WO2011125962A1 - Epoxy resin composition and cured product thereof - Google Patents
Epoxy resin composition and cured product thereof Download PDFInfo
- Publication number
- WO2011125962A1 WO2011125962A1 PCT/JP2011/058485 JP2011058485W WO2011125962A1 WO 2011125962 A1 WO2011125962 A1 WO 2011125962A1 JP 2011058485 W JP2011058485 W JP 2011058485W WO 2011125962 A1 WO2011125962 A1 WO 2011125962A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- epoxy resin
- resin composition
- cured product
- trimethylolpropane
- viscosity
- Prior art date
Links
- 239000003822 epoxy resin Substances 0.000 title claims abstract description 69
- 229920000647 polyepoxide Polymers 0.000 title claims abstract description 69
- 239000000203 mixture Substances 0.000 title claims abstract description 25
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims abstract description 33
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 claims abstract description 28
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000000460 chlorine Substances 0.000 claims abstract description 17
- 229910052801 chlorine Inorganic materials 0.000 claims abstract description 17
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000000178 monomer Substances 0.000 claims abstract description 3
- 238000004817 gas chromatography Methods 0.000 claims description 8
- 238000004458 analytical method Methods 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 4
- 239000004065 semiconductor Substances 0.000 abstract description 7
- 238000000576 coating method Methods 0.000 abstract description 6
- 239000011342 resin composition Substances 0.000 abstract description 6
- 239000000463 material Substances 0.000 abstract description 4
- 239000011248 coating agent Substances 0.000 abstract description 3
- 238000007789 sealing Methods 0.000 abstract description 3
- 239000002131 composite material Substances 0.000 abstract description 2
- 239000002648 laminated material Substances 0.000 abstract description 2
- 238000004587 chromatography analysis Methods 0.000 abstract 1
- 239000000047 product Substances 0.000 description 18
- 229920005989 resin Polymers 0.000 description 16
- 239000011347 resin Substances 0.000 description 16
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 15
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 15
- 238000006243 chemical reaction Methods 0.000 description 14
- -1 acetone Alcohols Chemical class 0.000 description 13
- 239000003795 chemical substances by application Substances 0.000 description 13
- 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 13
- 230000000052 comparative effect Effects 0.000 description 11
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-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 8
- 150000002989 phenols Chemical class 0.000 description 8
- 238000000034 method Methods 0.000 description 7
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 6
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 6
- IMHDGJOMLMDPJN-UHFFFAOYSA-N biphenyl-2,2'-diol Chemical compound OC1=CC=CC=C1C1=CC=CC=C1O IMHDGJOMLMDPJN-UHFFFAOYSA-N 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
- 238000000199 molecular distillation Methods 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Natural products CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 5
- 239000004593 Epoxy Substances 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- 125000003700 epoxy group Chemical group 0.000 description 5
- 229920003986 novolac Polymers 0.000 description 5
- 230000000704 physical effect Effects 0.000 description 5
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical compound C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 description 4
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 4
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 4
- YXVFYQXJAXKLAK-UHFFFAOYSA-N biphenyl-4-ol Chemical group C1=CC(O)=CC=C1C1=CC=CC=C1 YXVFYQXJAXKLAK-UHFFFAOYSA-N 0.000 description 4
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 4
- 230000007423 decrease Effects 0.000 description 4
- QWVGKYWNOKOFNN-UHFFFAOYSA-N o-cresol Chemical compound CC1=CC=CC=C1O QWVGKYWNOKOFNN-UHFFFAOYSA-N 0.000 description 4
- 239000000049 pigment Substances 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 4
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- IXCOKTMGCRJMDR-UHFFFAOYSA-N 9h-fluorene;phenol Chemical compound OC1=CC=CC=C1.OC1=CC=CC=C1.C1=CC=C2CC3=CC=CC=C3C2=C1 IXCOKTMGCRJMDR-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 3
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 3
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 3
- 150000008065 acid anhydrides Chemical class 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
- VCCBEIPGXKNHFW-UHFFFAOYSA-N biphenyl-4,4'-diol Chemical compound C1=CC(O)=CC=C1C1=CC=C(O)C=C1 VCCBEIPGXKNHFW-UHFFFAOYSA-N 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 229910052736 halogen Inorganic materials 0.000 description 3
- 150000002367 halogens Chemical class 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 239000011344 liquid material Substances 0.000 description 3
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 229960001755 resorcinol Drugs 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 150000005846 sugar alcohols Polymers 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- WYURNTSHIVDZCO-UHFFFAOYSA-N tetrahydrofuran Substances C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 3
- 238000001721 transfer moulding Methods 0.000 description 3
- 239000001993 wax Substances 0.000 description 3
- 239000008096 xylene Substances 0.000 description 3
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 description 2
- RGHHSNMVTDWUBI-UHFFFAOYSA-N 4-hydroxybenzaldehyde Chemical compound OC1=CC=C(C=O)C=C1 RGHHSNMVTDWUBI-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
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 description 2
- HTZCNXWZYVXIMZ-UHFFFAOYSA-M benzyl(triethyl)azanium;chloride Chemical compound [Cl-].CC[N+](CC)(CC)CC1=CC=CC=C1 HTZCNXWZYVXIMZ-UHFFFAOYSA-M 0.000 description 2
- 239000004918 carbon fiber reinforced polymer Substances 0.000 description 2
- XENVCRGQTABGKY-ZHACJKMWSA-N chlorohydrin Chemical compound CC#CC#CC#CC#C\C=C\C(Cl)CO XENVCRGQTABGKY-ZHACJKMWSA-N 0.000 description 2
- 239000007822 coupling agent Substances 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 239000003063 flame retardant Substances 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 2
- 150000002460 imidazoles Chemical class 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- 239000011256 inorganic filler Substances 0.000 description 2
- 229910003475 inorganic filler Inorganic materials 0.000 description 2
- 230000010354 integration Effects 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- VYKXQOYUCMREIS-UHFFFAOYSA-N methylhexahydrophthalic anhydride Chemical compound C1CCCC2C(=O)OC(=O)C21C VYKXQOYUCMREIS-UHFFFAOYSA-N 0.000 description 2
- NXPPAOGUKPJVDI-UHFFFAOYSA-N naphthalene-1,2-diol Chemical compound C1=CC=CC2=C(O)C(O)=CC=C21 NXPPAOGUKPJVDI-UHFFFAOYSA-N 0.000 description 2
- 239000003973 paint Substances 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 229920001296 polysiloxane Polymers 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 230000000630 rising effect Effects 0.000 description 2
- 239000003566 sealing material Substances 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-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
- 238000005406 washing Methods 0.000 description 2
- KNDQHSIWLOJIGP-UMRXKNAASA-N (3ar,4s,7r,7as)-rel-3a,4,7,7a-tetrahydro-4,7-methanoisobenzofuran-1,3-dione Chemical compound O=C1OC(=O)[C@@H]2[C@H]1[C@]1([H])C=C[C@@]2([H])C1 KNDQHSIWLOJIGP-UMRXKNAASA-N 0.000 description 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
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 description 1
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical compound CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 description 1
- KJCVRFUGPWSIIH-UHFFFAOYSA-N 1-naphthol Chemical compound C1=CC=C2C(O)=CC=CC2=C1 KJCVRFUGPWSIIH-UHFFFAOYSA-N 0.000 description 1
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 description 1
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 1
- SBASXUCJHJRPEV-UHFFFAOYSA-N 2-(2-methoxyethoxy)ethanol Chemical compound COCCOCCO SBASXUCJHJRPEV-UHFFFAOYSA-N 0.000 description 1
- 125000001731 2-cyanoethyl group Chemical class [H]C([H])(*)C([H])([H])C#N 0.000 description 1
- SHYARJUKNREDGB-UHFFFAOYSA-N 2-ethyl-5-methyl-4,5-dihydro-1h-imidazole Chemical compound CCC1=NCC(C)N1 SHYARJUKNREDGB-UHFFFAOYSA-N 0.000 description 1
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 description 1
- VWSLLSXLURJCDF-UHFFFAOYSA-N 2-methyl-4,5-dihydro-1h-imidazole Chemical compound CC1=NCCN1 VWSLLSXLURJCDF-UHFFFAOYSA-N 0.000 description 1
- VEORPZCZECFIRK-UHFFFAOYSA-N 3,3',5,5'-tetrabromobisphenol A Chemical compound C=1C(Br)=C(O)C(Br)=CC=1C(C)(C)C1=CC(Br)=C(O)C(Br)=C1 VEORPZCZECFIRK-UHFFFAOYSA-N 0.000 description 1
- YBRVSVVVWCFQMG-UHFFFAOYSA-N 4,4'-diaminodiphenylmethane Chemical compound C1=CC(N)=CC=C1CC1=CC=C(N)C=C1 YBRVSVVVWCFQMG-UHFFFAOYSA-N 0.000 description 1
- ULKLGIFJWFIQFF-UHFFFAOYSA-N 5K8XI641G3 Chemical compound CCC1=NC=C(C)N1 ULKLGIFJWFIQFF-UHFFFAOYSA-N 0.000 description 1
- MWSKJDNQKGCKPA-UHFFFAOYSA-N 6-methyl-3a,4,5,7a-tetrahydro-2-benzofuran-1,3-dione Chemical compound C1CC(C)=CC2C(=O)OC(=O)C12 MWSKJDNQKGCKPA-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- MQJKPEGWNLWLTK-UHFFFAOYSA-N Dapsone Chemical compound C1=CC(N)=CC=C1S(=O)(=O)C1=CC=C(N)C=C1 MQJKPEGWNLWLTK-UHFFFAOYSA-N 0.000 description 1
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- 239000004606 Fillers/Extenders Substances 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- OKIZCWYLBDKLSU-UHFFFAOYSA-M N,N,N-Trimethylmethanaminium chloride Chemical compound [Cl-].C[N+](C)(C)C OKIZCWYLBDKLSU-UHFFFAOYSA-M 0.000 description 1
- VPWQYIHLKGZHTP-UHFFFAOYSA-N O1CCOCC1.C(CC)OCC Chemical compound O1CCOCC1.C(CC)OCC VPWQYIHLKGZHTP-UHFFFAOYSA-N 0.000 description 1
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 229920001665 Poly-4-vinylphenol Polymers 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 1
- ISKQADXMHQSTHK-UHFFFAOYSA-N [4-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=C(CN)C=C1 ISKQADXMHQSTHK-UHFFFAOYSA-N 0.000 description 1
- BWVAOONFBYYRHY-UHFFFAOYSA-N [4-(hydroxymethyl)phenyl]methanol Chemical compound OCC1=CC=C(CO)C=C1 BWVAOONFBYYRHY-UHFFFAOYSA-N 0.000 description 1
- IKHGUXGNUITLKF-XPULMUKRSA-N acetaldehyde Chemical compound [14CH]([14CH3])=O IKHGUXGNUITLKF-XPULMUKRSA-N 0.000 description 1
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 125000002723 alicyclic group Chemical group 0.000 description 1
- 150000008431 aliphatic amides Chemical class 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- 229910000410 antimony oxide Inorganic materials 0.000 description 1
- 150000004982 aromatic amines Chemical class 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 235000012216 bentonite Nutrition 0.000 description 1
- KXHPPCXNWTUNSB-UHFFFAOYSA-M benzyl(trimethyl)azanium;chloride Chemical compound [Cl-].C[N+](C)(C)CC1=CC=CC=C1 KXHPPCXNWTUNSB-UHFFFAOYSA-M 0.000 description 1
- 230000001588 bifunctional effect Effects 0.000 description 1
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 description 1
- 235000013539 calcium stearate Nutrition 0.000 description 1
- 239000008116 calcium stearate Substances 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000004203 carnauba wax Substances 0.000 description 1
- 235000013869 carnauba wax Nutrition 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 239000004359 castor oil Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000000748 compression moulding Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 229910002026 crystalline silica Inorganic materials 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 description 1
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- ZZTCPWRAHWXWCH-UHFFFAOYSA-N diphenylmethanediamine Chemical compound C=1C=CC=CC=1C(N)(N)C1=CC=CC=C1 ZZTCPWRAHWXWCH-UHFFFAOYSA-N 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 239000012776 electronic material Substances 0.000 description 1
- 239000003480 eluent Substances 0.000 description 1
- 239000008393 encapsulating agent Substances 0.000 description 1
- 238000005538 encapsulation Methods 0.000 description 1
- 238000006735 epoxidation reaction Methods 0.000 description 1
- 238000006266 etherification reaction Methods 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000005350 fused silica glass Substances 0.000 description 1
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 150000002462 imidazolines Chemical class 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000011810 insulating material Substances 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 238000004255 ion exchange chromatography Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 229940018564 m-phenylenediamine Drugs 0.000 description 1
- 239000002075 main ingredient Substances 0.000 description 1
- 238000011326 mechanical measurement Methods 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 239000006082 mold release agent Substances 0.000 description 1
- 150000004780 naphthols Chemical class 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 150000002903 organophosphorus compounds Chemical class 0.000 description 1
- VTRUBDSFZJNXHI-UHFFFAOYSA-N oxoantimony Chemical compound [Sb]=O VTRUBDSFZJNXHI-UHFFFAOYSA-N 0.000 description 1
- 238000012536 packaging technology Methods 0.000 description 1
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000013034 phenoxy resin Substances 0.000 description 1
- 229920006287 phenoxy resin Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 150000008442 polyphenolic compounds Chemical class 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 238000004382 potting Methods 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 229920002545 silicone oil Polymers 0.000 description 1
- 239000001632 sodium acetate Substances 0.000 description 1
- 235000017281 sodium acetate Nutrition 0.000 description 1
- 229910000679 solder Inorganic materials 0.000 description 1
- 239000011343 solid material Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- YMBCJWGVCUEGHA-UHFFFAOYSA-M tetraethylammonium chloride Chemical compound [Cl-].CC[N+](CC)(CC)CC YMBCJWGVCUEGHA-UHFFFAOYSA-M 0.000 description 1
- DDFYFBUWEBINLX-UHFFFAOYSA-M tetramethylammonium bromide Chemical compound [Br-].C[N+](C)(C)C DDFYFBUWEBINLX-UHFFFAOYSA-M 0.000 description 1
- 230000000930 thermomechanical effect Effects 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 239000013008 thixotropic agent Substances 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 150000003918 triazines Chemical class 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
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 description 1
- 239000004246 zinc acetate Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/02—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
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/42—Polycarboxylic acids; Anhydrides, halides or low molecular weight esters thereof
- C08G59/4215—Polycarboxylic acids; Anhydrides, halides or low molecular weight esters thereof cycloaliphatic
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/68—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the catalysts used
- C08G59/688—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the catalysts used containing phosphorus
-
- 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
Definitions
- the present invention is essential for use in glycidyl ethers of trimethylolpropane which are low in viscosity, low in organic chlorine content, and high in heat resistance, which are suitable mainly for the electric sealing materials such as semiconductor encapsulant applications.
- the present invention relates to a resin composition blended as a component, and a cured product thereof.
- Epoxy resins There are various epoxy resins from liquid to solid, and since epoxy resins are excellent in reactivity with the curing agent, they are easy to handle, and when crosslinked by the curing agent, they become cured resins having a large crosslinking density, which is excellent. It exhibits heat resistance, moisture resistance, chemical resistance, electrical properties, etc., and is widely used in the electrical and electronic fields. Epoxy resins have been used in a wide range of industrial applications, but their performance requirements have become increasingly sophisticated in recent years. For example, there is a semiconductor sealing material in a representative field of resin compositions containing an epoxy resin as a main ingredient, but in recent years, along with the improvement of the degree of integration of semiconductor elements, the package size tends to be larger and thinner.
- liquid materials generally have the disadvantage of being less reliable than solid materials used for transfer molding. This is because the liquid material has an upper limit of viscosity, and there are restrictions on the epoxy resin, curing agent, filler, etc. to be used.
- epoxy resins having an alcohol raw material are mentioned as epoxy resins excellent in low viscosity, epoxy resins having an alcohol raw material generally contain a large amount of chlorine, and the heat resistance and hygroscopicity of cured products are low at present.
- the epoxy resin of a trimethylol propane is mentioned as an epoxy resin which is excellent in low viscosity and high heat resistance of hardened
- An object of the present invention is to provide an epoxy resin composition which gives a cured product having a low viscosity and excellent heat resistance and moisture resistance, as well as a cured product thereof.
