WO2015012467A1 - Compound containing phosphonium ion, epoxy resin composition containing same, and device manufactured by using same - Google Patents
Compound containing phosphonium ion, epoxy resin composition containing same, and device manufactured by using same Download PDFInfo
- Publication number
- WO2015012467A1 WO2015012467A1 PCT/KR2014/001628 KR2014001628W WO2015012467A1 WO 2015012467 A1 WO2015012467 A1 WO 2015012467A1 KR 2014001628 W KR2014001628 W KR 2014001628W WO 2015012467 A1 WO2015012467 A1 WO 2015012467A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- epoxy resin
- substituted
- unsubstituted
- resin composition
- group
- Prior art date
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- 239000003822 epoxy resin Substances 0.000 title claims abstract description 191
- 229920000647 polyepoxide Polymers 0.000 title claims abstract description 191
- 239000000203 mixture Substances 0.000 title claims abstract description 133
- 150000001875 compounds Chemical class 0.000 title claims abstract description 77
- -1 phosphonium ion Chemical class 0.000 title claims abstract description 45
- 125000004432 carbon atom Chemical group C* 0.000 claims description 46
- 239000005011 phenolic resin Substances 0.000 claims description 35
- 239000003795 chemical substances by application Substances 0.000 claims description 33
- 239000003054 catalyst Substances 0.000 claims description 32
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 17
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 claims description 16
- 125000003118 aryl group Chemical group 0.000 claims description 14
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims description 14
- 229910052739 hydrogen Inorganic materials 0.000 claims description 13
- 239000001257 hydrogen Substances 0.000 claims description 13
- 125000000217 alkyl group Chemical group 0.000 claims description 12
- 125000000008 (C1-C10) alkyl group Chemical group 0.000 claims description 11
- 229920003986 novolac Polymers 0.000 claims description 11
- 239000004065 semiconductor Substances 0.000 claims description 11
- 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 10
- 239000011256 inorganic filler Substances 0.000 claims description 10
- 229910003475 inorganic filler Inorganic materials 0.000 claims description 10
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 9
- 239000004305 biphenyl Substances 0.000 claims description 8
- 235000010290 biphenyl Nutrition 0.000 claims description 8
- 125000001072 heteroaryl group Chemical group 0.000 claims description 8
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 8
- 238000001721 transfer moulding Methods 0.000 claims description 8
- 125000006736 (C6-C20) aryl group Chemical group 0.000 claims description 7
- 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 7
- 229930003836 cresol Natural products 0.000 claims description 7
- 125000006376 (C3-C10) cycloalkyl group Chemical group 0.000 claims description 6
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 claims description 6
- 238000007789 sealing Methods 0.000 claims description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 5
- 125000003700 epoxy group Chemical group 0.000 claims description 5
- 229920001568 phenolic resin Polymers 0.000 claims description 5
- 229930185605 Bisphenol Natural products 0.000 claims description 4
- 229910052799 carbon Inorganic materials 0.000 claims description 4
- 125000000592 heterocycloalkyl group Chemical group 0.000 claims description 4
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 claims description 3
- LJBWJFWNFUKAGS-UHFFFAOYSA-N 2-[bis(2-hydroxyphenyl)methyl]phenol Chemical compound OC1=CC=CC=C1C(C=1C(=CC=CC=1)O)C1=CC=CC=C1O LJBWJFWNFUKAGS-UHFFFAOYSA-N 0.000 claims description 3
- JIGUICYYOYEXFS-UHFFFAOYSA-N 3-tert-butylbenzene-1,2-diol Chemical compound CC(C)(C)C1=CC=CC(O)=C1O JIGUICYYOYEXFS-UHFFFAOYSA-N 0.000 claims description 3
- 125000002723 alicyclic group Chemical group 0.000 claims description 3
- 239000004844 aliphatic epoxy resin Substances 0.000 claims description 3
- VCCBEIPGXKNHFW-UHFFFAOYSA-N biphenyl-4,4'-diol Chemical group C1=CC(O)=CC=C1C1=CC=C(O)C=C1 VCCBEIPGXKNHFW-UHFFFAOYSA-N 0.000 claims description 3
- IMHDGJOMLMDPJN-UHFFFAOYSA-N dihydroxybiphenyl Natural products OC1=CC=CC=C1C1=CC=CC=C1O IMHDGJOMLMDPJN-UHFFFAOYSA-N 0.000 claims description 3
- ZZTCPWRAHWXWCH-UHFFFAOYSA-N diphenylmethanediamine Chemical compound C=1C=CC=CC=1C(N)(N)C1=CC=CC=C1 ZZTCPWRAHWXWCH-UHFFFAOYSA-N 0.000 claims description 3
- 125000000623 heterocyclic group Chemical group 0.000 claims description 3
- 239000004843 novolac epoxy resin Substances 0.000 claims description 3
- 239000010680 novolac-type phenolic resin Substances 0.000 claims description 3
- 229920003987 resole Polymers 0.000 claims description 3
- 125000003003 spiro group Chemical group 0.000 claims description 3
- 150000003505 terpenes Chemical class 0.000 claims description 3
- 235000007586 terpenes Nutrition 0.000 claims description 3
- KJCVRFUGPWSIIH-UHFFFAOYSA-N 1-naphthol Chemical compound C1=CC=C2C(O)=CC=CC2=C1 KJCVRFUGPWSIIH-UHFFFAOYSA-N 0.000 claims description 2
- ORLQHILJRHBSAY-UHFFFAOYSA-N [1-(hydroxymethyl)cyclohexyl]methanol Chemical compound OCC1(CO)CCCCC1 ORLQHILJRHBSAY-UHFFFAOYSA-N 0.000 claims description 2
- 150000008065 acid anhydrides Chemical class 0.000 claims description 2
- AFEQENGXSMURHA-UHFFFAOYSA-N oxiran-2-ylmethanamine Chemical compound NCC1CO1 AFEQENGXSMURHA-UHFFFAOYSA-N 0.000 claims description 2
- FTDXCHCAMNRNNY-UHFFFAOYSA-N phenol Chemical compound OC1=CC=CC=C1.OC1=CC=CC=C1 FTDXCHCAMNRNNY-UHFFFAOYSA-N 0.000 claims description 2
- 239000004848 polyfunctional curative Substances 0.000 claims description 2
- 239000000126 substance Substances 0.000 abstract description 12
- 238000001723 curing Methods 0.000 description 100
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 72
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 27
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 25
- 238000003860 storage Methods 0.000 description 18
- 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 18
- 238000006243 chemical reaction Methods 0.000 description 17
- 239000007787 solid Substances 0.000 description 17
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 12
- 230000000694 effects Effects 0.000 description 12
- 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 11
- 239000002244 precipitate Substances 0.000 description 10
- 239000000377 silicon dioxide Substances 0.000 description 10
- 239000007788 liquid Substances 0.000 description 9
- 239000000463 material Substances 0.000 description 9
- XYFCBTPGUUZFHI-UHFFFAOYSA-O phosphonium Chemical compound [PH4+] XYFCBTPGUUZFHI-UHFFFAOYSA-O 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 8
- 238000004895 liquid chromatography mass spectrometry Methods 0.000 description 8
- 150000003839 salts Chemical group 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- 239000002245 particle Substances 0.000 description 7
- 238000010521 absorption reaction Methods 0.000 description 6
- 239000000654 additive Substances 0.000 description 6
- 150000001450 anions Chemical class 0.000 description 6
- 239000007822 coupling agent Substances 0.000 description 6
- 230000007423 decrease Effects 0.000 description 6
- 238000005259 measurement Methods 0.000 description 6
- 229920005989 resin Polymers 0.000 description 6
- 239000011347 resin Substances 0.000 description 6
- 239000011342 resin composition Substances 0.000 description 6
- 229920002545 silicone oil Polymers 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 5
- 239000002313 adhesive film Substances 0.000 description 5
- 239000003960 organic solvent Substances 0.000 description 5
- 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 5
- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical compound O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 description 4
- GQHTUMJGOHRCHB-UHFFFAOYSA-N 2,3,4,6,7,8,9,10-octahydropyrimido[1,2-a]azepine Chemical compound C1CCCCN2CCCN=C21 GQHTUMJGOHRCHB-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 4
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Natural products P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 4
- 230000000996 additive effect Effects 0.000 description 4
- 229910052802 copper Inorganic materials 0.000 description 4
- 239000010949 copper Substances 0.000 description 4
- 235000014113 dietary fatty acids Nutrition 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
- 238000001704 evaporation Methods 0.000 description 4
- 239000000194 fatty acid Substances 0.000 description 4
- 229930195729 fatty acid Natural products 0.000 description 4
- 150000004665 fatty acids Chemical class 0.000 description 4
- 230000009477 glass transition Effects 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 238000000465 moulding Methods 0.000 description 4
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 239000003086 colorant Substances 0.000 description 3
- 238000005336 cracking Methods 0.000 description 3
- 230000003111 delayed effect Effects 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 125000000524 functional group Chemical group 0.000 description 3
- 229910052736 halogen Inorganic materials 0.000 description 3
- 150000002367 halogens Chemical class 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 238000013035 low temperature curing Methods 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 150000002924 oxiranes Chemical group 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- 238000007142 ring opening reaction Methods 0.000 description 3
- 238000012546 transfer Methods 0.000 description 3
- 229940005561 1,4-benzoquinone Drugs 0.000 description 2
- SGUVLZREKBPKCE-UHFFFAOYSA-N 1,5-diazabicyclo[4.3.0]-non-5-ene Chemical compound C1CCN=C2CCCN21 SGUVLZREKBPKCE-UHFFFAOYSA-N 0.000 description 2
- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical compound C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-N 0.000 description 2
- DEPDDPLQZYCHOH-UHFFFAOYSA-N 1h-imidazol-2-amine Chemical compound NC1=NC=CN1 DEPDDPLQZYCHOH-UHFFFAOYSA-N 0.000 description 2
- UUEWCQRISZBELL-UHFFFAOYSA-N 3-trimethoxysilylpropane-1-thiol Chemical compound CO[Si](OC)(OC)CCCS UUEWCQRISZBELL-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- 0 Cc1ccc(**)cc1 Chemical compound Cc1ccc(**)cc1 0.000 description 2
- 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 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 150000001340 alkali metals Chemical class 0.000 description 2
- 150000001350 alkyl halides Chemical class 0.000 description 2
- 125000003277 amino group Chemical group 0.000 description 2
- 150000004982 aromatic amines Chemical class 0.000 description 2
- 150000001502 aryl halides Chemical class 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 238000005452 bending Methods 0.000 description 2
- 150000001639 boron compounds Chemical class 0.000 description 2
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 description 2
- 239000006229 carbon black Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 229910002026 crystalline silica Inorganic materials 0.000 description 2
- 150000002460 imidazoles Chemical class 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 2
- PAVKBQLPQCDVNI-UHFFFAOYSA-N n',n'-diethyl-n-(9-methoxy-5,11-dimethyl-6h-pyrido[4,3-b]carbazol-1-yl)propane-1,3-diamine Chemical compound N1C2=CC=C(OC)C=C2C2=C1C(C)=C1C=CN=C(NCCCN(CC)CC)C1=C2C PAVKBQLPQCDVNI-UHFFFAOYSA-N 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 150000002902 organometallic compounds Chemical class 0.000 description 2
- 150000002903 organophosphorus compounds Chemical class 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 150000002989 phenols Chemical class 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 230000001737 promoting effect Effects 0.000 description 2
- 230000003014 reinforcing effect Effects 0.000 description 2
- 238000000682 scanning probe acoustic microscopy Methods 0.000 description 2
- 235000012239 silicon dioxide Nutrition 0.000 description 2
- 229910000679 solder Inorganic materials 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- IHCDKJZZFOUARO-UHFFFAOYSA-M sulfacetamide sodium Chemical compound O.[Na+].CC(=O)[N-]S(=O)(=O)C1=CC=C(N)C=C1 IHCDKJZZFOUARO-UHFFFAOYSA-M 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- 239000013589 supplement Substances 0.000 description 2
- 150000003512 tertiary amines Chemical class 0.000 description 2
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 description 2
- IANQTJSKSUMEQM-UHFFFAOYSA-N 1-benzofuran Chemical group C1=CC=C2OC=CC2=C1 IANQTJSKSUMEQM-UHFFFAOYSA-N 0.000 description 1
- FCEHBMOGCRZNNI-UHFFFAOYSA-N 1-benzothiophene Chemical group C1=CC=C2SC=CC2=C1 FCEHBMOGCRZNNI-UHFFFAOYSA-N 0.000 description 1
- BDHGFCVQWMDIQX-UHFFFAOYSA-N 1-ethenyl-2-methylimidazole Chemical compound CC1=NC=CN1C=C BDHGFCVQWMDIQX-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
- XUZIWKKCMYHORT-UHFFFAOYSA-N 2,4,6-tris(diaminomethyl)phenol Chemical compound NC(N)C1=CC(C(N)N)=C(O)C(C(N)N)=C1 XUZIWKKCMYHORT-UHFFFAOYSA-N 0.000 description 1
- OAYXUHPQHDHDDZ-UHFFFAOYSA-N 2-(2-butoxyethoxy)ethanol Chemical compound CCCCOCCOCCO OAYXUHPQHDHDDZ-UHFFFAOYSA-N 0.000 description 1
- BFSVOASYOCHEOV-UHFFFAOYSA-N 2-diethylaminoethanol Chemical compound CCN(CC)CCO BFSVOASYOCHEOV-UHFFFAOYSA-N 0.000 description 1
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 1
- YTWBFUCJVWKCCK-UHFFFAOYSA-N 2-heptadecyl-1h-imidazole Chemical compound CCCCCCCCCCCCCCCCCC1=NC=CN1 YTWBFUCJVWKCCK-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
- 125000003504 2-oxazolinyl group Chemical group O1C(=NCC1)* 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
- BCHZICNRHXRCHY-UHFFFAOYSA-N 2h-oxazine Chemical group N1OC=CC=C1 BCHZICNRHXRCHY-UHFFFAOYSA-N 0.000 description 1
- GZFGOTFRPZRKDS-UHFFFAOYSA-N 4-bromophenol Chemical compound OC1=CC=C(Br)C=C1 GZFGOTFRPZRKDS-UHFFFAOYSA-N 0.000 description 1
- VOLRSQPSJGXRNJ-UHFFFAOYSA-N 4-nitrobenzyl bromide Chemical compound [O-][N+](=O)C1=CC=C(CBr)C=C1 VOLRSQPSJGXRNJ-UHFFFAOYSA-N 0.000 description 1
- ULKLGIFJWFIQFF-UHFFFAOYSA-N 5K8XI641G3 Chemical compound CCC1=NC=C(C)N1 ULKLGIFJWFIQFF-UHFFFAOYSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 1
- 125000000041 C6-C10 aryl group Chemical group 0.000 description 1
- RZTDESRVPFKCBH-UHFFFAOYSA-N Cc(cc1)ccc1-c1ccc(C)cc1 Chemical compound Cc(cc1)ccc1-c1ccc(C)cc1 RZTDESRVPFKCBH-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 229920000742 Cotton Polymers 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 239000004594 Masterbatch (MB) Substances 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical group N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- FZWLAAWBMGSTSO-UHFFFAOYSA-N Thiazole Chemical group C1=CSC=N1 FZWLAAWBMGSTSO-UHFFFAOYSA-N 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- JCUWIFNLGQZZRA-UHFFFAOYSA-N [Ag].Cc1cnc(NS(=O)(=O)c2ccc(N)cc2)nc1 Chemical compound [Ag].Cc1cnc(NS(=O)(=O)c2ccc(N)cc2)nc1 JCUWIFNLGQZZRA-UHFFFAOYSA-N 0.000 description 1
- UVTGXFAWNQTDBG-UHFFFAOYSA-N [Fe].[Pb] Chemical compound [Fe].[Pb] UVTGXFAWNQTDBG-UHFFFAOYSA-N 0.000 description 1
- QRKLHFLNBRHKGG-UHFFFAOYSA-N [Na].CCCNS(=O)(=O)c1ccc(C)cc1 Chemical compound [Na].CCCNS(=O)(=O)c1ccc(C)cc1 QRKLHFLNBRHKGG-UHFFFAOYSA-N 0.000 description 1
- 150000001242 acetic acid derivatives Chemical class 0.000 description 1
- 125000002777 acetyl group Chemical group [H]C([H])([H])C(*)=O 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 239000004840 adhesive resin Substances 0.000 description 1
- 229920006223 adhesive resin Polymers 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
- 150000001408 amides Chemical class 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- 229910000410 antimony oxide Inorganic materials 0.000 description 1
- 229920006231 aramid fiber Polymers 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 125000002785 azepinyl group Chemical group 0.000 description 1
- WZJYKHNJTSNBHV-UHFFFAOYSA-N benzo[h]quinoline Chemical group C1=CN=C2C3=CC=CC=C3C=CC2=C1 WZJYKHNJTSNBHV-UHFFFAOYSA-N 0.000 description 1
- 125000003236 benzoyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C(*)=O 0.000 description 1
- AGEZXYOZHKGVCM-UHFFFAOYSA-N benzyl bromide Chemical compound BrCC1=CC=CC=C1 AGEZXYOZHKGVCM-UHFFFAOYSA-N 0.000 description 1
- 239000004841 bisphenol A epoxy resin Substances 0.000 description 1
- 239000004842 bisphenol F epoxy resin Substances 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 229910052792 caesium Inorganic materials 0.000 description 1
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 239000000378 calcium silicate Substances 0.000 description 1
- 229910052918 calcium silicate Inorganic materials 0.000 description 1
- OYACROKNLOSFPA-UHFFFAOYSA-N calcium;dioxido(oxo)silane Chemical compound [Ca+2].[O-][Si]([O-])=O OYACROKNLOSFPA-UHFFFAOYSA-N 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000004203 carnauba wax Substances 0.000 description 1
- 235000013869 carnauba wax Nutrition 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- XEHUIDSUOAGHBW-UHFFFAOYSA-N chromium;pentane-2,4-dione Chemical compound [Cr].CC(=O)CC(C)=O.CC(=O)CC(C)=O.CC(=O)CC(C)=O XEHUIDSUOAGHBW-UHFFFAOYSA-N 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 229910052570 clay Inorganic materials 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 239000004035 construction material Substances 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 125000000753 cycloalkyl group Chemical group 0.000 description 1
- RGBIPJJZHWFFGE-UHFFFAOYSA-N cyclohexa-2,5-diene-1,4-dione;triphenylphosphane Chemical compound O=C1C=CC(=O)C=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RGBIPJJZHWFFGE-UHFFFAOYSA-N 0.000 description 1
- VEIOBOXBGYWJIT-UHFFFAOYSA-N cyclohexane;methanol Chemical compound OC.OC.C1CCCCC1 VEIOBOXBGYWJIT-UHFFFAOYSA-N 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 230000001066 destructive effect Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 125000005331 diazinyl group Chemical group N1=NC(=CC=C1)* 0.000 description 1
- LVTCZSBUROAWTE-UHFFFAOYSA-N diethyl(phenyl)phosphane Chemical compound CCP(CC)C1=CC=CC=C1 LVTCZSBUROAWTE-UHFFFAOYSA-N 0.000 description 1
- HASCQPSFPAKVEK-UHFFFAOYSA-N dimethyl(phenyl)phosphine Chemical compound CP(C)C1=CC=CC=C1 HASCQPSFPAKVEK-UHFFFAOYSA-N 0.000 description 1
- XXBDWLFCJWSEKW-UHFFFAOYSA-N dimethylbenzylamine Chemical compound CN(C)CC1=CC=CC=C1 XXBDWLFCJWSEKW-UHFFFAOYSA-N 0.000 description 1
- LLZAIAIZAVMQIG-UHFFFAOYSA-N diphenyl(propan-2-yl)phosphane Chemical compound C=1C=CC=CC=1P(C(C)C)C1=CC=CC=C1 LLZAIAIZAVMQIG-UHFFFAOYSA-N 0.000 description 1
- AAXGWYDSLJUQLN-UHFFFAOYSA-N diphenyl(propyl)phosphane Chemical compound C=1C=CC=CC=1P(CCC)C1=CC=CC=C1 AAXGWYDSLJUQLN-UHFFFAOYSA-N 0.000 description 1
- 239000002305 electric material Substances 0.000 description 1
- 239000012776 electronic material Substances 0.000 description 1
- 239000003623 enhancer Substances 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- JDVIRCVIXCMTPU-UHFFFAOYSA-N ethanamine;trifluoroborane Chemical compound CCN.FB(F)F JDVIRCVIXCMTPU-UHFFFAOYSA-N 0.000 description 1
- WUOIAOOSKMHJOV-UHFFFAOYSA-N ethyl(diphenyl)phosphane Chemical compound C=1C=CC=CC=1P(CC)C1=CC=CC=C1 WUOIAOOSKMHJOV-UHFFFAOYSA-N 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229910052730 francium Inorganic materials 0.000 description 1
- KLMCZVJOEAUDNE-UHFFFAOYSA-N francium atom Chemical compound [Fr] KLMCZVJOEAUDNE-UHFFFAOYSA-N 0.000 description 1
- 125000002541 furyl group Chemical group 0.000 description 1
- 239000005350 fused silica glass Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 239000004845 glycidylamine epoxy resin Substances 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 125000004404 heteroalkyl group Chemical group 0.000 description 1
- 125000005549 heteroarylene group Chemical group 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 125000006588 heterocycloalkylene group Chemical group 0.000 description 1
- AVGTYNJIWPQPIH-UHFFFAOYSA-N hexan-1-amine;trifluoroborane Chemical compound FB(F)F.CCCCCCN AVGTYNJIWPQPIH-UHFFFAOYSA-N 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 1
- 125000001041 indolyl group Chemical group 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 125000000842 isoxazolyl group Chemical group 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 239000004850 liquid epoxy resins (LERs) Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 1
- 239000001095 magnesium carbonate Substances 0.000 description 1
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- UJNZOIKQAUQOCN-UHFFFAOYSA-N methyl(diphenyl)phosphane Chemical compound C=1C=CC=CC=1P(C)C1=CC=CC=C1 UJNZOIKQAUQOCN-UHFFFAOYSA-N 0.000 description 1
- 125000000250 methylamino group Chemical group [H]N(*)C([H])([H])[H] 0.000 description 1
- BFXIKLCIZHOAAZ-UHFFFAOYSA-N methyltrimethoxysilane Chemical compound CO[Si](C)(OC)OC BFXIKLCIZHOAAZ-UHFFFAOYSA-N 0.000 description 1
- YMSBXUULUGGCMJ-UHFFFAOYSA-N n-(4-aminophenyl)sulfonylbenzamide;sodium Chemical compound [Na].C1=CC(N)=CC=C1S(=O)(=O)NC(=O)C1=CC=CC=C1 YMSBXUULUGGCMJ-UHFFFAOYSA-N 0.000 description 1
- VSWALKINGSNVAR-UHFFFAOYSA-N naphthalen-1-ol;phenol Chemical compound OC1=CC=CC=C1.C1=CC=C2C(O)=CC=CC2=C1 VSWALKINGSNVAR-UHFFFAOYSA-N 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- BMGNSKKZFQMGDH-FDGPNNRMSA-L nickel(2+);(z)-4-oxopent-2-en-2-olate Chemical compound [Ni+2].C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O BMGNSKKZFQMGDH-FDGPNNRMSA-L 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- VTRUBDSFZJNXHI-UHFFFAOYSA-N oxoantimony Chemical compound [Sb]=O VTRUBDSFZJNXHI-UHFFFAOYSA-N 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 150000003003 phosphines Chemical class 0.000 description 1
- 125000004437 phosphorous atom Chemical group 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 238000011417 postcuring Methods 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 125000000561 purinyl group Chemical group N1=C(N=C2N=CNC2=C1)* 0.000 description 1
- 125000004309 pyranyl group Chemical group O1C(C=CC=C1)* 0.000 description 1
- 125000003373 pyrazinyl group Chemical group 0.000 description 1
- 125000003226 pyrazolyl group Chemical group 0.000 description 1
- 125000002098 pyridazinyl group Chemical group 0.000 description 1
- 125000004076 pyridyl group Chemical group 0.000 description 1
- VTGOHKSTWXHQJK-UHFFFAOYSA-N pyrimidin-2-ol Chemical group OC1=NC=CC=N1 VTGOHKSTWXHQJK-UHFFFAOYSA-N 0.000 description 1
- 125000000714 pyrimidinyl group Chemical group 0.000 description 1
- 125000001422 pyrrolinyl group Chemical group 0.000 description 1
- 125000002943 quinolinyl group Chemical group N1=C(C=CC2=CC=CC=C12)* 0.000 description 1
- 125000001567 quinoxalinyl group Chemical group N1=C(C=NC2=CC=CC=C12)* 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 229910052701 rubidium Inorganic materials 0.000 description 1
- IGLNJRXAVVLDKE-UHFFFAOYSA-N rubidium atom Chemical compound [Rb] IGLNJRXAVVLDKE-UHFFFAOYSA-N 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- FZHAPNGMFPVSLP-UHFFFAOYSA-N silanamine Chemical compound [SiH3]N FZHAPNGMFPVSLP-UHFFFAOYSA-N 0.000 description 1
- 239000011863 silicon-based powder Substances 0.000 description 1
- 229920005573 silicon-containing polymer Polymers 0.000 description 1
- 229920002050 silicone resin Polymers 0.000 description 1
- 229920002379 silicone rubber Polymers 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 125000000547 substituted alkyl group Chemical group 0.000 description 1
- TXDNPSYEJHXKMK-UHFFFAOYSA-N sulfanylsilane Chemical compound S[SiH3] TXDNPSYEJHXKMK-UHFFFAOYSA-N 0.000 description 1
- 229940124530 sulfonamide Drugs 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 125000004853 tetrahydropyridinyl group Chemical group N1(CCCC=C1)* 0.000 description 1
- 230000000930 thermomechanical effect Effects 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 150000008334 thiadiazines Chemical group 0.000 description 1
- 125000001544 thienyl group Chemical group 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 125000004306 triazinyl group Chemical group 0.000 description 1
- QLAGHGSFXJZWKY-UHFFFAOYSA-N triphenylborane;triphenylphosphane Chemical compound C1=CC=CC=C1B(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 QLAGHGSFXJZWKY-UHFFFAOYSA-N 0.000 description 1
- JABYJIQOLGWMQW-UHFFFAOYSA-N undec-4-ene Chemical compound CCCCCCC=CCCC JABYJIQOLGWMQW-UHFFFAOYSA-N 0.000 description 1
- 239000001993 wax Substances 0.000 description 1
- NHXVNEDMKGDNPR-UHFFFAOYSA-N zinc;pentane-2,4-dione Chemical compound [Zn+2].CC(=O)[CH-]C(C)=O.CC(=O)[CH-]C(C)=O NHXVNEDMKGDNPR-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/54—Quaternary phosphonium compounds
- C07F9/5456—Arylalkanephosphonium compounds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C311/00—Amides of sulfonic acids, i.e. compounds having singly-bound oxygen atoms of sulfo groups replaced by nitrogen atoms, not being part of nitro or nitroso groups
- C07C311/15—Sulfonamides having sulfur atoms of sulfonamide groups bound to carbon atoms of six-membered aromatic rings
- C07C311/16—Sulfonamides having sulfur atoms of sulfonamide groups bound to carbon atoms of six-membered aromatic rings having the nitrogen atom of at least one of the sulfonamide groups bound to hydrogen atoms or to an acyclic carbon atom
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C311/00—Amides of sulfonic acids, i.e. compounds having singly-bound oxygen atoms of sulfo groups replaced by nitrogen atoms, not being part of nitro or nitroso groups
- C07C311/50—Compounds containing any of the groups, X being a hetero atom, Y being any atom
- C07C311/51—Y being a hydrogen or a carbon atom
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D239/00—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings
- C07D239/02—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings
- C07D239/24—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members
- C07D239/28—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, directly attached to ring carbon atoms
- C07D239/32—One oxygen, sulfur or nitrogen atom
- C07D239/42—One nitrogen atom
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/54—Quaternary phosphonium compounds
- C07F9/5442—Aromatic phosphonium compounds (P-C aromatic linkage)
-
- 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
- C08G59/68—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 catalysts used
- C08G59/688—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 catalysts used containing phosphorus
Definitions
- the present invention relates to a phosphonium ion-containing compound, an epoxy resin composition comprising the same, and a device manufactured using the same.
