JP7268256B1 - Epoxy resin, curable resin composition, and cured product thereof - Google Patents
Epoxy resin, curable resin composition, and cured product thereof Download PDFInfo
- Publication number
- JP7268256B1 JP7268256B1 JP2022575301A JP2022575301A JP7268256B1 JP 7268256 B1 JP7268256 B1 JP 7268256B1 JP 2022575301 A JP2022575301 A JP 2022575301A JP 2022575301 A JP2022575301 A JP 2022575301A JP 7268256 B1 JP7268256 B1 JP 7268256B1
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- Prior art keywords
- epoxy resin
- parts
- resin composition
- curable resin
- formula
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- 239000003822 epoxy resin Substances 0.000 title claims abstract description 49
- 229920000647 polyepoxide Polymers 0.000 title claims abstract description 49
- 239000011342 resin composition Substances 0.000 title claims abstract description 33
- 238000005227 gel permeation chromatography Methods 0.000 claims description 23
- 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 abstract description 10
- 239000002904 solvent Substances 0.000 description 26
- 238000006243 chemical reaction Methods 0.000 description 25
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 24
- -1 methyl isobutyl Chemical group 0.000 description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 21
- 230000015572 biosynthetic process Effects 0.000 description 19
- 238000003786 synthesis reaction Methods 0.000 description 19
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 18
- 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 18
- 238000012360 testing method Methods 0.000 description 18
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 17
- 239000005011 phenolic resin Substances 0.000 description 17
- 150000002989 phenols Chemical class 0.000 description 17
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 15
- 230000001070 adhesive effect Effects 0.000 description 15
- 239000000853 adhesive Substances 0.000 description 14
- 239000003795 chemical substances by application Substances 0.000 description 14
- 229920005989 resin Polymers 0.000 description 13
- 239000011347 resin Substances 0.000 description 13
- 238000010438 heat treatment Methods 0.000 description 12
- 239000000758 substrate Substances 0.000 description 12
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 11
- 239000012044 organic layer Substances 0.000 description 11
- 229920001568 phenolic resin Polymers 0.000 description 11
- 239000000047 product Substances 0.000 description 11
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 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
- 239000007864 aqueous solution Substances 0.000 description 9
- 150000001875 compounds Chemical class 0.000 description 9
- 239000011256 inorganic filler Substances 0.000 description 9
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 8
- 229910003475 inorganic filler Inorganic materials 0.000 description 8
- 239000007787 solid Substances 0.000 description 8
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 7
- 125000003118 aryl group Chemical group 0.000 description 7
- 239000003054 catalyst Substances 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- 239000004065 semiconductor Substances 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
- 229930185605 Bisphenol Natural products 0.000 description 6
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 6
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 description 6
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 6
- 238000005406 washing Methods 0.000 description 6
- 239000004593 Epoxy Substances 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- 150000001299 aldehydes Chemical class 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 239000007822 coupling agent Substances 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- 238000002156 mixing 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
- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Chemical compound CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 description 4
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 4
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-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
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 4
- 239000000835 fiber Substances 0.000 description 4
- 239000011810 insulating material Substances 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 description 4
- 239000002798 polar solvent Substances 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
- 239000003566 sealing material Substances 0.000 description 4
- HHVIBTZHLRERCL-UHFFFAOYSA-N sulfonyldimethane Chemical compound CS(C)(=O)=O HHVIBTZHLRERCL-UHFFFAOYSA-N 0.000 description 4
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- SJRJJKPEHAURKC-UHFFFAOYSA-N N-Methylmorpholine Chemical compound CN1CCOCC1 SJRJJKPEHAURKC-UHFFFAOYSA-N 0.000 description 3
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 3
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- 239000004927 clay Substances 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000012776 electronic material Substances 0.000 description 3
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 3
- 150000002576 ketones Chemical class 0.000 description 3
- 238000000465 moulding Methods 0.000 description 3
- 230000007935 neutral effect Effects 0.000 description 3
- 239000003973 paint Substances 0.000 description 3
- 238000010926 purge Methods 0.000 description 3
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 239000002699 waste material Substances 0.000 description 3
- 239000003799 water insoluble solvent 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
- 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 class C1=CC=C2C(O)=CC=CC2=C1 KJCVRFUGPWSIIH-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
- UFERIGCCDYCZLN-UHFFFAOYSA-N 3a,4,7,7a-tetrahydro-1h-indene Chemical compound C1C=CCC2CC=CC21 UFERIGCCDYCZLN-UHFFFAOYSA-N 0.000 description 2
- RGHHSNMVTDWUBI-UHFFFAOYSA-N 4-hydroxybenzaldehyde Chemical class OC1=CC=C(C=O)C=C1 RGHHSNMVTDWUBI-UHFFFAOYSA-N 0.000 description 2
- INYHZQLKOKTDAI-UHFFFAOYSA-N 5-ethenylbicyclo[2.2.1]hept-2-ene Chemical compound C1C2C(C=C)CC1C=C2 INYHZQLKOKTDAI-UHFFFAOYSA-N 0.000 description 2
- ULKLGIFJWFIQFF-UHFFFAOYSA-N 5K8XI641G3 Chemical compound CCC1=NC=C(C)N1 ULKLGIFJWFIQFF-UHFFFAOYSA-N 0.000 description 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-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
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 2
- SXRSQZLOMIGNAQ-UHFFFAOYSA-N Glutaraldehyde Chemical class O=CCCCC=O SXRSQZLOMIGNAQ-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 class OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-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
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-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
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
- 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
- XMUZQOKACOLCSS-UHFFFAOYSA-N [2-(hydroxymethyl)phenyl]methanol Chemical compound OCC1=CC=CC=C1CO XMUZQOKACOLCSS-UHFFFAOYSA-N 0.000 description 2
- IKHGUXGNUITLKF-XPULMUKRSA-N acetaldehyde Chemical compound [14CH]([14CH3])=O IKHGUXGNUITLKF-XPULMUKRSA-N 0.000 description 2
- 150000008065 acid anhydrides Chemical class 0.000 description 2
- 239000003377 acid catalyst Substances 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 150000001298 alcohols Chemical class 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
- 150000001412 amines Chemical class 0.000 description 2
- 239000003849 aromatic solvent Substances 0.000 description 2
- 150000003935 benzaldehydes Chemical class 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
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 description 2
- VHRGRCVQAFMJIZ-UHFFFAOYSA-N cadaverine Chemical compound NCCCCCN VHRGRCVQAFMJIZ-UHFFFAOYSA-N 0.000 description 2
- 239000004918 carbon fiber reinforced polymer Substances 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
- 238000002485 combustion reaction Methods 0.000 description 2
- 239000002131 composite material Substances 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
- 239000013078 crystal Substances 0.000 description 2
- BGTOWKSIORTVQH-UHFFFAOYSA-N cyclopentanone Chemical compound O=C1CCCC1 BGTOWKSIORTVQH-UHFFFAOYSA-N 0.000 description 2
- 150000005205 dihydroxybenzenes Chemical class 0.000 description 2
- 238000005538 encapsulation Methods 0.000 description 2
- 238000006735 epoxidation reaction Methods 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 239000005350 fused silica glass Substances 0.000 description 2
- 150000002366 halogen compounds Chemical class 0.000 description 2
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 2
- 230000001771 impaired effect Effects 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
- 239000005453 ketone based solvent Substances 0.000 description 2
- 238000004898 kneading Methods 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- 238000005259 measurement Methods 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
- 239000006082 mold release agent Substances 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-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 class 0.000 description 2
- SJYNFBVQFBRSIB-UHFFFAOYSA-N norbornadiene Chemical compound C1=CC2C=CC1C2 SJYNFBVQFBRSIB-UHFFFAOYSA-N 0.000 description 2
- 229920003986 novolac Polymers 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
- 150000003003 phosphines Chemical class 0.000 description 2
- 150000004714 phosphonium salts Chemical class 0.000 description 2
- ZWLUXSQADUDCSB-UHFFFAOYSA-N phthalaldehyde Chemical class O=CC1=CC=CC=C1C=O ZWLUXSQADUDCSB-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
- 238000004382 potting Methods 0.000 description 2
- 238000010248 power generation Methods 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 239000001294 propane Substances 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
- 229960004889 salicylic acid Drugs 0.000 description 2
- 150000003505 terpenes Chemical class 0.000 description 2
- 235000007586 terpenes Nutrition 0.000 description 2
- USFPINLPPFWTJW-UHFFFAOYSA-N tetraphenylphosphonium Chemical compound C1=CC=CC=C1[P+](C=1C=CC=CC=1)(C=1C=CC=CC=1)C1=CC=CC=C1 USFPINLPPFWTJW-UHFFFAOYSA-N 0.000 description 2
- 238000001721 transfer moulding Methods 0.000 description 2
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 description 2
- 239000002966 varnish 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
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- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 238000006798 ring closing metathesis reaction Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 1
- 229920002545 silicone oil Polymers 0.000 description 1
- 239000011973 solid acid Substances 0.000 description 1
- 229910052596 spinel Inorganic materials 0.000 description 1
- 239000011029 spinel Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 1
- 150000003457 sulfones Chemical class 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- DDFYFBUWEBINLX-UHFFFAOYSA-M tetramethylammonium bromide Chemical compound [Br-].C[N+](C)(C)C DDFYFBUWEBINLX-UHFFFAOYSA-M 0.000 description 1
- BRKFQVAOMSWFDU-UHFFFAOYSA-M tetraphenylphosphanium;bromide Chemical compound [Br-].C1=CC=CC=C1[P+](C=1C=CC=CC=1)(C=1C=CC=CC=1)C1=CC=CC=C1 BRKFQVAOMSWFDU-UHFFFAOYSA-M 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- AYEKOFBPNLCAJY-UHFFFAOYSA-O thiamine pyrophosphate Chemical compound CC1=C(CCOP(O)(=O)OP(O)(O)=O)SC=[N+]1CC1=CN=C(C)N=C1N AYEKOFBPNLCAJY-UHFFFAOYSA-O 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 230000007704 transition Effects 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
- COIOYMYWGDAQPM-UHFFFAOYSA-N tris(2-methylphenyl)phosphane Chemical compound CC1=CC=CC=C1P(C=1C(=CC=CC=1)C)C1=CC=CC=C1C COIOYMYWGDAQPM-UHFFFAOYSA-N 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 239000001993 wax Substances 0.000 description 1
- 239000010457 zeolite 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
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/02—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
- C08G59/063—Polycondensates containing more than one epoxy group per molecule of polyhydroxy compounds with epihalohydrins or precursors thereof of polyhydric phenols with epihalohydrins
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
- C08G59/32—Epoxy compounds containing three or more epoxy groups
-
- 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 & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Epoxy Resins (AREA)
Abstract
本発明は、その硬化物が耐熱性、難燃性、耐トラッキング性に優れるエポキシ樹脂、硬化性樹脂組成物を提供する。下記式(1)で表されるエポキシ樹脂。【化1】TIFF0007268256000010.tif86160(式(1)中、nは繰り返し数の平均値であり、1<n<20である。)The present invention provides epoxy resins and curable resin compositions whose cured products are excellent in heat resistance, flame retardancy and tracking resistance. An epoxy resin represented by the following formula (1). [Formula 1] TIFF0007268256000010.tif86160 (In formula (1), n is the average number of repetitions, and 1<n<20.)
