 parts, 126 parts of 3-cyclohexenecarboxylic acid and 2 parts of paratoluenesulfonic acid were added, and the reaction was carried out under heating and refluxing for 10 hours while removing water.
- the diolefin compound of the present invention is washed twice with 50 parts of a 10% aqueous sodium hydrogen carbonate solution, the organic layer obtained is washed twice with 50 parts of water, and then the organic solvent is concentrated with a rotary evaporator. 187 parts of (D-1) was obtained.
- the shape was liquid, the purity by gas chromatography was 96%, and the result of analysis by gel permeation chromatography confirmed that the purity was> 98%.
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Abstract
Description
ところが、LED製品の発光波長の短波長化(主に青色発光をするLED製品で480nm以下の場合を示す)が進んだ結果、短波長の光の影響で前記封止材料がLEDチップ上で着色し最終的にはLED製品として、照度が低下してしまうという指摘がされている。
そこで、3,4-エポキシシクロヘキシルメチル-3’,4’エポキシシクロヘキシルカルボキシレートに代表される脂環式エポキシ樹脂は、芳香環を有するグリシジルエーテルタイプのエポキシ樹脂組成物と比較し透明性の点で優れていることから、LED封止材として積極的に検討がなされてきた(特許文献1、2)。 Conventionally, an epoxy resin composition has been employed as a sealing material for optical semiconductor elements such as LED products in terms of a balance between performance and economy. In particular, glycidyl ether type epoxy resin compositions typified by bisphenol A type epoxy resins having excellent balance of heat resistance, transparency and mechanical properties have been widely used.
However, as a result of the shortening of the emission wavelength of LED products (mainly the case of LED products emitting blue light of 480 nm or less), the sealing material is colored on the LED chip due to the influence of light of short wavelengths. However, it has been pointed out that the illuminance will eventually decrease as an LED product.
Therefore, alicyclic epoxy resins represented by 3,4-epoxycyclohexylmethyl-3 ′, 4 ′ epoxycyclohexyl carboxylate are more transparent than glycidyl ether type epoxy resin compositions having an aromatic ring. Since it is excellent, it has been actively studied as an LED sealing material (Patent Documents 1 and 2).
しかし、該シロキサン骨格を導入した樹脂類は通常のエポキシ樹脂に比べ、硬化物の硬度が不十分なため、配線に使用される金ワイヤーが振動によって切れる、また基板との接着性が不足して剥がされやすいなどの欠点が指摘されている(特許文献4)。 In general, it is known that an epoxy resin having a siloxane skeleton introduced is more stable to heat and light than an epoxy resin having no siloxane skeleton introduced. Therefore, when applied to a sealing material for LED products, it has been said that in terms of coloring on the LED chip, it is more durable than an epoxy resin that does not introduce a siloxane skeleton.
However, since the resin containing the siloxane skeleton has insufficient hardness of the cured product compared to a normal epoxy resin, the gold wire used for the wiring is cut by vibration, and the adhesion to the substrate is insufficient. Disadvantages such as easy peeling are pointed out (Patent Document 4).
しかしながら、特許文献4に記載される組成であると、オルガノポリシロキサンの架橋密度が高く、また脂環式エポキシ樹脂の含有量が多いため、接着性には優れるものの硬化物が硬くなりすぎてしまい、LED封止をした際にチップに応力がかかりやすくなることが判った。またこれに起因して、点灯中の照度劣化が激しいという問題が生じることが判った。 In order to solve such a problem, in Patent Document 4, an epoxy resin having an organopolysiloxane structure having a high crosslinking density (containing silicon atoms having three bonded oxygen atoms in a proportion exceeding 40 mol% per all silicon atoms). Attempts have been made to use alicyclic epoxy resins in combination.
However, the composition described in Patent Document 4 has a high crosslinking density of the organopolysiloxane and a high content of the alicyclic epoxy resin, so that the cured product becomes too hard although it has excellent adhesion. It has been found that stress is easily applied to the chip when the LED is sealed. Further, it has been found that this causes a problem that illuminance deterioration during lighting is severe.
(1) エポキシシクロヘキシル基含有オルガノポリシロキサン(A)、脂環式エポキシ樹脂(B)および酸無水物(C)を含有し、エポキシシクロヘキシル基含有オルガノポリシロキサン(A)と脂環式エポキシ樹脂(B)の総量に占める脂環式エポキシ樹脂(B)の量が1.5~40重量%であることを特徴とする硬化性樹脂組成物。
(2) エポキシシクロヘキシル基含有オルガノポリシロキサン(A)、脂環式エポキシ樹脂(B)および酸無水物(C)を含有し、エポキシシクロヘキシル基含有オルガノポリシロキサン(A)と脂環式エポキシ樹脂(B)の総量に占める脂環式エポキシ樹脂(B)の量が2~40重量%であることを特徴とする硬化性樹脂組成物。
(3) エポキシシクロヘキシル基含有オルガノポリシロキサン(A)と脂環式エポキシ樹脂(B)の総量に占める脂環式エポキシ樹脂(B)の含有量が、10×(エポキシシクロヘキシル基含有オルガノポリシロキサン(A)の重量平均分子量)÷(エポキシシクロヘキシル基含有オルガノポリシロキサン(A)のエポキシ当量)重量%以下であることを特徴とする上記(1)または(2)記載の硬化性樹脂組成物。
(4) さらに多価カルボン酸(D)を含むことを特徴とする上記(1)~(3)の何れか一項に記載の硬化性樹脂組成物。
(5) 前記多価カルボン酸(D)が、炭素数5以上の2~6官能の多価アルコールと飽和脂肪族環状酸無水物との反応により得られた化合物であることを特徴とする上記(4)に記載の硬化性樹脂組成物。
(6) 前記エポキシシクロヘキシル基含有オルガノポリシロキサン(A)が、その構造中にフェニル基を有することを特徴とする上記(1)~(5)のいずれか一項に記載の硬化性樹脂組成物。
(7) 前記エポキシシクロヘキシル基含有オルガノポリシロキサン(A)が、ジメチル置換、ジフェニル置換またはこれらの混合物からなる鎖状シリコーン部位と、エポキシシクロヘキシル基を有する三次元縮合体部位(シルセスキオキサン部位)とを有するブロック型の化合物であることを特徴とする上記(1)~(6)のいずれか一項に記載の硬化性樹脂組成物。
(8) 上記(1)~(7)のいずれか一項に記載の硬化性樹脂組成物を硬化してなる硬化物。
(9) 上記(1)~(7)のいずれか一項記載の硬化性樹脂組成物からなる光半導体封止用硬化性樹脂組成物。
(10) 上記(9)記載の光半導体封止用硬化性樹脂組成物で硬化および封止して得られることを特徴とする光半導体装置。 As a result of intensive studies to achieve the above object, the present inventors have completed the present invention shown below.
(1) An epoxycyclohexyl group-containing organopolysiloxane (A), an alicyclic epoxy resin (B), and an acid anhydride (C), and an epoxycyclohexyl group-containing organopolysiloxane (A) and an alicyclic epoxy resin ( A curable resin composition, wherein the amount of the alicyclic epoxy resin (B) in the total amount of B) is 1.5 to 40% by weight.
(2) Contains an epoxycyclohexyl group-containing organopolysiloxane (A), an alicyclic epoxy resin (B) and an acid anhydride (C), and includes an epoxycyclohexyl group-containing organopolysiloxane (A) and an alicyclic epoxy resin ( A curable resin composition, wherein the amount of the alicyclic epoxy resin (B) in the total amount of B) is 2 to 40% by weight.
(3) The content of the alicyclic epoxy resin (B) in the total amount of the epoxycyclohexyl group-containing organopolysiloxane (A) and the alicyclic epoxy resin (B) is 10 × (epoxycyclohexyl group-containing organopolysiloxane ( The curable resin composition according to (1) or (2), wherein the weight average molecular weight of A) / (epoxy equivalent of epoxycyclohexyl group-containing organopolysiloxane (A)) is not more than wt%.
(4) The curable resin composition according to any one of (1) to (3) above, further comprising a polyvalent carboxylic acid (D).
(5) The above polyvalent carboxylic acid (D) is a compound obtained by reacting a bi- to hexafunctional polyhydric alcohol having 5 or more carbon atoms with a saturated aliphatic cyclic acid anhydride. Curable resin composition as described in (4).
(6) The curable resin composition according to any one of (1) to (5) above, wherein the epoxycyclohexyl group-containing organopolysiloxane (A) has a phenyl group in its structure. .
(7) The epoxysiloxane group-containing organopolysiloxane (A) is a chain-like silicone moiety comprising dimethyl-substituted, diphenyl-substituted or a mixture thereof, and a three-dimensional condensate moiety having an epoxycyclohexyl group (silsesquioxane moiety). The curable resin composition according to any one of the above (1) to (6), which is a block-type compound having:
(8) A cured product obtained by curing the curable resin composition according to any one of (1) to (7) above.
(9) A curable resin composition for optical semiconductor encapsulation, comprising the curable resin composition according to any one of (1) to (7) above.
(10) An optical semiconductor device obtained by curing and sealing with the curable resin composition for optical semiconductor encapsulation described in (9) above.
本発明の硬化性樹脂組成物は、エポキシシクロヘキシル基含有オルガノポリシロキサン(A)、脂環式エポキシ樹脂(B)および酸無水物(C)を含有する。
エポキシシクロヘキシル基含有オルガノポリシロキサン(A)は、少なくともその分子中にエポキシシクロヘキシル基を有するエポキシ樹脂であり、一般的にエポキシシクロヘキシル基を有するトリアルコキシシランを原料に用いるゾル-ゲル反応により合成することができる。具体的には、日本国特開2004-256609号公報、日本国特開2004-346144号公報、WO2004/072150号公報、日本国特開2006-8747号公報、WO2006/003990号公報、日本国特開2006-104248号公報、WO2007/135909号公報、日本国特開2004-10849号公報、日本国特開2004-359933号公報、WO2005/100445号公報、日本国特開2008-174640号公報などに記載の三次元に広がる網の目状の構造を有したシルセスキオキサンタイプのオルガノポリシロキサンが挙げられる。 Hereinafter, it describes about the curable resin composition of this invention.
The curable resin composition of the present invention contains an epoxycyclohexyl group-containing organopolysiloxane (A), an alicyclic epoxy resin (B), and an acid anhydride (C).
The epoxycyclohexyl group-containing organopolysiloxane (A) is an epoxy resin having an epoxycyclohexyl group in at least its molecule, and is generally synthesized by a sol-gel reaction using trialkoxysilane having an epoxycyclohexyl group as a raw material. Can do. Specifically, Japanese Unexamined Patent Publication No. 2004-256609, Japanese Unexamined Patent Publication No. 2004-346144, WO 2004/072150, Japanese Unexamined Patent Publication No. 2006-8747, WO 2006/003990, Japanese Special JP 2006-104248, WO 2007/135909, JP 2004-10849, JP 2004-359933, WO 2005/100445, JP 2008-174640, etc. Examples thereof include silsesquioxane type organopolysiloxane having the three-dimensional network structure described above.
また、通常の単純な三次元網目構造のシロキサン化合物では得られる硬化物が硬くなりすぎるため、硬さを緩和する構造とすることが望まれる。本発明においては特にシリコーンセグメントと、ゾル-ゲル反応により得られる前述のシルセスキオキサン構造とを1分子中に有するブロック構造体とすることが好ましい(以下、ブロック型シロキサン化合物(A1)と称する)。即ち、ブロック型シロキサン化合物(A1)は、鎖状シリコーン部位とシルセスキオキサン構造からなる三次元縮合体部位とを1分子中に有するブロック構造体である。 The structure of the organopolysiloxane in the present invention is not particularly limited, but a substance having an aromatic group in the structure is preferable in terms of compatibility.
Moreover, since the cured | curing material obtained becomes hard too much with the normal siloxane compound of a simple three-dimensional network structure, it is desired to make it the structure which eases hardness. In the present invention, it is particularly preferable to use a block structure having a silicone segment and the aforementioned silsesquioxane structure obtained by sol-gel reaction in one molecule (hereinafter referred to as block type siloxane compound (A1)). ). That is, the block-type siloxane compound (A1) is a block structure having a chain silicone moiety and a three-dimensional condensate moiety composed of a silsesquioxane structure in one molecule.
以下、各原料について詳細に説明する。 The block type siloxane compound (A1) is produced using, for example, an alkoxysilane compound (a) represented by the general formula (1) and a silicone oil (b) represented by the general formula (2) as raw materials as described below. If necessary, the alkoxysilane compound (c) represented by the general formula (3) can be used as a raw material. The chain silicone part of the block type siloxane compound (A1) is formed from silicone oil (b), and the three-dimensional network silsesquioxane part is alkoxysilane (a) (and, if necessary, alkoxysilane (c )).
Hereinafter, each raw material will be described in detail.
XSi(OR2)3 (1)
一般式(1)中のXとしては、エポキシシクロヘキシル基を有する有機基であれば特に制限はない。例えば、β-(3,4-エポキシシクロヘキシル)エチル基、γ-(3,4-エポキシシクロヘキシル)プロピル基、β-(3,4エポキシシクロヘキシル)プロピル基、β-(3,4-エポキシシクロヘキシル)ブチル基等のエポキシ基を持ったシクロヘキシル基で置換された炭素数1~5のアルキル基が挙げられる。これらの中で、エポキシ基を有するシクロヘキシル基で置換された炭素数1~3のアルキル基が好ましく、特にβ-(3,4-エポキシシクロヘキシル)エチル基が好ましい。 The alkoxysilane compound (a) is represented by the following formula (1).
XSi (OR 2 ) 3 (1)
X in the general formula (1) is not particularly limited as long as it is an organic group having an epoxycyclohexyl group. For example, β- (3,4-epoxycyclohexyl) ethyl group, γ- (3,4-epoxycyclohexyl) propyl group, β- (3,4-epoxycyclohexyl) propyl group, β- (3,4-epoxycyclohexyl) Examples thereof include an alkyl group having 1 to 5 carbon atoms substituted with a cyclohexyl group having an epoxy group such as a butyl group. Among these, an alkyl group having 1 to 3 carbon atoms substituted with a cyclohexyl group having an epoxy group is preferable, and a β- (3,4-epoxycyclohexyl) ethyl group is particularly preferable.
一般式(2)中、複数存在するR3は互いに同一であっても異なっていてもよく、炭素数1~10のアルキル基、炭素数6~14のアリール基、炭素数2~10のアルケニル基を示す。また、一般式(2)中、mは繰り返し数を表す。
炭素数1~10のアルキル基としては、炭素数1~10の直鎖状、分岐状もしくは環状のアルキル基が挙げられ、例えば、メチル基、エチル基、n-プロピル基、i-プロピル基、n-ブチル基、i-ブチル基、sec-ブチル基、t-ブチル基、n-ペンチル基、i-ペンチル基、アミル基、n-ヘキシル基、シクロペンチル基、シクロヘキシル基、オクチル基、2-エチルヘキシル基、ノニル基、デシル基等を挙げることができる。これらの中で、耐光性を考慮すると、メチル基、エチル基、シクロヘキシル基、n-プロピル基が好ましい。
炭素数6~14のアリール基としては、例えば、フェニル基、o-トリル基、m-トリル基、p-トリル基、キシリル基等を挙げることができる。
炭素数2~10のアルケニル基としては、ビニル基、1-メチルビニル基、アリル基、プロペニル基、ブテニル基、ペンテニル基、ヘキセニル基等のアルケニル基等を挙げることができる。
R3は耐光性、耐熱性の観点から、メチル基、フェニル基、シクロヘキシル基、n-プロピル基が好ましく、特にメチル基、フェニル基が好ましい。なお、本発明においては特に相溶性の面から、少なくとも置換基の一部にフェニル基を有する物が好ましい。 Is a chain silicone oil having a silanol group at the end having a structure represented by:
In the general formula (2), a plurality of R 3 may be the same or different from each other, and may be an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 14 carbon atoms, or an alkenyl having 2 to 10 carbon atoms. Indicates a group. In general formula (2), m represents the number of repetitions.
Examples of the alkyl group having 1 to 10 carbon atoms include linear, branched or cyclic alkyl groups having 1 to 10 carbon atoms, such as a methyl group, an ethyl group, an n-propyl group, an i-propyl group, n-butyl group, i-butyl group, sec-butyl group, t-butyl group, n-pentyl group, i-pentyl group, amyl group, n-hexyl group, cyclopentyl group, cyclohexyl group, octyl group, 2-ethylhexyl Group, nonyl group, decyl group and the like. Of these, methyl group, ethyl group, cyclohexyl group and n-propyl group are preferable in consideration of light resistance.
Examples of the aryl group having 6 to 14 carbon atoms include a phenyl group, an o-tolyl group, an m-tolyl group, a p-tolyl group, and a xylyl group.
Examples of the alkenyl group having 2 to 10 carbon atoms include alkenyl groups such as vinyl group, 1-methylvinyl group, allyl group, propenyl group, butenyl group, pentenyl group and hexenyl group.
R 3 is preferably a methyl group, a phenyl group, a cyclohexyl group or an n-propyl group from the viewpoints of light resistance and heat resistance, and particularly preferably a methyl group or a phenyl group. In the present invention, those having a phenyl group in at least a part of the substituents are particularly preferable from the viewpoint of compatibility.
メーカー:島津製作所
カラム:ガードカラム SHODEX GPC LF-G LF-804(3本)
流速:1.0ml/min.
カラム温度:40℃
使用溶剤:THF(テトラヒドロフラン)
検出器:RI(示差屈折検出器) Various conditions of GPC Manufacturer: Shimadzu Corporation Column: Guard column SHODEX GPC LF-G LF-804 (3)
Flow rate: 1.0 ml / min.
Column temperature: 40 ° C
Solvent: THF (tetrahydrofuran)
Detector: RI (differential refraction detector)
R4Si(OR5)3 (3) Next, the alkoxysilane (c) will be described in detail. The alkoxysilane (c) has a structure of the following formula (3).