- the low viscosity epoxy resin characterized by having a body ratio of 35% or more, a total chlorine content of 0.3% by weight or less, and a viscosity at 25 ° C. of 300 mPa ⁇ s or less is blended as an essential component It is an epoxy resin composition.
- the present invention is a cured product obtained by curing the epoxy resin composition.
- the epoxy resin composition using the epoxy resin of the present invention has excellent low viscosity, and a cured product obtained by curing the same has excellent performance in heat resistance and moisture resistance, so a heavy corrosion protection paint is obtained.
- Paint applications such as powder coatings, PCM coatings and can coatings, civil engineering and construction applications, bonding applications, electrical insulation applications, electric and electronic parts applications such as semiconductor chip tacks, printed wiring boards and carbon fiber reinforced plastics (CFRP In particular, it can be suitably used for printed wiring boards, insulating materials in the field of electricity and electronics such as semiconductor encapsulation, and the like.
- the ratio of triglycidyl is 35% or more. If the triglycidyl ratio is 35% or less, the physical properties such as Tg of the cured product decrease, and the resin viscosity increases, which is not preferable, and is preferably 50% or more, more preferably 75% or more.
- the polyglycidyl ether of trimethylolpropane used in the present invention has a total chlorine content of 0.3% by weight or less, preferably 0.2% by weight or less.
- the polyglycidyl ether of trimethylolpropane used in the present invention has a viscosity of 300 mPa ⁇ s or less at 25 ° C. When the viscosity at 25 ° C. exceeds 300 mPa ⁇ s, the dilution efficiency decreases, which is not preferable.
- the method of reacting trimethylolpropane with epichlorohydrin can be carried out in the same manner as a conventional epoxidation reaction. For example, after blending and dissolving an excess of epichlorohydrin with respect to the hydroxyl group of trimethylolpropane, a method of reacting in the range of 40 to 120 ° C. for 1 to 10 hours in the presence of an alkali metal hydroxide may be mentioned.
- the reaction it is preferable to carry out the reaction at 50 to 90 ° C.
- the alkali metal hydroxide used in the above reaction include lithium hydroxide, sodium hydroxide, potassium hydroxide, calcium hydroxide and the like, with sodium hydroxide and potassium hydroxide being particularly preferable.
- the alkali may be an aqueous solution or a solid, but for ease of handling it is preferable to use an aqueous solution.
- the amount of the alkali metal hydroxide used is usually 0.7 to 3.0 equivalents, preferably 0.8 to 2.0 equivalents, per equivalent of the alcoholic hydroxyl group.
- the amount of epichlorohydrin used is 1 to 10 equivalents, preferably 2 to 6 equivalents, per equivalent of the hydroxyl group of polyhydric alcohol. When the amount of epichlorohydrin used is less than 1 equivalent, polymerization tends to proceed and the yield of the desired chlorohydrin ether decreases.
- a quaternary ammonium salt may be added as a catalyst as needed to allow the reaction to proceed simply.
- examples of quaternary ammonium salts that can be used include tetramethyl ammonium chloride, tetramethyl ammonium bromide, benzyltrimethyl ammonium chloride, benzyltriethyl ammonium chloride and the like.
- the amount of quaternary ammonium salt used is usually 0.05 to 10% by weight, preferably 0.1 to 1% by weight, based on the amount of polyhydric alcohol used.
- the reaction can be carried out in a solvent which does not react with the epoxy group.
- aromatic hydrocarbons such as toluene, xylene and benzene, ketones such as methyl isobutyl ketone, methyl ethyl ketone, cyclohexanone and acetone Alcohols such as propanol and butanol
- Glycol ethers such as diethylene glycol methyl ether, propylene glycol methyl ether and dipropylene glycol methyl ether
- Aliphatic ethers such as diethyl ether, dibutyl ether and ethyl propyl ether Dioxane and tetrahydrofuran
- Alicyclic ethers, dimethyl sulfoxide and the like can be mentioned, and two or more of them can be used in combination.
- the amount of these solvents used is 200 parts by weight or less, preferably 5 to 150 parts by weight, and more preferably 10 to 100 parts by weight with respect to 100 parts by weight of epihalohydrin.
- the reaction system water content is preferably 0.1% or more and less than 2.0%. When the water content in the system is lower than 0.1%, the reaction proceeds slowly. When the water content in the system is 2.0% or more, the glycidyl etherification reaction is inhibited by the influence of the water, and the contained chlorine becomes high.
- organic solvent used herein examples include methyl isobutyl ketone, toluene, xylene, cyclohexanone, methanol, ethanol, propanol, butanol and the like, among which methyl isobutyl ketone, toluene and xylene are preferable, and a mixed solvent thereof is also preferable. good.
- excess epihalohydrin is distilled off, dissolved in a solvent, filtered, washed with water to remove inorganic salts, and then the solvent is distilled off to obtain trimethylol used in the present invention.
- the obtained epoxy resin is further added to the amount of remaining hydrolysable halogen from the viewpoint of reducing the amount of hydrolyzable halogen. Then, 1 to 30 times amount of alkali metal hydroxide is added, and purification reaction is carried out at a temperature of 60 to 90 ° C. for 10 minutes to 2 hours, followed by neutralization, washing with water, etc. And by-product salts can be removed, and the solvent can be further distilled off under reduced pressure to obtain further purified polyglycidyl ether of trimethylolpropane used in the present invention.
- the epoxy resin composition of the present invention is an epoxy resin composition comprising an epoxy resin and a curing agent as essential components, wherein the polyglycidyl ether of trimethylolpropane according to claim 1 is blended as an epoxy resin component as an essential component. It is.
- any of those generally known as curing agents for epoxy resins can be used. For example, dicyandiamide, polyhydric phenols, acid anhydrides, aromatic and aliphatic amines and the like.
- polyhydric phenols for example, bisphenol A, bisphenol F, bisphenol S, fluorene bisphenol, 4,4'-biphenol, 2,2'-biphenol, hydroquinone, resorcinol, naphthalenediol, etc.
- phenols, naphthols, or divalent phenols such as bisphenol A, bisphenol F, bisphenol S, fluorene bisphenol, 4,4'-biphenol, 2,2'-biphenol, hydroquinone, resorcin, naphthalenediol and the like
- polyphenolic compounds synthesized from condensing agents such as formaldehyde, acetaldehyde, benzaldehyde, p-hydroxybenzaldehyde and p-xylylene glycol.
- Examples of the acid anhydride include phthalic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, methylhymic anhydride, nadic anhydride, trimellitic anhydride and the like.
- aromatic amines such as 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylpropane, 4,4'-diaminodiphenyl sulfone, m-phenylenediamine, p-xylylenediamine, etc., ethylenediamine, There are aliphatic amines such as hexamethylenediamine, diethylenetriamine and triethylenetetramine.
- the amount of the known conventional curing agent used is preferably 0.4 to 2.0 equivalents of the functional group of the curing agent to 1 equivalent of the epoxy group which is the functional group of the epoxy resin, and 0.5 to 1.5 equivalents of More preferably, particularly preferably 0.5 to 1.0 equivalents. If the amount of the curing agent is less than 0.4 equivalent to 1 equivalent of epoxy group, or if the equivalent is 2.0 equivalents, curing may be incomplete and a good cured product may not be obtained.
- one or more of these curing agents may be mixed and used.
- epoxy resin in this case, all common epoxy resins having two or more epoxy groups in the molecule can be used.
- bifunctional phenols such as bisphenol A, bisphenol S, fluorene bisphenol, 4,4'-biphenol, 2,2'-biphenol, hydroquinone and resorcin, or tris- (4-hydroxydiphenyl) methane
- Glycidyl derived from trivalent or higher phenols such as 1,1,2,2-tetrakis (4-hydroxydiphenyl) ethane, phenol novolac, o-cresol novolac or halogenated bisphenols such as tetrabromobisphenol A
- examples thereof include etherified products, polyglycidyl ethers of alcohols such as polyethylene glycol and polypropylene glycol, polyglycidyl amines such as diaminodiphenylmethane, and alicyclic epoxy resins.
- epoxy resins can be used alone or in combination of two or more.
- the blending amount of the polyglycidyl ether of trimethylolpropane according to the present invention is preferably in the range of 5 to 100%, preferably 60 to 100% in the entire epoxy resin.
- an oligomer or polymer compound such as polyester, polyamide, polyimide, polyether, polyurethane, petroleum resin, indencumarone resin, phenoxy resin and the like may be appropriately blended.
- blend additives such as an inorganic filler, a pigment, a flame retardant, a thixotropy imparting agent, a coupling agent, and a fluidity improver.
- inorganic filler include spherical or crushed fused silica, silica powder such as crystalline silica, alumina powder, glass powder, mica, talc, calcium carbonate, alumina, hydrated alumina and the like.
- the pigment include organic or inorganic extender pigments and scale-like pigments.
- the thixotropic agent include silicones, castor oils, aliphatic amide waxes, polyethylene oxide waxes, organic bentonites, and the like.
- mold release agents such as carnauba wax and OP wax
- coupling agents such as ⁇ -glycidoxypropyltrimethoxysilane
- colorants such as carbon black
- Flame retardants such as antimony oxide, stress reducing agents such as silicone oil, lubricants such as calcium stearate
- known curing accelerators can be used in the resin composition of the present invention.
- imidazoles such as 2-methylimidazole, 2-ethyl-4-methylimidazole, imidazolines such as 2-methylimidazoline, 2-ethyl-4-methylimidazoline, triazine salts of imidazole compounds, cyanoethyl salts, Various salts such as cyanoethyl trimellitic acid salt, metal compounds such as zinc acetate and sodium acetate, quaternary ammonium salts such as tetraethyl ammonium chloride, amide compounds, organic phosphorus compounds such as triphenylphosphine and the like. Can.
- the compounding ratio of these curing accelerators is 0.01 to 5 parts by weight, more preferably 0.1 to 2 parts by weight with respect to 100 parts by weight of the epoxy resin of the present invention.
- the epoxy resin cured product of the present invention can be obtained by heating the above-mentioned epoxy resin composition.
- As a method for obtaining a cured product casting, pouring, potting, dipping, drip coating, transfer molding, compression molding, etc. are suitably used, and the temperature at that time is usually in the range of 100 ° C. to 300 ° C. .
- Equipment Tosoh Corporation GPC8220 Separation column: TSKgel G2000HXL, TSKgel G2000HXL, TSKgel G1000HXL connected in series Column temperature: 40 ° C
- Eluent Tetrahydrofuran at 1 ml / min flow rate detector: RI detector
- TMP trimethylolpropane
- 652 parts of epichlorohydrin 65.2 parts of diethylene glycol dimethyl ether in a 1-L glass flask equipped with a stirrer, thermometer, nitrogen gas introduction device, dropping device, cooling pipe and oil / water separation device 6.5 parts of water was charged and dissolved by heating to 60 ° C.
- the ratio of diglycidyl body (2GE): triglycidyl body (3GE) was 0:60:40.
- the properties of the obtained resin are described in Table 1.
- Example 2 The same operation as in Example 1 was carried out except that the amount of 99% sodium hydroxide was changed from 77.3 parts to 116.0 parts, to obtain 154.5 g of an epoxy resin.
- the properties of the obtained resin are described in Table 1. Comparative Example 1 The same operation as in Example 1 was carried out except that 6.5 parts of water was changed to 0.65 parts, to obtain 148.2 g of an epoxy resin.
- the properties of the obtained resin are described in Table 1. Comparative example 2 Tohto Kasei YH-300 (trimethylolpropane glycidyl ether).
- the properties of the resin are described in Table 1.
- Example 3 The epoxy resin D (hereinafter referred to as epoxy resin A) obtained in Example 1 is subjected to molecular distillation at a pressure of 0.3 pa and a temperature of 125 to 135 ° C. using a thin film molecular distillation machine KDL-4 manufactured by Fintech Co., Ltd. I got The properties of the obtained resin are described in Table 2.
- Example 4 The epoxy resin E obtained by avoiding molecular distillation of the epoxy resin obtained in Example 2 (hereinafter, epoxy resin B) as in Example 3 was obtained. The properties of the obtained resin are described in Table 2. Comparative example 3 The epoxy resin F which did not go through molecular distillation similarly to Example 3 with the epoxy resin (following epoxy resin C) obtained in Example 1 was obtained. The properties of the obtained resin are described in Table 2. Comparative example 4 An epoxy resin G not subjected to molecular distillation was obtained in the same manner as in Example 3 for YH-300 manufactured by Tohto Kasei Co., Ltd. The properties of the obtained resin are described in Table 2.
- RIKACID MH-700 methyl hexahydrophthalic acid anhydride, acid anhydride equivalent 168 g / eq, Shin Nippon Rika Co., Ltd.
- hysicoline PX-4ET organic phosphonium salt compound, Nippon Chemical Co., Ltd.
- the epoxy resin composition was obtained by using the composition shown in Table 3. The numerical values in the table indicate parts by weight in the formulation.
- the resulting epoxy resin composition was molded at 100 ° C. for 2 hours, and post cured at 140 ° C. for 12 hours to obtain a cured test piece, which was then subjected to various physical property measurements. The results are shown in Table 3.
- test method and evaluation method of hardening physical property are as follows.
- the cured product Tg was measured at a temperature rising rate of 10 ° C./min using a thermo-mechanical measurement device (manufactured by Seiko Instruments Inc.).
- the water absorption rate was taken as a weight increase change rate after absorbing moisture for 50 hours under the conditions of 23 ° C. and 100% RH using a circular test piece of 50 mm in diameter and 5 mm in thickness.
- the amount of ionic impurities was determined by measuring the chloride ion by ion chromatography using the extracted ions after the pressure cooker test at 105 ° C. for 20 hours, and converting it to the solid content.
- Examples 5 and 6 using the epoxy resins A and B show high cured product Tg and low water absorption. Moreover, compared with the comparative example 6 using YH-300, the amount of PCT chlorine extraction is significantly smaller. Similarly, Examples 7 and 8 in which epoxy resins D and E are used show higher cured product Tg and lower water absorption as compared with Comparative Example 7 in which epoxy resin F is used. Further, compared to Comparative Example 8 in which the epoxy resin G was used, the PCT chlorine extraction amount was significantly smaller.
- a cured product having a high Tg and an excellent moisture resistance can be obtained while being excellent in low viscosity.
- Useful resin compositions are obtained, and the technical meaning is significant.
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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)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
A high Tg cured product having a excellent low viscosity and excellent moisture resistance can be obtained by using an epoxy resin composition formed by combining a trimethylolpropane glycidyl ether as an essential component and is characterized in that the ratio of a triglycidyl body in the n = 0 component (a trimethylolpropane glycidyl ether monomer included in a trimethylolpropane polyglycidyl ether) in gas chromatographic analysis is at least 35%, the total amount of chlorine is no more than 0.3%, and the viscosity at 25°C is no more than 300 mPa⋅s. As a result, a cured product can be produced that has excellent heat resistance and moisture resistance sufficient for a normal range of use, and a resin composition is obtained that is useful in the sealing of electric and electronic components such as semiconductor elements, and as a coating material, laminated material, composite material, or the like, which is technically significant.
Description
本発明は、主として半導体封止材用途をはじめとした電気絶縁材料等の電気電子産業用に好適な、低粘度で、有機塩素量が少なく、耐熱性の高い、トリメチロールプロパンのグリシジルエーテルを必須成分として配合してなる樹脂組成物、ならびにその硬化物に関するものである。
The present invention is essential for use in glycidyl ethers of trimethylolpropane which are low in viscosity, low in organic chlorine content, and high in heat resistance, which are suitable mainly for the electric sealing materials such as semiconductor encapsulant applications. The present invention relates to a resin composition blended as a component, and a cured product thereof.
