KR101184292B1 - Novel epoxy compounds and their flame-retarding epoxy resin compositions - Google Patents
Novel epoxy compounds and their flame-retarding epoxy resin compositions Download PDFInfo
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- KR101184292B1 KR101184292B1 KR20100054444A KR20100054444A KR101184292B1 KR 101184292 B1 KR101184292 B1 KR 101184292B1 KR 20100054444 A KR20100054444 A KR 20100054444A KR 20100054444 A KR20100054444 A KR 20100054444A KR 101184292 B1 KR101184292 B1 KR 101184292B1
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- KR
- South Korea
- Prior art keywords
- epoxy resin
- formula
- resin composition
- curing agent
- epoxy
- Prior art date
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- 239000003822 epoxy resin Substances 0.000 title claims abstract description 106
- 229920000647 polyepoxide Polymers 0.000 title claims abstract description 106
- 239000000203 mixture Substances 0.000 title claims abstract description 53
- 150000001875 compounds Chemical class 0.000 title claims abstract description 29
- 239000004593 Epoxy Substances 0.000 title abstract description 26
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 26
- 229920005989 resin Polymers 0.000 claims abstract description 18
- 239000011347 resin Substances 0.000 claims abstract description 18
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims abstract description 8
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 7
- 239000000126 substance Substances 0.000 claims description 19
- 229920003986 novolac Polymers 0.000 claims description 16
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 13
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 claims description 10
- 239000005011 phenolic resin Substances 0.000 claims description 8
- -1 glycidyl ester Chemical class 0.000 claims description 7
- 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 claims description 7
- 229920000768 polyamine Polymers 0.000 claims description 6
- 239000004305 biphenyl Substances 0.000 claims description 5
- 235000010290 biphenyl Nutrition 0.000 claims description 5
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 claims description 5
- 239000000654 additive Substances 0.000 claims description 4
- 230000000996 additive effect Effects 0.000 claims description 4
- 150000001412 amines Chemical class 0.000 claims description 3
- 125000003118 aryl group Chemical group 0.000 claims description 3
- 239000011256 inorganic filler Substances 0.000 claims description 3
- 229910003475 inorganic filler Inorganic materials 0.000 claims description 3
- 150000003839 salts Chemical class 0.000 claims description 3
- 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 claims description 2
- BCCBAUPSUDQAGM-UHFFFAOYSA-N 1-phenylbiphenylene Chemical group C1=CC=CC=C1C1=CC=CC2=C1C1=CC=CC=C12 BCCBAUPSUDQAGM-UHFFFAOYSA-N 0.000 claims description 2
- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 claims description 2
- 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 claims description 2
- 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 claims description 2
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 claims description 2
- 239000004952 Polyamide Substances 0.000 claims description 2
- 150000008065 acid anhydrides Chemical class 0.000 claims description 2
- 125000001931 aliphatic group Chemical group 0.000 claims description 2
- 239000007822 coupling agent Substances 0.000 claims description 2
- 229930003836 cresol Natural products 0.000 claims description 2
- AFEQENGXSMURHA-UHFFFAOYSA-N oxiran-2-ylmethanamine Chemical compound NCC1CO1 AFEQENGXSMURHA-UHFFFAOYSA-N 0.000 claims description 2
- 150000003003 phosphines Chemical class 0.000 claims description 2
- 229920002647 polyamide Polymers 0.000 claims description 2
- 150000003512 tertiary amines Chemical class 0.000 claims description 2
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 claims 2
- 150000002460 imidazoles Chemical class 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 15
- 239000004065 semiconductor Substances 0.000 abstract description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 7
- 238000002844 melting Methods 0.000 abstract description 6
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 abstract description 5
- 239000003063 flame retardant Substances 0.000 abstract description 5
- 239000000853 adhesive Substances 0.000 abstract description 4
- 230000001070 adhesive effect Effects 0.000 abstract description 4
- 239000003973 paint Substances 0.000 abstract description 3
- 229910052736 halogen Inorganic materials 0.000 abstract description 2
- 150000002367 halogens Chemical class 0.000 abstract description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 abstract 1
- 238000010521 absorption reaction Methods 0.000 abstract 1
- 238000000465 moulding Methods 0.000 abstract 1
- 229910052698 phosphorus Inorganic materials 0.000 abstract 1
- 239000011574 phosphorus Substances 0.000 abstract 1
- 239000003566 sealing material Substances 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 23
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 21
- 239000000047 product Substances 0.000 description 19
- 238000000034 method Methods 0.000 description 13
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 12
- MQJKPEGWNLWLTK-UHFFFAOYSA-N Dapsone Chemical compound C1=CC(N)=CC=C1S(=O)(=O)C1=CC=C(N)C=C1 MQJKPEGWNLWLTK-UHFFFAOYSA-N 0.000 description 10
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 9
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 9
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 9
- 230000015572 biosynthetic process Effects 0.000 description 8
- QWVGKYWNOKOFNN-UHFFFAOYSA-N o-cresol Chemical compound CC1=CC=CC=C1O QWVGKYWNOKOFNN-UHFFFAOYSA-N 0.000 description 8
- 238000003786 synthesis reaction Methods 0.000 description 8
- 239000002904 solvent Substances 0.000 description 7
- 238000002411 thermogravimetry Methods 0.000 description 7
- YJTKZCDBKVTVBY-UHFFFAOYSA-N 1,3-Diphenylbenzene Chemical group C1=CC=CC=C1C1=CC=CC(C=2C=CC=CC=2)=C1 YJTKZCDBKVTVBY-UHFFFAOYSA-N 0.000 description 6
- XXBDWLFCJWSEKW-UHFFFAOYSA-N dimethylbenzylamine Chemical compound CN(C)CC1=CC=CC=C1 XXBDWLFCJWSEKW-UHFFFAOYSA-N 0.000 description 6
- 238000005538 encapsulation Methods 0.000 description 6
- 229920000642 polymer Polymers 0.000 description 6
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 5
- 239000007864 aqueous solution Substances 0.000 description 5
- 229910052801 chlorine Inorganic materials 0.000 description 5
- 239000000460 chlorine Substances 0.000 description 5
- 230000017525 heat dissipation Effects 0.000 description 5
- 230000008018 melting Effects 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 4
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- 238000002485 combustion reaction Methods 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000000113 differential scanning calorimetry Methods 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 4
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 3
- AXNUJYHFQHQZBE-UHFFFAOYSA-N 3-methylbenzene-1,2-diamine Chemical compound CC1=CC=CC(N)=C1N AXNUJYHFQHQZBE-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 239000006227 byproduct Substances 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 125000003700 epoxy group Chemical group 0.000 description 3
- XYIBRDXRRQCHLP-UHFFFAOYSA-N ethyl acetoacetate Chemical compound CCOC(=O)CC(C)=O XYIBRDXRRQCHLP-UHFFFAOYSA-N 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 239000004843 novolac epoxy resin Substances 0.000 description 3
- 239000012044 organic layer Substances 0.000 description 3
- 229920001568 phenolic resin Polymers 0.000 description 3
- 230000000704 physical effect Effects 0.000 description 3
- 239000004848 polyfunctional curative Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 239000008096 xylene Substances 0.000 description 3
- HDXVSZWKIHQDES-LFYBBSHMSA-N (e)-1,3-bis(4-methoxyphenyl)prop-2-en-1-one Chemical compound C1=CC(OC)=CC=C1\C=C\C(=O)C1=CC=C(OC)C=C1 HDXVSZWKIHQDES-LFYBBSHMSA-N 0.000 description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 2
- BXIXXXYDDJVHDL-UHFFFAOYSA-N 4-Chloro-ortho-phenylenediamine Chemical compound NC1=CC=C(Cl)C=C1N BXIXXXYDDJVHDL-UHFFFAOYSA-N 0.000 description 2
- NTPLXRHDUXRPNE-UHFFFAOYSA-N 4-methoxyacetophenone Chemical compound COC1=CC=C(C(C)=O)C=C1 NTPLXRHDUXRPNE-UHFFFAOYSA-N 0.000 description 2
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 2
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 2
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 239000004809 Teflon Substances 0.000 description 2
- 229920006362 Teflon® Polymers 0.000 description 2
- 229960000583 acetic acid Drugs 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 150000001491 aromatic compounds Chemical class 0.000 description 2
- IYJMFNNRVITCDG-UHFFFAOYSA-N biphenylene;phenol Chemical group OC1=CC=CC=C1.C1=CC=C2C3=CC=CC=C3C2=C1 IYJMFNNRVITCDG-UHFFFAOYSA-N 0.000 description 2
- 229910052794 bromium Inorganic materials 0.000 description 2