Description
本発明は特定構造を有するエポキシ樹脂、硬化性樹脂組成物、およびその硬化物に関する。 TECHNICAL FIELD The present invention relates to an epoxy resin having a specific structure, a curable resin composition, and a cured product thereof.
エポキシ樹脂は、電気的性質(誘電率・誘電正接、絶縁性)、機械的性質、接着性、熱的性質(耐熱性など)などに優れているため、注型品、積層板、IC封止材料等の電気・電子分野、構造用材料、接着剤、塗料等の分野で幅広く用いられている。 Epoxy resin is excellent in electrical properties (dielectric constant/dielectric loss tangent, insulating properties), mechanical properties, adhesive properties, and thermal properties (heat resistance, etc.). It is widely used in the fields of electrical and electronic materials, structural materials, adhesives, and paints.
近年、電気・電子分野においては、樹脂組成物の難燃性、耐湿性、密着性、誘電特性等の性能向上、高純度化、フィラー(無機または有機充填剤)を高充填させるための低粘度化、成型サイクルを短くするための反応性向上等の諸特性の一層の向上が求められている(特許文献1)。また、構造用材料としては航空宇宙材料、レジャー・スポーツ器具用途などにおいて軽量で機械物性の優れた材料が求められている。特に半導体封止分野、基板(基板自体、もしくはその周辺材料)においては、その半導体の変遷に従い、薄層化、スタック化、システム化、三次元化と複雑になっていき、非常に高いレベルの耐熱性や高流動性といった要求特性が求められている。 In recent years, in the electrical and electronic fields, performance improvements such as flame retardancy, moisture resistance, adhesion, and dielectric properties of resin compositions, high purity, low viscosity for high filling of fillers (inorganic or organic fillers) There is a demand for further improvement in various properties such as improved reactivity in order to shorten the molding cycle (Patent Document 1). In addition, as structural materials, lightweight materials with excellent mechanical properties are required for use in aerospace materials, leisure and sports equipment, and the like. Especially in the field of semiconductor encapsulation, substrates (substrates themselves or their peripheral materials) have become more complicated with thinning, stacking, systematization, and three-dimensionalization in accordance with the transition of semiconductors. Required properties such as heat resistance and high fluidity are required.
さらに、自動運転技術の発展や電気自動車の市場の広がりにつれて、各種電源基板やインバータ基板において、FR-4基板ではこれまで要求されなかった耐トラッキング性(CTI耐性:Comparative Tracking Index 耐性)が要求されるようになっている。 Furthermore, with the development of automatic driving technology and the expansion of the electric vehicle market, various power supply boards and inverter boards are required to have tracking resistance (CTI resistance: Comparative Tracking Index resistance), which has not been required for FR-4 boards. It has become so.
一般に、炭化しやすい構造をもつエポキシ樹脂は耐トラッキング性が悪いことが知られているが、一方で、炭化しやすい構造をもつエポキシ樹脂は難燃性が高いことが知られている。 Generally, it is known that an epoxy resin having a structure that easily carbonizes has poor tracking resistance, while an epoxy resin that has a structure that easily carbonizes is known to have high flame retardancy.
樹脂組成物の耐熱性を向上させる目的で芳香族架橋ユニットを導入することがあるが、この場合、主骨格が芳香族であることから炭化しやすく、耐トラッキング特性は低下する。また、高分子量化により耐熱性を向上させた場合には、分子量が大きくなることで熱分解温度が上昇して耐トラッキング特性が低下する。つまり、耐熱性と耐トラッキング特性はトレードオフの関係がある(非特許文献1)。 An aromatic cross-linking unit is sometimes introduced for the purpose of improving the heat resistance of the resin composition, but in this case, since the main skeleton is aromatic, it is easily carbonized, and the tracking resistance deteriorates. Further, when the heat resistance is improved by increasing the molecular weight, the thermal decomposition temperature rises due to the increase in the molecular weight, and the tracking resistance deteriorates. In other words, there is a trade-off relationship between heat resistance and tracking resistance (Non-Patent Document 1).
このような背景から、高い耐熱性を発現するとともに、難燃性と耐トラッキング性を併せ持つ材料の開発が望まれている。 Against this background, there is a demand for the development of materials that exhibit high heat resistance as well as flame retardancy and tracking resistance.
特に、太陽光発電や風力発電、EVなどの用途においては、耐トラッキング特性が重要視されており、比較トラッキング指数(CTI)が600を超えることが求められている。 In particular, in applications such as photovoltaic power generation, wind power generation, and EV, tracking resistance is considered important, and a comparative tracking index (CTI) exceeding 600 is required.
本発明は、上記の課題に鑑み、その硬化物が耐熱性、難燃性、耐トラッキング性に優れるエポキシ樹脂、硬化性樹脂組成物を提供することを目的とする。 SUMMARY OF THE INVENTION In view of the above problems, an object of the present invention is to provide an epoxy resin and a curable resin composition whose cured product is excellent in heat resistance, flame retardancy and tracking resistance.
本発明者らは上記課題を解決するために鋭意研究した結果、本発明を完成させるに到った。すなわち本発明は以下の[1]~[6]に関する。なお、本願において「(数値1)~(数値2)」は上下限値を含むことを示す。
[1]
下記式(1)で表されるエポキシ樹脂。The present inventors have completed the present invention as a result of intensive research to solve the above problems. That is, the present invention relates to the following [1] to [6]. In the present application, "(numerical value 1) to (numerical value 2)" indicate that upper and lower limits are included.
[1]
An epoxy resin represented by the following formula (1).
(式(1)中、nは繰り返し数の平均値であり、1<n<20である。)
[2]
下記式(2)で表されるエポキシ樹脂。(In formula (1), n is the average number of repetitions, and 1<n<20.)
[2]
An epoxy resin represented by the following formula (2).
(式(2)中、nは繰り返し数の平均値であり、1<n<20である。)
[3]
ゲルパーミエーションクロマトグラフィー(GPC)による重量平均分子量が400~3000である前項[1]または[2]に記載のエポキシ樹脂。
[4]
前項[1]乃至[3]のいずれか一項に記載のエポキシ樹脂を含有する硬化性樹脂組成物。
[5]
さらに、硬化促進剤を含有する前項[4]に記載の硬化性樹脂組成物。
[6]
前項[4]または[5]に記載の硬化性樹脂組成物を硬化した硬化物。(In formula (2), n is the average number of repetitions, and 1<n<20.)
[3]
The epoxy resin according to the preceding item [1] or [2], which has a weight average molecular weight of 400 to 3000 as determined by gel permeation chromatography (GPC).
[4]
A curable resin composition containing the epoxy resin according to any one of [1] to [3] above.
[5]
The curable resin composition according to [4] above, further comprising a curing accelerator.
[6]
A cured product obtained by curing the curable resin composition according to [4] or [5] above.
本発明は特定構造を有するエポキシ樹脂、硬化性樹脂組成物およびその硬化物に関するものであり、その硬化物は耐トラッキング性、耐熱性、難燃性を有する。
そのため、本発明は電気電子部品用絶縁材料(高信頼性半導体封止材料など)及び積層板(プリント配線板、ビルドアップ基板など)やCFRPを始めとする各種複合材料、接着剤、塗料等に有用である。TECHNICAL FIELD The present invention relates to an epoxy resin having a specific structure, a curable resin composition, and a cured product thereof, and the cured product has tracking resistance, heat resistance, and flame retardancy.
Therefore, the present invention can be applied to insulating materials for electric and electronic parts (such as highly reliable semiconductor sealing materials), laminated boards (printed wiring boards, build-up boards, etc.), various composite materials such as CFRP, adhesives, paints, etc. Useful.
以下、本発明を詳細に説明する。 The present invention will be described in detail below.
本発明のエポキシ樹脂は、下記式(1)で表される。 The epoxy resin of the present invention is represented by the following formula (1).
(式(1)中、nは繰り返し数の平均値であり、1<n<20である。) (In formula (1), n is the average number of repetitions, and 1<n<20.)
前記式(1)で表される化合物は、芳香環密度を維持しながらも炭化しにくいイソプロピリデン構造を多数導入した分子設計とすることで優れた耐トラッキング性、耐熱性、難燃性を有する。 The compound represented by the formula (1) has excellent tracking resistance, heat resistance, and flame retardancy by adopting a molecular design that introduces a large number of isopropylidene structures that are difficult to carbonize while maintaining the density of the aromatic ring. .
前記式(1)中、nの値はゲルパーミエーションクロマトグラフィー(GPC、検出器:RI)の測定により求められた数平均分子量、あるいは分離したピークの各々の面積比から算出することが出来る。nの値は1<n<15であることがさらに好ましく、1<n<10であることが特に好ましい。 In the formula (1), the value of n can be calculated from the number average molecular weight determined by gel permeation chromatography (GPC, detector: RI) or from the area ratio of each separated peak. More preferably, the value of n is 1<n<15, and most preferably 1<n<10.
GPC測定による重量平均分子量が400~4500であることが好ましく、より好ましくは500~4000であり、さらに好ましくは1000~3000である。重量平均分子量が400未満のときは分子量増加による耐熱性向上効果を得ることが難しい。また、重量平均分子量が4500より大きいときは水洗等による精製が困難となることに加え、半導体封止材等に使用する際に粘度が高すぎて流動性が確保できず配線間の充填が難しくなるほか、基板用途においてもプリプレグの流動性が確保しづらくなり、配線の埋め込み性が損なわれる。 The weight average molecular weight by GPC measurement is preferably 400-4500, more preferably 500-4000, still more preferably 1000-3000. When the weight average molecular weight is less than 400, it is difficult to obtain the effect of improving heat resistance by increasing the molecular weight. In addition, when the weight average molecular weight is more than 4500, purification by water washing etc. becomes difficult, and when used as a semiconductor encapsulant etc., the viscosity is too high to ensure fluidity and it is difficult to fill between wirings. In addition, it becomes difficult to ensure the fluidity of the prepreg in substrate applications, and the embedding of wiring is impaired.
前記式(1)で表されるエポキシ樹脂は、通常、常温で半固形~固体の樹脂状であり、その軟化点は100℃以下であることが好ましく、さらに好ましくは90℃以下である。軟化点が100℃より高い場合、粘度が高く、プリプレグ作成時に繊維含浸性が低下する。また、そのエポキシ当量は200~1000g/eqであることが好ましく、さらに好ましくは280~800g/eq、特に好ましくは290~700g/eq、最も好ましくは295~600g/eqである。また、その150℃でのICI粘度は0.01~1.2Pa・sであることが好ましく、0.01~1.0Pa・sであることがより好ましく、さらに好ましくは0.01~0.8Pa・sである。上記の範囲であれば、封止材組成物とした際に、封止材としての適切な流動性を確保することができる。 The epoxy resin represented by the above formula (1) is usually in the form of a semi-solid to solid resin at room temperature, and its softening point is preferably 100° C. or lower, more preferably 90° C. or lower. If the softening point is higher than 100° C., the viscosity is high and the fiber impregnation property is lowered during prepreg production. The epoxy equivalent is preferably 200-1000 g/eq, more preferably 280-800 g/eq, particularly preferably 290-700 g/eq, and most preferably 295-600 g/eq. Also, the ICI viscosity at 150° C. is preferably 0.01 to 1.2 Pa·s, more preferably 0.01 to 1.0 Pa·s, still more preferably 0.01 to 0.01 Pa·s. 8 Pa·s. If it is said range, when it is set as a sealing material composition, the fluidity|liquidity suitable as a sealing material can be ensured.