エポキシ樹脂は液状から固形まで様々なものがあり、またエポキシ樹脂は硬化剤との反応性に優れていることから取り扱い易く、硬化剤により架橋させた場合に大きな架橋密度を有する硬化樹脂となり、優れた耐熱性、耐湿性、耐薬品性、電気特性等を示すものであり電気・電子分野に多く使用されている。
エポキシ樹脂は工業的に幅広い用途で使用されてきているが、その要求性能は近年ますます高度化している。例えば、エポキシ樹脂を主剤とする樹脂組成物の代表的分野に半導体封止材料があるが、近年、半導体素子の集積度の向上に伴い、パッケージサイズが大面積化、薄型化に向かうとともに、実装方式も表面実装化への移行が進展しており、より半田耐熱性に優れた材料の開発が望まれている。
また最近では、高集積化、高密度実装化の技術動向により、従来の金型を利用したトランスファー成形によるパッケージに変わり、ハイブリッドＩＣ、チップオンボード、テープキャリアパッケージ、プラスチックピングリッドアレイ、プラスチックボールグリッドアレイ等、金型を使用しないで液状材料を用いて封止し、実装する方式が増えてきている。しかし、一般に液状材料はトランスファー成形に用いる固形材料に比べて信頼性が低い欠点がある。これは、液状材料に粘度の上限があり、用いるエポキシ樹脂、硬化剤、充填剤等に制約があるからである。
これらの問題点を克服するため、主剤となるエポキシ樹脂及び硬化剤には、低粘度化、低吸湿化、高耐熱化が望まれている。低粘度エポキシ樹脂としてはビスフェノールＡ型エポキシ樹脂、ビスフェノールＦ型エポキシ樹脂等が一般に広く知られているが、低粘度性の点で充分ではない。低粘度性に優れるエポキシ樹脂としてアルコール原料のエポキシ樹脂が挙げられるが、一般にアルコール原料のエポキシ樹脂は塩素量が多く、硬化物の耐熱性、吸湿性でも性能が低いのが現状である。そこで低粘度性に優れ、硬化物の耐熱性の高いエポキシ樹脂として、トリメチロールプロパンのエポキシ樹脂が挙げられる。
トリメチロールプロパンのエポキシ樹脂として東都化成社製ＹＨ−３００、ナガセケムテック社製デナコールＥＸ−３１８があるがそれぞれ全塩素量が５％以上と多く、電子材料用途には不向きであった。また末端基純度が低く硬化物のＴｇが低いという問題点があった。 There are various epoxy resins from liquid to solid, and since epoxy resins are excellent in reactivity with the curing agent, they are easy to handle, and when crosslinked by the curing agent, they become cured resins having a large crosslinking density, which is excellent. It exhibits heat resistance, moisture resistance, chemical resistance, electrical properties, etc., and is widely used in the electrical and electronic fields.
Epoxy resins have been used in a wide range of industrial applications, but their performance requirements have become increasingly sophisticated in recent years. For example, there is a semiconductor sealing material in a representative field of resin compositions containing an epoxy resin as a main ingredient, but in recent years, along with the improvement of the degree of integration of semiconductor elements, the package size tends to be larger and thinner. With regard to the method as well, the transition to surface mounting has progressed, and development of a material having more excellent solder heat resistance is desired.
Recently, with the trend of high integration and high density packaging technology, the package has been changed to transfer molding using conventional mold, hybrid IC, chip on board, tape carrier package, plastic pin grid array, plastic ball grid Methods for sealing and mounting using a liquid material without using a mold, such as an array, are increasing. However, liquid materials generally have the disadvantage of being less reliable than solid materials used for transfer molding. This is because the liquid material has an upper limit of viscosity, and there are restrictions on the epoxy resin, curing agent, filler, etc. to be used.
In order to overcome these problems, it is desired to lower the viscosity, reduce the moisture absorption, and increase the heat resistance of the epoxy resin and the curing agent as main components. As a low viscosity epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, etc. are generally widely known, but they are not sufficient in the point of low viscosity. Although epoxy resins having an alcohol raw material are mentioned as epoxy resins excellent in low viscosity, epoxy resins having an alcohol raw material generally contain a large amount of chlorine, and the heat resistance and hygroscopicity of cured products are low at present. Then, the epoxy resin of a trimethylol propane is mentioned as an epoxy resin which is excellent in low viscosity and high heat resistance of hardened | cured material.
There are YH-300 manufactured by Tohto Kasei Co., Ltd. and Denacol EX-318 manufactured by Nagase Chemtech Co., Ltd. as epoxy resins for trimethylolpropane, but the total chlorine content is as large as 5% or more, respectively, which is unsuitable for electronic material applications. In addition, there is a problem that the terminal group purity is low and the Tg of the cured product is low.
エポキシ樹脂は工業的に幅広い用途で使用されてきているが、その要求性能は近年ますます高度化している。例えば、エポキシ樹脂を主剤とする樹脂組成物の代表的分野に半導体封止材料があるが、近年、半導体素子の集積度の向上に伴い、パッケージサイズが大面積化、薄型化に向かうとともに、実装方式も表面実装化への移行が進展しており、より半田耐熱性に優れた材料の開発が望まれている。
また最近では、高集積化、高密度実装化の技術動向により、従来の金型を利用したトランスファー成形によるパッケージに変わり、ハイブリッドＩＣ、チップオンボード、テープキャリアパッケージ、プラスチックピングリッドアレイ、プラスチックボールグリッドアレイ等、金型を使用しないで液状材料を用いて封止し、実装する方式が増えてきている。しかし、一般に液状材料はトランスファー成形に用いる固形材料に比べて信頼性が低い欠点がある。これは、液状材料に粘度の上限があり、用いるエポキシ樹脂、硬化剤、充填剤等に制約があるからである。
これらの問題点を克服するため、主剤となるエポキシ樹脂及び硬化剤には、低粘度化、低吸湿化、高耐熱化が望まれている。低粘度エポキシ樹脂としてはビスフェノールＡ型エポキシ樹脂、ビスフェノールＦ型エポキシ樹脂等が一般に広く知られているが、低粘度性の点で充分ではない。低粘度性に優れるエポキシ樹脂としてアルコール原料のエポキシ樹脂が挙げられるが、一般にアルコール原料のエポキシ樹脂は塩素量が多く、硬化物の耐熱性、吸湿性でも性能が低いのが現状である。そこで低粘度性に優れ、硬化物の耐熱性の高いエポキシ樹脂として、トリメチロールプロパンのエポキシ樹脂が挙げられる。
トリメチロールプロパンのエポキシ樹脂として東都化成社製ＹＨ−３００、ナガセケムテック社製デナコールＥＸ−３１８があるがそれぞれ全塩素量が５％以上と多く、電子材料用途には不向きであった。また末端基純度が低く硬化物のＴｇが低いという問題点があった。 There are various epoxy resins from liquid to solid, and since epoxy resins are excellent in reactivity with the curing agent, they are easy to handle, and when crosslinked by the curing agent, they become cured resins having a large crosslinking density, which is excellent. It exhibits heat resistance, moisture resistance, chemical resistance, electrical properties, etc., and is widely used in the electrical and electronic fields.
Epoxy resins have been used in a wide range of industrial applications, but their performance requirements have become increasingly sophisticated in recent years. For example, there is a semiconductor sealing material in a representative field of resin compositions containing an epoxy resin as a main ingredient, but in recent years, along with the improvement of the degree of integration of semiconductor elements, the package size tends to be larger and thinner. With regard to the method as well, the transition to surface mounting has progressed, and development of a material having more excellent solder heat resistance is desired.
Recently, with the trend of high integration and high density packaging technology, the package has been changed to transfer molding using conventional mold, hybrid IC, chip on board, tape carrier package, plastic pin grid array, plastic ball grid Methods for sealing and mounting using a liquid material without using a mold, such as an array, are increasing. However, liquid materials generally have the disadvantage of being less reliable than solid materials used for transfer molding. This is because the liquid material has an upper limit of viscosity, and there are restrictions on the epoxy resin, curing agent, filler, etc. to be used.
In order to overcome these problems, it is desired to lower the viscosity, reduce the moisture absorption, and increase the heat resistance of the epoxy resin and the curing agent as main components. As a low viscosity epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, etc. are generally widely known, but they are not sufficient in the point of low viscosity. Although epoxy resins having an alcohol raw material are mentioned as epoxy resins excellent in low viscosity, epoxy resins having an alcohol raw material generally contain a large amount of chlorine, and the heat resistance and hygroscopicity of cured products are low at present. Then, the epoxy resin of a trimethylol propane is mentioned as an epoxy resin which is excellent in low viscosity and high heat resistance of hardened | cured material.
There are YH-300 manufactured by Tohto Kasei Co., Ltd. and Denacol EX-318 manufactured by Nagase Chemtech Co., Ltd. as epoxy resins for trimethylolpropane, but the total chlorine content is as large as 5% or more, respectively, which is unsuitable for electronic material applications. In addition, there is a problem that the terminal group purity is low and the Tg of the cured product is low.
本発明の目的は、低粘度で、かつ耐熱性、耐湿性に優れた硬化物を与えるエポキシ樹脂組成物、ならびにその硬化物を提供することである。
An object of the present invention is to provide an epoxy resin composition which gives a cured product having a low viscosity and excellent heat resistance and moisture resistance, as well as a cured product thereof.
すなわち本発明は、トリメチロールプロパンのポリグリシジルエーテルであって、ガスクロマトグラフィー分析におけるｎ＝０成分（トリメチロールプロパンのポリグリシジルエーテルに含有されるトリメチロールプロパングリシジルエーテル単量体）中のトリグリシジル体の比率が３５％以上であり、全塩素量が０．３重量％以下、２５℃での粘度が３００ｍＰａ・ｓ以下であることを特徴とする低粘度エポキシ樹脂を必須成分として配合してなるエポキシ樹脂組成物である。
また、本発明は、前記エポキシ樹脂組成物硬化してなる硬化物である。 That is, the present invention is a polyglycidyl ether of trimethylolpropane, which is triglycidyl in n = 0 component (trimethylolpropane glycidyl ether monomer contained in polyglycidyl ether of trimethylolpropane) in gas chromatography analysis. The low viscosity epoxy resin characterized by having a body ratio of 35% or more, a total chlorine content of 0.3% by weight or less, and a viscosity at 25 ° C. of 300 mPa · s or less is blended as an essential component It is an epoxy resin composition.
Further, the present invention is a cured product obtained by curing the epoxy resin composition.
また、本発明は、前記エポキシ樹脂組成物硬化してなる硬化物である。 That is, the present invention is a polyglycidyl ether of trimethylolpropane, which is triglycidyl in n = 0 component (trimethylolpropane glycidyl ether monomer contained in polyglycidyl ether of trimethylolpropane) in gas chromatography analysis. The low viscosity epoxy resin characterized by having a body ratio of 35% or more, a total chlorine content of 0.3% by weight or less, and a viscosity at 25 ° C. of 300 mPa · s or less is blended as an essential component It is an epoxy resin composition.
Further, the present invention is a cured product obtained by curing the epoxy resin composition.
本発明のエポキシ樹脂を用いたエポキシ樹脂組成物は、優れた低粘度性を有するとともに、これを硬化して得られる硬化物は、耐熱性、耐湿性に優れた性能を有するため、重防食塗料、粉体塗料、ＰＣＭ塗料、缶塗料等の塗料用途や土木・建設用途、接着用途、電気絶縁用、半導体チップ仮止剤等の電気・電子部品用途及びプリント配線板や炭素繊維強化プラスチック（ＣＦＲＰ）を始めとする各種複合材料用途等に適し、特に、プリント配線板、半導体封止等の電気・電子分野の絶縁材料等に好適に使用することができる。
The epoxy resin composition using the epoxy resin of the present invention has excellent low viscosity, and a cured product obtained by curing the same has excellent performance in heat resistance and moisture resistance, so a heavy corrosion protection paint is obtained. , Paint applications such as powder coatings, PCM coatings and can coatings, civil engineering and construction applications, bonding applications, electrical insulation applications, electric and electronic parts applications such as semiconductor chip tacks, printed wiring boards and carbon fiber reinforced plastics (CFRP In particular, it can be suitably used for printed wiring boards, insulating materials in the field of electricity and electronics such as semiconductor encapsulation, and the like.