- 238000006482 condensation reaction Methods 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 150000004985 diamines Chemical class 0.000 description 2
- 235000014113 dietary fatty acids Nutrition 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 239000008393 encapsulating agent Substances 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 239000000194 fatty acid Substances 0.000 description 2
- 229930195729 fatty acid Natural products 0.000 description 2
- 150000004665 fatty acids Chemical class 0.000 description 2
- NIHNNTQXNPWCJQ-UHFFFAOYSA-N fluorene Chemical compound C1=CC=C2CC3=CC=CC=C3C2=C1 NIHNNTQXNPWCJQ-UHFFFAOYSA-N 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- ZRSNZINYAWTAHE-UHFFFAOYSA-N p-methoxybenzaldehyde Chemical compound COC1=CC=C(C=O)C=C1 ZRSNZINYAWTAHE-UHFFFAOYSA-N 0.000 description 2
- 238000000197 pyrolysis Methods 0.000 description 2
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- 238000005979 thermal decomposition reaction Methods 0.000 description 2
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 239000001993 wax Substances 0.000 description 2
- RQKBFJCBPJAERT-UHFFFAOYSA-N 1,3-diphenylprop-2-en-1-one Chemical compound C=1C=CC=CC=1C(=O)C=CC1=CC=CC=C1.C=1C=CC=CC=1C(=O)C=CC1=CC=CC=C1 RQKBFJCBPJAERT-UHFFFAOYSA-N 0.000 description 1
- XJKSTNDFUHDPQJ-UHFFFAOYSA-N 1,4-diphenylbenzene Chemical group C1=CC=CC=C1C1=CC=C(C=2C=CC=CC=2)C=C1 XJKSTNDFUHDPQJ-UHFFFAOYSA-N 0.000 description 1
- CIPOCPJRYUFXLL-UHFFFAOYSA-N 2,3,4-tris[(dimethylamino)methyl]phenol Chemical compound CN(C)CC1=CC=C(O)C(CN(C)C)=C1CN(C)C CIPOCPJRYUFXLL-UHFFFAOYSA-N 0.000 description 1
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 description 1
- ZCUJYXPAKHMBAZ-UHFFFAOYSA-N 2-phenyl-1h-imidazole Chemical compound C1=CNC(C=2C=CC=CC=2)=N1 ZCUJYXPAKHMBAZ-UHFFFAOYSA-N 0.000 description 1
- AGEKBMLRLTVUGG-UHFFFAOYSA-N 3,5-bis(4-methoxyphenyl)cyclohex-2-en-1-one Chemical compound C1=CC(OC)=CC=C1C1CC(C=2C=CC(OC)=CC=2)=CC(=O)C1 AGEKBMLRLTVUGG-UHFFFAOYSA-N 0.000 description 1
- 125000004172 4-methoxyphenyl group Chemical group [H]C1=C([H])C(OC([H])([H])[H])=C([H])C([H])=C1* 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- 229930185605 Bisphenol Natural products 0.000 description 1
- OKIZCWYLBDKLSU-UHFFFAOYSA-M N,N,N-Trimethylmethanaminium chloride Chemical compound [Cl-].C[N+](C)(C)C OKIZCWYLBDKLSU-UHFFFAOYSA-M 0.000 description 1
- UEEJHVSXFDXPFK-UHFFFAOYSA-N N-dimethylaminoethanol Chemical compound CN(C)CCO UEEJHVSXFDXPFK-UHFFFAOYSA-N 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- 150000001343 alkyl silanes Chemical class 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 229910000410 antimony oxide Inorganic materials 0.000 description 1
- 125000003710 aryl alkyl group Chemical group 0.000 description 1
- KXHPPCXNWTUNSB-UHFFFAOYSA-M benzyl(trimethyl)azanium;chloride Chemical compound [Cl-].C[N+](C)(C)CC1=CC=CC=C1 KXHPPCXNWTUNSB-UHFFFAOYSA-M 0.000 description 1
- 150000001638 boron Chemical class 0.000 description 1
- 239000012267 brine Substances 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 238000007707 calorimetry Methods 0.000 description 1
- 239000004918 carbon fiber reinforced polymer Substances 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
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- GPAYUJZHTULNBE-UHFFFAOYSA-N diphenylphosphine Chemical compound C=1C=CC=CC=1PC1=CC=CC=C1 GPAYUJZHTULNBE-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000012776 electronic material Substances 0.000 description 1
- 238000006735 epoxidation reaction Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
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- 239000003365 glass fiber Substances 0.000 description 1
- 150000003944 halohydrins Chemical class 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
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- 238000001819 mass spectrum Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
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- XLSZMDLNRCVEIJ-UHFFFAOYSA-N methylimidazole Natural products CC1=CNC=N1 XLSZMDLNRCVEIJ-UHFFFAOYSA-N 0.000 description 1
- 239000012778 molding material Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
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- 239000003960 organic solvent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- VTRUBDSFZJNXHI-UHFFFAOYSA-N oxoantimony Chemical compound [Sb]=O VTRUBDSFZJNXHI-UHFFFAOYSA-N 0.000 description 1
- 230000036284 oxygen consumption Effects 0.000 description 1
- 229930184652 p-Terphenyl Natural products 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 150000004986 phenylenediamines Chemical class 0.000 description 1
- RPGWZZNNEUHDAQ-UHFFFAOYSA-N phenylphosphine Chemical compound PC1=CC=CC=C1 RPGWZZNNEUHDAQ-UHFFFAOYSA-N 0.000 description 1
- 229920002120 photoresistant polymer Polymers 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- YLLIGHVCTUPGEH-UHFFFAOYSA-M potassium;ethanol;hydroxide Chemical compound [OH-].[K+].CCO YLLIGHVCTUPGEH-UHFFFAOYSA-M 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
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- 239000011342 resin composition Substances 0.000 description 1
- 230000004044 response Effects 0.000 description 1
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- FZHAPNGMFPVSLP-UHFFFAOYSA-N silanamine Chemical class [SiH3]N FZHAPNGMFPVSLP-UHFFFAOYSA-N 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229910001961 silver nitrate Inorganic materials 0.000 description 1
- QDRKDTQENPPHOJ-UHFFFAOYSA-N sodium ethoxide Chemical compound [Na+].CC[O-] QDRKDTQENPPHOJ-UHFFFAOYSA-N 0.000 description 1
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- DQFBYFPFKXHELB-VAWYXSNFSA-N trans-chalcone Chemical compound C=1C=CC=CC=1C(=O)\C=C\C1=CC=CC=C1 DQFBYFPFKXHELB-VAWYXSNFSA-N 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
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Abstract
본 발명은 하기 화학식 2로 표시되는 3관능성 [1,1';3',1'']Terphenyl-4,5',4''-triol 화합물을 에폭시화한 저융점의 에폭시 수지 및 상기 에폭시 수지에 경화제 등을 더 포함하여 이루어지는 에폭시 수지 조성물과 이 조성물로부터 얻어지는 에폭시 수지 경화물에 관한 것이다. 본 발명의 따른 에폭시 수지 경화물은 할로겐계 화합물이나 인계 난연제를 사용하지 않고도 높은 난연성을 나타내고 내충격성, 내흡수성, 내열성이 우수하여 반도체 밀봉재, 인쇄 회로 기판, 도료, 접착, 주형 용도 등에 적합하게 사용할 수 있다.
[화학식 2]
상기식에서 R 은 C1 -12의 알킬, 페닐, p 는 0~2의 정수이다.The present invention is a low-melting epoxy resin and the epoxy epoxidized trifunctional [1,1 ';3', 1 ''] Terphenyl-4,5 ', 4''-triol compound represented by the following formula (2) It is related with the epoxy resin composition which further contains a hardening | curing agent etc. in resin, and the epoxy resin hardened | cured material obtained from this composition. The cured epoxy resin according to the present invention has high flame resistance without using a halogen-based compound or phosphorus flame retardant, and has excellent impact resistance, water absorption, and heat resistance, so that the epoxy resin cured product can be suitably used for semiconductor sealing materials, printed circuit boards, paints, adhesives, molding applications, and the like. Can be.
(2)
In which R is alkyl, phenyl, a C 1 -12 p is an integer of 0-2.
Description
본 발명은 저융점 및 고내열성의 구조로 난연성을 부여할 수 있는 에폭시 수지, 에폭시 수지 조성물 및 그의 경화물에 관한 것이다.
The present invention relates to an epoxy resin, an epoxy resin composition, and a cured product thereof, which can impart flame retardance with a low melting point and high heat resistance structure.
전기 제품이나 반도체용의 에폭시 수지는 전기적인 저항에 의해 화재가 발생할 우려가 있기 때문에 고내열성과 난연 특성이 필요하다. 최근의 패키지에 요구되는 반도체 봉지수지는 난연성을 부여하기 위한 재료로서 브롬화합물과 산화안티몬의 조합이 일반적으로 사용되고 있으나, 대(對) 환경측면에서 두 물질 모두 규제 대상이며, 사용자들도 이들 물질을 배제한 재료를 요구하고 있다. Epoxy resins for electrical appliances and semiconductors require fire resistance due to electrical resistance, and therefore require high heat resistance and flame resistance. The semiconductor encapsulation resin required for recent packages is generally used as a material for imparting flame retardancy, but a combination of bromine compound and antimony oxide is generally used. However, both substances are regulated in terms of environmental environment. I ask for the material which I removed.
연소성이 적은 폴리머들은 근본적으로 열에 의해 많은 챠르(char)를 생성하여 폴리머의 표면에 방화층을 형성하여 열에 의해 분해되어 방출되는 가연성 가스를 차단하여 연소가 계속되는 것을 막아 주며, 낮은 방열률(放熱率, Heat Release Rate, HRR)을 갖는다. 방열량(Heat Release capacity, HRC)은 단위 무게에서 방출되는 최대의 열량으로 정의되며, 물질의 고유성질로써 인화성(Flammability)을 예측하는 주요 지표로서 방열률(HRR)을 평가하는 기준이 된다(Richard N. Walters, Richard E. Lyon, Journal of Applied Polymer Science , 87(3), 548 - 563, 2002). Low combustible polymers essentially create a large number of chars by heat, forming a fireproof layer on the surface of the polymer to block the combustible gases that are decomposed and released by heat, preventing combustion from continuing and a low heat dissipation rate. , Heat Release Rate, HRR). Heat release capacity (HRC) is defined as the maximum amount of heat released from a unit weight, and is a criterion for evaluating the heat dissipation rate (HRR) as a major index for predicting flammability as the material's unique property (Richard N Walters, Richard E. Lyon, Journal of Applied Polymer Science , 87 (3), 548-563, 2002).