前記式(1)で表されるエポキシ樹脂の好ましい構造の一例としては下記式(2)で表されるエポキシ樹脂を挙げることができる。 An example of a preferable structure of the epoxy resin represented by the formula (1) is an epoxy resin represented by the following formula (2).
(式(2)中、nは繰り返し数の平均値であり、1<n<20である。) (In formula (2), n is the average number of repetitions, and 1<n<20.)
前記式(2)中のnの好ましい範囲は、前記式(1)と同じである。 A preferred range of n in the formula (2) is the same as in the formula (1).
前記式(2)で表されるエポキシ樹脂は結晶性が低く、溶剤溶解性や溶剤中での結晶析出リスク低減することができる。 The epoxy resin represented by the formula (2) has low crystallinity, and can reduce the solvent solubility and the risk of crystal precipitation in the solvent.
本発明のエポキシ樹脂の製法は特に限定されないが、たとえば下記式(3)で表されるフェノール樹脂とエピハロヒドリンを溶剤、触媒の存在下に付加もしくは閉環反応させることで得ることができる。エピハロヒドリンの使用量はフェノール樹脂のフェノール性水酸基1モルに対し通常1.0~20.0モル、好ましくは1.5~10.0モルである。 Although the method for producing the epoxy resin of the present invention is not particularly limited, it can be obtained, for example, by adding or ring-closing a phenol resin represented by the following formula (3) and epihalohydrin in the presence of a solvent and a catalyst. The amount of epihalohydrin to be used is generally 1.0 to 20.0 mol, preferably 1.5 to 10.0 mol, per 1 mol of phenolic hydroxyl group of the phenolic resin.
(式(3)中、nは繰り返し数の平均値であり、1<n<20である。) (In formula (3), n is the average number of repetitions, and 1<n<20.)
前記式(3)中のnの好ましい範囲は、前記式(1)と同じである。 A preferred range of n in the formula (3) is the same as in the formula (1).
前記式(3)で表されるフェノール樹脂は、GPC測定による重量平均分子量が400~4500であることが好ましく、より好ましくは500~4000であり、さらに好ましくは1000~3000である。水酸基当量の好ましい範囲としては、100~300g/eqであり、より好ましくは120~250g/eqであり、さらに好ましくは120~230g/eqである。150℃における溶融粘度(ICI粘度)の好ましい範囲としては、0.01~3.0Pa・s、より好ましくは0.02~2.0Pa・s、さらに好ましくは0.02~1.5Pa・sである。軟化点の好ましい範囲としては、40~180℃、より好ましくは50~150℃、さらに好ましくは60~140℃である。軟化点が40℃未満のときは分子量増加による耐熱性向上効果を得ることが難しい。また、軟化点が180℃より高いときは水洗等による精製が困難となることに加え、半導体封止材等の硬化剤に使用する際、もしくはエポキシ化物とした際に、粘度が高すぎて流動性が確保できず配線間の充填が難しくなるほか、基板用途においてもプリプレグの流動性が確保しづらくなり、配線の埋め込み性が損なわれる。 The phenol resin represented by the formula (3) preferably has a weight average molecular weight of 400 to 4,500, more preferably 500 to 4,000, and still more preferably 1,000 to 3,000 as measured by GPC. A preferable range of hydroxyl equivalent is 100 to 300 g/eq, more preferably 120 to 250 g/eq, and still more preferably 120 to 230 g/eq. The preferred range of melt viscosity (ICI viscosity) at 150° C. is 0.01 to 3.0 Pa·s, more preferably 0.02 to 2.0 Pa·s, and still more preferably 0.02 to 1.5 Pa·s. is. A preferred softening point range is 40 to 180°C, more preferably 50 to 150°C, and even more preferably 60 to 140°C. When the softening point is less than 40°C, it is difficult to obtain the effect of improving the heat resistance by increasing the molecular weight. In addition, when the softening point is higher than 180°C, it becomes difficult to purify by washing with water. In addition, it becomes difficult to secure the fluidity of the prepreg in the substrate application, and the embedding property of the wiring is impaired.
エポキシ化反応において使用できるアルカリ金属水酸化物としては水酸化ナトリウム、水酸化カリウム等が挙げられる。アルカリ金属水酸化物は固形物であっても、その水溶液を使用してもよい。水溶液を使用する場合は該アルカリ金属水酸化物の水溶液を連続的に反応系内に添加すると共に減圧下または常圧下連続的に水及びエピハロヒドリンを留出させ、更に分液して水を除去し、エピハロヒドリンを反応系内に連続的に戻す方法でもよい。アルカリ金属水酸化物の使用量はフェノール樹脂のフェノール性水酸基1モルに対して通常0.9~2.5モルであり、好ましくは0.95~1.5モルである。アルカリ金属水酸化物の使用量が少ないと反応が十分に進行しない。一方で、フェノール樹脂のフェノール性水酸基1モルに対して2.5モルを超えるアルカリ金属水酸化物の過剰使用は不必要な廃棄物の副生を招く。 Examples of alkali metal hydroxides that can be used in the epoxidation reaction include sodium hydroxide and potassium hydroxide. The alkali metal hydroxide may be solid or its aqueous solution may be used. When an aqueous solution is used, an 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 the water is removed by liquid separation. Alternatively, epihalohydrin may be continuously returned to the reaction system. The amount of the alkali metal hydroxide to be used is generally 0.9 to 2.5 mol, preferably 0.95 to 1.5 mol, per 1 mol of the phenolic hydroxyl group of the phenolic resin. If the amount of alkali metal hydroxide used is too small, the reaction will not proceed sufficiently. On the other hand, excessive use of alkali metal hydroxide exceeding 2.5 mol per 1 mol of phenolic hydroxyl groups in the phenolic resin leads to unnecessary waste by-production.
上記反応を促進するためにテトラメチルアンモニウムクロライド、テトラメチルアンモニウムブロマイド、トリメチルベンジルアンモニウムクロライド等の4級アンモニウム塩を触媒として添加しても良い。4級アンモニウム塩の使用量としてはフェノール樹脂のフェノール性水酸基1モルに対し通常0.1~15gであり、好ましくは0.2~10gである。使用量が少なすぎると十分な反応促進効果が得られず、使用量が多すぎるとエポキシ樹脂中に残存する4級アンモニウム塩量が増えてしまうため、電気信頼性を悪化させる原因ともなり得る。 A quaternary ammonium salt such as tetramethylammonium chloride, tetramethylammonium bromide or trimethylbenzylammonium chloride may be added as a catalyst to promote the above reaction. The amount of the quaternary ammonium salt to be used is usually 0.1 to 15 g, preferably 0.2 to 10 g, per 1 mol of the phenolic hydroxyl group of the phenolic resin. If the amount used is too small, a sufficient reaction acceleration effect cannot be obtained, and if the amount used is too large, the amount of quaternary ammonium salt remaining in the epoxy resin increases, which may cause deterioration in electrical reliability.
エポキシ化反応の際、メタノール、エタノール、イソプロピルアルコールなどのアルコール類、ジメチルスルホン、ジメチルスルホキシド、テトラヒドロフラン、ジオキサン等の非プロトン性極性溶媒などを添加して反応を行うことが反応進行上好ましい。アルコール類を使用する場合、その使用量はエピハロヒドリンの使用量に対し通常2~50重量%、好ましくは4~20重量%である。また非プロトン性極性溶媒を用いる場合、その使用量はエピハロヒドリンの使用量に対し通常5~100重量%、好ましくは10~80重量%である。反応温度は通常30~90℃であり、好ましくは35~80℃である。反応時間は通常0.5~100時間であり、好ましくは1~30時間である。
反応終了後、反応物を水洗後、または水洗無しに加熱減圧下でエピハロヒドリンや溶媒等を除去する。また更に加水分解性ハロゲンの少ないエポキシ樹脂とするために、回収したエポキシ樹脂をトルエン、メチルイソブチルケトンなどの溶剤に溶解し、水酸化ナトリウム、水酸化カリウムなどのアルカリ金属水酸化物の水溶液を加えて反応を行い、閉環を確実なものにすることもできる。この場合アルカリ金属水酸化物の使用量はグリシジル化に使用したフェノール樹脂のフェノール性水酸基1モルに対して通常0.01~0.3モル、好ましくは0.05~0.2モルである。反応温度は通常50~120℃、反応時間は通常0.5~24時間である。反応終了後、生成した塩を濾過、水洗などにより除去し、更に加熱減圧下溶剤を留去することにより本発明のエポキシ樹脂が得られる。During the epoxidation reaction, it is preferable to add an alcohol such as methanol, ethanol and isopropyl alcohol, and an aprotic polar solvent such as dimethylsulfone, dimethylsulfoxide, tetrahydrofuran and dioxane to proceed with the reaction. When alcohols are used, the amount used is generally 2-50% by weight, preferably 4-20% by weight, based on the amount of epihalohydrin used. When an aprotic polar solvent is used, its amount is generally 5-100% by weight, preferably 10-80% by weight, based on the amount of epihalohydrin used. The reaction temperature is usually 30-90°C, preferably 35-80°C. The reaction time is usually 0.5 to 100 hours, preferably 1 to 30 hours.
After completion of the reaction, epihalohydrin, solvent and the like are removed from the reaction product under heating and reduced pressure after washing with water or without washing with water. In order to further reduce the hydrolyzable halogen content of the epoxy resin, the recovered epoxy resin is dissolved in a solvent such as toluene or methyl isobutyl ketone, and an aqueous solution of an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide is added. can also be used to ensure ring closure. In this case, the alkali metal hydroxide is used in an amount of 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 glycidylation. The reaction temperature is generally 50-120° C., and the reaction time is generally 0.5-24 hours. After completion of the reaction, the salt produced is removed by filtration, washing with water, etc., and the solvent is distilled off under heating and reduced pressure to obtain the epoxy resin of the present invention.
