TW202237572A - Epoxy resin and production method therefor, curable resin composition, and cured product thereof - Google Patents
Epoxy resin and production method therefor, curable resin composition, and cured product thereof Download PDFInfo
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- TW202237572A TW202237572A TW111107844A TW111107844A TW202237572A TW 202237572 A TW202237572 A TW 202237572A TW 111107844 A TW111107844 A TW 111107844A TW 111107844 A TW111107844 A TW 111107844A TW 202237572 A TW202237572 A TW 202237572A
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- Prior art keywords
- epoxy resin
- formula
- resin composition
- weight
- represented
- Prior art date
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- 239000003822 epoxy resin Substances 0.000 title claims abstract description 78
- 229920000647 polyepoxide Polymers 0.000 title claims abstract description 78
- 239000011342 resin composition Substances 0.000 title claims description 12
- 238000004519 manufacturing process Methods 0.000 title claims description 9
- 125000003118 aryl group Chemical group 0.000 claims abstract description 10
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 6
- 125000001424 substituent group Chemical group 0.000 claims abstract description 6
- -1 dicyclopentadiene compound Chemical class 0.000 claims description 32
- 239000005011 phenolic resin Substances 0.000 claims description 24
- 150000002989 phenols Chemical class 0.000 claims description 20
- 239000003795 chemical substances by application Substances 0.000 claims description 19
- 238000005227 gel permeation chromatography Methods 0.000 claims description 17
- YBYIRNPNPLQARY-UHFFFAOYSA-N 1H-indene Chemical compound C1=CC=C2CC=CC2=C1 YBYIRNPNPLQARY-UHFFFAOYSA-N 0.000 claims description 8
- 150000002430 hydrocarbons Chemical group 0.000 claims description 4
- 150000001412 amines Chemical class 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 33
- 239000000203 mixture Substances 0.000 abstract description 21
- 238000010521 absorption reaction Methods 0.000 abstract description 13
- 125000004432 carbon atom Chemical group C* 0.000 abstract 1
- 125000001183 hydrocarbyl group Chemical group 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 22
- 239000002904 solvent Substances 0.000 description 22
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 18
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 18
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 18
- 239000000853 adhesive Substances 0.000 description 12
- 239000000047 product Substances 0.000 description 12
- 230000001070 adhesive effect Effects 0.000 description 11
- 238000000034 method Methods 0.000 description 11
- 229920005989 resin Polymers 0.000 description 11
- 239000011347 resin Substances 0.000 description 11
- 230000015572 biosynthetic process Effects 0.000 description 10
- 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 10
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 10
- 239000000463 material Substances 0.000 description 10
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 9
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 9
- 239000004918 carbon fiber reinforced polymer Substances 0.000 description 9
- 239000003054 catalyst Substances 0.000 description 9
- 238000003786 synthesis reaction Methods 0.000 description 9
- 150000001875 compounds Chemical class 0.000 description 8
- 239000011256 inorganic filler Substances 0.000 description 8
- 229910003475 inorganic filler Inorganic materials 0.000 description 8
- 239000012044 organic layer Substances 0.000 description 8
- 239000000126 substance Substances 0.000 description 8
- 239000000758 substrate Substances 0.000 description 8
- 229930185605 Bisphenol Natural products 0.000 description 7
- 239000004593 Epoxy Substances 0.000 description 7
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 7
- 125000000217 alkyl group Chemical group 0.000 description 7
- 238000010438 heat treatment Methods 0.000 description 7
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical class C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 description 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 6
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 6
- 239000004065 semiconductor Substances 0.000 description 6
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 description 5
- 238000005574 benzylation reaction Methods 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 239000007822 coupling agent Substances 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 4
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 4
- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Chemical compound CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 4
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 4
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 description 4
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 4
- 239000000654 additive Substances 0.000 description 4
- 150000001299 aldehydes Chemical class 0.000 description 4
- 239000000835 fiber Substances 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 238000000465 moulding Methods 0.000 description 4
- 229920001568 phenolic resin Polymers 0.000 description 4
- YGSDEFSMJLZEOE-UHFFFAOYSA-N salicylic acid Chemical compound OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 description 4
- 238000007789 sealing Methods 0.000 description 4
- 239000002699 waste material Substances 0.000 description 4
- 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 3
- QMMFVYPAHWMCMS-UHFFFAOYSA-N Dimethyl sulfide Chemical compound CSC QMMFVYPAHWMCMS-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-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
- 239000004698 Polyethylene Substances 0.000 description 3
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 3
- 230000002378 acidificating effect Effects 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 3
- 239000011810 insulating material Substances 0.000 description 3
- 150000002576 ketones Chemical class 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 230000007935 neutral effect Effects 0.000 description 3
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 description 3
- 229920000573 polyethylene Polymers 0.000 description 3
- 239000004848 polyfunctional curative Substances 0.000 description 3
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 3
- 239000000565 sealant Substances 0.000 description 3
- 239000003566 sealing material Substances 0.000 description 3
- KJPRLNWUNMBNBZ-QPJJXVBHSA-N (E)-cinnamaldehyde Chemical class O=C\C=C\C1=CC=CC=C1 KJPRLNWUNMBNBZ-QPJJXVBHSA-N 0.000 description 2
- FMGGHNGKHRCJLL-UHFFFAOYSA-N 1,2-bis(chloromethyl)benzene Chemical group ClCC1=CC=CC=C1CCl FMGGHNGKHRCJLL-UHFFFAOYSA-N 0.000 description 2
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 2
- DNMIWTRPMLDNKJ-UHFFFAOYSA-N 1-(dichloromethyl)-2-phenylbenzene Chemical group ClC(Cl)C1=CC=CC=C1C1=CC=CC=C1 DNMIWTRPMLDNKJ-UHFFFAOYSA-N 0.000 description 2
- MODAACUAXYPNJH-UHFFFAOYSA-N 1-(methoxymethyl)-4-[4-(methoxymethyl)phenyl]benzene Chemical group C1=CC(COC)=CC=C1C1=CC=C(COC)C=C1 MODAACUAXYPNJH-UHFFFAOYSA-N 0.000 description 2
- IYSVFZBXZVPIFA-UHFFFAOYSA-N 1-ethenyl-4-(4-ethenylphenyl)benzene Chemical group C1=CC(C=C)=CC=C1C1=CC=C(C=C)C=C1 IYSVFZBXZVPIFA-UHFFFAOYSA-N 0.000 description 2
- SDRZFSPCVYEJTP-UHFFFAOYSA-N 1-ethenylcyclohexene Chemical compound C=CC1=CCCCC1 SDRZFSPCVYEJTP-UHFFFAOYSA-N 0.000 description 2
- KJCVRFUGPWSIIH-UHFFFAOYSA-N 1-naphthol Chemical group C1=CC=C2C(O)=CC=CC2=C1 KJCVRFUGPWSIIH-UHFFFAOYSA-N 0.000 description 2
- KWRSKZMCJVFUGU-UHFFFAOYSA-N 1h-inden-1-ol Chemical compound C1=CC=C2C(O)C=CC2=C1 KWRSKZMCJVFUGU-UHFFFAOYSA-N 0.000 description 2
- UFERIGCCDYCZLN-UHFFFAOYSA-N 3a,4,7,7a-tetrahydro-1h-indene Chemical compound C1C=CCC2CC=CC21 UFERIGCCDYCZLN-UHFFFAOYSA-N 0.000 description 2
- NWIVYGKSHSJHEF-UHFFFAOYSA-N 4-[(4-amino-3,5-diethylphenyl)methyl]-2,6-diethylaniline Chemical compound CCC1=C(N)C(CC)=CC(CC=2C=C(CC)C(N)=C(CC)C=2)=C1 NWIVYGKSHSJHEF-UHFFFAOYSA-N 0.000 description 2
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-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
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical group OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- IKHGUXGNUITLKF-XPULMUKRSA-N acetaldehyde Chemical compound [14CH]([14CH3])=O IKHGUXGNUITLKF-XPULMUKRSA-N 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- 150000001408 amides Chemical class 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 238000005452 bending Methods 0.000 description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 2
- 239000012965 benzophenone Substances 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000005266 casting Methods 0.000 description 2
- KJPRLNWUNMBNBZ-UHFFFAOYSA-N cinnamic aldehyde Chemical class O=CC=CC1=CC=CC=C1 KJPRLNWUNMBNBZ-UHFFFAOYSA-N 0.000 description 2
- 229940117916 cinnamic aldehyde Drugs 0.000 description 2
- 239000004927 clay Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- MLUCVPSAIODCQM-NSCUHMNNSA-N crotonaldehyde Chemical class C\C=C\C=O MLUCVPSAIODCQM-NSCUHMNNSA-N 0.000 description 2
- MLUCVPSAIODCQM-UHFFFAOYSA-N crotonaldehyde Chemical class CC=CC=O MLUCVPSAIODCQM-UHFFFAOYSA-N 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- 150000005205 dihydroxybenzenes Chemical class 0.000 description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000012776 electronic material Substances 0.000 description 2
- 238000006735 epoxidation reaction Methods 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- IPCSVZSSVZVIGE-UHFFFAOYSA-N hexadecanoic acid Chemical compound CCCCCCCCCCCCCCCC(O)=O IPCSVZSSVZVIGE-UHFFFAOYSA-N 0.000 description 2
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 150000002469 indenes Chemical class 0.000 description 2
- 239000011229 interlayer Substances 0.000 description 2
