JPS63264623A - Heat-resistant and flame-retardant epoxy resin composition - Google Patents
Heat-resistant and flame-retardant epoxy resin compositionInfo
- Publication number
- JPS63264623A JPS63264623A JP16112787A JP16112787A JPS63264623A JP S63264623 A JPS63264623 A JP S63264623A JP 16112787 A JP16112787 A JP 16112787A JP 16112787 A JP16112787 A JP 16112787A JP S63264623 A JPS63264623 A JP S63264623A
- Authority
- JP
- Japan
- Prior art keywords
- formula
- epoxy resin
- formulas
- carbon atoms
- resin composition
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000003822 epoxy resin Substances 0.000 title claims abstract description 133
- 229920000647 polyepoxide Polymers 0.000 title claims abstract description 133
- 239000000203 mixture Substances 0.000 title claims abstract description 95
- 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 title claims abstract description 11
- 239000003063 flame retardant Substances 0.000 title claims abstract description 11
- 239000004593 Epoxy Substances 0.000 claims abstract description 70
- 150000001875 compounds Chemical class 0.000 claims abstract description 44
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 27
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical class C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 claims abstract description 26
- 239000003054 catalyst Substances 0.000 claims abstract description 15
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims abstract description 8
- 229930185605 Bisphenol Natural products 0.000 claims abstract description 6
- 125000003118 aryl group Chemical group 0.000 claims abstract description 4
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 claims abstract description 3
- 125000000753 cycloalkyl group Chemical group 0.000 claims abstract description 3
- 230000005494 condensation Effects 0.000 claims abstract 2
- 238000009833 condensation Methods 0.000 claims abstract 2
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims description 51
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 36
- 125000004432 carbon atom Chemical group C* 0.000 claims description 27
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 27
- -1 glycidoxy group Chemical group 0.000 claims description 23
- 229910052736 halogen Inorganic materials 0.000 claims description 16
- 150000002367 halogens Chemical class 0.000 claims description 16
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 15
- 239000000126 substance Substances 0.000 claims description 14
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical class C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 claims description 8
- 230000001588 bifunctional effect Effects 0.000 claims description 5
- 125000005843 halogen group Chemical group 0.000 claims description 5
- WFQDPXQJWBLPPU-UHFFFAOYSA-N 2,6-dibromo-4-[1-(3,5-dibromo-4-hydroxyphenyl)ethyl]phenol Chemical compound C=1C(Br)=C(O)C(Br)=CC=1C(C)C1=CC(Br)=C(O)C(Br)=C1 WFQDPXQJWBLPPU-UHFFFAOYSA-N 0.000 claims description 4
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical class C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 claims description 3
- VGECBJVJEVYXBY-UHFFFAOYSA-N 2-[[4-[4,4-bis[5-tert-butyl-2-methyl-4-(oxiran-2-ylmethoxy)phenyl]butan-2-yl]-2-tert-butyl-5-methylphenoxy]methyl]oxirane Chemical compound C=1C(C(C)(C)C)=C(OCC2OC2)C=C(C)C=1C(C)CC(C=1C(=CC(OCC2OC2)=C(C=1)C(C)(C)C)C)C(C(=C1)C)=CC(C(C)(C)C)=C1OCC1CO1 VGECBJVJEVYXBY-UHFFFAOYSA-N 0.000 claims description 2
- HTVITOHKHWFJKO-UHFFFAOYSA-N Bisphenol B Chemical class C=1C=C(O)C=CC=1C(C)(CC)C1=CC=C(O)C=C1 HTVITOHKHWFJKO-UHFFFAOYSA-N 0.000 claims description 2