R 4 Si (OR 5 ) 3 (3)
一般式(3)中、複数存在するR5は互いに同一であっても異なっていても良く、炭素数1~10の直鎖状、分岐状もしくは環状のアルキル基を示す。例えば、メチル基、エチル基、n-プロピル基、i-プロピル基、n-ブチル基、i-ブチル基、tert-ブチル基、n-ペンチル基、n-ヘキシル基、シクロペンチル基、シクロヘキシル基等が挙げられる。これらR5は、相溶性、反応性等の反応条件の観点から、メチル基又はエチル基であることが好ましい。 In the general formula (3), R 4 represents a methyl group, a phenyl group or a glycidyl group.
In the general formula (3), a plurality of R 5 may be the same or different and each represents a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms. For example, methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, tert-butyl group, n-pentyl group, n-hexyl group, cyclopentyl group, cyclohexyl group, etc. Can be mentioned. R 5 is preferably a methyl group or an ethyl group from the viewpoint of reaction conditions such as compatibility and reactivity.
当量値が200を超えるとブロック型シロキサン化合物(A1)を用いた硬化物が硬くなりすぎて目的の低弾性率特性が低下する。 As a reaction ratio of alkoxysilane (a), silicone oil (b), and alkoxysilane (c), alkoxysilane (a) (and used as necessary) with respect to 1 equivalent of silanol group of silicone oil (b). The reaction is preferably carried out at an equivalent value of the alkoxy group in the alkoxysilane (c)) of 1.5 to 200, preferably 2 to 200, particularly preferably 2 to 100.
When the equivalent value exceeds 200, the cured product using the block-type siloxane compound (A1) becomes too hard and the desired low elastic modulus characteristic is lowered.
ブロック型シロキサン化合物(A1)の製造方法としては以下の(i)、(ii)で示される製造工程を経ることが好ましい。
製造工程(i):シラノール末端シリコーンオイル(b)とアルコキシ基を有するアルコキシシラン(a)(および必要に応じて添加されるアルコキシシラン(c))の脱アルコール縮合を行なう工程
製造工程(ii):水を添加しアルコキシシラン(a)(および必要に応じて添加されるアルコキシシラン(c))のアルコキシ基同士の加水分解縮合を行なう工程
製造工程(i)、(ii)は各工程を経由すればどのような順に反応を行ってもかまわない。 Hereinafter, a preferred method for producing the block type siloxane compound (A1) will be specifically described.
As a manufacturing method of a block type siloxane compound (A1), it is preferable to pass through the manufacturing process shown by the following (i) and (ii).
Production step (i): A step of carrying out dealcoholization condensation of silanol-terminated silicone oil (b) and alkoxysilane (a) having an alkoxy group (and alkoxysilane (c) added if necessary) (ii) : A step of hydrolyzing and condensing the alkoxy groups of alkoxysilane (a) (and alkoxysilane (c) added if necessary) by adding water Production steps (i) and (ii) go through each step The reaction can be performed in any order.
<製造方法(イ)>
まず、製造工程(i)として末端にシラノール基を有するシリコーンオイル(b)とアルコキシ基を有するケイ素化合物であるアルコキシシラン(a)(および必要に応じて添加されるアルコキシシラン(c))との脱アルコール縮合反応により、シリコーンオイル末端をアルコキシシラン変性することにより、アルコキシシラン変性体(d)を得る工程を行う。
次いで製造工程(ii)としてアルコキシ基を有するケイ素化合物であるアルコキシシラン(a)(および必要に応じて添加されるアルコキシシラン(c))、および製造工程(i)で得られたシリコーンオイルのアルコキシシラン変性体(d)に水を添加してアルコキシ基同士の加水分解縮合反応を行う工程を経ることによりブロック型シロキサン化合物(A1)を製造する方法。
<製造方法(ロ)>
まず、製造工程(ii)としてアルコキシシラン(a)(および必要に応じて添加されるアルコキシシラン(c))の水の添加によるアルコキシ基同士の加水分解縮合反応を行うことで分子内にアルコキシ基を有するシルセスキオキサン(e)を得る工程を行う。
次いで製造工程(i)としてシリコーンオイル(b)とシルセスキオキサン(e)との反応により、シルセスキオキサン構造に残存するアルコキシ基とシラノール基の脱アルコール縮合反応させる工程を経ることにより、ブロック型シロキサン化合物(A1)を製造する方法。
<製造方法(ハ)>
まず、製造工程(i)として末端にシラノール基を有するシリコーンオイル(b)とアルコキシシラン(a)(および必要に応じて添加されるアルコキシシラン(c))との脱アルコール縮合反応により、シリコーンオイル末端をアルコキシシラン変性することによりアルコキシシラン変性体(d)とした後、系内に水を添加し、ワンポットで製造工程(ii)として残存するアルコキシシラン(a)(およびアルコキシシラン(c))、およびアルコキシラン変性体(d)のアルコキシ基同士の加水分解縮合反応を行うことによりブロック型シロキサン化合物(A1)を製造する方法。 Specific examples of preferred production methods include the following three production methods.
<Manufacturing method (I)>
First, as a production step (i), a silicone oil (b) having a silanol group at the terminal and an alkoxysilane (a) which is a silicon compound having an alkoxy group (and an alkoxysilane (c) which is added if necessary) A step of obtaining an alkoxysilane-modified product (d) by performing alkoxysilane modification on the terminal of the silicone oil by a dealcoholization condensation reaction is performed.
Next, alkoxysilane (a) which is a silicon compound having an alkoxy group as production step (ii) (and alkoxysilane (c) added if necessary), and alkoxy of the silicone oil obtained in production step (i) A method for producing a block-type siloxane compound (A1) by passing water through the silane-modified product (d) and subjecting it to a hydrolytic condensation reaction between alkoxy groups.
<Manufacturing method (b)>
First, as a production step (ii), an alkoxy group in the molecule is obtained by performing a hydrolysis-condensation reaction between alkoxy groups by adding water of alkoxysilane (a) (and alkoxysilane (c) added as necessary). The process of obtaining silsesquioxane (e) which has this is performed.
Then, through a reaction of silicone oil (b) and silsesquioxane (e) as a production step (i), a step of dealcoholization condensation reaction of the alkoxy group and silanol group remaining in the silsesquioxane structure, A method for producing a block-type siloxane compound (A1).
<Manufacturing method (c)>
First, as a production step (i), a silicone oil is obtained by a dealcoholization condensation reaction between a silicone oil (b) having a silanol group at the terminal and an alkoxysilane (a) (and an alkoxysilane (c) added as necessary). An alkoxysilane-modified body (d) is obtained by modifying the terminal with alkoxysilane, then water is added to the system, and alkoxysilane (a) (and alkoxysilane (c)) remaining as a production step (ii) in one pot And a method of producing a block-type siloxane compound (A1) by carrying out a hydrolysis-condensation reaction between alkoxy groups of the alkoxysilane modified product (d).
以下、さらに具体的に製造方法(ハ)について述べる。
ワンポットで反応させる場合、前述の製造方法(ハ)と逆の順番、すなわち、製造工程(ii)の後に製造工程(i)を行なうと、製造工程(ii)で形成されたアルコキシ基を有するシルセスキオキサンオリゴマーとシリコーンオイル(b)とが、相溶せず、後の製造工程(i)において脱アルコール縮合重合が進行せず、シリコーンオイルが取り残されてしまう可能性が高い。一方で、製造方法(ハ)のように製造工程(i)の後にワンポットで製造工程(ii)を行なう方法を用いれば、シリコーンオイル(b)とアルコキシシラン(a)やアルコキシラン(c)との相溶性が比較的高いため、前述のように相溶せずに反応が進行しない、という問題は回避できる。さらにはシラノール基に対して未反応の低分子アルコキシシランが多量に存在することになるため、反応性の観点からも好ましい。ワンポットで行なう場合、まず製造工程(i)において、シリコーンオイル(b)とアルコキシシラン(a)(および必要に応じて添加されるアルコキシシラン(c))の脱アルコール縮合を行ない、シリコーンオイルの末端をアルコキシシリル変性させ、アルコキシシラン変性体(d)を得る。製造工程(i)においては水を添加していないので、アルコキシ基同士の加水分解縮合は起こらず、シラノール基1当量に対して、アルコキシ基を3当量以上用いて反応させた場合、アルコキシシラン変性体(d)は下記式(4)で示されるような構造で存在していると考えられる。 In the present invention, from the viewpoint of shortening the production process, it is preferable to use the above production method (c) in which the reaction is sequentially carried out in one pot.
Hereinafter, the production method (c) will be described more specifically.
When the reaction is carried out in one pot, the silanol having an alkoxy group formed in the production step (ii) is performed in the reverse order of the production method (c) described above, that is, when the production step (ii) is performed after the production step (ii). There is a high possibility that the sesquioxane oligomer and the silicone oil (b) are not compatible with each other, the dealcoholization condensation polymerization does not proceed in the subsequent production step (i), and the silicone oil is left behind. On the other hand, if the method of performing manufacturing process (ii) in one pot after manufacturing process (i) like manufacturing method (c) is used, silicone oil (b) and alkoxysilane (a) or alkoxylane (c) Since the compatibility is relatively high, the problem that the reaction does not proceed without compatibility as described above can be avoided. Furthermore, since a large amount of unreacted low-molecular alkoxysilane is present with respect to the silanol group, it is preferable from the viewpoint of reactivity. In the case of carrying out in one pot, first, in the production step (i), the dealcohol condensation of the silicone oil (b) and the alkoxysilane (a) (and the alkoxysilane (c) added if necessary) is performed, and the terminal of the silicone oil is obtained. Is modified with alkoxysilyl to obtain an alkoxysilane-modified product (d). Since water is not added in the production step (i), hydrolysis condensation between alkoxy groups does not occur, and when the reaction is performed using 3 equivalents or more of alkoxy groups per 1 equivalent of silanol groups, the alkoxysilane modification The body (d) is considered to exist in a structure represented by the following formula (4).
製造工程(ii)では、下記に示す(I)~(III)の反応が起きている。
(I)系中に残存しているアルコキシシラン(a)(および必要に応じて添加されるアルコキシシラン(c))のアルコキシ基同士の縮合反応。
(II)製造工程(i)で得られたアルコキシシラン変性体(d)とアルコキシシラン(a)(および必要に応じて添加されるアルコキシシラン(c))のアルコキシ基同士の縮合反応。
(III)製造工程(i)で得られたアルコキシシラン変性体(d)と(I)で生成したアルコキシシラン(a)(および必要に応じて添加されるアルコキシシラン(c))の部分縮合物のアルコキシ基同士の縮合反応。
製造工程(ii)においては上記反応が複合して起こり、シルセスキオキサン構造部位の形成と、さらにシリコーンオイル由来の鎖状シリコーン部位との縮合が同時に行なわれる。 After the production step (i) is completed, a second-stage reaction (production step (ii)) is performed in which water is added as it is to hydrolyze and condense alkoxy groups.
In the production step (ii), the following reactions (I) to (III) occur.
(I) A condensation reaction between alkoxy groups of the alkoxysilane (a) remaining in the system (and the alkoxysilane (c) added if necessary).
(II) A condensation reaction between the alkoxy groups of the alkoxysilane-modified product (d) obtained in the production step (i) and the alkoxysilane (a) (and the alkoxysilane (c) added as necessary).
(III) Partial condensate of the alkoxysilane modified product (d) obtained in the production step (i) and the alkoxysilane (a) (and optionally added alkoxysilane (c)) produced in (I) Condensation reaction between alkoxy groups.
In the production step (ii), the above reaction occurs in combination, and the formation of the silsesquioxane structure portion and the condensation with the chain silicone portion derived from silicone oil are simultaneously performed.
触媒の添加方法は、直接添加するか、可溶性の溶剤等に溶解させた状態で使用する。その中でもメタノール、エタノール、プロパノール、ブタノール等のアルコール類に触媒をあらかじめ溶解させた状態で添加するのが好ましい。この際に、水などを用いた水溶液として添加することは、前記したように、アルコキシシラン(a)(および必要に応じて添加されるアルコキシシラン(c))の縮合を一方的に進行させ、それにより生成したシルセスキオキサンオリゴマーと、シリコーンオイル(b)とが相溶せず白濁する可能性がある。 The production of the block type siloxane compound (A1) can be carried out without a catalyst, but if it is no catalyst, the reaction proceeds slowly, and it is preferably carried out in the presence of a catalyst from the viewpoint of shortening the reaction time. As the catalyst that can be used, any compound that exhibits acidity or basicity can be used. Examples of the acidic catalyst include inorganic acids such as hydrochloric acid, sulfuric acid and nitric acid, and organic acids such as formic acid, acetic acid and oxalic acid. Examples of basic catalysts include sodium hydroxide, potassium hydroxide, lithium hydroxide, alkali metal hydroxides such as cesium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, etc. Inorganic bases such as alkali metal carbonates and organic bases such as ammonia, triethylamine, diethylenetriamine, n-butylamine, dimethylaminoethanol, triethanolamine, and tetramethylammonium hydroxide can be used. Among these, an inorganic base is particularly preferable in terms of easy catalyst removal from the product, and sodium hydroxide and potassium hydroxide are particularly preferable. The amount of the catalyst added is usually 0.001 to 7.5% by weight, preferably 0, based on the total weight of the alkoxysilane (a) (and the alkoxysilane (c) added if necessary) in the reaction system. 0.01 to 5% by weight.
As a method for adding the catalyst, it is added directly or used in a state dissolved in a soluble solvent or the like. Among them, it is preferable to add the catalyst in a state in which the catalyst is dissolved in advance in alcohols such as methanol, ethanol, propanol and butanol. At this time, adding as an aqueous solution using water or the like causes the condensation of the alkoxysilane (a) (and the alkoxysilane (c) to be added as necessary) unilaterally as described above, The silsesquioxane oligomer produced thereby and the silicone oil (b) may not be compatible with each other and may become cloudy.
中和反応には酸性または塩基性を示す化合物であれば使用することができる。酸性を示す化合物の例としては、塩酸、硫酸、硝酸等の無機酸や蟻酸、酢酸、蓚酸等の有機酸が挙げられる。また、塩基性を示す化合物の例としては、水酸化ナトリウム、水酸化カリウム、水酸化リチウム、水酸化セシウムのようなアルカリ金属水酸化物、炭酸ナトリウム、炭酸カリウム、炭酸水素ナトリウム、炭酸水素カリウムのようなアルカリ金属炭酸塩、燐酸、燐酸二水素ナトリウム、燐酸水素二ナトリウム、燐酸トリナトリウム、ポリ燐酸、トリポリ燐酸ナトリウムのようなリン酸塩類等の無機塩基、アンモニア、トリエチルアミン、ジエチレントリアミン、n-ブチルアミン、ジメチルアミノエタノール、トリエタノールアミン、テトラメチルアンモニウムハイドロオキサイド等の有機塩基を使用することができる。これらの中でも、特に生成物からの除去が容易である点で無機塩基もしくは無機酸が好ましく、さらに好ましくは中性付近へのpHの調整がより容易である燐酸塩類などである。 In this reaction, the catalyst may be removed only by washing with water, but the reaction is carried out under acidic or basic conditions. It is preferable to remove the adsorbent by filtration after adsorbing the catalyst using
Any compound that exhibits acidity or basicity can be used for the neutralization reaction. Examples of the compound exhibiting acidity include inorganic acids such as hydrochloric acid, sulfuric acid and nitric acid, and organic acids such as formic acid, acetic acid and oxalic acid. Examples of compounds showing basicity include alkali metal hydroxides such as sodium hydroxide, potassium hydroxide, lithium hydroxide and cesium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate. Inorganic bases such as alkali metal carbonates, phosphoric acid, sodium dihydrogen phosphate, disodium hydrogen phosphate, trisodium phosphate, phosphates such as polyphosphoric acid, sodium tripolyphosphate, ammonia, triethylamine, diethylenetriamine, n-butylamine, Organic bases such as dimethylaminoethanol, triethanolamine, and tetramethylammonium hydroxide can be used. Among these, in particular, inorganic bases or inorganic acids are preferable because they can be easily removed from the product, and phosphates that can more easily adjust the pH to near neutral are more preferable.
活性白土としては、例えば、東新化成社製として、活性白土SA35、SA1、T、R-15、E、ニッカナイトG-36、G-153、G-168が、水沢化学工業社製として、ガレオンアース、ミズカエースなどが挙げられる。活性炭としては、例えば、味の素ファインテクノ社製として、CL-H、Y-10S、Y-10SFがフタムラ化学社製として、S、Y、FC、DP、SA1000、K、A、KA、M、CW130BR、CW130AR、GM130Aなどが挙げられる。ゼオライトとしては、例えば、ユニオン昭和社製として、モレキュラーシーブ3A、4A、5A、13Xなどが挙げられる。合成吸着剤としては、例えば、協和化学社製として、キョーワード100、200、300、400、500、600、700、1000、2000や、ローム・アンド・ハース社製として、アンバーリスト15JWET、15DRY、16WET、31WET、A21、アンバーライトIRA400JCl、IRA403BLCl、IRA404JClや、ダウ・ケミカル社製、ダウエックス66、HCR-S、HCR-W2、MAC-3などが挙げられる。
吸着剤を反応液に加え、攪拌、加熱等の処理を行い、触媒を吸着した後に、吸着剤をろ過、さらには残渣を水洗することによって、触媒、吸着剤を除くことができる。 Examples of the adsorbent include activated clay, activated carbon, zeolite, inorganic / organic synthetic adsorbent, ion exchange resin, and the like, and specific examples include the following products.