인쇄 회로 기판 등의 전자 부품 분야, 복합 재료용 매트릭스, 포토레지스트 재료 및 반도체 봉지재 등에 사용되는 에폭시 수지 조성물은 가연성분을 감소시키는 방법으로 무기 필러를 고충전하기 때문에 혼합 및 가공성을 위하여 에폭시 수지가 50 ~ 100 ℃ 이하의 낮은 용융점을 요구하고 있다. 특히, 반도체 봉지 재료 분야에서는 소형 경량화와 다핀화 및 고밀도 실장이 가능한 BGA(Ball grid Array), CSP(Chip Size Package)라고 하는 표면 실장 패키지로의 이행과 납을 함유하지 않는 무연화로의 대응에 의해 리플로우 처리온도가 높아져서 고내열화, 내습화로 대표되는 성능의 향상이 요구되고 있다. 예를 들면, 아랄킬 구조의 페놀 수지를 에폭시화 시킨 수지, 메톡시메틸렌기가 도입된 비페닐(biphenyl), 나프탈렌 등의 방향족 화합물을 페놀과 축합 반응시켜 얻은 페놀 수지로부터 얻은 에폭시 수지가 반도체용 봉지재로서 알려져 있으나, 극단적인 관능기 농도의 저하에 의해, 경화성의 현저한 저하를 피할 수 없다(일본공개공보 제1996-301980호, 일본공개공보 제2007-217469, 일본공개공보 제2007-137943). Epoxy resin compositions used in the field of electronic components such as printed circuit boards, composite materials, photoresist materials and semiconductor encapsulants have high filling properties of inorganic fillers by reducing combustible components. A low melting point of ˜100 ° C. or less is required. Particularly in the field of semiconductor encapsulation materials, the transition to surface mount packages such as ball grid array (BGA) and chip size package (CSP), which enables compact, lightweight, multi-pin, and high-density mounting, and response to lead-free lead-free As the reflow treatment temperature is increased, the performance improvement represented by high heat resistance and moisture resistance is required. For example, an epoxy resin obtained from a phenol resin obtained by condensation reaction of an aromatic compound such as a resin obtained by epoxidizing an aralkyl structure phenol resin, a biphenyl and a naphthalene having a methoxymethylene group introduced therein with a phenol is encapsulated for semiconductors. Although it is known as ash, a remarkable decrease in hardenability cannot be avoided due to the decrease in the concentration of the functional group (JP-A-1996-301980, JP-A-2007-217469, JP-A-2007-137943).
최근에는 IC회로의 고집적화에 수반하여 고 밀도실장용 패키지에 대한 요구로 종래의 페놀 수지로는 그 요구 성능에 대응하는 것이 어려워지고 있어서, 연화점이나 용융점도가 더 낮고, 내습성, 내충격성, 내열성 등의 물리적 성질도 만족케 하는 에폭시 화합물의 구조로서 결정성 화합물을 이용하여 에폭시 수지를 개발하고 있다. 예를 들면, 결정성의 플루오렌형 에폭시 수지 조성물이나(국내공개공보 제2004-116630호), 3,3'-디페닐-4,4‘-디히도록시페닐의 에폭시 수지(일본공개공보 제2000-248050호) 및 파라-터페닐(p-terphenyl)의 에폭시 화합물의 수지(일본공개공보 제2006-273989호) 등의 반도체 봉지용 에폭시 수지 조성물이 알려져 있으나, 양호한 성형성 및 자기소화성을 완전히 만족시키는 반도체 봉지용 소재로서 충분하지 않다. 또한 이관능성 터페닐(terphenyl) 에폭시 화합물은 비대칭적인 구조로서 유동성이 우수하여 내습성, 내열성, 성형성을 갖는 수지라고 공지되어 있으나, 에폭시 화합물의 전구체인 이관능성 터페닐(terphenyl)의 제조 방법이 언급되지 않아서 실용적인 측면에서 불만족스럽다는 문제점이 있었다(일본공개공보 제1997-25328호).
In recent years, with the high integration of IC circuits, it has become difficult to meet the required performance with conventional phenol resins due to the demand for high-density packaging packages, resulting in lower softening point and melt viscosity, and higher moisture resistance, impact resistance, and heat resistance. Epoxy resins have been developed using crystalline compounds as structures of epoxy compounds that also satisfy physical properties such as these. For example, a crystalline fluorene type epoxy resin composition (Domestic Publication No. 2004-116630), or an epoxy resin of 3,3'-diphenyl-4,4'-dichoxyphenyl (Japanese Laid-Open Publication No. 2000) -248050) and epoxy resin compositions for semiconductor encapsulation, such as resins of epoxy compounds of p-terphenyl (Japanese Laid-Open Patent Publication No. 2006-273989), but are fully satisfactory in good moldability and self-extinguishing properties. It is not enough as a material for semiconductor encapsulation. In addition, the difunctional terphenyl epoxy compound is an asymmetric structure and is known as a resin having excellent fluidity, moisture resistance, heat resistance, and moldability, but a method of preparing a difunctional terphenyl which is a precursor of an epoxy compound is known. There was a problem of unsatisfaction in practical terms because it was not mentioned (Japanese Laid-Open Publication No. 1997-25328).
이에 본 발명자들은 터페닐(terphenyl) 화합물의 높은 내열성과 비대칭구조에 의한 낮은 연화점을 예상하고, 그 화합물들에 대한 에폭시 수지를 연구한 결과 성형성이 우수하고, 내열성이 높은 구조로 고난연성을 부여할 수 있는 에폭시 수지를 완성하게 되었다.The present inventors anticipate high heat resistance of the terphenyl compound and low softening point due to the asymmetric structure, and the epoxy resins for the compounds have been studied. Epoxy resin can be completed.
따라서 본 발명은 성형성이 우수하고, 고내열성 및 고난연성을 부여할 수 있는 3관능성 터페닐(terphenyl) 화합물을 이용한 에폭시 수지를 제공하는 것을 첫 번째 과제로 한다.Therefore, the present invention is to provide an epoxy resin using a trifunctional terphenyl compound excellent in moldability and capable of providing high heat resistance and high flame retardancy.
또한 본 발명은 내열성 및 내습성(내수성)이 우수하고 내충격성 및 저융점(저연화점)을 나타내는 전기전자 제품용 절연재료(고신뢰성 봉지재료), 적층판(프린트 배선판)이나 CFRP 등의 각종 복합재료, 접착제 및 도료 등에 유용한 에폭시 수지 조성물 및 이의 경화물을 제공하는 것을 그 두 번째 과제로 한다.
In addition, the present invention provides various composite materials such as insulation materials (high reliability encapsulation materials), laminated boards (printed wiring boards), CFRP, etc., for electrical and electronic products, which have excellent heat resistance and moisture resistance (water resistance) and exhibit impact resistance and low melting point (low softening point). It is a 2nd subject to provide the epoxy resin composition useful for adhesives, coating materials, etc., and its hardened | cured material.
본 발명은 하기 화학식 1로 표시되는 에폭시 수지에 관한 것이다:The present invention relates to an epoxy resin represented by the following general formula (1):
[화학식 1][Formula 1]
상기 화학식 1에서 R은 서로 독립적으로 C1-C12의 알킬 또는 페닐이며, p는 0 ~ 2의 정수이며; n은 0 ~ 10 의 정수이다.
R in Formula 1 is independently of each other C 1 -C 12 alkyl or phenyl, p is an integer of 0 to 2; n is an integer of 0-10.
또한 본 발명은 상기 화학식 1로 표시되는 에폭시 수지와 경화제를 포함하는 것을 특징으로 하는 에폭시 수지 조성물 및 이의 경화물에 관한 것이다.
In addition, the present invention relates to an epoxy resin composition and a cured product thereof, comprising an epoxy resin represented by Formula 1 and a curing agent.
본 발명의 에폭시 수지는 내열성이 우수하여 별도의 난연제 및 난연조제의 첨가 없이도 우수한 난연성을 나타냄으로서 반도체 봉지재, 인쇄 회로 기판, 접착, 도료, 주형 용도 등에 적합한 용도를 제공한다. 상기 난연성으로 인해 본 에폭시 수지가 각종 가전제품 및 공업제품 등에 사용되는 경우 인체 안전성을 더욱 높이고, 나아가서는 환경 안정성에도 기여할 수 있다는 장점이 있다. 즉 본 발명에 따른 새로운 난연성 에폭시 수지는 인체에 유해한 물질로부터의 인간을 지켜주며, 환경 보호에도 기여할 수 있다는 장점이 있다.
The epoxy resin of the present invention is excellent in heat resistance and exhibits excellent flame resistance without the addition of a separate flame retardant and a flame retardant aid, thereby providing an application suitable for semiconductor encapsulants, printed circuit boards, adhesives, paints, mold applications, and the like. Due to the flame retardancy, when the present epoxy resin is used in various home appliances and industrial products, there is an advantage that it can further increase the safety of the human body and further contribute to the environmental stability. That is, the new flame retardant epoxy resin according to the present invention has the advantage of protecting human from harmful substances to human body and contributing to environmental protection.
도 1은 상기 화학식 1로 표시된 에폭시 화합물의 DSC (Differential Scanning Calorimetry)를 측정한 그래프로서 에폭시 화합물의 녹는점을 나타낸다.
도 2 및 3은 화학식 1로 표시된 에폭시 화합물과 경화제를 사용하여 얻은 에폭시 수지 경화물의 질소 상태에서 측정한 TGA (Thermogravimetry analysis)그래프이다.FIG. 1 is a graph measuring DSC (Differential Scanning Calorimetry) of an epoxy compound represented by Chemical Formula 1, showing a melting point of an epoxy compound.
2 and 3 are TGA (Thermogravimetry analysis) graphs measured in the nitrogen state of the cured epoxy resin obtained using the epoxy compound represented by Formula 1 and a curing agent.
본 발명은 내습성, 내충격성, 내열성 및 자기 소화성이 우수한 하기 화학식 2로 표시되는 3관능성인 [1,1';3',1'']Terphenyl-4,5',4''-triol 화합물과 이를 이용한 에폭시 수지, 에폭시 수지 조성물 및 이를 경화하여 얻은 에폭시 수지 경화물에 관한 것이다.
The present invention is a trifunctional [1,1 ';3', 1 ''] terphenyl-4,5 ', 4''-triol compound represented by the following Chemical Formula 2 having excellent moisture resistance, impact resistance, heat resistance, and self-extinguishing ability. It relates to an epoxy resin, an epoxy resin composition and a cured epoxy resin obtained by curing the same.
본 발명을 상세히 설명하면 다음과 같다.The present invention is described in detail as follows.
본 발명에서 하기 화학식 1로 표시되는 에폭시 수지는 하기 화학식 2로 표시되는 3관능성 [1,1';3',1'']Terphenyl-4,5',4''-triol 화합물을 하기 화학식 3으로 표시되는 에피할로히드린과 반응시킴으로써 얻을 수 있다.In the present invention, the epoxy resin represented by the following formula (1) is a trifunctional [1,1 '; 3', 1 ''] terphenyl-4,5 ', 4' '-triol compound represented by the following formula (2) It can obtain by reacting with epihalohydrin represented by 3.