ここで、前記式(3)で表されるフェノール樹脂の製法について説明する。前記式(3)で表されるフェノール樹脂の製法は特に限定されないが、例えば、ビスフェノールAおよびα,α,α’,α’-テトラメチルベンゼンジメタノール(もしくはジイソプロペニルベンゼン、あるいは、α,α,α’,α’-テトラメチルベンゼンジフルオリド、α,α,α’,α’-テトラメチルベンゼンジクロリド、α,α,α’,α’-テトラメチルベンゼンジブロミド、α,α,α’,α’-テトラメチルベンゼンジアイオダイド等のハロゲン化合物)を酸触媒下、溶剤中で反応させることで目的のフェノール樹脂を得ることができる。この際、原料としてはメタ位に置換された原料を用いることが好ましい。具体的には、α,α,α’,α’-テトラメチル-1,3-ベンゼンジメタノール、1,3-ジイソプロペニルベンゼンのほか、α,α,α’,α’-テトラメチル-1,3-ベンゼンジフルオリド、α,α,α’,α’-テトラメチル-1,3-ベンゼンジクロリド、α,α,α’,α’-テトラメチル-1,3-ベンゼンジブロミド、α,α,α’,α’-テトラメチル-1,3-ベンゼンジアイオダイド等のハロゲン化合物が挙げられる。メタ位に置換位置を持つ原料を使用することで、原料及び合成後の化合物の結晶性を低下させることができ、溶剤溶解性や溶剤中での結晶析出リスク低減することが可能である。合成の際には、酸触媒として塩酸、燐酸、硫酸、蟻酸、p-トルエンスルホン酸、メタンスルホン酸のほか、塩化アルミニウム、塩化亜鉛等のルイス酸、活性白土、酸性白土、ホワイトカーボン、ゼオライト、シリカアルミナ等の固体酸、酸性イオン交換樹脂等を用いることができる。これらは単独でも二種以上併用しても良い。触媒の使用量は、反応基質であるビスフェノールAおよびα,α,α’,α’-テトラメチルベンゼンジメタノール(もしくはジイソプロペニルベンゼン、あるいは、α,α,α’,α’-テトラメチルベンゼンジフルオリド、α,α,α’,α’-テトラメチルベンゼンジクロリド、α,α,α’,α’-テトラメチルベンゼンジブロミド、α,α,α’,α’-テトラメチルベンゼンジアイオダイド等のハロゲン化合物)の重量の総和に対して、0.01~10重量%、好ましくは0.1~5重量%である。触媒の使用量が多すぎるとビスフェノールAが分解する恐れがあり、少なすぎると反応の進行が遅くなる恐れがある。使用する溶剤としては、例えばトルエン、キシレンなどの芳香族溶剤、シクロヘキサン、n-ヘキサンなどの脂肪族溶剤、ジエチルエーテル、ジイソプロピルエーテルなどのエーテル類、酢酸エチル、酢酸ブチルなどのエステル系溶剤、メチルイソブチルケトン、シクロペンタノンなどのケトン系溶剤などの非水溶性溶剤が挙げられるがこれらに限定されるものではなく、2種以上を併用しても良い。また、前記非水溶性溶剤に加えて非プロトン性極性溶剤を併用することもできる。例えば、ジメチルスルホン、ジメチルスルホキシド、ジメチルホルムアミド、ジメチルアセトアミド、1,3-ジメチル-2-イミダゾリジノン、N-メチルピロリドンなどが挙げられ、2種以上を併用しても良い。非プロトン性極性溶剤を使用する場合は、併用する非水溶性溶剤よりも沸点の高いものを使用することが好ましい。反応温度は80~150℃が好ましく、90~140℃がより好ましく、100℃から130℃がさらに好ましい。反応温度が高すぎるとビスフェノールAが分解するおそれがあり、反応温度が低すぎると反応が十分に進行しない恐れがある。アルコール系原料を使用した時には水が副生されるため、昇温時に溶剤と共沸させながら系内から除去する。反応終了後、アルカリ水溶液等で酸性触媒を中和後、油層に非水溶性有機溶剤を加えて廃水が中性になるまで水洗を繰り返したのち、溶剤を加熱減圧下において除去する。活性白土やイオン交換樹脂を用いた場合は、反応終了後に反応液を濾過して触媒を除去する。 Here, a method for producing the phenolic resin represented by the formula (3) will be described. The method for producing the phenol resin represented by the formula (3) is not particularly limited. α,α',α'-tetramethylbenzenedifluoride, α,α,α',α'-tetramethylbenzenedichloride, α,α,α',α'-tetramethylbenzenedibromide, α,α,α A desired phenol resin can be obtained by reacting a halogen compound such as ',α'-tetramethylbenzene diiodide) in a solvent under an acid catalyst. In this case, it is preferable to use a material substituted at the meta position as the material. Specifically, in addition to α,α,α',α'-tetramethyl-1,3-benzenedimethanol and 1,3-diisopropenylbenzene, α,α,α',α'-tetramethyl- 1,3-benzenedifluoride, α,α,α',α'-tetramethyl-1,3-benzenedichloride, α,α,α',α'-tetramethyl-1,3-benzenedibromide, α , α,α',α'-tetramethyl-1,3-benzenediaiodide. By using a raw material having a substitution position at the meta position, the crystallinity of the raw material and the compound after synthesis can be reduced, and the solvent solubility and the risk of crystal precipitation in the solvent can be reduced. In addition to hydrochloric acid, phosphoric acid, sulfuric acid, formic acid, p-toluenesulfonic acid, and methanesulfonic acid as acid catalysts during synthesis, Lewis acids such as aluminum chloride and zinc chloride, activated clay, acid clay, white carbon, zeolite, A solid acid such as silica alumina, an acidic ion exchange resin, or the like can be used. These may be used alone or in combination of two or more. The amount of the catalyst used is the reaction substrate bisphenol A and α,α,α',α'-tetramethylbenzenedimethanol (or diisopropenylbenzene, or α,α,α',α'-tetramethylbenzene Difluoride, α,α,α',α'-tetramethylbenzene dichloride, α,α,α',α'-tetramethylbenzene dibromide, α,α,α',α'-tetramethylbenzene diiodide 0.01 to 10% by weight, preferably 0.1 to 5% by weight, based on the total weight of the halogen compounds such as If the amount of catalyst used is too large, bisphenol A may decompose, and if it is too small, the progress of the reaction may be slowed down. Examples of solvents to be used include aromatic solvents such as toluene and xylene, aliphatic solvents such as cyclohexane and n-hexane, ethers such as diethyl ether and diisopropyl ether, ester solvents such as ethyl acetate and butyl acetate, and methyl isobutyl. Water-insoluble solvents such as ketone-based solvents such as ketones and cyclopentanone are included, but are not limited to these, and two or more kinds may be used in combination. An aprotic polar solvent can also be used in combination with the water-insoluble solvent. Examples thereof include dimethylsulfone, dimethylsulfoxide, dimethylformamide, dimethylacetamide, 1,3-dimethyl-2-imidazolidinone, N-methylpyrrolidone and the like, and two or more of them may be used in combination. When an aprotic polar solvent is used, it is preferable to use one having a boiling point higher than that of the water-insoluble solvent used in combination. The reaction temperature is preferably 80 to 150°C, more preferably 90 to 140°C, even more preferably 100 to 130°C. If the reaction temperature is too high, bisphenol A may decompose, and if the reaction temperature is too low, the reaction may not proceed sufficiently. Since water is by-produced when an alcohol-based raw material is used, it is removed from the system while being azeotropically distilled with the solvent when the temperature is raised. After completion of the reaction, the acidic catalyst is neutralized with an alkaline aqueous solution or the like, and a non-water-soluble organic solvent is added to the oil layer, and washing is repeated until the wastewater becomes neutral, and then the solvent is removed under heating and reduced pressure. When activated clay or ion exchange resin is used, the reaction solution is filtered to remove the catalyst after completion of the reaction.
前記式(3)で表されるフェノール樹脂の好ましい構造の一例としては下記式(4)で表されるフェノール樹脂を挙げることができる。 An example of a preferable structure of the phenol resin represented by the formula (3) is a phenol resin represented by the following formula (4).
(式(4)中、nは繰り返し数の平均値であり、1<n<20である。) (In formula (4), n is the average number of repetitions, and 1<n<20.)
前記式(4)中のnの好ましい範囲は、前記式(1)と同じである。 A preferred range of n in the formula (4) is the same as in the formula (1).
以下、本発明の硬化性樹脂組成物について説明する。
本発明の硬化性樹脂組成物において、前記式(1)で表されるエポキシ樹脂は単独、または他のエポキシ樹脂と併用して使用することができる。併用する場合、前記式(1)で表されるエポキシ樹脂が全エポキシ樹脂中に占める割合は10~98重量%であることが好ましく、より好ましくは20~95重量%、さらに好ましくは30~95重量%である。添加量を10重量%以上とすることで耐トラッキング性向上や高耐熱性、難燃性を発現することができる。The curable resin composition of the present invention is described below.
In the curable resin composition of the present invention, the epoxy resin represented by formula (1) can be used alone or in combination with other epoxy resins. When used in combination, the ratio of the epoxy resin represented by the formula (1) to the total epoxy resin is preferably 10 to 98% by weight, more preferably 20 to 95% by weight, and still more preferably 30 to 95% by weight. % by weight. By setting the amount to be added to 10% by weight or more, tracking resistance can be improved, and high heat resistance and flame retardancy can be exhibited.
本発明のエポキシ樹脂と併用しうる他のエポキシ樹脂の具体例としては、ビスフェノール類(ビスフェノールA、ビスフェノールF、ビスフェノールS、ビフェノール、ビスフェノールAD等)もしくはフェノール類(フェノール、アルキル置換フェノール、芳香族置換フェノール、ナフトール、アルキル置換ナフトール、ジヒドロキシベンゼン、アルキル置換ジヒドロキシベンゼン、ジヒドロキシナフタレン等)と各種アルデヒド(ホルムアルデヒド、アセトアルデヒド、アルキルアルデヒド、ベンズアルデヒド、アルキル置換ベンズアルデヒド、ヒドロキシベンズアルデヒド、ナフトアルデヒド、グルタルアルデヒド、フタルアルデヒド、クロトンアルデヒド、シンナムアルデヒド等)との重縮合物;前記フェノール類と各種ジエン化合物(ジシクロペンタジエン、テルペン類、ビニルシクロヘキセン、ノルボルナジエン、ビニルノルボルネン、テトラヒドロインデン、ジビニルベンゼン、ジビニルビフェニル、ジイソプロペニルビフェニル、ブタジエン、イソプレン等)との重合物;前記フェノール類とケトン類(アセトン、メチルエチルケトン、メチルイソブチルケトン、アセトフェノン、ベンゾフェノン等)との重縮合物;前記フェノール類と芳香族ジメタノール類(ベンゼンジメタノール、ビフェニルジメタノール等)との重縮合物;前記フェノール類と芳香族ジクロロメチル類(α,α’-ジクロロキシレン、ビスクロロメチルビフェニル等)との重縮合物;前記フェノール類と芳香族ビスアルコキシメチル類(ビスメトキシメチルベンゼン、ビスメトキシメチルビフェニル、ビスフェノキシメチルビフェニル等)との重縮合物;前記ビスフェノール類と各種アルデヒドの重縮合物またはアルコール類等をグリシジル化したグリシジルエーテル系エポキシ樹脂、脂環式エポキシ樹脂、グリシジルアミン系エポキシ樹脂、グリシジルエステル系エポキシ樹脂等が挙げられるが、通常用いられるエポキシ樹脂であればこれらに限定されるものではない。これらは単独で用いてもよく、2種以上を用いてもよい。 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, croton aldehyde, cinnamaldehyde, etc.); the above phenols and various diene compounds (dicyclopentadiene, terpenes, vinylcyclohexene, norbornadiene, vinylnorbornene, tetrahydroindene, divinylbenzene, divinylbiphenyl, diisopropenylbiphenyl, butadiene , isoprene, etc.); polycondensates of the phenols and ketones (acetone, methyl ethyl ketone, methyl isobutyl ketone, acetophenone, benzophenone, etc.); the phenols and aromatic dimethanols (benzenedimethanol, biphenyl dimethanol, etc.); polycondensation products of the above phenols and aromatic dichloromethyls (α,α'-dichloroxylene, bischloromethylbiphenyl, etc.); the above phenols and aromatic bisalkoxymethyls (bismethoxymethylbenzene, bismethoxymethylbiphenyl, bisphenoxymethylbiphenyl, etc.) polycondensates; polycondensates of the above bisphenols and various aldehydes or glycidyl ether-based epoxy resins obtained by glycidylating alcohols, alicyclic Epoxy resins, glycidyl amine-based epoxy resins, glycidyl ester-based epoxy resins, and the like can be mentioned, but the epoxy resins are not limited to these as long as they are commonly used epoxy resins. These may be used independently and may use 2 or more types.