- 239000003973 paint Substances 0.000 abstract description 7
- 239000000565 sealant Substances 0.000 abstract description 6
- 238000000034 method Methods 0.000 description 24
- 229920005989 resin Polymers 0.000 description 22
- 239000011347 resin Substances 0.000 description 22
- 239000011521 glass Substances 0.000 description 19
- 239000001273 butane Substances 0.000 description 18
- 238000006243 chemical reaction Methods 0.000 description 18
- 239000004744 fabric Substances 0.000 description 18
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 18
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 18
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 15
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 15
- 229910052794 bromium Inorganic materials 0.000 description 15
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 description 15
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 11
- 239000002994 raw material Substances 0.000 description 10
- 239000000047 product Substances 0.000 description 9
- QWVGKYWNOKOFNN-UHFFFAOYSA-N o-cresol Chemical compound CC1=CC=CC=C1O QWVGKYWNOKOFNN-UHFFFAOYSA-N 0.000 description 8
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 239000007983 Tris buffer Substances 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 6
- 238000006266 etherification reaction Methods 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 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 5
- 239000007795 chemical reaction product Substances 0.000 description 5
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 4
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 4
- 150000003944 halohydrins Chemical class 0.000 description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 4
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 4
- 239000008096 xylene Substances 0.000 description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 3
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 3
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 239000000853 adhesive Substances 0.000 description 3
- 230000001070 adhesive effect Effects 0.000 description 3
- 150000001412 amines Chemical class 0.000 description 3
- 239000004841 bisphenol A epoxy resin Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000006704 dehydrohalogenation reaction Methods 0.000 description 3
- 239000000945 filler Substances 0.000 description 3
- 230000009477 glass transition Effects 0.000 description 3
- 239000012778 molding material Substances 0.000 description 3
- 239000011342 resin composition Substances 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- CMQUQOHNANGDOR-UHFFFAOYSA-N 2,3-dibromo-4-(2,4-dibromo-5-hydroxyphenyl)phenol Chemical compound BrC1=C(Br)C(O)=CC=C1C1=CC(O)=C(Br)C=C1Br CMQUQOHNANGDOR-UHFFFAOYSA-N 0.000 description 2
- IGZBSJAMZHNHKE-UHFFFAOYSA-N 2-[[4-[bis[4-(oxiran-2-ylmethoxy)phenyl]methyl]phenoxy]methyl]oxirane Chemical compound C1OC1COC(C=C1)=CC=C1C(C=1C=CC(OCC2OC2)=CC=1)C(C=C1)=CC=C1OCC1CO1 IGZBSJAMZHNHKE-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
- 241000238557 Decapoda Species 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 2
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 2
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 150000008065 acid anhydrides Chemical class 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 2
- 239000010425 asbestos Substances 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 239000003086 colorant Substances 0.000 description 2
- 239000003085 diluting agent Substances 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- 238000010292 electrical insulation Methods 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 239000003365 glass fiber Substances 0.000 description 2