- 239000003456 ion exchange resin Substances 0.000 description 2
- 229920003303 ion-exchange polymer Polymers 0.000 description 2
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 229940098779 methanesulfonic acid Drugs 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 2
- NXPPAOGUKPJVDI-UHFFFAOYSA-N naphthalene-1,2-diol Chemical class C1=CC=CC2=C(O)C(O)=CC=C21 NXPPAOGUKPJVDI-UHFFFAOYSA-N 0.000 description 2
- 150000004780 naphthols Chemical group 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- SJYNFBVQFBRSIB-UHFFFAOYSA-N norbornadiene Chemical compound C1=CC2C=CC1C2 SJYNFBVQFBRSIB-UHFFFAOYSA-N 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- KJIFKLIQANRMOU-UHFFFAOYSA-N oxidanium;4-methylbenzenesulfonate Chemical compound O.CC1=CC=C(S(O)(=O)=O)C=C1 KJIFKLIQANRMOU-UHFFFAOYSA-N 0.000 description 2
- 239000003973 paint Substances 0.000 description 2
- FJKROLUGYXJWQN-UHFFFAOYSA-N papa-hydroxy-benzoic acid Natural products OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 description 2
- WVDDGKGOMKODPV-ZQBYOMGUSA-N phenyl(114C)methanol Chemical compound O[14CH2]C1=CC=CC=C1 WVDDGKGOMKODPV-ZQBYOMGUSA-N 0.000 description 2
- IGALFTFNPPBUDN-UHFFFAOYSA-N phenyl-[2,3,4,5-tetrakis(oxiran-2-ylmethyl)phenyl]methanediamine Chemical compound C=1C(CC2OC2)=C(CC2OC2)C(CC2OC2)=C(CC2OC2)C=1C(N)(N)C1=CC=CC=C1 IGALFTFNPPBUDN-UHFFFAOYSA-N 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 239000002798 polar solvent Substances 0.000 description 2
- 238000006068 polycondensation reaction Methods 0.000 description 2
- 238000004382 potting Methods 0.000 description 2
- 238000010926 purge Methods 0.000 description 2
- KIDHWZJUCRJVML-UHFFFAOYSA-N putrescine Chemical compound NCCCCN KIDHWZJUCRJVML-UHFFFAOYSA-N 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 230000002787 reinforcement Effects 0.000 description 2
- 229960004889 salicylic acid Drugs 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- HHVIBTZHLRERCL-UHFFFAOYSA-N sulfonyldimethane Chemical compound CS(C)(=O)=O HHVIBTZHLRERCL-UHFFFAOYSA-N 0.000 description 2
- 150000003505 terpenes Chemical class 0.000 description 2
- 235000007586 terpenes Nutrition 0.000 description 2
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 2
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 description 2
- 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 2
- 239000002966 varnish Substances 0.000 description 2
- 229920002554 vinyl polymer Polymers 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 239000001993 wax Substances 0.000 description 2
- 239000008096 xylene Substances 0.000 description 2
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 2
- LTVUCOSIZFEASK-MPXCPUAZSA-N (3ar,4s,7r,7as)-3a-methyl-3a,4,7,7a-tetrahydro-4,7-methano-2-benzofuran-1,3-dione Chemical compound C([C@H]1C=C2)[C@H]2[C@H]2[C@]1(C)C(=O)OC2=O LTVUCOSIZFEASK-MPXCPUAZSA-N 0.000 description 1
- MUTGBJKUEZFXGO-OLQVQODUSA-N (3as,7ar)-3a,4,5,6,7,7a-hexahydro-2-benzofuran-1,3-dione Chemical compound C1CCC[C@@H]2C(=O)OC(=O)[C@@H]21 MUTGBJKUEZFXGO-OLQVQODUSA-N 0.000 description 1
- KMOUUZVZFBCRAM-OLQVQODUSA-N (3as,7ar)-3a,4,7,7a-tetrahydro-2-benzofuran-1,3-dione Chemical compound C1C=CC[C@@H]2C(=O)OC(=O)[C@@H]21 KMOUUZVZFBCRAM-OLQVQODUSA-N 0.000 description 1
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- DDFYFBUWEBINLX-UHFFFAOYSA-M tetramethylammonium bromide Chemical compound [Br-].C[N+](C)(C)C DDFYFBUWEBINLX-UHFFFAOYSA-M 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- KSBAEPSJVUENNK-UHFFFAOYSA-L tin(ii) 2-ethylhexanoate Chemical compound [Sn+2].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O KSBAEPSJVUENNK-UHFFFAOYSA-L 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000001721 transfer moulding Methods 0.000 description 1
- TUQOTMZNTHZOKS-UHFFFAOYSA-N tributylphosphine Chemical compound CCCCP(CCCC)CCCC TUQOTMZNTHZOKS-UHFFFAOYSA-N 0.000 description 1
- SRPWOOOHEPICQU-UHFFFAOYSA-N trimellitic anhydride Chemical compound OC(=O)C1=CC=C2C(=O)OC(=O)C2=C1 SRPWOOOHEPICQU-UHFFFAOYSA-N 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
- 235000005074 zinc chloride Nutrition 0.000 description 1
- 229910052845 zircon Inorganic materials 0.000 description 1
- GFQYVLUOOAAOGM-UHFFFAOYSA-N zirconium(iv) silicate Chemical compound [Zr+4].[O-][Si]([O-])([O-])[O-] GFQYVLUOOAAOGM-UHFFFAOYSA-N 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/02—Polycondensates containing more than one epoxy group per molecule
- C08G59/04—Polycondensates containing more than one epoxy group per molecule of polyhydroxy compounds with epihalohydrins or precursors thereof
- C08G59/06—Polycondensates containing more than one epoxy group per molecule of polyhydroxy compounds with epihalohydrins or precursors thereof of polyhydric phenols
- C08G59/08—Polycondensates containing more than one epoxy group per molecule of polyhydroxy compounds with epihalohydrins or precursors thereof of polyhydric phenols from phenol-aldehyde condensates
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/50—Amines
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
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- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Epoxy Resins (AREA)
Abstract
Description
本發明是有關於一種具有特定結構的環氧樹脂、硬化性樹脂組成物、及硬化性樹脂組成物的硬化物。The present invention relates to an epoxy resin having a specific structure, a curable resin composition, and a cured product of the curable resin composition.
環氧樹脂由於電氣性質(介電常數/介電損耗角正切、絕緣性)、機械性質、接著性、熱性質(耐熱性等)等優異,因此廣泛用於澆鑄成型品、積層板、積體電路(integrated circuit,IC)密封材料等電氣/電子領域、結構用材料、接著劑、塗料等領域中。Epoxy resins are widely used in casting moldings, laminates, and integrated circuits due to their excellent electrical properties (dielectric constant/dielectric loss tangent, insulation), mechanical properties, adhesiveness, and thermal properties (heat resistance, etc.) Electrical/electronic fields such as integrated circuit (IC) sealing materials, structural materials, adhesives, coatings, etc.
近年來,於電氣/電子領域中,要求樹脂組成物的阻燃性、耐濕性、密接性、介電特性等性能提高、高純度化、用於使填料(無機填充劑或有機填充劑)高度填充的低黏度化、用於縮短成型週期的反應性提高等諸特性的進一步提高(專利文獻1)。另外,作為結構用材料,於航空宇宙材料、休閒/體育器具用途等中,要求輕量且機械物性優異的材料。特別是於半導體密封領域、基板(基板自身、或其周邊材料)中,隨著該半導體的變遷,因薄層化、堆疊化、系統化、三維化而變得複雜,要求非常高水準的耐熱性或高流動性等要求特性。In recent years, in the field of electrical/electronics, it is required to improve the flame retardancy, moisture resistance, adhesiveness, dielectric properties, etc. of the resin composition, to increase its purity, and to use it as a filler (inorganic filler or organic filler) Further improvement of various characteristics such as low viscosity for high filling and improved reactivity for shortening molding cycle (Patent Document 1). In addition, as structural materials, materials that are lightweight and have excellent mechanical properties are required for aerospace materials, leisure and sports equipment applications, and the like. Especially in the field of semiconductor sealing and substrate (substrate itself or its surrounding materials), as the semiconductor changes, it becomes complicated due to thinning, stacking, systemization, and three-dimensionalization, and a very high level of heat resistance is required. Requirements such as stability or high fluidity.
作為環氧樹脂於結構用材料中的應用例,可列舉碳纖維強化塑膠(carbon fiber reinforced plastic,CFRP)。CFRP有效利用成型體為輕量且高強度的特性而被用於航空器用途的基體樹脂(matrix resin)中。 一般而言,作為CFRP等的基體樹脂中使用的樹脂,使用的是雙酚A型環氧樹脂、雙酚F型環氧樹脂、四縮水甘油基二胺基二苯基甲烷等材料。另外,於航空器用途中,使用的是四縮水甘油基二胺基二苯基甲烷等縮水甘油基胺型的環氧樹脂。 As an application example of epoxy resin in structural materials, carbon fiber reinforced plastic (carbon fiber reinforced plastic, CFRP) can be cited. CFRP is used in matrix resins for aircrafts by making use of the characteristics of lightweight and high-strength moldings. Generally, materials such as bisphenol A type epoxy resin, bisphenol F type epoxy resin, tetraglycidyldiaminodiphenylmethane, etc. are used as resins used for matrix resins such as CFRP. In addition, for aircraft applications, glycidylamine-type epoxy resins such as tetraglycidyldiaminodiphenylmethane are used.
近年來,對於CFRP的要求特性變得嚴格,於應用於航空宇宙用途或車輛等的結構材料的情況下,要求高耐熱性(專利文獻2)。縮水甘油胺系的材料具有高耐熱性,但吸水率高,存在吸水後的特性劣化的課題。另一方面,一般的縮水甘油醚型環氧樹脂的吸水率相對較低,但存在其彈性係數低的課題。因此,要求一種高耐熱性與高彈性係數、而且滿足低吸水率的材料。 [現有技術文獻] [專利文獻] In recent years, the properties required for CFRP have become stricter, and high heat resistance is required when applied to structural materials such as aerospace applications and vehicles (Patent Document 2). Glycidylamine-based materials have high heat resistance, but have a high water absorption rate, and there is a problem of deterioration of properties after water absorption. On the other hand, general glycidyl ether-type epoxy resins have relatively low water absorption, but have a problem of low modulus of elasticity. Therefore, a material with high heat resistance and high modulus of elasticity and low water absorption is required. [Prior art literature] [Patent Document]
[專利文獻1]日本專利特開2015-147854號公報 [專利文獻2]國際公開第2010/204173號 [Patent Document 1] Japanese Patent Laid-Open No. 2015-147854 [Patent Document 2] International Publication No. 2010/204173
[發明所欲解決之課題][Problem to be Solved by the Invention]
本發明鑒於上述課題,目的在於提供一種環氧樹脂、環氧樹脂組成物,其硬化物的低吸水性、高彈性優異。 [解決課題之手段] In view of the above problems, the present invention aims to provide an epoxy resin and an epoxy resin composition whose cured product is excellent in low water absorption and high elasticity. [Means to solve the problem]
本發明者等人為解決上述課題進行了努力研究,結果完成了本發明。即,本發明是有關於以下的[1]~[7]。再者,於本申請案中,「(數值1)~(數值2)」表示包括上限值及下限值。 [1] 一種環氧樹脂,由下述式(1)表示。 The inventors of the present invention have diligently studied to solve the above-mentioned problems, and as a result, completed the present invention. That is, the present invention relates to the following [1] to [7]. In addition, in this application, "(numerical value 1) - (numerical value 2)" means that an upper limit and a lower limit are included. [1] An epoxy resin represented by the following formula (1).