本発明について詳細に述べる。
本発明に係るトリメチロールプロパングリシジルエーテル（ｎ＝０成分）中には通常、モノグリシジル体、ジグリシジル体、トリグリシジル体が存在するが、本発明でトリグリシジル体比率は３５％以上である。トリグリシジル体比率が３５％以下では硬化物のＴｇ等の物性が低下し、また樹脂粘度が増加する為好ましくない為であり、好ましくは５０％以上、更に好ましくは７５％以上である。
本発明で用いるトリメチロールプロパンのポリグリシジルエーテルは全塩素量が０．３重量％以下で、好ましくは０．２重量％以下である。全塩素量が０．３重量％を超えると塩基性の硬化促進剤を用いた組成物の場合、硬化反応が阻害され、その結果硬化物の物性が低下する。また絶縁信頼性の低下が起こり、電気・電子分野での用途に好ましくない。
本発明で用いるトリメチロールプロパンのポリグリシジルエーテルは２５℃での粘度が３００ｍＰａ・ｓ以下である。２５℃での粘度が３００ｍＰａ・ｓを超えると希釈効率が低下する為好ましくない。
本発明で用いるトリメチロールプロパンのポリグリシジルエーテルは、低粘度性の観点から、ｎ＝０成分の含有率が５０％以上であることが好ましく、より好ましくは７０％以上、更に好ましくは９０％以上である。
トリメチロールプロパンをエピクロルヒドリンと反応させる方法は、通常のエポキシ化反応と同様に行うことができる。例えば、トリメチロールプロパンの水酸基に対して過剰のエピクロルヒドリンを配合し溶解した後、アルカリ金属水酸化物の存在下に、４０~１２０℃の範囲で１~１０時間反応させる方法が挙げられる。この場合、加水分解性塩素低減の観点からは、５０~９０℃で反応を行うことが好ましい。
上記反応において使用されるアルカリ金属水酸化物としては、水酸化リチウム、水酸化ナトリウム、水酸化カリウム、水酸化カルシウム等が挙げられるが、特に水酸化ナトリウム、水酸化カリウムが好ましい。アルカリ類は水溶液であっても固体であっても構わないが、取り扱いの容易さでは水溶液を用いることが好ましい。アルカリ金属水酸化物の使用量は通常アルコール性水酸基１当量に対して０．７~３．０当量であり、好ましくは０．８~２．０当量である。アルカリ金属水酸化物の使用量が多すぎると重合反応や副反応の促進につながり生産性が悪くなる。また、少なすぎるとトリメチロールプロパンとエピクロルヒドリンとの反応が不十分となりグリシジルエーテル化されないクロルヒドリン体が残存する為末端エポキシ基純度が低下する。
また上記エピクロルヒドリンの使用量は、多価アルコールの水酸基１当量に対して１~１０当量、好ましくは２~６当量がよい。エピクロルヒドリンの使用量が１当量より少ないと高分子化が進みやすくなって目的であるクロルヒドリンエーテルの収量が少なくなる。また１０当量より多いと全仕込み量に対する多価アルコール類の割合が少なくなり過ぎて生産性の低下となるため好ましくない。
前記反応を簡便に進行させるため、必要に応じて第四級アンモニウム塩を触媒として添加してもかまわない。用いることのできる第四級アンモニウム塩としては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、ベンジルトリメチルアンモニウムクロライド、ベンジルトリエチルアンモニウムクロライド等が挙げられる。第四級アンモニウム塩の使用量としては使用する多価アルコール類の量に対し通常０．０５~１０重量％であり、好ましくは０．１~１重量％である。
また、反応に際しては、エポキシ基とは反応しない溶媒中で行う事ができ、具体的にはトルエン、キシレン、ベンゼン等の芳香族炭化水素類、メチルイソブチルケトン、メチルエチルケトン、シクロヘキサノン、アセトン等のケトン類、プロパノール、ブタノール等のアルコール類、ジエチレングリコールメチルエーテル、プロピレングリコールメチルエーテル、ジプロピレングリコールメチルエーテル等のグリコールエーテル類、ジエチルエーテル、ジブチルエーテル、エチルプロピルエーテル等の脂肪族エーテル類、ジオキサン、テトラヒドロフラン等の脂環式エーテル類、ジメチルスルホキシド等が挙げられ、それら２種以上混合して使用することもできる。これら溶媒の使用量は、エピハロヒドリン１００重量部に対して、２００重量部以下であり、好ましくは５~１５０重量部の範囲であり、より好ましくは１０~１００重量部の範囲である。
反応の系内水分は０．１％以上２．０％未満である事が好ましい。系内の水分が０．１％より低くなると反応の進行が遅くなる。系内の水分が２．０％以上になると水分の影響によりグリシジルエーテル化反応が阻害され、含有塩素が高くなる為である。
前記反応により生じたグリシジルエーテル類を反応混合物から単離するには、例えば未反応エピクロルヒドリンおよび溶剤を減圧または常圧で留去、有機溶媒に溶解し反応混合物中に副生したアルカリ金属塩および過剰のアルカリ金属水酸化物を水洗、濾過などで分離し、次いで溶解に使用した有機溶媒を回収してグリシジルエーテル類を得る方法などがある。ここで使用する有機溶媒としては、メチルイソブチルケトン、トルエン、キシレン、シクロヘキサノン、メタノール、エタノール、プロパノール、ブタノール等が挙げられるが、なかでもメチルイソブチルケトン、トルエン及びキシレンが好ましく、またこれらの混合溶媒でも良い。
トリメチロールプロパンとエピクロルヒドリンとの反応終了後、過剰のエピハロヒドリンを留去し、溶剤に溶解し、濾過し、水洗して無機塩を除去し、次いで溶剤を留去することにより本発明で用いるトリメチロールプロパンのポリグリシジルエーテルを得ることができるが、加水分解性ハロゲン量が多すぎる場合は、加水分解性ハロゲン量低減の観点から、得られたエポキシ樹脂を更に、残存する加水分解性ハロゲン量に対して、１~３０倍量のアルカリ金属水酸化物を加え、６０~９０℃の温度で１０分~２時間精製反応を行なった後、中和、水洗等の方法で過剰のアルカリ金属水酸化物や副生塩を除去し、さらに溶媒を減圧留去すると、更に精製された本発明で用いるトリメチロールプロパンのポリグリシジルエーテルを得ることができる。また、反応により得られたトリメチロールプロパンのポリグリシジルエーテルを分子蒸留により精製したものを用いることができる。
本発明のエポキシ樹脂組成物は、エポキシ樹脂及び硬化剤を必須成分としてなるエポキシ樹脂組成物であって、エポキシ樹脂成分として請求項１記載のトリメチロールプロパンのポリグリシジルエーテルを必須成分として配合したものである。
請求項１記載のトリメチロールプロパンのポリグリシジルエーテルを必須成分とする場合の硬化剤としては、一般にエポキシ樹脂の硬化剤として知られているものはすべて使用できる。例えば、ジシアンジアミド、多価フェノール類、酸無水物類、芳香族及び脂肪族アミン類等がある。
具体的に例示すれば、多価フェノール類としては、例えば、ビスフェノールＡ、ビスフェノールＦ、ビスフェノールＳ、フルオレンビスフェノール、４，４’−ビフェノール、２，２’−ビフェノール、ハイドロキノン、レゾルシン、ナフタレンジオール等の２価のフェノール類、あるいは、トリス−（４−ヒドロキジフェニル）メタン、１，１，２，２−テトラキス（４−ヒドロキジフェニル）エタン、フェノールノボラック、ｏ−クレゾールノボラック、ナフトールノボラック、ポリビニルフェノール等に代表される３価以上のフェノール類がある。更には、フェノール類、ナフトール類または、ビスフェノールＡ、ビスフェノールＦ、ビスフェノールＳ、フルオレンビスフェノール、４，４’−ビフェノール、２，２’−ビフェノール、ハイドロキノン、レゾルシン、ナフタレンジオール等の２価のフェノール類と、ホルムアルデヒド、アセトアルデヒド、ベンズアルデヒド、ｐ−ヒドロキシベンズアルデヒド、ｐ−キシリレングリコール等の縮合剤とから合成される多価フェノール性化合物等がある。
酸無水物としては、無水フタル酸、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、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、メチル無水ハイミック酸、無水ナジック酸、無水トリメリット酸等がある。
アミン類としては、４，４’−ジアミノジフェニルメタン、４，４’−ジアミノジフェニルプロパン、４，４’−ジアミノジフェニルスルホン、ｍ−フェニレンジアミン、ｐ−キシリレンジアミン等の芳香族アミン類、エチレンジアミン、ヘキサメチレンジアミン、ジエチレントリアミン、トリエチレンテトラミン等の脂肪族アミン類がある。
前記した公知慣用の硬化剤の使用量はエポキシ樹脂の官能基であるエポキシ基１当量に対して硬化剤の官能基０．４~２．０当量が好ましく、０．５~１．５当量がより好ましく、特に好ましくは０．５~１．０当量である。エポキシ基１当量に対して硬化剤が０．４当量に満たない場合、あるいは２．０当量を肥える場合は、硬化が不完全になり良好な硬化物が得られない恐れがある。本発明のエポキシ樹脂組成物には、これら硬化剤の１種または２種以上を混合して用いることができる。
また、本発明のエポキシ樹脂組成物中には、エポキシ樹脂成分として、本発明に関わるトリメチロールプロパンのポリグリシジルエーテル以外に別種のエポキシ樹脂を配合してもよい。この場合のエポキシ樹脂としては、分子中にエポキシ基を２個以上有する通常のエポキシ樹脂はすべて使用できる。例を挙げれば、ビスフェノールＡ、ビスフェノールＳ、フルオレンビスフェノール、４，４’−ビフェノール、２，２’−ビフェノール、ハイドロキノン、レゾルシン等の２価のフェノール類、あるいは、トリス−（４−ヒドロキジフェニル）メタン、１，１，２，２−テトラキス（４−ヒドロキジフェニル）エタン、フェノールノボラック、ｏ−クレゾールノボラック等の３価以上のフェノール類、またはテトラブロモビスフェノールＡ等のハロゲン化ビスフェノール類から誘導されるグリシジルエーテル化物等、ポリエチレングリコールやポリプロピレングリコール等アルコール類のポリグリシジルエーテル類等、ジアミノジフェニルメタン等のポリグリシジルアミン類等、脂環式エポキシ樹脂等がある。これらのエポキシ樹脂は、１種または２種以上を混合して用いることができる。そして、本発明のエポキシ樹脂組成物の場合、本発明に関わるトリメチロールプロパンのポリグリシジルエーテルの配合量はエポキシ樹脂全体中、５~１００％、好ましくは６０~１００％の範囲であることがよい。
また、本発明のエポキシ樹脂組成物中には、ポリエステル、ポリアミド、ポリイミド、ポリエーテル、ポリウレタン、石油樹脂、インデンクマロン樹脂、フェノキシ樹脂等のオリゴマーまたは高分子化合物を適宜配合してもよいし、無機充填剤、顔料、難燃剤、チクソ性付与剤、カップリング剤、流動性向上剤等の添加剤を配合してもよい。無機充填剤としては、例えば、球状あるいは、破砕状の溶融シリカ、結晶シリカ等のシリカ粉末、アルミナ粉末、ガラス粉末、マイカ、タルク、炭酸カルシウム、アルミナまたは水和アルミナ等が挙げられる。顔料としては、有機系または無機系の体質顔料、鱗片状顔料等がある。チクソ性付与剤としては、シリコン系、ヒマシ油系、脂肪族アマイドワックス、酸化ポリエチレンワックス、有機ベントナイト系等を挙げることができる。また更に必要に応じて、本発明の樹脂組成物には、カルナバワックス、ＯＰワックス等の離型剤、γ−グリシドキシプロピルトリメトキシシラン等のカップリング剤、カーボンブラック等の着色剤、三酸化アンチモン等の難燃剤、シリコンオイル等の低応力化剤、ステアリン酸カルシウム等の滑剤等を使用できる。
更に、必要に応じて本発明の樹脂組成物には、公知の硬化促進剤を用いることができる。例を挙げれば、２−メチルイミダゾール、２−エチル−４−メチルイミダゾール等のイミダゾール類、２−メチルイミダゾリン、２−エチル−４−メチルイミダゾリン等のイミダゾリン類、イミダゾール化合物のトリアジン塩、シアノエチル塩、シアノエチルトリメリット酸塩などの各種塩類、酢酸亜鉛、酢酸ナトリウムなどの金属系化合物類、テトラエチルアンモニウムクロリドなどの第４級アンモニウム塩類、アミド化合物類、トリフェニルホスフィン等の有機リン化合物類などを挙げることができる。これら硬化促進剤の配合割合は、本発明のエポキシ樹脂１００質量部に対し、０．０１~５重量部、より好ましくは０．１~２重量部である。
本発明のエポキシ樹脂硬化物は、上記のエポキシ樹脂組成物を加熱することにより得ることができる。硬化物を得るための方法としては注型、注入、ポッティング、ディッピング、ドリップコーティング、トランスファー成形、圧縮成形等が好適に用いられ、その際の温度としては通常、１００℃~３００℃の範囲である。 The invention will be described in detail.
In the trimethylolpropane glycidyl ether (n = 0 component) according to the present invention, monoglycidyl, diglycidyl and triglycidyl are usually present, but in the present invention, the ratio of triglycidyl is 35% or more. If the triglycidyl ratio is 35% or less, the physical properties such as Tg of the cured product decrease, and the resin viscosity increases, which is not preferable, and is preferably 50% or more, more preferably 75% or more.
The polyglycidyl ether of trimethylolpropane used in the present invention has a total chlorine content of 0.3% by weight or less, preferably 0.2% by weight or less. When the total chlorine content exceeds 0.3% by weight, in the case of a composition using a basic curing accelerator, the curing reaction is inhibited, and as a result, the physical properties of the cured product are degraded. In addition, insulation reliability decreases, which is not preferable for applications in the electric and electronic fields.
The polyglycidyl ether of trimethylolpropane used in the present invention has a viscosity of 300 mPa · s or less at 25 ° C. When the viscosity at 25 ° C. exceeds 300 mPa · s, the dilution efficiency decreases, which is not preferable.
From the viewpoint of low viscosity, the content of the n = 0 component is preferably 50% or more, more preferably 70% or more, and still more preferably 90% or more from the viewpoint of low viscosity. It is.
The method of reacting trimethylolpropane with epichlorohydrin can be carried out in the same manner as a conventional epoxidation reaction. For example, after blending and dissolving an excess of epichlorohydrin with respect to the hydroxyl group of trimethylolpropane, a method of reacting in the range of 40 to 120 ° C. for 1 to 10 hours in the presence of an alkali metal hydroxide may be mentioned. In this case, from the viewpoint of reducing hydrolyzable chlorine, it is preferable to carry out the reaction at 50 to 90 ° C.
Examples of the alkali metal hydroxide used in the above reaction include lithium hydroxide, sodium hydroxide, potassium hydroxide, calcium hydroxide and the like, with sodium hydroxide and potassium hydroxide being particularly preferable. The alkali may be an aqueous solution or a solid, but for ease of handling it is preferable to use an aqueous solution. The amount of the alkali metal hydroxide used is usually 0.7 to 3.0 equivalents, preferably 0.8 to 2.0 equivalents, per equivalent of the alcoholic hydroxyl group. If the amount of the alkali metal hydroxide used is too large, the polymerization reaction and side reactions will be promoted, resulting in poor productivity. On the other hand, if the amount is too small, the reaction between trimethylolpropane and epichlorohydrin will be insufficient, and the chlorohydrin body which is not glycidyl-etherified will remain, so that the terminal epoxy group purity is lowered.
The amount of epichlorohydrin used is 1 to 10 equivalents, preferably 2 to 6 equivalents, per equivalent of the hydroxyl group of polyhydric alcohol. When the amount of epichlorohydrin used is less than 1 equivalent, polymerization tends to proceed and the yield of the desired chlorohydrin ether decreases. On the other hand, if the amount is more than 10 equivalents, the ratio of polyhydric alcohols to the total amount charged becomes too small, which is not preferable because the productivity is lowered.
A quaternary ammonium salt may be added as a catalyst as needed to allow the reaction to proceed simply. Examples of quaternary ammonium salts that can be used include tetramethyl ammonium chloride, tetramethyl ammonium bromide, benzyltrimethyl ammonium chloride, benzyltriethyl ammonium chloride and the like. The amount of quaternary ammonium salt used is usually 0.05 to 10% by weight, preferably 0.1 to 1% by weight, based on the amount of polyhydric alcohol used.
The reaction can be carried out in a solvent which does not react with the epoxy group. Specifically, aromatic hydrocarbons such as toluene, xylene and benzene, ketones such as methyl isobutyl ketone, methyl ethyl ketone, cyclohexanone and acetone Alcohols such as propanol and butanol, Glycol ethers such as diethylene glycol methyl ether, propylene glycol methyl ether and dipropylene glycol methyl ether Aliphatic ethers such as diethyl ether, dibutyl ether and ethyl propyl ether Dioxane and tetrahydrofuran Alicyclic ethers, dimethyl sulfoxide and the like can be mentioned, and two or more of them can be used in combination. The amount of these solvents used is 200 parts by weight or less, preferably 5 to 150 parts by weight, and more preferably 10 to 100 parts by weight with respect to 100 parts by weight of epihalohydrin.
The reaction system water content is preferably 0.1% or more and less than 2.0%. When the water content in the system is lower than 0.1%, the reaction proceeds slowly. When the water content in the system is 2.0% or more, the glycidyl etherification reaction is inhibited by the influence of the water, and the contained chlorine becomes high.
In order to isolate the glycidyl ethers produced by the above reaction from the reaction mixture, for example, unreacted epichlorohydrin and the solvent are distilled off under reduced pressure or normal pressure, dissolved in an organic solvent and by-produced alkali metal salt and excess in the reaction mixture These alkali metal hydroxides are separated by washing with water, filtration and the like, and then the organic solvent used for dissolution is recovered to obtain glycidyl ethers. Examples of the organic solvent used herein include methyl isobutyl ketone, toluene, xylene, cyclohexanone, methanol, ethanol, propanol, butanol and the like, among which methyl isobutyl ketone, toluene and xylene are preferable, and a mixed solvent thereof is also preferable. good.
After completion of the reaction between trimethylolpropane and epichlorohydrin, excess epihalohydrin is distilled off, dissolved in a solvent, filtered, washed with water to remove inorganic salts, and then the solvent is distilled off to obtain trimethylol used in the present invention. Although a polyglycidyl ether of propane can be obtained, when the amount of hydrolyzable halogen is too large, the obtained epoxy resin is further added to the amount of remaining hydrolysable halogen from the viewpoint of reducing the amount of hydrolyzable halogen. Then, 1 to 30 times amount of alkali metal hydroxide is added, and purification reaction is carried out at a temperature of 60 to 90 ° C. for 10 minutes to 2 hours, followed by neutralization, washing with water, etc. And by-product salts can be removed, and the solvent can be further distilled off under reduced pressure to obtain further purified polyglycidyl ether of trimethylolpropane used in the present invention. Moreover, what refine | purified the polyglycidyl ether of the trimethylol propane obtained by reaction by molecular distillation can be used.
The epoxy resin composition of the present invention is an epoxy resin composition comprising an epoxy resin and a curing agent as essential components, wherein the polyglycidyl ether of trimethylolpropane according to claim 1 is blended as an epoxy resin component as an essential component. It is.
In the case where the polyglycidyl ether of trimethylolpropane according to claim 1 is an essential component, any of those generally known as curing agents for epoxy resins can be used. For example, dicyandiamide, polyhydric phenols, acid anhydrides, aromatic and aliphatic amines and the like.
Specifically, as polyhydric phenols, for example, bisphenol A, bisphenol F, bisphenol S, fluorene bisphenol, 4,4'-biphenol, 2,2'-biphenol, hydroquinone, resorcinol, naphthalenediol, etc. Dihydric phenols, or tris- (4-hydroxydiphenyl) methane, 1,1,2,2-tetrakis (4-hydroxydiphenyl) ethane, phenol novolac, o-cresol novolac, naphthol novolac, polyvinylphenol etc. There are three or more valent phenols represented. Furthermore, phenols, naphthols, or divalent phenols such as bisphenol A, bisphenol F, bisphenol S, fluorene bisphenol, 4,4'-biphenol, 2,2'-biphenol, hydroquinone, resorcin, naphthalenediol and the like And polyphenolic compounds synthesized from condensing agents such as formaldehyde, acetaldehyde, benzaldehyde, p-hydroxybenzaldehyde and p-xylylene glycol.
Examples of the acid anhydride include phthalic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, methylhymic anhydride, nadic anhydride, trimellitic anhydride and the like.