- Epoxy resin is a material with low reaction shrinkage, excellent electrical and mechanical properties, and excellent workability and chemical resistance. It is used for matrix and coating of electric, electronic, construction, and composite materials.
- epoxy resins are used for sealing semiconductor devices, adhesive films, insulating resin sheets such as prepreg, circuit boards, solder resists, underfill agents, die bonding materials, component supplement resins, and the like.
- Epoxy resins are mixed with a curing agent rather than used alone, and then used after curing with a thermosetting material. At this time, since the performance of the epoxy resin depends on the three-dimensional structure generated after curing, the selection of the curing agent is important. Although many curing agents for epoxy resins have been developed, a curing catalyst is used together to catalyze the curing reaction. In the apparatus in which the epoxy resin composition is used, the curing is catalyzed only when the desired curing temperature is achieved for the purpose of improving the productivity at low temperature for the purpose of improving productivity, and for the handling property at the time of logistics storage. If not, a curing catalyst having high storage stability without curing catalyst activity is desired.
- the curing catalyst an adduct of triphenylphosphine and 1,4-benzoquinone, exhibits a hardening effect even at a relatively low temperature.
- the curing of the epoxy resin composition can be partially progressed by the heat added from the mixture, and the storage stability is lowered by promoting the curing even when the epoxy resin composition is stored at room temperature after mixing each component of the resin composition.
- the progress of the curing reaction may result in an increase in viscosity and a decrease in fluidity when the epoxy resin composition is a liquid, and may exhibit viscosity when the epoxy resin composition is a solid, and such a change in state may be uniform in the epoxy resin composition. Does not appear Therefore, when the epoxy resin composition is actually cured at a high temperature, the moldability decreases due to fluidity decrease, and the mechanical, electrical and chemical properties of the molded product may decrease.
- Another object of the present invention is to provide a compound for a curing catalyst that can catalyze the curing of epoxy resin even at low temperatures.
- the phosphonium ion containing compound of the present invention may be represented by the following Chemical Formula 1:
- R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 are as defined in the following detailed description).
- the epoxy resin composition of the present invention may include an epoxy resin, a curing agent, and a curing catalyst, and the curing catalyst may include the phosphonium ion-containing compound.
- the device of the present invention can be manufactured using the epoxy resin composition.
- the present invention provides a compound for a curing catalyst capable of catalyzing the curing of epoxy resins and promoting the curing of epoxy resins even at low temperatures.
- the present invention provides a compound for a curing catalyst having a high storage stability that catalyzes curing only when the desired curing temperature is reached, and when the curing temperature is not the desired curing temperature, the curing catalyst is not active.
- the present invention in the mixture containing the epoxy resin, the curing agent, etc.
- the phosphonium ion-containing compound of one embodiment of the present invention includes a phosphonium cation and a sulfonamide anion, and may be represented by, for example, the following Formula 1:
- R 1 , R 2 , R 3 , R 4 are each independently hydrogen, substituted or unsubstituted C 1-10 alkyl group, substituted or unsubstituted C 3-10 cycloalkyl group, substituted Or an unsubstituted aryl group having 6 to 20 carbon atoms, or a substituted or unsubstituted arylalkyl group having 7 to 21 carbon atoms,
- R 5 is hydrogen, a substituted or unsubstituted C1-C10 alkyl group, a substituted or unsubstituted C6-C20 aryl group, a substituted or unsubstituted C3-C20 cycloalkyl group, a substituted or unsubstituted C2 To 20 heterocycloalkyl group, substituted or unsubstituted arylalkyl group having 7 to 20 carbon atoms, substituted or unsubstituted heteroaryl group having 3 to 20 carbon atoms, or formula (2).
- R 11 is a substituted or unsubstituted C1-C10 alkyl group, a substituted or unsubstituted C6-C20 aryl group, a substituted or unsubstituted C3-C10 cycloalkyl group, or a substituted or unsubstituted C7-C10 Arylalkyl group of 20)
- R 6 , R 7 , R 8 , R 9 and R 10 are each independently hydrogen, a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, substituted or unsubstituted An arylalkyl group having 7 to 21 carbon atoms, or -NR'R "(wherein R 'and R" are hydrogen, an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 20 carbon atoms, and an arylalkyl group having 7 to 21 carbon atoms). )to be).
- substituted in “substituted or unsubstituted” is one or more hydrogen atoms of the functional group is a hydroxyl group, amino group, nitro group, halogen, unsubstituted C1-10 alkyl group, C6-C20 aryl group, carbon number It means substituted with a cycloalkyl group having 3 to 10, an arylalkyl group having 7 to 21 carbon atoms, and a heteroalkyl group having 1 to 10 carbon atoms.
- aryl group refers to a substituent in which all elements of a cyclic substituent have p-orbitals and p-orbitals form a conjugate, and are mono or fused (ie, rings in which carbon atoms divide adjacent pairs). It includes.
- heteroaryl group means that 1 to 3 atoms selected from the group consisting of nitrogen, oxygen, sulfur and phosphorus in the aryl group and the rest is carbon.
- 'hetero' in the 'heterocycloalkyl group', 'heteroaryl group', 'heterocycloalkylene group', and 'heteroarylene group' means a nitrogen, oxygen, sulfur or phosphorus atom.
- R 1 , R 2 , R 3 , and R 4 are substituted or unsubstituted aryl groups having 6 to 10 carbon atoms, or substituted or unsubstituted arylalkyl groups having 7 to 12 carbon atoms
- R 5 is substituted or unsubstituted A substituted alkyl group having 1 to 5 carbon atoms, a substituted or unsubstituted heteroaryl group having 3 to 20 carbon atoms, or Formula 2 above
- R 8 is —NH 2 , —NHR ′, or a substituted or unsubstituted carbon group having 1 to 5 carbon atoms
- It is an alkyl group of, and R ⁇ 6> , R ⁇ 7> , R ⁇ 9> , R ⁇ 10> is respectively independently hydrogen, a C1-C10 alkyl group, or a C6-C10 aryl group.
- R 5 is a substituted or unsubstituted alkyl group having 1 to 4 carbon atoms, a substituted or unsubstituted heteroaryl group having 3 to 20 carbon atoms, for example, a pyrazinyl group, a pyrimidinyl group, a pyridazinyl group, and the like.
- the phosphonium ion-containing compound may have a glass transition temperature of about 100 to 130 ° C., for example, about 120 to 125 ° C., and the phosphonium ion-containing compound may have a curing start temperature of about 90 ° C. by a differential scanning calorimeter (DSC). 120 °C, the curing peak temperature may be about 120 to 180 °C. In the above range, there may be the effect of low temperature curing.
- the curing start temperature means the temperature at which the exothermic polymerization reaction starts when the epoxy resin composition containing the phosphonium ion-containing compound is heated at a constant heating rate, and the curing peak temperature is the maximum exothermic peak when reacting under the above conditions. Means temperature.
- the phosphonium ion containing compound may be a water insoluble compound or a water soluble compound in salt form.
- Phosphonium ion containing compounds can be used as latent curing catalysts for compositions comprising at least one of an epoxy resin and a curing agent. That is, the phosphonium ion-containing compound is decomposed into a phosphine compound and a compound of an anion and a cation at about 90 to 175 ° C. when subjected to external energy such as heat.
- the resulting phosphine compound reacts with the epoxide group in the epoxy resin to undergo a ring-opening reaction.
- the ring opening reaction of the epoxide group is carried out by reaction with a hydroxyl group in the epoxy resin, and the chain terminal of the activated epoxy resin and the epoxide The reaction is catalyzed by the curing reaction.
- the phosphonium ion-containing compound catalyzes the curing reaction of the epoxy resin and the curing agent, and has high low temperature curing property and storage stability, and minimizes the viscosity change even in a range of time and temperature conditions in the mixture containing the epoxy resin and the curing agent.
- the "storage stability" is an activity that catalyzes curing only when the desired curing temperature is reached and there is no curing catalyst activity when the desired curing temperature is not achieved, so that the epoxy resin composition can be stored for a long time without changing the viscosity.
- the progress of the curing reaction may lead to an increase in viscosity and a decrease in fluidity when the epoxy resin composition is a liquid, and may exhibit viscosity when the epoxy resin composition is a solid.
- the epoxy resin has two or more epoxy groups in the molecule, bisphenol-type epoxy resins such as bisphenol A-type epoxy resin, bisphenol F-type epoxy resin, phenol novolak-type epoxy resin, tert- butyl catechol type epoxy Resin, naphthalene type epoxy resin, glycidylamine type epoxy resin, phenol aralkyl type epoxy resin, cresol novolak type epoxy resin, biphenyl type epoxy resin, linear aliphatic epoxy resin, alicyclic epoxy resin, heterocyclic epoxy resin, spiro Ring-containing epoxy resins, cyclohexanedimethanol type epoxy resins, halogenated epoxy resins, and the like, and these may be included alone or in combination of two or more thereof.
- the epoxy resin may be an epoxy resin having two or more epoxy groups and one or more hydroxyl groups in the molecule.
- the epoxy resin may include at least one of a solid epoxy resin, a liquid epoxy resin, and preferably a solid epoxy resin.
- the curing agent is a phenol aralkyl type phenol resin, phenol novolak type phenol resin, xylox phenol resin, cresol novolak type phenol resin, naphthol type phenol resin, terpene type phenol resin, polyfunctional phenol resin, dicyclo Pentadiene-based phenolic resins, novolac-type phenolic resins synthesized from bisphenol A and resol, polyhydric phenol compounds including tris (hydroxyphenyl) methane, dihydroxybiphenyl, acidic anhydrides including maleic anhydride and phthalic anhydride, Aromatic amines, such as meta-phenylenediamine, diaminodiphenylmethane, and diaminodiphenyl sulfone, etc. are mentioned.
- the curing agent may be a phenol resin having one or more hydroxyl groups.
- the phosphonium ion-containing compound may be included in about 0.01 to 10% by weight, for example about 0.01 to 5% by weight, for example about 0.02 to 1.5% by weight, for example about 0.05 to 1.5% by weight, in the epoxy resin composition. . In the above range, the curing reaction time is not delayed, and the fluidity of the composition can be ensured.
- Phosphonium ion-containing compounds can be prepared by conventional methods. For example, it may be prepared by reacting a phosphonium cation-containing compound of Formula 3 with an anion-containing compound of Formula 4:
- R 5 , R 6 , R 7 , R 8 , R 9 , R 10 are the same as defined in Formula 1, M is an alkali metal or Ag)
- Halogen is fluorine, chlorine, bromine or iodine and the alkali metal is lithium, sodium, potassium, rubidium, cesium or francium and the like.
- the phosphonium cation containing compound may be prepared by combining a phosphine compound with an alkyl halide, aryl halide, aralkyl halide, or the like under a solvent, or may be a phosphonium cation containing salt.
- the phosphine compound may be triphenylphosphine, methyldiphenylphosphine, dimethylphenylphosphine, ethyldiphenylphosphine, diphenylpropylphosphine, isopropyldiphenylphosphine, diethylphenylphosphine, and the like. This is not restrictive.
- the anion containing compound may be an anion containing salt.
- the reaction of Formula 3 and Formula 4 may be carried out in an organic solvent such as methylene chloride, acetonitrile, N, N-dimethylformamide, toluene, and the like, at about 10 to 50 ° C., for example at about 20 to 30 ° C., about 1 To 30 hours, for example about 10 to 30 hours, and the phosphonium cation-containing compound: the anion-containing compound can be reacted in a molar ratio of about 1: 0.9 to 1: 2.
- organic solvent such as methylene chloride, acetonitrile, N, N-dimethylformamide, toluene, and the like
- the reaction may be carried out by mixing Formula 3 and Formula 4, respectively, or by combining phosphine compounds with alkyl halides, aryl halides, or aralkyl halides to prepare phosphonium cation-containing compounds, and in situ without further separation.
- the reaction may be carried out by addition of an anion containing compound ( in situ ).
- the epoxy resin composition of one embodiment of the present invention may include an epoxy resin, a curing agent, and a curing catalyst, and the curing catalyst may include a phosphonium ion-containing compound.
- the epoxy resin composition can be cured even at low temperatures, and storage stability and the like may be good.
- Epoxy resin is bisphenol epoxy resin such as bisphenol A epoxy resin, bisphenol F epoxy resin, phenol novolac epoxy resin, tert-butyl catechol epoxy resin, naphthalene epoxy resin, glycidylamine epoxy resin, phenol Aralkyl type epoxy resin, cresol novolak type epoxy resin, biphenyl type epoxy resin, linear aliphatic epoxy resin, alicyclic epoxy resin, heterocyclic epoxy resin, spiro ring containing epoxy resin, cyclohexane dimethanol type epoxy resin, halogenated epoxy resin Or the like, and these may be included alone or in combination of two or more thereof.
- the epoxy resin may be a biphenyl type epoxy resin of Formula 5 and a phenol aralkyl type epoxy resin of Formula 6:
- R is an alkyl group having 1 to 4 carbon atoms, the average value of n is 0 to 7.
- the epoxy resin may be included in the composition about 1 to 90% by weight, for example about 2 to 17% by weight, for example about 3 to 15% by weight, for example about 3 to 12% by weight. In the above range, the curability of the composition may not be lowered.
- the curing agent is a phenol aralkyl type phenol resin, a phenol phenol novolak phenol resin, a xylock phenol resin, a cresol novolak phenol resin, a naphthol phenol resin, a terpene phenol resin, a polyfunctional phenol resin, a dicyclopentadiene phenol resin, Novolac-type phenolic resins synthesized from bisphenol A and resol, polyhydric phenol compounds including tris (hydroxyphenyl) methane, dihydroxybiphenyl, acid anhydrides including maleic anhydride and phthalic anhydride, meta-phenylenediamine, Aromatic amines, such as diamino diphenylmethane and diamino diphenyl sulfone, etc. are mentioned.
- the curing agent may use a phenol resin having one or more hydroxyl groups.
- the curing agent may use a xylox phenolic resin of Formula 7 and a phenol aralkyl type phenolic resin of Formula 8 below:
- the curing agent may be included in the epoxy resin composition in an amount of about 0.1 to 90% by weight, for example about 0.5 to 13% by weight, for example about 1 to 10% by weight, for example about 2 to 8% by weight. In the above range, the curability of the composition may not be lowered.
- the curing catalyst may include the phosphonium ion-containing compound of one embodiment of the present invention.
- the epoxy resin composition may further include a non-phosphonium curing catalyst that does not contain phosphonium.
- a non-phosphonium curing catalyst tertiary amines, organometallic compounds, organophosphorus compounds, imidazoles, boron compounds and the like can be used.
- Tertiary amines include benzyldimethylamine, triethanolamine, triethylenediamine, diethylaminoethanol, tri (dimethylaminomethyl) phenol, 2-2- (dimethylaminomethyl) phenol, 2,4,6-tris (diaminomethyl ) Phenol and tri-2-ethylhexyl acid salt.
- Organometallic compounds include chromium acetylacetonate, zinc acetylacetonate, nickel acetylacetonate and the like.
- Organophosphorus compounds include tris-4-methoxyphosphine, triphenylphosphine, triphenylphosphine triphenylborane, triphenylphosphine-1,4-benzoquinone adduct.
- Imidazoles include 2-methylimidazole, 2-phenylimidazole, 2-aminoimidazole, 2 - methyl-1-vinylimidazole, 2-ethyl-4-methylimidazole, 2-heptadecyl Imidazole and the like.
- boron compound examples include triphenylphosphine tetraphenylborate, tetraphenylboron salt, trifluoroborane-n-hexylamine, trifluoroborane monoethylamine, tetrafluoroboranetriethylamine, tetrafluoroboraneamine, and the like.
- triphenylphosphine tetraphenylborate tetraphenylboron salt
- trifluoroborane-n-hexylamine trifluoroborane monoethylamine
- tetrafluoroboranetriethylamine tetrafluoroboraneamine
- boron compound examples include triphenylphosphine tetraphenylborate, tetraphenylboron salt, trifluoroborane-n-hexylamine, trifluoroborane monoethylamine, tetrafluoroboranetrie
- undec-7-ene (1,8-diazabicyclo [5.4.0] undec-7-ene: DBU) and phenol novolak resin salts may be used.
- the curing catalyst it is also possible to use an epoxy resin or an adduct made by pre-reaction with a curing agent.
- the phosphonium ion-containing compound of one embodiment of the present invention in the total curing catalyst may be included in about 10 to 100% by weight, for example about 60 to 100% by weight, the curing reaction time is not delayed in the above range, the fluidity of the composition This may have a securing effect.
- the curing catalyst may be included in about 0.01 to 10% by weight, for example about 0.01 to 5% by weight, for example about 0.02 to 1.5% by weight, for example about 0.05 to 2.0% by weight of the epoxy resin composition. In the above range, the curing reaction time is not delayed, and the fluidity of the composition can be ensured.
- the epoxy resin composition may further include conventional additives.
- the additive may comprise one or more of a coupling agent, a release agent, a stress relaxer, a crosslinking enhancer, a leveling agent, a colorant.
- the coupling agent may use one or more selected from the group consisting of epoxysilane, aminosilane, mercaptosilane, alkylsilane and alkoxysilane, but is not limited thereto.
- the coupling agent may be included in about 0.1 to 1% by weight of the epoxy resin composition.
- the release agent may use one or more selected from the group consisting of paraffin wax, ester wax, higher fatty acid, higher fatty acid metal salt, natural fatty acid and natural fatty acid metal salt.
- the release agent may be included in about 0.1 to 1% by weight of the epoxy resin composition.
- the stress relieving agent may use one or more selected from the group consisting of modified silicone oils, silicone elastomers, silicone powders and silicone resins, but is not limited thereto.
- the stress relieving agent is preferably contained in about 0 to 6.5% by weight, for example about 0 to 1% by weight, for example about 0.1 to 1% by weight, in the epoxy resin composition, which may optionally be included, or both.
- the modified silicone oil is preferably a silicone polymer having excellent heat resistance, and the total epoxy resin composition by mixing one or two or more kinds of a silicone oil having an epoxy functional group, a silicone oil having an amine functional group, and a silicone oil having a carboxyl functional group. About 0.05 to 1.5% by weight.
- the silicone oil exceeds about 1.5% by weight or more, surface contamination is likely to occur and the resin bleed may be long, and when used below about 0.05% by weight, sufficient low modulus of elasticity may not be obtained. There may be.
- the silicon powder has a central particle size of about 15 ⁇ m or less, which does not act as a cause of the deterioration of moldability, and is contained in about 0 to 5 wt%, for example, about 0.1 to 5 wt% based on the total resin composition. Can be.
- the colorant may be carbon black and the like, and may be included in about 0.1 to 3% by weight of the epoxy resin composition.
- the additive may be included in about 0.1 to 10% by weight, for example about 0.1 to 3% by weight of the epoxy resin composition.
- the epoxy resin composition may further include an inorganic filler.
- Inorganic fillers can increase the mechanical properties and lower the stress of the composition.
- examples of inorganic fillers may include one or more of molten silica, crystalline silica, calcium carbonate, magnesium carbonate, alumina, magnesia, clay, talc, calcium silicate, titanium oxide, antimony oxide, and glass fibers. have.
- molten silica having a low coefficient of linear expansion is used to reduce stress.
- Fused silica refers to amorphous silica having a specific gravity of about 2.3 kW or less, including amorphous silica made by melting crystalline silica or synthesized from various raw materials.
- the shape and particle size of the molten silica are not particularly limited, but about 50 to 99% by weight of spherical molten silica having an average particle diameter of about 5 to 30 ⁇ m and about 1 to 50% by weight of spherical molten silica having an average particle diameter of about 0.001 to 1 ⁇ m.
- a molten silica mixture containing about 40 to 100% by weight relative to the total filler.
- the maximum particle diameter can be adjusted to any one of about 45 ⁇ m, about 55 ⁇ m, and about 75 ⁇ m according to the application.
- conductive carbon may be included as a foreign material on the silica surface, but it is also important to select a material having a small amount of polar foreign matter mixed therein.
- the amount of the inorganic filler used depends on the required physical properties such as formability, low stress, and high temperature strength.
- the inorganic filler may be included in about 70 to 95% by weight, for example about 75 to 92% by weight of the epoxy resin composition. In the above range, it is possible to ensure the flame retardancy, fluidity and reliability of the epoxy resin composition.
- the epoxy resin composition is curable at low temperatures, for example, the curing start temperature may be about 90 to 120 °C. In the above range, curing proceeds well even at low temperatures, and there may be an effect of low temperature curing.
- the epoxy resin composition contains a phosphonium ion-containing compound, which has a high storage stability, and even though the epoxy resin composition is stored for a predetermined time at a predetermined range of temperature, curing does not proceed, resulting in low viscosity change.