[化1] [chemical 1]
(式(1)中,n為重覆數,其平均值為1<n<20。R表示下述式(2)所表示的取代基。p分別表示0~4的實數,p的平均值為0.5~1.5。)(In the formula (1), n is the number of repetitions, and its average value is 1<n<20. R represents a substituent represented by the following formula (2). p represents a real number of 0 to 4, and the average value of p is 0.5~1.5.)
[化2] [Chem 2]
(式(2)中,*表示與式(1)的芳香環的鍵結部分。X表示氫原子或碳數1~6的烴基。q表示0~5的實數。)(In formula (2), * represents a bonding portion with the aromatic ring of formula (1). X represents a hydrogen atom or a hydrocarbon group having 1 to 6 carbons. q represents a real number of 0 to 5.)
[2] 一種環氧樹脂,由下述式(3)表示。 [2] An epoxy resin represented by the following formula (3).
[化3] [Chem 3]
(式(3)中,n為重覆數,其平均值為1<n<20。)(In formula (3), n is the number of repetitions, and its average value is 1<n<20.)
[3] 如前項[1]或[2]所述的環氧樹脂,其中,藉由凝膠滲透層析法(gel permeation chromatography,GPC)獲得的重量平均分子量為400~3000。 [4] 一種硬化性樹脂組成物,含有如前項[1]至[3]中任一項所述的環氧樹脂。 [5] 如前項[4]所述的硬化性樹脂組成物,更含有胺系硬化劑。 [6] 一種硬化物,將如前項[4]或[5]所述的硬化性樹脂組成物硬化而成。 [7] 一種環氧樹脂的製造方法,為如前項[1]至[3]中任一項所述的環氧樹脂的製造方法,包括:使二環戊二烯系化合物與酚系化合物的縮聚物和茚衍生物反應而獲得酚樹脂的步驟;及將所述酚樹脂環氧化的步驟。 [發明的效果] [3] The epoxy resin as described in item [1] or [2] above, wherein the weight average molecular weight obtained by gel permeation chromatography (GPC) is 400-3000. [4] A curable resin composition containing the epoxy resin according to any one of [1] to [3]. [5] The curable resin composition as described in [4] above further contains an amine-based curing agent. [6] A hardened product obtained by hardening the curable resin composition described in [4] or [5] above. [7] A kind of manufacture method of epoxy resin, is the manufacture method of epoxy resin as described in any one in preceding item [1] to [3], comprises: make the polycondensate of dicyclopentadiene compound and phenolic compound and a step of reacting an indene derivative to obtain a phenol resin; and a step of epoxidizing the phenol resin. [Effect of the invention]
本發明是有關於一種具有特定結構的環氧樹脂、硬化性樹脂組成物及硬化性樹脂組成物的硬化物,該硬化物具有低吸水性、高彈性。 因此,本發明可有效用於電氣電子零件用絕緣材料(高可靠性半導體密封材料等)及積層板(印刷配線板、增層基板等)或以CFRP為代表的各種複合材料、接著劑、塗料等中。 The present invention relates to an epoxy resin having a specific structure, a curable resin composition and a cured product of the curable resin composition, and the cured product has low water absorption and high elasticity. Therefore, the present invention can be effectively used for insulating materials for electric and electronic parts (high-reliability semiconductor sealing materials, etc.), laminated boards (printed wiring boards, build-up boards, etc.), or various composite materials represented by CFRP, adhesives, and paints. waiting.
以下,對本發明進行詳細說明。Hereinafter, the present invention will be described in detail.
本發明的環氧樹脂由下述式(1)表示。The epoxy resin of the present invention is represented by the following formula (1).
[化4] [chemical 4]
(式(1)中,n為重覆數,其平均值為1<n<20。R表示下述式(2)所表示的取代基。p分別表示0~4的實數,p的平均值為0.5~1.5。)(In the formula (1), n is the number of repetitions, and its average value is 1<n<20. R represents a substituent represented by the following formula (2). p represents a real number of 0 to 4, and the average value of p is 0.5~1.5.)
[化5] [chemical 5]
(式(2)中,*表示與式(1)的芳香環的鍵結部分。X表示氫原子或碳數1~6的烴基。q表示0~5的實數。)(In formula (2), * represents a bonding portion with the aromatic ring of formula (1). X represents a hydrogen atom or a hydrocarbon group having 1 to 6 carbons. q represents a real number of 0 to 5.)
所述式(1)中,n的平均值可根據藉由凝膠滲透層析法(GPC,檢測器:RI(折射率(refractive index))的測定而求出的數量平均分子量、或者分離出的波峰各自的面積比來算出。n的平均值進而較佳為1<n<10,特佳為1<n<5。In the formula (1), the average value of n can be obtained from the number average molecular weight obtained by measuring the gel permeation chromatography (GPC, detector: RI (refractive index)), or the isolated The average value of n is further preferably 1<n<10, particularly preferably 1<n<5.
所述式(1)所表示的環氧樹脂的取代基R由所述式(2)表示,X為氫原子時更佳。The substituent R of the epoxy resin represented by the above formula (1) is represented by the above formula (2), and X is more preferably a hydrogen atom.
所述式(1)中,p分別表示0~4的實數,p的平均值較佳為0.5~2.0,進而較佳為0.5~1.5,特佳為0.8~1.2。藉由p的平均值為0.5以上,容易示出高彈性係數及低吸水性,藉由p的平均值為2.0以下,可抑制黏度的顯著增加與耐熱性的顯著降低。In the formula (1), p represents a real number of 0 to 4, respectively, and the average value of p is preferably 0.5 to 2.0, more preferably 0.5 to 1.5, particularly preferably 0.8 to 1.2. When the average value of p is 0.5 or more, it is easy to show a high modulus of elasticity and low water absorption, and when the average value of p is 2.0 or less, a significant increase in viscosity and a significant decrease in heat resistance can be suppressed.
作為所述式(1)所表示的環氧樹脂的較佳結構的一例,可列舉下述式(3)所表示的環氧樹脂。An example of a preferable structure of the epoxy resin represented by the above formula (1) includes an epoxy resin represented by the following formula (3).
[化6] [chemical 6]
(式(3)中,n為重覆數,其平均值為1<n<20。)(In formula (3), n is the number of repetitions, and its average value is 1<n<20.)
所述式(3)中n的較佳範圍與所述式(1)相同。The preferred range of n in the formula (3) is the same as that of the formula (1).
本發明的環氧樹脂的製法並無特別限定,例如可藉由使下述式(4)所表示的酚樹脂與表鹵代醇於溶劑、觸媒的存在下進行加成或閉環反應而獲得。The production method of the epoxy resin of the present invention is not particularly limited, for example, it can be obtained by adding or ring-closing a phenol resin represented by the following formula (4) and an epihalohydrin in the presence of a solvent or a catalyst. .
[化7] [chemical 7]
(式(4)中,n為重覆數,其平均值為1<n<20。R表示下述式(5)所表示的取代基。p分別表示0~4的實數,p的平均值為0.5~1.5。)(In formula (4), n is the number of repetitions, and its average value is 1<n<20. R represents a substituent represented by the following formula (5). p represents a real number of 0 to 4, and the average value of p is 0.5~1.5.)
[化8] [chemical 8]
(式(5)中,*表示與式(4)的芳香環的鍵結部分。X表示氫原子或碳數1~6的烴基。q表示0~5的實數。)(In formula (5), * represents a bonding part with the aromatic ring of formula (4). X represents a hydrogen atom or a hydrocarbon group having 1 to 6 carbons. q represents a real number of 0 to 5.)
所述式(4)、式(5)的n、p、q、R、X的較佳範圍與所述式(1)、式(2)相同。The preferred ranges of n, p, q, R, and X in the formula (4) and formula (5) are the same as those in the formula (1) and formula (2).
此處,對所述式(4)所表示的酚樹脂的製法進行說明。 所述式(4)所表示的酚樹脂的製法並無特別限定。例如,藉由使茚或茚醇等苄基化劑於酸觸媒存在下與二環戊二烯型酚樹脂(二環戊二烯系化合物與酚系化合物的縮聚物)反應,可獲得目標酚樹脂。與苄基醇等苄基化劑相比,藉由茚或茚醇等茚衍生物所進行的改質,分子的剛性提高,因此能夠於不明顯損害耐熱性的情況下表現出高彈性係數、低吸水性。 Here, the method for producing the phenol resin represented by the formula (4) will be described. The method for producing the phenol resin represented by the formula (4) is not particularly limited. For example, by reacting a benzylation agent such as indene or indenol with a dicyclopentadiene type phenol resin (a polycondensation product of a dicyclopentadiene compound and a phenolic compound) in the presence of an acid catalyst, the target compound can be obtained. Phenolic resin. Compared with benzylation agents such as benzyl alcohol, modification by indene derivatives such as indene or indenol increases the rigidity of the molecule, so it is possible to exhibit a high modulus of elasticity, Low water absorption.
合成所述式(4)所表示的酚樹脂時使用的酸性觸媒可列舉:鹽酸、磷酸、硫酸、甲酸、氯化鋅、氯化鐵、氯化鋁、對甲苯磺酸、甲磺酸、活性白土、離子交換樹脂等。該些可單獨使用,亦可併用兩種以上。相對於所使用的酚性羥基,觸媒的使用量為0.1重量%~50重量%,較佳為1重量%~30重量%,若過多,則廢棄物增加,若過少,則反應進行變慢。The acidic catalyst used when synthesizing the phenol resin represented by the above formula (4) includes hydrochloric acid, phosphoric acid, sulfuric acid, formic acid, zinc chloride, ferric chloride, aluminum chloride, p-toluenesulfonic acid, methanesulfonic acid, Activated clay, ion exchange resin, etc. These may be used alone or in combination of two or more. The amount of the catalyst used is 0.1% to 50% by weight, preferably 1% to 30% by weight, with respect to the phenolic hydroxyl group used. If it is too much, waste will increase, and if it is too small, the reaction will slow down. .