As amines, aromatic amines such as 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylpropane, 4,4'-diaminodiphenyl sulfone, m-phenylenediamine, p-xylylenediamine, etc., ethylenediamine, There are aliphatic amines such as hexamethylenediamine, diethylenetriamine and triethylenetetramine.
The amount of the known conventional curing agent used is preferably 0.4 to 2.0 equivalents of the functional group of the curing agent to 1 equivalent of the epoxy group which is the functional group of the epoxy resin, and 0.5 to 1.5 equivalents of More preferably, particularly preferably 0.5 to 1.0 equivalents. If the amount of the curing agent is less than 0.4 equivalent to 1 equivalent of epoxy group, or if the equivalent is 2.0 equivalents, curing may be incomplete and a good cured product may not be obtained. In the epoxy resin composition of the present invention, one or more of these curing agents may be mixed and used.
Moreover, in the epoxy resin composition of this invention, you may mix | blend another kind of epoxy resin as an epoxy resin component other than the polyglycidyl ether of the trimethylol propane which concerns on this invention. As the epoxy resin in this case, all common epoxy resins having two or more epoxy groups in the molecule can be used. For example, bifunctional phenols such as bisphenol A, bisphenol S, fluorene bisphenol, 4,4'-biphenol, 2,2'-biphenol, hydroquinone and resorcin, or tris- (4-hydroxydiphenyl) methane Glycidyl derived from trivalent or higher phenols such as 1,1,2,2-tetrakis (4-hydroxydiphenyl) ethane, phenol novolac, o-cresol novolac or halogenated bisphenols such as tetrabromobisphenol A Examples thereof include etherified products, polyglycidyl ethers of alcohols such as polyethylene glycol and polypropylene glycol, polyglycidyl amines such as diaminodiphenylmethane, and alicyclic epoxy resins. These epoxy resins can be used alone or in combination of two or more. And in the case of the epoxy resin composition of the present invention, the blending amount of the polyglycidyl ether of trimethylolpropane according to the present invention is preferably in the range of 5 to 100%, preferably 60 to 100% in the entire epoxy resin. .
Further, in the epoxy resin composition of the present invention, an oligomer or polymer compound such as polyester, polyamide, polyimide, polyether, polyurethane, petroleum resin, indencumarone resin, phenoxy resin and the like may be appropriately blended. You may mix | blend additives, such as an inorganic filler, a pigment, a flame retardant, a thixotropy imparting agent, a coupling agent, and a fluidity improver. Examples of the inorganic filler include spherical or crushed fused silica, silica powder such as crystalline silica, alumina powder, glass powder, mica, talc, calcium carbonate, alumina, hydrated alumina and the like. Examples of the pigment include organic or inorganic extender pigments and scale-like pigments. Examples of the thixotropic agent include silicones, castor oils, aliphatic amide waxes, polyethylene oxide waxes, organic bentonites, and the like. Furthermore, if necessary, in the resin composition of the present invention, mold release agents such as carnauba wax and OP wax, coupling agents such as γ-glycidoxypropyltrimethoxysilane, colorants such as carbon black, and the like Flame retardants such as antimony oxide, stress reducing agents such as silicone oil, lubricants such as calcium stearate may be used.
Furthermore, if necessary, known curing accelerators can be used in the resin composition of the present invention. For example, imidazoles such as 2-methylimidazole, 2-ethyl-4-methylimidazole, imidazolines such as 2-methylimidazoline, 2-ethyl-4-methylimidazoline, triazine salts of imidazole compounds, cyanoethyl salts, Various salts such as cyanoethyl trimellitic acid salt, metal compounds such as zinc acetate and sodium acetate, quaternary ammonium salts such as tetraethyl ammonium chloride, amide compounds, organic phosphorus compounds such as triphenylphosphine and the like. Can. The compounding ratio of these curing accelerators is 0.01 to 5 parts by weight, more preferably 0.1 to 2 parts by weight with respect to 100 parts by weight of the epoxy resin of the present invention.
The epoxy resin cured product of the present invention can be obtained by heating the above-mentioned epoxy resin composition. As a method for obtaining a cured product, casting, pouring, potting, dipping, drip coating, transfer molding, compression molding, etc. are suitably used, and the temperature at that time is usually in the range of 100 ° C. to 300 ° C. .
本発明に係るトリメチロールプロパングリシジルエーテル（ｎ＝０成分）中には通常、モノグリシジル体、ジグリシジル体、トリグリシジル体が存在するが、本発明でトリグリシジル体比率は３５％以上である。トリグリシジル体比率が３５％以下では硬化物のＴｇ等の物性が低下し、また樹脂粘度が増加する為好ましくない為であり、好ましくは５０％以上、更に好ましくは７５％以上である。
本発明で用いるトリメチロールプロパンのポリグリシジルエーテルは全塩素量が０．３重量％以下で、好ましくは０．２重量％以下である。全塩素量が０．３重量％を超えると塩基性の硬化促進剤を用いた組成物の場合、硬化反応が阻害され、その結果硬化物の物性が低下する。また絶縁信頼性の低下が起こり、電気・電子分野での用途に好ましくない。
本発明で用いるトリメチロールプロパンのポリグリシジルエーテルは２５℃での粘度が３００ｍＰａ・ｓ以下である。２５℃での粘度が３００ｍＰａ・ｓを超えると希釈効率が低下する為好ましくない。
本発明で用いるトリメチロールプロパンのポリグリシジルエーテルは、低粘度性の観点から、ｎ＝０成分の含有率が５０％以上であることが好ましく、より好ましくは７０％以上、更に好ましくは９０％以上である。
トリメチロールプロパンをエピクロルヒドリンと反応させる方法は、通常のエポキシ化反応と同様に行うことができる。例えば、トリメチロールプロパンの水酸基に対して過剰のエピクロルヒドリンを配合し溶解した後、アルカリ金属水酸化物の存在下に、４０~１２０℃の範囲で１~１０時間反応させる方法が挙げられる。この場合、加水分解性塩素低減の観点からは、５０~９０℃で反応を行うことが好ましい。
上記反応において使用されるアルカリ金属水酸化物としては、水酸化リチウム、水酸化ナトリウム、水酸化カリウム、水酸化カルシウム等が挙げられるが、特に水酸化ナトリウム、水酸化カリウムが好ましい。アルカリ類は水溶液であっても固体であっても構わないが、取り扱いの容易さでは水溶液を用いることが好ましい。アルカリ金属水酸化物の使用量は通常アルコール性水酸基１当量に対して０．７~３．０当量であり、好ましくは０．８~２．０当量である。アルカリ金属水酸化物の使用量が多すぎると重合反応や副反応の促進につながり生産性が悪くなる。また、少なすぎるとトリメチロールプロパンとエピクロルヒドリンとの反応が不十分となりグリシジルエーテル化されないクロルヒドリン体が残存する為末端エポキシ基純度が低下する。
また上記エピクロルヒドリンの使用量は、多価アルコールの水酸基１当量に対して１~１０当量、好ましくは２~６当量がよい。エピクロルヒドリンの使用量が１当量より少ないと高分子化が進みやすくなって目的であるクロルヒドリンエーテルの収量が少なくなる。また１０当量より多いと全仕込み量に対する多価アルコール類の割合が少なくなり過ぎて生産性の低下となるため好ましくない。
前記反応を簡便に進行させるため、必要に応じて第四級アンモニウム塩を触媒として添加してもかまわない。用いることのできる第四級アンモニウム塩としては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、ベンジルトリメチルアンモニウムクロライド、ベンジルトリエチルアンモニウムクロライド等が挙げられる。第四級アンモニウム塩の使用量としては使用する多価アルコール類の量に対し通常０．０５~１０重量％であり、好ましくは０．１~１重量％である。
また、反応に際しては、エポキシ基とは反応しない溶媒中で行う事ができ、具体的にはトルエン、キシレン、ベンゼン等の芳香族炭化水素類、メチルイソブチルケトン、メチルエチルケトン、シクロヘキサノン、アセトン等のケトン類、プロパノール、ブタノール等のアルコール類、ジエチレングリコールメチルエーテル、プロピレングリコールメチルエーテル、ジプロピレングリコールメチルエーテル等のグリコールエーテル類、ジエチルエーテル、ジブチルエーテル、エチルプロピルエーテル等の脂肪族エーテル類、ジオキサン、テトラヒドロフラン等の脂環式エーテル類、ジメチルスルホキシド等が挙げられ、それら２種以上混合して使用することもできる。これら溶媒の使用量は、エピハロヒドリン１００重量部に対して、２００重量部以下であり、好ましくは５~１５０重量部の範囲であり、より好ましくは１０~１００重量部の範囲である。
反応の系内水分は０．１％以上２．０％未満である事が好ましい。系内の水分が０．１％より低くなると反応の進行が遅くなる。系内の水分が２．０％以上になると水分の影響によりグリシジルエーテル化反応が阻害され、含有塩素が高くなる為である。
前記反応により生じたグリシジルエーテル類を反応混合物から単離するには、例えば未反応エピクロルヒドリンおよび溶剤を減圧または常圧で留去、有機溶媒に溶解し反応混合物中に副生したアルカリ金属塩および過剰のアルカリ金属水酸化物を水洗、濾過などで分離し、次いで溶解に使用した有機溶媒を回収してグリシジルエーテル類を得る方法などがある。ここで使用する有機溶媒としては、メチルイソブチルケトン、トルエン、キシレン、シクロヘキサノン、メタノール、エタノール、プロパノール、ブタノール等が挙げられるが、なかでもメチルイソブチルケトン、トルエン及びキシレンが好ましく、またこれらの混合溶媒でも良い。
トリメチロールプロパンとエピクロルヒドリンとの反応終了後、過剰のエピハロヒドリンを留去し、溶剤に溶解し、濾過し、水洗して無機塩を除去し、次いで溶剤を留去することにより本発明で用いるトリメチロールプロパンのポリグリシジルエーテルを得ることができるが、加水分解性ハロゲン量が多すぎる場合は、加水分解性ハロゲン量低減の観点から、得られたエポキシ樹脂を更に、残存する加水分解性ハロゲン量に対して、１~３０倍量のアルカリ金属水酸化物を加え、６０~９０℃の温度で１０分~２時間精製反応を行なった後、中和、水洗等の方法で過剰のアルカリ金属水酸化物や副生塩を除去し、さらに溶媒を減圧留去すると、更に精製された本発明で用いるトリメチロールプロパンのポリグリシジルエーテルを得ることができる。また、反応により得られたトリメチロールプロパンのポリグリシジルエーテルを分子蒸留により精製したものを用いることができる。
本発明のエポキシ樹脂組成物は、エポキシ樹脂及び硬化剤を必須成分としてなるエポキシ樹脂組成物であって、エポキシ樹脂成分として請求項１記載のトリメチロールプロパンのポリグリシジルエーテルを必須成分として配合したものである。
請求項１記載のトリメチロールプロパンのポリグリシジルエーテルを必須成分とする場合の硬化剤としては、一般にエポキシ樹脂の硬化剤として知られているものはすべて使用できる。例えば、ジシアンジアミド、多価フェノール類、酸無水物類、芳香族及び脂肪族アミン類等がある。
具体的に例示すれば、多価フェノール類としては、例えば、ビスフェノールＡ、ビスフェノールＦ、ビスフェノールＳ、フルオレンビスフェノール、４，４’−ビフェノール、２，２’−ビフェノール、ハイドロキノン、レゾルシン、ナフタレンジオール等の２価のフェノール類、あるいは、トリス−（４−ヒドロキジフェニル）メタン、１，１，２，２−テトラキス（４−ヒドロキジフェニル）エタン、フェノールノボラック、ｏ−クレゾールノボラック、ナフトールノボラック、ポリビニルフェノール等に代表される３価以上のフェノール類がある。更には、フェノール類、ナフトール類または、ビスフェノールＡ、ビスフェノールＦ、ビスフェノールＳ、フルオレンビスフェノール、４，４’−ビフェノール、２，２’−ビフェノール、ハイドロキノン、レゾルシン、ナフタレンジオール等の２価のフェノール類と、ホルムアルデヒド、アセトアルデヒド、ベンズアルデヒド、ｐ−ヒドロキシベンズアルデヒド、ｐ−キシリレングリコール等の縮合剤とから合成される多価フェノール性化合物等がある。
酸無水物としては、無水フタル酸、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、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、メチル無水ハイミック酸、無水ナジック酸、無水トリメリット酸等がある。
アミン類としては、４，４’−ジアミノジフェニルメタン、４，４’−ジアミノジフェニルプロパン、４，４’−ジアミノジフェニルスルホン、ｍ−フェニレンジアミン、ｐ−キシリレンジアミン等の芳香族アミン類、エチレンジアミン、ヘキサメチレンジアミン、ジエチレントリアミン、トリエチレンテトラミン等の脂肪族アミン類がある。
前記した公知慣用の硬化剤の使用量はエポキシ樹脂の官能基であるエポキシ基１当量に対して硬化剤の官能基０．４~２．０当量が好ましく、０．５~１．５当量がより好ましく、特に好ましくは０．５~１．０当量である。エポキシ基１当量に対して硬化剤が０．４当量に満たない場合、あるいは２．０当量を肥える場合は、硬化が不完全になり良好な硬化物が得られない恐れがある。本発明のエポキシ樹脂組成物には、これら硬化剤の１種または２種以上を混合して用いることができる。
また、本発明のエポキシ樹脂組成物中には、エポキシ樹脂成分として、本発明に関わるトリメチロールプロパンのポリグリシジルエーテル以外に別種のエポキシ樹脂を配合してもよい。この場合のエポキシ樹脂としては、分子中にエポキシ基を２個以上有する通常のエポキシ樹脂はすべて使用できる。例を挙げれば、ビスフェノールＡ、ビスフェノールＳ、フルオレンビスフェノール、４，４’−ビフェノール、２，２’−ビフェノール、ハイドロキノン、レゾルシン等の２価のフェノール類、あるいは、トリス−（４−ヒドロキジフェニル）メタン、１，１，２，２−テトラキス（４−ヒドロキジフェニル）エタン、フェノールノボラック、ｏ−クレゾールノボラック等の３価以上のフェノール類、またはテトラブロモビスフェノールＡ等のハロゲン化ビスフェノール類から誘導されるグリシジルエーテル化物等、ポリエチレングリコールやポリプロピレングリコール等アルコール類のポリグリシジルエーテル類等、ジアミノジフェニルメタン等のポリグリシジルアミン類等、脂環式エポキシ樹脂等がある。これらのエポキシ樹脂は、１種または２種以上を混合して用いることができる。そして、本発明のエポキシ樹脂組成物の場合、本発明に関わるトリメチロールプロパンのポリグリシジルエーテルの配合量はエポキシ樹脂全体中、５~１００％、好ましくは６０~１００％の範囲であることがよい。
また、本発明のエポキシ樹脂組成物中には、ポリエステル、ポリアミド、ポリイミド、ポリエーテル、ポリウレタン、石油樹脂、インデンクマロン樹脂、フェノキシ樹脂等のオリゴマーまたは高分子化合物を適宜配合してもよいし、無機充填剤、顔料、難燃剤、チクソ性付与剤、カップリング剤、流動性向上剤等の添加剤を配合してもよい。無機充填剤としては、例えば、球状あるいは、破砕状の溶融シリカ、結晶シリカ等のシリカ粉末、アルミナ粉末、ガラス粉末、マイカ、タルク、炭酸カルシウム、アルミナまたは水和アルミナ等が挙げられる。顔料としては、有機系または無機系の体質顔料、鱗片状顔料等がある。チクソ性付与剤としては、シリコン系、ヒマシ油系、脂肪族アマイドワックス、酸化ポリエチレンワックス、有機ベントナイト系等を挙げることができる。また更に必要に応じて、本発明の樹脂組成物には、カルナバワックス、ＯＰワックス等の離型剤、γ−グリシドキシプロピルトリメトキシシラン等のカップリング剤、カーボンブラック等の着色剤、三酸化アンチモン等の難燃剤、シリコンオイル等の低応力化剤、ステアリン酸カルシウム等の滑剤等を使用できる。
更に、必要に応じて本発明の樹脂組成物には、公知の硬化促進剤を用いることができる。例を挙げれば、２−メチルイミダゾール、２−エチル−４−メチルイミダゾール等のイミダゾール類、２−メチルイミダゾリン、２−エチル−４−メチルイミダゾリン等のイミダゾリン類、イミダゾール化合物のトリアジン塩、シアノエチル塩、シアノエチルトリメリット酸塩などの各種塩類、酢酸亜鉛、酢酸ナトリウムなどの金属系化合物類、テトラエチルアンモニウムクロリドなどの第４級アンモニウム塩類、アミド化合物類、トリフェニルホスフィン等の有機リン化合物類などを挙げることができる。これら硬化促進剤の配合割合は、本発明のエポキシ樹脂１００質量部に対し、０．０１~５重量部、より好ましくは０．１~２重量部である。
本発明のエポキシ樹脂硬化物は、上記のエポキシ樹脂組成物を加熱することにより得ることができる。硬化物を得るための方法としては注型、注入、ポッティング、ディッピング、ドリップコーティング、トランスファー成形、圧縮成形等が好適に用いられ、その際の温度としては通常、１００℃~３００℃の範囲である。 The invention will be described in detail.