- 150000004820 halides Chemical class 0.000 description 2
- 150000002576 ketones Chemical class 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 229920003986 novolac Polymers 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000001294 propane Substances 0.000 description 2
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 2
- 230000003014 reinforcing effect Effects 0.000 description 2
- 229910052895 riebeckite Inorganic materials 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 150000003512 tertiary amines Chemical class 0.000 description 2
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 2
- YJTKZCDBKVTVBY-UHFFFAOYSA-N 1,3-Diphenylbenzene Chemical group C1=CC=CC=C1C1=CC=CC(C=2C=CC=CC=2)=C1 YJTKZCDBKVTVBY-UHFFFAOYSA-N 0.000 description 1
- XRQKNNNAKHZPSP-UHFFFAOYSA-N 1,3-dibromo-5-[2-(3,5-dibromo-4-methoxyphenyl)propan-2-yl]-2-methoxybenzene Chemical compound C1=C(Br)C(OC)=C(Br)C=C1C(C)(C)C1=CC(Br)=C(OC)C(Br)=C1 XRQKNNNAKHZPSP-UHFFFAOYSA-N 0.000 description 1
- RMSGQZDGSZOJMU-UHFFFAOYSA-N 1-butyl-2-phenylbenzene Chemical group CCCCC1=CC=CC=C1C1=CC=CC=C1 RMSGQZDGSZOJMU-UHFFFAOYSA-N 0.000 description 1
- YSUQLAYJZDEMOT-UHFFFAOYSA-N 2-(butoxymethyl)oxirane Chemical compound CCCCOCC1CO1 YSUQLAYJZDEMOT-UHFFFAOYSA-N 0.000 description 1
- DXEHULHXWHEJJD-UHFFFAOYSA-N 2-[(4-butylphenoxy)methyl]oxirane Chemical compound C1=CC(CCCC)=CC=C1OCC1OC1 DXEHULHXWHEJJD-UHFFFAOYSA-N 0.000 description 1
- MFYSUUPKMDJYPF-UHFFFAOYSA-N 2-[(4-methyl-2-nitrophenyl)diazenyl]-3-oxo-n-phenylbutanamide Chemical compound C=1C=CC=CC=1NC(=O)C(C(=O)C)N=NC1=CC=C(C)C=C1[N+]([O-])=O MFYSUUPKMDJYPF-UHFFFAOYSA-N 0.000 description 1
- PSDRGYGYQGTMSD-UHFFFAOYSA-N 2-[[2-[1-[2-(oxiran-2-ylmethoxy)phenyl]ethyl]phenoxy]methyl]oxirane Chemical compound C=1C=CC=C(OCC2OC2)C=1C(C)C1=CC=CC=C1OCC1CO1 PSDRGYGYQGTMSD-UHFFFAOYSA-N 0.000 description 1
- JFNFZPRUTDFBGN-UHFFFAOYSA-N 2-[[4-[4,4-bis[4-(oxiran-2-ylmethoxy)phenyl]butan-2-yl]phenoxy]methyl]oxirane Chemical compound C=1C=C(OCC2OC2)C=CC=1C(C)CC(C=1C=CC(OCC2OC2)=CC=1)C(C=C1)=CC=C1OCC1CO1 JFNFZPRUTDFBGN-UHFFFAOYSA-N 0.000 description 1
- 239000001763 2-hydroxyethyl(trimethyl)azanium Substances 0.000 description 1
- ULKLGIFJWFIQFF-UHFFFAOYSA-N 5K8XI641G3 Chemical compound CCC1=NC=C(C)N1 ULKLGIFJWFIQFF-UHFFFAOYSA-N 0.000 description 1
- 241000143060 Americamysis bahia Species 0.000 description 1
- 241000255789 Bombyx mori Species 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 235000019743 Choline chloride Nutrition 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 125000000174 L-prolyl group Chemical group [H]N1C([H])([H])C([H])([H])C([H])([H])[C@@]1([H])C(*)=O 0.000 description 1
- WMFYOYKPJLRMJI-UHFFFAOYSA-N Lercanidipine hydrochloride Chemical compound Cl.COC(=O)C1=C(C)NC(C)=C(C(=O)OC(C)(C)CN(C)CCC(C=2C=CC=CC=2)C=2C=CC=CC=2)C1C1=CC=CC([N+]([O-])=O)=C1 WMFYOYKPJLRMJI-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
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000004760 aramid Substances 0.000 description 1
- 150000004982 aromatic amines Chemical class 0.000 description 1
- 229920003235 aromatic polyamide Polymers 0.000 description 1
- XLRCXWHGTFHOKU-UHFFFAOYSA-M benzyl(dimethyl)sulfanium;chloride Chemical compound [Cl-].C[S+](C)CC1=CC=CC=C1 XLRCXWHGTFHOKU-UHFFFAOYSA-M 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- ZLFVRXUOSPRRKQ-UHFFFAOYSA-N chembl2138372 Chemical compound [O-][N+](=O)C1=CC(C)=CC=C1N=NC1=C(O)C=CC2=CC=CC=C12 ZLFVRXUOSPRRKQ-UHFFFAOYSA-N 0.000 description 1