As the activated clay, for example, Toshin Kasei Co., Ltd., activated clay SA35, SA1, T, R-15, E, Nikkanite G-36, G-153, G-168 are manufactured by Mizusawa Chemical Co., Ltd. Galeon Earth, Mizuka Ace, etc. are listed. As the activated carbon, for example, CL-H, Y-10S, Y-10SF manufactured by Ajinomoto Fine Techno Co., Ltd., S, Y, FC, DP, SA1000, K, A, KA, M, CW130BR manufactured by Phutamura Chemical Co., Ltd. , CW130AR, GM130A, and the like. Examples of zeolite include, for example, molecular sieves 3A, 4A, 5A, and 13X, manufactured by Union Showa. As a synthetic adsorbent, for example, Kyoward 100, 200, 300, 400, 500, 600, 700, 1000, 2000 manufactured by Kyowa Chemical Co., Ltd., Amberlist 15JWET, 15DRY, manufactured by Rohm and Haas Co., Ltd. 16WET, 31WET, A21, Amberlite IRA400JCl, IRA403BLCl, IRA404JCl, Dow Chemical Co., Dowex 66, HCR-S, HCR-W2, MAC-3, and the like.
The adsorbent is added to the reaction solution, followed by treatment such as stirring and heating to adsorb the catalyst, and then the adsorbent is filtered and the residue is washed with water to remove the catalyst and adsorbent.
重量平均分子量はGPC(ゲルパーミエーションクロマトグラフィー)を用いて下記条件下測定されたポリスチレン換算の重量平均分子量(Mw)である。 The appearance of the block-type siloxane compound (A1) thus obtained is usually colorless and transparent and is a liquid having fluidity at 25 ° C. The molecular weight is preferably 800 to 20,000, more preferably 1,000 to 10,000, and particularly preferably 1,500 to 6,000 as the weight average molecular weight measured by GPC. When the weight average molecular weight is less than 800, the heat resistance may be lowered. When the weight average molecular weight is more than 20,000, the viscosity is increased and the workability is adversely affected. The molecular weight is the equivalent ratio of alkoxysilane (a) (and optionally added alkoxysilane (c)) to silicone oil (b), the molecular weight of silicone oil (b), the amount of water added during the reaction, The reaction time and reaction temperature can be adjusted.
The weight average molecular weight is a polystyrene equivalent weight average molecular weight (Mw) measured using GPC (gel permeation chromatography) under the following conditions.
メーカー:島津製作所
カラム:ガードカラム SHODEX GPC LF-G LF-804(3本)
流速:1.0ml/min.
カラム温度:40℃
使用溶剤:THF(テトラヒドロフラン)
検出器:RI(示差屈折検出器) Various conditions of GPC Manufacturer: Shimadzu Corporation Column: Guard column SHODEX GPC LF-G LF-804 (3)
Flow rate: 1.0 ml / min.
Column temperature: 40 ° C
Solvent: THF (tetrahydrofuran)
Detector: RI (differential refraction detector)
存在するケイ素原子の割合は、ブロック型シロキサン化合物(A1)の1H NMR、29Si NMR、元素分析等によって求めることができる。 The ratio of silicon atoms bonded to three oxygens derived from silsesquioxane in the block type siloxane compound (A1) to the total silicon atoms is preferably 8 to 30 mol%, more preferably 8 to 25 mol%. When the ratio of silicon atoms bonded to three oxygens derived from silsesquioxane with respect to all silicon atoms is less than 8 mol%, the characteristics of the chain silicone sites appear and the cured product tends to be too soft. . Moreover, when it exceeds 30 mol%, the characteristic of the silsesquioxane structure site | part will express and hardened | cured material will become hard too much. If the cured product becomes too hard, the resin stress on the chip at the time of LED sealing increases, so that the illuminance deterioration of the LED tends to occur.
The proportion of silicon atoms present can be determined by 1 H NMR, 29 Si NMR, elemental analysis, etc. of the block siloxane compound (A1).
脂環式エポキシ樹脂(B)は、骨格にエポキシシクロヘキサン構造を有する化合物が好ましく、シクロヘキセン構造を有する化合物の酸化反応により得られるエポキシ樹脂が特に好ましい。
これらエポキシ樹脂としては、シクロヘキセンカルボン酸とアルコール類とのエステル化反応あるいはシクロヘキセンメタノールとカルボン酸類とのエステル化反応(Tetrahedron vol.36 p.2409 (1980)、Tetrahedron Letter p.4475 (1980)等に記載の手法)、あるいはシクロヘキセンアルデヒドのティシェンコ反応(日本国特開2003-170059号公報、日本国特開2004-262871号公報等に記載の手法)、さらにはシクロヘキセンカルボン酸エステルのエステル交換反応(日本国特開2006-052187号公報等に記載の手法)によって製造できる化合物を酸化した物などが挙げられる。
アルコール類としては、アルコール性水酸基を有する化合物であれば特に限定されないがエチレングリコール、プロピレングリコール、1,3-プロパンジオール、1,2-ブタンジオール、1,4-ブタンジオール、1,5-ペンタンジオール、1,6-ヘキサンジオール、シクロヘキサンジメタノール、2,4-ジエチルペンタンジオール、2-エチル-2-ブチル-1,3-プロパンジオール、ネオペンチルグリコール、トリシクロデカンジメタノール、ノルボルネンジオールなどのジオール類、グリセリン、トリメチロールエタン、トリメチロールプロパン、トリメチロールブタン、2-ヒドロキシメチル-1,4-ブタンジオールなどのトリオール類、ペンタエリスリトール、ジトリメチロールプロパンなどのテトラオール類などが挙げられる。またカルボン酸類としてはシュウ酸、マレイン酸、フマル酸、フタル酸、イソフタル酸、アジピン酸、シクロヘキサンジカルボン酸などが挙げられるがこれに限らない。 The curable resin composition of the present invention contains an alicyclic epoxy resin (B). The alicyclic epoxy resin (B) is introduced in order to impart toughness to the cured product.
The alicyclic epoxy resin (B) is preferably a compound having an epoxycyclohexane structure in the skeleton, and particularly preferably an epoxy resin obtained by an oxidation reaction of a compound having a cyclohexene structure.
These epoxy resins include esterification reaction of cyclohexene carboxylic acid and alcohols or esterification reaction of cyclohexene methanol and carboxylic acids (Tetrahedron vol.36 p.2409 (1980), Tetrahedron Letter p.4475 (1980), etc.) Described), or Tyschenko reaction of cyclohexene aldehyde (method described in Japanese Patent Application Laid-Open No. 2003-170059, Japanese Patent Application Laid-Open No. 2004-262871, etc.), and transesterification of cyclohexene carboxylic acid ester (Japan) And a compound obtained by oxidizing a compound that can be produced by a method described in Japanese Patent Laid-Open No. 2006-052187.
The alcohol is not particularly limited as long as it is a compound having an alcoholic hydroxyl group, but ethylene glycol, propylene glycol, 1,3-propanediol, 1,2-butanediol, 1,4-butanediol, 1,5-pentane. Diol, 1,6-hexanediol, cyclohexanedimethanol, 2,4-diethylpentanediol, 2-ethyl-2-butyl-1,3-propanediol, neopentyl glycol, tricyclodecane dimethanol, norbornenediol, etc. Diols, glycerol, trimethylolethane, trimethylolpropane, trimethylolbutane, triols such as 2-hydroxymethyl-1,4-butanediol, tetraols such as pentaerythritol, ditrimethylolpropane, etc. And the like. Examples of carboxylic acids include, but are not limited to, oxalic acid, maleic acid, fumaric acid, phthalic acid, isophthalic acid, adipic acid, and cyclohexanedicarboxylic acid.
これらエポキシ樹脂の具体例としては、ERL-4221、UVR-6105、ERL-4299(全て商品名、いずれもダウ・ケミカル製)、セロキサイド2021P、エポリードGT401、EHPE3150、EHPE3150CE(全て商品名、いずれもダイセル化学工業製)およびジシクロペンタジエンジエポキシドなどが挙げられるがこれらに限定されるものではない(参考文献:総説エポキシ樹脂 基礎編I p76-85)。
これらは単独で用いてもよく、2種以上併用してもよい。本発明においては、エポキシシクロヘキサン構造を有する化合物が耐ガス透過性を向上させる観点からも好ましい。 Furthermore, the acetal compound by the acetal reaction of a cyclohexene aldehyde derivative and an alcohol form is mentioned.
Specific examples of these epoxy resins include ERL-4221, UVR-6105, ERL-4299 (all trade names, all manufactured by Dow Chemical), Celoxide 2021P, Epolide GT401, EHPE3150, EHPE3150CE (all trade names, all Daicel) (Chemical Industry) and dicyclopentadiene diepoxide, and the like, but are not limited to these (Reference: Review Epoxy Resin Basic Edition I p76-85).
These may be used alone or in combination of two or more. In the present invention, a compound having an epoxycyclohexane structure is also preferable from the viewpoint of improving gas permeability resistance.
かかる配合比率で含有させることで、エポキシシクロヘキシル基含有オルガノポリシロキサン(A)-酸無水物(C)(および/または任意で添加される多価カルボン酸(D))の硬化の間に、脂環式エポキシ樹脂(B)-酸無水物(C)(および/または多価カルボン酸(D))の架橋を入れることができる。系中に脂環式エポキシ樹脂(B)が必要以上にあると、脂環式エポキシ樹脂(B)-酸無水物(C)(および/または多価カルボン酸(D))のみの硬化系が硬化物中を占めるため、鎖状シリコーン部位由来の柔軟性を損ね、脆く弱い硬化物となってしまう虞がある。また硬化物において前記脂環式エポキシ樹脂(B)-酸無水物(C)(および/または多価カルボン酸(D))のみの硬化系は他の部分に対する相溶性が低いため、樹脂濁りの原因となり、引いては光取出し効率の低下を招く虞がある。
脂環式エポキシ樹脂(B)を上記割合で配合することで鎖状シリコーン部位由来の柔軟性が効果的に発現し、より硬さと柔軟性のバランスに優れ、また光取出し効率を高めた硬化物を得ることが可能である。
上記式によれば、1分子当たりのエポキシ基量が多いほど、脂環式エポキシ樹脂(B)の導入量は多くなる。一方、1分子当たりのエポキシ基量が少ないほど、脂環式エポキシ樹脂(B)の導入量は少なくなる。
上記式より算出される割合Pは40以下(即ち、脂環式エポキシ樹脂(B)の最大含有量は40重量%以下)が望ましい。但し、割合Pは上述の1.5~40重量%の範囲内の量である。好ましくは脂環式エポキシ樹脂(B)が1.5~20重量%、且つ割合Pが40以下である。 In the present invention, the epoxy group dispersibility of the epoxycyclohexyl group-containing organopolysiloxane (A) refers to the weight average molecular weight of the epoxycyclohexyl group-containing organopolysiloxane (A) and the epoxycyclohexyl group-containing organopolysiloxane (A). It means a value divided by an epoxy equivalent (amount of resin containing 1 g equivalent of epoxy (unit: g / eq.)), Whereby the average of epoxy groups contained in one molecule of epoxycyclohexyl group-containing organopolysiloxane (A) The amount can be estimated. The present inventor can determine the amount of alicyclic epoxy resin (B) introduced based on the amount of epoxy groups per molecule, specifically, epoxycyclohexyl group-containing organopolysiloxane (A) and alicyclic epoxy. The amount (% by weight) of the alicyclic epoxy resin (B) in the total amount of the resin (B) is correlated with the amount of epoxy groups per molecule of the epoxycyclohexyl group-containing organopolysiloxane (A). It came to know by experiment. That is, the content (% by weight) of the alicyclic epoxy resin (B) is 10 × (weight average molecular weight of the epoxycyclohexyl group-containing organopolysiloxane (A)) ÷ (epoxycyclohexyl group-containing organopolysiloxane (A). By setting the epoxy equivalent) to less than wt% (ratio P), the flexibility derived from the chain silicone moiety is not impaired, and a cured product having an even better balance between hardness and flexibility can be obtained. Furthermore, an alicyclic epoxy It has been found that when the content (% by weight) of the resin (B) satisfies the above formula (ratio P), the occurrence of resin turbidity can be suppressed and the light extraction efficiency is improved.
By containing it in such a blending ratio, the epoxycyclohexyl group-containing organopolysiloxane (A) -acid anhydride (C) (and / or optionally added polycarboxylic acid (D)) is cured during the curing. Cyclic epoxy resin (B) -acid anhydride (C) (and / or polyvalent carboxylic acid (D)) crosslinks can be included. If the alicyclic epoxy resin (B) is more than necessary in the system, a curing system consisting only of the alicyclic epoxy resin (B) -acid anhydride (C) (and / or the polyvalent carboxylic acid (D)) will be formed. Since it occupies in the cured product, the flexibility derived from the chain silicone moiety is impaired, and there is a risk that the cured product becomes brittle and weak. Further, in the cured product, the curing system of only the alicyclic epoxy resin (B) -acid anhydride (C) (and / or polyvalent carboxylic acid (D)) has low compatibility with other parts, so This may cause a decrease in light extraction efficiency.
By blending the alicyclic epoxy resin (B) in the above proportion, the flexibility derived from the chain silicone moiety is effectively expressed, the cured product has a better balance between hardness and flexibility, and has improved light extraction efficiency. It is possible to obtain
According to the above formula, the greater the amount of epoxy groups per molecule, the greater the amount of alicyclic epoxy resin (B) introduced. On the other hand, the smaller the amount of epoxy groups per molecule, the smaller the amount of alicyclic epoxy resin (B) introduced.
The ratio P calculated from the above formula is desirably 40 or less (that is, the maximum content of the alicyclic epoxy resin (B) is 40% by weight or less). However, the ratio P is an amount within the range of 1.5 to 40% by weight described above. Preferably, the alicyclic epoxy resin (B) is 1.5 to 20% by weight and the ratio P is 40 or less.
酸無水物としては具体的には無水フタル酸、無水トリメリット酸、無水ピロメリット酸、無水マレイン酸、テトラヒドロ無水フタル酸、メチルテトラヒドロ無水フタル酸、無水メチルナジック酸、無水ナジック酸、ヘキサヒドロ無水フタル酸、メチルヘキサヒドロ無水フタル酸、ブタンテトラカルボン酸無水物、ビシクロ[2,2,1]ヘプタン-2,3-ジカルボン酸無水物、メチルビシクロ[2,2,1]ヘプタン-2,3-ジカルボン酸無水物、シクロヘキサン-1,2,4-トリカルボン酸-1,2-無水物、などの酸無水物が挙げられる。
特にメチルテトラヒドロ無水フタル酸、無水メチルナジック酸、無水ナジック酸、ヘキサヒドロ無水フタル酸、メチルヘキサヒドロ無水フタル酸、ブタンテトラカルボン酸無水物、ビシクロ[2,2,1]ヘプタン-2,3-ジカルボン酸無水物、メチルビシクロ[2,2,1]ヘプタン-2,3-ジカルボン酸無水物、シクロヘキサン-1,2,4-トリカルボン酸-1,2-無水物が好ましい。
さらに前記酸無水物のうち下記式(5) The curable resin composition of the present invention contains an acid anhydride (C) as a curing agent. The acid anhydride (C) is excellent in transparency and is excellent in workability because it is liquid.
Specific examples of acid anhydrides include phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, maleic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methyl nadic anhydride, nadic anhydride, hexahydrophthalic anhydride Acid, methylhexahydrophthalic anhydride, butanetetracarboxylic anhydride, bicyclo [2,2,1] heptane-2,3-dicarboxylic anhydride, methylbicyclo [2,2,1] heptane-2,3- And acid anhydrides such as dicarboxylic acid anhydride and cyclohexane-1,2,4-tricarboxylic acid-1,2-anhydride.
In particular, methyltetrahydrophthalic anhydride, methylnadic anhydride, nadic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, butanetetracarboxylic anhydride, bicyclo [2,2,1] heptane-2,3-dicarboxylic acid Preferred are acid anhydride, methylbicyclo [2,2,1] heptane-2,3-dicarboxylic acid anhydride, and cyclohexane-1,2,4-tricarboxylic acid-1,2-anhydride.
Further, among the acid anhydrides, the following formula (5)
本発明において、酸無水物(C)は他の硬化剤である多価カルボン酸(D)と併用されることが望ましく、併用する際の含有量は後述する多価カルボン酸(D)との割合で決定されることが望ましく、下記式の範囲が好ましい。
W1/(W1+W2)=0.05~0.70
(ただし、W1は多価カルボン酸(D)の配合重量部、W2は酸無水物(C)の配合重量部を示す。)
前記においてW1/(W1+W2)の範囲として、より好ましくは、0.05~0.60、さらに好ましくは0.10~0.55、特に好ましくは0.15~0.4である。0.05を下回ると、硬化時に酸無水物(C)の揮発が多くなる傾向が強く、好ましくない。0.70を越えると高い粘度となり、取り扱いが難しくなる。
酸無水物(C)と多価カルボン酸(D)を併用する場合、多価カルボン酸(D)の製造時に過剰の酸無水物(C)の中で製造し、多価カルボン酸(D)と酸無水物の混合物を作るという手法も操作の簡便性の面から好ましい。 The amount of the acid anhydride (C) used in the curable resin composition of the present invention is preferably 0.7 to 1.2 equivalents relative to 1 equivalent of the epoxy groups of all epoxy resins. When less than 0.7 equivalent or more than 1.2 equivalent with respect to 1 equivalent of epoxy group, curing may be incomplete and good cured properties may not be obtained. When used in combination with a curing agent such as a polyvalent carboxylic acid to be described later, the total amount of the curing agent used is preferably within the above range.
In the present invention, the acid anhydride (C) is preferably used in combination with the polyvalent carboxylic acid (D) which is another curing agent, and the content when used in combination with the polyvalent carboxylic acid (D) described later is It is desirable to be determined by a ratio, and the range of the following formula is preferable.
W1 / (W1 + W2) = 0.05-0.70
(W1 represents a blended part by weight of the polyvalent carboxylic acid (D), and W2 represents a blended part by weight of the acid anhydride (C).)
In the above, the range of W1 / (W1 + W2) is more preferably 0.05 to 0.60, still more preferably 0.10 to 0.55, and particularly preferably 0.15 to 0.4. If it is less than 0.05, there is a strong tendency to increase the volatilization of the acid anhydride (C) during curing, which is not preferable. If it exceeds 0.70, the viscosity becomes high and handling becomes difficult.