[화학식 1] [Formula 1]
[화학식 2][Formula 2]
[화학식3][Formula 3]
상기 화학식 1 내지 3에서 R은 서로 독립적으로 C1-C12의 알킬 또는 페닐이며, p는 0 ~ 2의 정수이며; n은 1 ~ 10 의 정수이며, X는 F, Cl, Br 또는 I이며, Y는 H 또는 CH3 이다.R in Formulas 1 to 3 independently of each other is C 1 -C 12 alkyl or phenyl, p is an integer of 0 to 2; n is an integer from 1 to 10, X is F, Cl, Br or I, and Y is H or CH 3 .
상기 에폭시화 반응에서 사용되는 에피할로히드린은 바람직하게는 에피클로로히드린을 사용하는 것이 공업적인 면에서 좋으며, 상기 에폭시 수지를 얻는 반응은 종래 공지된 방법을 제한 없이 사용할 수 있다. 예를 들면, 상기 화학식 2로 표시되는 화합물과 에피클로로히드린의 혼합물에 수산화나트륨 또는 수산화칼륨 등의 알칼리 금속 수산화물의 고체를 한꺼번에 가하거나, 20 ~ 120 ℃의 온도 범위에서 1 ~ 20 시간동안 서서히 적가함으로써 행해질 수 있다. The epihalohydrin used in the epoxidation reaction is preferably in the industrial aspect to use epichlorohydrin, the reaction to obtain the epoxy resin can be used without limitation conventionally known methods. For example, a solid of an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide is added to a mixture of the compound represented by Formula 2 and epichlorohydrin all at once, or slowly at a temperature range of 20 to 120 ° C. for 1 to 20 hours. It can be done by dropping.
상기 반응에서 에피할로히드린의 사용량은 상기 화학식 2로 표시되는 화합물의 수산화기(OH) 1 당량에 대하여 0.5 ~ 50 몰을 사용하는 것이 바람직하며, 더욱 바람직하게는 1 ~ 20 몰을 사용하는 것이 좋다. 상기 반응에서 알칼리 금속 수산화물의 사용량은 상기 화학식 2로 표시되는 화합물의 수산화기(OH) 1 당량에 대하여 0.5 ~ 1.5 몰을 사용하는 것이 바람직하며, 더욱 바람직하게는 0.7 ~ 1.2 몰을 사용하는 것이 좋다. 상기 반응의 용매로는 다이옥산, DMF, DMSO 등 비프로톤성 극성용매 또는 톨루엔, 크실렌 등의 비극성 용매를 사용할 수 있다.The amount of epihalohydrin used in the reaction is preferably 0.5 to 50 moles, more preferably 1 to 20 moles, per 1 equivalent of the hydroxyl group (OH) of the compound represented by Formula 2. good. The amount of the alkali metal hydroxide used in the reaction is preferably 0.5 to 1.5 moles, more preferably 0.7 to 1.2 moles per 1 equivalent of the hydroxyl group (OH) of the compound represented by the formula (2). As the solvent for the reaction, an aprotic polar solvent such as dioxane, DMF, DMSO, or a nonpolar solvent such as toluene or xylene can be used.
또한, 상기 화학식 2로 표시되는 화합물과 과량의 에피할로히드린을 사용하는 반응 혼합물에 테트라메틸 암모늄 클로라이드, 트리메틸 벤질 암모늄 클로라이드 등의 4급 암모늄염을 촉매로 첨가하여 50 ~ 150 ℃ 온도 범위에서 1 ~ 20 시간 동안 반응시키고, 얻어진 할로 히드린 에테르에 수산화나트륨, 수산화칼륨 등의 고체 또는 수산화물의 수용액을 가하고 20 ~ 150 ℃ 범위에서 1 ~ 20 시간 동안 반응시킴으로써 에폭시 수지를 얻을 수 있다. 상기 4급 암모늄염 촉매는 화학식 2로 표시되는 화합물의 수산기(OH) 1 당량에 대하여 0.001 ~ 0.2 몰을 사용하는 것이 바람직하며, 더욱 바람직하게는 0.05 ~ 0.1 몰을 사용하는 것이 좋다.In addition, a quaternary ammonium salt such as tetramethyl ammonium chloride or trimethyl benzyl ammonium chloride as a catalyst is added to the reaction mixture using the compound represented by Formula 2 and the excess epihalohydrin as a catalyst at a temperature in the range of 50 to 150 ° C. The reaction can be carried out for 20 hours, and an epoxy resin can be obtained by adding an aqueous solution of a solid or hydroxide such as sodium hydroxide and potassium hydroxide to the obtained halohydrin ether and reacting for 1 to 20 hours in the range of 20 to 150 ° C. The quaternary ammonium salt catalyst preferably uses 0.001 to 0.2 mol, more preferably 0.05 to 0.1 mol, based on 1 equivalent of hydroxyl group (OH) of the compound represented by Formula 2.
일반적으로, 상기 반응이 종료된 후 수세(또는 수세없이 가열 감압하에서)하여 과잉의 에피할로히드린을 제거한 뒤 톨루엔, 크실렌, 메틸 이소부틸케톤 등의 용매에 용해하고 수산화나트륨, 수산화칼륨 등의 알칼리 금속 수산화물의 수용액을 가하여 다시 한번 반응을 진행시켜 주는 것이 좋다. 이때 상기 알칼리 금속 수산화물의 사용량은 화학식 2로 표시되는 화합물의 수산기(OH) 1 당량에 대하여 0.1 ~ 0.2 몰을 사용하는 것이 바람직하며, 더욱 바람직하게는 0.05 ~ 0.1 몰을 사용하는 것이 좋다. 상기 반응은 50 ~ 120 ℃ 범위에서 0.5 ~ 2 시간 동안 반응시켜 주는 것이 바람직하다. 반응 종료 후, 부생한 소금을 수세하여 제거하고 가열? 감압 하에 톨루엔, 크실렌, 메틸 이소부틸케톤 등의 용매를 제거한다. 이와 같은 과정을 거침으로써 할로겐 함량이 적은 에폭시 수지를 얻을 수 있다는 장점이 있다. In general, after completion of the reaction, washing with water (or heating under reduced pressure without washing with water) to remove excess epihalohydrin and dissolving in a solvent such as toluene, xylene, methyl isobutyl ketone, and the like, such as sodium hydroxide and potassium hydroxide It is good to advance the reaction once again by adding an aqueous solution of alkali metal hydroxide. In this case, the alkali metal hydroxide may be used in an amount of 0.1 to 0.2 moles, more preferably 0.05 to 0.1 moles, based on 1 equivalent of the hydroxyl group (OH) of the compound represented by Formula 2. The reaction is preferably reacted for 0.5 to 2 hours in the range of 50 ~ 120 ℃. After the reaction, the by-product salt washed with water and heated? Under reduced pressure, solvents such as toluene, xylene and methyl isobutyl ketone are removed. Through such a process, there is an advantage that an epoxy resin having a low halogen content can be obtained.
상기와 같은 과정을 통해 얻어진 에폭시 수지는 세 개의 페놀성 OH기 중에서 한 개의 OH기가 에폭시화물이 되지 않은 화합물이 포함될 수 있고, 페놀성 OH기가 에폭시화물을 공격해서 생성된 올리고머형 또한 포함할 수 있다.
The epoxy resin obtained through the above process may include a compound in which one OH group does not become an epoxidized compound among three phenolic OH groups, and may also include an oligomer type generated by attacking the epoxidized phenolic group. .
본 발명의 하기 화학식 2의 3관능성 터페닐(terphenyl) 에폭시 화합물은 공지의 방법을 응용하여 제조할 수 있다(Journal of Medicinal Chemistry, 2009, 52(7), 2036; Journal of Organic chemistry, 1997, 62, 8215; Journal of Organic chemistry, 1960, 25, 1229 ; ibid, 1962, 27, 4101).The trifunctional terphenyl epoxy compound of formula 2 of the present invention can be prepared by applying a known method (Journal of Medicinal Chemistry, 2009, 52 (7), 2036; Journal of Organic chemistry, 1997, 62, 8215; Journal of Organic chemistry, 1960, 25, 1229; ibid , 1962, 27, 4101).
[화학식2](2)
상기 화학식 2에서, R은 서로 독립적으로 C1-C12의 알킬 또는 페닐이며, p는 0 ~ 2의 정수이다.
In Formula 2, R is independently of each other C 1 -C 12 alkyl or phenyl, p is an integer of 0 to 2.
상기 합성방법의 예를 들면, 하기 화학식 4로 표시되는 벤잘아세토페논(benzalacetophenone)을 아세토아세트산 에스터(acetoacetic ester)를 이용하여 축합반응 시킴으로써 하기 화학식 5로 표시되는 3,5-디페닐-2-사이클로헥센-1-온(3,5-diphenyl-2-cyclohexene-1-one)을 제조하고, 이것을 다시 방향족으로 산화시켜 목적하는 화합물인 하기 화학식 6으로 표시되는 3관능성 터페닐(terphenyl) 에폭시 화합물을 얻을 수 있다. 상기 반응 온도는 200 ℃ ~ 300 ℃ 범위가 바람직하며, 더욱 바람직하게는 250 ~ 270 ℃범위가 바람직하다. 상기 반응 온도가 200 ℃보다 낮으면 반응이 불완전하게 일어난다는 문제점이 있으며, 상기 반응 온도가 300 ℃ 이상일 경우에는 부생성물이 생성되어 수율이 낮아진다는 문제점이 있다. 상기 반응의 반응 시간은 20 분 ~ 3 시간 정도가 바람직하며, 더욱 바람직하게는 30 분 ~ 1 시간 정도가 좋다. 상기 반응 시간이 20 분 이하인 경우 반응이 불완전하다는 문제점이 있으며, 상기 반응이 3 시간을 초과하는 경우 부생성물이 생성되어 수율이 낮아진다는 문제점이 있다.As an example of the synthesis method, 3,5-diphenyl-2-cyclo represented by the following formula (5) by condensation reaction of benzalacetophenone (benzalacetophenone) represented by the following formula (4) using acetoacetic ester (acetoacetic ester) A hexen-1-one (3,5-diphenyl-2-cyclohexene-1-one) was prepared and oxidized to an aromatic compound to form a trifunctional terphenyl epoxy compound represented by the following formula (6). Can be obtained. The reaction temperature is preferably in the range of 200 ° C to 300 ° C, more preferably in the range of 250 to 270 ° C. If the reaction temperature is lower than 200 ℃ there is a problem that the reaction occurs incompletely, if the reaction temperature is 300 ℃ or more there is a problem that the by-products are generated, the yield is lowered. The reaction time of the reaction is preferably about 20 minutes to 3 hours, more preferably about 30 minutes to 1 hour. If the reaction time is 20 minutes or less, there is a problem that the reaction is incomplete, if the reaction is more than 3 hours there is a problem that the by-products are generated and the yield is low.