本発明の硬化性樹脂組成物において使用しうる硬化剤としては、アミン系硬化剤、酸無水物系硬化剤、アミド系硬化剤、フェノール系硬化剤などが挙げられる。使用できる硬化剤の具体例としては、例えばo-フェニレンジアミン、m-フェニレンジアミン、p-フェニレンジアミン、4,4’-ジアミノジフェニルスルホン、3,4’-ジアミノジフェニルスルホン、3,3’-ジアミノジフェニルスルホン、2,2’-ジアミノジフェニルスルホン、ジエチルトルエンジアミン、ジメチルチオトルエンジアミン、ジアミノジフェニルメタン、3,3’-ジメチル-4,4’-ジアミノジフェニルメタン、3,3’-ジエチル-4,4’-ジアミノジフェニルメタン、4,4’-ジアミノ-3,3’-ジエチル-5,5’-ジメチルジフェニルメタン、4,4’-ジアミノ-3,3’,5,5’-テトラメチルジフェニルメタン、4,4’-ジアミノ-3,3’,5,5’-テトラエチルジフェニルメタン、4,4’-ジアミノ-3,3’,5,5’-テトライソプロピルジフェニルメタン、4,4’-メチレンビス(N-メチルアニリン)、ビス(アミノフェニル)フルオレン、3,4’-ジアミノジフェニルエーテル、4,4’-ジアミノジフェニルエーテル、2,2’-ビス[4-(4-アミノフェノキシ)フェニル]プロパン、ビス[4-(4-アミノフェノキシ)フェニル]スルホン、1,3’-ビス(4-アミノフェノキシ)ベンゼン、1,4’-ビス(4-アミノフェノキシ)ベンゼン、1,4’-ビス(4-アミノフェノキシ)ビフェニル、4,4’-(1,3-フェニレンジイソプロピリデン)ビスアニリン、4,4’-(1,4-フェニレンジイソプロピリデン)ビスアニリン、ナフタレンジアミン、ベンジジン、ジメチルベンジジン、国際公開第2017/170551号合成例1および合成例2に記載の芳香族アミン化合物等の芳香族アミン化合物、1,3-ビス(アミノメチル)シクロヘキサン、イソホロンジアミン、4,4’-メチレンビス(シクロヘキシルアミン)、ノルボルナンジアミン、エチレンジアミン、プロパンジアミン、テトラメチレンジアミン、ペンタメチレンジアミン、ヘキサメチレンジアミン、ダイマージアミン、トリエチレンテトラミン等の脂肪族アミン等が挙げられるが、これに限定されず、組成物に付与したい特性に応じ好適に用いることができる。ポットライフを確保するためには芳香族アミンを使用することが好ましく、即硬化性を付与したい場合には脂肪族アミンを使用することが好ましい。2官能成分を主成分として含有するアミン系化合物を硬化剤として用いることで、硬化反応時、直線性の高いネットワークを構築することができ、特に優れた強靭性を発現することができる。また、ジシアンジアミド、リノレン酸の2量体とエチレンジアミンとより合成されるポリアミド樹脂等のアミド系化合物;無水フタル酸、無水トリメリット酸、無水ピロメリット酸、無水マレイン酸、テトラヒドロ無水フタル酸、メチルテトラヒドロ無水フタル酸、無水メチルナジック酸、ヘキサヒドロ無水フタル酸、メチルヘキサヒドロ無水フタル酸等の酸無水物系化合物;ビスフェノール類(ビスフェノールA、ビスフェノールF、ビスフェノールS、ビフェノール、ビスフェノールAD等)もしくはフェノール類(フェノール、アルキル置換フェノール、芳香族置換フェノール、ナフトール、アルキル置換ナフトール、ジヒドロキシベンゼン、アルキル置換ジヒドロキシベンゼン、ジヒドロキシナフタレン等)と各種アルデヒド(ホルムアルデヒド、アセトアルデヒド、アルキルアルデヒド、ベンズアルデヒド、アルキル置換ベンズアルデヒド、ヒドロキシベンズアルデヒド、ナフトアルデヒド、グルタルアルデヒド、フタルアルデヒド、クロトンアルデヒド、シンナムアルデヒド等)との重縮合物、または前記フェノール類と各種ジエン化合物(ジシクロペンタジエン、テルペン類、ビニルシクロヘキセン、ノルボルナジエン、ビニルノルボルネン、テトラヒドロインデン、ジビニルベンゼン、ジビニルビフェニル、ジイソプロペニルビフェニル、ブタジエン、イソプレン等)との重合物、または前記フェノール類とケトン類(アセトン、メチルエチルケトン、メチルイソブチルケトン、アセトフェノン、ベンゾフェノン等)との重縮合物、または前記フェノール類と芳香族ジメタノール類(ベンゼンジメタノール、ビフェニルジメタノール等)との重縮合物、または前記フェノール類と芳香族ジクロロメチル類(α,α’-ジクロロキシレン、ビスクロロメチルビフェニル等)との重縮合物、または前記フェノール類と芳香族ビスアルコキシメチル類(ビスメトキシメチルベンゼン、ビスメトキシメチルビフェニル、ビスフェノキシメチルビフェニル等)との重縮合物、または前記ビスフェノール類と各種アルデヒドの重縮合物、及びこれらの変性物等のフェノール系化合物;イミダゾール、トリフルオロボラン-アミン錯体、グアニジン誘導体などが挙げられるがこれらに限定されることはない。 Curing agents that can be used in the curable 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 usable curing agents include o-phenylenediamine, m-phenylenediamine, p-phenylenediamine, 4,4′-diaminodiphenylsulfone, 3,4′-diaminodiphenylsulfone, 3,3′-diamino Diphenylsulfone, 2,2'-diaminodiphenylsulfone, diethyltoluenediamine, dimethylthiotoluenediamine, diaminodiphenylmethane, 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'-tetramethyldiphenylmethane, 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′-diaminodiphenyl ether, 4,4′-diaminodiphenyl ether, 2,2′-bis[4-(4-aminophenoxy)phenyl]propane, bis[4-(4- aminophenoxy)phenyl]sulfone, 1,3′-bis(4-aminophenoxy)benzene, 1,4′-bis(4-aminophenoxy)benzene, 1,4′-bis(4-aminophenoxy)biphenyl, 4 ,4'-(1,3-phenylenediisopropylidene)bisaniline, 4,4'-(1,4-phenylenediisopropylidene)bisaniline, naphthalenediamine, benzidine, dimethylbenzidine, International Publication No. 2017/170551 synthesis example 1 and aromatic amine compounds described in Synthesis Example 2, 1,3-bis(aminomethyl)cyclohexane, isophoronediamine, 4,4'-methylenebis(cyclohexylamine), norbornanediamine, ethylenediamine, propane Aliphatic amines such as diamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, dimerdiamine, and triethylenetetramine are included, but are not limited thereto, and can be suitably used depending on the properties desired to be imparted to the composition. can. It is preferable to use an aromatic amine in order to secure a pot life, and it is preferable to use an aliphatic amine in order to impart quick curing. By using an amine-based compound containing a bifunctional component as a main component as a curing agent, a highly linear network can be constructed during the curing reaction, and particularly excellent toughness can be expressed. Also, amide compounds such as polyamide resin synthesized from dicyandiamide, dimer of linolenic acid and ethylenediamine; phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, maleic anhydride, tetrahydrophthalic anhydride, methyltetrahydro Acid anhydride compounds such as phthalic anhydride, methylnadic anhydride, hexahydrophthalic anhydride, and methylhexahydrophthalic anhydride; 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, naphtho aldehyde, glutaraldehyde, phthalaldehyde, crotonaldehyde, cinnamaldehyde, etc.), or the above phenols and various diene compounds (dicyclopentadiene, terpenes, vinylcyclohexene, norbornadiene, vinylnorbornene, tetrahydroindene, divinylbenzene , divinylbiphenyl, diisopropenylbiphenyl, butadiene, isoprene, etc.), or polycondensates of the above phenols and ketones (acetone, methyl ethyl ketone, methyl isobutyl ketone, acetophenone, benzophenone, etc.), or the above phenols and aromatic dimethanols (benzenedimethanol, biphenyldimethanol, etc.), or polycondensates of the phenols and aromatic dichloromethyls (α,α'-dichloroxylene, bischloromethylbiphenyl, etc.) Condensates, or polycondensates of the phenols and aromatic bisalkoxymethyls (bismethoxymethylbenzene, bismethoxymethylbiphenyl, bisphenoxymethylbiphenyl, etc.), or polycondensates of the bisphenols and various aldehydes, and Phenolic compounds such as modified products thereof; imidazole, trifluoroborane-amine complexes, guanidine derivatives, etc., but not limited to these.
本発明の硬化性樹脂組成物において硬化剤の使用量は、エポキシ樹脂のエポキシ基1当量に対して0.5~1.5当量が好ましく、0.6~1.2当量が特に好ましい。0.5~1.5当量とすることで良好な硬化物性を得ることができる。 The amount of the curing agent used in the curable resin composition of the present invention is preferably 0.5 to 1.5 equivalents, particularly preferably 0.6 to 1.2 equivalents, per equivalent of the epoxy group of the epoxy resin. Good cured physical properties can be obtained by setting the equivalent weight to 0.5 to 1.5.