When the acid anhydride (C) and the polyvalent carboxylic acid (D) are used in combination, the polyhydric carboxylic acid (D) is produced in excess of the acid anhydride (C) during the production of the polyvalent carboxylic acid (D). A method of making a mixture of acid and acid anhydride is also preferable from the viewpoint of simplicity of operation.
2~6官能の多価アルコールとしては、アルコール性水酸基を有する化合物であれば特に限定されないがエチレングリコール、プロピレングリコール、1,3-プロパンジオール、1,2-ブタンジオール、1,4-ブタンジオール、1,5-ペンタンジオール、1,6-ヘキサンジオール、シクロヘキサンジメタノール、2,4-ジエチルペンタンジオール、2-エチル-2-ブチル-1,3-プロパンジオール、ネオペンチルグリコール、トリシクロデカンジメタノール、ノルボルネンジオール、カルビノール変性シリコンオイルなどのジオール類、グリセリン、トリメチロールエタン、トリメチロールプロパン、トリメチロールブタン、2-ヒドロキシメチル-1,4-ブタンジオールなどのトリオール類、ペンタエリスリトール、ジトリメチロールプロパンなどのテトラオール類、ジペンタエリスリトールなどのヘキサオール類などが挙げられる。 As the polyvalent carboxylic acid (D), a bi- to hexa-functional carboxylic acid is particularly preferable, and a compound obtained by reacting a bi- to hexa-functional polyhydric alcohol having 5 or more carbon atoms with an acid anhydride is more preferable. Furthermore, the polycarboxylic acid whose said acid anhydride is a saturated aliphatic cyclic acid anhydride is preferable.
The bi- to hexafunctional polyhydric alcohol is not particularly limited as long as it is a compound having an alcoholic hydroxyl group, but ethylene glycol, propylene glycol, 1,3-propanediol, 1,2-butanediol, 1,4-butanediol. 1,5-pentanediol, 1,6-hexanediol, cyclohexanedimethanol, 2,4-diethylpentanediol, 2-ethyl-2-butyl-1,3-propanediol, neopentyl glycol, tricyclodecanedi Diols such as methanol, norbornenediol, carbinol modified silicone oil, triols such as glycerol, trimethylolethane, trimethylolpropane, trimethylolbutane, 2-hydroxymethyl-1,4-butanediol, pentaerythritol, dito Examples include tetraols such as limethylolpropane and hexaols such as dipentaerythritol.
に示される化合物が好ましい。 (In Formula (4A), R 8 represents an alkylene group having 1 to 10 carbon atoms, R 7 represents a methyl group or a phenyl group, and p represents an average value of 1 to 100.)
The compound shown by these is preferable.
付加反応の条件としては特に指定はないが、具体的な反応条件の1つとしては酸無水物、多価アルコールを無触媒、無溶剤の条件下、40~150℃で反応させ加熱し、反応終了後、そのまま取り出す、という手法が挙げられるが、本反応条件に限定されるものではない。 Examples of acid anhydrides include methyltetrahydrophthalic anhydride, methyl nadic anhydride, nadic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, butanetetracarboxylic anhydride, bicyclo [2,2,1] heptane- 2,3-dicarboxylic acid anhydride, methylbicyclo [2,2,1] heptane-2,3-dicarboxylic acid anhydride, cyclohexane-1,2,4-tricarboxylic acid-1,2-anhydride and the like are preferable, Of these, methylhexahydrophthalic anhydride and cyclohexane-1,2,4-tricarboxylic acid-1,2-anhydride are preferred.
Although there is no particular designation for the conditions for the addition reaction, one specific reaction condition is that the acid anhydride and polyhydric alcohol are reacted at 40 to 150 ° C. under non-catalytic and solvent-free conditions and heated. Although the method of taking out as it is after completion | finish is mentioned, It is not limited to this reaction conditions.
亜鉛塩および/または亜鉛錯体(E)としては亜鉛イオンを中心元素とした塩および/または錯体であって、好ましくは、カウンターイオンおよび/または配位子として燐酸エステルまたは燐酸を有する。
特に、燐酸、炭素数1~30のアルキル基の燐酸エステル(モノアルキルエステル体、ジアルキルエステル体、トリアルキルエステル体、もしくはそれらの混合物)の亜鉛塩および/または亜鉛錯体が好ましい。前記においてアルキル基としてはメチル基、イソプロピル基、ブチル基、2-エチルヘキシル基、オクチル基、イソデシル基、イソステアリル基、デカニル基、セチル基などが挙げられる。 The curable resin composition of the present invention preferably contains a zinc salt and / or a zinc complex (E) as a curing accelerator.
The zinc salt and / or zinc complex (E) is a salt and / or complex having a zinc ion as a central element, and preferably has a phosphate ester or phosphoric acid as a counter ion and / or a ligand.
In particular, zinc salts and / or zinc complexes of phosphoric acid and phosphoric acid esters (monoalkyl esters, dialkyl esters, trialkyl esters, or mixtures thereof) having 1 to 30 carbon atoms are preferred. Examples of the alkyl group include methyl, isopropyl, butyl, 2-ethylhexyl, octyl, isodecyl, isostearyl, decanyl, and cetyl groups.
特に含有される燐酸エステル中、モノアルキルエステル体、ジアルキルエステル体、トリアルキルエステル体のモル比(ガスクロマトグラフィーの純度で代替。ただし、トリメチルシリル化を行う必要があるため、感度に差が出てしまう。)において、トリメチルシリル化処理をした段階で、モノアルキルエステル体の存在量が50面積%以上であることが好ましい。
さらに得られた燐酸エステルを例えば炭酸亜鉛、水酸化亜鉛などと反応させることで、本発明に使用する亜鉛塩および/または亜鉛錯体が得られる(特許文献 EP699708号公報)。 In the present invention, a phosphoric ester of an alkyl group having 3 to 15 carbon atoms is particularly preferred, and the ester may be a mixture or a single product, but the main component is preferably a monoalkyl phosphate.
In particular, the molar ratio of monoalkyl ester, dialkyl ester, and trialkyl ester in the phosphoric acid ester contained (substitute with the purity of gas chromatography. However, since trimethylsilylation is required, there is a difference in sensitivity. In this case, the amount of the monoalkyl ester compound is preferably 50 area% or more at the stage of the trimethylsilylation treatment.
Furthermore, the zinc salt and / or zinc complex used for this invention are obtained by making the obtained phosphoric ester react with zinc carbonate, zinc hydroxide, etc. (patent document EP699708 gazette).
また、上記亜鉛塩および/または亜鉛錯体(E)としては、カルボン酸亜鉛(2-エチルヘキサン酸亜鉛、ステアリン酸亜鉛、ベヘン酸亜鉛、ミスチリン酸亜鉛等)を使用することもでき、中でも炭素数3~20のアルキルカルボン酸亜鉛が好ましい。 As the details of the zinc salt and / or zinc complex of such phosphate ester, the ratio of phosphorus atom to zinc atom (P / Zn) is preferably 1.2 to 2.3, more preferably 1.3 to 2.0. . Particularly preferred is 1.4 to 1.9. That is, in a particularly preferred form, the amount of phosphate ester (or phosphate derived from phosphate ester) is 2.0 moles or less per mole of zinc ion, and not a simple ionic structure, some molecules are ion-bonded (or arranged). Those having a structure related by coordinate bond are preferred. Such a zinc salt and / or zinc complex can also be obtained, for example, by the technique described in Japanese Patent Publication No. 2003-51495.
Further, as the zinc salt and / or zinc complex (E), zinc carboxylate (zinc 2-ethylhexanoate, zinc stearate, zinc behenate, zinc myristate, etc.) can be used. 3-20 zinc alkylcarboxylates are preferred.
前記アミン化合物としては、例えば、テトラキス(1,2,2,6,6-ペンタメチル-4-ピペリジル)=1,2,3,4-ブタンテトラカルボキシラート、テトラキス(2,2,6,6-トトラメチル-4-ピペリジル)=1,2,3,4-ブタンテトラカルボキシラート、1,2,3,4-ブタンテトラカルボン酸と1,2,2,6,6-ペンタメチル-4-ピペリジノールおよび3,9-ビス(2-ヒドロキシ-1,1-ジメチルエチル)-2,4,8,10-テトラオキサスピロ[5.5]ウンデカンとの混合エステル化物、デカン二酸ビス(2,2,6,6-テトラメチル-4-ピペリジル)セバケート、ビス(1-ウンデカンオキシ-2,2,6,6-テトラメチルピペリジン-4-イル)カーボネート、2,2,6,6,-テトラメチル-4-ピペリジルメタクリレート、ビス(2,2,6,6-テトラメチル-4-ピペリジル)セバケート、ビス(1,2,2,6,6-ペンタメチル-4-ピペリジル)セバケート、4-ベンゾイルオキシ-2,2,6,6-テトラメチルピペリジン、1-〔2-〔3-(3,5-ジ-tert-ブチル-4-ヒドロキシフェニル)プロピオニルオキシ〕エチル〕-4-〔3-(3,5-ジ-tert-ブチル-4-ヒドロキシフェニル)プロピオニルオキシ〕-2,2,6,6-テトラメチルピペリジン、1,2,2,6,6-ペンタメチル-4-ピペリジニル-メタアクリレート、ビス(1,2,2,6,6-ペンタメチル-4-ピペリジニル)〔〔3,5-ビス(1,1-ジメチルエチル)-4-ヒドロキシフェニル〕メチル〕ブチルマロネート、デカン二酸ビス(2,2,6,6-テトラメチル-1(オクチルオキシ)-4-ピペリジニル)エステル,1,1-ジメチルエチルヒドロペルオキシドとオクタンの反応生成物、N,N′,N″,N″′-テトラキス-(4,6-ビス-(ブチル-(N-メチル-2,2,6,6-テトラメチルピペリジン-4-イル)アミノ)-トリアジン-2-イル)-4,7-ジアザデカン-1,10-ジアミン、ジブチルアミン・1,3,5-トリアジン・N,N′-ビス(2,2,6,6-テトラメチル-4-ピペリジル-1,6-ヘキサメチレンジアミンとN-(2,2,6,6-テトラメチル-4-ピペリジル)ブチルアミンの重縮合物、ポリ〔〔6-(1,1,3,3-テトラメチルブチル)アミノ-1,3,5-トリアジン-2,4-ジイル〕〔(2,2,6,6-テトラメチル-4-ピペリジル)イミノ〕ヘキサメチレン〔(2,2,6,6-テトラメチル-4-ピペリジル)イミノ〕〕、コハク酸ジメチルと4-ヒドロキシ-2,2,6,6-テトラメチル-1-ピペリジンエタノールの重合物、2,2,4,4-テトラメチル-20-(β-ラウリルオキシカルボニル)エチル-7-オキサ-3,20-ジアザジスピロ〔5・1・11・2〕ヘネイコサン-21-オン、β-アラニン,N,-(2,2,6,6-テトラメチル-4-ピペリジニル)-ドデシルエステル/テトラデシルエステル、N-アセチル-3-ドデシル-1-(2,2,6,6-テトラメチル-4-ピペリジニル)ピロリジン-2,5-ジオン、2,2,4,4-テトラメチル-7-オキサ-3,20-ジアザジスピロ〔5,1,11,2〕ヘネイコサン-21-オン、2,2,4,4-テトラメチル-21-オキサ-3,20-ジアザジシクロ-〔5,1,11,2〕-ヘネイコサン-20-プロパン酸ドデシルエステル/テトラデシルエステル、プロパンジオイックアシッド,〔(4-メトキシフェニル)-メチレン〕-ビス(1,2,2,6,6-ペンタメチル-4-ピペリジニル)エステル、2,2,6,6-テトラメチル-4-ピペリジノールの高級脂肪酸エステル、1,3-ベンゼンジカルボキシアミド,N,N′-ビス(2,2,6,6-テトラメチル-4-ピペリジニル)等のヒンダートアミン系化合物等が挙げられる。 When the curable resin composition of the present invention is used in an optical material, particularly an optical semiconductor encapsulant, it contains a hindered amine compound as a light stabilizer and a phosphorus compound as an antioxidant as particularly preferable components. That is preferred.
Examples of the amine compound include tetrakis (1,2,2,6,6-pentamethyl-4-piperidyl) = 1,2,3,4-butanetetracarboxylate, tetrakis (2,2,6,6- Totramethyl-4-piperidyl) = 1,2,3,4-butanetetracarboxylate, 1,2,3,4-butanetetracarboxylic acid and 1,2,2,6,6-pentamethyl-4-piperidinol and 3 , 9-bis (2-hydroxy-1,1-dimethylethyl) -2,4,8,10-tetraoxaspiro [5.5] undecane mixed ester, decanedioic acid bis (2,2,6 , 6-Tetramethyl-4-piperidyl) sebacate, bis (1-undecanoxy-2,2,6,6-tetramethylpiperidin-4-yl) carbonate, 2,2,6,6, -tetrame Ru-4-piperidyl methacrylate, bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, 4-benzoyloxy -2,2,6,6-tetramethylpiperidine, 1- [2- [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionyloxy] ethyl] -4- [3- (3 , 5-di-tert-butyl-4-hydroxyphenyl) propionyloxy] -2,2,6,6-tetramethylpiperidine, 1,2,2,6,6-pentamethyl-4-piperidinyl-methacrylate, bis (1,2,2,6,6-pentamethyl-4-piperidinyl) [[3,5-bis (1,1-dimethylethyl) -4-hydroxyphenyl] methyl] bu Lumalonate, bis (2,2,6,6-tetramethyl-1 (octyloxy) -4-piperidinyl) ester decanedioate, reaction product of 1,1-dimethylethyl hydroperoxide and octane, N, N ′, N ″, N ″ ′-tetrakis- (4,6-bis- (butyl- (N-methyl-2,2,6,6-tetramethylpiperidin-4-yl) amino) -triazin-2-yl)- 4,7-diazadecane-1,10-diamine, dibutylamine, 1,3,5-triazine, N, N'-bis (2,2,6,6-tetramethyl-4-piperidyl-1,6-hexa Polycondensate of methylenediamine and N- (2,2,6,6-tetramethyl-4-piperidyl) butylamine, poly [[6- (1,1,3,3-tetramethylbutyl) amino-1,3 , 5-Triazine -2,4-diyl] [(2,2,6,6-tetramethyl-4-piperidyl) imino] hexamethylene [(2,2,6,6-tetramethyl-4-piperidyl) imino]], Polymer of dimethyl acid and 4-hydroxy-2,2,6,6-tetramethyl-1-piperidineethanol, 2,2,4,4-tetramethyl-20- (β-lauryloxycarbonyl) ethyl-7- Oxa-3,20-diazadispiro [5,1,11,2] heneicosan-21-one, β-alanine, N,-(2,2,6,6-tetramethyl-4-piperidinyl) -dodecyl ester / tetra Decyl ester, N-acetyl-3-dodecyl-1- (2,2,6,6-tetramethyl-4-piperidinyl) pyrrolidine-2,5-dione, 2,2,4,4-tetramethyl-7- Oki -3,20-diazadispiro [5,1,11,2] heneicosan-21-one, 2,2,4,4-tetramethyl-21-oxa-3,20-diazadicyclo- [5,1,11, 2] -Heneicosane-20-propanoic acid dodecyl ester / tetradecyl ester, propanedioic acid, [(4-methoxyphenyl) -methylene] -bis (1,2,2,6,6-pentamethyl-4-piperidinyl) Ester, higher fatty acid ester of 2,2,6,6-tetramethyl-4-piperidinol, 1,3-benzenedicarboxamide, N, N′-bis (2,2,6,6-tetramethyl-4- And hindered amine compounds such as piperidinyl).
例えば、チバスペシャリティケミカルズ製として、TINUVIN765、TINUVIN770DF、TINUVIN144、TINUVIN123、TINUVIN622LD、TINUVIN152、CHIMASSORB944、アデカ製として、LA-52、LA-57、LA-62、LA-63P、LA-77Y、LA-81、LA-82、LA-87などが挙げられる。 The following commercially available products can be used as the amine compound that is the light stabilizer.
For example, as manufactured by Ciba Specialty Chemicals, TINUVIN 765, TINUVIN 770DF, TINUVIN 144, TINUVIN 123, TINUVIN 622LD, TINUVIN 152, CHIMASSORB 944, manufactured by ADEKA, LA-52, LA-57, LA-62, LA-63P, LA-77Y, LA-81, LA-82, LA-87 and the like can be mentioned.
例えば、アデカ製として、アデカスタブPEP-4C、アデカスタブPEP-8、アデカスタブPEP-24G、アデカスタブPEP-36、アデカスタブHP-10、アデカスタブ2112、アデカスタブ260、アデカスタブ522A、アデカスタブ1178、アデカスタブ1500、アデカスタブC、アデカスタブ135A、アデカスタブ3010、アデカスタブTPPが挙げられる。 A commercial item can also be used for the said phosphorus compound.
For example, ADK STAB PEP-4C, ADK STAB PEP-8, ADK STAB PEP-24G, ADK STAB PEP-36, ADK STAB HP-10, ADK STAB 2112, ADK STAB 260, ADK STAB 522A, ADK STAB 1178, ADK STAB 1500, ADK STAB C, and ADK STAB C 135A, ADK STAB 3010, and ADK STAB TPP.
これらは下記に示す他のエポキシ樹脂、硬化剤、各種添加剤とも併用することができる。 The curable resin composition of the present invention includes an epoxycyclohexyl group-containing organopolysiloxane (A) and an alicyclic epoxy resin (B) as an epoxy resin, and an acid anhydride (C) and a polyvalent carboxylic acid (D) as a curing agent. It is preferable to contain. The curable resin composition of the present invention comprises an epoxycyclohexyl group-containing organopolysiloxane (A) and an alicyclic epoxy resin (B) as an epoxy resin, and an acid anhydride (C) and a polyvalent carboxylic acid (as a curing agent). D) It is preferable to contain a zinc salt and / or a zinc complex (E) as an additive. Furthermore, the curable resin composition of the present invention preferably contains a hindered amine light stabilizer and a phosphorus-containing antioxidant as additives.