상기 반응에서 시작물질인 하기 화학식 4로 표시되는 벤잘아세토페논(benzalacetophenone)의 합성예는 본 명세서의 실시예 부분에 상세하게 기재되어 있다. 또한 상기 과정 중 방향족으로 산화시키는 과정은 공지의 방법을 사용할 수 있으며, 예를 들면, 황(Sulfur) 촉매 하에서 환류를 통해 산화시킬 수 있다(Synthesis, 392 (1981)). 상기 반응 과정을 하기 반응식 1에 나타내었다.Synthesis examples of benzalacetophenone represented by the following formula (4), which is a starting material in the reaction, are described in detail in the Examples section of the present specification. In addition, the process of oxidizing to aromatic may use a known method, for example, it can be oxidized through reflux under a sulfur catalyst (Synthesis, 392 (1981)). The reaction process is shown in Scheme 1 below.
[반응식 1][Reaction Scheme 1]
[화학식 7][Formula 7]
[화학식 8][Formula 8]
[화학식 9][Chemical Formula 9]
[화학식 10][Formula 10]
본 발명의 에폭시 수지 조성물은 경화제를 함유하며, 사용할 수 있는 경화제의 종류에는 제한을 두지 않지만, 바람직하게는 하기 화학식 11 ~ 화학식 13으로 표시되는 페놀 노볼락 수지, 크레졸 노볼락 수지, 비페닐 함유 페닐 노볼락 수지, 페놀-p-크실렌계 수지 및 페닐 비페닐렌계 페놀 수지 등의 페놀계 경화제, 지방족 폴리아민, 폴리아미드 폴리아민 및 하기 화학식 14 ~ 화학식 16으로 표시되는 방향족 폴리아민 등의 아민계 경화제, 디시안 디아미드 류, 무수 헥사히드로프탈산 및 무수 메틸테트라히드로프탈산 등의 산 무수물계 경화제를 사용할 수 있다. 이들은 단독으로 사용해도 좋고 2 종 이상 병행하여 사용해도 좋다. 본 발명의 에폭시 수지 조성물 중에 경화제의 사용량은 에폭시 수지의 에폭시기 1 당량에 대하여 0.5 ~ 1.5 당량이 바람직하고, 더욱 바람직하게는 0.6 ~ 1.2 당량을 사용하는 것이 좋다. 상기 경화제를 에폭시 수지의 에폭시기 1 당량에 대하여 0.5 미만으로 사용하게 되는 경우 충분히 경화되지 않아서 물성이 나빠지는 문제점이 있고, 에폭시 수지의 에폭시기 1 당량에 대하여 1.5 당량을 초과하여 사용하는 경우에도 경화밀도가 작아져서 물성이 낮아지는 문제점이 있다.Although the epoxy resin composition of this invention contains a hardening | curing agent and does not limit the kind of hardening | curing agent which can be used, Preferably it is phenol novolak resin, cresol novolak resin represented by following formula (11)-formula (13), biphenyl containing phenyl Phenolic curing agents such as novolak resins, phenol-p-xylene resins and phenyl biphenylene-based phenol resins, amine curing agents such as aliphatic polyamines, polyamide polyamines and aromatic polyamines represented by the following formulas (14) to (16) Acid anhydride type hardeners, such as diamide, hexahydrophthalic anhydride and methyltetrahydrophthalic anhydride, can be used. These may be used independently or may be used in combination of 2 or more type. As for the usage-amount of a hardening | curing agent in the epoxy resin composition of this invention, 0.5-1.5 equivalent is preferable with respect to 1 equivalent of epoxy groups of an epoxy resin, More preferably, 0.6-1.2 equivalent is used. When the curing agent is used in less than 0.5 equivalent to 1 equivalent of epoxy group of epoxy resin, there is a problem of not being sufficiently cured, resulting in poor physical properties, even when using more than 1.5 equivalents to 1 equivalent of epoxy group of epoxy resin. There is a problem that the physical properties are lowered.
[화학식 11][Formula 11]
[화학식 12][Chemical Formula 12]
[화학식 13][Chemical Formula 13]
[화학식 14][Formula 14]
[화학식 15][Formula 15]
[화학식 16][Chemical Formula 16]
본 발명의 상기 에폭시 수지 조성물에는 경화촉진제를 첨가하는 것이 바람직하다. 첨가되는 경화촉진제는 당업계에 사용되는 것을 제한 없이 사용할 수 있지만, 바람직하게는 벤질디메틸아민, 트리에탄올아민, 트리에틸렌디아민, 디메틸아미노에탄올, 트리(디메틸아미노메틸)페놀 등의 3급 아민류, 2-메틸이미다졸, 2-페닐이미다졸 등의 이미다졸류, 트리페닐포스핀, 트리페닐포스핀과 파라벤조페논의 배위화합물, 디페닐포스핀, 페닐포스핀 등의 유기포스핀류, 테트라페닐포스포니움 테트라페닐보레이트, 트리페닐포스핀 테트라페닐보레이트 등의 테트라페닐보론염 등을 사용할 수 있으며, 이 중 1종 또는 2종 이상을 함께 사용할 수 있다. 상기 경화촉진제의 사용량은 에폭시 수지 및 경화제 사용량의 총합 100 중량부에 대하여 0.005 ~ 2.0 중량부로 사용하는 것이 바람직하며, 더욱 바람직하게는 0.01 ~ 1.0 중량부로 사용하는 것이 좋다. It is preferable to add a hardening accelerator to the said epoxy resin composition of this invention. Although the curing accelerator to be added can be used without limitation in the art, preferably tertiary amines such as benzyldimethylamine, triethanolamine, triethylenediamine, dimethylaminoethanol, tri (dimethylaminomethyl) phenol, 2- Imidazoles such as methylimidazole and 2-phenylimidazole, coordination compounds of triphenylphosphine and tribenzophenone, organic phosphines such as diphenylphosphine and phenylphosphine, tetraphenylphosph Tetraphenyl boron salts, such as a ponium tetraphenyl borate and a triphenyl phosphine tetraphenyl borate, etc. can be used, One or two or more of these can be used together. The amount of the curing accelerator is preferably used in an amount of 0.005 to 2.0 parts by weight, and more preferably 0.01 to 1.0 part by weight, based on 100 parts by weight of the total amount of the epoxy resin and the curing agent.
본 발명의 에폭시 조성물에는 필요에 따라 공지의 첨가제를 추가하여 사용할 수 있다. 상기 첨가제의 종류에는 제한이 없으나, 바람직하게는 실리카, 알루미나, 활석 및 유리섬유 등의 무기 충진제, 고급 지방산, 고급 지방산 금속염, 에스테르계 왁스 및 천연왁스 등의 이형제, 에폭시실란, 아미노실란 및 알킬실란 등의 커플링제 등을 필요에 따라 사용할 수 있다.The epoxy composition of this invention can add and use a well-known additive as needed. The type of the additive is not limited, but preferably, inorganic fillers such as silica, alumina, talc and glass fibers, release agents such as higher fatty acids, higher fatty acid metal salts, ester waxes and natural waxes, epoxysilanes, aminosilanes and alkylsilanes. Coupling agents, such as these, can be used as needed.
본 발명의 에폭시 수지 조성물은 경화 과정을 거침으로써 에폭시 수지 경화물로 만들 수 있다. 상기 경화 과정은 당업계에 사용되는 방법을 제한 없이 사용할 수 있다. 예를 들면, 상기 얻어진 에폭시 수지 조성물을 통상 130 ~ 170 ℃의 온도범위에서 30 ~ 500 초간 예비 경화하고, 150 ~ 200 ℃의 온도 범위에서 2 ~ 16 시간 동안 경화함으로써 충분한 경화 반응이 진행되고 본 발명의 경화물이 얻어진다. 또는 에폭시 수지 조성물의 성분을 용제에 균일 분산하거나 용해시키고, 용매를 제거한 후 경화시키는 방법도 행할 수 있다.The epoxy resin composition of the present invention can be made into a cured epoxy resin by undergoing a curing process. The curing process may be used without limitation the methods used in the art. For example, the epoxy resin composition obtained above is usually cured for 30 to 500 seconds at a temperature range of 130 to 170 ° C., and then cured for 2 to 16 hours at a temperature range of 150 to 200 ° C., thereby allowing sufficient curing reaction to proceed. Hardened | cured material of is obtained. Alternatively, a method of uniformly dispersing or dissolving the components of the epoxy resin composition in a solvent, removing the solvent, and curing may also be performed.
상기와 같이 얻어진 본 발명의 에폭시 수지는 고내열성, 내습성 및 고접착성을 갖는다. 따라서 본 발명의 에폭시 수지는 내열성, 내습성, 고접착력이 요구되는 광범위한 분야에서 이용할 수 있다. 구체적으로는 절연재료, 적층판, 봉지재료 등의 모든 전기, 전자 재료의 배합 성분으로서 유용하며, 또한 성형재료, 복합재료 및 도료, 접착 등의 분야에도 이용될 수 있다.
The epoxy resin of this invention obtained as mentioned above has high heat resistance, moisture resistance, and high adhesiveness. Therefore, the epoxy resin of the present invention can be used in a wide range of fields requiring heat resistance, moisture resistance, and high adhesion. Specifically, it is useful as a compounding component of all electrical and electronic materials such as insulating materials, laminates, encapsulation materials, and can also be used in fields such as molding materials, composite materials, paints, and adhesives.
이하 본 발명을 실시예에 의하여 상세히 설명하지만, 본 발명이 실시예에 의해 한정되는 것은 아니다.