上記硬化剤を用いて硬化反応を行う際には硬化促進剤を併用しても差し支えない。使用できる硬化促進剤としては、例えば、2-メチルイミダゾール、2-エチルイミダゾール、2-フェニルイミダゾール、2-エチル-4-メチルイミダゾール等のイミダゾール類、2-(ジメチルアミノメチル)フェノール、トリエチレンジアミン、トリエタノールアミン、1,8-ジアザビシクロ(5,4,0)ウンデセン-7等の第3級アミン類、トリフェニルホスフィン、トリ(トルイル)ホスフィン、テトラフェニルホスホニウムブロマイド、テトラフェニルホスホニウムテトラフェニルボレート等のホスフィン類やホスホニウム化合物、トリブチルホスフィン等の有機ホスフィン類、オクチル酸スズなどの金属化合物、テトラフェニルホスホニウム・テトラフェニルボレート、テトラフェニルホスホニウム・エチルトリフェニルボレート等のテトラ置換ホスホニウム・テトラ置換ボレート、2-エチル-4-メチルイミダゾール・テトラフェニルボレート、N-メチルモルホリン・テトラフェニルボレート等のテトラフェニルボロン塩、安息香酸、フタル酸、イソフタル酸、テレフタル酸、ナフトエ酸、サリチル酸等のカルボン酸系化合物などが挙げられる。アミン系化合物とエポキシ樹脂の硬化反応を促進する観点からサリチル酸等のカルボン酸系化合物が好ましい。硬化促進剤は、エポキシ樹脂100重量部に対して0.01~15重量部が必要に応じ用いられる。 When performing a curing reaction using the curing agent, a curing accelerator may be used in combination. Curing accelerators that can be used include, for example, imidazoles such as 2-methylimidazole, 2-ethylimidazole, 2-phenylimidazole, 2-ethyl-4-methylimidazole, 2-(dimethylaminomethyl)phenol, triethylenediamine, Tertiary amines such as triethanolamine, 1,8-diazabicyclo(5,4,0)undecene-7, triphenylphosphine, tri(toluyl)phosphine, tetraphenylphosphonium bromide, tetraphenylphosphonium tetraphenylborate, etc. Phosphines and phosphonium compounds, organic phosphines such as tributylphosphine, metal compounds such as tin octylate, tetraphenylphosphonium/tetraphenylborate, tetrasubstituted phosphonium/tetrasubstituted borate such as tetraphenylphosphonium/ethyltriphenylborate, 2- Tetraphenylboron salts such as ethyl-4-methylimidazole/tetraphenylborate, N-methylmorpholine/tetraphenylborate, carboxylic acid compounds such as benzoic acid, phthalic acid, isophthalic acid, terephthalic acid, naphthoic acid, salicylic acid, etc. mentioned. A carboxylic acid compound such as salicylic acid is preferred from the viewpoint of promoting the curing reaction between the amine compound and the epoxy resin. The curing accelerator is used in an amount of 0.01 to 15 parts by weight based on 100 parts by weight of the epoxy resin.
更に、本発明の硬化性樹脂組成物には、必要に応じて無機充填剤を添加することができる。無機充填剤としては、結晶シリカ、溶融シリカ、アルミナ、ジルコン、珪酸カルシウム、炭酸カルシウム、炭化ケイ素、窒化ケイ素、窒化ホウ素、ジルコニア、フォステライト、ステアタイト、スピネル、チタニア、タルク等の粉体またはこれらを球形化したビーズ等が挙げられるが、これらに限定されるものではない。これらは単独で用いてもよく、2種以上を用いてもよい。これら無機充填剤は、用途によりその使用量は異なるが、例えば半導体の封止剤用途に使用する場合は硬化性樹脂組成物の硬化物の耐熱性、耐湿性、力学的性質、難燃性などの面から硬化性樹脂組成物中で20重量%以上占める割合で使用するのが好ましく、より好ましくは30重量%以上であり、特にリードフレームとの線膨張率を向上させるために70~95重量%を占める割合で使用することがさらに好ましい。 Furthermore, an inorganic filler can be added to the curable resin composition of the present invention, if necessary. Inorganic fillers include powders of crystalline silica, fused silica, alumina, zircon, calcium silicate, calcium carbonate, silicon carbide, silicon nitride, boron nitride, zirconia, fosterite, steatite, spinel, titania, talc, etc. Beads formed by spheroidizing are included, but are not limited to these. These may be used independently and may use 2 or more types. The amount of these inorganic fillers used varies depending on the application. From the aspect of the curable resin composition, it is preferably used in a proportion of 20% by weight or more, more preferably 30% by weight or more, and in particular 70 to 95% by weight in order to improve the coefficient of linear expansion with the lead frame % is more preferable.
本発明の硬化性樹脂組成物には成形時の金型との離型を良くするために離型剤を配合することができる。離型剤としては従来公知のものいずれも使用できるが、例えばカルナバワックス、モンタンワックスなどのエステル系ワックス、ステアリン酸、パルミチン酸などの脂肪酸およびこれらの金属塩、酸化ポリエチレン、非酸化ポリエチレンなどのポリオレフィン系ワックスなどが挙げられる。これらは単独で使用しても2種以上併用しても良い。これら離型剤の配合量は全有機成分に対して0.5~3重量%が好ましい。これより少なすぎると金型からの離型が悪く、多すぎるとリードフレームなどとの接着が悪くなる。 The curable resin composition of the present invention may contain a mold release agent to improve release from the mold during molding. As the mold release agent, any of those conventionally known can be used. system waxes and the like. These may be used alone or in combination of two or more. The blending amount of these release agents is preferably 0.5 to 3% by weight based on the total organic components. If the amount is too small, the release from the mold will be poor, and if the amount is too large, adhesion to the lead frame or the like will be poor.
本発明の硬化性樹脂組成物には無機充填剤と樹脂成分との接着性を高めるためにカップリング剤を配合することができる。カップリング剤としては従来公知のものをいずれも使用できるが、例えばビニルアルコキシシラン、エポキシアルコキシシラン、スチリルアルコキシシラン、メタクリロキシアルコキシシラン、アクリロキシアルコキシシラン、アミノアルコキシシラン、メルカプトアルコキシシラン、イソシアナートアルコキシシランなどの各種アルコキシシラン化合物、アルコキシチタン化合物、アルミニウムキレート類などが挙げられる。これらは単独で使用しても2種以上併用しても良い。カップリング剤の添加方法は、カップリング剤であらかじめ無機充填剤表面を処理した後、樹脂と混練しても良いし、樹脂にカップリング剤を混合してから無機充填剤を混練しても良い。 A coupling agent can be added to the curable resin composition of the present invention in order to increase the adhesion between the inorganic filler and the resin component. Any known coupling agent can be used, for example vinylalkoxysilane, epoxyalkoxysilane, styrylalkoxysilane, methacryloxyalkoxysilane, acryloxyalkoxysilane, aminoalkoxysilane, mercaptoalkoxysilane, isocyanatoalkoxy. Examples include various alkoxysilane compounds such as silane, alkoxytitanium compounds, and aluminum chelates. These may be used alone or in combination of two or more. The coupling agent may be added by first treating the surface of the inorganic filler with the coupling agent and then kneading it with the resin, or by mixing the coupling agent with the resin and then kneading the inorganic filler. .
更に本発明の硬化性樹脂組成物には、必要に応じて公知の添加剤を配合することが出来る。用いうる添加剤の具体例としては、ポリブタジエン及びこの変性物、アクリロニトリル共重合体の変性物、ポリフェニレンエーテル、ポリスチレン、ポリエチレン、ポリイミド、フッ素樹脂、マレイミド系化合物、シアネートエステル系化合物、シリコーンゲル、シリコーンオイル、並びにカーボンブラック、フタロシアニンブルー、フタロシアニングリーン等の着色剤などが挙げられる。 Further, the curable resin composition of the present invention may contain known additives as required. Specific examples of additives that can be used include polybutadiene and its modified products, modified acrylonitrile copolymers, polyphenylene ethers, polystyrene, polyethylene, polyimide, fluororesins, maleimide compounds, cyanate ester compounds, silicone gels, and silicone oils. and coloring agents such as carbon black, phthalocyanine blue and phthalocyanine green.
本発明の硬化性樹脂組成物は、上記各成分を均一に混合することにより得られる。本発明の硬化性樹脂組成物は従来知られている方法と同様の方法で容易にその硬化物とすることができる。例えば、エポキシ樹脂と硬化剤、並びに必要により硬化促進剤、無機充填剤、離型剤、シランカップリング剤及び添加剤とを必要に応じて押出機、ニーダ、ロール等を用いて均一になるまで充分に混合することより本発明の硬化性樹脂組成物を得て、これを溶融注型法あるいはトランスファー成型法やインジェクション成型法、圧縮成型法などによって成型し、更に80~200℃で2~10時間に加熱することにより硬化物を得ることができる。 The curable resin composition of the present invention is obtained by uniformly mixing the above components. The curable resin composition of the present invention can be easily cured by the same method as conventionally known methods. For example, an epoxy resin and a curing agent, and if necessary, a curing accelerator, an inorganic filler, a release agent, a silane coupling agent, and an additive are mixed until uniform using an extruder, a kneader, a roll, etc. The curable resin composition of the present invention is obtained by thorough mixing, which is molded by a melt casting method, a transfer molding method, an injection molding method, a compression molding method, or the like. A cured product can be obtained by heating for a period of time.
また本発明の硬化性樹脂組成物は必要に応じて溶剤を含んでいてもよい。溶剤を含む硬化性樹脂組成物(ワニス)はガラス繊維、カーボン繊維、ポリエステル繊維、ポリアミド繊維、アルミナ繊維、紙などの繊維状物質(基材)に含浸させ加熱乾燥して得たプリプレグを熱プレス成形することにより、本発明の硬化性樹脂組成物の硬化物とすることができる。この硬化性樹脂組成物の溶剤含量は、内割りで通常10~70重量%、好ましくは15~70重量%程度である。溶剤としては例えばγ-ブチロラクトン類、N-メチルピロリドン、N,N-ジメチルホルムアミド、N,N-ジメチルアセトアミド、N,N-ジメチルイミダゾリジノン等のアミド系溶剤;テトラメチレンスルフォン等のスルフォン類;ジエチレングリコールジメチルエーテル、ジエチレングリコールジエチルエーテル、プロピレングリコールモノメチルエーテル、プロピレングリコールモノメチルエーテルモノアセテート、プロピレングリコールモノブチルエーテル等のエーテル系溶剤、好ましくは低級(炭素数1~3)アルキレングリコールのモノ又はジ低級(炭素数1~3)アルキルエーテル;メチルエチルケトン、メチルイソブチルケトン等のケトン系溶剤、より好ましくは2つのアルキル基が同一でも異なってもよい。ジ低級(炭素数1~3)アルキルケトン;トルエン、キシレンなどの芳香族系溶剤等が挙げられる。これらは単独であっても、また2以上の混合溶媒であってもよい。 Moreover, the curable resin composition of the present invention may contain a solvent, if necessary. A curable resin composition (varnish) containing a solvent is obtained by impregnating a fibrous substance (base material) such as glass fiber, carbon fiber, polyester fiber, polyamide fiber, alumina fiber, paper, etc., followed by heating and drying to obtain a prepreg, which is hot-pressed. By molding, a cured product of the curable resin composition of the present invention can be obtained. The solvent content of this curable resin composition is usually 10 to 70% by weight, preferably about 15 to 70% by weight. Examples of the solvent include amide solvents such as γ-butyrolactones, N-methylpyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide and N,N-dimethylimidazolidinone; sulfones such as tetramethylenesulfone; Ether solvents such as diethylene glycol dimethyl ether, diethylene glycol diethyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether monoacetate, propylene glycol monobutyl ether, preferably lower (1 to 3 carbon atoms) alkylene glycol mono- or di-lower (1 carbon atom) 3) Alkyl ethers; ketone-based solvents such as methyl ethyl ketone and methyl isobutyl ketone, more preferably two alkyl groups may be the same or different. Di-lower (C 1-3) alkyl ketones; aromatic solvents such as toluene and xylene; These may be used alone or as a mixed solvent of two or more.