In the trimethylolpropane glycidyl ether (n = 0 component) according to the present invention, monoglycidyl, diglycidyl and triglycidyl are usually present, but in the present invention, the ratio of triglycidyl is 35% or more. If the triglycidyl ratio is 35% or less, the physical properties such as Tg of the cured product decrease, and the resin viscosity increases, which is not preferable, and is preferably 50% or more, more preferably 75% or more.
The polyglycidyl ether of trimethylolpropane used in the present invention has a total chlorine content of 0.3% by weight or less, preferably 0.2% by weight or less. When the total chlorine content exceeds 0.3% by weight, in the case of a composition using a basic curing accelerator, the curing reaction is inhibited, and as a result, the physical properties of the cured product are degraded. In addition, insulation reliability decreases, which is not preferable for applications in the electric and electronic fields.
The polyglycidyl ether of trimethylolpropane used in the present invention has a viscosity of 300 mPa · s or less at 25 ° C. When the viscosity at 25 ° C. exceeds 300 mPa · s, the dilution efficiency decreases, which is not preferable.
From the viewpoint of low viscosity, the content of the n = 0 component is preferably 50% or more, more preferably 70% or more, and still more preferably 90% or more from the viewpoint of low viscosity. It is.
The method of reacting trimethylolpropane with epichlorohydrin can be carried out in the same manner as a conventional epoxidation reaction. For example, after blending and dissolving an excess of epichlorohydrin with respect to the hydroxyl group of trimethylolpropane, a method of reacting in the range of 40 to 120 ° C. for 1 to 10 hours in the presence of an alkali metal hydroxide may be mentioned. In this case, from the viewpoint of reducing hydrolyzable chlorine, it is preferable to carry out the reaction at 50 to 90 ° C.
Examples of the alkali metal hydroxide used in the above reaction include lithium hydroxide, sodium hydroxide, potassium hydroxide, calcium hydroxide and the like, with sodium hydroxide and potassium hydroxide being particularly preferable. The alkali may be an aqueous solution or a solid, but for ease of handling it is preferable to use an aqueous solution. The amount of the alkali metal hydroxide used is usually 0.7 to 3.0 equivalents, preferably 0.8 to 2.0 equivalents, per equivalent of the alcoholic hydroxyl group. If the amount of the alkali metal hydroxide used is too large, the polymerization reaction and side reactions will be promoted, resulting in poor productivity. On the other hand, if the amount is too small, the reaction between trimethylolpropane and epichlorohydrin will be insufficient, and the chlorohydrin body which is not glycidyl-etherified will remain, so that the terminal epoxy group purity is lowered.
The amount of epichlorohydrin used is 1 to 10 equivalents, preferably 2 to 6 equivalents, per equivalent of the hydroxyl group of polyhydric alcohol. When the amount of epichlorohydrin used is less than 1 equivalent, polymerization tends to proceed and the yield of the desired chlorohydrin ether decreases. On the other hand, if the amount is more than 10 equivalents, the ratio of polyhydric alcohols to the total amount charged becomes too small, which is not preferable because the productivity is lowered.
A quaternary ammonium salt may be added as a catalyst as needed to allow the reaction to proceed simply. Examples of quaternary ammonium salts that can be used include tetramethyl ammonium chloride, tetramethyl ammonium bromide, benzyltrimethyl ammonium chloride, benzyltriethyl ammonium chloride and the like. The amount of quaternary ammonium salt used is usually 0.05 to 10% by weight, preferably 0.1 to 1% by weight, based on the amount of polyhydric alcohol used.
The reaction can be carried out in a solvent which does not react with the epoxy group. Specifically, aromatic hydrocarbons such as toluene, xylene and benzene, ketones such as methyl isobutyl ketone, methyl ethyl ketone, cyclohexanone and acetone Alcohols such as propanol and butanol, Glycol ethers such as diethylene glycol methyl ether, propylene glycol methyl ether and dipropylene glycol methyl ether Aliphatic ethers such as diethyl ether, dibutyl ether and ethyl propyl ether Dioxane and tetrahydrofuran Alicyclic ethers, dimethyl sulfoxide and the like can be mentioned, and two or more of them can be used in combination. The amount of these solvents used is 200 parts by weight or less, preferably 5 to 150 parts by weight, and more preferably 10 to 100 parts by weight with respect to 100 parts by weight of epihalohydrin.
The reaction system water content is preferably 0.1% or more and less than 2.0%. When the water content in the system is lower than 0.1%, the reaction proceeds slowly. When the water content in the system is 2.0% or more, the glycidyl etherification reaction is inhibited by the influence of the water, and the contained chlorine becomes high.
In order to isolate the glycidyl ethers produced by the above reaction from the reaction mixture, for example, unreacted epichlorohydrin and the solvent are distilled off under reduced pressure or normal pressure, dissolved in an organic solvent and by-produced alkali metal salt and excess in the reaction mixture These alkali metal hydroxides are separated by washing with water, filtration and the like, and then the organic solvent used for dissolution is recovered to obtain glycidyl ethers. Examples of the organic solvent used herein include methyl isobutyl ketone, toluene, xylene, cyclohexanone, methanol, ethanol, propanol, butanol and the like, among which methyl isobutyl ketone, toluene and xylene are preferable, and a mixed solvent thereof is also preferable. good.
After completion of the reaction between trimethylolpropane and epichlorohydrin, excess epihalohydrin is distilled off, dissolved in a solvent, filtered, washed with water to remove inorganic salts, and then the solvent is distilled off to obtain trimethylol used in the present invention. Although a polyglycidyl ether of propane can be obtained, when the amount of hydrolyzable halogen is too large, the obtained epoxy resin is further added to the amount of remaining hydrolysable halogen from the viewpoint of reducing the amount of hydrolyzable halogen. Then, 1 to 30 times amount of alkali metal hydroxide is added, and purification reaction is carried out at a temperature of 60 to 90 ° C. for 10 minutes to 2 hours, followed by neutralization, washing with water, etc. And by-product salts can be removed, and the solvent can be further distilled off under reduced pressure to obtain further purified polyglycidyl ether of trimethylolpropane used in the present invention. Moreover, what refine | purified the polyglycidyl ether of the trimethylol propane obtained by reaction by molecular distillation can be used.
The epoxy resin composition of the present invention is an epoxy resin composition comprising an epoxy resin and a curing agent as essential components, wherein the polyglycidyl ether of trimethylolpropane according to claim 1 is blended as an epoxy resin component as an essential component. It is.
In the case where the polyglycidyl ether of trimethylolpropane according to claim 1 is an essential component, any of those generally known as curing agents for epoxy resins can be used. For example, dicyandiamide, polyhydric phenols, acid anhydrides, aromatic and aliphatic amines and the like.
Specifically, as polyhydric phenols, for example, bisphenol A, bisphenol F, bisphenol S, fluorene bisphenol, 4,4'-biphenol, 2,2'-biphenol, hydroquinone, resorcinol, naphthalenediol, etc. Dihydric phenols, or tris- (4-hydroxydiphenyl) methane, 1,1,2,2-tetrakis (4-hydroxydiphenyl) ethane, phenol novolac, o-cresol novolac, naphthol novolac, polyvinylphenol etc. There are three or more valent phenols represented. Furthermore, phenols, naphthols, or divalent phenols such as bisphenol A, bisphenol F, bisphenol S, fluorene bisphenol, 4,4'-biphenol, 2,2'-biphenol, hydroquinone, resorcin, naphthalenediol and the like And polyphenolic compounds synthesized from condensing agents such as formaldehyde, acetaldehyde, benzaldehyde, p-hydroxybenzaldehyde and p-xylylene glycol.
Examples of the acid anhydride include phthalic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, methylhymic anhydride, nadic anhydride, trimellitic anhydride and the like.
As amines, aromatic amines such as 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylpropane, 4,4'-diaminodiphenyl sulfone, m-phenylenediamine, p-xylylenediamine, etc., ethylenediamine, There are aliphatic amines such as hexamethylenediamine, diethylenetriamine and triethylenetetramine.
The amount of the known conventional curing agent used is preferably 0.4 to 2.0 equivalents of the functional group of the curing agent to 1 equivalent of the epoxy group which is the functional group of the epoxy resin, and 0.5 to 1.5 equivalents of More preferably, particularly preferably 0.5 to 1.0 equivalents. If the amount of the curing agent is less than 0.4 equivalent to 1 equivalent of epoxy group, or if the equivalent is 2.0 equivalents, curing may be incomplete and a good cured product may not be obtained. In the epoxy resin composition of the present invention, one or more of these curing agents may be mixed and used.
Moreover, in the epoxy resin composition of this invention, you may mix | blend another kind of epoxy resin as an epoxy resin component other than the polyglycidyl ether of the trimethylol propane which concerns on this invention. As the epoxy resin in this case, all common epoxy resins having two or more epoxy groups in the molecule can be used. For example, bifunctional phenols such as bisphenol A, bisphenol S, fluorene bisphenol, 4,4'-biphenol, 2,2'-biphenol, hydroquinone and resorcin, or tris- (4-hydroxydiphenyl) methane Glycidyl derived from trivalent or higher phenols such as 1,1,2,2-tetrakis (4-hydroxydiphenyl) ethane, phenol novolac, o-cresol novolac or halogenated bisphenols such as tetrabromobisphenol A Examples thereof include etherified products, polyglycidyl ethers of alcohols such as polyethylene glycol and polypropylene glycol, polyglycidyl amines such as diaminodiphenylmethane, and alicyclic epoxy resins. These epoxy resins can be used alone or in combination of two or more. And in the case of the epoxy resin composition of the present invention, the blending amount of the polyglycidyl ether of trimethylolpropane according to the present invention is preferably in the range of 5 to 100%, preferably 60 to 100% in the entire epoxy resin. .
Further, in the epoxy resin composition of the present invention, an oligomer or polymer compound such as polyester, polyamide, polyimide, polyether, polyurethane, petroleum resin, indencumarone resin, phenoxy resin and the like may be appropriately blended. You may mix | blend additives, such as an inorganic filler, a pigment, a flame retardant, a thixotropy imparting agent, a coupling agent, and a fluidity improver. Examples of the inorganic filler include spherical or crushed fused silica, silica powder such as crystalline silica, alumina powder, glass powder, mica, talc, calcium carbonate, alumina, hydrated alumina and the like. Examples of the pigment include organic or inorganic extender pigments and scale-like pigments. Examples of the thixotropic agent include silicones, castor oils, aliphatic amide waxes, polyethylene oxide waxes, organic bentonites, and the like. Furthermore, if necessary, in the resin composition of the present invention, mold release agents such as carnauba wax and OP wax, coupling agents such as γ-glycidoxypropyltrimethoxysilane, colorants such as carbon black, and the like Flame retardants such as antimony oxide, stress reducing agents such as silicone oil, lubricants such as calcium stearate may be used.
Furthermore, if necessary, known curing accelerators can be used in the resin composition of the present invention. For example, imidazoles such as 2-methylimidazole, 2-ethyl-4-methylimidazole, imidazolines such as 2-methylimidazoline, 2-ethyl-4-methylimidazoline, triazine salts of imidazole compounds, cyanoethyl salts, Various salts such as cyanoethyl trimellitic acid salt, metal compounds such as zinc acetate and sodium acetate, quaternary ammonium salts such as tetraethyl ammonium chloride, amide compounds, organic phosphorus compounds such as triphenylphosphine and the like. Can. The compounding ratio of these curing accelerators is 0.01 to 5 parts by weight, more preferably 0.1 to 2 parts by weight with respect to 100 parts by weight of the epoxy resin of the present invention.
The epoxy resin cured product of the present invention can be obtained by heating the above-mentioned epoxy resin composition. As a method for obtaining a cured product, casting, pouring, potting, dipping, drip coating, transfer molding, compression molding, etc. are suitably used, and the temperature at that time is usually in the range of 100 ° C. to 300 ° C. .