視需要可使用甲苯、二甲苯等有機溶劑進行反應,亦可於無溶劑下進行反應。例如,向由二環戊二烯系化合物與酚系化合物的縮聚物獲得的酚樹脂和苄基化劑的混合溶液中添加酸性觸媒後,於觸媒包含水的情況下,較佳為藉由共沸將水自系統內除去。然後一邊自系統內除去溶劑一邊升溫,於100℃~220℃、較佳為120℃~180℃下進行1小時~50小時、較佳為2小時~20小時反應。於使用醇系苄基化劑時會副生成水,因此於升溫時一邊使水與溶劑共沸一邊自系統內除去。反應結束後,利用鹼水溶液等中和酸性觸媒,然後向油層中加入非水溶性有機溶劑,反覆水洗直至廢水變為中性為止,然後於加熱減壓下將溶劑及過量的苄基化劑去除。於使用活性白土或離子交換樹脂的情況下,於反應結束後對反應液進行過濾而將觸媒去除。If necessary, organic solvents such as toluene and xylene may be used for the reaction, or the reaction may be performed without a solvent. For example, after adding an acidic catalyst to a mixed solution of a phenol resin obtained from a polycondensate of a dicyclopentadiene compound and a phenolic compound and a benzylation agent, if the catalyst contains water, it is preferable to use Water was removed from the system by azeotropy. Then, the temperature is raised while removing the solvent from the system, and the reaction is carried out at 100° C. to 220° C., preferably 120° C. to 180° C., for 1 hour to 50 hours, preferably 2 hours to 20 hours. When an alcohol-based benzylation agent is used, water is by-produced, so water and the solvent are azeotropically removed from the system when the temperature is raised. After the reaction is over, neutralize the acidic catalyst with an aqueous alkali solution, etc., then add a non-water-soluble organic solvent to the oil layer, wash with water repeatedly until the waste water becomes neutral, and then dissolve the solvent and excess benzylation agent under heating and reduced pressure. remove. In the case of using activated clay or ion exchange resin, the reaction liquid is filtered after the reaction to remove the catalyst.
接下來,對本發明的環氧樹脂的製法進行說明。 如上所述,本發明的環氧樹脂的製法並無特別限定,例如可藉由使所述式(4)所表示的酚樹脂與表鹵代醇於溶劑、觸媒的存在下進行加成或閉環反應而獲得。 相對於酚樹脂的酚性羥基1莫耳,表鹵代醇的使用量通常為1.0莫耳~20.0莫耳,較佳為1.5莫耳~10.0莫耳。 Next, the production method of the epoxy resin of this invention is demonstrated. As mentioned above, the preparation method of the epoxy resin of the present invention is not particularly limited, for example, by adding the phenol resin represented by the formula (4) and the epihalohydrin in the presence of a solvent or a catalyst, or obtained by a ring-closing reaction. The amount of epihalohydrin used is usually 1.0 to 20.0 moles, preferably 1.5 to 10.0 moles per 1 mole of the phenolic hydroxyl group of the phenol resin.
作為環氧化反應中可使用的鹼金屬氫氧化物,可列舉氫氧化鈉、氫氧化鉀等。鹼金屬氫氧化物可為固體物質,亦可使用其水溶液。於使用水溶液的情況下,可為以下方法:將該鹼金屬氫氧化物的水溶液連續地添加至反應系統內,並且於減壓下或常壓下連續蒸餾出水及表鹵代醇,進而進行分液以將水去除,使表鹵代醇連續返回反應系統內。相對於酚樹脂的酚性羥基1莫耳,鹼金屬氫氧化物的使用量通常為0.9莫耳~2.5莫耳,較佳為0.95莫耳~1.5莫耳。若鹼金屬氫氧化物的使用量少,則反應不會充分進行。另一方面,相對於酚樹脂的酚性羥基1莫耳而過量使用超過2.5莫耳的鹼金屬氫氧化物的情況會導致副生成不必要的廢棄物。Sodium hydroxide, potassium hydroxide, etc. are mentioned as an alkali metal hydroxide which can be used for an epoxidation reaction. The alkali metal hydroxide may be a solid substance, and its aqueous solution may also be used. In the case of using an aqueous solution, the following method can be used: the aqueous solution of the alkali metal hydroxide is continuously added to the reaction system, and water and epihalohydrin are continuously distilled off under reduced pressure or normal pressure, and then separated. Liquid to remove water, so that the epihalohydrin is continuously returned to the reaction system. The amount of the alkali metal hydroxide used is usually 0.9 to 2.5 moles, preferably 0.95 to 1.5 moles per 1 mole of the phenolic hydroxyl group of the phenol resin. When the usage-amount of alkali metal hydroxide is small, reaction will not fully progress. On the other hand, excessive use of the alkali metal hydroxide exceeding 2.5 mol with respect to 1 mol of the phenolic hydroxyl group of the phenolic resin leads to unnecessary waste by-product.
為了促進所述反應,亦可添加四甲基氯化銨、四甲基溴化銨、三甲基苄基氯化銨等四級銨鹽作為觸媒。作為四級銨鹽的使用量,相對於酚樹脂的酚性羥基1莫耳,通常為0.1 g~15 g,較佳為0.2 g~10 g。若使用量過少,則無法獲得充分的反應促進效果,若使用量過多,則於環氧樹脂中殘存的四級銨鹽量增加,因此亦有可能成為使電可靠性劣化的原因。In order to promote the reaction, a quaternary ammonium salt such as tetramethylammonium chloride, tetramethylammonium bromide, trimethylbenzyl ammonium chloride may be added as a catalyst. The usage-amount of a quaternary ammonium salt is 0.1 g-15 g normally with respect to 1 mole of phenolic hydroxyl groups of a phenol resin, Preferably it is 0.2 g-10 g. If the amount used is too small, a sufficient reaction acceleration effect cannot be obtained. If the amount used is too large, the amount of quaternary ammonium salt remaining in the epoxy resin will increase, which may also cause deterioration of electrical reliability.
於環氧化反應時,就反應進行方面而言,較佳為添加甲醇、乙醇、異丙醇等醇類、二甲基碸、二甲基亞碸、四氫呋喃、二噁烷等非質子性極性溶媒等進行反應。於使用醇類的情況下,其使用量相對於表鹵代醇的使用量通常為2重量%~50重量%,較佳為4重量%~20重量%。另外,於使用非質子性極性溶媒的情況下相對於表鹵代醇的使用量通常為5重量%~100重量%,較佳為10重量%~80重量%。反應溫度通常為30℃~90℃,較佳為35℃~80℃。反應時間通常為0.5小時~100小時,較佳為1小時~30小時。 於反應結束後,在對反應物進行水洗後、或者不進行水洗而於加熱減壓下將表鹵代醇及溶媒等去除。另外,為了製成水解性鹵素更少的環氧樹脂,亦可將回收的環氧樹脂溶解於甲苯、甲基異丁基酮等溶劑中,並加入氫氧化鈉、氫氧化鉀等鹼金屬氫氧化物的水溶液進行反應,而使閉環可靠。該情況下,相對於縮水甘油化中使用的酚樹脂的酚性羥基1莫耳,鹼金屬氫氧化物的使用量通常為0.01莫耳~0.3莫耳,較佳為0.05莫耳~0.2莫耳。反應溫度通常為50℃~120℃,反應時間通常為0.5小時~24小時。於反應結束後,將所生成的鹽藉由過濾、水洗等去除,進而於加熱減壓下將溶劑蒸餾去除,藉此獲得本發明的環氧樹脂。 In the epoxidation reaction, it is preferable to add alcohols such as methanol, ethanol, and isopropanol, and aprotic polar solvents such as dimethylsulfone, dimethylsulfoxide, tetrahydrofuran, and dioxane in terms of reaction progress. Wait for the reaction. When alcohols are used, the amount used is usually 2% by weight to 50% by weight, preferably 4% by weight to 20% by weight, based on the amount of epihalohydrin used. Moreover, when using an aprotic polar solvent, the usage-amount with respect to an epihalohydrin is normally 5 weight% - 100 weight%, Preferably it is 10 weight% - 80 weight%. The reaction temperature is usually 30°C to 90°C, preferably 35°C to 80°C. The reaction time is usually 0.5 hour to 100 hours, preferably 1 hour to 30 hours. After completion of the reaction, the reactant is washed with water or without washing with water, and the epihalohydrin, the solvent, and the like are removed under heating and reduced pressure. In addition, in order to make an epoxy resin with less hydrolyzable halogens, the recovered epoxy resin can also be dissolved in solvents such as toluene and methyl isobutyl ketone, and alkali metal hydrogen such as sodium hydroxide and potassium hydroxide can be added. Aqueous solutions of the oxides react to allow reliable ring closure. In this case, the amount of the alkali metal hydroxide used is usually 0.01 to 0.3 mol, preferably 0.05 to 0.2 mol, per 1 mol of the phenolic hydroxyl group of the phenolic resin used for glycidation. . The reaction temperature is usually 50°C to 120°C, and the reaction time is usually 0.5 hour to 24 hours. After the reaction, the generated salt is removed by filtration, washing with water, etc., and the solvent is distilled off under reduced pressure under heating, thereby obtaining the epoxy resin of the present invention.
本發明的環氧樹脂通常於常溫下為半固體~固體的樹脂狀,其軟化點較佳為100℃以下,進而較佳為80℃以下。於軟化點高於100℃的情況下,黏度高,製作預浸體時纖維含浸性降低。另外,其環氧當量較佳為200 g/eq~1000 g/eq,進而較佳為300 g/eq~800 g/eq,特佳為300 g/eq~700 g/eq,最佳為330 g/eq~600 g/eq。The epoxy resin of the present invention is usually a semi-solid to solid resin at normal temperature, and its softening point is preferably below 100°C, more preferably below 80°C. When the softening point is higher than 100°C, the viscosity is high, and the impregnation of fibers decreases when making a prepreg. In addition, the epoxy equivalent is preferably from 200 g/eq to 1000 g/eq, more preferably from 300 g/eq to 800 g/eq, particularly preferably from 300 g/eq to 700 g/eq, most preferably from 330 g/eq g/eq~600 g/eq.
以下,對本發明的環氧樹脂組成物進行說明。 於本發明的環氧樹脂組成物中,式(1)所表示的環氧樹脂可單獨使用、或與其他環氧樹脂併用。於併用的情況下,式(1)所表示的環氧樹脂於所有環氧樹脂中所佔的比例較佳為10重量%~98重量%,更佳為20重量%~95重量%,進而較佳為30重量%~95重量%。藉由將添加量設為10重量%以上,可表現出彈性係數的提高及低吸水性。 Hereinafter, the epoxy resin composition of this invention is demonstrated. In the epoxy resin composition of the present invention, the epoxy resin represented by formula (1) may be used alone or in combination with other epoxy resins. In the case of combined use, the proportion of the epoxy resin represented by formula (1) in all epoxy resins is preferably 10% by weight to 98% by weight, more preferably 20% by weight to 95% by weight, and more preferably Preferably, it is 30% by weight to 95% by weight. By making the addition amount 10 weight% or more, the improvement of an elastic modulus and low water absorption can be expressed.