- the epoxy resin composition may have a viscosity change rate of about 16% or less, for example, about 0 to 15.5% of Equation 1 below:
- Viscosity Change Rate
- A is the viscosity (unit: cPs) measured at 25 °C of the epoxy resin composition
- B is the viscosity (unit: cPs) measured at 25 °C after leaving the epoxy resin composition at 25 °C conditions for 24 hours)
- the storage stability is high and the curing is catalyzed only when the desired curing temperature is reached, and when the curing temperature is not the desired curing activity, there is no curing catalyst activity. There may be no degradation in mechanical, electrical and chemical properties.
- the epoxy resin composition may have a flow length of about 59 to 75 inches by a transfer molding press at 175 ° C. and 70 kgf / cm 2 in EMMI-1-66. In the above range, it can be used for the use of the epoxy resin composition.
- the epoxy resin composition may have a curing shrinkage ratio of less than about 0.4%, for example about 0.01 to 0.39%, measured by the following equation:
- Cure Shrinkage
- C is the length of the specimen obtained by transfer molding press the epoxy resin composition at 175 °C, 70kgf / cm 2
- D is the specimen obtained after curing the specimen at 170 ⁇ 180 °C 4 hours, and cooled Is the length of).
- the curing shrinkage rate is low can be used for the use of the epoxy resin composition.
- epoxy resin resin composition of the present invention requires epoxy resin compositions such as semiconductor device sealing applications, adhesive resins, insulating resin sheets such as prepregs, circuit boards, solder resists, underfill agents, die bonding materials, and component supplement resin applications. It can be applied to a wide range of uses, but is not limited thereto.
- the epoxy resin composition of the present invention may be used for sealing semiconductor devices, and may include an epoxy resin, a curing agent, a phosphonium ion-containing compound-containing curing catalyst, an inorganic filler, and an additive.
- the epoxy resin may be included in about 2 to 17% by weight, for example about 3 to 12% by weight, the flowability, flame retardancy, and reliability of the epoxy resin composition in the above range, it may contain a phosphonium ion compound It may include about 0.01 to 5% by weight of the curing catalyst, for example about 0.05 to 1.5% by weight and does not generate a large amount of unreacted epoxy group and phenolic hydroxyl group in the above range can be excellent in reliability, about 0.5 to about It may be included in 13% by weight, for example about 2 to 8% by weight and does not generate a large amount of unreacted epoxy group and phenolic hydroxyl group in the above range may be excellent in reliability, about 70 to 95% by weight inorganic filler, eg For example, it may include about 75 to 92% by weight and may ensure the flame retardancy, flowability and reliability of the epoxy resin composition in the above range, about 0.1 to 10% by weight additives, for example About 0.1 to 3% by weight of cotton.
- Epoxy resins in the epoxy resin composition may be used alone, or may be included as a compound added by a preliminary reaction such as a melt master batch with an additive such as a curing agent, a curing catalyst, a releasing agent, a coupling agent, and a stress relaxation agent. have.
- the method for producing the epoxy resin composition is not particularly limited, but the components contained in the composition are uniformly mixed by using a Henschel mixer or a Lodige mixer, and then melt kneaded at about 90 to 120 ° C. with a roll mill or kneader. It can be prepared through the cooling and grinding process.
- a low pressure transfer molding method may be most commonly used. However, it can also be molded by an injection molding method or a casting method.
- a semiconductor device of a copper lead frame, an iron lead frame, or a lead frame pre-plated with at least one material selected from the group consisting of palladium with nickel and copper on the lead frame, or an organic laminate frame can be manufactured. Can be.
- the epoxy resin composition may be applied to a support film and cured to be used as an adhesive film for a printed wiring board.
- the adhesive film may be formed by dissolving the organic solvent composition, for example, by dissolving the organic solvent composition, applying the composition with the support film as a support, and drying the organic solvent by heating or hot air spraying.
- Ketones such as acetone and methyl ethyl ketone, acetate esters such as ethyl acetate and butyl acetate, carbitols such as cellosolve and butyl carbitol, aromatic hydrocarbons such as toluene, and amide solvents such as diketylformamide It may be used alone or in combination of two or more.
- Drying conditions are not particularly limited, but the drying conditions are such that the content of the organic solvent in the coating layer is about 10% by weight or less, and may be dried at about 50 to 100 ° C. for about 1 to 10 minutes.
- the support film may be polyolefin such as polyethylene or polypropylene, polyester such as polyethylene terephthalate, polycarbonate, polyimide, or the like, and the thickness of the support film may be about 10 to 150 ⁇ m.
- the epoxy resin composition can be used as a prepreg by impregnating a sheet-like reinforcing base material and heating and semi-curing, and there is no particular limitation on the reinforcing base material, and it is commonly used in prepreg, and fibers for prepreg such as glass cross and aramid fiber Can be
- the device of one embodiment of the present invention can be manufactured using the epoxy resin composition.
- the device may be a semiconductor device sealed using an epoxy resin composition, a semiconductor device or display device including the same, a multilayer wiring board including an adhesive film formed from the epoxy resin composition, and the like.
- Example 9 an epoxy resin composition was prepared in the same manner except that the compound of Example 2 was used instead of the compound of Example 1.
- Example 9 an epoxy resin composition was prepared in the same manner except that the compound of Example 3 was used instead of the compound of Example 1.
- Example 9 an epoxy resin composition was prepared in the same manner except that the compound of Example 4 was used instead of the compound of Example 1.
- Example 9 7.5 parts by weight of the biphenyl type epoxy resin, 4.8 parts by weight of the xylock type phenol resin, 0.1 parts by weight of the compound of Example 1, 86 parts by weight of the inorganic filler, 0.6 parts by weight of the coupling agent, 0.5 parts by weight of the release agent, 0.5 An epoxy resin composition was prepared in the same manner except for mixing the parts by weight.
- Example 9 an epoxy resin composition was prepared in the same manner except that a phenol aralkyl type epoxy resin was used instead of a biphenyl type epoxy resin.
- Example 9 an epoxy resin composition was prepared in the same manner except that a cresol novolac epoxy resin was used instead of the biphenyl epoxy resin.
- Example 9 an epoxy resin composition was prepared in the same manner except that a phenol novolak type phenol resin was used instead of the xylock type phenol resin.
- Example 9 an epoxy resin composition was prepared in the same manner except that a phenol aralkyl type phenol resin was used instead of the xylock type phenol resin.
- Example 9 an epoxy resin composition was prepared in the same manner except that 0.1 part by weight of the compound of Example 1 and 0.1 part by weight of triphenylphosphine were used instead of 0.2 part by weight of the compound of Example 1.
- Example 9 an epoxy resin composition was prepared in the same manner except that the compound of Example 5 was used instead of the compound of Example 1.
- Example 9 an epoxy resin composition was prepared in the same manner except that the compound of Example 6 was used instead of the compound of Example 1.
- Example 9 an epoxy resin composition was prepared in the same manner except that the compound of Example 7 was used instead of the compound of Example 1.
- Example 9 an epoxy resin composition was prepared in the same manner except that the compound of Example 8 was used instead of the compound of Example 1.
- Example 9 an epoxy resin composition was prepared in the same manner except that the compound of Example 1 was not used.
- Example 9 an epoxy resin composition was prepared in the same manner except that triphenylphosphine was used instead of the compound of Example 1.
- Example 9 an epoxy resin composition was prepared in the same manner except for using the addition product of triphenylphosphine and 1,4-benzoquinone in place of the compound of Example 1.
- Flowability (inch) Flow length was measured using a transfer molding press at 175 ° C. and 70 kgf / cm 2 using an evaluation mold according to EMMI-1-66. The higher the measured value, the better the fluidity.
- Cure Shrinkage
- C is the length of the specimen obtained by transfer molding press the epoxy resin composition at 175 °C, 70kgf / cm 2
- D is the specimen obtained after curing the specimen at 170 ⁇ 180 °C 4 hours, and cooled Is the length of).
- TMA thermomechanical analyzer
- Moisture absorption rate (%) the resin composition prepared in the above Examples and Comparative Examples, the mold temperature 170 ⁇ 180 °C, clamp pressure 70kgf / cm 2 , transfer pressure 1000psi, transfer rate 0.5 ⁇ 1cm / s, curing time 120 Molded under the condition of seconds to obtain a cured specimen in the form of a disk having a diameter of 50mm, 1.0mm thick.
- the obtained specimens were placed in an oven at 170 to 180 ° C., and after 4 hours of post-curing (PMC: post molding cure), they were left at 85 ° C. and 85 RH% relative humidity for 168 hours, and then the weight change due to moisture absorption was measured. The moisture absorption was calculated by 3.
- Moisture absorption rate (weight of test piece after moisture absorption-weight of test piece before absorption) ⁇ (weight of test piece before absorption) ⁇ 100
- Adhesion force (kgf): A copper metal element is prepared in a standard suitable for a measurement measurement mold, and the resin composition prepared in Example and Comparative Example is prepared on the prepared test piece with a mold temperature of 170 to 180 ° C. and a clamp pressure of 70 kgf / cm. 2 , the transfer pressure 1000psi, the feed rate 0.5 ⁇ 1cm / s, the curing time was molded under the conditions of 120 seconds to obtain a cured specimen. The obtained specimens were put in an oven at 170 to 180 ° C. and post-cured (PMC: post molding cure) for 4 hours. At this time, the area of the epoxy resin composition in contact with the specimen is 40 ⁇ 1mm 2 , the adhesion measurement was measured by the average value after measuring by using a universal testing machine (UTM) for 12 specimens for each measurement process.
- UPM universal testing machine
- Viscosity change rate The viscosity was measured at 25 ° C. of the epoxy resin composition, the epoxy resin composition was left at 25 ° C. for 24 hours, and then the viscosity was measured at 25 ° C., and calculated according to Equation 1 below. Viscosity was measured using the Malcolm biaxial double cylindrical rotary viscometer PM-2A. The lower the viscosity change rate, the harder the epoxy resin composition, which means that the storage stability is higher.
- Viscosity Change Rate
- A is the viscosity measured at 25 °C of the epoxy resin composition (unit: cPs)
- B is the viscosity measured at 25 °C after leaving the epoxy resin composition at 25 °C 24 hours (unit: cPs) to be)
- Shore-D Using a multi-plunger system (MPS) molding machine equipped with a mold for exposed thin quad flat package (eTQFP) packages having a width of 24 mm, a length of 24 mm, and a thickness of 1 mm containing copper metal elements. After curing the epoxy resin composition to be evaluated at 175 ° C. for 50, 60, 70, 80 and 90 seconds, the hardness of the cured product according to the curing time was measured with a Shore-D hardness tester directly on the package on the mold. The higher the value, the better the degree of curing.
- MPS multi-plunger system
- the composition containing the phosphonium ion-containing compound of the present invention was high fluidity, low cure shrinkage rate, it was confirmed to have a high cure degree even in a short cure time when comparing the degree of cure by curing time. In addition, even after 72 hours, there was no difference in fluidity and the viscosity change rate was low, thereby confirming high storage stability. In addition, it was confirmed that no external crack occurred, good crack resistance, and no peeling occurred.
- composition of the comparative example which does not contain the phosphonium ion-containing compound of the present invention or contains a curing catalyst that does not contain phosphonium ions instead of the phosphonium ion-containing compound has low storage stability, high curing shrinkage rate, and fluidity. It was also confirmed that the low, can not implement the effects of the present invention when used in the package.
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Abstract
The present invention relates to a compound containing phosphonium ion of a chemical formula 1, an epoxy resin composition containing the same, and a device manufactured by using the same.
Description
본 발명은 포스포늄 이온 함유 화합물, 이를 포함하는 에폭시수지 조성물 및 이를 사용하여 제조된 장치에 관한 것이다.The present invention relates to a phosphonium ion-containing compound, an epoxy resin composition comprising the same, and a device manufactured using the same.
에폭시수지는 반응수축성이 낮고 전기적, 기계적 성질이 우수하며 가공성, 내약품성이 우수한 재료로 전기, 전자, 건축, 복합재료의 매트릭스 및 코팅 등에 사용되고 있다. 예를 들면, 에폭시수지는 반도체 소자 밀봉 용도, 접착필름, 프리프레그(prepreg) 등의 절연수지시트, 회로기판, 솔더레지스트, 언더필제, 다이본딩재, 부품 보충 수지 등에 사용되고 있다.Epoxy resin is a material with low reaction shrinkage, excellent electrical and mechanical properties, and excellent workability and chemical resistance. It is used for matrix and coating of electric, electronic, construction, and composite materials. For example, epoxy resins are used for sealing semiconductor devices, adhesive films, insulating resin sheets such as prepreg, circuit boards, solder resists, underfill agents, die bonding materials, component supplement resins, and the like.
에폭시수지는 단독으로 사용되기 보다는 경화제와 혼합되어, 열경화성 물질로 경화된 후 사용된다. 이때 경화 후 생성되는 3차원 구조에 의해 에폭시수지의 성능이 좌우되므로 경화제의 선택이 중요하다. 기존 에폭시수지용 경화제가 많이 개발되었지만, 경화 반응을 촉매하기 위해 경화 촉매를 함께 사용한다. 에폭시수지 조성물이 사용되는 장치에 있어서, 생산성의 향상을 목적으로 저온에서도 경화 가능하게 하는 저온경화성과, 물류 보관시의 취급성의 향상을 목적으로 원하는 경화온도가 될 때에만 경화를 촉매시키고 원하는 경화온도가 아닐 때에는 경화 촉매 활성이 없는 저장안정성이 높은 경화 촉매가 요구되고 있다. 트리페닐포스핀(triphenylphosphine)과 1,4-벤조퀴논(1,4-benzoquinone)의 부가생성물인 경화촉매는 비교적 저온에서도 경화촉진효과가 나타나서 경화 이전에 에폭시수지 등과 혼합될 때 발생하는 열 또는 외부로부터 더해지는 열에 의해 에폭시수지 조성물의 경화를 일부 진행시킬 수 있고 수지 조성물의 각 성분을 혼합한 후 에폭시수지 조성물을 상온에서 보관하는 경우에도 경화를 촉진시킴으로써 저장안정성이 떨어진다는 문제점이 있다. 이러한 경화반응의 진행은 에폭시수지 조성물이 액체인 경우 점도의 상승, 유동성 저하를 가져올 수 있고, 에폭시수지 조성물이 고체인 경우 점성을 발현시킬 수 있으며, 이러한 상태의 변화는 에폭시수지 조성물 내에서 균일하게 나타나지 않는다. 따라서, 실제로 에폭시수지 조성물을 고온에서 경화반응 시켰을 때 유동성 저하에 따른 성형성 저하, 성형 제품의 기계적, 전기적, 화학적 특성이 저하될 수 있다.Epoxy resins are mixed with a curing agent rather than used alone, and then used after curing with a thermosetting material. At this time, since the performance of the epoxy resin depends on the three-dimensional structure generated after curing, the selection of the curing agent is important. Although many curing agents for epoxy resins have been developed, a curing catalyst is used together to catalyze the curing reaction. In the apparatus in which the epoxy resin composition is used, the curing is catalyzed only when the desired curing temperature is achieved for the purpose of improving the productivity at low temperature for the purpose of improving productivity, and for the handling property at the time of logistics storage. If not, a curing catalyst having high storage stability without curing catalyst activity is desired. The curing catalyst, an adduct of triphenylphosphine and 1,4-benzoquinone, exhibits a hardening effect even at a relatively low temperature. There is a problem in that the curing of the epoxy resin composition can be partially progressed by the heat added from the mixture, and the storage stability is lowered by promoting the curing even when the epoxy resin composition is stored at room temperature after mixing each component of the resin composition. The progress of the curing reaction may result in an increase in viscosity and a decrease in fluidity when the epoxy resin composition is a liquid, and may exhibit viscosity when the epoxy resin composition is a solid, and such a change in state may be uniform in the epoxy resin composition. Does not appear Therefore, when the epoxy resin composition is actually cured at a high temperature, the moldability decreases due to fluidity decrease, and the mechanical, electrical and chemical properties of the molded product may decrease.
본 발명의 목적은 에폭시수지의 경화를 촉매할 수 있는 경화촉매용 화합물을 제공하는 것이다.It is an object of the present invention to provide a compound for a curing catalyst capable of catalyzing the curing of epoxy resins.
본 발명의 다른 목적은 저온에서도 에폭시수지의 경화를 촉매할 수 있는 경화촉매용 화합물을 제공하는 것이다.Another object of the present invention is to provide a compound for a curing catalyst that can catalyze the curing of epoxy resin even at low temperatures.
본 발명의 또 다른 목적은 원하는 경화온도가 될 때에만 경화를 촉매시키고 원하는 경화온도가 아닐 때에는 경화 촉매 활성이 없게 하는 저장안정성이 높은 경화촉매용 화합물을 제공하는 것이다.It is still another object of the present invention to provide a compound for a storage catalyst having a high storage stability, which catalyzes curing only when the desired curing temperature is reached, and when the curing temperature is not the desired curing activity.
본 발명의 포스포늄 이온 함유 화합물은 하기 화학식 1로 표시될 수 있다:The phosphonium ion containing compound of the present invention may be represented by the following Chemical Formula 1:
<화학식 1><Formula 1>
(상기 화학식 1에서, R1, R2, R3, R4, R5, R6, R7, R8, R9, R10은 하기 상세한 설명에서 정의한 바와 같다).(In Chemical Formula 1, R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 are as defined in the following detailed description).
본 발명의 에폭시수지 조성물은 에폭시수지, 경화제, 및 경화촉매를 포함하고, 상기 경화촉매는 상기 포스포늄 이온 함유 화합물을 포함할 수 있다.The epoxy resin composition of the present invention may include an epoxy resin, a curing agent, and a curing catalyst, and the curing catalyst may include the phosphonium ion-containing compound.
본 발명의 장치는 상기 에폭시수지 조성물을 사용하여 제조될 수 있다.The device of the present invention can be manufactured using the epoxy resin composition.
본 발명은 에폭시수지의 경화를 촉매할 수 있고, 저온에서도 에폭시수지의 경화를 촉진할 수 있는 경화촉매용 화합물을 제공하였다. 또한, 본 발명은 원하는 경화온도가 될 때에만 경화를 촉매시키고 원하는 경화온도가 아닐 때에는 경화 촉매 활성이 없게 하는 저장안정성이 높은 경화촉매용 화합물을 제공하였다. 또한, 본 발명은 에폭시수지, 경화제 등을 포함하는 혼합물에서 소정 범위의 시간 및 온도 조건에서도 점도 변화를 최소화하여 에폭시수지 조성물을 고온에서 경화반응 시켰을 때 유동성 저하에 따른 성형성 저하, 성형 제품의 기계적, 전기적, 화학적 특성이 저하가 없게 하는 경화촉매용 화합물을 제공하였다.The present invention provides a compound for a curing catalyst capable of catalyzing the curing of epoxy resins and promoting the curing of epoxy resins even at low temperatures. In addition, the present invention provides a compound for a curing catalyst having a high storage stability that catalyzes curing only when the desired curing temperature is reached, and when the curing temperature is not the desired curing temperature, the curing catalyst is not active. In addition, the present invention in the mixture containing the epoxy resin, the curing agent, etc. in a predetermined range of time and temperature conditions to minimize the change in viscosity when the epoxy resin composition at high temperature hardening reaction due to fluidity decrease, the mechanical properties of the molded product There was provided a compound for a curing catalyst such that the electrical and chemical properties were not deteriorated.
본 발명 일 실시예의 포스포늄 이온 함유 화합물은 포스포늄 양이온과 술폰아미드 음이온을 포함하고, 예를 들면 하기 화학식 1로 표시될 수 있다:The phosphonium ion-containing compound of one embodiment of the present invention includes a phosphonium cation and a sulfonamide anion, and may be represented by, for example, the following Formula 1:
<화학식 1><Formula 1>
(상기 화학식 1에서, R1, R2, R3, R4은 각각 독립적으로, 수소, 치환 또는 비치환된 탄소수 1 내지 10의 알킬기, 치환 또는 비치환된 탄소수 3 내지 10의 시클로알킬기, 치환 또는 비치환된 탄소수 6 내지 20의 아릴기, 또는 치환 또는 비치환된 탄소수 7 내지 21의 아릴알킬기이고,(In Formula 1, R 1 , R 2 , R 3 , R 4 are each independently hydrogen, substituted or unsubstituted C 1-10 alkyl group, substituted or unsubstituted C 3-10 cycloalkyl group, substituted Or an unsubstituted aryl group having 6 to 20 carbon atoms, or a substituted or unsubstituted arylalkyl group having 7 to 21 carbon atoms,
R5는 수소, 치환 또는 비치환된 탄소수 1 내지 10의 알킬기, 치환 또는 비치환된 탄소수 6 내지 20의 아릴기, 치환 또는 비치환된 탄소수 3 내지 20의 시클로알킬기, 치환 또는 비치환된 탄소수 2 내지 20의 헤테로시클로알킬기, 치환 또는 비치환된 탄소수 7 내지 20의 아릴알킬기, 치환 또는 비치환된 탄소수 3 내지 20의 헤테로아릴기, 또는 하기 화학식 2이다.R 5 is hydrogen, a substituted or unsubstituted C1-C10 alkyl group, a substituted or unsubstituted C6-C20 aryl group, a substituted or unsubstituted C3-C20 cycloalkyl group, a substituted or unsubstituted C2 To 20 heterocycloalkyl group, substituted or unsubstituted arylalkyl group having 7 to 20 carbon atoms, substituted or unsubstituted heteroaryl group having 3 to 20 carbon atoms, or formula (2).
<화학식 2><Formula 2>
(상기 화학식 2에서, *는 화학식 1에서 N에 대한 연결부위이고,(In Formula 2, * is a linking portion to N in Formula 1,
R11은 치환 또는 비치환된 탄소수 1 내지 10의 알킬기, 치환 또는 비치환된 탄소수 6 내지 20의 아릴기, 치환 또는 비치환된 탄소수 3 내지 10의 시클로알킬기 또는, 치환 또는 비치환된 탄소수 7 내지 20의 아릴알킬기이다)R 11 is a substituted or unsubstituted C1-C10 alkyl group, a substituted or unsubstituted C6-C20 aryl group, a substituted or unsubstituted C3-C10 cycloalkyl group, or a substituted or unsubstituted C7-C10 Arylalkyl group of 20)
R6, R7, R8, R9, R10은 각각 독립적으로, 수소, 치환 또는 비치환된 탄소수 1 내지 10의 알킬기, 치환 또는 비치환된 탄소수 6 내지 20의 아릴기, 치환 또는 비치환된 탄소수 7 내지 21의 아릴알킬기, 또는 -NR'R"(상기에서, R', R"은 수소, 탄소수 1 내지 10의 알킬기, 탄소수 6 내지 20의 아릴기, 탄소수 7 내지 21의 아릴알킬기이다)이다).R 6 , R 7 , R 8 , R 9 and R 10 are each independently hydrogen, a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, substituted or unsubstituted An arylalkyl group having 7 to 21 carbon atoms, or -NR'R "(wherein R 'and R" are hydrogen, an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 20 carbon atoms, and an arylalkyl group having 7 to 21 carbon atoms). )to be).
본 명세서에서 "치환 또는 비치환된"에서 "치환"은 해당 작용기 중 하나 이상의 수소 원자가 수산기, 아미노기, 니트로기, 할로겐, 비치환된 탄소수 1 내지 10의 알킬기, 탄소수 6 내지 20의 아릴기, 탄소수 3 내지 10의 시클로알킬기, 탄소수 7 내지 21의 아릴알킬기, 탄소수 1 내지 10의 헤테로알킬기로 치환된 것을 의미한다. 본 명세서에서 '아릴기'는 환형인 치환기의 모든 원소가 p-오비탈을 가지며 p-오비탈이 공액을 형성하는 치환기를 의미하고, 모노 또는 융합 (즉, 탄소 원자들이 인접한 쌍들을 나눠 가지는 고리) 작용기를 포함한다. 본 명세서에서 '헤테로아릴기'는 아릴기 내에 질소, 산소, 황 및 인으로 이루어진 군에서 선택되는 원자가 1 내지 3개 포함되고 나머지는 탄소인 것을 의미한다. 본 명세서에서 '헤테로시클로알킬기', '헤테로아릴기', '헤테로시클로알킬렌기', '헤테로아릴렌기'에서 '헤테로'는 질소, 산소, 황 또는 인 원자를 의미한다.As used herein, "substituted" in "substituted or unsubstituted" is one or more hydrogen atoms of the functional group is a hydroxyl group, amino group, nitro group, halogen, unsubstituted C1-10 alkyl group, C6-C20 aryl group, carbon number It means substituted with a cycloalkyl group having 3 to 10, an arylalkyl group having 7 to 21 carbon atoms, and a heteroalkyl group having 1 to 10 carbon atoms. As used herein, "aryl group" refers to a substituent in which all elements of a cyclic substituent have p-orbitals and p-orbitals form a conjugate, and are mono or fused (ie, rings in which carbon atoms divide adjacent pairs). It includes. In the present specification, the "heteroaryl group" means that 1 to 3 atoms selected from the group consisting of nitrogen, oxygen, sulfur and phosphorus in the aryl group and the rest is carbon. In the present specification, 'hetero' in the 'heterocycloalkyl group', 'heteroaryl group', 'heterocycloalkylene group', and 'heteroarylene group' means a nitrogen, oxygen, sulfur or phosphorus atom.