- SGMZJAMFUVOLNK-UHFFFAOYSA-M choline chloride Chemical compound [Cl-].C[N+](C)(C)CCO SGMZJAMFUVOLNK-UHFFFAOYSA-M 0.000 description 1
- 229960003178 choline chloride Drugs 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 229910052570 clay Inorganic materials 0.000 description 1
- 230000008094 contradictory effect Effects 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- XCJYREBRNVKWGJ-UHFFFAOYSA-N copper(II) phthalocyanine Chemical compound [Cu+2].C12=CC=CC=C2C(N=C2[N-]C(C3=CC=CC=C32)=N2)=NC1=NC([C]1C=CC=CC1=1)=NC=1N=C1[C]3C=CC=CC3=C2[N-]1 XCJYREBRNVKWGJ-UHFFFAOYSA-N 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- PXBRQCKWGAHEHS-UHFFFAOYSA-N dichlorodifluoromethane Chemical group FC(F)(Cl)Cl PXBRQCKWGAHEHS-UHFFFAOYSA-N 0.000 description 1
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 1
- CZZYITDELCSZES-UHFFFAOYSA-N diphenylmethane Chemical compound C=1C=CC=CC=1CC1=CC=CC=C1 CZZYITDELCSZES-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- 229910000403 monosodium phosphate Inorganic materials 0.000 description 1
- 235000019799 monosodium phosphate Nutrition 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000000123 paper Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 150000004714 phosphonium salts Chemical group 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 1
- IEQIEDJGQAUEQZ-UHFFFAOYSA-N phthalocyanine Chemical compound N1C(N=C2C3=CC=CC=C3C(N=C3C4=CC=CC=C4C(=N4)N3)=N2)=C(C=CC=C2)C2=C1N=C1C2=CC=CC=C2C4=N1 IEQIEDJGQAUEQZ-UHFFFAOYSA-N 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920000768 polyamine Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 239000012451 post-reaction mixture Substances 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- AJPJDKMHJJGVTQ-UHFFFAOYSA-M sodium dihydrogen phosphate Chemical compound [Na+].OP(O)([O-])=O AJPJDKMHJJGVTQ-UHFFFAOYSA-M 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-O sulfonium group Chemical group [SH3+] RWSOTUBLDIXVET-UHFFFAOYSA-O 0.000 description 1
- WPZJSWWEEJJSIZ-UHFFFAOYSA-N tetrabromobisphenol-F Natural products C1=C(Br)C(O)=C(Br)C=C1CC1=CC(Br)=C(O)C(Br)=C1 WPZJSWWEEJJSIZ-UHFFFAOYSA-N 0.000 description 1
- HWCKGOZZJDHMNC-UHFFFAOYSA-M tetraethylammonium bromide Chemical compound [Br-].CC[N+](CC)(CC)CC HWCKGOZZJDHMNC-UHFFFAOYSA-M 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
- ZTXFOCMYRCGSMU-UHFFFAOYSA-M tetramethylphosphanium;bromide Chemical compound [Br-].C[P+](C)(C)C ZTXFOCMYRCGSMU-UHFFFAOYSA-M 0.000 description 1
- TVVPMLFGPYQGTG-UHFFFAOYSA-M tetramethylphosphanium;iodide Chemical compound [I-].C[P+](C)(C)C TVVPMLFGPYQGTG-UHFFFAOYSA-M 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- TUQOTMZNTHZOKS-UHFFFAOYSA-N tributylphosphine Chemical compound CCCCP(CCCC)CCCC TUQOTMZNTHZOKS-UHFFFAOYSA-N 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Landscapes
- Epoxy Resins (AREA)
Abstract
Description
【発明の詳細な説明】
（産業上の利用分野）
本発明は、エポキシ樹脂組成物に関し、よシ詳細には、
特定の３官能性エポキシ化合物とハロゲン化ビスフェノ
ール類とを反応させることによりて得られる耐熱性およ
び難燃性に優れたエポキシ樹脂組成物に関する。DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to an epoxy resin composition, and more specifically,
The present invention relates to an epoxy resin composition with excellent heat resistance and flame retardancy obtained by reacting a specific trifunctional epoxy compound with a halogenated bisphenol.
さらに、本発明は耐熱性１機械的特性などに優れた新規
エポキシ樹脂に関する。Furthermore, the present invention relates to a new epoxy resin that is excellent in heat resistance, mechanical properties, and the like.
（従来技術）
エポキシ樹脂に芳香族ポリアミン、脂肪族？リアミン、
ポリアミドアミン、アミンアダクト、ジシアンジアミド
、酸無水物、フェノールノポラ。(Prior art) Aromatic polyamine or aliphatic in epoxy resin? Liamin,
Polyamide amine, amine adduct, dicyandiamide, acid anhydride, phenol nopora.