以下に本発明の実施例および比較例を挙げ詳細に説明する。本発明はこれらの実施例に限定されるものではない。なお例中の部は質量部、％は質量％を意味する。また、物性値は次の方法により測定した。
エポキシ当量はＪＩＳ Ｋ ７２３６の規定に従い測定した。
全塩素量はＪＩＳ Ｋ ７２４３−３の規定に従い測定した。
粘度は、ＪＩＳ Ｋ−７２３３、単一円筒回転粘度計法により測定した。
ガスクロマトグラフィー測定は、以下の条件で測定した。
モノ、ジ、トリグリシジル体の含有量はそれぞれガスクロマトグラフィー分析の結果得られるピークの面積％を表す。
装置 ：島津製作所社製「ＧＣ−１４Ｂ」
カラム ：ガラス製パックドカラム 長さ１．１ｍ、直径３．２ｍｍ
充填剤 ：ｓｉｌｉｃｏｎｅ ＯＶ−１７
担体 ：ｃｈｒｏｍｏｓｏｒｂ Ｗ ＡＷ−ＤＭＣＳ
フローコントローラー：水素５０ｋＰａ、空気５０ｋＰａ、キャリア５０ｋＰａ、プライマリ４００ｋＰａ
カラム流量 ：５０ｍｌ／ｍｉｎ
ＩＮＪＥＣＴＩＯＮ温度：２８０℃、ＦＩＤ温度：３２０℃、カラム温度：１６０℃×２ｍｉｎ、昇温速度：２０℃／ｍｉｎ、最終カラム温度：３００℃×５ｍｉｎ
サンプル ：５ｗｔ％アセトン溶液
注入量 ：２μＬ
ＧＰＣ測定は、以下の条件で測定した。ｎ＝０含有量はＧＰＣ分析の結果得られるピークの面積％を表す。
機器 ：東ソー株式会社ＧＰＣ８２２０
分離カラム：ＴＳＫｇｅｌ Ｇ２０００ＨＸＬ，ＴＳＫｇｅｌ Ｇ２０００ＨＸＬ，ＴＳＫｇｅｌ Ｇ１０００ＨＸＬを直列で連結
カラム温 ：４０℃
溶離液 ：テトラヒドロフランを１ｍｌ／ｍｉｎの流速
検出器 ：ＲＩ検出器
実施例１
撹拌噐、温度計、窒素ガス導入装置、滴下装置、冷却管及び油水分離装置を備えた内容量１Ｌのガラスフラスコにトリメチロールプロパン（ＴＭＰ）９０部、エピクロルヒドリン６５２部、ジエチレングリコールジメチルエーテル６５．２部、水６．５部を仕込みを仕込み、窒素ガスを流しながら６０℃まで加熱して溶解した。６０℃迄昇温後、９９％水酸化ナトリウム７７．３部を投入し同温度で６時間反応を行った。濾過により生成した塩を除き、エピクロロヒドリンを留去し、トルエン５００部に溶解した。８０℃迄昇温後、４９．１％水酸化ナトリウム水溶液０．３２部および温水１．２５部を加えて同温度で１時間精製反応を実施した。その後温水２５部を加えて攪拌、分液し樹脂溶液を脱水濾過、トルエンを蒸留して除去して、１６４．２ｇのエポキシ樹脂を得た。この樹脂のエポキシ当量は１２８ｇ／ｅｑ、粘度１５０ｍＰａ・ｓ／２５℃、全塩素０．２３％、ＧＰＣによるｎ＝０純度は５８％、ガスクロマトグラフィーによるｎ＝０成分のモノグリシジル体（１ＧＥ）：ジグリシジル体（２ＧＥ）：トリグリシジル体（３ＧＥ）比率は０：６０：４０であった。得られた樹脂の性状を表１に記載した。
実施例２
９９％水酸化ナトリウムを７７．３部から１１６．０部に変更した以外は、実施例１と同様の操作を行い１５４．５ｇのエポキシ樹脂を得た。この樹脂のエポキシ当量は１２５ｇ／ｅｑ、全塩素量は０．２５％、ＧＰＣによるｎ＝０純度は５０％、ガスクロマトグラフィーによるｎ＝０成分のモノ：ジ：トリグリシジル体比率は０：３８：６２であった。得られた樹脂の性状を表１に記載した。
比較例１
水６．５部を０．６５部に変更した以外は、実施例１と同様の操作を行い１４８．２ｇのエポキシ樹脂を得た。この樹脂のエポキシ当量は１３５ｇ／ｅｑ、全塩素量は０．２５％、ＧＰＣによるｎ＝０純度は５０％、ガスクロマトグラフィーによるｎ＝０成分のモノ：ジ：トリグリシジル体比率は０：７５：２５であった。得られた樹脂の性状を表１に記載した。
比較例２
東都化成社製ＹＨ−３００（トリメチロールプロパングリシジルエーテル）。ＹＨ−３００のエポキシ当量は１４２ｇ／ｅｑ、粘度１４７ｍＰａ・ｓ／２５℃、全塩素５．０％、ＧＰＣによるｎ＝０純度は２９％、 ガスクロマトグラフィーによるｎ＝０成分のモノ：ジ：トリグリシジル体比率は０：８１：１９であった。樹脂の性状を表１に記載した。
実施例３
実施例１で得られたエポキシ樹脂（以下エポキシ樹脂Ａ）をフィンテック社製 薄膜分子蒸留機ＫＤＬ−４を使用して、圧力０．３ｐａ、温度１２５~１３５℃で分子蒸留を行いエポキシ樹脂Ｄを得た。得られた樹脂の性状を表２に記載した。
実施例４
実施例２で得られたエポキシ樹脂（以下エポキシ樹脂Ｂ）を実施例３と同様に分子蒸留を行こないエポキシ樹脂Ｅを得た。得られた樹脂の性状を表２に記載した。
比較例３
実施例１で得られたエポキシ樹脂（以下エポキシ樹脂Ｃ）を実施例３と同様に分子蒸留を行こないエポキシ樹脂Ｆを得た。得られた樹脂の性状を表２に記載した。
比較例４
東都化成社製ＹＨ−３００を実施例３と同様に分子蒸留を行こないエポキシ樹脂Ｇを得た。得られた樹脂の性状を表２に記載した。
実施例５、６比較例５，６実施例７、８比較例７，８
エポキシ樹脂成分として、東都化成社製ＹＤ−８１２５を１００重量部に対してエポキシ樹脂Ａ~エポキシ樹脂Ｇ、ＹＨ−３００を混合粘度が１０００ｍＰａ・ｓ／２５℃になるような割合で配合した。硬化剤として、リカシッドＭＨ−７００（無水メチルヘキサヒドロフタル酸、酸無水物当量１６８ｇ／ｅｑ、新日本理化製）、硬化促進剤として、ヒシコーリンＰＸ−４ＥＴ（有機ホスホニウム塩化合物、日本化学製）を用い、表３に示す配合でエポキシ樹脂組成物を得た。なお、表中の数値は配合における重量部を示す。
このエポキシ樹脂組成物を用いて１００℃で２時間かけて成形し、更に１４０℃にて１２時間ポストキュアを行い、硬化物試験片を得た後、各種物性測定に供した。結果を表３に示す。
なお、硬化物性の試験方法及び評価方法は以下の通りである。
（１）硬化物Ｔｇは、熱機械測定装置（セイコー電子社製）を用いて１０℃／分の昇温速度で測定した。
（２）吸水率は、直径５０ｍｍ、厚さ５ｍｍの円形の試験片を用いて、２３℃、１００％ＲＨの条件で５０時間吸湿させた後の重量増加変化率とした。
（３）イオン性不純物量は、１０５℃、２０時間のプレッシャークッカーテストを行った後の抽出イオン分をイオンクロマトグラフィーにて、塩素イオンを測定し、固形分に換算して求めた。
エポキシ樹脂Ａ、Ｂを用いた実施例５、６はエポキシ樹脂Ｃを用いた比較例５に比較して高い硬化物Ｔｇと低い吸水率を示す。またＹＨ−３００を用いた比較例６に比較してＰＣＴ塩素抽出量が大幅に少ない。
同様に、エポキシ樹脂Ｄ、Ｅを用いた実施例７、８はエポキシ樹脂Ｆを用いた比較例７に比較して高い硬化物Ｔｇと低い吸水率を示す。またエポキシ樹脂Ｇを用いた比較例８に比較してＰＣＴ塩素抽出量が大幅に少ない。
Hereinafter, Examples and Comparative Examples of the present invention will be described in detail. The present invention is not limited to these examples. In the examples, "part" means "mass part" and "%" means mass%. The physical property values were measured by the following methods.
The epoxy equivalent was measured in accordance with JIS K 7236.
The total chlorine content was measured in accordance with JIS K 7243-3.
The viscosity was measured by a single cylindrical rotational viscometer method according to JIS K-7233.
Gas chromatography was measured under the following conditions.
The contents of mono-, di- and triglycidyl forms each represent the area% of the peak obtained as a result of gas chromatography analysis.
Device: "GC-14B" manufactured by Shimadzu Corporation
Column: Glass packed column 1.1 m in length, 3.2 mm in diameter
Filler: silicone OV-17
Carrier: chromosorb W AW-DMCS
Flow controller: Hydrogen 50kPa, air 50kPa, carrier 50kPa, primary 400kPa
Column flow rate: 50 ml / min
INJECTION temperature: 280 ° C., FID temperature: 320 ° C., column temperature: 160 ° C. × 2 min, temperature rising rate: 20 ° C./min, final column temperature: 300 ° C. × 5 min
Sample: Injection amount of 5wt% acetone solution: 2μL
GPC measurement was performed under the following conditions. n = 0 content represents the area% of the peak obtained as a result of GPC analysis.
Equipment: Tosoh Corporation GPC8220
Separation column: TSKgel G2000HXL, TSKgel G2000HXL, TSKgel G1000HXL connected in series Column temperature: 40 ° C
Eluent: Tetrahydrofuran at 1 ml / min flow rate detector: RI detector Example 1
90 parts of trimethylolpropane (TMP), 652 parts of epichlorohydrin, 65.2 parts of diethylene glycol dimethyl ether in a 1-L glass flask equipped with a stirrer, thermometer, nitrogen gas introduction device, dropping device, cooling pipe and oil / water separation device 6.5 parts of water was charged and dissolved by heating to 60 ° C. while flowing nitrogen gas. After raising the temperature to 60 ° C., 77.3 parts of 99% sodium hydroxide was added, and the reaction was carried out at the same temperature for 6 hours. The salt formed by filtration was removed, and epichlorohydrin was distilled off and dissolved in 500 parts of toluene. After raising the temperature to 80 ° C., 0.32 parts of a 49.1% aqueous sodium hydroxide solution and 1.25 parts of hot water were added, and a purification reaction was carried out at the same temperature for 1 hour. Thereafter, 25 parts of hot water was added, and the mixture was stirred and separated, and the resin solution was subjected to dehydration filtration and toluene removal by distillation to obtain 164.2 g of an epoxy resin. The epoxy equivalent of this resin is 128 g / eq, viscosity 150 mPa · s / 25 ° C, total chlorine 0.23%, n = 0 purity by GPC 58%, n = 0 monoglycidyl form (1 GE) by gas chromatography The ratio of diglycidyl body (2GE): triglycidyl body (3GE) was 0:60:40. The properties of the obtained resin are described in Table 1.
Example 2
The same operation as in Example 1 was carried out except that the amount of 99% sodium hydroxide was changed from 77.3 parts to 116.0 parts, to obtain 154.5 g of an epoxy resin. The epoxy equivalent of this resin is 125 g / eq, the total chlorine content is 0.25%, n = 0 purity by GPC is 50%, the ratio of mono: di: triglycidyl compound of n = 0 component by gas chromatography is 0:38 : 62. The properties of the obtained resin are described in Table 1.
Comparative Example 1
The same operation as in Example 1 was carried out except that 6.5 parts of water was changed to 0.65 parts, to obtain 148.2 g of an epoxy resin. The epoxy equivalent of this resin is 135 g / eq, the total chlorine content is 0.25%, n = 0 purity by GPC is 50%, the ratio of mono: di: triglycidyl compound of n = 0 component by gas chromatography is 0:75 : 25. The properties of the obtained resin are described in Table 1.
Comparative example 2
Tohto Kasei YH-300 (trimethylolpropane glycidyl ether). The epoxy equivalent of YH-300 is 142 g / eq, viscosity 147 mPa · s / 25 ° C, total chlorine 5.0%, n = 0 purity by GPC 29%, n = 0 component by gas chromatography Mono: di: tri: The glycidyl compound ratio was 0:81:19. The properties of the resin are described in Table 1.
Example 3
The epoxy resin D (hereinafter referred to as epoxy resin A) obtained in Example 1 is subjected to molecular distillation at a pressure of 0.3 pa and a temperature of 125 to 135 ° C. using a thin film molecular distillation machine KDL-4 manufactured by Fintech Co., Ltd. I got The properties of the obtained resin are described in Table 2.
Example 4
The epoxy resin E obtained by avoiding molecular distillation of the epoxy resin obtained in Example 2 (hereinafter, epoxy resin B) as in Example 3 was obtained. The properties of the obtained resin are described in Table 2.
Comparative example 3
The epoxy resin F which did not go through molecular distillation similarly to Example 3 with the epoxy resin (following epoxy resin C) obtained in Example 1 was obtained. The properties of the obtained resin are described in Table 2.
Comparative example 4
An epoxy resin G not subjected to molecular distillation was obtained in the same manner as in Example 3 for YH-300 manufactured by Tohto Kasei Co., Ltd. The properties of the obtained resin are described in Table 2.
Examples 5, 6 Comparative Examples 5, 6 Example 7, 8 Comparative Examples 7, 8
Epoxy resin A to epoxy resin G and YH-300 were blended at a mixing viscosity of 1000 mPa · s / 25 ° C. per 100 parts by weight of YD-8125 manufactured by Tohto Kasei Co., Ltd. as an epoxy resin component. RIKACID MH-700 (methyl hexahydrophthalic acid anhydride, acid anhydride equivalent 168 g / eq, Shin Nippon Rika Co., Ltd.) as a curing agent, and hysicoline PX-4ET (organic phosphonium salt compound, Nippon Chemical Co., Ltd.) as a curing accelerator The epoxy resin composition was obtained by using the composition shown in Table 3. The numerical values in the table indicate parts by weight in the formulation.
The resulting epoxy resin composition was molded at 100 ° C. for 2 hours, and post cured at 140 ° C. for 12 hours to obtain a cured test piece, which was then subjected to various physical property measurements. The results are shown in Table 3.
In addition, the test method and evaluation method of hardening physical property are as follows.
(1) The cured product Tg was measured at a temperature rising rate of 10 ° C./min using a thermo-mechanical measurement device (manufactured by Seiko Instruments Inc.).
(2) The water absorption rate was taken as a weight increase change rate after absorbing moisture for 50 hours under the conditions of 23 ° C. and 100% RH using a circular test piece of 50 mm in diameter and 5 mm in thickness.
(3) The amount of ionic impurities was determined by measuring the chloride ion by ion chromatography using the extracted ions after the pressure cooker test at 105 ° C. for 20 hours, and converting it to the solid content.
As compared with Comparative Example 5 in which the epoxy resin C was used, Examples 5 and 6 using the epoxy resins A and B show high cured product Tg and low water absorption. Moreover, compared with the comparative example 6 using YH-300, the amount of PCT chlorine extraction is significantly smaller.
Similarly, Examples 7 and 8 in which epoxy resins D and E are used show higher cured product Tg and lower water absorption as compared with Comparative Example 7 in which epoxy resin F is used. Further, compared to Comparative Example 8 in which the epoxy resin G was used, the PCT chlorine extraction amount was significantly smaller.