예를 들면, R1, R2, R3, R4는 치환 또는 비치환된 탄소수 6 내지 10의 아릴기, 또는 치환 또는 비치환된 탄소수 7 내지 12의 아릴알킬기이고, R5는 치환 또는 비치환된 탄소수 1 내지 5의 알킬기, 치환 또는 비치환된 탄소수 3 내지 20의 헤테로아릴기, 또는 상기 화학식 2이고, R8은 -NH2, -NHR', 또는 치환 또는 비치환된 탄소수 1 내지 5의 알킬기이고, R6, R7, R9, R10는 각각 독립적으로, 수소, 탄소수 1 내지 10의 알킬기, 또는 탄소수 6 내지 10의 아릴기이다. For example, R 1 , R 2 , R 3 , and R 4 are substituted or unsubstituted aryl groups having 6 to 10 carbon atoms, or substituted or unsubstituted arylalkyl groups having 7 to 12 carbon atoms, and R 5 is substituted or unsubstituted A substituted alkyl group having 1 to 5 carbon atoms, a substituted or unsubstituted heteroaryl group having 3 to 20 carbon atoms, or Formula 2 above, and R 8 is —NH 2 , —NHR ′, or a substituted or unsubstituted carbon group having 1 to 5 carbon atoms It is an alkyl group of, and R <6> , R <7> , R <9> , R <10> is respectively independently hydrogen, a C1-C10 alkyl group, or a C6-C10 aryl group.
예를 들면, R5는 치환 또는 비치환된 탄소수 1 내지 4의 알킬기, 치환 또는 비치환된 탄소수 3 내지 20의 헤테로아릴기, 예를 들면 피라지닐기, 피리미디닐기, 피리다지닐기 등의 디아지닐기, 피리딜기, 트리아지닐기, 티아졸기, 옥사진기, 이속사졸기, 푸라닐기, 티오페닐기, 퀴놀리닐기, 인돌릴기, 푸린기, 벤조푸란기, 벤조피리딘기, 벤조티오펜기, 벤조티에핀기, 벤조퀴놀린기, 피라졸기, 피란기, 아제핀기, 피리미디논기, 티아디아진기, 퀴녹살린기, 피롤린기, 테트라히드로피리딘기, 옥사졸린기, 디하이드로티아디아진기, 또는 R11이 치환 또는 비치환된 탄소수 1 내지 5의 알킬기, 치환 또는 비치환된 탄소수 6 내지 10의 아릴기인 화학식 2, 예를 들면 아세틸기 또는 벤조일기일 수 있다.For example, R 5 is a substituted or unsubstituted alkyl group having 1 to 4 carbon atoms, a substituted or unsubstituted heteroaryl group having 3 to 20 carbon atoms, for example, a pyrazinyl group, a pyrimidinyl group, a pyridazinyl group, and the like. Diazinyl group, pyridyl group, triazinyl group, thiazole group, oxazine group, isoxazole group, furanyl group, thiophenyl group, quinolinyl group, indolyl group, purine group, benzofuran group, benzopyridine group, benzothiophene group, Benzothiene group, benzoquinoline group, pyrazole group, pyran group, azepine group, pyrimidinone group, thiadiazine group, quinoxaline group, pyrroline group, tetrahydropyridine group, oxazoline group, dihydrothiadiazine group, or R 11 It may be a substituted or unsubstituted alkyl group having 1 to 5 carbon atoms, a substituted or unsubstituted aryl group having 6 to 10 carbon atoms, for example, an acetyl group or a benzoyl group.
포스포늄 이온 함유 화합물은 유리전이온도가 약 100 내지 130℃, 예를 들면 약 120 내지 125℃가 될 수 있고, 포스포늄 이온 함유 화합물은 시차주사열량계(DSC)에 의한 경화개시온도가 약 90 내지 120℃, 경화피크온도가 약 120 내지 180℃가 될 수 있다. 상기 범위에서, 저온 경화의 효과가 있을 수 있다. 경화개시온도는 포스포늄 이온 함유 화합물을 포함하는 에폭시수지 조성물을 일정 승온 속도로 가열하였을 때 발열 중합 반응이 시작되는 온도를 의미하고, 경화피크온도는 상기 조건에서 반응시켰을 때 발열 피크가 최대가 되는 온도를 의미한다.The phosphonium ion-containing compound may have a glass transition temperature of about 100 to 130 ° C., for example, about 120 to 125 ° C., and the phosphonium ion-containing compound may have a curing start temperature of about 90 ° C. by a differential scanning calorimeter (DSC). 120 ℃, the curing peak temperature may be about 120 to 180 ℃. In the above range, there may be the effect of low temperature curing. The curing start temperature means the temperature at which the exothermic polymerization reaction starts when the epoxy resin composition containing the phosphonium ion-containing compound is heated at a constant heating rate, and the curing peak temperature is the maximum exothermic peak when reacting under the above conditions. Means temperature.
포스포늄 이온 함유 화합물은 수불용성 화합물 또는 염 형태의 수용성 화합물이 될 수 있다.The phosphonium ion containing compound may be a water insoluble compound or a water soluble compound in salt form.
포스포늄 이온 함유 화합물은 에폭시 수지, 경화제 중 하나 이상을 포함하는 조성물을 위한 잠재성 경화 촉매로 사용될 수 있다. 즉, 포스포늄 이온 함유 화합물은 열 등의 외부 에너지를 받게 되면, 약 90 내지 175℃에서 하기 반응식 1과 같이 포스핀 화합물, 및 음이온과 양이온의 화합물로 분해된다.Phosphonium ion containing compounds can be used as latent curing catalysts for compositions comprising at least one of an epoxy resin and a curing agent. That is, the phosphonium ion-containing compound is decomposed into a phosphine compound and a compound of an anion and a cation at about 90 to 175 ° C. when subjected to external energy such as heat.
<반응식 1><Scheme 1>
(상기 반응식 1에서, R1, R2, R3, R4, R5, R6, R7, R8, R9, R10는 상기 화학식 1에서 정의한 바와 같다).(In Scheme 1, R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 are the same as defined in Formula 1 above).
생성된 포스핀 화합물이 에폭시수지 내 에폭사이드기와 반응하여 개환 반응을 하게 되고, 개환반응 후 에폭시수지 내 수산기와의 반응에 의한 에폭사이드기의 개환반응, 활성화된 에폭시수지의 사슬 말단과 에폭사이드의 반응 등으로 인해 경화반응을 촉매하게 된다.The resulting phosphine compound reacts with the epoxide group in the epoxy resin to undergo a ring-opening reaction.After the ring-opening reaction, the ring opening reaction of the epoxide group is carried out by reaction with a hydroxyl group in the epoxy resin, and the chain terminal of the activated epoxy resin and the epoxide The reaction is catalyzed by the curing reaction.
포스포늄 이온 함유 화합물은 에폭시수지와 경화제의 경화반응을 촉매함과 동시에, 저온 경화성과 저장안정성이 높고, 에폭시수지, 경화제 등을 포함하는 혼합물에서 소정 범위의 시간 및 온도 조건에서도 점도 변화를 최소화할 수 있는 에폭시수지 조성물을 제공할 수 있는 효과가 있다. 상기 "저장 안정성"은 원하는 경화온도가 될 때에만 경화를 촉매시키고 원하는 경화온도가 아닐 때에는 경화 촉매 활성이 없는 활성으로서, 그 결과 점도 변화 없이도 에폭시수지 조성물을 장시간 동안 저장할 수 있게 한다. 일반적으로 경화반응의 진행은 에폭시수지 조성물이 액체인 경우 점도의 상승, 유동성 저하를 가져올 수 있고, 에폭시수지 조성물이 고체인 경우 점성을 발현시킬 수 있다.The phosphonium ion-containing compound catalyzes the curing reaction of the epoxy resin and the curing agent, and has high low temperature curing property and storage stability, and minimizes the viscosity change even in a range of time and temperature conditions in the mixture containing the epoxy resin and the curing agent. There is an effect that can provide an epoxy resin composition that can be. The "storage stability" is an activity that catalyzes curing only when the desired curing temperature is reached and there is no curing catalyst activity when the desired curing temperature is not achieved, so that the epoxy resin composition can be stored for a long time without changing the viscosity. In general, the progress of the curing reaction may lead to an increase in viscosity and a decrease in fluidity when the epoxy resin composition is a liquid, and may exhibit viscosity when the epoxy resin composition is a solid.
일 구체예에 따르면, 에폭시수지는 분자 중에 2개 이상의 에폭시기를 갖는 것으로, 비스페놀 A형 에폭시수지, 비스페놀 F형 에폭시수지 등의 비스페놀형 에폭시수지, 페놀노볼락형 에폭시 수지, tert-부틸 카테콜형 에폭시수지, 나프탈렌형 에폭시수지, 글리시딜아민형 에폭시수지, 페놀아랄킬형 에폭시수지, 크레졸노볼락형 에폭시수지, 비페닐형 에폭시수지, 선형 지방족에폭시수지, 지환식에폭시수지, 복소환식 에폭시수지, 스피로환 함유 에폭시수지, 시클로헥산디메탄올형 에폭시수지, 할로겐화 에폭시 수지 등이 될 수 있고, 이들은 단독 또는 2종 이상 혼합하여 포함될 수도 있다. 예를 들면, 에폭시수지는 분자 중에 2개 이상의 에폭시기 및 1개 이상의 수산기를 갖는 에폭시수지일 수 있다. 에폭시수지는 고상의 에폭시수지, 액상의 에폭시수지, 중 하나 이상을 포함할 수 있고 바람직하게는 고상의 에폭시수지를 사용할 수 있다.According to one embodiment, the epoxy resin has two or more epoxy groups in the molecule, bisphenol-type epoxy resins such as bisphenol A-type epoxy resin, bisphenol F-type epoxy resin, phenol novolak-type epoxy resin, tert- butyl catechol type epoxy Resin, naphthalene type epoxy resin, glycidylamine type epoxy resin, phenol aralkyl type epoxy resin, cresol novolak type epoxy resin, biphenyl type epoxy resin, linear aliphatic epoxy resin, alicyclic epoxy resin, heterocyclic epoxy resin, spiro Ring-containing epoxy resins, cyclohexanedimethanol type epoxy resins, halogenated epoxy resins, and the like, and these may be included alone or in combination of two or more thereof. For example, the epoxy resin may be an epoxy resin having two or more epoxy groups and one or more hydroxyl groups in the molecule. The epoxy resin may include at least one of a solid epoxy resin, a liquid epoxy resin, and preferably a solid epoxy resin.
일 구체예에 따르면, 경화제는 페놀아랄킬형 페놀수지, 페놀노볼락형 페놀수지, 자일록형 페놀수지, 크레졸 노볼락형 페놀수지, 나프톨형 페놀수지, 테르펜형 페놀수지, 다관능형 페놀수지, 디시클로펜타디엔계 페놀수지, 비스페놀 A와 레졸로부터 합성된 노볼락형 페놀수지, 트리스(하이드록시페닐)메탄, 디하이드록시바이페닐을 포함하는 다가 페놀 화합물, 무수 말레인산 및 무수 프탈산을 포함하는 산무수물, 메타-페닐렌디아민, 디아미노디페닐메탄, 디아미노디페닐설폰 등의 방향족 아민 등을 들 수 있다. 바람직하게는, 경화제는 1개 이상의 수산기를 갖는 페놀수지일 수 있다.According to one embodiment, the curing agent is a phenol aralkyl type phenol resin, phenol novolak type phenol resin, xylox phenol resin, cresol novolak type phenol resin, naphthol type phenol resin, terpene type phenol resin, polyfunctional phenol resin, dicyclo Pentadiene-based phenolic resins, novolac-type phenolic resins synthesized from bisphenol A and resol, polyhydric phenol compounds including tris (hydroxyphenyl) methane, dihydroxybiphenyl, acidic anhydrides including maleic anhydride and phthalic anhydride, Aromatic amines, such as meta-phenylenediamine, diaminodiphenylmethane, and diaminodiphenyl sulfone, etc. are mentioned. Preferably, the curing agent may be a phenol resin having one or more hydroxyl groups.
포스포늄 이온 함유 화합물은 에폭시수지 조성물 중 약 0.01 내지 10중량%, 예를 들면 약 0.01 내지 5중량%, 예를 들면 약 0.02 내지 1.5중량%, 예를 들면 약 0.05 내지 1.5중량%로 포함될 수 있다. 상기 범위에서, 경화 반응 시간이 지연되지 않고, 조성물의 유동성이 확보될 수 있다.The phosphonium ion-containing compound may be included in about 0.01 to 10% by weight, for example about 0.01 to 5% by weight, for example about 0.02 to 1.5% by weight, for example about 0.05 to 1.5% by weight, in the epoxy resin composition. . In the above range, the curing reaction time is not delayed, and the fluidity of the composition can be ensured.
포스포늄 이온 함유 화합물은 통상의 방법으로 제조될 수 있다. 예를 들면, 하기 화학식 3의 포스포늄 양이온 함유 화합물과, 하기 화학식 4의 음이온 함유 화합물을 반응시켜 제조될 수 있다:Phosphonium ion-containing compounds can be prepared by conventional methods. For example, it may be prepared by reacting a phosphonium cation-containing compound of Formula 3 with an anion-containing compound of Formula 4:
<화학식 3><Formula 3>
(상기 화학식 3에서, R1, R2, R3, R4는 상기 화학식 1에서 정의한 바와 같고, X는 할로겐이다) (In Chemical Formula 3, R 1 , R 2 , R 3 , R 4 are the same as defined in Chemical Formula 1, and X is a halogen.)
<화학식 4><Formula 4>
(상기 화학식 4에서, R5, R6, R7, R8, R9, R10는 상기 화학식 1에서 정의한 바와 같고, M은 알칼리금속 또는 Ag이다)(In Formula 4, R 5 , R 6 , R 7 , R 8 , R 9 , R 10 are the same as defined in Formula 1, M is an alkali metal or Ag)
할로겐은 플루오르, 염소, 브롬 또는 요오드이고, 알칼리금속은 리튬, 나트륨, 칼륨, 루비듐, 세슘 또는 프란슘 등이다.Halogen is fluorine, chlorine, bromine or iodine and the alkali metal is lithium, sodium, potassium, rubidium, cesium or francium and the like.
포스포늄 양이온 함유 화합물은 용매 하에 포스핀 화합물과 알킬 할라이드 ,아릴 할라이드 또는 아랄킬 할라이드 등을 결합시켜 제조되거나, 포스포늄 양이온 함유 염이 될 수 있다. 포스핀 화합물은 트리페닐포스핀, 메틸디페닐포스핀, 디메틸페닐포스핀, 에틸디페닐포스핀, 디페닐프로필포스핀, 이소프로필디페닐포스핀, 디에틸페닐포스핀 등이 될 수 있지만, 이에 제한되지 않는다. 음이온 함유 화합물은 음이온 함유 염이 될 수 있다.The phosphonium cation containing compound may be prepared by combining a phosphine compound with an alkyl halide, aryl halide, aralkyl halide, or the like under a solvent, or may be a phosphonium cation containing salt. The phosphine compound may be triphenylphosphine, methyldiphenylphosphine, dimethylphenylphosphine, ethyldiphenylphosphine, diphenylpropylphosphine, isopropyldiphenylphosphine, diethylphenylphosphine, and the like. This is not restrictive. The anion containing compound may be an anion containing salt.
화학식 3과 화학식 4의 반응은 메틸렌클로라이드, 아세토니트릴, N,N-디메틸포름아미드, 톨루엔 등의 유기 용매에서 수행될 수 있고, 약 10 내지 50℃ 예를 들면 약 20 내지 30℃에서, 약 1 내지 30시간 예를 들면 약 10 내지 30시간 수행될 수 있고, 포스포늄 양이온 함유 화합물: 음이온 함유 화합물은 약 1:0.9 내지 1:2의 몰수비로 반응할 수 있다. 상기 반응은 화학식 3과 화학식 4를 각각 혼합하여 수행될 수 있고, 또는 포스핀 화합물과 알킬 할라이드, 아릴 할라이드 또는 아랄킬 할라이드 등을 결합시켜 포스포늄 양이온 함유 화합물을 제조하고, 추가적인 분리 공정 없이 인 시투(in situ)로 음이온 함유 화합물을 첨가하여 반응시킬 수도 있다. The reaction of Formula 3 and Formula 4 may be carried out in an organic solvent such as methylene chloride, acetonitrile, N, N-dimethylformamide, toluene, and the like, at about 10 to 50 ° C., for example at about 20 to 30 ° C., about 1 To 30 hours, for example about 10 to 30 hours, and the phosphonium cation-containing compound: the anion-containing compound can be reacted in a molar ratio of about 1: 0.9 to 1: 2. The reaction may be carried out by mixing Formula 3 and Formula 4, respectively, or by combining phosphine compounds with alkyl halides, aryl halides, or aralkyl halides to prepare phosphonium cation-containing compounds, and in situ without further separation. The reaction may be carried out by addition of an anion containing compound ( in situ ).
본 발명 일 실시예의 에폭시수지 조성물은 에폭시 수지, 경화제 및 경화 촉매를 포함하고, 경화 촉매는 포스포늄 이온 함유 화합물을 포함할 수 있다. 그 결과, 에폭시수지 조성물은 저온에서도 경화 가능하고, 저장 안정성 등이 좋을 수 있다.The epoxy resin composition of one embodiment of the present invention may include an epoxy resin, a curing agent, and a curing catalyst, and the curing catalyst may include a phosphonium ion-containing compound. As a result, the epoxy resin composition can be cured even at low temperatures, and storage stability and the like may be good.
에폭시수지Epoxy resin
에폭시수지는 비스페놀 A형 에폭시수지, 비스페놀 F형 에폭시수지 등의 비스페놀형 에폭시수지, 페놀노볼락형 에폭시 수지, tert-부틸 카테콜형 에폭시수지, 나프탈렌형 에폭시수지, 글리시딜아민형 에폭시수지, 페놀아랄킬형 에폭시수지, 크레졸노볼락형 에폭시수지, 비페닐형 에폭시수지, 선형지방족에폭시수지, 지환식에폭시수지, 복소환식 에폭시수지, 스피로환 함유 에폭시수지, 시클로헥산디메탄올형 에폭시수지, 할로겐화 에폭시 수지 등이 될 수 있고, 이들은 단독 또는 2종 이상 혼합하여 포함될 수도 있다.Epoxy resin is bisphenol epoxy resin such as bisphenol A epoxy resin, bisphenol F epoxy resin, phenol novolac epoxy resin, tert-butyl catechol epoxy resin, naphthalene epoxy resin, glycidylamine epoxy resin, phenol Aralkyl type epoxy resin, cresol novolak type epoxy resin, biphenyl type epoxy resin, linear aliphatic epoxy resin, alicyclic epoxy resin, heterocyclic epoxy resin, spiro ring containing epoxy resin, cyclohexane dimethanol type epoxy resin, halogenated epoxy resin Or the like, and these may be included alone or in combination of two or more thereof.
일 구체예에서, 에폭시수지는 하기 화학식 5의 비페닐형 에폭시수지, 하기 화학식 6의 페놀아랄킬형 에폭시수지가 될 수 있다:In one embodiment, the epoxy resin may be a biphenyl type epoxy resin of Formula 5 and a phenol aralkyl type epoxy resin of Formula 6:
<화학식 5><Formula 5>
(상기 화학식 5에서, R은 탄소수 1 내지 4의 알킬기, n의 평균치는 0 내지 7이다.)(In Formula 5, R is an alkyl group having 1 to 4 carbon atoms, the average value of n is 0 to 7.)
<화학식 6><Formula 6>
(상기 화학식 6에서, n의 평균치는 1 내지 7이다).(In Formula 6, the average value of n is 1 to 7).
에폭시수지는 조성물 중 고형분 기준으로 약 1 내지 90중량%, 예를 들면 약 2 내지 17중량%, 예를 들면 약 3 내지 15중량%, 예를 들면 약 3 내지 12중량% 포함될 수 있다. 상기 범위에서, 조성물의 경화성이 저하되지 않을 수 있다.The epoxy resin may be included in the composition about 1 to 90% by weight, for example about 2 to 17% by weight, for example about 3 to 15% by weight, for example about 3 to 12% by weight. In the above range, the curability of the composition may not be lowered.
경화제Hardener
경화제는 페놀아랄킬형 페놀수지, 페놀노볼락형 페놀수지, 자일록형 페놀수지, 크레졸 노볼락형 페놀수지, 나프톨형 페놀수지, 테르펜형 페놀수지, 다관능형 페놀수지, 디시클로펜타디엔계 페놀수지, 비스페놀 A와 레졸로부터 합성된 노볼락형 페놀수지, 트리스(하이드록시페닐)메탄, 디하이드록시바이페닐을 포함하는 다가 페놀 화합물, 무수 말레인산 및 무수 프탈산을 포함하는 산무수물, 메타-페닐렌디아민, 디아미노디페닐메탄, 디아미노디페닐설폰 등의 방향족 아민 등을 들 수 있다. 경화제는 하나 이상의 수산기를 갖는 페놀수지를 사용할 수 있다.The curing agent is a phenol aralkyl type phenol resin, a phenol phenol novolak phenol resin, a xylock phenol resin, a cresol novolak phenol resin, a naphthol phenol resin, a terpene phenol resin, a polyfunctional phenol resin, a dicyclopentadiene phenol resin, Novolac-type phenolic resins synthesized from bisphenol A and resol, polyhydric phenol compounds including tris (hydroxyphenyl) methane, dihydroxybiphenyl, acid anhydrides including maleic anhydride and phthalic anhydride, meta-phenylenediamine, Aromatic amines, such as diamino diphenylmethane and diamino diphenyl sulfone, etc. are mentioned. The curing agent may use a phenol resin having one or more hydroxyl groups.
일 구체예에서, 경화제는 하기 화학식 7의 자일록형 페놀수지, 하기 화학식 8의 페놀아랄킬형 페놀수지를 사용할 수 있다:In one embodiment, the curing agent may use a xylox phenolic resin of Formula 7 and a phenol aralkyl type phenolic resin of Formula 8 below:
<화학식 7><Formula 7>
(상기 화학식 7에서 n의 평균치는 0 내지 7이다.)(In Formula 7, the average value of n is 0 to 7.)
<화학식 8><Formula 8>
(상기 화학식 8에서 n의 평균치는 1 내지 7이다)(The average value of n in the formula (8) is 1 to 7)
경화제는 에폭시수지 조성물 중 고형분 기준으로 약 0.1 내지 90중량%, 예를 들면 약 0.5 내지 13중량%, 예를 들면 약 1 내지 10중량%, 예를 들면 약 2 내지 8중량% 포함될 수 있다. 상기 범위에서, 조성물의 경화성이 저하되지 않을 수 있다.The curing agent may be included in the epoxy resin composition in an amount of about 0.1 to 90% by weight, for example about 0.5 to 13% by weight, for example about 1 to 10% by weight, for example about 2 to 8% by weight. In the above range, the curability of the composition may not be lowered.
경화 촉매는 본 발명 일 실시예의 포스포늄 이온 함유 화합물을 포함할 수 있다.The curing catalyst may include the phosphonium ion-containing compound of one embodiment of the present invention.