り樹脂系などの各種硬化剤を配合したものが、接着剤、
塗料、成形材料、注型材料などとして用いられておシ、
またかかる配合物を溶剤でフェス化し、これを補強用基
材に含浸、塗布させ、積層板成形用として用いられるこ
とも従来から周知である。Adhesives, which contain various hardening agents such as resin-based
It is used as paint, molding material, casting material, etc.
It is also conventionally well known that such a compound is made into a face with a solvent, impregnated and coated on a reinforcing base material, and used for forming a laminate.
ところで、近年特に電気・電子分野における小型化、精
密化に伴ない、電子部品の接着剤、絶縁塗料、封止材、
積層板などの用途においては、高温使用時の信頼性を高
めるために、耐熱性の向上が強く求められている。即ち
、従来市販されているビスフェノールＡ型エポキシ樹脂
を用いて調製された接着剤、塗料、封止材、積層板など
は、熱変形温度もしくは電気絶縁性が概して低く、その
結果として信頼性に欠けるという問題がみられた。By the way, in recent years, with the miniaturization and precision in the electrical and electronic fields in particular, adhesives, insulating paints, sealants, and
In applications such as laminates, there is a strong demand for improved heat resistance in order to increase reliability during high-temperature use. That is, adhesives, paints, sealants, laminates, etc. prepared using conventionally commercially available bisphenol A epoxy resins generally have low heat distortion temperatures or electrical insulation properties, and as a result, lack reliability. This problem was observed.
また、とれら電気・電子分野で使用される材料には、さ
らに高い儀燃性が要求され、例えば、積層板（例えばガ
ラスクロスとエポキシ樹脂とを積層させたグリント回路
基板）の材料として使用される難燃性ニーキシ樹脂とし
ては、ビスフェノールＡ型エポキシ樹脂、例えばエポキ
シ当蓋１９０程度の液状ビスフェノールＡ里エポキシ樹
脂とテトラブロムビスフェノールＡとを反応して得られ
る直鎖状のエポキシ樹脂が知られている。この直鎖状エ
ポキシ樹脂を例えば積層成形に使用されている汎用性の
高い硬化剤であるジシアンジアミドを使用して硬化した
場合、硬化物（ブロム金貸２０〜２２重量％）のガラス
転移温度（Ｔｇ）は１２０〜１３０℃と低いものである
。この硬化物の耐熱性を高めるために、上記エポキシ樹
脂にオルソクレゾールノボラック型エポキシ樹脂、フェ
ノールノボ２．り型エポキシ樹脂等の多官能性エポキシ
樹脂を多量に添加すると、難燃性が低下すると共に成形
性が不良にな）、これら多官能性エポキシ樹脂の添加量
が制限されるという欠点がある。Furthermore, materials used in the electrical and electronic fields are required to have even higher flame resistance, and are used, for example, as materials for laminated boards (for example, glint circuit boards made by laminating glass cloth and epoxy resin). As the flame-retardant Nyxy resin, bisphenol A type epoxy resin, for example, a linear epoxy resin obtained by reacting a liquid bisphenol A-type epoxy resin with an epoxy weight of about 190% and tetrabromo bisphenol A, is known. There is. When this linear epoxy resin is cured using, for example, dicyandiamide, which is a highly versatile curing agent used in laminated molding, the glass transition temperature (Tg ) is as low as 120-130°C. In order to increase the heat resistance of this cured product, an orthocresol novolac type epoxy resin, phenol novo 2. Addition of a large amount of a polyfunctional epoxy resin such as a polyfunctional epoxy resin reduces flame retardancy and poor moldability), which limits the amount of polyfunctional epoxy resin added.
このように従来公知のエポキシ樹脂においては。In this way, in conventionally known epoxy resins.
耐熱性と難燃性とは相反する性質であル、耐熱性と難燃
性とが共に優れたエポキシ樹脂は知られていない。高性
能化が要求される電子分野において、高温時における硬
化物の信頼性を高めるためＫ。Heat resistance and flame retardancy are contradictory properties, and no epoxy resin is known that has both excellent heat resistance and flame retardancy. In the electronic field where high performance is required, K is used to increase the reliability of cured products at high temperatures.