These can be used in combination with other epoxy resins, curing agents and various additives described below.
硬化剤成分として、酸無水物(C)や多価カルボン酸(D)以外に他の硬化剤を併用する場合、酸無水物(C)と多価カルボン酸(D)の総重量の全硬化剤中に占める割合は30重量%以上が好ましく、特に40重量%以上が好ましい。 Curing agents that can be used in combination with acid anhydride (C) or polyvalent carboxylic acid (D) as the curing agent component include, for example, amine compounds, acid anhydride compounds, amide compounds, phenol compounds, carboxylic acid compounds. Etc. Specific examples of curing agents that can be used include amines and polyamide compounds (diaminodiphenylmethane, diethylenetriamine, triethylenetetramine, diaminodiphenylsulfone, isophoronediamine, dicyandiamide, polyamide resin synthesized from ethylenediamine and dimer of linolenic acid, etc.) , Reaction product of acid anhydride and silicone alcohol (phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, maleic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methyl nadic anhydride, anhydrous Nadic acid, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, butanetetracarboxylic anhydride, bicyclo [2,2,1] heptane-2,3-dicarboxylic anhydride, methylbicyclo [2,2,1] Hepta -Reaction products of acid anhydrides such as -2,3-dicarboxylic acid anhydride and cyclohexane-1,2,4-tricarboxylic acid-1,2-anhydride and silicone alcohols such as carbinol-modified silicone) Polyphenols (bisphenol A, bisphenol F, bisphenol S, fluorene bisphenol, terpene diphenol, 4,4'-biphenol, 2,2'-biphenol, 3,3 ', 5,5'-tetramethyl- [ 1,1′-biphenyl] -4,4′-diol, hydroquinone, resorcin, naphthalenediol, tris- (4-hydroxyphenyl) methane, 1,1,2,2-tetrakis (4-hydroxyphenyl) ethane, phenol (Phenol, alkyl-substituted phenol, naphthol, alkyl-substituted naphthol, dihydro Sibenzene, dihydroxynaphthalene, etc.) and formaldehyde, acetaldehyde, benzaldehyde, p-hydroxybenzaldehyde, o-hydroxybenzaldehyde, p-hydroxyacetophenone, o-hydroxyacetophenone, dicyclopentadiene, furfural, 4,4'-bis (chloromethyl)- 1,1′-biphenyl, 4,4′-bis (methoxymethyl) -1,1′-biphenyl, 1,4′-bis (chloromethyl) benzene, 1,4′-bis (methoxymethyl) benzene, etc. Polycondensates and modified products thereof, halogenated bisphenols such as tetrabromobisphenol A, condensates of terpenes and phenols) and others (imidazole, trifluoroborane-amine complexes, guanidine derivatives, etc.) But this It is not limited to these. These may be used alone or in combination of two or more.
When other curing agents are used in addition to the acid anhydride (C) and polyvalent carboxylic acid (D) as the curing agent component, total curing of the total weight of the acid anhydride (C) and the polyvalent carboxylic acid (D) The proportion in the agent is preferably 30% by weight or more, and particularly preferably 40% by weight or more.
エポキシ基1当量に対して、0.7当量に満たない場合、あるいは1.2当量を超える場合、いずれも硬化が不完全となり良好な硬化物性が得られない恐れがある。 In the curable resin composition of the present invention, the epoxy resin component containing the epoxycyclohexyl group-containing organopolysiloxane (A) and the alicyclic epoxy resin (B) as essential components, and the acid anhydride (C) as essential components The blending ratio of the curing agent component as a component is such that the curing agent component is 0.7 to 1.2 equivalents, particularly preferably 0.75 to 1.10 equivalents per 1 equivalent of epoxy group of the epoxy resin component. It is preferable to use a curing agent.
When less than 0.7 equivalent or more than 1.2 equivalent with respect to 1 equivalent of epoxy group, curing may be incomplete and good cured properties may not be obtained.
使用できる硬化促進剤としては、2-メチルイミダゾール、2-フェニルイミダゾール、2-ウンデシルイミダゾール、2-ヘプタデシルイミダゾール、2-フェニル-4-メチルイミダゾール、1-ベンジル-2-フェニルイミダゾール、1-ベンジル-2-メチルイミダゾール、1-シアノエチル-2-メチルイミダゾール、1-シアノエチル-2-フェニルイミダゾール、1-シアノエチル-2-ウンデシルイミダゾール、2,4-ジアミノ-6(2'-メチルイミダゾール(1'))エチル-s-トリアジン、2,4-ジアミノ-6(2'-ウンデシルイミダゾール(1'))エチル-s-トリアジン、2,4-ジアミノ-6(2'-エチル,4-メチルイミダゾール(1'))エチル-s-トリアジン、2,4-ジアミノ-6(2'-メチルイミダゾール(1'))エチル-s-トリアジン・イソシアヌル酸付加物、2-メチルイミダゾールイソシアヌル酸の2:3付加物、2-フェニルイミダゾールイソシアヌル酸付加物、2-フェニル-3,5-ジヒドロキシメチルイミダゾール、2-フェニル-4-ヒドロキシメチル-5-メチルイミダゾール、1-シアノエチル-2-フェニル-3,5-ジシアノエトキシメチルイミダゾールの各種イミダゾール類、および、それらイミダゾール類とフタル酸、イソフタル酸、テレフタル酸、トリメリット酸、ピロメリット酸、ナフタレンジカルボン酸、マレイン酸、蓚酸等の多価カルボン酸との塩類、ジシアンジアミド等のアミド類、1,8-ジアザ-ビシクロ(5.4.0)ウンデセン-7等のジアザ化合物およびそれらのテトラフェニルボレート、フェノールノボラック等の塩類、前記多価カルボン酸類、又はホスフィン酸類との塩類、テトラブチルアンモニュウムブロマイド、セチルトリメチルアンモニュウムブロマイド、トリオクチルメチルアンモニュウムブロマイド等のアンモニュウム塩、トリフェニルホスフィン、トリ(トルイル)ホスフィン、テトラフェニルホスホニウムブロマイド、テトラフェニルホスホニウムテトラフェニルボレート等のホスフィン類やホスホニウム化合物、2,4,6-トリスアミノメチルフェノール等のフェノール類、アミンアダクト、オクチル酸スズ等の金属化合物等、およびこれら硬化促進剤をマイクロカプセルにしたマイクロカプセル型硬化促進剤等が挙げられる。これら硬化促進剤のどれを用いるかは、例えば透明性、硬化速度、作業条件といった得られる透明樹脂組成物に要求される特性によって適宜選択される。硬化促進剤は、硬化性組成物に含まれるエポキシ樹脂成分100重量部に対し通常0.001~15重量部の範囲で使用される。 The curable resin composition of the present invention preferably further contains a curing catalyst. When the zinc salt and / or zinc complex (E) is contained in the curable composition, the zinc salt and / or zinc complex (E) itself acts as a curing catalyst, so Although it does not need to be added separately, other curing catalysts can be used in combination.
Examples of curing accelerators that can be used include 2-methylimidazole, 2-phenylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-phenylimidazole, 1- Benzyl-2-methylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-undecylimidazole, 2,4-diamino-6 (2′-methylimidazole (1 ')) Ethyl-s-triazine, 2,4-diamino-6 (2'-undecylimidazole (1')) ethyl-s-triazine, 2,4-diamino-6 (2'-ethyl, 4-methyl) Imidazole (1 ′)) ethyl-s-triazine, 2,4-diamino-6 (2′-methyl) Imidazole (1 ')) ethyl-s-triazine isocyanuric acid adduct, 2-methylimidazole isocyanuric acid 2: 3 adduct, 2-phenylimidazole isocyanuric acid adduct, 2-phenyl-3,5-dihydroxymethylimidazole , 2-phenyl-4-hydroxymethyl-5-methylimidazole, various imidazoles of 1-cyanoethyl-2-phenyl-3,5-dicyanoethoxymethylimidazole, and imidazoles and phthalic acid, isophthalic acid, terephthalic acid , Salts with polyvalent carboxylic acids such as trimellitic acid, pyromellitic acid, naphthalene dicarboxylic acid, maleic acid and succinic acid, amides such as dicyandiamide, 1,8-diaza-bicyclo (5.4.0) undecene-7 Diaza compounds and their tetrapheni Salts such as borates and phenol novolaks, salts with the above polycarboxylic acids, or phosphinic acids, ammonium salts such as tetrabutylammonium bromide, cetyltrimethylammonium bromide, trioctylmethylammonium bromide, triphenylphosphine, tri (tolyl) phosphine Phosphines and phosphonium compounds such as tetraphenylphosphonium bromide and tetraphenylphosphonium tetraphenylborate, phenols such as 2,4,6-trisaminomethylphenol, metal compounds such as amine adducts and tin octylate, and curing thereof Examples thereof include a microcapsule-type curing accelerator having a microcapsule as an accelerator. Which of these curing accelerators is used is appropriately selected depending on characteristics required for the obtained transparent resin composition, such as transparency, curing speed, and working conditions. The curing accelerator is usually used in the range of 0.001 to 15 parts by weight with respect to 100 parts by weight of the epoxy resin component contained in the curable composition.
本発明の硬化性樹脂組成物には、リン含有化合物を難燃性付与成分として含有させることもできる。リン含有化合物としては反応型のものでも添加型のものでもよい。リン含有化合物の具体例としては、トリメチルホスフェート、トリエチルホスフェート、トリクレジルホスフェート、トリキシリレニルホスフェート、クレジルジフェニルホスフェート、クレジル-2,6-ジキシリレニルホスフェート、1,3-フェニレンビス(ジキシリレニルホスフェート)、1,4-フェニレンビス(ジキシリレニルホスフェート)、4,4'-ビフェニル(ジキシリレニルホスフェート)等のリン酸エステル類;9,10-ジヒドロ-9-オキサ-10-ホスファフェナントレン-10-オキサイド、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-オキサイド等のホスファン類;エポキシ樹脂と前記ホスファン類の活性水素とを反応させて得られるリン含有エポキシ化合物、赤リン等が挙げられるが、リン酸エステル類、ホスファン類またはリン含有エポキシ化合物が好ましく、1,3-フェニレンビス(ジキシリレニルホスフェート)、1,4-フェニレンビス(ジキシリレニルホスフェート)、4,4'-ビフェニル(ジキシリレニルホスフェート)またはリン含有エポキシ化合物が特に好ましい。リン含有化合物の含有量はリン含有化合物/硬化性組成物に含まれるエポキシ樹脂=0.1~0.6(重量比)が好ましい。0.1未満では難燃性が不十分であり、0.6を超えると硬化物の吸湿性、誘電特性に悪影響を及ぼす懸念がある。 The curable resin composition of the present invention may contain various additives and auxiliary materials as listed below.
The curable resin composition of the present invention may contain a phosphorus-containing compound as a flame retardant component. The phosphorus-containing compound may be a reactive type or an additive type. Specific examples of phosphorus-containing compounds include trimethyl phosphate, triethyl phosphate, tricresyl phosphate, trixylylenyl phosphate, cresyl diphenyl phosphate, cresyl-2,6-dixylylenyl phosphate, 1,3-phenylenebis ( Phosphoric esters such as dixylylenyl phosphate), 1,4-phenylenebis (dixylylenyl phosphate), 4,4′-biphenyl (dixylylenyl phosphate); 9,10-dihydro-9-oxa Phosphanes such as -10-phosphaphenanthrene-10-oxide, 10 (2,5-dihydroxyphenyl) -10H-9-oxa-10-phosphaphenanthrene-10-oxide; epoxy resin and active hydrogen of the phosphanes A phosphorus-containing product obtained by reacting with Poxy compounds, red phosphorus and the like can be mentioned. Phosphate esters, phosphanes or phosphorus-containing epoxy compounds are preferable, and 1,3-phenylenebis (dixylylenyl phosphate), 1,4-phenylenebis (dixylylene). Nyl phosphate), 4,4′-biphenyl (dixylylenyl phosphate) or phosphorus-containing epoxy compounds are particularly preferred. The content of the phosphorus-containing compound is preferably an epoxy resin contained in the phosphorus-containing compound / curable composition = 0.1 to 0.6 (weight ratio). If it is less than 0.1, the flame retardancy is insufficient, and if it exceeds 0.6, there is a concern that it may adversely affect the hygroscopicity and dielectric properties of the cured product.
フェノール化合物としては特に限定はされず、例えば、2,6-ジ-tert-ブチル-4-メチルフェノール、n-オクタデシル-3-(3,5-ジ-tert-ブチル-4-ヒドロキシフェニル)プロピオネート、テトラキス[メチレン-3-(3,5-ジ-tert-ブチル-4-ヒドロキシフェニル)プロピオネート]メタン、2,4-ジ-tert-ブチル-6-メチルフェノール、1,6-ヘキサンジオール-ビス-[3-(3,5-ジ-tert-ブチル-4-ヒドロキシフェニル)プロピオネート]、トリス(3,5-ジ-tert-ブチル-4-ヒドロキシベンジル)-イソシアヌレイト、1,3,5-トリメチル-2,4,6-トリス(3,5-ジ-tert-ブチル-4-ヒドロキシベンジル)ベンゼン、ペンタエリスリチル-テトラキス[3-(3,5-ジ-tert-ブチル-4-ヒドロキシフェニル)プロピオネート]、3,9-ビス-〔2-[3-(3-tert-ブチル-4-ヒドロキシ-5-メチルフェニル)-プロピオニルオキシ]-1,1-ジメチルエチル〕-2,4,8,10-テトラオキサスピロ〔5,5〕ウンデカン、トリエチレングリコール-ビス[3-(3-t-ブチル-5-メチル-4-ヒドロキシフェニル)プロピオネート]、2,2'-ブチリデンビス(4,6-ジ-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)、2,2'-メチレンビス(4-メチル-6-tert-ブチルフェノール)、2,2'-メチレンビス(4-エチル-6-tert-ブチルフェノール)、2-tert-ブチル-6-(3-tert-ブチル-2-ヒドロキシ-5-メチルベンジル)-4-メチルフェノールアクリレート、2-[1-(2-ヒドロキシ-3,5-ジ-tert-ペンチルフェニル)エチル]-4,6-ジ-tert-ペンチルフェニルアクリレート、4,4'-チオビス(3-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)、2-tert-ブチル-4-メチルフェノール、2,4-ジ-tert-ブチルフェノール、2,4-ジ-tert-ペンチルフェノール、4,4'-チオビス(3-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)、ビス-[3,3-ビス-(4'-ヒドロキシ-3'-tert-ブチルフェニル)-ブタノイックアシッド]-グリコールエステル、2,4-ジ-tert-ブチルフェノール、2,4-ジ-tert-ペンチルフェノール、2-[1-(2-ヒドロキシ-3,5-ジ-tert-ペンチルフェニル)エチル]-4,6-ジ-tert-ペンチルフェニルアクリレート、ビス-[3,3-ビス-(4'-ヒドロキシ-3'-tert-ブチルフェニル)-ブタノイックアシッド]-グリコールエステル等が挙げられる。 The curable resin composition of the present invention can contain a phenolic compound as an antioxidant.
The phenol compound is not particularly limited, and examples thereof include 2,6-di-tert-butyl-4-methylphenol and n-octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate. Tetrakis [methylene-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] methane, 2,4-di-tert-butyl-6-methylphenol, 1,6-hexanediol-bis -[3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], tris (3,5-di-tert-butyl-4-hydroxybenzyl) -isocyanurate, 1,3,5 -Trimethyl-2,4,6-tris (3,5-di-tert-butyl-4-hydroxybenzyl) benzene, pentaerythrine Lithyl-tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], 3,9-bis- [2- [3- (3-tert-butyl-4-hydroxy-5- Methylphenyl) -propionyloxy] -1,1-dimethylethyl] -2,4,8,10-tetraoxaspiro [5,5] undecane, triethylene glycol-bis [3- (3-t-butyl-5 -Methyl-4-hydroxyphenyl) propionate], 2,2′-butylidenebis (4,6-di-tert-butylphenol), 4,4′-butylidenebis (3-methyl-6-tert-butylphenol), 2,2 '-Methylenebis (4-methyl-6-tert-butylphenol), 2,2'-methylenebis (4-ethyl-6-tert-butylphenol) 2-tert-butyl-6- (3-tert-butyl-2-hydroxy-5-methylbenzyl) -4-methylphenol acrylate, 2- [1- (2-hydroxy-3,5-di-) tert-pentylphenyl) ethyl] -4,6-di-tert-pentylphenyl acrylate, 4,4′-thiobis (3-methyl-6-tert-butylphenol), 4,4′-butylidenebis (3-methyl-6) -Tert-butylphenol), 2-tert-butyl-4-methylphenol, 2,4-di-tert-butylphenol, 2,4-di-tert-pentylphenol, 4,4'-thiobis (3-methyl-6) -Tert-butylphenol), 4,4'-butylidenebis (3-methyl-6-tert-butylphenol), bis- [3 3-bis- (4′-hydroxy-3′-tert-butylphenyl) -butanoic acid] -glycol ester, 2,4-di-tert-butylphenol, 2,4-di-tert-pentylphenol, 2 -[1- (2-hydroxy-3,5-di-tert-pentylphenyl) ethyl] -4,6-di-tert-pentylphenyl acrylate, bis- [3,3-bis- (4′-hydroxy- 3'-tert-butylphenyl) -butanoic acid] -glycol ester and the like.