作為可與本發明的環氧樹脂併用的其他環氧樹脂的具體例,可列舉:雙酚類(雙酚A、雙酚F、雙酚S、聯苯酚、雙酚AD等)或酚類(苯酚、烷基取代苯酚、芳香族取代苯酚、萘酚、烷基取代萘酚、二羥基苯、烷基取代二羥基苯、二羥基萘等)與各種醛(甲醛、乙醛、烷基醛、苯甲醛、烷基取代苯甲醛、羥基苯甲醛、萘醛、戊二醛、鄰苯二甲醛、巴豆醛、肉桂醛等)的縮聚物;所述酚類與各種二烯化合物(二環戊二烯、萜烯類、乙烯基環己烯、降冰片二烯、乙烯基降冰片烯、四氫茚、二乙烯基苯、二乙烯基聯苯、二異丙烯基聯苯、丁二烯、異戊二烯等)的聚合物;所述酚類與酮類(丙酮、甲基乙基酮、甲基異丁基酮、苯乙酮、二苯甲酮等)的縮聚物;所述酚類與芳香族二甲醇類(苯二甲醇、聯苯二甲醇等)的縮聚物;所述酚類與芳香族二氯甲基類(α,α'-二氯二甲苯、雙氯甲基聯苯等)的縮聚物;所述酚類與芳香族雙烷氧基甲基類(雙甲氧基甲基苯、雙甲氧基甲基聯苯、雙苯氧基甲基聯苯等)的縮聚物;所述雙酚類與各種醛的縮聚物或將醇類等加以縮水甘油化而得的縮水甘油醚系環氧樹脂、脂環式環氧樹脂、縮水甘油胺系環氧樹脂、縮水甘油酯系環氧樹脂等,只要為通常所使用的環氧樹脂則並不限定於該些。該些可單獨使用,亦可使用兩種以上。Specific examples of other epoxy resins that can be used in combination with the epoxy resin of the present invention include: bisphenols (bisphenol A, bisphenol F, bisphenol S, biphenol, bisphenol AD, etc.) or phenols ( Phenol, alkyl substituted phenol, aromatic substituted phenol, naphthol, alkyl substituted naphthol, dihydroxybenzene, alkyl substituted dihydroxybenzene, dihydroxynaphthalene, etc.) and various aldehydes (formaldehyde, acetaldehyde, alkylaldehyde, benzaldehyde, alkyl-substituted benzaldehyde, hydroxybenzaldehyde, naphthaldehyde, glutaraldehyde, phthalaldehyde, crotonaldehyde, cinnamaldehyde, etc.); said phenols with various diene compounds (dicyclopentadiene olefins, terpenes, vinyl cyclohexene, norbornadiene, vinyl norbornene, tetrahydroindene, divinylbenzene, divinylbiphenyl, diisopropenylbiphenyl, butadiene, isopropene Pentadiene, etc.); polycondensates of said phenols and ketones (acetone, methyl ethyl ketone, methyl isobutyl ketone, acetophenone, benzophenone, etc.); said phenols Condensation products with aromatic dimethanols (benzenedimethanol, biphenyldimethanol, etc.); said phenols and aromatic dichloromethyls (α,α'-dichloroxylene, dichloromethylbiphenyl etc.); polycondensation of said phenols with aromatic bis-alkoxymethyls (bismethoxymethylbenzene, bismethoxymethylbiphenyl, bisphenoxymethylbiphenyl, etc.) products; polycondensates of the bisphenols and various aldehydes or glycidyl ether epoxy resins, alicyclic epoxy resins, glycidylamine epoxy resins, glycidol The ester-based epoxy resin and the like are not limited to these as long as they are commonly used epoxy resins. These may be used alone, or two or more kinds may be used.
作為可於本發明的環氧樹脂組成物中使用的硬化劑,可列舉:胺系硬化劑、酸酐系硬化劑、醯胺系硬化劑、酚系硬化劑等。作為可使用的硬化劑的具體例,例如可列舉鄰苯二胺、間苯二胺、對苯二胺、4,4'-二胺基二苯基碸、3,4'-二胺基二苯基碸、3,3'-二胺基二苯基碸、2,2'-二胺基二苯基碸、二乙基甲苯二胺、二甲基硫代甲苯二胺、二胺基二苯基甲烷、3,3'-二甲基-4,4'-二胺基二苯基甲烷、3,3'-二乙基-4,4'-二胺基二苯基甲烷、4,4'-二胺基-3,3'-二乙基-5,5'-二甲基二苯基甲烷、4,4'-二胺基-3,3',5,5'-四甲基二苯基甲烷、4,4'-二胺基-3,3',5,5'-四乙基二苯基甲烷、4,4'-二胺基-3,3',5,5'-四異丙基二苯基甲烷、4,4'-亞甲基雙(N-甲基苯胺)、雙(胺基苯基)芴、3,4'-二胺基二苯基醚、4,4'-二胺基二苯基醚、2,2'-雙[4-(4-胺基苯氧基)苯基]丙烷、雙[4-(4-胺基苯氧基)苯基]碸、1,3'-雙(4-胺基苯氧基)苯、1,4'-雙(4-胺基苯氧基)苯、1,4'-雙(4-胺基苯氧基)聯苯、4,4'-(1,3-伸苯基二亞異丙基)雙苯胺、4,4'-(1,4-伸苯基二亞異丙基)雙苯胺、萘二胺、聯苯胺、二甲基聯苯胺、國際公開第2017/170551號合成例1及合成例2中記載的芳香族胺化合物等芳香族胺化合物;1,3-雙(胺基甲基)環己烷、異佛爾酮二胺、4,4'-亞甲基雙(環己基胺)、降冰片烷二胺、乙二胺、丙二胺、四亞甲基二胺、五亞甲基二胺、六亞甲基二胺、二聚物二胺、三乙四胺等脂肪族胺等,但並不限定於此,可根據對組成物欲賦予的特性適宜地使用。為了確保適用期,較佳為使用芳香族胺,於欲賦予即時硬化性的情況下,較佳為使用脂肪族胺。藉由使用含有二官能成分作為主要成分的胺系化合物作為硬化劑,可於硬化反應時構築直線性高的網絡(network),從而可表現出特別優異的強韌性。另外,可列舉二氰二胺、由次亞麻油酸的二聚體及乙二胺合成的聚醯胺樹脂等醯胺系化合物;鄰苯二甲酸酐、偏苯三甲酸酐、均苯四甲酸酐、馬來酸酐、四氫鄰苯二甲酸酐、甲基四氫鄰苯二甲酸酐、甲基納迪克酸酐、六氫鄰苯二甲酸酐、甲基六氫鄰苯二甲酸酐等酸酐系化合物;雙酚類(雙酚A、雙酚F、雙酚S、聯苯酚、雙酚AD等)或酚類(苯酚、烷基取代苯酚、芳香族取代苯酚、萘酚、烷基取代萘酚、二羥基苯、烷基取代二羥基苯、二羥基萘等)與各種醛(甲醛、乙醛、烷基醛、苯甲醛、烷基取代苯甲醛、羥基苯甲醛、萘醛、戊二醛、鄰苯二甲醛、巴豆醛、肉桂醛等)的縮聚物,或者所述酚類與各種二烯化合物(二環戊二烯、萜烯類、乙烯基環己烯、降冰片二烯、乙烯基降冰片烯、四氫茚、二乙烯基苯、二乙烯基聯苯、二異丙烯基聯苯、丁二烯、異戊二烯等)的聚合物,或者所述酚類與酮類(丙酮、甲基乙基酮、甲基異丁基酮、苯乙酮、二苯甲酮等)的縮聚物,或者所述酚類與芳香族二甲醇類(苯二甲醇、聯苯二甲醇等)的縮聚物,或者所述酚類與芳香族二氯甲基類(α,α'-二氯二甲苯、雙氯甲基聯苯等)的縮聚物,或者所述酚類與芳香族雙烷氧基甲基類(雙甲氧基甲基苯、雙甲氧基甲基聯苯、雙苯氧基甲基聯苯等)的縮聚物,或者所述雙酚類與各種醛的縮聚物、及該些的改質物等酚系化合物;咪唑、三氟硼烷-胺錯合物、胍衍生物等,但並不限定於該些。Examples of the curing agent that can be used in the epoxy resin composition of the present invention include amine-based curing agents, acid anhydride-based curing agents, amide-based curing agents, and phenol-based curing agents. Specific examples of hardeners that can be used include o-phenylenediamine, m-phenylenediamine, p-phenylenediamine, 4,4'-diaminodiphenylene, 3,4'-diaminodiphenyl Phenylphenylene, 3,3'-diaminodiphenylene, 2,2'-diaminodiphenylene, diethyltoluenediamine, dimethylthiotoluenediamine, diaminodiphenyl Phenylmethane, 3,3'-dimethyl-4,4'-diaminodiphenylmethane, 3,3'-diethyl-4,4'-diaminodiphenylmethane, 4, 4'-diamino-3,3'-diethyl-5,5'-dimethyldiphenylmethane, 4,4'-diamino-3,3',5,5'-tetramethyl diphenylmethane, 4,4'-diamino-3,3',5,5'-tetraethyldiphenylmethane, 4,4'-diamino-3,3',5,5 '-Tetraisopropyldiphenylmethane, 4,4'-methylenebis(N-methylaniline), bis(aminophenyl)fluorene, 3,4'-diaminodiphenylether, 4,4'-Diaminodiphenyl ether, 2,2'-bis[4-(4-aminophenoxy)phenyl]propane, bis[4-(4-aminophenoxy)benzene base] benzene, 1,3'-bis(4-aminophenoxy)benzene, 1,4'-bis(4-aminophenoxy)benzene, 1,4'-bis(4-aminophenoxy)benzene Oxy)biphenyl, 4,4'-(1,3-phenylenediisopropylidene)bisaniline, 4,4'-(1,4-phenylenediisopropylidene)bisaniline, Aromatic amine compounds such as naphthalene diamine, benzidine, dimethylbenzidine, aromatic amine compounds described in Synthesis Example 1 and Synthesis Example 2 of International Publication No. 2017/170551; 1,3-bis(aminomethyl ) cyclohexane, isophorone diamine, 4,4'-methylene bis (cyclohexylamine), norbornane diamine, ethylene diamine, propylene diamine, tetramethylene diamine, pentamethylene Aliphatic amines such as methyldiamine, hexamethylenediamine, dimerdiamine, triethylenetetramine, etc. are not limited thereto, and can be used appropriately according to the properties to be imparted to the composition. In order to secure a pot life, it is preferable to use an aromatic amine, and it is preferable to use an aliphatic amine when immediate hardening property is to be imparted. By using an amine compound containing a difunctional component as a main component as a curing agent, a highly linear network can be constructed during the curing reaction, thereby exhibiting particularly excellent toughness. In addition, amide-based compounds such as dicyandiamine, polyamide resin synthesized from linolenic acid dimer and ethylenediamine; phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, etc. , maleic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylnadic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride and other acid anhydride compounds ; bisphenols (bisphenol A, bisphenol F, bisphenol S, biphenol, bisphenol AD, etc.) or phenols (phenol, alkyl substituted phenol, aromatic substituted phenol, naphthol, alkyl substituted naphthol, Dihydroxybenzene, alkyl substituted dihydroxybenzene, dihydroxynaphthalene, etc.) and various aldehydes (formaldehyde, acetaldehyde, alkylaldehyde, benzaldehyde, alkyl phthalaldehyde, crotonaldehyde, cinnamaldehyde, etc.), or said phenols with various diene compounds (dicyclopentadiene, terpenes, vinylcyclohexene, norbornadiene, vinyl norbornadiene, norbornene, tetrahydroindene, divinylbenzene, divinylbiphenyl, diisopropenylbiphenyl, butadiene, isoprene, etc.), or said phenols with ketones (acetone, methyl ethyl ketone, methyl isobutyl ketone, acetophenone, benzophenone, etc.) polycondensate, or the polycondensate of the phenols and aromatic dichloromethyls (α, α'-dichloroxylene, dichloromethylbiphenyl, etc.), or the polycondensates of the phenols and aromatic bis-alkoxy Polycondensates of methyl groups (bismethoxymethylbenzene, bismethoxymethylbiphenyl, bisphenoxymethylbiphenyl, etc.), or polycondensates of said bisphenols and various aldehydes, and Phenolic compounds such as modified substances of these; imidazole, trifluoroborane-amine complexes, guanidine derivatives, etc., but are not limited to these.