耐熱性と難燃性とが共に優れているエポキシ樹脂が強く
要望されている。There is a strong demand for epoxy resins that have both excellent heat resistance and flame retardancy.
さらに、上記オルソクレゾールノがラック型エポキシ樹
脂、フェノールノ＆？、り型エポキシ樹脂等の多官能性
エポキシ樹脂からの硬化物は、弾性率が高いので硬くて
脆く、ヒートショックによるクラックが発生し易いなど
のように機械的特性が劣るものである。そのため、耐熱
性および機械的特性が共に優れているエポキシ樹脂が強
く要望されている。Furthermore, the above-mentioned orthocresol is a lac-type epoxy resin, phenol &? A cured product made from a polyfunctional epoxy resin such as a polyester epoxy resin has a high elastic modulus, so it is hard and brittle, and has poor mechanical properties such as being susceptible to cracking due to heat shock. Therefore, there is a strong demand for epoxy resins that have excellent heat resistance and mechanical properties.
（発明の目的）
本発明者は、特定の構造を有する３官能性エポキシ化合
物と、ハロゲン化ビスフェノール類とを、触媒の存在下
に反応させて得られたエポキシ樹脂組成物が優れた耐熱
性と難燃性とを兼ね備えていることを見出した。さらに
、本発明者等は、特定の構造式を有する３官能性エポキ
シ樹脂が耐熱性と機械的特性とにおいて共に優れている
ことを見出した。(Objective of the Invention) The present inventor has discovered that an epoxy resin composition obtained by reacting a trifunctional epoxy compound having a specific structure with a halogenated bisphenol in the presence of a catalyst has excellent heat resistance. It was discovered that the material also has flame retardancy. Furthermore, the present inventors have discovered that a trifunctional epoxy resin having a specific structural formula is excellent in both heat resistance and mechanical properties.
本発明の目的は、硬化することによって、耐熱性と難燃
性とに共に優れている絶縁塗料、封止材、成形製品を製
造することのできる新規なエポキシ樹脂組成物を提供す
ることでおる。An object of the present invention is to provide a novel epoxy resin composition that can be cured to produce insulating paints, sealants, and molded products that have excellent heat resistance and flame retardancy. .
本発明の他の目的は、硬化することによって、耐熱性と
難燃性とに共に優れておシ、高温時において機械的強度
、電気絶縁性等の信頼性が向上した積層物を製造するこ
とのできる新規なエポキシ樹脂組成物を提供するととて
ちる。Another object of the present invention is to produce a laminate which, by curing, has excellent heat resistance and flame retardancy, and has improved reliability in mechanical strength, electrical insulation, etc. at high temperatures. We aim to provide a novel epoxy resin composition that can
（発明の構成）
本発明によれば、
囚 下記一般式（Ｉ）
式中、Ｒ１およびＲ２は水素原子、炭素原子数１〜１２
のアルキル基、アリール基または炭素原子数３〜６のシ
クロアルキル基であシ、Ｒ３は水素原子または炭素原子
数１〜１ｏのアルキル基であシ、
ｎは０又は１の数であシ、
２は一般式（１ｍ）
ここで、人は水素原子またはメチル基であるで表わされ
る基であシ、
Ｙは一般式（Ｉｂ）
または一般式（Ｉａ）
Ｒ４
ここで、Ｒ４，ＲＳ、Ｒ６及びＲアは、夫々独立に水素
原子または炭素原子１〜４個から成るアルキル基である
、
で表わされる３官能性エポキシ化合物、又は該３官能性
エポキシ化合物及びビスフェノール類とエピクロルヒド
リンとの縮合によシ得られた２官能性エポキシ化合物の
組み合わせと。(Structure of the Invention) According to the present invention, the following general formula (I) in which R1 and R2 are hydrogen atoms and have 1 to 12 carbon atoms
is an alkyl group, aryl group or cycloalkyl group having 3 to 6 carbon atoms, R3 is a hydrogen atom or an alkyl group having 1 to 1 o carbon atoms, n is a number of 0 or 1, 2 is a group represented by general formula (1m), where human is a hydrogen atom or a methyl group, and Y is general formula (Ib) or general formula (Ia) R4, where R4, RS, R6 and R is each independently a hydrogen atom or an alkyl group consisting of 1 to 4 carbon atoms, or a trifunctional epoxy compound represented by and a combination of the obtained bifunctional epoxy compounds.