Hereinafter, the present invention will be described in detail by way of examples, but the present invention is not limited by the examples.
하기 실시예에 있어서, 에폭시 당량, 점도, 연화점 및 가수분해성 염소 농도는 이하의 조건으로 측정했다.In the following example, epoxy equivalent, viscosity, softening point, and hydrolyzable chlorine concentration were measured on condition of the following.
(1) 에폭시 당량 : JIS K-7236 법에 의해 측정하였다. 단위는 g/eq.(1) Epoxy equivalent: It measured by JIS K-7236 method. The unit is g / eq.
(2) 연화점 : JIS K-7234 법에 의해 측정하였다.(2) Softening point: It measured by JIS K-7234 method.
(3) 가수분해성 염소 농도 : 시료의 디옥산 용액에 1N KOH 에탄올 용액을 첨가하고 30 분간 환류하는 것에 따라 유리 염소량을 질산은 적정법에 의해 측정하고, 시료의 중량으로 나눈 값으로 측정하였다.(3) Hydrolyzable chlorine concentration: 1N KOH ethanol solution was added to the dioxane solution of the sample, and refluxed for 30 minutes. The amount of free chlorine was measured by titration of silver nitrate and divided by the weight of the sample.
(4) 열적 특성 : 수지의 열적 특성은 난연 시험편에서 일부 분쇄하여 얻은 분체를 사용하여 TGA (Thermogravimetry Analysis)롤 측정하였으며, 질소 분위기 하에서 10 ℃/min 승온 속도로 상온에서 900 ℃까지 측정하였고, 5 중량% 감소되었을 때의 온도를 얻어 평가하였다. 장비는 TA Instrument사의 Q500을 사용하였다.(4) Thermal Properties: The thermal properties of the resin were measured by TGA (Thermogravimetry Analysis) roll using powder obtained by pulverization in flame retardant test piece, measured from room temperature to 900 ° C at a temperature increase rate of 10 ° C / min under nitrogen atmosphere. The temperature at which the weight percentage was reduced was obtained and evaluated. The instrument used TA Instrument's Q500.
(5) 난연성 : 물질의 연소시 방출되는 방열률 (放熱率, Heat Release capacity, HRC)은 단위 무게에서 방출되는 최대의 열량으로 정의되는 물질의 고유성질이며, 폴리머의 인화성을 예측하는 지표로서 열연소유동열량측정기 (Pyrolysis Combustion Flow calorimetry, PCFC)로 평가하였으며, 방열률이 낮을수록 수지의 인화성이 낮아지므로 난연성이 우수한 것으로 예측하였다. PCFC는 고분자 물질의 방열량(HRC)과 총방열량을 측정하며, 방열량(HRC)은 산소 소모량에 따라 정해지며 가열속도에 따라 표정된다 (See, Journal of Applied Polymer Science , 87(3), 548 - 563, 2002).
(5) Flame retardancy: The heat release capacity (HRC) released during the combustion of a material is the intrinsic property of the material, which is defined as the maximum amount of heat released from the unit weight, and is an indicator for predicting the flammability of a polymer. It was evaluated by Pyrolysis Combustion Flow calorimetry (PCFC). The lower the heat release rate, the lower the flammability of the resin. PCFC measures the amount of heat dissipation (HRC) and total heat dissipation of a polymer, and the amount of heat dissipation (HRC) is determined according to the oxygen consumption and is expressed according to the heating rate (See, Journal of Applied Polymer Science , 87 (3) , 548-563, 2002).
합성예Synthetic example 1 : One : 3,5-3,5- BisBis -(4--(4- methoxymethoxy -- phenylphenyl )-) - cyclohexcyclohex -2--2- enoneenone 의 합성Synthesis of
NaOH 8 g을 메탄올 100 ml에 녹인 후, 4-methoxyacetophenone 30 g과 4-Methoxybenzaldehyde 27 g을 가하고 상온에서 두 시간 동안 교반하였다. 반응이 끝난 후 상온에서 식힌 후 에틸 아세테이트(Ethyl acetate)로 추출한 후 건조하여 1,3-Bis-(4-methoxy-phenyl)-propenone 48 g 을 얻었다(97 % 수율). After dissolving 8 g of NaOH in 100 ml of methanol, 30 g of 4-methoxyacetophenone and 27 g of 4-Methoxybenzaldehyde were added and stirred at room temperature for 2 hours. After the reaction, the mixture was cooled to room temperature, extracted with ethyl acetate, and dried to obtain 48 g of 1,3-Bis- (4-methoxy-phenyl) -propenone (97% yield).
1H NMR(CDCl3) : δ3.83 (S, 3H, OCH3), 3.87 (S, 3H, OCH3), 6.91-6.98 (dd, 4H.J=8.6, Ar), 7.40-7.45 (d, 1H, J=15.6, CH=CH), 7.57-7.60 (d, 1H, Ar, J=8.6), 7.75-7.80 (d, 1H, J=15.6, CH=CH),8.01-8.04 (d, 1H, J=9, Ar) 1 H NMR (CDCl 3 ): δ3.83 (S, 3H, OCH 3 ), 3.87 (S, 3H, OCH 3 ), 6.91-6.98 (dd, 4H.J = 8.6, Ar), 7.40-7.45 (d , 1H, J = 15.6, CH = CH), 7.57-7.60 (d, 1H, Ar, J = 8.6), 7.75-7.80 (d, 1H, J = 15.6, CH = CH), 8.01-8.04 (d, 1H, J = 9, Ar)
상기 얻어진 1,3-Bis-(4-methoxy-phenyl)-propenone 38 g과 에틸 아세토아세테이트(ethyl acetoacetate) 30 g을 NaOEt 1.9 g을 녹인 에탄올 70 ml에 넣고 20 시간 동안 환류하였다. NaOH 8.5 g을 20 % 수용액으로 제조하여 상기 반응물에 가하고 4 시간 동안 환류한 다음 상온에서 식혀 생성된 고체를 여과한 후 건조하여 3,5-Bis-(4-methoxy-phenyl)-cyclohex-2-enone 39.4 g을 얻었다. 38 g of 1,3-Bis- (4-methoxy-phenyl) -propenone obtained and 30 g of ethyl acetoacetate were added to 70 ml of ethanol in which 1.9 g of NaOEt was dissolved and refluxed for 20 hours. 8.5 g of NaOH was prepared in a 20% aqueous solution, added to the reaction product, refluxed for 4 hours, and the solid formed by cooling at room temperature was filtered and dried to obtain 3,5-Bis- (4-methoxy-phenyl) -cyclohex-2-. 39.4 g of enone were obtained.
1H NMR(CDCl3):δ2.62~2.72 (m, 2H), 2.73-2.90(m, 1H), 3.00-3.10(m, 1H), 3.30-3.48 (m, 1H), 3.78 (s, 3H, OCH3), 3.10 (s, 3H, OCH3),6.48 (d, 1H, CH=CAr), 6.88-7.02 (dd, 4H, Ar), 7.25 (d, 2H, Ar), 7.55 (d, 2H, Ar).
1 H NMR (CDCl 3 ): δ2.62 to 2.72 (m, 2H), 2.73-2.90 (m, 1H), 3.00-3.10 (m, 1H), 3.30-3.48 (m, 1H), 3.78 (s, 3H, OCH 3 ), 3.10 (s, 3H, OCH 3 ), 6.48 (d, 1H, CH = CAr), 6.88-7.02 (dd, 4H, Ar), 7.25 (d, 2H, Ar), 7.55 (d , 2H, Ar).
합성예Synthetic example 2 : 2 : [1,1';3',1''][1,1 '; 3', 1 ''] TerphenylTerphenyl -4,5',4''--4,5 ', 4' '- trioltriol 의 합성Synthesis of
3,5-Bis-(4-methoxy-phenyl)-cyclohex-2-enone 43 g과 유황 5.42 g을 혼합하고 250 ℃로 30 분간 가열한 후 반응이 완결된 뒤 이를 식히고 5 ml의 초산을 가하여 상온에서 교반하다가 디클로로메탄(dichloromethane)으로 추출하고 소금물로 세척하여 4,4''-Dimethoxy-[1,1';3',1'']terphenyl-5'-ol 42.4 g을 얻었다.Mix 43 g of 3,5-Bis- (4-methoxy-phenyl) -cyclohex-2-enone with 5.42 g of sulfur and 250 After heating at 30 ° C. for 30 minutes, the reaction was completed and the mixture was cooled and stirred at room temperature with 5 ml of acetic acid. The mixture was extracted with dichloromethane and washed with brine to give 4,4 ''-Dimethoxy- [1,1 '; 42.4 g of 3 ', 1'']terphenyl-5'-ol was obtained.
1H NMR(CDCl3):δ3.85 (s, 6H, 2 OCH3), 4.95 (s, 1H, OH), 7.0 (m, 6H, Ar),7.25 (m, 1H, Ar), 7.51 (m, 4H, Ar) 1 H NMR (CDCl 3 ): δ 3.85 (s, 6H, 2 OCH 3 ), 4.95 (s, 1H, OH), 7.0 (m, 6H, Ar), 7.25 (m, 1H, Ar), 7.51 ( m, 4H, Ar)
상기 얻어진 4,4''-Dimethoxy-[1,1';3',1'']terphenyl-5'-ol 42.4 g에 47% HBr 160 ml과 빙초산 160 ml를 넣고 환류하였다. 반응이 완결된 후 에틸 에터(etheyl ether)로 추출하여 목적물을 얻었다.In 42.4 g of the obtained 4,4 ''-Dimethoxy- [1,1 '; 3', 1 ''] terphenyl-5'-ol, 160 ml of 47% HBr and 160 ml of glacial acetic acid were added and refluxed. After the reaction was completed, the mixture was extracted with ethyl ether to obtain a target product.