於本發明的環氧樹脂組成物中,相對於環氧樹脂的環氧基1當量,硬化劑的使用量較佳為0.5當量~1.5當量,特佳為0.6當量~1.2當量。藉由設為0.5當量~1.5當量,可獲得良好的硬化物性。In the epoxy resin composition of the present invention, the amount of the curing agent used is preferably 0.5 to 1.5 equivalents, particularly preferably 0.6 to 1.2 equivalents, relative to 1 equivalent of epoxy groups in the epoxy resin. Favorable cured physical properties can be obtained by setting it as 0.5 equivalent - 1.5 equivalent.
當使用所述硬化劑進行硬化反應時,亦可併用硬化促進劑。作為可使用的硬化促進劑,例如可列舉:2-甲基咪唑、2-乙基咪唑、2-苯基咪唑、2-乙基-4-甲基咪唑等咪唑類;2-(二甲基胺基甲基)苯酚、三乙二胺、三乙醇胺、1,8-二氮雜雙環(5,4,0)十一烯-7等三級胺類;三苯基膦、二苯基膦、三丁基膦等有機膦類;辛酸錫等金屬化合物;四苯基鏻-四苯基硼酸鹽、四苯基鏻-乙基三苯基硼酸鹽等四取代鏻-四取代硼酸鹽;2-乙基-4-甲基咪唑-四苯基硼酸鹽、N-甲基嗎啉-四苯基硼酸鹽等四苯基硼鹽;苯甲酸、鄰苯二甲酸、間苯二甲酸、對苯二甲酸、萘甲酸、水楊酸等羧酸系化合物等。就促進胺系化合物與環氧樹脂的硬化反應的觀點而言,較佳為水楊酸等羧酸系化合物。相對於環氧樹脂100重量份,硬化促進劑可根據需要使用0.01重量份~15重量份。When the hardening reaction is performed using the hardening agent, a hardening accelerator may be used in combination. Examples of usable curing accelerators include imidazoles such as 2-methylimidazole, 2-ethylimidazole, 2-phenylimidazole, and 2-ethyl-4-methylimidazole; Aminomethyl)phenol, triethylenediamine, triethanolamine, 1,8-diazabicyclo(5,4,0)undecene-7 and other tertiary amines; triphenylphosphine, diphenylphosphine , tributylphosphine and other organic phosphines; metal compounds such as tin octoate; tetraphenylphosphonium-tetraphenylborate, tetraphenylphosphonium-ethyltriphenylborate and other tetrasubstituted phosphonium-tetrasubstituted borates; 2 -Ethyl-4-methylimidazole-tetraphenyl borate, N-methylmorpholine-tetraphenyl borate and other tetraphenyl boron salts; benzoic acid, phthalic acid, isophthalic acid, terephthalic acid Carboxylic acid compounds such as dicarboxylic acid, naphthoic acid, and salicylic acid, etc. From the viewpoint of accelerating the curing reaction between the amine compound and the epoxy resin, carboxylic acid compounds such as salicylic acid are preferred. The hardening accelerator can be used as needed in an amount of 0.01 to 15 parts by weight with respect to 100 parts by weight of the epoxy resin.
進而,於本發明的環氧樹脂組成物中,根據需要可添加無機填充劑。作為無機填充劑,可列舉晶體二氧化矽、熔融二氧化矽、氧化鋁、鋯石、矽酸鈣、碳酸鈣、碳化矽、氮化矽、氮化硼、氧化鋯、鎂橄欖石(forsterite)、塊滑石(steatite)、尖晶石、二氧化鈦、滑石等的粉體或將該些球形化而成的珠粒等,但並不限定於該些。該些可單獨使用,亦可使用兩種以上。該些無機填充劑根據用途的不同而其使用量不同,但例如當用於半導體的密封劑用途時,就環氧樹脂組成物的硬化物的耐熱性、耐濕性、力學性質、阻燃性等方面而言,較佳為以於環氧樹脂組成物中佔20重量%以上的比例使用,更佳為30重量%以上,特別是為了提高相對於引線框架的線膨脹率,進而較佳為以佔70重量%~95重量%的比例使用。Furthermore, an inorganic filler can be added to the epoxy resin composition of this invention as needed. Examples of inorganic fillers include crystalline silica, fused silica, alumina, zircon, calcium silicate, calcium carbonate, silicon carbide, silicon nitride, boron nitride, zirconia, forsterite , steatite, spinel, titanium dioxide, talc, and other powders, or beads obtained by spheroidizing these, but are not limited to these. These may be used alone, or two or more kinds may be used. The amount of these inorganic fillers differs depending on the application. For example, when used as a sealant for semiconductors, the heat resistance, moisture resistance, mechanical properties, and flame retardancy of the cured epoxy resin composition In terms of other aspects, it is preferable to use it in a proportion of more than 20% by weight in the epoxy resin composition, more preferably more than 30% by weight, especially in order to increase the linear expansion rate relative to the lead frame, and more preferably It is used in a proportion of 70% to 95% by weight.
於本發明的環氧樹脂組成物中,為了使成形時相對於模具的脫模良好,可調配脫模劑。作為脫模劑,可使用先前公知的任一者,例如可列舉:棕櫚蠟(carnauba wax)、褐煤蠟(montan wax)等酯系蠟;硬脂酸、棕櫚酸等脂肪酸及該些的金屬鹽;氧化聚乙烯、非氧化聚乙烯等聚烯烴系蠟等。該些可單獨使用,亦可併用兩種以上。該些脫模劑的調配量相對於所有有機成分較佳為0.5重量%~3重量%。若較此過少,則自模具的脫模變差,若較此過多,則與引線框架等的接著變差。In the epoxy resin composition of the present invention, a mold release agent may be blended in order to facilitate mold release from the mold during molding. As the release agent, any of the previously known ones can be used, for example, ester waxes such as carnauba wax and montan wax; fatty acids such as stearic acid and palmitic acid, and metal salts thereof ; Polyolefin-based waxes such as oxidized polyethylene and non-oxidized polyethylene. These may be used alone or in combination of two or more. It is preferable that the compounding quantity of these release agents is 0.5 weight% - 3 weight% with respect to all organic components. If the amount is too small, the release from the mold will deteriorate, and if the amount is too large, the adhesion to the lead frame and the like will deteriorate.
於本發明的環氧樹脂組成物中,為了提高無機填充劑與樹脂成分的接著性,可調配偶合劑。作為偶合劑,可使用先前公知的任一者,例如可列舉:乙烯基烷氧基矽烷、環氧基烷氧基矽烷、苯乙烯基烷氧基矽烷、甲基丙烯醯氧基烷氧基矽烷、丙烯醯氧基烷氧基矽烷、胺基烷氧基矽烷、巰基烷氧基矽烷、異氰酸基烷氧基矽烷等各種烷氧基矽烷化合物、烷氧基鈦化合物、鋁螯合物類等。該些可單獨使用,亦可併用兩種以上。關於偶合劑的添加方法,可於利用偶合劑預先對無機填充劑表面進行處理後與樹脂混練,亦可於在樹脂中混合偶合劑後再混練無機填充劑。In the epoxy resin composition of the present invention, in order to improve the adhesion between the inorganic filler and the resin component, a coupling agent can be formulated. As the coupling agent, any of the previously known ones can be used, for example, vinyl alkoxysilane, epoxy alkoxysilane, styryl alkoxysilane, methacryloxyalkoxysilane , acryloxyalkoxysilane, aminoalkoxysilane, mercaptoalkoxysilane, isocyanatoalkoxysilane and other alkoxysilane compounds, alkoxytitanium compounds, aluminum chelates Wait. These may be used alone or in combination of two or more. Regarding the method of adding the coupling agent, the surface of the inorganic filler can be pre-treated with the coupling agent and then kneaded with the resin, or the inorganic filler can be kneaded after mixing the coupling agent in the resin.
進而,於本發明的環氧樹脂組成物中,可根據需要而調配公知的添加劑。作為可使用的添加劑的具體例,可列舉:聚丁二烯及其改質物、丙烯腈共聚物的改質物、聚苯醚、聚苯乙烯、聚乙烯、聚醯亞胺、氟樹脂、馬來醯亞胺系化合物、氰酸酯系化合物、矽酮凝膠、矽油、以及碳黑、酞青藍、酞青綠等著色劑等。Furthermore, in the epoxy resin composition of this invention, a well-known additive can be mix|blended as needed. Specific examples of additives that can be used include: polybutadiene and its modified products, modified products of acrylonitrile copolymers, polyphenylene ether, polystyrene, polyethylene, polyimide, fluororesin, and Imide-based compounds, cyanate-based compounds, silicone gel, silicone oil, and colorants such as carbon black, phthalocyanine blue, and phthalocyanine green.