また、剥離フィルム上に前記エポキシ樹脂ワニスを塗布し加熱下で溶剤を除去、Bステージ化を行うことによりシート状の接着剤(単にシートとも言う。)を得ることができる。このシート状接着剤は多層基板などにおける層間絶縁層として使用することができる。 Also, a sheet-like adhesive (also referred to simply as a sheet) can be obtained by coating the release film with the epoxy resin varnish, removing the solvent under heating, and performing B-stage. This sheet-like adhesive can be used as an interlayer insulating layer in multilayer substrates and the like.
本発明で得られる硬化物は各種用途に使用できる。詳しくはエポキシ樹脂等の熱硬化性樹脂が使用される一般の用途が挙げられ、例えば、接着剤、塗料、コーティング剤、成形材料(シート、フィルム、FRP等を含む)、絶縁材料(プリント基板、電線被覆等を含む)、封止剤の他、他樹脂等への添加剤等が挙げられる。 The cured product obtained by the present invention can be used for various purposes. More specifically, general applications where thermosetting resins such as epoxy resins are used include adhesives, paints, coating agents, molding materials (including sheets, films, FRP, etc.), insulating materials (printed circuit boards, wire coating, etc.), sealing agents, additives to other resins, and the like.
接着剤としては、土木用、建築用、自動車用、一般事務用、医療用の接着剤の他、電子材料用の接着剤が挙げられる。これらのうち電子材料用の接着剤としては、ビルドアップ基板等の多層基板の層間接着剤、ダイボンディング剤、アンダーフィル等の半導体用接着剤、BGA補強用アンダーフィル、異方性導電性フィルム(ACF)、異方性導電性ペースト(ACP)等の実装用接着剤等が挙げられる。 Adhesives include adhesives for civil engineering, construction, automobiles, general office and medical use, as well as adhesives for electronic materials. Among them, adhesives for electronic materials include interlayer adhesives for multilayer substrates such as build-up substrates, die bonding agents, adhesives for semiconductors such as underfill, underfill for BGA reinforcement, anisotropic conductive films ( ACF), mounting adhesives such as anisotropic conductive paste (ACP), and the like.
封止剤としては、コンデンサ、トランジスタ、ダイオード、発光ダイオード、IC、LSI用などのポッティング、ディッピング、トランスファーモールド封止、IC、LSI類のCOB、COF、TABなど用のといったポッティング封止、フリップチップ用のアンダーフィル、QFP、BGA、CSPなどのICパッケージ類実装時の封止(補強用アンダーフィルを含む)などを挙げることができる。 Potting, dipping, transfer mold sealing for capacitors, transistors, diodes, light-emitting diodes, ICs, LSIs, etc., potting sealing for COBs, COFs, TABs of ICs, LSIs, flip chips, etc. and sealing (including reinforcing underfill) when mounting IC packages such as QFP, BGA, and CSP.
次に本発明を実施例により更に具体的に説明するが、以下において部は特に断わりのない限り重量部である。尚、本発明はこれら実施例に限定されるものではない。また実施例において、エポキシ当量はJIS K-7236、軟化点はJIS K-7234に準じた方法で測定した。軟化点は、METTLER TOLEDO社 軟化点測定器 FP90を用い測定した。水酸基当量は、サンプルをピリジン溶液中、無水酢酸を用いてアセチル化を行い、アセチル化完了後に水で残存する酸無水物を分解し、これを0.5NのKOHエタノール溶液を用いて電位差滴定機で滴定することで遊離の酢酸量を測定を行い、その結果から水酸基当量を求めた。 EXAMPLES Next, the present invention will be described in more detail with reference to examples. In the following, all parts are parts by weight unless otherwise specified. However, the present invention is not limited to these examples. In the examples, the epoxy equivalent was measured according to JIS K-7236, and the softening point was measured according to JIS K-7234. The softening point was measured using a softening point measuring instrument FP90 manufactured by METTLER TOLEDO. The hydroxyl equivalent is determined by acetylating a sample in a pyridine solution using acetic anhydride, decomposing the remaining acid anhydride with water after the acetylation is completed, and then using a 0.5 N KOH ethanol solution to potentiometrically titrate. The amount of free acetic acid was measured by titration with , and the hydroxyl equivalent was determined from the results.
・GPC(ゲルパーミエーションクロマトグラフィー)分析
カラム:SHODEX GPC KF-601(2本)、KF-602、KF-602.5、KF-603
流速:0.5ml/min.
カラム温度:40℃
使用溶剤:THF(テトラヒドロフラン)
検出器:RI(示差屈折検出器)・GPC (gel permeation chromatography) analysis column: SHODEX GPC KF-601 (2 columns), KF-602, KF-602.5, KF-603
Flow rate: 0.5 ml/min.
Column temperature: 40°C
Solvent used: THF (tetrahydrofuran)
Detector: RI (differential refraction detector)
[合成例1]
トルエン250部、ビスフェノールA142.7部、α,α,α’,α’-テトラメチルベンゼンジメタノール97.1部、パラトルエンスルホン酸2.5部を加え、125℃に昇温し6時間反応させた。廃液が中性になるまで有機層を水洗後濃縮し、フェノール樹脂(P1)を褐色固形樹脂として192部得た。数平均分子量Mn:1279、重量平均分子量Mw:1774、水酸基当量は203.8g/eq、ICI粘度(150℃)は0.82Pa・s、軟化点は98.0℃であった。GPCチャートを図1に示す。[Synthesis Example 1]
250 parts of toluene, 142.7 parts of bisphenol A, 97.1 parts of α,α,α',α'-tetramethylbenzenedimethanol and 2.5 parts of p-toluenesulfonic acid were added, heated to 125°C and reacted for 6 hours. let me The organic layer was washed with water until the waste liquid became neutral and then concentrated to obtain 192 parts of a phenolic resin (P1) as a brown solid resin. The number average molecular weight Mn was 1279, the weight average molecular weight Mw was 1774, the hydroxyl equivalent was 203.8 g/eq, the ICI viscosity (150°C) was 0.82 Pa·s, and the softening point was 98.0°C. A GPC chart is shown in FIG.
[合成例2]
温度計、冷却管、分留管、撹拌機を取り付けたフラスコに窒素パージを施しながら、合成例1で得られたフェノール樹脂(P1)180部、エピクロルヒドリン326.7部、ジメチルスルホキシド163.3部、水3.6部を加え、内温を50℃まで昇温した。水酸化ナトリウム37.8部を1.5時間かけて分割添加後、55℃で2時間、70℃で1時間反応させた。加熱減圧下で未反応のエピクロルヒドリンおよび溶剤を留去した。MIBK500部を加え、水500部で有機層を1回洗浄した。有機層を反応容器に戻し、30wt%水酸化ナトリウム水溶液11.9部を加え、75℃で1時間反応させた。放冷後、水100部で有機層を4回洗浄し、加熱減圧下、溶剤を留去し、うす黄色固形樹脂として目的化合物(E1)を201部得た。数平均分子量Mn:1253、重量平均分子量Mw:1947、エポキシ当量は298.6g/eq、ICI粘度(150℃)は0.44Pa・s、軟化点は80.9℃であった。GPCチャートを図2に示す。[Synthesis Example 2]
While purging a flask equipped with a thermometer, a cooling tube, a fractionating tube, and a stirrer, 180 parts of the phenolic resin (P1) obtained in Synthesis Example 1, 326.7 parts of epichlorohydrin, and 163.3 parts of dimethyl sulfoxide were added. , and 3.6 parts of water were added, and the internal temperature was raised to 50°C. After adding 37.8 parts of sodium hydroxide in portions over 1.5 hours, the mixture was reacted at 55°C for 2 hours and at 70°C for 1 hour. Unreacted epichlorohydrin and the solvent were distilled off under heating and reduced pressure. 500 parts of MIBK was added, and the organic layer was washed once with 500 parts of water. The organic layer was returned to the reaction vessel, 11.9 parts of a 30 wt % sodium hydroxide aqueous solution was added, and the mixture was reacted at 75° C. for 1 hour. After standing to cool, the organic layer was washed four times with 100 parts of water, and the solvent was distilled off under heating and reduced pressure to obtain 201 parts of the target compound (E1) as a pale yellow solid resin. The number average molecular weight Mn was 1253, the weight average molecular weight Mw was 1947, the epoxy equivalent was 298.6 g/eq, the ICI viscosity (150°C) was 0.44 Pa·s, and the softening point was 80.9°C. A GPC chart is shown in FIG.
[合成例3]
トルエン200部、フェノール235.3部、α,α,α’,α’-テトラメチルベンゼンジメタノール388.5部、パラトルエンスルホン酸7.6部を加え、125℃に昇温し5時間反応させた。トルエン200部を加え、廃液が中性になるまで有機層を水洗後濃縮し、フェノール樹脂(P2)を薄黄色固形樹脂として475部得た。数平均分子量Mn:822、重量平均分子量Mw:1181、水酸基当量は254.0g/eqであった。GPCチャートを図3に示す。[Synthesis Example 3]
200 parts of toluene, 235.3 parts of phenol, 388.5 parts of α,α,α',α'-tetramethylbenzenedimethanol and 7.6 parts of p-toluenesulfonic acid were added, heated to 125°C and reacted for 5 hours. let me 200 parts of toluene was added, and the organic layer was washed with water until the waste liquid became neutral and then concentrated to obtain 475 parts of a phenolic resin (P2) as a pale yellow solid resin. The number average molecular weight Mn was 822, the weight average molecular weight Mw was 1181, and the hydroxyl group equivalent was 254.0 g/eq. A GPC chart is shown in FIG.