에폭시수지 조성물은 포스포늄을 포함하지 않는 비-포스포늄 경화 촉매를 더 포함할 수 있다. 비-포스포늄 경화촉매는 3급 아민, 유기금속화합물, 유기인화합물, 이미다졸, 및 붕소화합물 등이 사용 가능하다. 3급 아민에는 벤질디메틸아민, 트리에탄올아민, 트리에틸렌디아민, 디에틸아미노에탄올, 트리(디메틸아미노메틸)페놀, 2-2-(디메틸아미노메틸)페놀, 2,4,6-트리스(디아미노메틸)페놀과 트리-2-에틸헥실산염 등이 있다. 유기 금속화합물에는 크로뮴아세틸아세토네이트, 징크아세틸아세토네이트, 니켈아세틸아세토네이트 등이 있다. 유기인화합물에는 트리스-4-메톡시포스핀, 트리페닐포스핀, 트리페닐포스핀트리페닐보란, 트리페닐포스핀-1,4-벤조퀴논 부가물 등이 있다. 이미다졸류에는 2-메틸이미다졸, 2-페닐이미다졸, 2-아미노이미다졸, 2-메틸-1-비닐이미다졸, 2-에틸-4-메틸이미다졸, 2-헵타데실이미다졸 등이 있다. 붕소화합물에는 트리페닐포스핀 테트라페닐보레이트, 테트라페닐보론염, 트리플루오로보란-n-헥실아민, 트리플루오로보란모노에틸아민, 테트라플루오로보란트리에틸아민, 테트라플루오로보란아민 등이 있다. 이외에도 1,5-디아자바이시클로[4.3.0]논-5-엔(1,5-diazabicyclo[4.3.0]non-5-ene: DBN), 1,8-디아자바이시클로[5.4.0]운덱-7-엔(1,8-diazabicyclo[5.4.0]undec-7-ene: DBU) 및 페놀노볼락 수지염 등을 사용할 수 있다. 경화촉매는 에폭시수지 또는 경화제와 선반응하여 만든 부가물을 사용하는 것도 가능하다. The epoxy resin composition may further include a non-phosphonium curing catalyst that does not contain phosphonium. As the non-phosphonium curing catalyst, tertiary amines, organometallic compounds, organophosphorus compounds, imidazoles, boron compounds and the like can be used. Tertiary amines include benzyldimethylamine, triethanolamine, triethylenediamine, diethylaminoethanol, tri (dimethylaminomethyl) phenol, 2-2- (dimethylaminomethyl) phenol, 2,4,6-tris (diaminomethyl ) Phenol and tri-2-ethylhexyl acid salt. Organometallic compounds include chromium acetylacetonate, zinc acetylacetonate, nickel acetylacetonate and the like. Organophosphorus compounds include tris-4-methoxyphosphine, triphenylphosphine, triphenylphosphine triphenylborane, triphenylphosphine-1,4-benzoquinone adduct. Imidazoles include 2-methylimidazole, 2-phenylimidazole, 2-aminoimidazole, 2 - methyl-1-vinylimidazole, 2-ethyl-4-methylimidazole, 2-heptadecyl Imidazole and the like. Examples of the boron compound include triphenylphosphine tetraphenylborate, tetraphenylboron salt, trifluoroborane-n-hexylamine, trifluoroborane monoethylamine, tetrafluoroboranetriethylamine, tetrafluoroboraneamine, and the like. . In addition, 1,5- diazabicyclo [4.3.0] non-5-ene (1, 5- diazabicyclo [4.3.0] non-5-ene: DBN), 1, 8- diazabicyclo [5.4. 0] undec-7-ene (1,8-diazabicyclo [5.4.0] undec-7-ene: DBU) and phenol novolak resin salts may be used. As the curing catalyst, it is also possible to use an epoxy resin or an adduct made by pre-reaction with a curing agent.
전체 경화촉매 중 본 발명 일 실시예의 포스포늄 이온 함유 화합물은 약 10 내지 100중량%, 예를 들면 약 60 내지 100중량%로 포함될 수 있고, 상기 범위에서 경화 반응 시간이 지연되지 않고, 조성물의 유동성이 확보 효과가 있을 수 있다. The phosphonium ion-containing compound of one embodiment of the present invention in the total curing catalyst may be included in about 10 to 100% by weight, for example about 60 to 100% by weight, the curing reaction time is not delayed in the above range, the fluidity of the composition This may have a securing effect.
경화 촉매는 에폭시수지 조성물 중 약 0.01 내지 10중량%, 예를 들면 약 0.01 내지 5중량%, 예를 들면 약 0.02 내지 1.5중량%, 예를 들면 약 0.05 내지 2.0중량%로 포함될 수 있다. 상기 범위에서, 경화 반응 시간이 지연되지 않고, 조성물의 유동성이 확보될 수 있다.The curing catalyst may be included in about 0.01 to 10% by weight, for example about 0.01 to 5% by weight, for example about 0.02 to 1.5% by weight, for example about 0.05 to 2.0% by weight of the epoxy resin composition. In the above range, the curing reaction time is not delayed, and the fluidity of the composition can be ensured.
에폭시수지 조성물은 통상의 첨가제를 더 포함할 수 있다. 구체예에서, 첨가제는 커플링제, 이형제, 응력 완화제, 가교 증진제, 레벨링제, 착색제 중 하나 이상을 포함할 수 있다.The epoxy resin composition may further include conventional additives. In an embodiment, the additive may comprise one or more of a coupling agent, a release agent, a stress relaxer, a crosslinking enhancer, a leveling agent, a colorant.
커플링제는 에폭시실란, 아미노실란, 머캡토실란, 알킬실란 및 알콕시실란으로 이루어진 군으로부터 선택되는 1종 이상을 사용할 수 있지만, 이에 제한되지 않는다. 커플링제는 에폭시 수지 조성물 중 약 0.1 내지 1중량%로 포함될 수 있다.The coupling agent may use one or more selected from the group consisting of epoxysilane, aminosilane, mercaptosilane, alkylsilane and alkoxysilane, but is not limited thereto. The coupling agent may be included in about 0.1 to 1% by weight of the epoxy resin composition.
이형제는 파라핀계 왁스, 에스테르계 왁스, 고급 지방산, 고급 지방산 금속염, 천연 지방산 및 천연 지방산 금속염으로 이루어진 군으로부터 선택되는 1종 이상을 사용할 수 있다. 이형제는 에폭시 수지 조성물 중 약 0.1 내지 1중량%로 포함될 수 있다.The release agent may use one or more selected from the group consisting of paraffin wax, ester wax, higher fatty acid, higher fatty acid metal salt, natural fatty acid and natural fatty acid metal salt. The release agent may be included in about 0.1 to 1% by weight of the epoxy resin composition.
응력 완화제는 변성 실리콘 오일, 실리콘 엘라스토머, 실리콘 파우더 및 실리콘 레진으로 이루어진 군으로부터 선택되는 1종 이상을 사용할 수 있지만, 이에 제한되지 않는다. 응력 완화제는 에폭시 수지 조성물 중 약 0 내지 6.5중량%, 예를 들면 약 0 내지 1중량%, 예를 들면 약 0.1 내지 1중량%로 함유되는 것이 바람직한데, 선택적으로 함유될 수도 있고, 양자 모두 함유될 수도 있다. 이때, 변성 실리콘 오일로는 내열성이 우수한 실리콘 중합체가 좋으며, 에폭시 관능기를 갖는 실리콘 오일, 아민 관능기를 갖는 실리콘 오일 및 카르복실 관능기를 갖는 실리콘 오일 등을 1종 또는 2종 이상 혼합하여 전체 에폭시 수지 조성물에 대해 약 0.05 내지 1.5 중량% 사용할 수 있다. 다만, 실리콘 오일을 약 1.5 중량% 이상 초과할 경우에는 표면 오염이 발생하기 쉽고 레진 블리드(bleed)가 길어질 우려가 있으며, 약 0.05 중량% 미만으로 사용 시에는 충분한 저탄성률을 얻을 수가 없게 되는 문제점이 있을 수 있다. 또한, 실리콘 파우더는 중심입경이 약 15㎛ 이하인 것이 성형성 저하의 원인으로 작용하지 않기에 특히 바람직하며, 전체 수지 조성물에 대하여 약 0 내지 5중량%, 예를 들면 약 0.1 내지 5중량%로 함유될 수 있다.The stress relieving agent may use one or more selected from the group consisting of modified silicone oils, silicone elastomers, silicone powders and silicone resins, but is not limited thereto. The stress relieving agent is preferably contained in about 0 to 6.5% by weight, for example about 0 to 1% by weight, for example about 0.1 to 1% by weight, in the epoxy resin composition, which may optionally be included, or both. May be At this time, the modified silicone oil is preferably a silicone polymer having excellent heat resistance, and the total epoxy resin composition by mixing one or two or more kinds of a silicone oil having an epoxy functional group, a silicone oil having an amine functional group, and a silicone oil having a carboxyl functional group. About 0.05 to 1.5% by weight. However, if the silicone oil exceeds about 1.5% by weight or more, surface contamination is likely to occur and the resin bleed may be long, and when used below about 0.05% by weight, sufficient low modulus of elasticity may not be obtained. There may be. In addition, it is particularly preferable that the silicon powder has a central particle size of about 15 μm or less, which does not act as a cause of the deterioration of moldability, and is contained in about 0 to 5 wt%, for example, about 0.1 to 5 wt% based on the total resin composition. Can be.
착색제는 카본블랙 등이 될 수 있고, 에폭시수지 조성물 중 약 0.1 내지 3중량%로 포함될 수 있다.The colorant may be carbon black and the like, and may be included in about 0.1 to 3% by weight of the epoxy resin composition.
첨가제는 에폭시 수지 조성물 중 약 0.1 내지 10중량%, 예를 들면 약 0.1 내지 3중량%로 포함될 수 있다.The additive may be included in about 0.1 to 10% by weight, for example about 0.1 to 3% by weight of the epoxy resin composition.
에폭시수지 조성물은 무기충전제를 더 포함할 수 있다. 무기충전제는 조성물의 기계적 물성의 향상과 저응력화를 높일 수 있다. 무기충전제의 예로는 용융실리카, 결정성실리카, 탄산칼슘, 탄산마그네슘, 알루미나, 마그네시아, 클레이(clay), 탈크(talc), 규산칼슘, 산화티탄, 산화안티몬, 유리섬유 중 하나 이상을 포함할 수 있다. The epoxy resin composition may further include an inorganic filler. Inorganic fillers can increase the mechanical properties and lower the stress of the composition. Examples of inorganic fillers may include one or more of molten silica, crystalline silica, calcium carbonate, magnesium carbonate, alumina, magnesia, clay, talc, calcium silicate, titanium oxide, antimony oxide, and glass fibers. have.
바람직하게는 저응력화를 위해서 선팽창계수가 낮은 용융실리카를 사용한다. 용융실리카는 진비중이 약 2.3 이하인 비결정성 실리카를 의미하는 것으로 결정성 실리카를 용융하여 만들거나 다양한 원료로부터 합성한 비결정성 실리카도 포함된다. 용융실리카의 형상 및 입경은 특별히 한정되지는 않지만, 평균 입경 약 5 내지 30㎛의 구상용융실리카를 약 50 내지 99중량%, 평균입경 약 0.001 내지 1㎛의 구상용융실리카를 약 1 내지 50중량%를 포함한 용융실리카 혼합물을 전체 충전제에 대하여 약 40 내지 100중량%가 되도록 포함하는 것이 좋다. 또한, 용도에 맞춰 그 최대 입경을 약 45㎛, 약 55㎛, 및 약 75㎛ 중 어느 하나로 조정해서 사용할 수가 있다. 상기 용융구상실리카에는 도전성의 카본이 실리카 표면에 이물질로서 포함되는 경우가 있으나 극성 이물질의 혼입이 적은 물질을 선택하는 것도 중요하다. Preferably, molten silica having a low coefficient of linear expansion is used to reduce stress. Fused silica refers to amorphous silica having a specific gravity of about 2.3 kW or less, including amorphous silica made by melting crystalline silica or synthesized from various raw materials. The shape and particle size of the molten silica are not particularly limited, but about 50 to 99% by weight of spherical molten silica having an average particle diameter of about 5 to 30 µm and about 1 to 50% by weight of spherical molten silica having an average particle diameter of about 0.001 to 1 µm. It is preferable to include a molten silica mixture containing about 40 to 100% by weight relative to the total filler. In addition, the maximum particle diameter can be adjusted to any one of about 45 µm, about 55 µm, and about 75 µm according to the application. In the molten spherical silica, conductive carbon may be included as a foreign material on the silica surface, but it is also important to select a material having a small amount of polar foreign matter mixed therein.
무기충전제의 사용량은 성형성, 저응력성, 및 고온강도 등의 요구 물성에 따라 다르다. 구체예에서는 무기충전제는 에폭시수지 조성물 중 약 70 내지 95중량%, 예를 들면 약 75 내지 92중량%로 포함될 수 있다. 상기 범위에서, 에폭시수지 조성물의 난연성, 유동성 및 신뢰성을 확보할 수 있다.The amount of the inorganic filler used depends on the required physical properties such as formability, low stress, and high temperature strength. In embodiments, the inorganic filler may be included in about 70 to 95% by weight, for example about 75 to 92% by weight of the epoxy resin composition. In the above range, it is possible to ensure the flame retardancy, fluidity and reliability of the epoxy resin composition.
에폭시수지 조성물은 저온에서도 경화가능하고, 예를 들면 경화개시온도는 약 90내지 120℃가 될 수 있다. 상기 범위에서, 저온에서도 경화가 충분히 진행되어, 저온 경화의 효과가 있을 수 있다. The epoxy resin composition is curable at low temperatures, for example, the curing start temperature may be about 90 to 120 ℃. In the above range, curing proceeds well even at low temperatures, and there may be an effect of low temperature curing.
에폭시수지 조성물은 포스포늄 이온 함유 화합물을 포함함으로써 저장안정성이 높아, 소정 범위의 온도에서 소정 시간 저장하더라도 경화가 진행되지 않아 점도의 변화가 낮다. 일 구체예에 따르면, 에폭시수지 조성물은 하기 식 1의 점도변화율이 약 16% 이하, 예를 들면 약 0 내지 15.5%가 될 수 있다:The epoxy resin composition contains a phosphonium ion-containing compound, which has a high storage stability, and even though the epoxy resin composition is stored for a predetermined time at a predetermined range of temperature, curing does not proceed, resulting in low viscosity change. According to one embodiment, the epoxy resin composition may have a viscosity change rate of about 16% or less, for example, about 0 to 15.5% of Equation 1 below:
<식 1><Equation 1>
점도변화율 = ｜B-A｜ / A x 100Viscosity Change Rate = ｜ B-A ｜ / A x 100
(상기 식 1에서, A는 에폭시수지 조성물의 25℃에서 측정한 점도(단위:cPs), B는 에폭시수지 조성물을 25℃ 조건에서 24 시간 방치한 후 25℃에서 측정한 점도(단위:cPs)이다) 상기 범위에서, 저장안정성이 높아 원하는 경화온도가 될 때에만 경화를 촉매시키고 원하는 경화온도가 아닐 때에는 경화 촉매 활성이 없고, 실제로 고온에서 경화반응 시켰을 때 유동성 저하에 따른 성형성 저하, 성형 제품의 기계적, 전기적, 화학적 특성 저하가 없을 수 있다.(In Formula 1, A is the viscosity (unit: cPs) measured at 25 ℃ of the epoxy resin composition, B is the viscosity (unit: cPs) measured at 25 ℃ after leaving the epoxy resin composition at 25 ℃ conditions for 24 hours) In the above range, the storage stability is high and the curing is catalyzed only when the desired curing temperature is reached, and when the curing temperature is not the desired curing activity, there is no curing catalyst activity. There may be no degradation in mechanical, electrical and chemical properties.
에폭시수지 조성물은 EMMI-1-66에서 175℃, 70kgf/cm2에서 트랜스퍼 몰딩 프레스에 의한 유동길이가 약 59 내지 75inch가 될 수 있다. 상기 범위에서, 에폭시수지 조성물의 용도로 사용될 수 있다.The epoxy resin composition may have a flow length of about 59 to 75 inches by a transfer molding press at 175 ° C. and 70 kgf / cm 2 in EMMI-1-66. In the above range, it can be used for the use of the epoxy resin composition.
에폭시수지 조성물은 하기 식 2에 의해 측정된 경화수축률이 약 0.4% 미만, 예를 들면 약 0.01 내지 0.39%가 될 수 있다:The epoxy resin composition may have a curing shrinkage ratio of less than about 0.4%, for example about 0.01 to 0.39%, measured by the following equation:
[식 2][Equation 2]
경화수축률 = ｜C - D｜/ C x 100Cure Shrinkage = ｜ C-D ｜ / C x 100
(상기 식 2에서, C는 에폭시수지 조성물을 175℃, 70kgf/cm2에서 트랜스퍼 몰딩 프레스하여 얻은 시편의 길이, D는 상기 시편을 170~180℃에서 4시간 후경화하고, 냉각시킨 후 얻은 시편의 길이이다). 상기 범위에서, 경화수축률이 낮아 에폭시수지 조성물의 용도로 사용될 수 있다.(In Formula 2, C is the length of the specimen obtained by transfer molding press the epoxy resin composition at 175 ℃, 70kgf / cm 2 , D is the specimen obtained after curing the specimen at 170 ~ 180 ℃ 4 hours, and cooled Is the length of). In the above range, the curing shrinkage rate is low can be used for the use of the epoxy resin composition.
본 발명의 에폭시수지 수지 조성물의 용도는 반도체 소자 밀봉용도, 접착필름, 프리프레그 등의 절연수지시트, 회로기판, 솔더레지스트, 언더필제, 다이본딩재, 부품 보충 수지 용도 등의 에폭시수지 조성물이 필요로 하는 광범위한 용도에 적용될 수 있으며, 이에 제한되는 것은 아니다.The use of the epoxy resin resin composition of the present invention requires epoxy resin compositions such as semiconductor device sealing applications, adhesive resins, insulating resin sheets such as prepregs, circuit boards, solder resists, underfill agents, die bonding materials, and component supplement resin applications. It can be applied to a wide range of uses, but is not limited thereto.
(1)반도체 소자 밀봉용도(1) semiconductor element sealing
본 발명의 에폭시수지 조성물은 반도체 소자 밀봉용도로 사용될 수 있고, 에폭시수지, 경화제, 포스포늄 이온 함유 화합물 함유 경화촉매, 무기충진제, 첨가제를 포함할 수 있다.The epoxy resin composition of the present invention may be used for sealing semiconductor devices, and may include an epoxy resin, a curing agent, a phosphonium ion-containing compound-containing curing catalyst, an inorganic filler, and an additive.
일 구체예에 의하면, 에폭시수지 약 2 내지 17중량%, 예를 들면 약 3 내지 12중량%로 포함될 수 있고 상기 범위에서 에폭시 수지 조성물의 유동성, 난연성, 신뢰성이 좋을 수 있고, 포스포늄 이온 화합물 함유 경화 촉매 약 0.01 내지 5중량%, 예를 들면 약 0.05 내지 1.5중량%를 포함할 수 있고 상기 범위에서 미반응된 에폭시기 및 페놀성 수산기가 다량 발생하지 않아 신뢰성이 우수할 수 있고, 경화제 약 0.5 내지 13중량%, 예를 들면 약 2 내지 8중량%로 포함될 수 있고 상기 범위에서 미반응된 에폭시기 및 페놀성 수산기가 다량 발생하지 않아 신뢰성이 우수할 수 있고, 무기충진제 약 70 내지 95중량%, 예를 들면 약 75 내지 92중량%를 포함할 수 있고 상기 범위에서 에폭시 수지 조성물의 난연성, 유동성 및 신뢰성을 확보할 수 있고, 첨가제 약 0.1 내지 10중량%, 예를 들면 약 0.1 내지 3중량%를 포함할 수 있다. According to one embodiment, the epoxy resin may be included in about 2 to 17% by weight, for example about 3 to 12% by weight, the flowability, flame retardancy, and reliability of the epoxy resin composition in the above range, it may contain a phosphonium ion compound It may include about 0.01 to 5% by weight of the curing catalyst, for example about 0.05 to 1.5% by weight and does not generate a large amount of unreacted epoxy group and phenolic hydroxyl group in the above range can be excellent in reliability, about 0.5 to about It may be included in 13% by weight, for example about 2 to 8% by weight and does not generate a large amount of unreacted epoxy group and phenolic hydroxyl group in the above range may be excellent in reliability, about 70 to 95% by weight inorganic filler, eg For example, it may include about 75 to 92% by weight and may ensure the flame retardancy, flowability and reliability of the epoxy resin composition in the above range, about 0.1 to 10% by weight additives, for example About 0.1 to 3% by weight of cotton.
에폭시수지 조성물 중 에폭시수지는 단독으로 사용되거나, 경화제, 경화촉매, 이형제, 커플링제, 및 응력완화제 등의 첨가제와 멜트 마스터 배치(melt master batch)와 같은 선반응을 시켜 만든 부가 화합물로도 포함될 수 있다. 에폭시 수지 조성물을 제조하는 방법은 특별히 제한되지 않지만, 조성물에 포함되는 각 구성성분을 헨셀 믹서나 뢰디게 믹서를 이용하여 균일하게 혼합한 후, 롤 밀이나 니이더로 약 90~120℃에서 용융 혼련하고, 냉각 및 분쇄 과정을 거쳐 제조될 수 있다. Epoxy resins in the epoxy resin composition may be used alone, or may be included as a compound added by a preliminary reaction such as a melt master batch with an additive such as a curing agent, a curing catalyst, a releasing agent, a coupling agent, and a stress relaxation agent. have. The method for producing the epoxy resin composition is not particularly limited, but the components contained in the composition are uniformly mixed by using a Henschel mixer or a Lodige mixer, and then melt kneaded at about 90 to 120 ° C. with a roll mill or kneader. It can be prepared through the cooling and grinding process.
본 발명의 조성물을 이용하여 반도체 소자를 밀봉하는 방법은 저압 트랜스퍼 성형 방법이 가장 일반적으로 사용될 수 있다. 그러나, 인젝션(injection) 성형 방법이나 캐스팅(casting) 방법 등의 방법으로도 성형될 수 있다. 상기 방법에 의해 구리 리드프레임, 철 리드프레임, 또는 상기 리드프레임에 니켈 및 구리로 팔라듐으로 이루어진 군으로부터 선택되는 1종 이상의 물질로 프리플레이팅된 리드프레임, 또는 유기계 라미네이트 프레임의 반도체 소자를 제조할 수 있다.As a method of sealing a semiconductor device using the composition of the present invention, a low pressure transfer molding method may be most commonly used. However, it can also be molded by an injection molding method or a casting method. By the above method, a semiconductor device of a copper lead frame, an iron lead frame, or a lead frame pre-plated with at least one material selected from the group consisting of palladium with nickel and copper on the lead frame, or an organic laminate frame can be manufactured. Can be.
(2)접착 필름(2) adhesive film
에폭시수지 조성물은 지지필름 위에 도포하고 경화시켜 프린트 배선판용 접착필름 용도로 사용될 수 있다. 접착필름은 당업자에게 공지된 방법, 예를 들면 유기 용제 조성물을 용해시키고, 지지필름을 지지체로 하여 조성물을 도포하고, 가열 또는 열풍 분사 등에 의해 유기용제를 건조시켜 형성할 수 있고, 유기 용제로는 아세톤, 메틸에틸케톤 등의 케톤류, 아세트산에틸, 아세트산부틸 등의 아세트산에스테르류, 셀로솔브, 부틸카르비톨 등의 카르비톨류, 톨루엔 등의 방향족탄화수소류, 디케틸포름아미드 등의 아미드계 용제 등이 될 수 있고, 단독 또는 2종 이상 혼합하여 사용될 수 있다. 건조 조건은 특별히 제한되지 않지만, 도포층 중 유기용제의 함유율이 약 10중량% 이하가 되도록 건조시키는 것으로서, 약 50 내지 100℃에서 약 1 내지 10분 동안 건조시킬 수 있다. 지지필름으로는 폴리에틸렌, 폴리프로필렌 등의 폴리올레핀, 폴리에틸렌테레프탈레이트 등의 폴리에스테르, 폴리카보네이트, 폴리이미드 등이 될 수 있고, 지지필름의 두께는 약 10 내지 150㎛가 될 수 있다. The epoxy resin composition may be applied to a support film and cured to be used as an adhesive film for a printed wiring board. The adhesive film may be formed by dissolving the organic solvent composition, for example, by dissolving the organic solvent composition, applying the composition with the support film as a support, and drying the organic solvent by heating or hot air spraying. Ketones such as acetone and methyl ethyl ketone, acetate esters such as ethyl acetate and butyl acetate, carbitols such as cellosolve and butyl carbitol, aromatic hydrocarbons such as toluene, and amide solvents such as diketylformamide It may be used alone or in combination of two or more. Drying conditions are not particularly limited, but the drying conditions are such that the content of the organic solvent in the coating layer is about 10% by weight or less, and may be dried at about 50 to 100 ° C. for about 1 to 10 minutes. The support film may be polyolefin such as polyethylene or polypropylene, polyester such as polyethylene terephthalate, polycarbonate, polyimide, or the like, and the thickness of the support film may be about 10 to 150 μm.