本發明的環氧樹脂組成物藉由將上述各成分均勻地混合而獲得。本發明的環氧樹脂組成物可藉由與先前已知的方法同樣的方法容易地製成其硬化物。例如,藉由根據需要使用擠出機、捏合機、輥等將環氧樹脂與硬化劑、以及視需要的硬化促進劑、無機填充劑、脫模劑、矽烷偶合劑及添加劑充分混合至均勻,獲得本發明的環氧樹脂組成物,將其藉由熔融澆鑄法或轉注成型法、射出成型法、壓縮成型法等成型,進而於80℃~200℃下加熱2小時~10小時,藉此可獲得硬化物。The epoxy resin composition of the present invention is obtained by uniformly mixing the above-mentioned components. The epoxy resin composition of the present invention can be easily produced into its cured product by the same method as the conventionally known method. For example, by sufficiently mixing epoxy resin with hardener, and hardening accelerator, inorganic filler, release agent, silane coupling agent, and additives as needed to uniformity using extruder, kneader, roll, etc. as needed, Obtain the epoxy resin composition of the present invention, mold it by melt casting method or transfer molding method, injection molding method, compression molding method, etc., and then heat at 80°C to 200°C for 2 hours to 10 hours, whereby it can be Get hardened.
另外,本發明的環氧樹脂組成物根據需要亦可包含溶劑。使包含溶劑的環氧樹脂組成物(環氧樹脂清漆)含浸於玻璃纖維、碳纖維、聚酯纖維、聚醯胺纖維、氧化鋁纖維、紙等纖維狀物質(基材)中並進行加熱乾燥而獲得預浸體,對所得的預浸體進行熱壓成形,藉此可製成本發明的環氧樹脂組成物的硬化物。該環氧樹脂組成物的溶劑含量以內部比例計通常為10重量%~70重量%,較佳為15重量%~70重量%左右。作為溶劑,例如可列舉:γ-丁內酯類;N-甲基吡咯啶酮、N,N-二甲基甲醯胺、N,N-二甲基乙醯胺、N,N-二甲基咪唑啶酮等醯胺系溶劑;四亞甲基碸等碸類;二乙二醇二甲醚、二乙二醇二乙醚、丙二醇單甲醚、丙二醇單甲醚乙酸酯、丙二醇單丁醚等醚系溶劑,較佳為低級(碳數1~3)烷二醇的單或二低級(碳數1~3)烷基醚;甲基乙基酮、甲基異丁基酮等酮系溶劑,更佳為兩個烷基可相同亦可不同的二低級(碳數1~3)烷基酮;甲苯、二甲苯等芳香族系溶劑等。該些可單獨使用,另外亦可為兩種以上的混合溶媒。Moreover, the epoxy resin composition of this invention may contain a solvent as needed. Impregnate an epoxy resin composition (epoxy resin varnish) containing a solvent into a fibrous material (base material) such as glass fiber, carbon fiber, polyester fiber, polyamide fiber, alumina fiber, paper, etc., and heat and dry it. A prepreg is obtained, and the obtained prepreg is thermocompressed to produce a cured product of the epoxy resin composition of the present invention. The solvent content of the epoxy resin composition is usually 10% by weight to 70% by weight, preferably about 15% by weight to 70% by weight, based on the internal ratio. Examples of solvents include: γ-butyrolactones; N-methylpyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide, N,N-dimethyl Amide-based solvents such as imidazolidinone; Tetramethylene glycol and other solvents; Diethylene glycol dimethyl ether, diethylene glycol diethyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monobutyl Ether-based solvents such as ether, preferably mono- or di-lower (1-3) alkyl ethers of lower (1-3 carbon number) alkanediols; ketones such as methyl ethyl ketone and methyl isobutyl ketone A solvent, more preferably a di-lower (1-3 carbon number) alkyl ketone whose two alkyl groups may be the same or different; aromatic solvents such as toluene and xylene, and the like. These may be used alone, or may be a mixed solvent of two or more.
另外,藉由於剝離膜上塗佈所述環氧樹脂清漆,並於加熱下將溶劑去除而進行B階段化,可獲得片狀的接著劑(本發明的片)。該片狀接著劑可用作多層基板等中的層間絕緣層。In addition, a sheet-shaped adhesive agent (sheet of the present invention) can be obtained by applying the above-mentioned epoxy resin varnish on a release film, removing the solvent under heating, and performing B-stage formation. This sheet-like adhesive can be used as an interlayer insulating layer in a multilayer substrate or the like.
本發明中所得的硬化物可用於各種用途。詳細而言,可列舉使用環氧樹脂等熱硬化性樹脂的一般用途,例如,可列舉:接著劑、塗料、塗敷劑、成形材料(包括片、膜、FRP等)、絕緣材料(包括印刷基板、電線包覆等)、密封劑、以及此外的向其他樹脂等中的添加劑等。The cured product obtained in the present invention can be used in various applications. Specifically, general applications using thermosetting resins such as epoxy resins are listed, for example, adhesives, paints, coating agents, molding materials (including sheets, films, FRP, etc.), insulating materials (including printing Substrates, wire coverings, etc.), sealants, and other additives to other resins, etc.
作為接著劑,可列舉:土木用、建築用、汽車用、一般事務用、醫療用的接著劑以及此外的電子材料用的接著劑。該些中,作為電子材料用的接著劑,可列舉:增層基板等多層基板的層間接著劑、晶粒接合劑、底部填充劑等半導體用接著劑;球柵陣列(ball grid array,BGA)增強用底部填充劑、異向性導電性膜(anisotropic conductive film,ACF)、異向性導電性膏(anisotropic conductive paste,ACP)等安裝用接著劑等。Examples of the adhesive include those for civil engineering, construction, automobiles, general office work, medical treatment, and other electronic materials. Among these, adhesives for electronic materials include: interlayer adhesives for multilayer substrates such as build-up substrates; adhesives for semiconductors such as die bonding agents and underfills; ball grid arrays (BGA) Underfill for reinforcement, anisotropic conductive film (ACF), anisotropic conductive paste (ACP) and other mounting adhesives.
作為密封劑,可列舉:用於電容器、電晶體、二極體、發光二極體、IC、大規模積體電路(large scale integration circuit,LSI)等的灌注密封、浸漬密封、轉移模具密封;用於IC、LSI類的板上晶片(chip on board,COB)、膜上晶片(chip on film,COF)、捲帶自動接合(tape automated bonding,TAB)等之類的灌注密封;用於覆晶的底部填充劑;四面扁平封裝(quad flat package,QFP)、球柵陣列(BGA)、晶片尺寸封裝(chip size package,CSP)等IC封裝類安裝時的密封(包括增強用底部填充劑)等。 [實施例] Examples of the sealant include potting, dipping, and transfer mold sealing for capacitors, transistors, diodes, light-emitting diodes, ICs, and large scale integration circuits (LSI); Used for potting and sealing of chip on board (COB), chip on film (COF), tape automated bonding (TAB), etc. of IC and LSI; Underfill for crystals; sealing for IC packages such as quad flat package (QFP), ball grid array (BGA), and chip size package (CSP) during installation (including underfill for reinforcement) Wait. [Example]
接下來,藉由實施例對本發明更具體地進行說明,以下只要無特別說明,則份為重量份。再者,本發明並不限定於該些實施例。另外,於實施例中,環氧當量藉由依據日本工業標準(Japanese Industrial Standards,JIS)K-7236的方法測定,軟化點藉由依據JIS K-7234的方法測定。Next, the present invention will be described more specifically by way of examples, and unless otherwise specified, parts are parts by weight. In addition, this invention is not limited to these Examples. In addition, in the examples, the epoxy equivalent was measured by a method based on Japanese Industrial Standards (Japanese Industrial Standards, JIS) K-7236, and the softening point was measured by a method based on JIS K-7234.
・GPC(凝膠滲透層析)分析 管柱:SHODEX GPC KF-601(兩根)、KF-602、KF-602.5、KF-603 流速:0.5 ml/min. 管柱溫度:40℃ 使用溶劑:THF(四氫呋喃) 檢測器:RI(示差折射檢測器) ・GPC (gel permeation chromatography) analysis Column: SHODEX GPC KF-601 (two), KF-602, KF-602.5, KF-603 Flow rate: 0.5ml/min. Column temperature: 40°C Solvent used: THF (tetrahydrofuran) Detector: RI (Differential Refractive Detector)
[合成例1] 加入甲苯100份、二環戊二烯型酚樹脂(羥基當量:168 g/eq.)84份、茚58.0份、甲磺酸5份,升溫至125℃並反應6小時。加入甲苯150份,對有機層進行水洗直至廢液變為中性為止後加以濃縮,獲得酚樹脂(P1)115份。數量平均分子量Mn:686,重量平均分子量Mw:854,羥基當量為284.2 g/eq。將GPC圖示於圖1。 [Synthesis Example 1] Add 100 parts of toluene, 84 parts of dicyclopentadiene-type phenol resin (hydroxyl equivalent: 168 g/eq.), 58.0 parts of indene, and 5 parts of methanesulfonic acid, heat up to 125° C., and react for 6 hours. After adding 150 parts of toluene, the organic layer was washed with water until the waste liquid became neutral, and then concentrated to obtain 115 parts of phenol resin (P1). The number average molecular weight Mn: 686, the weight average molecular weight Mw: 854, the hydroxyl equivalent is 284.2 g/eq. The GPC profile is shown in FIG. 1 .
[實施例1] 一邊對安裝有溫度計、冷卻管、分餾管、攪拌機的燒瓶實施氮吹掃,一邊加入實施例1中所得的酚樹脂(P1)110份、表氯醇143份、二甲基亞碸35.8份、水1.4份,將內溫升溫至45℃。歷時1.5小時分批添加氫氧化鈉16份後,於45℃下反應2小時,於70℃下反應1小時。於加熱減壓下將未反應的表氯醇及溶劑蒸餾去除。加入MIBK 150份,利用水100份清洗一次有機層。將有機層放回反應容器中,加入30 wt%氫氧化鈉水溶液15份,於70℃下反應2小時。放置冷卻後,利用水100份清洗四次有機層,於加熱減壓下將溶劑蒸餾去除,獲得作為褐色固體樹脂的目標化合物(E1)123份。數量平均分子量Mn:723,重量平均分子量Mw:953,環氧當量為360.5 g/eq.,ICI黏度(150℃)為1.07 Pa·s,軟化點為95.2℃。將GPC圖示於圖2。 [Example 1] While carrying out nitrogen purging to the flask equipped with thermometer, cooling pipe, fractionating pipe and stirrer, add 110 parts of phenol resin (P1) obtained in Example 1, 143 parts of epichlorohydrin, 35.8 parts of dimethyl sulfide, 1.4 parts of water, and the internal temperature was raised to 45°C. After adding 16 parts of sodium hydroxide in batches over 1.5 hours, it was reacted at 45° C. for 2 hours, and then reacted at 70° C. for 1 hour. Unreacted epichlorohydrin and solvent were distilled off under reduced pressure. 150 parts of MIBK was added, and the organic layer was washed once with 100 parts of water. Put the organic layer back into the reaction container, add 15 parts of 30 wt% sodium hydroxide aqueous solution, and react at 70° C. for 2 hours. After standing to cool, the organic layer was washed four times with 100 parts of water, and the solvent was distilled off under reduced pressure under heating to obtain 123 parts of the target compound (E1) as a brown solid resin. The number average molecular weight Mn: 723, the weight average molecular weight Mw: 953, the epoxy equivalent is 360.5 g/eq., the ICI viscosity (150°C) is 1.07 Pa·s, and the softening point is 95.2°C. The GPC profile is shown in FIG. 2 .