例えば、チバスペシャリティケミカルズ製としてIRGANOX1010、IRGANOX1035、IRGANOX1076、IRGANOX1135、IRGANOX245、IRGANOX259、IRGANOX295、IRGANOX3114IRGANOX1098、IRGANOX1520L、アデカ製としては、アデカスタブAO-20、アデカスタブAO-30、アデカスタブAO-40、アデカスタブAO-50、アデカスタブAO-60、アデカスタブAO-70、アデカスタブAO-80、アデカスタブAO-90、アデカスタブAO-330、住友化学工業製として、SumilizerGA-80、Sumilizer MDP-S、Sumilizer BBM-S、Sumilizer GM、Sumilizer GS(F)、Sumilizer GPなどが挙げられる。 A commercial item can also be used for the said phenolic compound.
For example, IRGANOX1010, IRGANOX1035, IRGANOX1076, IRGANOX1135, IRGANOX245, IRGANOX259, IRGANOX3114, IRGANOX1098, IRGANOX1520L, Adekastab AO-20A Adeka Stub AO-60, Adeka Stub AO-70, Adeka Stub AO-80, Adeka Stub AO-90, Adeka Stub AO-330, manufactured by Sumitomo Chemical Co., Ltd. r GS (F), and the like Sumilizer GP.
注入方法としては、ディスペンサー、トランスファー成形、射出成形等が挙げられる。
加熱は、熱風循環式、赤外線、高周波等の方法が使用できる。
加熱条件は例えば80~230℃で1分~24時間程度が好ましい。加熱硬化の際に発生する内部応力を低減する目的で、例えば80~120℃、30分~5時間予備硬化させた後に、120~180℃、30分~10時間の条件で後硬化させることができる。 As a molding method of the sealing material, as described above, an injection method in which the sealing material is injected into the mold frame in which the substrate on which the semiconductor chip is fixed is inserted and then heat-cured and molded, and the sealing material is formed on the mold. A compression molding method or the like in which a semiconductor chip fixed on a substrate is immersed therein and heat-cured and then released from a mold is used.
Examples of the injection method include dispenser, transfer molding, injection molding and the like.
For the heating, methods such as hot air circulation, infrared rays and high frequency can be used.
For example, the heating conditions are preferably 80 to 230 ° C. for about 1 minute to 24 hours. For the purpose of reducing internal stress generated during heat-curing, for example, after pre-curing at 80 to 120 ° C. for 30 minutes to 5 hours, post-curing is performed at 120 to 180 ° C. for 30 minutes to 10 hours. it can.
(1)分子量:ゲルパーミエーションクロマトグラフィー(GPC)法により、下記条件下測定されたポリスチレン換算、重量平均分子量を算出した。
GPCの各種条件
メーカー:島津製作所
カラム:ガードカラム SHODEX GPC LF-G LF-804(3本)
流速:1.0ml/min.
カラム温度:40℃
使用溶剤:THF(テトラヒドロフラン)
検出器:RI(示差屈折検出器)
(2)エポキシ当量:JIS K-7236に記載の方法で測定。
(3)粘度:東機産業株式会社製E型粘度計(TV-20)を用いて25℃で測定。 In addition, each physical property value in an Example was measured with the following method.
(1) Molecular weight: Polystyrene conversion and weight average molecular weight measured under the following conditions were calculated by gel permeation chromatography (GPC) method.
Various conditions of GPC Manufacturer: Shimadzu Corporation Column: Guard column SHODEX GPC LF-G LF-804 (3)
Flow rate: 1.0 ml / min.
Column temperature: 40 ° C
Solvent: THF (tetrahydrofuran)
Detector: RI (differential refraction detector)
(2) Epoxy equivalent: Measured by the method described in JIS K-7236.
(3) Viscosity: Measured at 25 ° C. using an E-type viscometer (TV-20) manufactured by Toki Sangyo Co., Ltd.
製造工程(i)として、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285部、重量平均分子量1900(GPC測定値)のシラノール末端メチルフェニルシリコーンオイル475部(シラノール当量950、GPCを用いて測定した重量平均分子量の半分として算出した。)、0.5%水酸化カリウム(KOH)メタノール溶液40部を反応容器に仕込み、バス温度を75℃に設定し、昇温した。昇温後、還流下にて8時間反応させた。
製造工程(ii)として、メタノールを655部追加後、50%蒸留水メタノール溶液123部を60分かけて滴下し、還流下75℃にて8時間反応させた。反応終了後、5%リン酸2水素ナトリウム水溶液で中和後、80℃でメタノールの約90%を蒸留回収した。次いで、メチルイソブチルケトン(MIBK)750部を添加し、水洗を3回繰り返した。得られた有機相を減圧下、100℃で溶媒を除去することによりエポキシシクロヘキシル基含有オルガノポリシロキサン(S-1)620部を得た。得られた化合物(S-1)のエポキシ当量は605g/eq.、重量平均分子量は2120、外観は無色透明の液状樹脂であった。また割合Pの値は35であり、シルセスキオキサン由来の、3つの酸素に結合しているケイ素原子の全ケイ素原子に対する割合は約18モル%であった。 (Synthesis Example 1)
As production step (i), 285 parts of β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 475 parts of silanol-terminated methylphenyl silicone oil having a weight average molecular weight of 1900 (GPC measurement value) (silanol equivalent 950, using GPC) 40 parts of 0.5% potassium hydroxide (KOH) methanol solution was charged into the reaction vessel, the bath temperature was set to 75 ° C., and the temperature was raised. After raising the temperature, the reaction was carried out under reflux for 8 hours.
As a manufacturing process (ii), after adding 655 parts of methanol, 123 parts of methanol solution of 50% distilled water was added dropwise over 60 minutes and reacted at 75 ° C. for 8 hours under reflux. After completion of the reaction, the mixture was neutralized with 5% aqueous sodium dihydrogen phosphate solution, and about 90% of methanol was recovered by distillation at 80 ° C. Next, 750 parts of methyl isobutyl ketone (MIBK) was added, and washing with water was repeated three times. By removing the solvent from the obtained organic phase at 100 ° C. under reduced pressure, 620 parts of an epoxycyclohexyl group-containing organopolysiloxane (S-1) was obtained. The epoxy equivalent of the obtained compound (S-1) was 605 g / eq. The weight average molecular weight was 2120, and the appearance was a colorless and transparent liquid resin. Moreover, the value of the ratio P was 35, and the ratio of silicon atoms bonded to three oxygens derived from silsesquioxane to all silicon atoms was about 18 mol%.
製造工程(i)として、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375部、重量平均分子量1900(GPC測定値)のシラノール末端メチルフェニルシリコーンオイル475部(シラノール当量950、GPCを用いて測定した重量平均分子量の半分として算出した。)、0.5%水酸化カリウム(KOH)メタノール溶液40部を反応容器に仕込み、バス温度を75℃に設定し、昇温した。昇温後、還流下にて8時間反応させた。
製造工程(ii)として、メタノールを655部追加後、50%蒸留水メタノール溶液144部を60分かけて滴下し、還流下75℃にて8時間反応させた。反応終了後、5%リン酸2水素ナトリウム水溶液で中和後、80℃でメタノールの約90%を蒸留回収した。次いで、メチルイソブチルケトン(MIBK)750部を添加し、水洗を3回繰り返した。得られた有機相を減圧下、100℃で溶媒を除去することによりエポキシシクロヘキシル基含有オルガノポリシロキサン(S-2)647部を得た。得られた化合物(S-2)のエポキシ当量は541g/eq.、重量平均分子量は2100、外観は無色透明の液状樹脂であった。また割合Pの値は39であり、シルセスキオキサン由来の、3つの酸素に結合しているケイ素原子の全ケイ素原子に対する割合は約20モル%であった。 (Synthesis Example 2)
As production step (i), 375 parts of β- (3,4 epoxycyclohexyl) ethyltrimethoxysilane, 475 parts of silanol-terminated methylphenyl silicone oil having a weight average molecular weight of 1900 (GPC measurement value) (silanol equivalent 950, GPC) were used. 40 parts of 0.5% potassium hydroxide (KOH) methanol solution was charged into the reaction vessel, the bath temperature was set to 75 ° C., and the temperature was raised. After raising the temperature, the reaction was carried out under reflux for 8 hours.
As a manufacturing process (ii), after adding 655 parts of methanol, 144 parts of 50% distilled water methanol solution was added dropwise over 60 minutes, and reacted at 75 ° C. for 8 hours under reflux. After completion of the reaction, the mixture was neutralized with 5% aqueous sodium dihydrogen phosphate solution, and about 90% of methanol was recovered by distillation at 80 ° C. Next, 750 parts of methyl isobutyl ketone (MIBK) was added, and washing with water was repeated three times. By removing the solvent from the obtained organic phase at 100 ° C. under reduced pressure, 647 parts of epoxycyclohexyl group-containing organopolysiloxane (S-2) was obtained. The epoxy equivalent of the obtained compound (S-2) was 541 g / eq. The weight average molecular weight was 2,100, and the appearance was a colorless and transparent liquid resin. Further, the value of the ratio P was 39, and the ratio of silicon atoms bonded to three oxygens derived from silsesquioxane to all silicon atoms was about 20 mol%.
製造工程(i)として、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263部、重量平均分子量1900(GPC測定値)のシラノール末端メチルフェニルシリコーンオイル475部(シラノール当量950、GPCを用いて測定した重量平均分子量の半分として算出した。)、0.5%水酸化カリウム(KOH)メタノール溶液40部を反応容器に仕込み、バス温度を75℃に設定し、昇温した。昇温後、還流下にて8時間反応させた。
製造工程(ii)として、メタノールを655部追加後、50%蒸留水メタノール溶液115部を60分かけて滴下し、還流下75℃にて8時間反応させた。反応終了後、5%リン酸2水素ナトリウム水溶液で中和後、80℃でメタノールの約90%を蒸留回収した。次いで、メチルイソブチルケトン(MIBK)750部を添加し、水洗を3回繰り返した。得られた有機相を減圧下、100℃で溶媒を除去することによりエポキシシクロヘキシル基含有オルガノポリシロキサン(S-3)605部を得た。得られた化合物(S-3)のエポキシ当量は636g/eq.、重量平均分子量は2090、外観は無色透明の液状樹脂であった。また割合Pの値は33であり、シルセスキオキサン由来の、3つの酸素に結合しているケイ素原子の全ケイ素原子に対する割合は約17モル%であった。 (Synthesis Example 3)
As production step (i), 263 parts of β- (3,4 epoxycyclohexyl) ethyltrimethoxysilane, 475 parts of silanol-terminated methylphenylsilicone oil having a weight average molecular weight of 1900 (measured GPC value) (silanol equivalent 950, using GPC) 40 parts of 0.5% potassium hydroxide (KOH) methanol solution was charged into the reaction vessel, the bath temperature was set to 75 ° C., and the temperature was raised. After raising the temperature, the reaction was carried out under reflux for 8 hours.
As a manufacturing process (ii), after adding 655 parts of methanol, 115 parts of 50% distilled water methanol solution was added dropwise over 60 minutes and reacted at 75 ° C. for 8 hours under reflux. After completion of the reaction, the mixture was neutralized with 5% aqueous sodium dihydrogen phosphate solution, and about 90% of methanol was recovered by distillation at 80 ° C. Next, 750 parts of methyl isobutyl ketone (MIBK) was added, and washing with water was repeated three times. By removing the solvent from the obtained organic phase at 100 ° C. under reduced pressure, 605 parts of an epoxycyclohexyl group-containing organopolysiloxane (S-3) was obtained. The epoxy equivalent of the obtained compound (S-3) was 636 g / eq. The weight average molecular weight was 2090, and the appearance was a colorless and transparent liquid resin. Further, the value of the ratio P was 33, and the ratio of silicon atoms bonded to three oxygens derived from silsesquioxane to all silicon atoms was about 17 mol%.
製造工程(i)として、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106部、重量平均分子量1700(GPC測定値)のシラノール末端メチルフェニルシリコーンオイル234部(シラノール当量850、GPCを用いて測定した重量平均分子量の半分として算出した。)、0.5%水酸化カリウム(KOH)メタノール溶液18部(KOH部数としては、0.09部)を反応容器に仕込み、バス温度を75℃に設定し、昇温した。昇温後、還流下にて8時間反応させた。
製造工程(ii)として、メタノールを305部追加後、50%蒸留水メタノール溶液86.4部を60分かけて滴下し、還流下75℃にて8時間反応させた。反応終了後、5%リン酸2水素ナトリウム水溶液で中和後、80℃でメタノールの蒸留回収を行った。メチルイソブチルケトン(MIBK)380部を添加し、水洗を3回繰り返した。次いで有機相を減圧下、100℃で溶媒を除去することによりエポキシシクロヘキシル基含有オルガノポリシロキサン(S-4)300部を得た。得られた化合物(S-4)のエポキシ当量は729g/eq.、重量平均分子量は2200、外観は無色透明の液状樹脂であった。また割合Pの値は30であり、シルセスキオキサン由来の、3つの酸素に結合しているケイ素原子の全ケイ素原子に対する割合は約15モル%であった。 (Synthesis Example 4)
As production step (i), 106 parts of β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 234 parts of silanol-terminated methylphenyl silicone oil having a weight average molecular weight of 1700 (measured GPC value) (silanol equivalent 850, using GPC) It was calculated as half of the measured weight average molecular weight.), 18 parts of 0.5% potassium hydroxide (KOH) methanol solution (0.09 parts as KOH parts) was charged into the reaction vessel, and the bath temperature was 75 ° C. Set and warm. After raising the temperature, the reaction was carried out under reflux for 8 hours.
As a manufacturing process (ii), after adding 305 parts of methanol, 86.4 parts of 50% distilled water methanol solution was added dropwise over 60 minutes, and reacted at 75 ° C. under reflux for 8 hours. After completion of the reaction, the reaction mixture was neutralized with 5% aqueous sodium dihydrogen phosphate solution, and methanol was recovered by distillation at 80 ° C. 380 parts of methyl isobutyl ketone (MIBK) was added, and washing with water was repeated three times. Subsequently, the solvent was removed from the organic phase at 100 ° C. under reduced pressure to obtain 300 parts of an epoxycyclohexyl group-containing organopolysiloxane (S-4). The epoxy equivalent of the obtained compound (S-4) was 729 g / eq. The weight average molecular weight was 2200, and the appearance was a colorless and transparent liquid resin. Further, the value of the ratio P was 30, and the ratio of silicon atoms bonded to three oxygens derived from silsesquioxane to all silicon atoms was about 15 mol%.
製造工程(i)として、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39.4部、重量平均分子量1900(GPC測定値)のシラノール末端メチルフェニルシリコーンオイル137部(シラノール当量950、GPCを用いて測定した重量平均分子量の半分として算出した。)、0.5%水酸化カリウム(KOH)メタノール溶液10部を反応容器に仕込み、バス温度を75℃に設定し、昇温した。昇温後、還流下にて10時間反応させた。
製造工程(ii)として、メタノールを140部追加後、50%蒸留水メタノール溶液17.3部を60分かけて滴下し、還流下75℃にて8時間反応させた。反応終了後、5%リン酸2水素ナトリウム水溶液で中和後、80℃でメタノールの約90%を蒸留回収した。次いで、メチルイソブチルケトン(MIBK)200部を添加し、水洗を3回繰り返した。得られた有機相を減圧下、100℃で溶媒を除去することによりエポキシシクロヘキシル基含有オルガノポリシロキサン(S-5)152部を得た。得られた化合物(S-5)のエポキシ当量は1040g/eq.、重量平均分子量は2290、外観は無色透明の液状樹脂であった。また割合Pの値は22であり、シルセスキオキサン由来の、3つの酸素に結合しているケイ素原子の全ケイ素原子に対する割合は約10モル%であった。 (Synthesis Example 5)
As the production step (i), 39.4 parts of β- (3,4 epoxycyclohexyl) ethyltrimethoxysilane, 137 parts of silanol-terminated methylphenyl silicone oil having a weight average molecular weight of 1900 (measured by GPC) (silanol equivalent: 950, GPC) 10 parts of 0.5% potassium hydroxide (KOH) methanol solution was charged into the reaction vessel, the bath temperature was set to 75 ° C., and the temperature was raised. After raising the temperature, the reaction was carried out under reflux for 10 hours.
As a manufacturing process (ii), after adding 140 parts of methanol, 17.3 parts of 50% distilled water methanol solution was added dropwise over 60 minutes, and reacted at 75 ° C. for 8 hours under reflux. After completion of the reaction, the mixture was neutralized with 5% aqueous sodium dihydrogen phosphate solution, and about 90% of methanol was recovered by distillation at 80 ° C. Subsequently, 200 parts of methyl isobutyl ketone (MIBK) was added, and washing with water was repeated three times. The solvent was removed from the obtained organic phase at 100 ° C. under reduced pressure to obtain 152 parts of an epoxycyclohexyl group-containing organopolysiloxane (S-5). The epoxy equivalent of the obtained compound (S-5) was 1040 g / eq. The weight average molecular weight was 2290, and the appearance was a colorless and transparent liquid resin. Further, the value of the ratio P was 22, and the ratio of silicon atoms bonded to three oxygens derived from silsesquioxane to all silicon atoms was about 10 mol%.
撹拌機、還流冷却管、撹拌装置を備えたフラスコに、窒素パージを施しながらトリシクロデカンジメタノール20部(OXEA製 TCD-AlcholDM)、メチルヘキサヒドロフタル酸無水物(新日本理化製、リカシッドMH 以下、酸無水物CDA-1と称す)100部を加え、40℃で3時間反応後70℃で1時間加熱撹拌を行うことで(GPCによりトリシクロデカンジメタノールの消失(1面積%以下)を確認した。)多価カルボン酸と酸無水物を含有する硬化剤組成物(H-1)が120部得られた。得られた無色の液状樹脂であり、GPCによる純度は多価カルボン酸(下記式(F))を55面積%、メチルヘキサヒドロフタル酸無水物が45面積%であった。また、官能基当量は201g/eq.であった。 (Synthesis Example 6 (adjustment of curing agent composition (H-1)))
A flask equipped with a stirrer, reflux condenser, and stirrer is purged with nitrogen while 20 parts of tricyclodecane dimethanol (TCD-AlcholDM manufactured by OXEA), methylhexahydrophthalic anhydride (manufactured by Shin Nippon Rika, Ricacid MH) Hereinafter, 100 parts of acid anhydride CDA-1) was added, reacted at 40 ° C. for 3 hours, and then heated and stirred at 70 ° C. for 1 hour (disappearance of tricyclodecane dimethanol by GPC (1 area% or less)) 120 parts of a curing agent composition (H-1) containing a polyvalent carboxylic acid and an acid anhydride were obtained. The obtained colorless liquid resin had a GPC purity of 55 area% for polycarboxylic acid (following formula (F)) and 45 area% for methylhexahydrophthalic anhydride. The functional group equivalent was 201 g / eq. Met.