(3)프리프레그(3) prepreg
에폭시수지 조성물은 시트형 보강기재에 함침시키고, 가열하여 반경화시킴으로써 프리프레그로 사용할 수 있고, 보강기재로는 특별한 제한되는 것은 없고 프리프레그에 상용되는 것으로서, 유리크로스, 아라미드 섬유 등의 프리프레그용 섬유가 될 수 있다.The epoxy resin composition can be used as a prepreg by impregnating a sheet-like reinforcing base material and heating and semi-curing, and there is no particular limitation on the reinforcing base material, and it is commonly used in prepreg, and fibers for prepreg such as glass cross and aramid fiber Can be
본 발명 일 실시예의 장치는 상기 에폭시수지 조성물을 사용하여 제조될 수 있다. 예를 들면, 장치는 에폭시수지 조성물을 사용하여 밀봉된 반도체 소자, 이를 포함하는 반도체 장치 또는 디스플레이 장치, 에폭시수지 조성물로부터 형성된 접착필름을 포함하는 다층 배선 기판 등이 될 수 있다.The device of one embodiment of the present invention can be manufactured using the epoxy resin composition. For example, the device may be a semiconductor device sealed using an epoxy resin composition, a semiconductor device or display device including the same, a multilayer wiring board including an adhesive film formed from the epoxy resin composition, and the like.
이하, 본 발명을 실시예에 의거 더욱 상세히 설명하나, 실시예에 의거 본 발명이 한정되는 것은 아니다.Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to Examples.
실시예 1Example 1
Triphenylphosphine 2.6g 및 4-Nitrobenzyl bromide 2.2g을 Toluene 30ml에 녹인 후 110℃에서 3시간 동안 반응을 진행시키고 생성된 침전을 거르고 건조하여 고형물 3.0g을 얻어내었다. 얻어낸 고형물 3.0g을 Methylene chloride 50ml에 녹인 후 Sodium Sulfadiazine 1.2g과 25℃에서 24시간 반응시킨 후 침전을 걸러낸 뒤 얻어낸 liquid를 감압증류(evaporating)과정을 통해 고형물 1.0g을 얻었고, NMR 데이타로 하기 화학식 9의 화합물임을 확인하였다.After dissolving 2.6 g of triphenylphosphine and 2.2 g of 4-Nitrobenzyl bromide in 30 ml of toluene, the reaction was performed at 110 ° C. for 3 hours, and the resulting precipitate was filtered and dried to obtain 3.0 g of a solid. 3.0 g of the obtained solid was dissolved in 50 ml of Methylene chloride, reacted with Sodium Sulfadiazine 1.2 g at 25 ° C. for 24 hours, and the precipitate was filtered. The obtained liquid was evaporated under reduced pressure to obtain 1.0 g of solid, which was obtained by NMR data. It was confirmed that the compound of Formula 9.
<화학식 9><Formula 9>
1H NMR (400 MHz, DMSO) 8.30 (d, J = 2.2 Hz, 2H), 8.10 (m, 2H), 7.93 (m, 3H), 7.82-7.65 (m, 14H), 7.27 (m, 2H), 6.75 (d, J = 2.2 Hz, 2H), 6.50 (m, 1H), 5.45 (d, J= 5.2Hz, 2H), 1,62 (br s, 2H) ppm; 13C NMR (100 MHz, DMSO) 169.2, 157.8, 157.7, 151.9, 145.5, 135.1, 134.4, 131.2, 130.2, 130.1, 129.9, 129.8, 128.1, 128.0, 122.4, 122.8, 118.8, 118.1, 116.6, 116.5, 110.5 ppm; 31P NMR (166 MHz, DMSO) 24.29 ppm; LC-MS m/z = 647 (M+); Anal. Calcd for C35H30N5O4PS: C, 64.90; H, 4.67; N, 10.81; S, 4.95. Found: C, 64.97; H, 4.56; N, 10.99; S, 4.58. 1 H NMR (400 MHz, DMSO) 8.30 (d, J = 2.2 Hz, 2H), 8.10 (m, 2H), 7.93 (m, 3H), 7.82-7.65 (m, 14H), 7.27 (m, 2H) , 6.75 (d, J = 2.2 Hz, 2H), 6.50 (m, 1H), 5.45 (d, J = 5.2 Hz, 2H), 1,62 (br s, 2H) ppm; 13 C NMR (100 MHz, DMSO) 169.2, 157.8, 157.7, 151.9, 145.5, 135.1, 134.4, 131.2, 130.2, 130.1, 129.9, 129.8, 128.1, 128.0, 122.4, 122.8, 118.8, 118.1, 116.6, 116.5, 110.5 ppm; 31 P NMR (166 MHz, DMSO) 24.29 ppm; LC-MS m / z = 647 (M + ); Anal. Calcd for C 35 H 30 N 5 O 4 PS: C, 64.90; H, 4.67; N, 10.81; S, 4.95. Found: C, 64.97; H, 4.56; N, 10.99; S, 4.58.
실시예 2Example 2
Triphenylphosphine 2.6g 및 Benzyl bromide 1.7g을 Toluene 30ml에 녹인 후 110℃에서 3시간 동안 반응을 진행시키고 생성된 침전을 거르고 건조하여 고형물 3.0g을 얻어내었다. 얻어낸 고형물 3.0g을 Methylene chloride 50ml에 녹인 후 Sodium Sulfadiazine 1.2g과 상온에서 24시간 반응시킨 후 침전을 걸러낸 뒤 얻어낸 liquid를 감압증류(evaporating)과정을 통해 고형물 1.0g을 얻었고, NMR 데이타로 하기 화학식 10의 화합물임을 확인하였다.After dissolving 2.6 g of triphenylphosphine and 1.7 g of benzyl bromide in 30 ml of toluene, the reaction was carried out at 110 ° C. for 3 hours, and the resulting precipitate was filtered and dried to obtain 3.0 g of a solid. 3.0 g of the obtained solid was dissolved in 50 ml of Methylene chloride, and then reacted with Sodium Sulfadiazine 1.2 g at room temperature for 24 hours. After filtering out the precipitate, the obtained liquid was evaporated under reduced pressure to obtain 1.0 g of solid, which was obtained by NMR data. It was confirmed that the compound of 10.
<화학식 10><Formula 10>
1H NMR (400 MHz, DMSO) 8.31 (d, J = 2.2 Hz, 2H), 7.90-6.94 (m, 22H), 6.74 (d, J = 2.2 Hz, 2H), 6.58 (m, 1H), 5.48 (d, J= 5.4Hz, 2H), 2.1 (br s, 2H) ppm; 13C NMR (100 MHz, DMSO) 169.3, 157.9, 157.8, 151.6, 135.1, 134.5, 134.4, 131.2, 130.2, 130.1, 129.9, 129.8, 129.7, 128.3, 128.2, 128.1, 127.8, 118.8, 118.1, 116.6, 116.5, 110.3 ppm; 31P NMR (166 MHz, DMSO) 24.15 ppm; LC-MS m/z = 602 (M+); Anal. Calcd for C35H31N4O2PS: C, 69.75; H, 5.18; N, 9.30; S, 5.31. Found: C, 69.48; H, 5.37; N, 9.33; S, 5.52. 1 H NMR (400 MHz, DMSO) 8.31 (d, J = 2.2 Hz, 2H), 7.90-6.94 (m, 22H), 6.74 (d, J = 2.2 Hz, 2H), 6.58 (m, 1H), 5.48 (d, J = 5.4 Hz, 2H), 2.1 (br s, 2H) ppm; 13 C NMR (100 MHz, DMSO) 169.3, 157.9, 157.8, 151.6, 135.1, 134.5, 134.4, 131.2, 130.2, 130.1, 129.9, 129.8, 129.7, 128.3, 128.2, 128.1, 127.8, 118.8, 118.1, 116.6, 116.5 , 110.3 ppm; 31 P NMR (166 MHz, DMSO) 24.15 ppm; LC-MS m / z = 602 (M + ); Anal. Calcd for C 35 H 31 N 4 O 2 PS: C, 69.75; H, 5. 18; N, 9.30; S, 5.31. Found: C, 69.48; H, 5. 37; N, 9.33; S, 5.52.
실시예 3Example 3
Tetraphenylphosphonium Bromide 3.0g을 Methylene chloride 50ml에 녹인 후 Silver 4-amino-N-(5-methyl-2-pyrimidinyl)-Benzenesulfonamide 1.2g과 상온에서 24시간 반응시킨 후 침전을 걸러낸 뒤 얻어낸 liquid를 감압증류(evaporating)과정을 통해 고형물 1.0g을 얻었고, NMR 데이타로 하기 화학식 11의 화합물임을 확인하였다.After dissolving 3.0 g of tetraphenylphosphonium Bromide in 50 ml of Methylene chloride and reacting with 1.2 g of Silver 4-amino-N- (5-methyl-2-pyrimidinyl) -Benzenesulfonamide for 24 hours at room temperature, the precipitate was filtered and the resulting liquid was distilled under reduced pressure. By evaporating) to obtain a solid 1.0g, it was confirmed that the compound of formula 11 by NMR data.
<화학식 11><Formula 11>
1H NMR (400 MHz, DMSO) 8.17 (s, 2H), 8.05-7.65 (m, 22H), 6.74 (d, J = 2.2 Hz, 2H), 2.0 (br s, 2H) ppm; 13C NMR (100 MHz, DMSO) 167.0, 157.7, 157.6, 151.6, 135.1, 134.2, 134.1, 130.3, 130.2, 130.0,129.7, 128.1, 128.0, 118.8, 118.5, 118.0, 116.6, 116.5, 24.3 ppm; 31P NMR (166 MHz, DMSO) 24.30 ppm; LC-MS m/z = 602 (M+); Anal. Calcd for C35H31N4O2PS: C, 69.75; H, 5.18; N, 9.30; S, 5.31. Found: C, 69.76; H, 5.44; N, 9.57; S, 5.64. 1 H NMR (400 MHz, DMSO) 8.17 (s, 2H), 8.05-7.65 (m, 22H), 6.74 (d, J = 2.2 Hz, 2H), 2.0 (br s, 2H) ppm; 13 C NMR (100 MHz, DMSO) 167.0, 157.7, 157.6, 151.6, 135.1, 134.2, 134.1, 130.3, 130.2, 130.0, 129.7, 128.1, 128.0, 118.8, 118.5, 118.0, 116.6, 116.5, 24.3 ppm; 31 P NMR (166 MHz, DMSO) 24.30 ppm; LC-MS m / z = 602 (M + ); Anal. Calcd for C 35 H 31 N 4 O 2 PS: C, 69.75; H, 5. 18; N, 9.30; S, 5.31. Found: C, 69.76; H, 5. 44; N, 9.57; S, 5.64.
실시예 4Example 4
Tetraphenylphosphonium Bromide 3.0g을 Methylene chloride 50ml에 녹인 후 Silver 4-(methylamino)-N-(pyrimidin-2-yl)benzenesulfonamide 1.2g과 상온에서 24시간 반응시킨 후 침전을 걸러낸 뒤 얻어낸 liquid를 감압증류(evaporating)과정을 통해 고형물 1.0g을 얻었고, NMR 데이타로 하기 화학식 12의 화합물임을 확인하였다.After dissolving 3.0 g of tetraphenylphosphonium Bromide in 50 ml of Methylene chloride and reacting with 1.2 g of Silver 4- (methylamino) -N- (pyrimidin-2-yl) benzenesulfonamide for 24 hours at room temperature, the precipitate was filtered and evaporated under reduced pressure. ) To obtain a solid 1.0g, it was confirmed by the NMR data that the compound of formula 12.
<화학식 12><Formula 12>
1H NMR (400 MHz, DMSO) 8.38 (d, J = 2.2 Hz, 2H), 8.05-7.65 (m, 22H), 6.71 (d, J = 2.2 Hz, 2H), 6.58 (m, 1H), 3.40 (br s, 1H), 2.78 (s, 3H) ppm; 13C NMR (100 MHz, DMSO) 169.1, 157.9, 157.8, 150.8, 135.1, 134.2, 134.1, 130.3, 130.2, 128.2, 128.1, 128.0, 118.8, 118.5, 113.9, 113.8, 110.3, 29.7 ppm; 31P NMR (166 MHz, DMSO) 24.28 ppm; LC-MS m/z = 602 (M+); Anal. Calcd for C35H31N4O2PS: C, 69.75; H, 5.18; N, 9.30; S, 5.31. Found: C, 69.43; H, 5.15; N, 9.64; S, 5.38. 1 H NMR (400 MHz, DMSO) 8.38 (d, J = 2.2 Hz, 2H), 8.05-7.65 (m, 22H), 6.71 (d, J = 2.2 Hz, 2H), 6.58 (m, 1H), 3.40 (br s, 1 H), 2.78 (s, 3 H) ppm; 13 C NMR (100 MHz, DMSO) 169.1, 157.9, 157.8, 150.8, 135.1, 134.2, 134.1, 130.3, 130.2, 128.2, 128.1, 128.0, 118.8, 118.5, 113.9, 113.8, 110.3, 29.7 ppm; 31 P NMR (166 MHz, DMSO) 24.28 ppm; LC-MS m / z = 602 (M + ); Anal. Calcd for C 35 H 31 N 4 O 2 PS: C, 69.75; H, 5. 18; N, 9.30; S, 5.31. Found: C, 69.43; H, 5. 15; N, 9.64; S, 5.38.
실시예 5Example 5
Tetraphenylphosphonium Bromide 3.0g과 Sodium 4-methyl-N-propylbenzenesulfonamide 2.5g을 Methylene chloride/ H2O 1:1 용액 50ml에 녹인 후 상온에서 24시간 반응시킨 후 침전을 걸러낸 뒤 얻어낸 liquid를 감압증류(evaporating)과정을 통해 고형물 3.0g을 얻었고, NMR 데이타로 하기 화학식 13의 화합물임을 확인하였다.After dissolving 3.0 g of tetraphenylphosphonium Bromide and 2.5 g of sodium 4-methyl-N-propylbenzenesulfonamide in 50 ml of Methylene chloride / H 2 O 1: 1 solution, reacting at room temperature for 24 hours, filtering the precipitate and evaporating the obtained liquid 3.0 g of a solid was obtained through the procedure, and the NMR data confirmed that the compound was represented by Chemical Formula 13.
<화학식 13><Formula 13>
1H NMR (400 MHz, DMSO) 7.96 (t, J = 2.4 Hz, 4H), 7.85-7.80 (m, 8H), 7.75-7.70 (m, 8H), 7.69 (d, J = 6.0 Hz, 2H), 7.27 (d, J = 6.0 Hz, 2H), 3.16 (t, J = 6.4 Hz, 2H), 2.35 (s, 3H), 1.59 (m, 2H), 0.96 (t, J = 7.2 Hz, 2H) ppm; 13C NMR (100 MHz, DMSO) 141.6, 137.4, 137.3, 129.4, 128.9, 128.8, 127.2, 45.0, 24.3, 22.3, 11.2 ppm; 31P NMR (166 MHz, DMSO) 24.20 ppm; LC-MS m/z = 551 (M+); Anal. Calcd for C34H34NO2PS: C, 74.02; H, 6.21; N, 2.54; S, 5.81. Found: C, 74.34; H, 6.19; N, 2.87; S, 5.69. 1 H NMR (400 MHz, DMSO) 7.96 (t, J = 2.4 Hz, 4H), 7.85-7.80 (m, 8H), 7.75-7.70 (m, 8H), 7.69 (d, J = 6.0 Hz, 2H) , 7.27 (d, J = 6.0 Hz, 2H), 3.16 (t, J = 6.4 Hz, 2H), 2.35 (s, 3H), 1.59 (m, 2H), 0.96 (t, J = 7.2 Hz, 2H) ppm; 13 C NMR (100 MHz, DMSO) 141.6, 137.4, 137.3, 129.4, 128.9, 128.8, 127.2, 45.0, 24.3, 22.3, 11.2 ppm; 31 P NMR (166 MHz, DMSO) 24.20 ppm; LC-MS m / z = 551 (M + ); Anal. Calcd for C 34 H 34 NO 2 PS: C, 74.02; H, 6. 21; N, 2.54; S, 5.81. Found: C, 74.34; H, 6. 19; N, 2.87; S, 5.69.
실시예 6Example 6
Tetraphenylphosphonium Bromide 3.0g 과 Sodium N-(4-aminophenylsulfonyl)benzamide 3.0g을 Methylene chloride/ H2O 1:1 용액 50ml에 녹인 후 상온에서 24시간 반응시킨 후 침전을 걸러낸 뒤 얻어낸 liquid를 감압증류(evaporating)과정을 통해 고형물 3.2g을 얻어내었고, NMR 데이타로 하기 화학식 14의 화합물임을 확인하였다.After dissolving 3.0 g of tetraphenylphosphonium Bromide and 3.0 g of sodium N- (4-aminophenylsulfonyl) benzamide in 50 ml of Methylene chloride / H 2 O 1: 1 solution, reacting at room temperature for 24 hours, filtering the precipitate and evaporating the liquid obtained 3.2g of a solid was obtained through the process, and it was confirmed that the compound of Formula 14 was obtained by NMR data.
<화학식 14><Formula 14>
1H NMR (400 MHz, DMSO) 7.97 (t, J = 2.6 Hz, 4H), 7.88 (d, J = 2.2 Hz, 2H), 7.84-7.81 (m, 8H), 7.76-7.72 (m, 8H), 7.52 (d, J = 6.0 Hz, 2H), 7.31-7.25 (m, 3H), 6.47 (d, J = 6.0 Hz, 2H), 5.23 (s, 2H) ppm; 13C NMR (100 MHz, DMSO) 170.1, 151.6, 137.3, 134.2, 132.2, 129.7, 128.9, 128,8, 128.1, 127.5, 116.6 ppm; 31P NMR (166 MHz, DMSO) 24.10 ppm; LC-MS m/z = 614 (M+); Anal. Calcd for C37H31N2O3PS: C, 72.30; H, 5.08; N, 4.56; S, 5.22. Found: C, 72.42; H, 5.14; N, 4.75; S, 5.38. 1 H NMR (400 MHz, DMSO) 7.97 (t, J = 2.6 Hz, 4H), 7.88 (d, J = 2.2 Hz, 2H), 7.84-7.81 (m, 8H), 7.76-7.72 (m, 8H) , 7.52 (d, J = 6.0 Hz, 2H), 7.31-7.25 (m, 3H), 6.47 (d, J = 6.0 Hz, 2H), 5.23 (s, 2H) ppm; 13 C NMR (100 MHz, DMSO) 170.1, 151.6, 137.3, 134.2, 132.2, 129.7, 128.9, 128,8, 128.1, 127.5, 116.6 ppm; 31 P NMR (166 MHz, DMSO) 24.10 ppm; LC-MS m / z = 614 (M + ); Anal. Calcd for C 37 H 31 N 2 O 3 PS: C, 72.30; H, 5.08; N, 4.56; S, 5.22. Found: C, 72.42; H, 5. 14; N, 4.75; S, 5.38.
실시예 7Example 7
Tetraphenylphosphonium Bromide 3.0g과 Sodium Sulfacetamide 2.7g을 Methylene chloride/ H2O 1:1 용액 50ml에 녹인 후 상온에서 24시간 반응시킨 후 침전을 걸러낸 뒤 얻어낸 liquid를 감압증류(evaporating)과정을 통해 고형물 3.0g을 얻어내었고, NMR 데이타로 하기 화학식 15의 화합물임을 확인하였다.Dissolve 3.0 g of tetraphenylphosphonium Bromide and 2.7 g of Sodium Sulfacetamide in 50 ml of Methylene chloride / H 2 O 1: 1 solution, react at room temperature for 24 hours, filter the precipitate, and evaporate the liquid obtained by evaporating the solid. It was obtained, and confirmed by the NMR data that the compound of formula 15.
<화학식 15><Formula 15>
1H NMR (400 MHz, DMSO) 7.97 (t, J = 2.6 Hz, 4H), 7.84-7.81 (m, 8H), 7.76-7.72 (m, 8H), 7.42 (d, J = 6.6 Hz, 2H), 6.47 (d, J = 6.6 Hz, 2H), 5.23 (s, 2H), 1.66 (s, 3H)ppm; 13C NMR (100 MHz, DMSO) 173.2, 151.6, 137.4, 137.3, 129.7, 128.9, 128.8, 128.1, 116.6, 21.9 ppm; 31P NMR (166 MHz, DMSO) 24.30 ppm; LC-MS m/z = 552 (M+); Anal. Calcd for C32H29N2O3PS: C, 69.55; H, 5.29; N, 5.07; S, 5.80. Found: C, 69.48; H, 5.37; N, 5.11; S, 5.74. 1 H NMR (400 MHz, DMSO) 7.97 (t, J = 2.6 Hz, 4H), 7.84-7.81 (m, 8H), 7.76-7.72 (m, 8H), 7.42 (d, J = 6.6 Hz, 2H) , 6.47 (d, J = 6.6 Hz, 2H), 5.23 (s, 2H), 1.66 (s, 3H) ppm; 13 C NMR (100 MHz, DMSO) 173.2, 151.6, 137.4, 137.3, 129.7, 128.9, 128.8, 128.1, 116.6, 21.9 ppm; 31 P NMR (166 MHz, DMSO) 24.30 ppm; LC-MS m / z = 552 (M + ); Anal. Calcd for C 32 H 29 N 2 O 3 PS: C, 69.55; H, 5. 29; N, 5.07; S, 5.80. Found: C, 69.48; H, 5. 37; N, 5.11; S, 5.74.
실시예 8Example 8
Triphenylphosphine 2.6g과 4-bromophenol 1.6g을 Ethylene glycol 5ml에서 녹인 후 180℃에서 5시간 동안 반응을 진행시키고 침전을 거르고 건조하여 고형물 2.2g을 얻어내었다. 얻어낸 고형물 3.0g을 Sodium sulfacetamide 2.7g과 Methylene chloride/ H2O 1:1 용액 50ml에 녹인 후 상온에서 24시간 반응시킨 후 MC 층을 취하여 얻어낸 liquid를 감압증류(evaporating)과정을 통해 고형물 4.0g을 얻어내었고, NMR 데이타로 하기 화학식 16의 화합물임을 확인하였다.After dissolving 2.6 g of triphenylphosphine and 1.6 g of 4-bromophenol in 5 ml of ethylene glycol, the reaction was carried out at 180 ° C. for 5 hours, and the precipitate was filtered and dried to obtain 2.2 g of a solid. 3.0 g of the solid obtained was dissolved in 2.7 g of sodium sulfacetamide and 50 ml of Methylene chloride / H 2 O 1: 1 solution. The mixture was reacted at room temperature for 24 hours. The MC layer was removed, and the obtained liquid was evaporated under reduced pressure (4.0 g). It was obtained, and confirmed by NMR data that the compound of the formula (16).
<화학식 16><Formula 16>
1H NMR (400 MHz, DMSO) 7.97-7.90 (m, 3H), 7.78-7.65 (m, 12H), 7.42 (d, J = 6.6 Hz, 2H), 7.38 (d, J = 8.6 Hz, 2H), 6.97 (d, J = 8.6 Hz, 2H), 6.47 (d, J = 6.6 Hz, 2H), 5.54 (s, 1H), 4.12 (br, 2H), 1.66 (s, 3H) ppm; 13C NMR (100 MHz, DMSO) 173.1, 158.6, 151.6, 138.7, 137.4, 137.3, 129.7, 128.9, 128.8, 128.1, 116.6, 115.9, 21.9 ppm; 31P NMR (166 MHz, DMSO) 24.20 ppm; LC-MS m/z = 568 (M+); Anal. Calcd for C32H29N2O4PS: C, 67.59; H, 5.14; N, 4.93; S, 5.64. Found: C, 67.47; H, 5.29; N, 4.84; S, 5.49. 1 H NMR (400 MHz, DMSO) 7.97-7.90 (m, 3H), 7.78-7.65 (m, 12H), 7.42 (d, J = 6.6 Hz, 2H), 7.38 (d, J = 8.6 Hz, 2H) , 6.97 (d, J = 8.6 Hz, 2H), 6.47 (d, J = 6.6 Hz, 2H), 5.54 (s, 1H), 4.12 (br, 2H), 1.66 (s, 3H) ppm; 13 C NMR (100 MHz, DMSO) 173.1, 158.6, 151.6, 138.7, 137.4, 137.3, 129.7, 128.9, 128.8, 128.1, 116.6, 115.9, 21.9 ppm; 31 P NMR (166 MHz, DMSO) 24.20 ppm; LC-MS m / z = 568 (M + ); Anal. Calcd for C 32 H 29 N 2 O 4 PS: C, 67.59; H, 5. 14; N, 4.93; S, 5.64. Found: C, 67.47; H, 5. 29; N, 4.84; S, 5.49.