[合成例2] 加入二環戊二烯型酚樹脂(羥基當量:168 g/eq.)84份、苄基醇54.2份、對甲苯磺酸一水合物1.4份,一邊將生成水蒸餾去除一邊升溫至150℃並反應3小時。加入甲苯100份,對有機層進行水洗直至廢液變為中性為止後加以濃縮,獲得酚樹脂(P2)95份。數量平均分子量Mn:699,重量平均分子量Mw:769,羥基當量為258.1 g/eq。將GPC圖示於圖3。 [Synthesis Example 2] Add 84 parts of dicyclopentadiene-type phenol resin (hydroxyl equivalent: 168 g/eq.), 54.2 parts of benzyl alcohol, and 1.4 parts of p-toluenesulfonic acid monohydrate, and heat up to 150°C while distilling off the generated water. React for 3 hours. 100 parts of toluene was added, and the organic layer was washed with water until the waste liquid became neutral, and then concentrated to obtain 95 parts of phenol resin (P2). The number average molecular weight Mn: 699, the weight average molecular weight Mw: 769, the hydroxyl equivalent is 258.1 g/eq. The GPC profile is shown in FIG. 3 .
[合成例3] 一邊對安裝有溫度計、冷卻管、分餾管、攪拌機的燒瓶實施氮吹掃,一邊加入合成例2中所得的酚樹脂(P2)80份、表氯醇115份、二甲基亞碸28.7份、水1.3份,將內溫升溫至45℃。歷時1.5小時分批添加氫氧化鈉12.8份後,於45℃下反應2小時,於70℃下反應1小時。於加熱減壓下將未反應的表氯醇及溶劑蒸餾去除。加入MIBK 146份,利用水100份清洗一次有機層。將有機層放回反應容器中,加入30 wt%氫氧化鈉水溶液15份,於70℃下反應2小時。放置冷卻後,利用水100份清洗三次有機層,於加熱減壓下將溶劑蒸餾去除,獲得作為褐色固體樹脂的目標化合物(E2)。數量平均分子量Mn:698,重量平均分子量Mw:824,環氧當量為332.1 g/eq. ,ICI黏度(150℃)為0.08 Pa·s,軟化點為59.8℃。將GPC圖示於圖4。 [Synthesis Example 3] While carrying out nitrogen purging to the flask equipped with a thermometer, a cooling pipe, a fractionating pipe, and a stirrer, 80 parts of phenol resin (P2), 115 parts of epichlorohydrin, 28.7 parts of dimethylsulfoxide, and 1.3 parts of water, and the internal temperature was raised to 45°C. After adding 12.8 parts of sodium hydroxide in batches over 1.5 hours, it was reacted at 45° C. for 2 hours, and then reacted at 70° C. for 1 hour. Unreacted epichlorohydrin and solvent were distilled off under reduced pressure. 146 parts of MIBK were added, and the organic layer was washed once with 100 parts of water. Put the organic layer back into the reaction container, add 15 parts of 30 wt% sodium hydroxide aqueous solution, and react at 70° C. for 2 hours. After standing to cool, the organic layer was washed three times with 100 parts of water, and the solvent was distilled off under reduced pressure under heating to obtain the target compound (E2) as a brown solid resin. The number average molecular weight Mn: 698, the weight average molecular weight Mw: 824, the epoxy equivalent is 332.1 g/eq., the ICI viscosity (150°C) is 0.08 Pa·s, and the softening point is 59.8°C. The GPC profile is shown in FIG. 4 .
[實施例2、比較例1~比較例3] 使用實施例1中所得的環氧樹脂(E1)、合成例3中所得的環氧樹脂(E2)、雙酚F型環氧樹脂(RE-304S,日本化藥公司製造,環氧當量:169 g/eq.)、源自二環戊二烯型酚樹脂的環氧樹脂(XD-1000-2L,日本化藥公司製造,環氧當量:238 g/eq.,ICI黏度(150℃):0.05,軟化點:55.4℃)、及作為硬化劑的4,4'-亞甲基雙(2,6-二乙基苯胺)(日本化藥公司製造,卡亞邦得(KAYABOND)C-300S),並以表1的比例(重量份)進行調配,使用混合輥均勻地進行混合/混練,進而進行脫模後,以160℃下2小時、180℃下6小時的條件進行硬化,獲得評價用試驗片。 [Example 2, Comparative Example 1 to Comparative Example 3] Use the epoxy resin (E1) obtained in Example 1, the epoxy resin (E2) obtained in Synthesis Example 3, and bisphenol F-type epoxy resin (RE-304S, manufactured by Nippon Kayaku Co., Ltd., epoxy equivalent: 169 g/eq.), epoxy resin derived from dicyclopentadiene type phenolic resin (XD-1000-2L, manufactured by Nippon Kayaku Co., Ltd., epoxy equivalent: 238 g/eq., ICI viscosity (150°C): 0.05, softening point: 55.4°C), and 4,4'-methylenebis(2,6-diethylaniline) as a hardening agent (manufactured by Nippon Kayaku Co., Ltd., Kayabond (KAYABOND) C-300S ), and prepared in the ratio (parts by weight) in Table 1, uniformly mixed/kneaded with a mixing roller, and then released from the mold, hardened under the conditions of 2 hours at 160°C and 6 hours at 180°C to obtain evaluation Use a test piece.
<硬化物性測定> 將於下述條件下對評價用試驗片進行測定而得的結果示於表1。 <Measurement of hardened physical properties> Table 1 shows the results obtained by measuring the test pieces for evaluation under the following conditions.
<耐熱性試驗> 使用動態黏彈性試驗機測定玻璃轉移溫度(tanδ為最大值時的溫度)。 ・動態黏彈性測定器:TA儀器(TA-instruments)製造的DMA-2980 ・升溫速度:2℃/分鐘 <Heat Resistance Test> The glass transition temperature (the temperature at which tan δ becomes the maximum value) was measured using a dynamic viscoelasticity testing machine. ・Dynamic viscoelasticity measuring device: DMA-2980 manufactured by TA-instruments ・Heating rate: 2°C/min
<彎曲彈性係數> 依據JIS K-6911進行測定。 ・滕喜龍(Tensilon):RTG-1310(A&D有限公司(A&D Company, Limited)製造) ・測定溫度:室溫 <Bending coefficient of elasticity> Measurement was performed in accordance with JIS K-6911. ・Tensilon: RTG-1310 (manufactured by A&D Company, Limited) ・Measurement temperature: room temperature
<吸水率> 根據將直徑5 cm×厚度4 mm的圓盤狀的試驗片於100℃浸水條件下保持24小時後的質量變化來算出。 <Water Absorption> Calculated from the mass change after holding a disk-shaped test piece having a diameter of 5 cm×a thickness of 4 mm under 100° C. water immersion conditions for 24 hours.
[表1]
根據表1的結果確認到,實施例2具有高耐熱性、高彈性係數、低吸水性。 [產業上之可利用性] From the results in Table 1, it was confirmed that Example 2 has high heat resistance, high modulus of elasticity, and low water absorption. [Industrial availability]
本發明的環氧樹脂可有效用於電氣電子零件用絕緣材料(高可靠性半導體密封材料等)及積層板(印刷配線板、BGA用基板、增層基板等)、接著劑(導電性接著劑等)或以CFRP為代表的各種複合材料用、塗料等用途中,特別是可有效用於以強烈要求高彈性係數的CFRP為代表的各種複合材料用途。The epoxy resin of the present invention can be effectively used as insulating materials for electrical and electronic parts (high reliability semiconductor sealing materials, etc.), laminated boards (printed wiring boards, substrates for BGA, build-up substrates, etc.), adhesives (conductive adhesives) etc.) or various composite materials represented by CFRP, coatings, etc., especially, it can be effectively used for various composite materials represented by CFRP that strongly requires a high modulus of elasticity.
無none
圖1表示合成例1的GPC圖。 圖2表示實施例1的GPC圖。 圖3表示合成例2的GPC圖。 圖4表示合成例3的GPC圖。 FIG. 1 shows a GPC chart of Synthesis Example 1. FIG. 2 shows the GPC chart of Example 1. FIG. 3 shows a GPC chart of Synthesis Example 2. FIG. 4 shows a GPC chart of Synthesis Example 3.
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JPH10265650A (en) * | 1997-03-27 | 1998-10-06 | Hitachi Chem Co Ltd | Epoxy resin molding material for use in sealing electronic part and electronic part |
JP5050923B2 (en) | 2008-02-27 | 2012-10-17 | 住友ベークライト株式会社 | Epoxy resin composition for semiconductor encapsulation and semiconductor device |
JP5215909B2 (en) | 2009-02-27 | 2013-06-19 | 富士フイルム株式会社 | Cloth material for rubbing and rubbing treatment method using the same |
JP6366052B2 (en) | 2014-02-06 | 2018-08-01 | 日本化薬株式会社 | Modified epoxy resin and curable resin composition |
JP6764885B2 (en) | 2018-01-11 | 2020-10-07 | Jfeケミカル株式会社 | Thermosetting resin composition and its cured product |
-
2021
- 2021-03-30 JP JP2021056836A patent/JP7132385B1/en active Active
-
2022
- 2022-03-04 TW TW111107844A patent/TW202237572A/en unknown
- 2022-03-08 KR KR1020237019237A patent/KR20230161416A/en unknown
- 2022-03-08 WO PCT/JP2022/010112 patent/WO2022209642A1/en active Application Filing
- 2022-03-08 CN CN202280007736.4A patent/CN116670199A/en active Pending
Also Published As
Publication number | Publication date |
---|---|
CN116670199A (en) | 2023-08-29 |
JP2022154013A (en) | 2022-10-13 |
JP7132385B1 (en) | 2022-09-06 |
WO2022209642A1 (en) | 2022-10-06 |
KR20230161416A (en) | 2023-11-27 |
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