エポキシ当量はＪＩＳ Ｋ ７２３６の規定に従い測定した。
全塩素量はＪＩＳ Ｋ ７２４３−３の規定に従い測定した。
粘度は、ＪＩＳ Ｋ−７２３３、単一円筒回転粘度計法により測定した。
ガスクロマトグラフィー測定は、以下の条件で測定した。
モノ、ジ、トリグリシジル体の含有量はそれぞれガスクロマトグラフィー分析の結果得られるピークの面積％を表す。
装置 ：島津製作所社製「ＧＣ−１４Ｂ」
カラム ：ガラス製パックドカラム 長さ１．１ｍ、直径３．２ｍｍ
充填剤 ：ｓｉｌｉｃｏｎｅ ＯＶ−１７
担体 ：ｃｈｒｏｍｏｓｏｒｂ Ｗ ＡＷ−ＤＭＣＳ
フローコントローラー：水素５０ｋＰａ、空気５０ｋＰａ、キャリア５０ｋＰａ、プライマリ４００ｋＰａ
カラム流量 ：５０ｍｌ／ｍｉｎ
ＩＮＪＥＣＴＩＯＮ温度：２８０℃、ＦＩＤ温度：３２０℃、カラム温度：１６０℃×２ｍｉｎ、昇温速度：２０℃／ｍｉｎ、最終カラム温度：３００℃×５ｍｉｎ
サンプル ：５ｗｔ％アセトン溶液
注入量 ：２μＬ
ＧＰＣ測定は、以下の条件で測定した。ｎ＝０含有量はＧＰＣ分析の結果得られるピークの面積％を表す。
機器 ：東ソー株式会社ＧＰＣ８２２０
分離カラム：ＴＳＫｇｅｌ Ｇ２０００ＨＸＬ，ＴＳＫｇｅｌ Ｇ２０００ＨＸＬ，ＴＳＫｇｅｌ Ｇ１０００ＨＸＬを直列で連結
カラム温 ：４０℃
溶離液 ：テトラヒドロフランを１ｍｌ／ｍｉｎの流速
検出器 ：ＲＩ検出器
実施例１
撹拌噐、温度計、窒素ガス導入装置、滴下装置、冷却管及び油水分離装置を備えた内容量１Ｌのガラスフラスコにトリメチロールプロパン（ＴＭＰ）９０部、エピクロルヒドリン６５２部、ジエチレングリコールジメチルエーテル６５．２部、水６．５部を仕込みを仕込み、窒素ガスを流しながら６０℃まで加熱して溶解した。６０℃迄昇温後、９９％水酸化ナトリウム７７．３部を投入し同温度で６時間反応を行った。濾過により生成した塩を除き、エピクロロヒドリンを留去し、トルエン５００部に溶解した。８０℃迄昇温後、４９．１％水酸化ナトリウム水溶液０．３２部および温水１．２５部を加えて同温度で１時間精製反応を実施した。その後温水２５部を加えて攪拌、分液し樹脂溶液を脱水濾過、トルエンを蒸留して除去して、１６４．２ｇのエポキシ樹脂を得た。この樹脂のエポキシ当量は１２８ｇ／ｅｑ、粘度１５０ｍＰａ・ｓ／２５℃、全塩素０．２３％、ＧＰＣによるｎ＝０純度は５８％、ガスクロマトグラフィーによるｎ＝０成分のモノグリシジル体（１ＧＥ）：ジグリシジル体（２ＧＥ）：トリグリシジル体（３ＧＥ）比率は０：６０：４０であった。得られた樹脂の性状を表１に記載した。
実施例２
９９％水酸化ナトリウムを７７．３部から１１６．０部に変更した以外は、実施例１と同様の操作を行い１５４．５ｇのエポキシ樹脂を得た。この樹脂のエポキシ当量は１２５ｇ／ｅｑ、全塩素量は０．２５％、ＧＰＣによるｎ＝０純度は５０％、ガスクロマトグラフィーによるｎ＝０成分のモノ：ジ：トリグリシジル体比率は０：３８：６２であった。得られた樹脂の性状を表１に記載した。
比較例１
水６．５部を０．６５部に変更した以外は、実施例１と同様の操作を行い１４８．２ｇのエポキシ樹脂を得た。この樹脂のエポキシ当量は１３５ｇ／ｅｑ、全塩素量は０．２５％、ＧＰＣによるｎ＝０純度は５０％、ガスクロマトグラフィーによるｎ＝０成分のモノ：ジ：トリグリシジル体比率は０：７５：２５であった。得られた樹脂の性状を表１に記載した。
比較例２
東都化成社製ＹＨ−３００（トリメチロールプロパングリシジルエーテル）。ＹＨ−３００のエポキシ当量は１４２ｇ／ｅｑ、粘度１４７ｍＰａ・ｓ／２５℃、全塩素５．０％、ＧＰＣによるｎ＝０純度は２９％、 ガスクロマトグラフィーによるｎ＝０成分のモノ：ジ：トリグリシジル体比率は０：８１：１９であった。樹脂の性状を表１に記載した。
実施例１で得られたエポキシ樹脂（以下エポキシ樹脂Ａ）をフィンテック社製 薄膜分子蒸留機ＫＤＬ−４を使用して、圧力０．３ｐａ、温度１２５~１３５℃で分子蒸留を行いエポキシ樹脂Ｄを得た。得られた樹脂の性状を表２に記載した。
実施例４
実施例２で得られたエポキシ樹脂（以下エポキシ樹脂Ｂ）を実施例３と同様に分子蒸留を行こないエポキシ樹脂Ｅを得た。得られた樹脂の性状を表２に記載した。
比較例３
実施例１で得られたエポキシ樹脂（以下エポキシ樹脂Ｃ）を実施例３と同様に分子蒸留を行こないエポキシ樹脂Ｆを得た。得られた樹脂の性状を表２に記載した。
比較例４
東都化成社製ＹＨ−３００を実施例３と同様に分子蒸留を行こないエポキシ樹脂Ｇを得た。得られた樹脂の性状を表２に記載した。
エポキシ樹脂成分として、東都化成社製ＹＤ−８１２５を１００重量部に対してエポキシ樹脂Ａ~エポキシ樹脂Ｇ、ＹＨ−３００を混合粘度が１０００ｍＰａ・ｓ／２５℃になるような割合で配合した。硬化剤として、リカシッドＭＨ−７００（無水メチルヘキサヒドロフタル酸、酸無水物当量１６８ｇ／ｅｑ、新日本理化製）、硬化促進剤として、ヒシコーリンＰＸ−４ＥＴ（有機ホスホニウム塩化合物、日本化学製）を用い、表３に示す配合でエポキシ樹脂組成物を得た。なお、表中の数値は配合における重量部を示す。
このエポキシ樹脂組成物を用いて１００℃で２時間かけて成形し、更に１４０℃にて１２時間ポストキュアを行い、硬化物試験片を得た後、各種物性測定に供した。結果を表３に示す。
なお、硬化物性の試験方法及び評価方法は以下の通りである。
（１）硬化物Ｔｇは、熱機械測定装置（セイコー電子社製）を用いて１０℃／分の昇温速度で測定した。
（２）吸水率は、直径５０ｍｍ、厚さ５ｍｍの円形の試験片を用いて、２３℃、１００％ＲＨの条件で５０時間吸湿させた後の重量増加変化率とした。
（３）イオン性不純物量は、１０５℃、２０時間のプレッシャークッカーテストを行った後の抽出イオン分をイオンクロマトグラフィーにて、塩素イオンを測定し、固形分に換算して求めた。
エポキシ樹脂Ａ、Ｂを用いた実施例５、６はエポキシ樹脂Ｃを用いた比較例５に比較して高い硬化物Ｔｇと低い吸水率を示す。またＹＨ−３００を用いた比較例６に比較してＰＣＴ塩素抽出量が大幅に少ない。
同様に、エポキシ樹脂Ｄ、Ｅを用いた実施例７、８はエポキシ樹脂Ｆを用いた比較例７に比較して高い硬化物Ｔｇと低い吸水率を示す。またエポキシ樹脂Ｇを用いた比較例８に比較してＰＣＴ塩素抽出量が大幅に少ない。
The epoxy equivalent was measured in accordance with JIS K 7236.
The total chlorine content was measured in accordance with JIS K 7243-3.
The viscosity was measured by a single cylindrical rotational viscometer method according to JIS K-7233.
Gas chromatography was measured under the following conditions.
The contents of mono-, di- and triglycidyl forms each represent the area% of the peak obtained as a result of gas chromatography analysis.
Device: "GC-14B" manufactured by Shimadzu Corporation
Column: Glass packed column 1.1 m in length, 3.2 mm in diameter
Filler: silicone OV-17
Carrier: chromosorb W AW-DMCS
Flow controller: Hydrogen 50kPa, air 50kPa, carrier 50kPa, primary 400kPa
Column flow rate: 50 ml / min
INJECTION temperature: 280 ° C., FID temperature: 320 ° C., column temperature: 160 ° C. × 2 min, temperature rising rate: 20 ° C./min, final column temperature: 300 ° C. × 5 min
Sample: Injection amount of 5wt% acetone solution: 2μL
GPC measurement was performed under the following conditions. n = 0 content represents the area% of the peak obtained as a result of GPC analysis.
Equipment: Tosoh Corporation GPC8220
Separation column: TSKgel G2000HXL, TSKgel G2000HXL, TSKgel G1000HXL connected in series Column temperature: 40 ° C
Eluent: Tetrahydrofuran at 1 ml / min flow rate detector: RI detector Example 1
90 parts of trimethylolpropane (TMP), 652 parts of epichlorohydrin, 65.2 parts of diethylene glycol dimethyl ether in a 1-L glass flask equipped with a stirrer, thermometer, nitrogen gas introduction device, dropping device, cooling pipe and oil / water separation device 6.5 parts of water was charged and dissolved by heating to 60 ° C. while flowing nitrogen gas. After raising the temperature to 60 ° C., 77.3 parts of 99% sodium hydroxide was added, and the reaction was carried out at the same temperature for 6 hours. The salt formed by filtration was removed, and epichlorohydrin was distilled off and dissolved in 500 parts of toluene. After raising the temperature to 80 ° C., 0.32 parts of a 49.1% aqueous sodium hydroxide solution and 1.25 parts of hot water were added, and a purification reaction was carried out at the same temperature for 1 hour. Thereafter, 25 parts of hot water was added, and the mixture was stirred and separated, and the resin solution was subjected to dehydration filtration and toluene removal by distillation to obtain 164.2 g of an epoxy resin. The epoxy equivalent of this resin is 128 g / eq, viscosity 150 mPa · s / 25 ° C, total chlorine 0.23%, n = 0 purity by GPC 58%, n = 0 monoglycidyl form (1 GE) by gas chromatography The ratio of diglycidyl body (2GE): triglycidyl body (3GE) was 0:60:40. The properties of the obtained resin are described in Table 1.
Example 2
The same operation as in Example 1 was carried out except that the amount of 99% sodium hydroxide was changed from 77.3 parts to 116.0 parts, to obtain 154.5 g of an epoxy resin. The epoxy equivalent of this resin is 125 g / eq, the total chlorine content is 0.25%, n = 0 purity by GPC is 50%, the ratio of mono: di: triglycidyl compound of n = 0 component by gas chromatography is 0:38 : 62. The properties of the obtained resin are described in Table 1.
Comparative Example 1
The same operation as in Example 1 was carried out except that 6.5 parts of water was changed to 0.65 parts, to obtain 148.2 g of an epoxy resin. The epoxy equivalent of this resin is 135 g / eq, the total chlorine content is 0.25%, n = 0 purity by GPC is 50%, the ratio of mono: di: triglycidyl compound of n = 0 component by gas chromatography is 0:75 : 25. The properties of the obtained resin are described in Table 1.
Comparative example 2
Tohto Kasei YH-300 (trimethylolpropane glycidyl ether). The epoxy equivalent of YH-300 is 142 g / eq, viscosity 147 mPa · s / 25 ° C, total chlorine 5.0%, n = 0 purity by GPC 29%, n = 0 component by gas chromatography Mono: di: tri: The glycidyl compound ratio was 0:81:19. The properties of the resin are described in Table 1.
The epoxy resin D (hereinafter referred to as epoxy resin A) obtained in Example 1 is subjected to molecular distillation at a pressure of 0.3 pa and a temperature of 125 to 135 ° C. using a thin film molecular distillation machine KDL-4 manufactured by Fintech Co., Ltd. I got The properties of the obtained resin are described in Table 2.
Example 4
The epoxy resin E obtained by avoiding molecular distillation of the epoxy resin obtained in Example 2 (hereinafter, epoxy resin B) as in Example 3 was obtained. The properties of the obtained resin are described in Table 2.
Comparative example 3
The epoxy resin F which did not go through molecular distillation similarly to Example 3 with the epoxy resin (following epoxy resin C) obtained in Example 1 was obtained. The properties of the obtained resin are described in Table 2.
Comparative example 4
An epoxy resin G not subjected to molecular distillation was obtained in the same manner as in Example 3 for YH-300 manufactured by Tohto Kasei Co., Ltd. The properties of the obtained resin are described in Table 2.
Epoxy resin A to epoxy resin G and YH-300 were blended at a mixing viscosity of 1000 mPa · s / 25 ° C. per 100 parts by weight of YD-8125 manufactured by Tohto Kasei Co., Ltd. as an epoxy resin component. RIKACID MH-700 (methyl hexahydrophthalic acid anhydride, acid anhydride equivalent 168 g / eq, Shin Nippon Rika Co., Ltd.) as a curing agent, and hysicoline PX-4ET (organic phosphonium salt compound, Nippon Chemical Co., Ltd.) as a curing accelerator The epoxy resin composition was obtained by using the composition shown in Table 3. The numerical values in the table indicate parts by weight in the formulation.
The resulting epoxy resin composition was molded at 100 ° C. for 2 hours, and post cured at 140 ° C. for 12 hours to obtain a cured test piece, which was then subjected to various physical property measurements. The results are shown in Table 3.
In addition, the test method and evaluation method of hardening physical property are as follows.
(1) The cured product Tg was measured at a temperature rising rate of 10 ° C./min using a thermo-mechanical measurement device (manufactured by Seiko Instruments Inc.).
(2) The water absorption rate was taken as a weight increase change rate after absorbing moisture for 50 hours under the conditions of 23 ° C. and 100% RH using a circular test piece of 50 mm in diameter and 5 mm in thickness.
(3) The amount of ionic impurities was determined by measuring the chloride ion by ion chromatography using the extracted ions after the pressure cooker test at 105 ° C. for 20 hours, and converting it to the solid content.
As compared with Comparative Example 5 in which the epoxy resin C was used, Examples 5 and 6 using the epoxy resins A and B show high cured product Tg and low water absorption. Moreover, compared with the comparative example 6 using YH-300, the amount of PCT chlorine extraction is significantly smaller.
Similarly, Examples 7 and 8 in which epoxy resins D and E are used show higher cured product Tg and lower water absorption as compared with Comparative Example 7 in which epoxy resin F is used. Further, compared to Comparative Example 8 in which the epoxy resin G was used, the PCT chlorine extraction amount was significantly smaller.
本発明によるエポキシ樹脂を用いると、低粘度性に優れるとともに、Ｔｇが高く耐湿性優れた硬化物が得られる。これは、通常の使用範囲において必要十分な耐熱性で湿性優れた硬化物が製造可能になり、半導体素子に代表される電気・電子部品等の封止、コーティング材料、積層材料、複合材料等に有用な樹脂組成物が得られ、その技術上の意味に大きなものがある。
When the epoxy resin according to the present invention is used, a cured product having a high Tg and an excellent moisture resistance can be obtained while being excellent in low viscosity. This makes it possible to produce a cured product with excellent heat resistance and moisture resistance that is necessary and sufficient in the normal use range, and for sealing of electrical and electronic parts represented by semiconductor elements, coating materials, laminate materials, composite materials, etc. Useful resin compositions are obtained, and the technical meaning is significant.
Claims (2)
- ガスクロマトグラフィー分析におけるｎ＝０成分（トリメチロールプロパンのポリグリシジルエーテルに含有されるトリメチロールプロパングリシジルエーテル単量体）中のトリグリシジル体の比率が３５％以上であり、全塩素量が０．３％以下、２５℃での粘度が３００ｍＰａ・ｓ以下であることを特徴とするトリメチロールプロパンのポリグリシジルエーテルを必須成分として配合してなるエポキシ樹脂組成物。 The ratio of the triglycidyl compound in the n = 0 component (trimethylolpropane glycidyl ether monomer contained in the polyglycidyl ether of trimethylolpropane) in gas chromatography analysis is 35% or more, and the total chlorine content is 0. An epoxy resin composition comprising, as an essential component, a polyglycidyl ether of trimethylolpropane, which has a viscosity of 3 mPa% or less and 300 mPa · s or less at 25 ° C.
- 請求項１記載のエポキシ樹脂組成物を硬化してなる硬化物。 A cured product obtained by curing the epoxy resin composition according to claim 1.
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| JP2021161242A (en) * | 2020-03-31 | 2021-10-11 | 日鉄ケミカル＆マテリアル株式会社 | Curable resin composition, and tow prepreg using the same |
| CN113651945A (en) * | 2021-08-13 | 2021-11-16 | 江苏扬农化工集团有限公司 | Glycidyl ether epoxy resin and preparation method thereof |
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| CN108383808A (en) * | 2018-03-15 | 2018-08-10 | 中国林业科学研究院林产化学工业研究所 | A kind of preparation method of epoxide diluent |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001106766A (en) * | 1999-10-08 | 2001-04-17 | Toto Kasei Co Ltd | Flame-retarded liquid epoxy resin composition |
| JP2003246782A (en) * | 2001-12-20 | 2003-09-02 | Nippon Steel Chem Co Ltd | Liquid epoxy compound |
| US6677468B1 (en) * | 2001-07-24 | 2004-01-13 | Loctite Corporation | Methods of reducing chloride content in epoxy compounds |
| JP2004083711A (en) * | 2002-08-26 | 2004-03-18 | Nippon Steel Chem Co Ltd | Liquid epoxy resin composition |
| JP2004231787A (en) * | 2003-01-30 | 2004-08-19 | Nippon Steel Chem Co Ltd | Epoxy resin diluent, epoxy resin composition and cured epoxy resin |
| JP2009265450A (en) * | 2008-04-26 | 2009-11-12 | Nippon Kayaku Co Ltd | Photosensitive resin composition for microelectronic mechanical system (mems) and cured product of the same |
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Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001106766A (en) * | 1999-10-08 | 2001-04-17 | Toto Kasei Co Ltd | Flame-retarded liquid epoxy resin composition |
| US6677468B1 (en) * | 2001-07-24 | 2004-01-13 | Loctite Corporation | Methods of reducing chloride content in epoxy compounds |
| JP2003246782A (en) * | 2001-12-20 | 2003-09-02 | Nippon Steel Chem Co Ltd | Liquid epoxy compound |
| JP2004083711A (en) * | 2002-08-26 | 2004-03-18 | Nippon Steel Chem Co Ltd | Liquid epoxy resin composition |
| JP2004231787A (en) * | 2003-01-30 | 2004-08-19 | Nippon Steel Chem Co Ltd | Epoxy resin diluent, epoxy resin composition and cured epoxy resin |
| JP2009265450A (en) * | 2008-04-26 | 2009-11-12 | Nippon Kayaku Co Ltd | Photosensitive resin composition for microelectronic mechanical system (mems) and cured product of the same |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2021161242A (en) * | 2020-03-31 | 2021-10-11 | 日鉄ケミカル＆マテリアル株式会社 | Curable resin composition, and tow prepreg using the same |
| JP7512064B2 (en) | 2020-03-31 | 2024-07-08 | 日鉄ケミカル＆マテリアル株式会社 | CURABLE RESIN COMPOSITION AND TOW PREPREG USING SAME |
| CN113651945A (en) * | 2021-08-13 | 2021-11-16 | 江苏扬农化工集团有限公司 | Glycidyl ether epoxy resin and preparation method thereof |
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| TWI498349B (en) | 2015-09-01 |
| JP5744010B2 (en) | 2015-07-01 |
| JPWO2011125962A1 (en) | 2013-07-11 |
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