撹拌機、還流冷却管、撹拌装置を備えたフラスコに、窒素パージを施しながら2,4-ジエチルペンタンジオール20部(協和発酵ケミカル製 キョーワジオールPD-9)、酸無水物(CDA-1)100部を加え、40℃で3時間反応後70℃で1時間加熱撹拌を行うことで(GPCにより2,4-ジエチルペンタンジオールの消失(1面積%以下)を確認した。)多価カルボン酸と酸無水物を含有する硬化剤組成物(H-2)が120部得られた。得られた無色の液状樹脂であり、GPCによる純度は多価カルボン酸(下記式(G))を50面積%、酸無水物(CDA-1)が50面積%であった。また、官能基当量は201g/eq.であった。 (Synthesis Example 7 (Preparation of curing agent composition (H-2)))
A flask equipped with a stirrer, a reflux condenser, and a stirrer is purged with nitrogen while 20 parts of 2,4-diethylpentanediol (Kyowa Hakko Chemical Kyowadiol PD-9), acid anhydride (CDA-1) 100 The reaction was carried out at 40 ° C. for 3 hours and then heated and stirred at 70 ° C. for 1 hour (disappearance of 2,4-diethylpentanediol (1 area% or less) was confirmed by GPC). 120 parts of a curing agent composition (H-2) containing an acid anhydride was obtained. The resulting colorless liquid resin had a GPC purity of 50 area% for polyvalent carboxylic acid (formula (G) below) and 50 area% for acid anhydride (CDA-1). The functional group equivalent was 201 g / eq. Met.
JIS K6253に準拠してショアD硬度の測定を行なった。 (Hardness (Shore D))
The Shore D hardness was measured according to JIS K6253.
実施例及び比較例で得られた硬化性樹脂組成物を真空脱泡20分間実施後、横7mm、縦5cm、厚み約800μmの試験片用金型に静かに注型し、その後上からポリイミドフィルムでフタをした。その注型物を前述の条件で硬化させ動的粘弾性用試験片を得た。これらの試験片を用い、下記に示した条件で、動的粘弾性試験(DMA測定)を実施した。
・測定条件
動的粘弾性測定器:TA-instruments製、DMA-2980
測定温度範囲:-30℃~280℃
温速度:2℃/分
試験片サイズ:5mm×50mmに切り出した物を使用した(厚みは約800μm)。
・解析条件
Tg:DMA測定に於けるTan-δのピーク点をTgとした。 (Heat resistance test (DMA measurement))
The curable resin compositions obtained in the examples and comparative examples were vacuum degassed for 20 minutes, and then gently poured into a test piece mold having a width of 7 mm, a length of 5 cm, and a thickness of about 800 μm, and then a polyimide film from above. Covered with. The cast was cured under the above conditions to obtain a dynamic viscoelastic test piece. Using these test pieces, a dynamic viscoelasticity test (DMA measurement) was performed under the conditions shown below.
Measurement conditions Dynamic viscoelasticity measuring device: DMA-2980, manufactured by TA-instruments
Measurement temperature range: -30 ° C to 280 ° C
Temperature rate: 2 ° C./min Test piece size: A material cut into 5 mm × 50 mm was used (thickness was about 800 μm).
Analysis conditions Tg: Tan-δ peak point in DMA measurement was defined as Tg.
Agメッキを施した25mm×50mm×厚み2mmのSUS基材の端に接着面積25mm×10mmになるように、実施例及び比較例で得られた硬化性樹脂組成物を均一に塗布(塗布重量は0.012~0.015gで統一)し、該塗布面に、上から同様の基材を貼り合わせて大型クリップで接着面を固定し、所定の硬化時間、熱硬化させることで、引っ張りせん断用サンプルとした。これらのサンプルを用い、下記に示した条件で、引っ張りせん断試験を実施した。
・測定条件
テンシロン:オリエンテック製 RTA-500
測定モード:引っ張り
移動速度:3mm/分
・解析条件
引っ張りせん断強度は、破断最大値を取り、接着面積当たりに変換した。 (Silver adhesion test (tensile shear test))
Uniformly apply the curable resin compositions obtained in the examples and comparative examples to the end of an SUS base material of 25 mm × 50 mm × thickness 2 mm subjected to Ag plating so that the adhesion area is 25 mm × 10 mm. The same base material is bonded to the coated surface from above, and the adhesive surface is fixed with a large clip, and cured for a predetermined curing time, for tensile shearing. A sample was used. Using these samples, a tensile shear test was performed under the conditions shown below.
・ Measurement conditions Tensilon: RTA-500 from Orientec
Measurement mode: Tensile Movement speed: 3 mm / min / Analysis conditions The tensile shear strength takes the maximum value of breakage, and is converted per bonded area.
また、比較例2は実施例1と同等の硬度(D)を有する硬化物を得るべく作成したものであるが、両者を比較すると、耐熱特性であるTgは同程度まで引き上げることはできたが、接着強度は実施例1の方が大幅に高い。またこのことは比較例1と実施例2の比較評価からも判断できる。
すなわち、脂環式エポキシ樹脂を1.5~40重量%で、好ましくは割合P(重量%)の範囲内で添加することで、ポリシロキサン構造では達成できないレベルの接着強度を発現させることができることが明らかとなった。 In Table 1, when Comparative Example 1 and Example 1 and Example 2 and Comparative Example 3 are compared, the cycloaliphatic epoxy resin is 1.5 to 40% by weight, preferably within the range of the ratio P (% by weight). It was confirmed that the inclusion of contains not only the hardness (D) but also the heat resistance Tg and the adhesive strength.
Further, Comparative Example 2 was prepared to obtain a cured product having the same hardness (D) as Example 1, but when both were compared, Tg, which is a heat resistance property, could be raised to the same extent. The adhesive strength of Example 1 is significantly higher. This can also be judged from comparative evaluation between Comparative Example 1 and Example 2.
That is, by adding the alicyclic epoxy resin in an amount of 1.5 to 40% by weight, preferably within the range of the ratio P (% by weight), it is possible to develop a level of adhesive strength that cannot be achieved with a polysiloxane structure. Became clear.
得られた硬化性樹脂組成物を用い、以下に示す要領で、硬化性樹脂組成物の安定性と硬化物の硬度の評価を行なった。結果を表2に合わせて示す。なお、硬化条件は110℃×2時間の予備硬化の後140℃×5時間である。 For the epoxy resin (S-1) and alicyclic epoxy resin (CAE-1) obtained in the synthesis example, the curing agent composition (H-1) obtained in the synthesis example, and zinc phosphate phosphate as the curing accelerator Complex (C-2 King Industry Corporation XC-9206), hindered amine (TINUVIN 770DF made by L-1 Ciba Specialty Chemical), antioxidant (O-1 Adeka Adeka Stub 260) was used as the light stabilizer, and the following The curable resin compositions of Example 3 and Comparative Example 4 were obtained by blending at a blending ratio (parts by weight) shown in Table 2 and performing defoaming for 20 minutes.
Using the obtained curable resin composition, the stability of the curable resin composition and the hardness of the cured product were evaluated in the manner described below. The results are shown in Table 2. The curing conditions are 140 ° C. × 5 hours after 110 ° C. × 2 hours of preliminary curing.
25℃における粘度(E型回転式粘度計)を配合直後と6時間後でそれぞれ測定をし、その粘度の上昇の度合いで安定性を評価した。 (Stability test)
Viscosity at 25 ° C. (E-type rotary viscometer) was measured immediately after blending and after 6 hours, and the stability was evaluated by the degree of increase in the viscosity.
JIS K6253に準拠してショアD硬度の測定を行なった。 (Hardness (Shore D))
The Shore D hardness was measured according to JIS K6253.
実施例および比較例の硬化性樹脂組成物を、30mm×20mm×高さ1mmになるように耐熱テープでダムを作成したガラス基板上に静かに注型した。その注型物を、110℃×3時間の予備硬化の後150℃×1時間で硬化させ、厚さ1mmの透過率用試験片を得た。460nmにおけるそれぞれの硬化物の透過率を比較した。 (Transmissivity test)
The curable resin compositions of Examples and Comparative Examples were gently cast on a glass substrate on which a dam was created with a heat-resistant tape so as to be 30 mm × 20 mm × height 1 mm. The cast was cured at 110 ° C. for 3 hours and then cured at 150 ° C. for 1 hour to obtain a test piece for transmittance having a thickness of 1 mm. The transmittance of each cured product at 460 nm was compared.
実施例及び比較例の硬化性樹脂組成物を、真空で20分間脱泡した後、底面直径5cm、高さ2cmのアルミカップに静かに注型した。その注型物を、上記透過率試験と同様の硬化条件の下、オーブンの中に入れて硬化させ、厚さ2mmの透過性用試験片を得た。これらの試験片を用い、紫外線照射前後における透過率(測定波長:375nm、400nm、465nm)を分光光度計により測定し、その変化率を算出した。紫外線照射条件は以下の通りである。
紫外線照射機:アイ スーパー UVテスター SUV-W11
温度:60℃
照射エネルギー:50~60mW/cm2
照射時間:100時間 (UV durability transmission test)
The curable resin compositions of Examples and Comparative Examples were defoamed in a vacuum for 20 minutes, and then gently cast into an aluminum cup having a bottom diameter of 5 cm and a height of 2 cm. The cast was placed in an oven and cured under the same curing conditions as in the above transmittance test to obtain a test piece for permeability having a thickness of 2 mm. Using these test pieces, the transmittance (measurement wavelength: 375 nm, 400 nm, 465 nm) before and after ultraviolet irradiation was measured with a spectrophotometer, and the rate of change was calculated. The ultraviolet irradiation conditions are as follows.
UV irradiation machine: Eye Super UV Tester SUV-W11
Temperature: 60 ° C
Irradiation energy: 50-60 mW / cm 2
Irradiation time: 100 hours
得られた硬化性樹脂組成物を用い、シリンジに充填し精密吐出装置を用いて、中心発光波465nmのチップを搭載した外径5mm角、および外径3mm角表面実装型LEDパッケージに注型した。その注型物を加熱炉に投入して、120℃で1時間、さらに150℃で3時間の硬化処理をしてLEDパッケージを作成した。点灯試験は、規定電流である30mAの倍の60mAでの点灯試験を行った(加速試験)。詳細な条件は下記に示した。測定項目としては、200時間点灯前後の照度を、積分球を使用して測定し、試験用LEDの照度の保持率を算出した。また、本試験は駆動環境を多湿高温下で行なった。 (LED lighting test)
The obtained curable resin composition was filled into a syringe and cast into a surface-mount LED package having an outer diameter of 5 mm square and an outer diameter of 3 mm square on which a chip having a central emission wave of 465 nm was mounted using a precision discharge device. . The cast product was put into a heating furnace and cured at 120 ° C. for 1 hour and further at 150 ° C. for 3 hours to prepare an LED package. In the lighting test, a lighting test was performed at 60 mA which is twice the specified current of 30 mA (acceleration test). Detailed conditions are shown below. As a measurement item, the illuminance before and after lighting for 200 hours was measured using an integrating sphere, and the illuminance retention rate of the test LED was calculated. In this test, the driving environment was performed under high humidity and high temperature.
発光波長:465nm
駆動方式:定電流方式、60mA(発光素子規定電流は30mA)
駆動環境:85℃、85% -Detailed lighting conditions Light emission wavelength: 465nm
Drive system: constant current system, 60 mA (light emitting element regulation current is 30 mA)
Driving environment: 85 ° C, 85%
得られた硬化性樹脂組成物を用い、シリンジに充填し精密吐出装置を用いて、中心発光波465nmのチップを搭載した外径5mm角表面実装型LEDパッケージに注型した。その注型物を加熱炉に投入して、120℃で1時間、さらに150℃で3時間の硬化処理をしてLEDパッケージを作成した。下記条件でLEDパッケージを腐食性ガス中に放置し、封止内部の銀メッキされたリードフレーム部の色の変化を観察した。結果については、表5に示した。
・測定条件
腐食ガス:硫化アンモニウム20%水溶液(硫黄成分が銀と反応した場合に黒く変色する)
接触方法:広口ガラス瓶の中に、硫化アンモニウム水溶液の容器と前記LEDパッケージを混在させ、広口ガラス瓶の蓋をして密閉状況下、揮発した硫化アンモニウムガスとLEDパッケージを接触させた。
・解析条件
腐食の判定:LEDパッケージ内部のリードフレームが黒く変色(黒化という)した時間を観察し、その変色時間が長い物ほど、耐腐食ガス性に優れていると判断した。観察は10分後、2時間後、6時間後で取り出して確認をし、評価は変色無しの物を○、茶色~褐色の物を×、完全に黒化した物を××と記した。 (Corrosion gas permeability test)
Using the obtained curable resin composition, it was filled into a syringe and cast into a surface-mount type LED package having an outer diameter of 5 mm and mounted with a chip having a central emission wave of 465 nm using a precision discharge device. The cast product was put into a heating furnace and cured at 120 ° C. for 1 hour and further at 150 ° C. for 3 hours to prepare an LED package. The LED package was left in a corrosive gas under the following conditions, and the color change of the silver-plated lead frame part inside the seal was observed. The results are shown in Table 5.
・ Measurement conditions Corrosion gas: Ammonium sulfide 20% aqueous solution (turns black when sulfur component reacts with silver)
Contact method: A container of an ammonium sulfide aqueous solution and the LED package were mixed in a wide-mouth glass bottle, and the wide-mouth glass bottle was covered to bring the volatilized ammonium sulfide gas into contact with the LED package in a sealed state.
-Analysis conditions Determination of corrosion: The time when the lead frame inside the LED package was discolored black (referred to as blackening) was observed, and it was determined that the longer the discoloration time, the better the corrosion resistance. Observations were taken out after 10 minutes, 2 hours, and 6 hours for confirmation, and evaluations were indicated as ○ for undiscolored products, × for brown-brown materials, and XX for completely blackened materials.
撹拌機、還流冷却管、撹拌装置を備えたフラスコに、窒素パージを施しながら両末端カルビノール変性シリコーン(X22-160AS信越化学工業(株)製 、式(4A)において、R7がメチル基でR8がプロポキシエチレン基である化合物。)500部、リカシッドMH(4-メチルヘキサヒドロ無水フタル酸、新日本理化製)168部を反応容器に仕込み、80℃で4時間反応させた。これにより無色透明液体の多価カルボン酸(H-4)668部を得た。 Synthesis example A
A flask equipped with a stirrer, a reflux condenser, and a stirrer was purged with nitrogen while both ends of the carbinol-modified silicone (X22-160AS manufactured by Shin-Etsu Chemical Co., Ltd., formula (4A), wherein R 7 is a methyl group) A compound in which R 8 is a propoxyethylene group.) 500 parts and 168 parts of Ricacid MH (4-methylhexahydrophthalic anhydride, manufactured by Shin Nippon Chemical Co., Ltd.) were charged into a reaction vessel and reacted at 80 ° C. for 4 hours. As a result, 668 parts of a colorless transparent liquid, polyvalent carboxylic acid (H-4) was obtained.
合成例において得られたエポキシ樹脂(S-2)、脂環式エポキシ樹脂(CAE-1)に対し、合成例Aで得られた多価カルボン酸(H-4)を用い、2-エチルヘキサン酸亜鉛(ホープ製薬(株)製 以下、C-3と称す) 、ヒンダートアミン(LA-81 アデカ製 以下、L-3と称す)、リン化合物(アデカ260 以下、O-4と称す)使用し、下記表6に示す配合比(重量部)で配合し、20分間脱泡を行い、本発明または比較用の硬化性樹脂組成物を得た。
得られた硬化性樹脂組成物を用い、以下に示す要領で各種試験を行った。結果を表6に合わせて示す。 Examples AF, Comparative Examples A and B
Using the polyvalent carboxylic acid (H-4) obtained in Synthesis Example A against the epoxy resin (S-2) and alicyclic epoxy resin (CAE-1) obtained in Synthesis Example, 2-ethylhexane Use of zinc acid (made by Hope Pharmaceutical Co., Ltd., hereinafter referred to as C-3), hindered amine (manufactured by LA-81 Adeka, hereinafter referred to as L-3), phosphorus compound (Adeca 260, hereinafter referred to as O-4) And it mix | blended with the compounding ratio (weight part) shown in following Table 6, performed defoaming for 20 minutes, and obtained the curable resin composition for this invention or for a comparison.
Using the obtained curable resin composition, various tests were performed in the following manner. The results are shown in Table 6.