실시예 9Example 9
비페닐형 에폭시수지(NC-3000, Nippon Kayaku) 7.5중량부, 자일록형 페놀수지(HE100C-10, Air Water) 4.7중량부, 실시예 1의 화합물 0.2중량부, 평균입경 18㎛의 구상 용융실리카와 평균입경 0.5㎛의 구상 용융실리카의 9:1중량비의 혼합물인 무기충전제 86중량부, 머캡토프로필트리메톡시실란(KBM-803, Shinetsu) 0.3중량부와 메틸트리메톡시실란(SZ-6070, Dow Corning Chemical)의 0.3중량부의 혼합물인 커플링제 0.6중량부, 이형제로 카르나우바왁스 0.5중량부, 착색제로 카본블랙(MA-600, Matsusita Chemical) 0.5중량부를 혼합하고, 헨젤 믹서를 사용하여 균일하게 혼합하여 분말 상태의 조성물을 얻었다. 그런 다음, 연속 니이더를 이용하여 95℃에서 용융 혼련한 후 냉각 및 분쇄하여 에폭시수지 조성물을 제조하였다.7.5 parts by weight of biphenyl type epoxy resin (NC-3000, Nippon Kayaku), 4.7 parts by weight of xylock type phenolic resin (HE100C-10, Air Water), 0.2 parts by weight of compound of Example 1, spherical molten silica having an average particle diameter of 18 µm. And 86 parts by weight of an inorganic filler, a mixture of mercaptopropyltrimethoxysilane (KBM-803, Shinetsu), and methyltrimethoxysilane (SZ-6070), which are mixtures of a 9: 1 weight ratio of spherical molten silica having an average particle diameter of 0.5 μm. 0.6 parts by weight of a coupling agent, 0.3 parts by weight of Dow Corning Chemical), 0.5 parts by weight of carnauba wax as a release agent, and 0.5 parts by weight of carbon black (MA-600, Matsusita Chemical) as a colorant, and using a Hansel mixer. The mixture was uniformly obtained to obtain a powdery composition. Then, melt kneading at 95 ° C. using a continuous kneader followed by cooling and pulverization to prepare an epoxy resin composition.
실시예 10Example 10
실시예 9에서, 실시예 1의 화합물 대신에, 실시예 2의 화합물을 사용한 것을 제외하고는 동일한 방법으로, 에폭시수지 조성물을 제조하였다.In Example 9, an epoxy resin composition was prepared in the same manner except that the compound of Example 2 was used instead of the compound of Example 1.
실시예 11Example 11
실시예 9에서, 실시예 1의 화합물 대신에, 실시예 3의 화합물을 사용한 것을 제외하고는 동일한 방법으로, 에폭시수지 조성물을 제조하였다.In Example 9, an epoxy resin composition was prepared in the same manner except that the compound of Example 3 was used instead of the compound of Example 1.
실시예 12Example 12
실시예 9에서, 실시예 1의 화합물 대신에, 실시예 4의 화합물을 사용한 것을 제외하고는 동일한 방법으로, 에폭시수지 조성물을 제조하였다.In Example 9, an epoxy resin composition was prepared in the same manner except that the compound of Example 4 was used instead of the compound of Example 1.
실시예 13Example 13
실시예 9에서, 비페닐형 에폭시수지 7.5중량부, 자일록형 페놀수지 4.8중량부, 실시예 1의 화합물 0.1중량부, 무기충전제 86중량부, 커플링제 0.6중량부, 이형제 0.5중량부, 착색제 0.5중량부를 혼합한 것을 제외하고는 동일한 방법으로 에폭시수지 조성물을 제조하였다.In Example 9, 7.5 parts by weight of the biphenyl type epoxy resin, 4.8 parts by weight of the xylock type phenol resin, 0.1 parts by weight of the compound of Example 1, 86 parts by weight of the inorganic filler, 0.6 parts by weight of the coupling agent, 0.5 parts by weight of the release agent, 0.5 An epoxy resin composition was prepared in the same manner except for mixing the parts by weight.
실시예 14Example 14
실시예 9에서, 비페닐형 에폭시수지 대신에 페놀아랄킬형 에폭시수지를 사용한 것을 제외하고는 동일한 방법으로 에폭시수지 조성물을 제조하였다.In Example 9, an epoxy resin composition was prepared in the same manner except that a phenol aralkyl type epoxy resin was used instead of a biphenyl type epoxy resin.
실시예 15Example 15
실시예 9에서, 비페닐형 에폭시수지 대신에 크레졸노볼락형 에폭시수지를 사용한 것을 제외하고는 동일한 방법으로 에폭시수지 조성물을 제조하였다.In Example 9, an epoxy resin composition was prepared in the same manner except that a cresol novolac epoxy resin was used instead of the biphenyl epoxy resin.
실시예 16Example 16
실시예 9에서, 자일록형 페놀수지 대신에 페놀노볼락형 페놀수지를 사용한 것을 제외하고는 동일한 방법으로 에폭시수지 조성물을 제조하였다.In Example 9, an epoxy resin composition was prepared in the same manner except that a phenol novolak type phenol resin was used instead of the xylock type phenol resin.
실시예 17Example 17
실시예 9에서, 자일록형 페놀수지 대신에 페놀아랄킬형 페놀수지를 사용한 것을 제외하고는 동일한 방법으로 에폭시수지 조성물을 제조하였다.In Example 9, an epoxy resin composition was prepared in the same manner except that a phenol aralkyl type phenol resin was used instead of the xylock type phenol resin.
실시예 18Example 18
실시예 9에서, 실시예 1의 화합물 0.2중량부 대신에, 실시예 1의 화합물 0.1중량부와 트리페닐포스핀 0.1중량부의 혼합물을 사용한 것을 제외하고는 동일한 방법으로 에폭시수지 조성물을 제조하였다.In Example 9, an epoxy resin composition was prepared in the same manner except that 0.1 part by weight of the compound of Example 1 and 0.1 part by weight of triphenylphosphine were used instead of 0.2 part by weight of the compound of Example 1.
실시예 19Example 19
실시예 9에서, 실시예 1의 화합물 대신에, 실시예 5의 화합물을 사용한 것을 제외하고는 동일한 방법으로, 에폭시수지 조성물을 제조하였다.In Example 9, an epoxy resin composition was prepared in the same manner except that the compound of Example 5 was used instead of the compound of Example 1.
실시예 20Example 20
실시예 9에서, 실시예 1의 화합물 대신에, 실시예 6의 화합물을 사용한 것을 제외하고는 동일한 방법으로, 에폭시수지 조성물을 제조하였다.In Example 9, an epoxy resin composition was prepared in the same manner except that the compound of Example 6 was used instead of the compound of Example 1.
실시예 21Example 21
실시예 9에서, 실시예 1의 화합물 대신에, 실시예 7의 화합물을 사용한 것을 제외하고는 동일한 방법으로, 에폭시수지 조성물을 제조하였다.In Example 9, an epoxy resin composition was prepared in the same manner except that the compound of Example 7 was used instead of the compound of Example 1.
실시예 22Example 22
실시예 9에서, 실시예 1의 화합물 대신에, 실시예 8의 화합물을 사용한 것을 제외하고는 동일한 방법으로, 에폭시수지 조성물을 제조하였다.In Example 9, an epoxy resin composition was prepared in the same manner except that the compound of Example 8 was used instead of the compound of Example 1.
비교예 1Comparative Example 1
실시예 9에서, 실시예 1의 화합물을 사용하지 않은 것을 제외하고는 동일한 방법으로, 에폭시수지 조성물을 제조하였다.In Example 9, an epoxy resin composition was prepared in the same manner except that the compound of Example 1 was not used.
비교예 2Comparative Example 2
실시예 9에서, 실시예 1 화합물의 대신에 트리페닐포스핀을 사용한 것을 제외하고는 동일한 방법으로, 에폭시수지 조성물을 제조하였다.In Example 9, an epoxy resin composition was prepared in the same manner except that triphenylphosphine was used instead of the compound of Example 1.
비교예 3Comparative Example 3
실시예 9에서, 실시예 1 화합물의 대신에 트리페닐포스핀과 1,4-벤조퀴논의 부가 생성물을 사용한 것을 제외하고는 동일한 방법으로, 에폭시수지 조성물을 제조하였다.In Example 9, an epoxy resin composition was prepared in the same manner except for using the addition product of triphenylphosphine and 1,4-benzoquinone in place of the compound of Example 1.
실시예와 비교예에서 제조한 에폭시수지 조성물에 대해 하기 표 1과 표 2의 물성을 평가하였다.The physical properties of Table 1 and Table 2 were evaluated for the epoxy resin compositions prepared in Examples and Comparative Examples.
표 1
Table 1
| 실시예 | |||||||||||
| 9 | 10 | 11 | 12 | 13 | 14 | 15 | 16 | 17 | |||
| 기본물성 | 유동성(inch) | 73 | 71 | 74 | 73 | 67 | 65 | 71 | 69 | 68 | |
| 경화수축률(%) | 0.35 | 0.34 | 0.37 | 0.38 | 0.33 | 0.35 | 0.34 | 0.33 | 0.33 | ||
| 유리전이온도(℃) | 122 | 123 | 124 | 124 | 121 | 123 | 121 | 123 | 121 | ||
| 흡습율(%) | 0.24 | 0.25 | 0.24 | 0.24 | 0.25 | 0.25 | 0.24 | 0.24 | 0.25 | ||
| 부착력(kgf) | 77 | 74 | 75 | 74 | 76 | 74 | 75 | 77 | 76 | ||
| 점도변화율(%) | 8.1 | 7.8 | 7.7 | 7.9 | 8.2 | 7.8 | 7.9 | 7.6 | 7.7 | ||
| 패키지평가 | 경화시간별 경화도(Shore-D) | 50초 | 71 | 69 | 72 | 70 | 68 | 69 | 70 | 69 | 71 |
| 60초 | 73 | 71 | 74 | 72 | 70 | 71 | 72 | 72 | 74 | ||
| 70초 | 75 | 73 | 76 | 75 | 73 | 75 | 75 | 74 | 75 | ||
| 80초 | 78 | 76 | 76 | 76 | 74 | 75 | 76 | 74 | 76 | ||
| 90초 | 78 | 76 | 78 | 77 | 74 | 75 | 76 | 74 | 76 | ||
| 저장안정성 | 24hr | 98% | 97% | 97% | 96% | 98% | 97% | 98% | 98% | 98% | |
| 48hr | 94% | 95% | 94% | 92% | 96% | 94% | 96% | 96% | 95% | ||
| 72hr | 91% | 93% | 90% | 89% | 92% | 91% | 92% | 93% | 92% | ||
| 신뢰성 | 외관크랙발생수 | 0 | 0 | 0 | 0 | 0 | 0 | 0 | 0 | 0 | |
| 박리발생수 | 0 | 0 | 0 | 0 | 0 | 0 | 0 | 0 | 0 | ||
| 시험한 반도체 수 | 88 | 88 | 88 | 88 | 88 | 88 | 88 | 88 | 88 | ||
| Example | |||||||||||
| 9 | 10 | 11 | 12 | 13 | 14 | 15 | 16 | 17 | |||
| Basic property | Inch | 73 | 71 | 74 | 73 | 67 | 65 | 71 | 69 | 68 | |
| Hardening Shrinkage (%) | 0.35 | 0.34 | 0.37 | 0.38 | 0.33 | 0.35 | 0.34 | 0.33 | 0.33 | ||
| Glass transition temperature (℃) | 122 | 123 | 124 | 124 | 121 | 123 | 121 | 123 | 121 | ||
| Hygroscopicity (%) | 0.24 | 0.25 | 0.24 | 0.24 | 0.25 | 0.25 | 0.24 | 0.24 | 0.25 | ||
| Adhesion force (kgf) | 77 | 74 | 75 | 74 | 76 | 74 | 75 | 77 | 76 | ||
| Viscosity Change Rate (%) | 8.1 | 7.8 | 7.7 | 7.9 | 8.2 | 7.8 | 7.9 | 7.6 | 7.7 | ||
| Package Evaluation | Curing degree by curing time (Shore-D) | 50 seconds | 71 | 69 | 72 | 70 | 68 | 69 | 70 | 69 | 71 |
| 60 seconds | 73 | 71 | 74 | 72 | 70 | 71 | 72 | 72 | 74 | ||
| 70 seconds | 75 | 73 | 76 | 75 | 73 | 75 | 75 | 74 | 75 | ||
| 80 sec | 78 | 76 | 76 | 76 | 74 | 75 | 76 | 74 | 76 | ||
| 90 sec | 78 | 76 | 78 | 77 | 74 | 75 | 76 | 74 | 76 | ||
| Storage stability | 24hr | 98% | 97% | 97% | 96% | 98% | 97% | 98% | 98% | 98% | |
| 48hr | 94% | 95% | 94% | 92% | 96% | 94% | 96% | 96% | 95% | ||
| 72hr | 91% | 93% | 90% | 89% | 92% | 91% | 92% | 93% | 92% | ||
| responsibility | Exterior cracking water | 0 | 0 | 0 | 0 | 0 | 0 | 0 | 0 | 0 | |
| Peeling water | 0 | 0 | 0 | 0 | 0 | 0 | 0 | 0 | 0 | ||
| Number of semiconductors tested | 88 | 88 | 88 | 88 | 88 | 88 | 88 | 88 | 88 | ||
표 2
TABLE 2
| 실시예 | 비교예 | |||||||||
| 18 | 19 | 20 | 21 | 22 | 1 | 2 | 3 | |||
| 기본물성 | 유동성(inch) | 59 | 70 | 71 | 72 | 74 | x* | 52 | 58 | |
| 경화수축률(%) | 0.39 | 0.35 | 0.33 | 0.34 | 0.33 | x | 0.42 | 0.40 | ||
| 유리전이온도(℃) | 122 | 124 | 124 | 123 | 123 | x | 121 | 122 | ||
| 흡습율(%) | 0.25 | 0.24 | 0.25 | 0.24 | 0.24 | x | 0.25 | 0.26 | ||
| 부착력(kgf) | 74 | 73 | 74 | 75 | 75 | x | 72 | 74 | ||
| 점도변화율(%) | 15.2 | 8.3 | 8.0 | 7.7 | 7.5 | x | 27.3 | 30.2 | ||
| 패키지평가 | 경화시간별경화도(Shore-D) | 50초 | 62 | 69 | 70 | 71 | 69 | x | 52 | 60 |
| 60초 | 63 | 71 | 72 | 73 | 71 | x | 60 | 64 | ||
| 70초 | 66 | 72 | 73 | 74 | 72 | x | 64 | 66 | ||
| 80초 | 69 | 73 | 75 | 74 | 73 | x | 67 | 70 | ||
| 90초 | 71 | 73 | 75 | 74 | 73 | x | 67 | 71 | ||
| 저장안정성 | 24hr | 91% | 97% | 97% | 97% | 97% | x | 90% | 92% | |
| 48hr | 87% | 95% | 94% | 95% | 95% | x | 84% | 88% | ||
| 72hr | 81% | 91% | 93% | 94% | 91% | x | 74% | 79% | ||
| 신뢰성 | 외관크랙발생수 | 0 | 0 | 0 | 0 | 0 | x | 0 | 0 | |
| 박리발생수 | 0 | 0 | 0 | 0 | 0 | x | 45 | 20 | ||
| 시험한반도체수 | 88 | 88 | 88 | 88 | 88 | 88 | 88 | 88 | ||
| Example | Comparative example | |||||||||
| 18 | 19 | 20 | 21 | 22 | One | 2 | 3 | |||
| Basic property | Inch | 59 | 70 | 71 | 72 | 74 | x * | 52 | 58 | |
| Hardening Shrinkage (%) | 0.39 | 0.35 | 0.33 | 0.34 | 0.33 | x | 0.42 | 0.40 | ||
| Glass transition temperature (℃) | 122 | 124 | 124 | 123 | 123 | x | 121 | 122 | ||
| Hygroscopicity (%) | 0.25 | 0.24 | 0.25 | 0.24 | 0.24 | x | 0.25 | 0.26 | ||
| Adhesive force (kgf) | 74 | 73 | 74 | 75 | 75 | x | 72 | 74 | ||
| Viscosity Change Rate (%) | 15.2 | 8.3 | 8.0 | 7.7 | 7.5 | x | 27.3 | 30.2 | ||
| Package Evaluation | Hardening time by curing time (Shore-D) | 50 seconds | 62 | 69 | 70 | 71 | 69 | x | 52 | 60 |
| 60 seconds | 63 | 71 | 72 | 73 | 71 | x | 60 | 64 | ||
| 70 seconds | 66 | 72 | 73 | 74 | 72 | x | 64 | 66 | ||
| 80 sec | 69 | 73 | 75 | 74 | 73 | x | 67 | 70 | ||
| 90 sec | 71 | 73 | 75 | 74 | 73 | x | 67 | 71 | ||
| Storage stability | 24hr | 91% | 97% | 97% | 97% | 97% | x | 90% | 92% | |
| 48hr | 87% | 95% | 94% | 95% | 95% | x | 84% | 88% | ||
| 72hr | 81% | 91% | 93% | 94% | 91% | x | 74% | 79% | ||
| responsibility | Exterior cracking water | 0 | 0 | 0 | 0 | 0 | x | 0 | 0 | |
| Peeling occurrence | 0 | 0 | 0 | 0 | 0 | x | 45 | 20 | ||
| Number of semiconductors tested | 88 | 88 | 88 | 88 | 88 | 88 | 88 | 88 | ||
참고:X*는 경화가 되지 않아 데이터 측정이 불가하였음.Note: X * is not cured and data measurement is not possible.
(1) 유동성(inch): EMMI-1-66에 준하여 평가용 금형을 사용하여 175℃, 70kgf/cm2에서 트랜스퍼 몰딩 프레스(transfer molding press)를 이용하여 유동 길이를 측정하였다. 측정값이 높을수록 유동성이 우수하다.(1) Flowability (inch): Flow length was measured using a transfer molding press at 175 ° C. and 70 kgf / cm 2 using an evaluation mold according to EMMI-1-66. The higher the measured value, the better the fluidity.
(2)경화 수축율(%): 굴곡 강도 시편 제작용 금형을 사용하여 175℃, 70kgf/cm2에서 트랜스퍼 몰딩 프레스(transfer molding press)를 이용하여 성형시편(125mm×12.6mm×6.4mm)을 얻었다. 얻은 시편을 170~180℃의 오븐에 넣어 4시간 동안 후경화(PMC:post molding cure)시킨 다음 냉각한 후 시험편의 길이를 캘리퍼스로 측정하였다. 경화 수축율은 다음과 같은 식 2로부터 계산하였다.(2) Hardening shrinkage (%): A molded specimen (125 mm x 12.6 mm x 6.4 mm) was obtained using a transfer molding press at 175 ° C and 70 kgf / cm 2 using a bending strength test piece mold. . The obtained specimen was placed in an oven at 170 ° C. to 180 ° C. for 4 hours, post-cured (PMC: post molding cure), and then cooled. The length of the specimen was measured by a caliper. Cure shrinkage was calculated from the following equation (2).
[식 2][Equation 2]
경화수축률 = ｜C - D｜/ C x 100Cure Shrinkage = ｜ C-D ｜ / C x 100
(상기 식 2에서, C는 에폭시 수지 조성물을 175℃, 70kgf/cm2에서 트랜스퍼 몰딩 프레스하여 얻은 시편의 길이, D는 상기 시편을 170~180℃에서 4시간 후경화하고, 냉각시킨 후 얻은 시편의 길이이다).(In Formula 2, C is the length of the specimen obtained by transfer molding press the epoxy resin composition at 175 ℃, 70kgf / cm 2 , D is the specimen obtained after curing the specimen at 170 ~ 180 ℃ 4 hours, and cooled Is the length of).
(3) 유리전이온도(℃): 수지 조성물의 열기계 분석기(Thermomechanical Analyzer, TMA)를 이용하여 측정하였다. 이 때 TMA는 25℃에서 분당 10℃씩 온도를 상승시켜 300℃까지 측정하는 조건으로 설정하였다.(3) Glass transition temperature (° C.): Measured using a thermomechanical analyzer (TMA) of the resin composition. At this time, TMA was set to the conditions of increasing the temperature by 10 ℃ per minute at 25 ℃ measured to 300 ℃.
(4) 흡습율(%): 상기 실시예와 비교예에서 제조된 수지 조성물을 금형 온도 170~180℃, 클램프 압력 70kgf/cm2, 이송 압력 1000psi, 이송 속도 0.5~1cm/s, 경화 시간 120초의 조건으로 성형하여 직경 50mm, 두께 1.0mm의 디스크 형태의 경화 시편을 얻었다. 얻은 시편을 170~180℃의 오븐에 넣어 4시간 동안 후경화(PMC:post molding cure)시킨 직후 85℃, 85RH% 상대 습도 조건 하에서 168시간 동안 방치시킨 후 흡습에 의한 무게 변화를 측정하여 다음 식 3에 의하여 흡습율을 계산하였다.(4) Moisture absorption rate (%): the resin composition prepared in the above Examples and Comparative Examples, the mold temperature 170 ~ 180 ℃, clamp pressure 70kgf / cm 2 , transfer pressure 1000psi, transfer rate 0.5 ~ 1cm / s, curing time 120 Molded under the condition of seconds to obtain a cured specimen in the form of a disk having a diameter of 50mm, 1.0mm thick. The obtained specimens were placed in an oven at 170 to 180 ° C., and after 4 hours of post-curing (PMC: post molding cure), they were left at 85 ° C. and 85 RH% relative humidity for 168 hours, and then the weight change due to moisture absorption was measured. The moisture absorption was calculated by 3.
[식 3][Equation 3]
흡습율 = (흡습 후 시험편의 무게-흡습 전 시험편의 무게)÷(흡습 전 시험편의 무게)×100Moisture absorption rate = (weight of test piece after moisture absorption-weight of test piece before absorption) ÷ (weight of test piece before absorption) × 100
(5) 부착력(kgf): 구리 금속 소자를 부착 측정용 금형에 맞는 규격으로 준비하고, 준비된 시험편에 상기 실시예와 비교예에서 제조된 수지 조성물을 금형 온도 170~180℃, 클램프 압력 70kgf/cm2, 이송 압력 1000psi, 이송 속도 0.5~1cm/s, 경화 시간 120초의 조건으로 성형하여 경화 시편을 얻었다. 얻은 시편을 170~180℃의 오븐에 넣어 4시간 동안 후경화(PMC:post molding cure)시켰다. 이때 시편에 닿는 에폭시 수지 조성물의 면적은 40±1mm2이고, 부착력 측정은 각 측정 공정 당 12개의 시편에 대하여 UTM(Universal Testing Machine)을 이용하여 측정한 후 평균값으로 계산하였다.(5) Adhesion force (kgf): A copper metal element is prepared in a standard suitable for a measurement measurement mold, and the resin composition prepared in Example and Comparative Example is prepared on the prepared test piece with a mold temperature of 170 to 180 ° C. and a clamp pressure of 70 kgf / cm. 2 , the transfer pressure 1000psi, the feed rate 0.5 ~ 1cm / s, the curing time was molded under the conditions of 120 seconds to obtain a cured specimen. The obtained specimens were put in an oven at 170 to 180 ° C. and post-cured (PMC: post molding cure) for 4 hours. At this time, the area of the epoxy resin composition in contact with the specimen is 40 ± 1mm 2 , the adhesion measurement was measured by the average value after measuring by using a universal testing machine (UTM) for 12 specimens for each measurement process.