（６）ハロゲン化ビスフェノール類、
とを触媒の存在下で反応させて得られたハロゲン含有ニ
ブキシ樹脂から成る耐熱難燃性エポキシ樹脂組成物が提
供される。(6) A heat-resistant and flame-retardant epoxy resin composition comprising a halogen-containing niboxy resin obtained by reacting halogenated bisphenols with the present invention in the presence of a catalyst is provided.
また本発明によれば下記式（ＩＩ）、
式中、２はグリシドキシ基であシ、
Ｒ１及びＲ２の各々は水素原子又は炭素数４以下のアル
キル基であシ、
Ｘはハロゲン原子であシ、
ｍは１以上の数であシ、
Ｅは、式、
（式中、Ｒ１，Ｒ２及びＲｓの各々は水素原子又は炭素
数４以下のアルキル基を示し、ｎはゼ四又はｌである）
Ｙは、式、
Ｒ４
又は式、
目
−ＣＨ２−Ｃ−・−（Ｉｎｃ）
（式中、Ｒ４，Ｒ，、Ｒ４及びＲ７は、水素原子又は炭
素数４以下のアルキル基を示す、）で表わされる基であ
る、
で表わされ、３００乃至２０００の工４キシ尚量と５乃
至３０重量％のハロゲン含有量を有するハロゲン含有エ
ポキシ樹脂から成る耐熱難燃性エポキシ樹脂組成物が提
供される。According to the present invention, the following formula (II), where 2 is a glycidoxy group, each of R1 and R2 is a hydrogen atom or an alkyl group having 4 or less carbon atoms, and X is a halogen atom , m is a number of 1 or more, E is the formula, (in the formula, each of R1, R2 and Rs represents a hydrogen atom or an alkyl group having 4 or less carbon atoms, and n is 4 or 1) Y is represented by the formula, R4 or the formula -CH2-C-.-(Inc) (wherein R4, R,, R4 and R7 represent a hydrogen atom or an alkyl group having 4 or less carbon atoms); Provided is a heat-resistant, flame-retardant epoxy resin composition comprising a halogen-containing epoxy resin represented by the following formula, which is a group having a molecular weight of 300 to 2000 and a halogen content of 5 to 30% by weight.
本発明によれば更に下記式（ＩＩＩ）
・・・（ＩＩＩ）
式中、２はグリシドキシ基であシ、
Ｒ１及びＲ２の各々は水素原子又は炭素数４以下のアル
キル基であシ。According to the present invention, the following formula (III)...(III) In the formula, 2 is a glycidoxy group, and each of R1 and R2 is a hydrogen atom or an alkyl group having 4 or less carbon atoms.
ｘｉｔハロｒン原子であシ、
ｋは０又は１以上の数であシ、ｔは１以上の数であって
、３００乃至２０００のエポキシ当量と５乃至３０重量
％を有する様に選択される、Ｅは、式。xit is a halon atom, k is a number of 0 or 1 or more, t is a number of 1 or more, and is selected to have an epoxy equivalent weight of 300 to 2000 and 5 to 30% by weight. , E is the formula.
（式中、Ｒ４，Ｒ２及びＲ３の各々は水素原子又は炭素
数４以下のアルキル基を示し、ｎはゼロ又は１である）
Ｙは、式、
Ｒ。(In the formula, each of R4, R2 and R3 represents a hydrogen atom or an alkyl group having 4 or less carbon atoms, and n is zero or 1.) Y is the formula R.
（式中、Ｒ４，Ｒ５，Ｒ，及びＲ７は、水素原子又は炭
素数４以下のアルキル基を示す、）で表わされる基を示
す、
で表わされるハロゲン含有エポキシ樹脂から成る耐熱難
燃性エポキシ樹脂組成物が提供される。(In the formula, R4, R5, R, and R7 represent a hydrogen atom or an alkyl group having 4 or less carbon atoms) A heat-resistant flame-retardant epoxy resin made of a halogen-containing epoxy resin represented by A composition is provided.