得られた硬化性樹脂組成物を真空脱泡20分間実施後、シリンジに充填し精密吐出装置を使用して、発光波長465nmを持つ発光素子を搭載した表面実装型LEDに開口部が平面になるように注型した。120℃×3時間の予備硬化の後、150℃×2時間で硬化し、表面実装型LEDを封止した。得られた試験用LEDを30℃70%×72Hr吸湿後、高温観察装置(SMT Scope SK-5000 山陽精工株式会社製)を用い、以下のリフロー条件下での、試験用LEDのリフレクタ(ポリアミド製)からの剥がれを確認した。n=3でテストを行い、(NG数)/(テスト数)で評価する。
条件は25℃より2℃/秒で150℃まで昇温、その後、2分150℃で保持し、さらに2℃/秒で260℃まで昇温し、10秒の温度保持後、1.3℃/秒で室温まで冷却する、というものである。
(2)ヒートサイクルテスト
ヒートサイクル試験は、(1)と同様に配合・注型・硬化後、冷熱衝撃試験で-40℃×15分~120℃×15分のサイクルを昇温及び降温に要する時間を2分間として50回繰り返し、試験用LEDへのクラックの発生の有無を目視で観察した。n=5でテストを行い、評価結果は(NG数)/(テスト数)で示す。 (1) Reflow test;
The resulting curable resin composition is vacuum degassed for 20 minutes, then filled into a syringe, and using a precision discharge device, the opening is flat on a surface-mounted LED equipped with a light emitting element having an emission wavelength of 465 nm So casted. After pre-curing at 120 ° C. for 3 hours, curing was performed at 150 ° C. for 2 hours to seal the surface-mounted LED. After the obtained test LED absorbs moisture at 30 ° C. and 70% × 72 hours, using a high-temperature observation apparatus (SMT Scope SK-5000 manufactured by Sanyo Seiko Co., Ltd.), the test LED reflector (made of polyamide) under the following reflow conditions ) Was confirmed. The test is performed with n = 3, and the evaluation is performed by (number of NG) / (number of tests).
The temperature was raised from 25 ° C. to 150 ° C. at 2 ° C./second, then held at 150 ° C. for 2 minutes, further heated to 260 ° C. at 2 ° C./second, and maintained at 10 ° C., then 1.3 ° C. It cools to room temperature at / second.
(2) Heat cycle test As in (1), the heat cycle test requires a cycle of -40 ° C x 15 min to 120 ° C x 15 min for temperature rise and fall in the thermal shock test after blending, casting and curing. The time was repeated 50 times for 2 minutes, and the presence or absence of cracks in the test LED was visually observed. The test is performed with n = 5, and the evaluation result is expressed as (NG number) / (test number).
撹拌機、還流冷却管、撹拌装置、ディーンスターク管を備えたフラスコに、窒素パージを施しながらトルエン150部、2,4-ジエチル-1,5-ペンタンジオール(協和発酵ケミカル株式会社製 キョウワオールPD9)80部、3-シクロヘキセンカルボン酸126部、パラトルエンスルホン酸2部を加え、加熱還流下で10時間、水を除きながら反応を行った。反応終了後、10%炭酸水素ナトリウム水溶液50部で2回水洗、さらに得られた有機層を水50部で2回水洗した後、ロータリーエバポレータで有機溶剤を濃縮することで本発明のジオレフィン化合物(D-1)が187部得られた。形状は液状であり、ガスクロマトグラフィーによる純度は96%、ゲルパーミエーションクロマトグラフィーによる分析の結果、>98%の純度である事を確認した。 Synthesis example B
To a flask equipped with a stirrer, a reflux condenser, a stirrer, and a Dean-Stark tube, while purging with nitrogen, 150 parts of toluene and 2,4-diethyl-1,5-pentanediol (Kyowa Hakko Chemical Co., Ltd. Kyowa All PD9) ) 80 parts, 126 parts of 3-cyclohexenecarboxylic acid and 2 parts of paratoluenesulfonic acid were added, and the reaction was carried out under heating and refluxing for 10 hours while removing water. After completion of the reaction, the diolefin compound of the present invention is washed twice with 50 parts of a 10% aqueous sodium hydrogen carbonate solution, the organic layer obtained is washed twice with 50 parts of water, and then the organic solvent is concentrated with a rotary evaporator. 187 parts of (D-1) was obtained. The shape was liquid, the purity by gas chromatography was 96%, and the result of analysis by gel permeation chromatography confirmed that the purity was> 98%.
撹拌機、還流冷却管、撹拌装置を備えたフラスコに、窒素パージを施しながら水15部、12-タングストリン酸0.95部、燐酸水素2ナトリウム0.78部、ジ硬化牛脂アルキルジメチルアンモニウムアセテート2.7部(ライオンアクゾ製 50%ヘキサン溶液、アカード2HTアセテート)を加え、タングステン酸系触媒を生成させた後、トルエン120部、ジオレフィン化合物D-1を94部を加え、さらに再度攪拌することでエマルジョン状態の液とした。この溶液を50℃に昇温し、激しく攪拌しながら、35%過酸化水素水55部を加え、そのまま50℃で13時間攪拌した。GCにて反応の進行を確認したところ、反応終了後の基質のコンバ-ジョンは>99%であり、原料ピークは消失していた。
ついで1%苛性ソーダ水溶液で中和した後、20%チオ硫酸ソーダ水溶液25部を加え30分攪拌を行い、静置した。2層に分離した有機層を取り出し、ここに活性炭(NORIT製 CAP SUPER)20部、モンモリロナイト(クニミネ工業製 クニピアF)20部を加え、室温で3時間攪拌後、ろ過した。得られたろ液を水100部で3回水洗を行い、得られた有機層より、有機溶剤を留去することで脂環式エポキシ樹脂(CAE-2)を90部得た。エポキシ当量は216g/eq.であった。 Synthesis example C
A flask equipped with a stirrer, reflux condenser, and stirrer is purged with nitrogen while water 15 parts, 12-tungstophosphoric acid 0.95 parts, disodium hydrogen phosphate 0.78 parts, di-cured tallow alkyldimethylammonium acetate 2.7 parts (50% hexane solution made by Lion Akzo, Acquard 2HT acetate) was added to form a tungstic acid catalyst, 120 parts of toluene and 94 parts of diolefin compound D-1 were added, and the mixture was stirred again. Thus, a liquid in an emulsion state was obtained. The temperature of the solution was raised to 50 ° C., and while stirring vigorously, 55 parts of 35% aqueous hydrogen peroxide was added and stirred as it was at 50 ° C. for 13 hours. When the progress of the reaction was confirmed by GC, the substrate conversion after the completion of the reaction was> 99%, and the raw material peak disappeared.
Then, after neutralizing with 1% aqueous sodium hydroxide solution, 25 parts of 20% aqueous sodium thiosulfate solution was added, stirred for 30 minutes, and allowed to stand. The organic layer separated into two layers was taken out, 20 parts of activated carbon (CAP SUPER made by NORIT) and 20 parts of montmorillonite (Kunimine Industries Kunipia F) were added thereto, and the mixture was stirred at room temperature for 3 hours and then filtered. The obtained filtrate was washed three times with 100 parts of water, and 90 parts of alicyclic epoxy resin (CAE-2) was obtained by distilling off the organic solvent from the obtained organic layer. Epoxy equivalent was 216 g / eq. Met.
撹拌機、還流冷却管、撹拌装置、ディーンスターク管を備えたフラスコに、窒素パージを施しながらトルエン100部、3-シクロヘキセン-1-カルボン酸126部、トリシクロペンタデカンジメタノール98部、p-トルエンスルホン酸3部を加え、還流条件下、ディーンスターク管を用いて脱水しながら15時間反応を行った。反応終了後、トリポリ燐酸ソーダ5部、を加え、100℃で1時間攪拌した。室温まで冷却後、メチルイソブチルケトン300部を加え、水300部で3回水洗を行い、得られた有機層にシリカゲル100部、活性炭1部を加え、室温で2時間攪拌した後、ろ過を行った。得られたろ液より、溶剤等を除去することでジオレフィン化合物D-2を190部得た。 Synthesis example D
In a flask equipped with a stirrer, reflux condenser, stirrer, and Dean-Stark tube, while purging with nitrogen, 100 parts of toluene, 126 parts of 3-cyclohexene-1-carboxylic acid, 98 parts of tricyclopentadecane dimethanol, p-toluene 3 parts of sulfonic acid was added, and the reaction was carried out for 15 hours while dehydrating using a Dean-Stark tube under reflux conditions. After completion of the reaction, 5 parts of sodium tripolyphosphate was added and stirred at 100 ° C. for 1 hour. After cooling to room temperature, 300 parts of methyl isobutyl ketone was added, washed with 300 parts of water three times, 100 parts of silica gel and 1 part of activated carbon were added to the resulting organic layer, and the mixture was stirred at room temperature for 2 hours, followed by filtration. It was. 190 parts of diolefin compound D-2 was obtained by removing the solvent and the like from the obtained filtrate.
撹拌機、還流冷却管、撹拌装置を備えたフラスコに、窒素パージを施しながら水12部、12-タングストリン酸0.38部、燐酸0.56部、炭酸ソーダを加え、pHを4.7に調整した。更にトリオクチルメチルアンモニウムクロライド0.6部(東京化成製)を加え、タングステン酸系触媒を生成させた後、トルエン50部、ジオレフィン化合物D-2を41部を加え、さらに再度攪拌することでエマルジョン状態の液とした。この溶液を50℃に昇温し、激しく攪拌しながら、30%過酸化水素水24.8部を加え、そのまま50℃で15時間攪拌した。ついで1%苛性ソーダ水溶液20部、20%チオ硫酸ソーダ水溶液10部を加え1時間攪拌を行い、静置した。2層に分離した有機層を取り出し、更に得られた水層に30部のトルエンを加え、水層中の有機物を抽出。これをさらに2回繰り返し、得られた有機層を混合した。ここに活性炭(NORIT製 CAP SUPER)20部、モンモリロナイト(クニミネ工業製 クニピアF)20部を加え、室温で3時間攪拌後、ろ過した。得られたろ液を水100部で3回水洗を行い、得られた有機層より、有機溶剤を留去することで脂環式エポキシ樹脂(CAE-3)を40部得た。エポキシ当量は233g/eq.であった。 Synthesis example E
To a flask equipped with a stirrer, a reflux condenser, and a stirrer, 12 parts of water, 0.38 part of 12-tungstophosphoric acid, 0.56 part of phosphoric acid and sodium carbonate are added while purging with nitrogen, and the pH is 4.7. Adjusted. Further, 0.6 part of trioctylmethylammonium chloride (manufactured by Tokyo Chemical Industry) was added to produce a tungstic acid catalyst, and then 50 parts of toluene and 41 parts of diolefin compound D-2 were added and stirred again. An emulsion was obtained. The solution was warmed to 50 ° C., and 24.8 parts of 30% hydrogen peroxide was added with vigorous stirring, followed by stirring at 50 ° C. for 15 hours. Next, 20 parts of a 1% aqueous sodium hydroxide solution and 10 parts of a 20% aqueous sodium thiosulfate solution were added and stirred for 1 hour and allowed to stand. The organic layer separated into two layers was taken out, and 30 parts of toluene was added to the obtained aqueous layer to extract organic substances in the aqueous layer. This was repeated twice more and the resulting organic layers were mixed. 20 parts of activated carbon (CAP SUPER made by NORIT) and 20 parts of montmorillonite (Kunimine Industries Kunipia F) were added thereto, and the mixture was stirred at room temperature for 3 hours and then filtered. The obtained filtrate was washed three times with 100 parts of water, and 40 parts of alicyclic epoxy resin (CAE-3) was obtained by distilling off the organic solvent from the obtained organic layer. Epoxy equivalent was 233 g / eq. Met.
脂環式エポキシ樹脂(CAE-1)、合成例C、Eにおいて得られた脂環式エポキシ樹脂(CAE-2)(CAE-3)、同様に合成例5で得られたエポキシ樹脂(S-5)を使用し、下記表7に示す配合比(重量部)で配合して20分間脱泡を行うことにより、実施例、および比較例のエポキシ樹脂組成物を得た。得られたエポキシ樹脂組成物の濁りを目視により判断し、評価した。尚、エポキシ樹脂(S-5)のエポキシ当量は1040g/eq.、重量平均分子量は2290であり、割合Pの値は22である。 Example GK Comparative Example CD
Alicyclic epoxy resin (CAE-1), alicyclic epoxy resin (CAE-2) (CAE-3) obtained in Synthesis Examples C and E, and epoxy resin (S- 5) was used and blended at the blending ratio (parts by weight) shown in Table 7 below and defoamed for 20 minutes to obtain the epoxy resin compositions of Examples and Comparative Examples. The turbidity of the obtained epoxy resin composition was judged and evaluated visually. The epoxy equivalent of the epoxy resin (S-5) was 1040 g / eq. The weight average molecular weight is 2290, and the value of the ratio P is 22.
なお、本出願は、2010年3月2日付で出願された日本特許出願(特願2010-045927)に基づいており、その全体が引用により援用される。また、ここに引用されるすべての参照は全体として取り込まれる。 Although the invention has been described in detail with reference to specific embodiments, it will be apparent to those skilled in the art that various changes and modifications can be made without departing from the spirit and scope of the invention.
Note that this application is based on a Japanese patent application filed on March 2, 2010 (Japanese Patent Application No. 2010-045927), which is incorporated by reference in its entirety. Also, all references cited herein are incorporated as a whole.
Claims (10)
- エポキシシクロヘキシル基含有オルガノポリシロキサン(A)、脂環式エポキシ樹脂(B)および酸無水物(C)を含有し、エポキシシクロヘキシル基含有オルガノポリシロキサン(A)と脂環式エポキシ樹脂(B)の総量に占める脂環式エポキシ樹脂(B)の量が1.5~40重量%であることを特徴とする硬化性樹脂組成物。 It contains an epoxycyclohexyl group-containing organopolysiloxane (A), an alicyclic epoxy resin (B) and an acid anhydride (C), and includes an epoxycyclohexyl group-containing organopolysiloxane (A) and an alicyclic epoxy resin (B). A curable resin composition, wherein the amount of the alicyclic epoxy resin (B) in the total amount is 1.5 to 40% by weight.
- エポキシシクロヘキシル基含有オルガノポリシロキサン(A)、脂環式エポキシ樹脂(B)および酸無水物(C)を含有し、エポキシシクロヘキシル基含有オルガノポリシロキサン(A)と脂環式エポキシ樹脂(B)の総量に占める脂環式エポキシ樹脂(B)の量が2~40重量%であることを特徴とする硬化性樹脂組成物。 It contains an epoxycyclohexyl group-containing organopolysiloxane (A), an alicyclic epoxy resin (B) and an acid anhydride (C), and includes an epoxycyclohexyl group-containing organopolysiloxane (A) and an alicyclic epoxy resin (B). A curable resin composition, wherein the amount of the alicyclic epoxy resin (B) in the total amount is 2 to 40% by weight.
- エポキシシクロヘキシル基含有オルガノポリシロキサン(A)と脂環式エポキシ樹脂(B)の総量に占める脂環式エポキシ樹脂(B)の含有量が、10×(エポキシシクロヘキシル基含有オルガノポリシロキサン(A)の重量平均分子量)÷(エポキシシクロヘキシル基含有オルガノポリシロキサン(A)のエポキシ当量)重量%以下であることを特徴とする請求項1または2記載の硬化性樹脂組成物。 The content of the alicyclic epoxy resin (B) in the total amount of the epoxycyclohexyl group-containing organopolysiloxane (A) and the alicyclic epoxy resin (B) is 10 × (epoxycyclohexyl group-containing organopolysiloxane (A). 3. The curable resin composition according to claim 1 or 2, wherein the weight average molecular weight) / (epoxy equivalent of epoxycyclohexyl group-containing organopolysiloxane (A)) is not more than wt%.
- さらに多価カルボン酸(D)を含むことを特徴とする請求項1~3の何れか一項に記載の硬化性樹脂組成物。 The curable resin composition according to any one of claims 1 to 3, further comprising a polyvalent carboxylic acid (D).
- 前記多価カルボン酸(D)が、炭素数5以上の2~6官能の多価アルコールと飽和脂肪族環状酸無水物との反応により得られた化合物であることを特徴とする請求項4に記載の硬化性樹脂組成物。 5. The compound according to claim 4, wherein the polyvalent carboxylic acid (D) is a compound obtained by reacting a bi- to hexafunctional polyhydric alcohol having 5 or more carbon atoms with a saturated aliphatic cyclic acid anhydride. The curable resin composition described.
- 前記エポキシシクロヘキシル基含有オルガノポリシロキサン(A)が、その構造中にフェニル基を有することを特徴とする請求項1~5のいずれか一項に記載の硬化性樹脂組成物。 The curable resin composition according to any one of claims 1 to 5, wherein the epoxycyclohexyl group-containing organopolysiloxane (A) has a phenyl group in its structure.
- 前記エポキシシクロヘキシル基含有オルガノポリシロキサン(A)が、ジメチル置換、ジフェニル置換またはこれらの混合物からなる鎖状シリコーン部位と、エポキシシクロヘキシル基を有する三次元縮合体部位(シルセスキオキサン部位)とを有するブロック型の化合物であることを特徴とする請求項1~6のいずれか一項に記載の硬化性樹脂組成物。 The epoxycyclohexyl group-containing organopolysiloxane (A) has a chain silicone moiety composed of dimethyl substitution, diphenyl substitution or a mixture thereof, and a three-dimensional condensate moiety (silsesquioxane moiety) having an epoxycyclohexyl group. The curable resin composition according to any one of claims 1 to 6, which is a block-type compound.
- 請求項1~7のいずれか一項に記載の硬化性樹脂組成物を硬化してなる硬化物。 A cured product obtained by curing the curable resin composition according to any one of claims 1 to 7.
- 請求項1~7のいずれか一項記載の硬化性樹脂組成物からなる光半導体封止用硬化性樹脂組成物。 A curable resin composition for optical semiconductor encapsulation, comprising the curable resin composition according to any one of claims 1 to 7.
- 請求項9記載の光半導体封止用硬化性樹脂組成物で硬化および封止して得られることを特徴とする光半導体装置。 An optical semiconductor device obtained by curing and sealing with the curable resin composition for optical semiconductor encapsulation according to claim 9.
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Also Published As
Publication number | Publication date |
---|---|
TWI538959B (en) | 2016-06-21 |
CN102791760A (en) | 2012-11-21 |
KR20130036184A (en) | 2013-04-11 |
TW201137044A (en) | 2011-11-01 |
JP5878862B2 (en) | 2016-03-08 |
JPWO2011108588A1 (en) | 2013-06-27 |
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