(6) 점도변화율: 에폭시수지 조성물의 25℃에서 점도를 측정하고, 에폭시수지 조성물을 25℃조건에서 24시간 방치한 후 25℃에서 점도를 측정하고, 하기 식 1에 따라 계산하였다. 점도는 말콤 사제 모두축 이중 원통형 회전식 점도계 PM-2 A를 사용하여 측정하였다. 점도변화율이 낮을수록 에폭시수지 조성물이 경화되지 않아 저장안정성이 높음을 의미한다.(6) Viscosity change rate: The viscosity was measured at 25 ° C. of the epoxy resin composition, the epoxy resin composition was left at 25 ° C. for 24 hours, and then the viscosity was measured at 25 ° C., and calculated according to Equation 1 below. Viscosity was measured using the Malcolm biaxial double cylindrical rotary viscometer PM-2A. The lower the viscosity change rate, the harder the epoxy resin composition, which means that the storage stability is higher.
<식 1><Equation 1>
점도변화율 = ｜B-A｜ / A x 100Viscosity Change Rate = ｜ B-A ｜ / A x 100
(상기 식 1에서, A는 에폭시수지 조성물의 25℃에서 측정한 점도(단위:cPs), B는 에폭시수지 조성물을 25℃조건에서 24시간 방치한 후 25℃에서 측정한 점도(단위:cPs)이다) (In Formula 1, A is the viscosity measured at 25 ℃ of the epoxy resin composition (unit: cPs), B is the viscosity measured at 25 ℃ after leaving the epoxy resin composition at 25 ℃ 24 hours (unit: cPs) to be)
(7) 경화도(shore-D): 구리 금속 소자를 포함하는 가로 24mm, 세로 24mm, 두께 1mm인 eTQFP(exposed Thin Quad Flat Package) 패키지용 금형이 장착된 MPS(Multi Plunger System) 성형기를 이용하여 175℃에서 50, 60, 70, 80 그리고 90초간 평가하고자 하는 에폭시 수지 조성물을 경화시킨 후 금형 위의 패지지에 직접 Shore-D형 경도계로 경화시간에 따른 경화물의 경도를 측정하였다. 값이 높을 수록 경화도가 우수하다.(7) Shore-D: Using a multi-plunger system (MPS) molding machine equipped with a mold for exposed thin quad flat package (eTQFP) packages having a width of 24 mm, a length of 24 mm, and a thickness of 1 mm containing copper metal elements. After curing the epoxy resin composition to be evaluated at 175 ° C. for 50, 60, 70, 80 and 90 seconds, the hardness of the cured product according to the curing time was measured with a Shore-D hardness tester directly on the package on the mold. The higher the value, the better the degree of curing.
(8) 저장안정성: 에폭시수지 조성물을 25℃/50RH%로 설정된 항온항습기에 1주간 보존하면서 24시간 간격으로 상기 (1)의 유동성 측정과 같은 방법으로 유동길이를 측정하고, 제조 직후의 유동길이에 대한 백분율(%)을 구했다. 이 백분율의 수치가 클 수록 저장안정성이 양호한 것을 나타낸다.(8) Storage stability: The flow length was measured in the same manner as the flowability measurement of (1) at 24 hours intervals while preserving the epoxy resin composition in a constant temperature and humidity chamber set at 25 ° C / 50RH% for one week, and the flow length immediately after the preparation. The percentage for was obtained. The larger the value of this percentage, the better the storage stability.
(9) 신뢰성: 상기 휨 특성 평가용 eTQFP 패키지를 125℃에서 24시간 동안 건조시킨 후 5 사이클(1 사이클은 패키지를 -65℃에서 10분, 25℃에서 10분, 150℃에서 10분씩 방치하는 것을 나타냄)의 열충격 시험을 수행하였다. 이후 패키지를 85℃, 60% 상대 습도 조건 하에서 168시간 동안 방치시킨 후 260℃에서 30초 동안 IR 리플로우를 1회 통과시키는 것을 3회 반복하는 프리컨디션 조건 이후에 패키지의 외관 크랙 발생 유무를 광학 현미경으로 관찰하였다. 이후 비파괴 검사인 C-SAM(Scanning Acoustic Microscopy)를 이용하여 에폭시 수지 조성물과 리드프레임 간의 박리 발생 유무를 평가하였다. 패키지의 외관 크랙이 발생하거나 에폭시 수지 조성물과 리드프레임간의 박리가 발생할 경우에는 패키지의 신뢰성을 확보할 수 없다.(9) Reliability: After drying the eTQFP package for evaluation of bending characteristics for 24 hours at 125 ℃ (5 cycles (1 cycle is left for 10 minutes at -65 ℃, 10 minutes at 25 ℃, 10 minutes at 150 ℃) Thermal shock test). After the package was left at 85 ° C. and 60% relative humidity for 168 hours, the package was subjected to optical cracking after preconditioning, which was repeated three times at 260 ° C. for 30 seconds. It was observed under a microscope. Then, the presence of peeling between the epoxy resin composition and the lead frame was evaluated by using a non-destructive test C-SAM (Scanning Acoustic Microscopy). If the appearance cracks of the package or peeling between the epoxy resin composition and the lead frame occurs, the reliability of the package cannot be secured.
상기 표 1에서와 같이, 본 발명의 포스포늄 이온 함유 화합물을 포함하는 조성물은 유동성이 높고 경화수축률이 낮으며, 경화시간별 경화도를 비교할 때 짧은 경화시간에도 높은 경화도를 갖는 것으로 확인되었다. 또한, 72시간 이후에도 유동성의 차이가 없고 점도 변화율도 낮아서 저장안정성이 높음을 확인하였다. 또한, 외관 크랙이 발생하지 않고 내크랙성이 양호하며 박리발생이 없음을 확인하였다. As shown in Table 1, the composition containing the phosphonium ion-containing compound of the present invention was high fluidity, low cure shrinkage rate, it was confirmed to have a high cure degree even in a short cure time when comparing the degree of cure by curing time. In addition, even after 72 hours, there was no difference in fluidity and the viscosity change rate was low, thereby confirming high storage stability. In addition, it was confirmed that no external crack occurred, good crack resistance, and no peeling occurred.
반면에, 본 발명의 포스포늄 이온 함유 화합물을 포함하지 않거나, 포스포늄 이온 함유 화합물 대신에 포스포늄 이온을 포함하지 않는 경화 촉매를 포함하는 비교예의 조성물은 저장안정성이 낮고, 경화수축률도 높고, 유동성도 낮으며, 패키지에 사용시 본 발명의 효과를 구현할 수 없음을 확인하였다.On the other hand, the composition of the comparative example which does not contain the phosphonium ion-containing compound of the present invention or contains a curing catalyst that does not contain phosphonium ions instead of the phosphonium ion-containing compound has low storage stability, high curing shrinkage rate, and fluidity. It was also confirmed that the low, can not implement the effects of the present invention when used in the package.
Claims (18)
- 하기 화학식 1로 표시되는 포스포늄 이온 함유 화합물:Phosphonium ion-containing compounds represented by the following general formula (1):<화학식 1><Formula 1>
(상기 화학식 1에서, R1, R2, R3, R4은 각각 독립적으로, 수소, 치환 또는 비치환된 탄소수 1 내지 10의 알킬기, 치환 또는 비치환된 탄소수 3 내지 10의 시클로알킬기, 치환 또는 비치환된 탄소수 6 내지 20의 아릴기, 또는 치환 또는 비치환된 탄소수 7 내지 21의 아릴알킬기이고,(In Formula 1, R 1 , R 2 , R 3 , R 4 are each independently hydrogen, substituted or unsubstituted C 1-10 alkyl group, substituted or unsubstituted C 3-10 cycloalkyl group, substituted Or an unsubstituted aryl group having 6 to 20 carbon atoms, or a substituted or unsubstituted arylalkyl group having 7 to 21 carbon atoms,R5는 수소, 치환 또는 비치환된 탄소수 1 내지 10의 알킬기, 치환 또는 비치환된 탄소수 6 내지 20의 아릴기, 치환 또는 비치환된 탄소수 3 내지 20의 시클로알킬기, 치환 또는 비치환된 탄소수 2 내지 20의 헤테로시클로알킬기, 치환 또는 비치환된 탄소수 7 내지 20의 아릴알킬기, 치환 또는 비치환된 탄소수 3 내지 20의 헤테로아릴기, 또는 하기 화학식 2이다.R 5 is hydrogen, a substituted or unsubstituted C1-C10 alkyl group, a substituted or unsubstituted C6-C20 aryl group, a substituted or unsubstituted C3-C20 cycloalkyl group, a substituted or unsubstituted C2 To 20 heterocycloalkyl group, substituted or unsubstituted arylalkyl group having 7 to 20 carbon atoms, substituted or unsubstituted heteroaryl group having 3 to 20 carbon atoms, or formula (2).<화학식 2><Formula 2>
(상기 화학식 2에서, *는 화학식 1에서 N에 대한 연결부위이고,(In Formula 2, * is a linking portion to N in Formula 1,R11은 치환 또는 비치환된 탄소수 1 내지 10의 알킬기, 치환 또는 비치환된 탄소수 6 내지 20의 아릴기, 치환 또는 비치환된 탄소수 3 내지 10의 시클로알킬기 또는, 치환 또는 비치환된 탄소수 7 내지 20의 아릴알킬기이다)R 11 is a substituted or unsubstituted C1-C10 alkyl group, a substituted or unsubstituted C6-C20 aryl group, a substituted or unsubstituted C3-C10 cycloalkyl group, or a substituted or unsubstituted C7-C10 Arylalkyl group of 20)R6, R7, R8, R9, R10은 각각 독립적으로, 수소, 치환 또는 비치환된 탄소수 1 내지 10의 알킬기, 치환 또는 비치환된 탄소수 6 내지 20의 아릴기, 치환 또는 비치환된 탄소수 7 내지 21의 아릴알킬기, 또는 -NR'R"(상기에서, R', R"은 수소, 탄소수 1 내지 10의 알킬기, 탄소수 6 내지 20의 아릴기, 탄소수 7 내지 21의 아릴알킬기이다)이다).R 6 , R 7 , R 8 , R 9 and R 10 are each independently hydrogen, a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, substituted or unsubstituted An arylalkyl group having 7 to 21 carbon atoms, or -NR'R "(wherein R 'and R" are hydrogen, an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 20 carbon atoms, and an arylalkyl group having 7 to 21 carbon atoms). )to be). - 제1항에 있어서, 상기 포스포늄 이온 함유 화합물은 약 90 내지 175℃에서 하기 반응식 1로 분해되는 포스포늄 이온 함유 화합물:The phosphonium ion containing compound of claim 1, wherein the phosphonium ion containing compound is decomposed to Scheme 1 at about 90 to 175 ° C .:<반응식 1><Scheme 1>
(상기 반응식 1에서, R1, R2, R3, R4, R5, R6, R7, R8, R9, R10는 상기 화학식 1에서 정의한 바와 같다).(In Scheme 1, R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 are the same as defined in Formula 1 above). - 제1항에 있어서, 상기 R5는 치환 또는 비치환된 탄소수 1-4의 알킬기, 치환 또는 비치환된 탄소수 3 내지 20의 헤테로아릴기, 또는 R11이 치환 또는 비치환된 탄소수 1 내지 5의 알킬기 또는 치환 또는 비치환된 탄소수 6 내지 10의 아릴기인 화학식 2인 포스포늄 이온 함유 화합물.2. The method of claim 1, wherein R 5 is a substituted or unsubstituted alkyl group, a substituted or unsubstituted ring having a carbon number of 1 to 4 carbon atoms, 3 to 20 heteroaryl group, or R 11 is a substituted or unsubstituted group having 1 to 5 carbon atoms in the A phosphonium ion-containing compound represented by formula (2) which is an alkyl group or a substituted or unsubstituted aryl group having 6 to 10 carbon atoms.
- 하기 화학식 1로 표시되는 경화촉매:A curing catalyst represented by Formula 1 below:<화학식 1><Formula 1>
(상기 화학식 1에서, R1, R2, R3, R4은 각각 독립적으로, 수소, 치환 또는 비치환된 탄소수 1 내지 10의 알킬기, 치환 또는 비치환된 탄소수 3 내지 10의 시클로알킬기, 치환 또는 비치환된 탄소수 6 내지 20의 아릴기, 또는 치환 또는 비치환된 탄소수 7 내지 21의 아릴알킬기이고,(In Formula 1, R 1 , R 2 , R 3 , R 4 are each independently hydrogen, substituted or unsubstituted C 1-10 alkyl group, substituted or unsubstituted C 3-10 cycloalkyl group, substituted Or an unsubstituted aryl group having 6 to 20 carbon atoms, or a substituted or unsubstituted arylalkyl group having 7 to 21 carbon atoms,R5는 수소, 치환 또는 비치환된 탄소수 1 내지 10의 알킬기, 치환 또는 비치환된 탄소수 6 내지 20의 아릴기, 치환 또는 비치환된 탄소수 3 내지 20의 시클로알킬기, 치환 또는 비치환된 탄소수 2 내지 20의 헤테로시클로알킬기, 치환 또는 비치환된 탄소수 7 내지 20의 아릴알킬기, 치환 또는 비치환된 탄소수 3 내지 20의 헤테로아릴기, 또는 하기 화학식 2이다.R 5 is hydrogen, a substituted or unsubstituted C1-C10 alkyl group, a substituted or unsubstituted C6-C20 aryl group, a substituted or unsubstituted C3-C20 cycloalkyl group, a substituted or unsubstituted C2 To 20 heterocycloalkyl group, substituted or unsubstituted arylalkyl group having 7 to 20 carbon atoms, substituted or unsubstituted heteroaryl group having 3 to 20 carbon atoms, or formula (2).<화학식 2><Formula 2>
(상기 화학식 2에서, *는 화학식 1에서 N에 대한 연결부위이고,(In Formula 2, * is a linking portion to N in Formula 1,R11은 치환 또는 비치환된 탄소수 1 내지 10의 알킬기, 치환 또는 비치환된 탄소수 6 내지 20의 아릴기, 치환 또는 비치환된 탄소수 3 내지 10의 시클로알킬기 또는, 치환 또는 비치환된 탄소수 7 내지 20의 아릴알킬기이다)R 11 is a substituted or unsubstituted C1-C10 alkyl group, a substituted or unsubstituted C6-C20 aryl group, a substituted or unsubstituted C3-C10 cycloalkyl group, or a substituted or unsubstituted C7-C10 Arylalkyl group of 20)R6, R7, R8, R9, R10은 각각 독립적으로, 수소, 치환 또는 비치환된 탄소수 1 내지 10의 알킬기, 치환 또는 비치환된 탄소수 6 내지 20의 아릴기, 치환 또는 비치환된 탄소수 7 내지 21의 아릴알킬기, 또는 -NR'R"(상기에서, R', R"은 수소, 탄소수 1 내지 10의 알킬기, 탄소수 6 내지 20의 아릴기, 탄소수 7 내지 21의 아릴알킬기이다)이다).R 6 , R 7 , R 8 , R 9 and R 10 are each independently hydrogen, a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, substituted or unsubstituted An arylalkyl group having 7 to 21 carbon atoms, or -NR'R "(wherein R 'and R" are hydrogen, an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 20 carbon atoms, and an arylalkyl group having 7 to 21 carbon atoms). )to be). - 에폭시수지, 경화제, 및 경화촉매를 포함하고,Epoxy resin, hardener, and curing catalyst,상기 경화촉매는 제1항 내지 제3항 중 어느 한 항의 포스포늄 이온 함유 화합물을 포함하는 에폭시수지 조성물.The curing catalyst is an epoxy resin composition comprising a phosphonium ion-containing compound of any one of claims 1 to 3.
- 제5항에 있어서, 상기 에폭시수지는 분자 중에 2개 이상의 에폭시기 및 1개 이상의 수산기를 갖는 에폭시수지를 포함하는 에폭시수지 조성물.The epoxy resin composition of claim 5, wherein the epoxy resin comprises an epoxy resin having at least two epoxy groups and at least one hydroxyl group in a molecule thereof.
- 제5항에 있어서, 상기 에폭시수지는 비스페놀형 에폭시 수지, 페놀노볼락형 에폭시 수지, tert-부틸 카테콜형 에폭시수지, 나프탈렌형 에폭시수지, 글리시딜아민형 에폭시수지, 페놀아랄킬형 에폭시수지, 크레졸노볼락형 에폭시수지, 비페닐형 에폭시수지, 선형 지방족에폭시수지, 지환식에폭시수지, 복소환식 에폭시수지, 스피로환 함유 에폭시수지, 시클로헥산디메탄올형 에폭시수지, 할로겐화 에폭시 수지 수지 중 하나 이상을 포함하는 에폭시수지 조성물. The epoxy resin of claim 5, wherein the epoxy resin is a bisphenol epoxy resin, a phenol novolac epoxy resin, a tert-butyl catechol type epoxy resin, a naphthalene type epoxy resin, a glycidylamine type epoxy resin, a phenol aralkyl type epoxy resin, and a cresol. Contains at least one of novolak type epoxy resin, biphenyl type epoxy resin, linear aliphatic epoxy resin, alicyclic epoxy resin, heterocyclic epoxy resin, spiro ring containing epoxy resin, cyclohexanedimethanol type epoxy resin and halogenated epoxy resin Epoxy resin composition.
- 제5항에 있어서, 상기 경화제는 페놀수지를 포함하는 에폭시수지 조성물. The epoxy resin composition of claim 5, wherein the curing agent comprises a phenol resin.
- 제5항에 있어서, 상기 경화제는 페놀아랄킬형 페놀수지, 페놀노볼락형 페놀수지, 자일록형 페놀수지, 크레졸 노볼락형 페놀수지, 나프톨형 페놀수지, 테르펜형 페놀수지, 다관능형 페놀수지, 디시클로펜타디엔계 페놀수지, 비스페놀 A와 레졸로부터 합성된 노볼락형 페놀수지, 트리스(하이드록시페닐)메탄, 디하이드록시바이페닐, 산무수물, 메타-페닐렌디아민, 디아미노디페닐메탄, 디아미노디페닐설폰 중 하나 이상을 포함하는 에폭시수지 조성물.6. The curing agent according to claim 5, wherein the curing agent is a phenol aralkyl type phenol resin, a phenol phenol novolak type phenol resin, a xylox phenol resin, a cresol novolak type phenol resin, a naphthol type phenol resin, a terpene type phenol resin, a polyfunctional phenol resin, and a dish. Clopentadiene-based phenolic resins, novolac-type phenolic resins synthesized from bisphenol A and resol, tris (hydroxyphenyl) methane, dihydroxybiphenyl, acid anhydride, meta-phenylenediamine, diaminodiphenylmethane, dia Epoxy resin composition comprising at least one of minodiphenylsulfone.
- 제5항에 있어서, 상기 포스포늄 이온 함유 화합물은 상기 에폭시수지 조성물 중 0.01 내지 5중량%로 포함되는 에폭시수지 조성물.The epoxy resin composition of claim 5, wherein the phosphonium ion-containing compound is present in an amount of 0.01 to 5 wt% in the epoxy resin composition.
- 제5항에 있어서, 상기 포스포늄 이온 함유 화합물은 상기 경화촉매 중 약 10 내지 100중량%로 포함되는 에폭시수지 조성물.The epoxy resin composition of claim 5, wherein the phosphonium ion-containing compound is present in about 10 to 100% by weight of the curing catalyst.
- 제5항에 있어서, 상기 에폭시수지 조성물은 무기충진제를 더 포함하는 에폭시수지 조성물.The epoxy resin composition of claim 5, wherein the epoxy resin composition further comprises an inorganic filler.
- 제5항에 있어서, 상기 에폭시수지 조성물은 경화개시온도가 약 90 내지 120℃인 에폭시수지 조성물.The epoxy resin composition of claim 5, wherein the epoxy resin composition has a curing start temperature of about 90 to 120 ° C. 7.
- 제5항에 있어서, 상기 에폭시수지 조성물은 하기 식 1의 점도변화율이 약 16% 이하인 에폭시수지 조성물:The epoxy resin composition of claim 5, wherein the epoxy resin composition has a viscosity change rate of about 16% or less in Equation 1 below:<식 1><Equation 1>점도변화율 = ｜B-A｜ / A x 100Viscosity Change Rate = ｜ B-A ｜ / A x 100(상기 식 1에서, A는 에폭시수지 조성물의 25℃에서 측정한 점도(단위:cPs), B는 에폭시수지 조성물을 25℃조건에서 24 시간 방치한 후 25℃에서 측정한 점도(단위:cPs)이다).(In Formula 1, A is the viscosity (unit: cPs) measured at 25 ℃ of the epoxy resin composition, B is the viscosity (unit: cPs) measured at 25 ℃ after leaving the epoxy resin composition at 25 ℃ conditions for 24 hours) to be).
- 제5항에 있어서, 상기 에폭시수지 조성물은 EMMI-1-66에 의해 175℃, 70kgf/cm2에서 트랜스퍼 몰딩 프레스에 의한 유동길이가 약 59-75inch인 에폭시수지 조성물.According to claim 5, The epoxy resin composition has a flow length by the transfer molding press at 175 ℃, 70kgf / cm 2 by EMMI-1-66 An epoxy resin composition that is about 59-75 inches.
- 제5항에 있어서, 상기 에폭시수지 조성물은 하기 식 2의 경화수축률이 약 0.4% 미만인 에폭시수지 조성물:The epoxy resin composition of claim 5, wherein the epoxy resin composition has a curing shrinkage ratio of less than about 0.4% in the following Formula 2.[식 2][Equation 2]경화수축률 = ｜C - D｜/ C x 100Cure Shrinkage = ｜ C-D ｜ / C x 100(상기 식 2에서, C는 에폭시 수지 조성물을 175℃, 70kgf/cm2에서 트랜스퍼 몰딩 프레스하여 얻은 시편의 길이, D는 상기 시편을 170~180℃에서 4시간 후경화하고, 냉각시킨 후 얻은 시편의 길이이다).(In Formula 2, C is the length of the specimen obtained by transfer molding press the epoxy resin composition at 175 ℃, 70kgf / cm 2 , D is the specimen obtained after curing the specimen at 170 ~ 180 ℃ 4 hours, and cooled Is the length of).
- 제5항의 에폭시수지 조성물을 포함하는, 반도체 소자 밀봉용 에폭시수지 조성물.Epoxy resin composition for sealing a semiconductor device comprising the epoxy resin composition of claim 5.
- 제5항의 에폭시수지 조성물을 사용하여 제조된 장치.An apparatus manufactured using the epoxy resin composition of claim 5.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US14/907,643 US10047191B2 (en) | 2013-07-23 | 2014-02-27 | Compound containing phosphonium ion, epoxy resin composition containing same, and device manufactured by using same |
| CN201480041323.3A CN105636969B (en) | 2013-07-23 | 2014-02-27 | Compound, curing catalysts, epoxy resin component and the device using its manufacture of Han You Phosphonium ions |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR20130087028 | 2013-07-23 | ||
| KR10-2013-0087028 | 2013-07-23 | ||
| KR10-2014-0005608 | 2014-01-16 | ||
| KR1020140005608A KR101702704B1 (en) | 2013-07-23 | 2014-01-16 | Compound comprising phosphonium ion, epoxy resin composition comprising the same and apparatus prepared from using the same |
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| WO2015012467A1 true WO2015012467A1 (en) | 2015-01-29 |
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| JP4784698B1 (en) * | 2010-05-06 | 2011-10-05 | 横浜ゴム株式会社 | Thermosetting epoxy resin composition |
| JP2011219740A (en) * | 2010-03-23 | 2011-11-04 | Toray Ind Inc | Epoxy resin composition for fiber reinforced composite material, prepreg, and fiber reinforced composite material |
| JP2011231243A (en) * | 2010-04-28 | 2011-11-17 | Yokohama Rubber Co Ltd:The | Epoxy resin composition |
| WO2014024663A1 (en) * | 2012-08-09 | 2014-02-13 | 横浜ゴム株式会社 | Curing agent composition and epoxy resin composition containing same |
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- 2014-02-27 WO PCT/KR2014/001628 patent/WO2015012467A1/en active Application Filing
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2011219740A (en) * | 2010-03-23 | 2011-11-04 | Toray Ind Inc | Epoxy resin composition for fiber reinforced composite material, prepreg, and fiber reinforced composite material |
| JP2011231243A (en) * | 2010-04-28 | 2011-11-17 | Yokohama Rubber Co Ltd:The | Epoxy resin composition |
| JP4784698B1 (en) * | 2010-05-06 | 2011-10-05 | 横浜ゴム株式会社 | Thermosetting epoxy resin composition |
| WO2014024663A1 (en) * | 2012-08-09 | 2014-02-13 | 横浜ゴム株式会社 | Curing agent composition and epoxy resin composition containing same |
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