1H NMR(CDCl3):δ4.85 (3s, 3H, OH), 6.9 (m, 6H, Ar),7.50 (m, 5H, Ar)
1 H NMR (CDCl 3 ): δ4.85 (3s, 3H, OH), 6.9 (m, 6H, Ar), 7.50 (m, 5H, Ar)
합성예Synthetic example 3 : [1,1';3',1''] 3: [1,1 '; 3', 1 ''] TerphenylTerphenyl -4,5',4''--4,5 ', 4' '- trioltriol 화합물을 이용한 에폭시 수지의 합성( Synthesis of Epoxy Resin Using Compound TPETPE ))
상기 합성예 2의 [1,1';3',1'']Terphenyl-4,5',4''-triol 70 g과 이소프로필알콜 120 ml, 에피클로로히드린 236 ml, 증류수78 ml를 65 ℃의 오일조에서 혼합 교반하면서 녹이고, NaOH 30 g을 45 wt% 수용액으로 제조하여 15 분간 적가하고 동일 온도에서 2 시간 반응시킨 후 상온에서 식혔다. 유기층을 분리하고 과량의 에피클로로히드린을 감압 농축하여 제거한 다음, 100 ℃의 진공 오븐에서 3 시간 동안 감압하여 휘발성 유기물을 제거하였다. 잔사가 꺼내어 뜨거울 때 톨루엔 80 ml를 가하여 녹이고 70 ℃의 오일조에서 교반하면서 45 wt% NaOH 5 g을 5 분간 적가하고 30 분간 반응시킨 후 5 %의 NaH2PO4 수용액을 가하여 중화시켰다. 유기층이 중성이 되도록 증류수로 충분히 세척하고 유기층을 분리한 다음 MgSO4로 습기를 제거한 후 셀라이트(celite) 상에서 여과한 후 감압증류하여 유기용매를 증발 제거하였다. 잔사를 100 ℃의 진공 오븐에서 3 시간 감압하여 휘발성 유기물을 제거하여 목적물인 에폭시 수지 화합물을 얻었다. mp 103 ℃ (도 1의 Differential Scanning Calorimetry, DSC 참조), 에폭시 당량 149, 가수분해성 염소 530 ppm의 값을 나타내었다.70 g of [1,1 ';3', 1 ''] Terphenyl-4,5 ', 4''-triol of Synthesis Example 2, 120 ml of isopropyl alcohol, 236 ml of epichlorohydrin, and 78 ml of distilled water The mixture was dissolved with stirring in an oil bath at 65 ° C., 30 g of NaOH was prepared as a 45 wt% aqueous solution, added dropwise for 15 minutes, and reacted at the same temperature for 2 hours, followed by cooling at room temperature. The organic layer was separated, excess epichlorohydrin was removed by concentration under reduced pressure, and then volatile organics were removed by reducing the pressure in a vacuum oven at 100 ° C. for 3 hours. After the residue was dropwise added to 80 ml of toluene was taken out when hot, dissolved in 45 wt% NaOH 5 g with stirring at 70 ℃ oil bath for 5 min and 30 min and neutralized by adding an aqueous solution of 5% NaH 2 PO 4. The organic layer was sufficiently washed with distilled water to be neutral, the organic layer was separated and the moisture was removed with MgSO 4 , filtered over celite, and distilled under reduced pressure to evaporate the organic solvent. The residue was depressurized for 3 hours in a vacuum oven at 100 ° C. to remove volatile organics, thereby obtaining an epoxy resin compound as a target. mp 103 ° C. (see Differential Scanning Calorimetry, DSC in FIG. 1), epoxy equivalent 149, hydrolyzable chlorine 530 ppm.
1H NMR(CDCl3):δ2.78~2.80 (m, 3H), 2.92~2.95 (m, 3H),3.38~3.41(m, 3H), 3.98~4.04(m, 3H),4.26~4.31(m,3H), 6.99~7.06(m, 6H, Ar),7.54~7.57(m, 5H,Ar) 1 H NMR (CDCl 3 ): δ 2.78-2.80 (m, 3H), 2.92-2.95 (m, 3H), 3.38-3.41 (m, 3H), 3.98-4.04 (m, 3H), 4.26-4.31 ( m, 3H), 6.99-7.06 (m, 6H, Ar), 7.54-7.57 (m, 5H, Ar)
Mass Spectrum (EI) M+ 446 (100)
Mass Spectrum (EI) M + 446 (100)
실시예Example 1 : 에폭시 수지 1: epoxy resin 경화물의Cured product 제조 Produce
합성예 3에서 제조한 고상의 3 관능성 에폭시 수지(TPE) 1.49 g과 경화제인 페놀 노볼락(Phenol Novolac)수지 (제품명: KPH F2002) 1.07 g을 당량비에 맞춰 계량한 후 혼합하여 에틸아세테이트(Ethyl acetate) 3 ml를 넣어준 후 완전히 녹을 때까지 교반하였다. 에폭시 수지와 경화제가 완전히 녹았을 때 경화촉진제로서 벤질 디메틸아민(BDMA, benzyl dimethylamine)을 1.5 phr 넣고 15 분간 더 교반하여 샘플을 제조하였다. 테플론 시트에 혼합된 에폭시 혼합물을 부어 80 ℃의 진공오븐에서 용매를 완전히 제거한 후, 100 ℃의 건조오븐에서 10분 간 경화 후, 130 ℃에서 한 시간 경화를 진행한 후, 175 ℃에서 두 시간 후경화를 진행하여 에폭시 경화물을 얻었다. 상기 조성을 하기 표 1에 나타내었다.
1.49 g of solid-state trifunctional epoxy resin (TPE) prepared in Synthesis Example 3 and 1.07 g of a phenol novolak resin (product name: KPH F2002), which is a curing agent, were weighed to an equivalent ratio, mixed, and then ethyl acetate (Ethyl). acetate) 3 ml was added and stirred until completely dissolved. When the epoxy resin and the curing agent were completely dissolved, benzyl dimethylamine (BDMA) was added 1.5 phr as a curing accelerator, and the sample was further stirred for 15 minutes. Pour the epoxy mixture mixed on the Teflon sheet to completely remove the solvent in a vacuum oven at 80 ℃, then cure for 10 minutes in a dry oven at 100 ℃, proceeds for one hour at 130 ℃, after two hours at 175 ℃ Curing was advanced to obtain an epoxy cured product. The composition is shown in Table 1 below.
실시예Example 2 : 에폭시 수지 2: epoxy resin 경화물의Cured product 제조 Produce
상기와 실시예 1과 같은 방법으로 경화제를 페놀 노볼락(Phenol Novolac) 수지 대신 제품명 (Meiwa SS) 인 페놀-p-크실렌(phenol-p-xylene) 1.75 g을 사용하여 실시하였다. 상기 조성을 하기 표 1에 나타내었다.
Above and Example 1 In the same manner, the curing agent was carried out using 1.75 g of phenol-p-xylene, a product name (Meiwa SS), instead of the phenol novolac resin. The composition is shown in Table 1 below.
실시예Example 3 : 에폭시 수지 3: epoxy resin 경화물의Cured product 제조 Produce
상기와 실시예 1과 같은 방법으로 경화제를 페놀 노볼락(Phenol Novolac) 수지 대신 제품명 (Meiwa M) 인 페놀-비페닐렌(phenol-biphenylene) 2.10 g을 사용하여 실시하였다. 상기 조성을 하기 표 1에 나타내었다.
The curing agent was carried out in the same manner as in Example 1 and using 2.10 g of phenol-biphenylene, a product name (Meiwa M), instead of phenol novolac resin. The composition is shown in Table 1 below.
실시예Example 4 : 에폭시 수지 4: epoxy resin 경화물의Cured product 제조 Produce
합성예 3에서 제조한 고상의 3 관능성 에폭시 수지(TPE) 1.49 g과 경화제인 디아민(diamine)류 경화제인 4,4'-디아미노디페닐설폰(4,4'-diaminodiphenyl sulfone, 4,4'-DDS) 0.62 g을 당량비에 맞춰 계량한 후 혼합하여 에틸 아세테이트(Ethyl acetate) 3 ml를 넣어준 후 완전히 녹을 때까지 교반하였다. 에폭시와 경화제가 완전히 녹았을 때 경화촉진제(BDMA, benzyl dimethylamine)를 1.5phr 넣고 15분간 더 교반하여 샘플을 제조하였다. 테플론 시트에 혼합된 에폭시 혼합물을 부어 80 ℃ 진공오븐에서 용매를 완전히 제거하였다. 100 ℃의 건조오븐에서 10 분간 경화, 130 ℃에서 한 시간 경화를 진행한 후 175 ℃에서 두 시간 후경화를 진행하여 에폭시 경화물을 얻었다. 상기 조성을 하기 표 1에 나타내었다.
1.49 g of a solid trifunctional epoxy resin (TPE) prepared in Synthesis Example 3 and 4,4'-diaminodiphenyl sulfone (4,4'-diaminodiphenyl sulfone, 4,4) 0.62 g of '-DDS) was weighed according to the equivalent ratio, mixed, 3 ml of ethyl acetate was added, and the mixture was stirred until it was completely dissolved. When the epoxy and the curing agent were completely dissolved, 1.5 phr of a curing accelerator (BDMA, benzyl dimethylamine) was added thereto, followed by further stirring for 15 minutes to prepare a sample. The epoxy mixture mixed on the Teflon sheet was poured to completely remove the solvent in an 80 ° C. vacuum oven. After curing for 10 minutes in a drying oven at 100 ℃, curing for 1 hour at 130 ℃ and after curing for 2 hours at 175 ℃ to obtain an epoxy cured product. The composition is shown in Table 1 below.
실시예Example 5 : 에폭시 수지 5: epoxy resin 경화물의Cured product 제조 Produce
상기 실시예 4와 같은 방법으로 디아민(diamine)계 경화제로서 4,4'-디아미노디페닐 설폰(4,4'-diaminodiphenyl sulfone, 4,4'-DDS) 대신 2,3-디아미노톨루엔(2,3-diaminotoluene, 2,3-DT) 0.3 g을 사용하여 실시하였다. 상기 조성을 하기 표 1에 나타내었다.In the same manner as in Example 4, 2,3-diaminotoluene (4,4'-diaminodiphenyl sulfone, 4,4'-DDS) instead of 4,4'-diaminodiphenyl sulfone as a diamine-based curing agent ( 2,3-diaminotoluene, 2,3-DT) using 0.3 g. The composition is shown in Table 1 below.