[合成例4]
温度計、冷却管、分留管、撹拌機を取り付けたフラスコに窒素パージを施しながら、合成例3で得られたフェノール樹脂(P2)400部、エピクロルヒドリン582.7部、ジメチルスルホキシド291.4部、水6.4部を加え、内温を50℃まで昇温した。水酸化ナトリウム67.3部を1.5時間かけて分割添加後、55℃で2時間、70℃で1時間反応させた。加熱減圧下で未反応のエピクロルヒドリンおよび溶剤を留去した。MIBK900部を加え、水400部で有機層を1回洗浄した。有機層を反応容器に戻し、30wt%水酸化ナトリウム水溶液21.1部を加え、75℃で1時間反応させた。放冷後、水100部で有機層を6回洗浄し、加熱減圧下、溶剤を留去し、うす黄色固形樹脂として目的化合物(E2)を455部得た。数平均分子量Mn:827、重量平均分子量Mw:1352、エポキシ当量は334.0g/eq、ICI粘度(150℃)は0.17Pa・s、軟化点は69.7℃であった。GPCチャートを図4に示す。[Synthesis Example 4]
While purging a flask equipped with a thermometer, a cooling tube, a fractionating tube, and a stirrer, 400 parts of the phenolic resin (P2) obtained in Synthesis Example 3, 582.7 parts of epichlorohydrin, and 291.4 parts of dimethyl sulfoxide were added. , and 6.4 parts of water were added, and the internal temperature was raised to 50°C. After adding 67.3 parts of sodium hydroxide in portions over 1.5 hours, the mixture was reacted at 55°C for 2 hours and at 70°C for 1 hour. Unreacted epichlorohydrin and the solvent were distilled off under heating and reduced pressure. 900 parts of MIBK was added, and the organic layer was washed once with 400 parts of water. The organic layer was returned to the reaction vessel, 21.1 parts of a 30 wt % sodium hydroxide aqueous solution was added, and the mixture was reacted at 75° C. for 1 hour. After standing to cool, the organic layer was washed 6 times with 100 parts of water, and the solvent was distilled off under heating and reduced pressure to obtain 455 parts of the objective compound (E2) as a pale yellow solid resin. The number average molecular weight Mn was 827, the weight average molecular weight Mw was 1352, the epoxy equivalent was 334.0 g/eq, the ICI viscosity (150°C) was 0.17 Pa·s, and the softening point was 69.7°C. A GPC chart is shown in FIG.
[合成例5]
温度計、冷却管、分留管、撹拌機を取り付けたフラスコに窒素パージを施しながら、ビスフェノールAノボラック樹脂(特開2014-198755号に記載の比較例1を参考にして合成したビスフェノールAとホルムアルデヒドの縮合物、水酸基当量:118g/eq、ICI粘度(150℃)は検出限界(6.8Pa・s以上)、軟化点は120.6℃、数平均分子量Mn:1907、重量平均分子量Mw:4533、GPCチャートを図5に示す。)100部、エピクロルヒドリン415部、ジメチルスルホキシド157部、水28.2部を加え、内温を35℃まで昇温した。水酸化ナトリウム36.1部を3時間かけて分割添加後、35℃で2時間、70℃で0.5時間反応させた。加熱減圧下で未反応のエピクロルヒドリンおよび溶剤を留去した。MIBK440部を加え、水170部で有機層を1回洗浄した。有機層を反応容器に戻し、メタノール8部、水22.6部、30wt%水酸化ナトリウム水溶液22.6部を加え、75℃で1時間反応させた。放冷後、水100部で有機層を4回洗浄し、加熱減圧下、溶剤を留去し、うす黄色固形樹脂として目的化合物(E3)を147.5部得た。数平均分子量Mn:2233、重量平均分子量Mw:39351、エポキシ当量は199.0g/eq、ICI粘度(150℃)は1.22Pa・s、軟化点は81.6℃であった。GPCチャートを図6に示す。[Synthesis Example 5]
Bisphenol A novolak resin (synthesized with reference to Comparative Example 1 described in JP 2014-198755 A and formaldehyde while purging with nitrogen in a flask equipped with a thermometer, a condenser tube, a fractionating tube, and a stirrer. Condensate of, hydroxyl equivalent: 118 g / eq, ICI viscosity (150 ° C.) detection limit (6.8 Pa s or more), softening point 120.6 ° C., number average molecular weight Mn: 1907, weight average molecular weight Mw: 4533 , a GPC chart is shown in FIG. 5), 415 parts of epichlorohydrin, 157 parts of dimethylsulfoxide and 28.2 parts of water were added, and the internal temperature was raised to 35°C. After adding 36.1 parts of sodium hydroxide portionwise over 3 hours, the mixture was reacted at 35°C for 2 hours and at 70°C for 0.5 hours. Unreacted epichlorohydrin and the solvent were distilled off under heating and reduced pressure. 440 parts of MIBK was added, and the organic layer was washed once with 170 parts of water. The organic layer was returned to the reaction vessel, 8 parts of methanol, 22.6 parts of water, and 22.6 parts of 30 wt % sodium hydroxide aqueous solution were added and reacted at 75° C. for 1 hour. After standing to cool, the organic layer was washed four times with 100 parts of water, and the solvent was distilled off under heating and reduced pressure to obtain 147.5 parts of the target compound (E3) as a pale yellow solid resin. It had a number average molecular weight Mn of 2233, a weight average molecular weight Mw of 39351, an epoxy equivalent of 199.0 g/eq, an ICI viscosity (150°C) of 1.22 Pa·s, and a softening point of 81.6°C. A GPC chart is shown in FIG.
[実施例1、比較例1、2]
合成例2で得られたエポキシ樹脂(E1)、合成例4で得られたエポキシ樹脂(E2)および合成例5で得られたエポキシ樹脂(E3)それぞれに対し、硬化剤としてビフェニルアラルキル型フェノール樹脂(日本化薬社製 GPH-65)、触媒としてトリフェニルホスフィン(TPP、東京化成社製)、無機充填剤としてシリカゲル(溶融シリカ MSR-2212、龍森製)を表1に示す割合で配合し、ミキシングロールを用いて均一に混合・混練し、硬化性樹脂組成物を得た。
この硬化性樹脂組成物を粉砕後、タブレットマシーンにてタブレット化した。タブレット化した硬化性樹脂組成物をトランスファー成型(175℃ 60~15分)し、更に脱型後160℃×2時間+180℃×6時間の条件で硬化して、評価用試験片を得た。[Example 1, Comparative Examples 1 and 2]
For each of the epoxy resin (E1) obtained in Synthesis Example 2, the epoxy resin (E2) obtained in Synthesis Example 4, and the epoxy resin (E3) obtained in Synthesis Example 5, a biphenylaralkyl-type phenolic resin was used as a curing agent. (GPH-65 manufactured by Nippon Kayaku Co., Ltd.), triphenylphosphine (TPP, manufactured by Tokyo Kasei Co., Ltd.) as a catalyst, and silica gel (fused silica MSR-2212, manufactured by Tatsumori) as an inorganic filler in the proportions shown in Table 1. and uniformly mixed and kneaded using a mixing roll to obtain a curable resin composition.
This curable resin composition was pulverized and then tableted with a tablet machine. The tableted curable resin composition was subjected to transfer molding (175° C. for 60 to 15 minutes) and further cured under the conditions of 160° C.×2 hours+180° C.×6 hours after demolding to obtain test pieces for evaluation.
評価用試験片は下記条件で測定を行い、その結果を表1に示す。 The test pieces for evaluation were measured under the following conditions, and the results are shown in Table 1.
<耐熱性試験(Tg)>
動的粘弾性試験機を用いてガラス転移温度(tanδが最大値のときの温度)を測定した。
・動的粘弾性測定器:TA-instruments製DMA-2980
・昇温速度:2℃/分
・周波数:10Hz<Heat resistance test (Tg)>
A dynamic viscoelasticity tester was used to measure the glass transition temperature (the temperature at which tan δ reaches its maximum value).
・ Dynamic viscoelasticity measuring instrument: DMA-2980 manufactured by TA-instruments
・Temperature increase rate: 2°C/min ・Frequency: 10Hz
<耐トラッキング性試験(CTI)>
適合規格 IEC-Pub.60112-2003(第4版)及びJIS-C2134-2007
対象試験電圧 400V~600V
試験液 塩化アンモニウム 0.1%水溶液
滴下数 50滴 または試験片が破壊するまで実施
試験室の温度と湿度 21℃~23℃ 40~45%RH
試験装置 ヤマヨ試験機有限会社製 YST-112型 耐トラッキング試験機
試験サンプル形状 直径50mm 厚み 3mm
1枚につき1点測定<Tracking resistance test (CTI)>
Applicable standard IEC-Pub. 60112-2003 (4th edition) and JIS-C2134-2007
Target test voltage 400V to 600V
Test liquid 0.1% aqueous solution of ammonium chloride Number of drops 50 drops or until the test piece breaks Test room temperature and humidity 21°C to 23°C 40 to 45%RH
Test equipment YST-112 type tracking resistance tester manufactured by Yamayo Testing Machine Co., Ltd. Test sample shape Diameter 50 mm Thickness 3 mm
1 point measurement per sheet
<難燃性性試験>
試験片をクランプに垂直に保持し、バーナーの炎を19mmの青色炎に調節し、試験片の下端中央部に炎の9.5mmを10秒接炎する。接炎後バーナーを離して、燃焼継続時間を測定する。消炎後、直ちに10秒接炎した後、バーナーを離し、燃焼継続時間を測定する。各サンプル10回分の燃焼時間合計値を表1に示す。<Flame Retardancy Test>
The test piece is held vertically in a clamp, the burner flame is adjusted to a 19 mm blue flame, and a 9.5 mm flame is applied to the center of the lower end of the test piece for 10 seconds. After contacting the flame, remove the burner and measure the duration of combustion. Immediately after the flame is extinguished, the flame is applied for 10 seconds, the burner is removed, and the duration of combustion is measured. Table 1 shows the total burning time for 10 samples.
耐トラッキング試験の括弧内のnに続く数値はサンプル数を表す。比較例2の500Vの試験は1回目は13滴で試験片が破壊し、2回目は50滴においても試験片が破壊しなかったを表す。 The number following n in parentheses in the tracking resistance test represents the number of samples. In the 500 V test of Comparative Example 2, the test piece broke at 13 drops in the first time, and the test piece did not break at 50 drops in the second time.
表1の結果より、実施例1は高耐熱性、高い耐トラッキング性、および高い難燃性を有することが確認された。 From the results in Table 1, it was confirmed that Example 1 had high heat resistance, high tracking resistance, and high flame retardancy.
本発明のエポキシ樹脂は、電気電子部品用絶縁材料(高信頼性半導体封止材料など)及び積層板(プリント配線板、BGA用基板、ビルドアップ基板など)、接着剤(導電性接着剤など)やCFRPを始めとする各種複合材料用、塗料等の用途に有用であり、特に、耐トラッキング性を要求される電気電子部品用絶縁材料(高信頼性半導体封止材料など)及び積層板(プリント配線板、BGA用基板、ビルドアップ基板など)用途において有用である。
The epoxy resin of the present invention is used as an insulating material for electrical and electronic parts (such as a highly reliable semiconductor sealing material), a laminate (such as a printed wiring board, a BGA substrate, and a build-up substrate), and an adhesive (such as a conductive adhesive). It is useful for various composite materials such as CFRP and coatings, and is particularly useful for insulating materials for electrical and electronic parts that require tracking resistance (such as highly reliable semiconductor encapsulation materials) and laminates (printed wiring boards, BGA substrates, build-up substrates, etc.).
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JP2016074890A (en) * | 2014-10-03 | 2016-05-12 | 東京応化工業株式会社 | Curable composition |
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