실시예Example 6 : 에폭시 수지 6: epoxy resin 경화물의Cured product 제조 Produce
상기 실시예 4와 같은 방법으로 디아민(diamine)계 경화제로서 4,4'-디아미노디페닐 설폰(4,4'-diaminodiphenyl sulfone, 4,4'-DDS) 대신 4-클로로-1,2-페닐렌 디아민(4-chloro-1,2-phenylene diamine, 4-CoP) 0.36 g을 사용하여 실시하였다. 상기 조성을 하기 표 1에 나타내었다.
4-chloro-1,2- instead of 4,4'-diaminodiphenyl sulfone (4,4'-DDS) as a diamine curing agent in the same manner as in Example 4 0.36 g of phenylene diamine (4-chloro-1,2-phenylene diamine, 4-CoP) was used. The composition is shown in Table 1 below.
비교예Comparative example 1 : 에폭시 수지 1: epoxy resin 경화물의Cured product 제조 Produce
화학식 7의 o-크레졸 노볼락 에폭시 수지와 화학식 11의 페놀 노볼락 경화제를 이용하여 경화물을 얻었다. 상기 조성을 하기 표 1에 나타내었다.Hardened | cured material was obtained using the o-cresol novolak epoxy resin of Formula 7 and the phenol novolak hardener of Formula 11. The composition is shown in Table 1 below.
에폭시 수지o-cresol novolac
Epoxy resin
benzyl dimethylamineCuring accelerator (1.phr)
benzyl dimethylamine
o-크레졸 노볼락 에폭시 수지 : 에폭시 수지로서 에폭시 당량 196
phenol novolac : 화학식 6의 페놀수지로서 수산기 당량 106, 연화점 84℃
phenol-p-xylene : 화학식 7의 페놀수지로서 수산기 당량 203, 연화점 66℃
phenol biphenylene : 화학식 8의 페놀수지로서 수산기 당량 203, 연화점 66℃
4,4'-DDS: 화학식 9의 4,4'-diaminodiphenyl sulfone 으로서 아민기 당량 62
2,3-DT:화학식 10의 2,3-diaminotoluene로서 아민기 당량 30
4-CoP:화학식 11의 4-chloro-1,2-phenylene diamine로서 아민기 당량 35
당량비(OH/E) : 1Epoxy Resin: Epoxy Resin Epoxy Equivalent 149, Softening
o-cresol novolac epoxy resin: epoxy equivalent 196 as epoxy resin
phenol novolac: Phenolic resin of Chemical Formula 6, hydroxyl equivalent 106, softening point 84 ℃
phenol-p-xylene: Phenolic resin of Chemical Formula 7, hydroxyl equivalent 203, softening point 66 ℃
phenol biphenylene: Phenolic resin of Chemical Formula 8, hydroxyl equivalent 203, softening point 66 ℃
4,4'-DDS: Amines equivalent to 4,4'-diaminodiphenyl sulfone of Formula 9
2,3-DT: 2,3-diaminotoluene of Formula 10
4-CoP: Amino group equivalent 35 as 4-chloro-1,2-phenylene diamine of Formula 11
Equivalence ratio (OH / E): 1
실험예Experimental Example 1 : 에폭시 수지 조성물의 내열성 실험 1: Heat resistance test of epoxy resin composition
내열성은 TGA 를 사용하여 열적 특성으로 측정하였으며, 질소 분위기 하에서 10 ℃/min 승온 속도로 상온에서 800 ℃까지 측정하였고, 5 중량% 감소되었을 때의 온도를 얻어 평가하였다. 장비는 TA Instrument사의 Q500을 사용하였다. 본 발명의 상기 표 1에 나타낸 에폭시 수지 조성물의 TGA 를 사용하여 측정한 에폭시 경화물의 열분해 거동 결과를 도 2 및 3에 나타내었다. The heat resistance was measured by the thermal properties using TGA, measured at room temperature to 800 ℃ at a temperature rising rate of 10 ℃ / min in a nitrogen atmosphere, and was evaluated by obtaining a temperature when reduced by 5% by weight. The instrument used TA Instrument's Q500. The thermal decomposition behavior results of the epoxy cured product measured using TGA of the epoxy resin composition shown in Table 1 of the present invention are shown in FIGS. 2 and 3.
도 2 및 3은 질소 상태에서의 에폭시 수지 조성물의 에폭시 경화물의 열분해 거동을 나타내는 것으로, 400℃ 부근에서 급격한 질량감소가 시작되었으며, 800℃에서 챠르의 함량은 20-28 % 이었으며, 4,4'-DDS가 열안정성 및 잔여물 생성이 가장 우수함을 확인하였다.
2 and 3 show the thermal decomposition behavior of the epoxy cured product of the epoxy resin composition in the nitrogen state, the rapid mass reduction began around 400 ℃, the char content at 800 ℃ was 20-28%, 4,4 ' -DDS was found to have the best thermal stability and residue generation.
실험예Experimental Example 2 : 에폭시 수지 조성물의 난연성과 열적 특성평가 2: flame retardancy and thermal characteristic evaluation of epoxy resin composition
PCFC (Pyrolysis Combustion Flow Calorimeter)를 이용하여 에폭시 경화물의 인화성(Flammability)의 지표로 방열량(Heat Release Capacity)를 측정하였고, 방열량이 낮으면 수지의 인화성이 낮게 되어 난연성이 높게 되는 것을 예측할 수 있다. 1 회 측정 시 사용한 샘플의 양은 10 mg이었고, 각 샘플당 2 회씩 측정한 후 평균값을 나타내었고 결과를 하기 표 2에 정리하였다. Heat Release Capacity was measured as an index of the flammability of the cured epoxy by using the PCFC (Pyrolysis Combustion Flow Calorimeter). If the heat release amount is low, the flame retardancy of the resin is low and the flame retardancy is high. The amount of sample used for one measurement was 10 mg, the average value was measured after measuring twice each sample and the results are summarized in Table 2 below.
상기 표 2에 나타난 바와 같이, 본 발명에 의한 수지 조성물은 비교예 1에 사용된 o-크레졸 노볼락 에폭시 수지와 페놀 노볼락 수지와 비교하여 유사하거나 우수한 난연성을 나타내고 있음을 확인할 수 있다. As shown in Table 2, it can be seen that the resin composition according to the present invention exhibits similar or superior flame retardancy compared to the o-cresol novolac epoxy resin and phenol novolac resin used in Comparative Example 1.
따라서, 본 발명의 저융점의 에폭시 수지 화합물은 높은 내열성과 낮은 방열률(Heat Release Capacity)을 가짐으로서 우수한 난연성을 갖는다는 것을 알 수 있었다.Accordingly, it was found that the low melting point epoxy resin compound of the present invention has excellent flame resistance by having high heat resistance and low heat release capacity.
Claims (12)
[화학식 1]
상기 화학 식 1에서, R은 서로 독립적으로 C1-C12의 알킬 또는 페닐이며, p는 0 ~ 2의 정수 이며; n은 0 ~ 10의 정수이다.
[화학식 2]
상기 화학식 2에서, R은 서로 독립적으로 C1-C12의 알킬 또는 페닐이며, p는 0 ~ 2의 정수이다.
Epoxy resins represented by the following formula (1) characterized in that the compound represented by the formula (2) is epoxidized with an epihalohydrin compound.
[Formula 1]
In formula 1, R is independently of each other C 1 -C 12 alkyl or phenyl, p is an integer of 0 to 2; n is an integer of 0-10.
(2)
In Formula 2, R is independently of each other C 1 -C 12 alkyl or phenyl, p is an integer of 0 to 2.
[화학식 1]
상기 화학식 1에서, R 은 서로 독립적으로 C1-C12의 알킬 또는 페닐이며, p는 0 ~ 2의 정수이며; n은 0 ~ 10의 정수이다.
The novolak type epoxy resin, the biphenyl type epoxy resin, the bisphenol A type epoxy resin, the bisphenol F type epoxy resin, the bisphenol S type epoxy resin, the glycidyl amine type epoxy resin, and the glycidyl ester to the epoxy resin represented by General formula (1) Epoxy resin composition comprising a mixture and a curing agent of at least one epoxy resin selected from the group consisting of epoxy resins.
[Formula 1]
In Formula 1, R is independently of each other C 1 -C 12 Alkyl or phenyl, p is an integer of 0 to 2; n is an integer of 0-10.
[화학식 7]
[화학식 8]
[화학식 9]
[화학식 10]
The epoxy resin composition of claim 3, wherein the novolak-type epoxy resin is any one or more novolak-type epoxy resins selected from the group consisting of compounds represented by the following Chemical Formulas 7 to 10.
(7)
[Chemical Formula 8]
[Chemical Formula 9]
[Formula 10]
The epoxy resin composition of claim 3, wherein the curing agent is at least one curing agent selected from the group consisting of a phenolic curing agent, an amine curing agent, and an acid anhydride curing agent.
[화학식 11]
[화학식 12]
[화학식 13]
[화학식 14]
[화학식 15]
[화학식 16]
The phenol novolak resin, cresol novolak resin, biphenyl-containing phenyl novolak resin, phenol-p-xylene-based resin, phenyl biphenylene-based phenol resin according to claim 3 , An aliphatic polyamine, polyamide polyamine, epoxy resin, characterized in that at least one curing agent selected from the group consisting of aromatic polyamines represented by the following formulas (14) to (16), dicyanic diamide, hexahydrophthalic anhydride, methyl tetrahydrophthalic anhydride Composition.
(11)
[Chemical Formula 12]
[Chemical Formula 13]
[Chemical Formula 14]
[Chemical Formula 15]
[Chemical Formula 16]
The epoxy resin composition according to claim 3, further comprising a curing accelerator in the epoxy resin composition.
The epoxy resin composition of claim 8, wherein the curing accelerator is at least one curing accelerator selected from the group consisting of tertiary amines, imidazoles, organic phosphines, and tetraphenylborone salts.
The epoxy resin composition according to claim 3, further comprising an additive in the epoxy resin composition.
The epoxy resin composition of claim 10, wherein the additive is at least one selected from the group consisting of an inorganic filler, a mold releasing agent, and a coupling agent.
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