（作用）
本発明の工ｄ？キシ樹脂は、上記特定の３官能性エポキ
シ化合物とハロゲン化ビスフェノールトヲ反応させるこ
とによって得られるエポキシ樹脂であるために、後に示
す応用例と比較応用例との比較から明らかなように、従
来公知の難燃性エポキシ樹脂から得られた硬化物に比し
てはるかに優れた耐熱性を有し、且つハｐグンを含有し
ているため難燃性も優れた硬化物にすることができるも
のである。(Function) The method of the present invention d? Since the epoxy resin is an epoxy resin obtained by reacting the specific trifunctional epoxy compound mentioned above with halogenated bisphenol, it cannot be used in conventionally known It has much better heat resistance than cured products obtained from flame-retardant epoxy resins, and because it contains Hapgun, it can be made into cured products with excellent flame retardancy. be.
従って、本発明のエポキシ樹脂を例えばガラスクロスと
共に積層成形して硬化物にするととＫよシ、耐熱性およ
び難燃性が共に優れ高温時における信頼性の向上した特
に電子部品として有用な橙層物を得ることができる。Therefore, when the epoxy resin of the present invention is laminated and molded with, for example, glass cloth to form a cured product, an orange layer that is excellent in both K, heat resistance and flame retardance, and has improved reliability at high temperatures, is particularly useful as an electronic component. can get things.
更に本発明によるエポキシ樹脂は、３官能性エポキシ化
合物から誘導されていながら，メチルエチルケトン等の
有機溶媒に完全に溶解するなど、実質上線状でｒルを含
まない構造となっておシ、種々の用途に使用する場合に
作業性や加工性に優れているという利点をも与える。Further, although the epoxy resin according to the present invention is derived from a trifunctional epoxy compound, it has a substantially linear structure that does not contain any ruyl, such as being completely soluble in organic solvents such as methyl ethyl ketone, and has a variety of uses. It also has the advantage of being excellent in workability and processability when used for.
（発明の好適態様）
本発明のエポキシ樹脂を得るために用いる３官能性エポ
キシ化合物は前記一般式（１）で表わされるものである
が、一般に下記式（ １ −（１）） 。(Preferred Embodiment of the Invention) The trifunctional epoxy compound used to obtain the epoxy resin of the present invention is represented by the above general formula (1), and is generally represented by the following formula (1-(1)).
式中、
Ｒ，、Ｒ２及びＲ３の各々は水素原子又は炭素数４以下
のアルキル基であシ、
ｎは、０又は１の数であう、
Ｙは、前述した式（Ｉｂ）又は式（Ｉｅ）で表わされる
基を示す、
で表わされる化合物であることが望ましく、特に（１−
（１））式中、ｎは１であることが好適である。In the formula, each of R,, R2 and R3 is a hydrogen atom or an alkyl group having 4 or less carbon atoms, n is a number of 0 or 1, Y is the above-mentioned formula (Ib) or formula (Ie) It is desirable that the compound is a compound represented by a group represented by (1-
(1)) In the formula, n is preferably 1.
上記一般式（Ｉ）若しくは（Ｉ−（１））で表わされる
３官能性エポキシ化合物として特に好ましい物質は、例
えば、１，１．３−）リス（２−メチル−４−グリシド
キシ−５−三級ブチルフェニル）ブタン、１−〔α−メ
チル−α−（４′−グリシドキシフェニル）エチル）−
４−Ｃａ２．α′ −ビス（４１−グリシドキシフェニ
ル）エチル〕ベンゼン、トリス（４−グリシドキシフェ
ニル）メタン、１．１．１−トリス（４−グリシドキシ
フェニル）エタン、トリス（２−メチル−４−グリシド
キシ−５−三級ブチルフェニル）メタン、トリス（３゜
５−ツメチル−４−グリシドキシフェニル）メタン、ト
リス（３−三級ブチル−４−グリシドキシフェニル）メ
タン、トリス（３−メチル−４−グリシドキシ−５−三
級ブチルフェニル）メタン、トリス（２，５−ジメチル
−４−グリシドキシ）メタン、１，１．３−）リス（４
−グリシドキシフェニル）プロパン、１，１．３−）リ
ス（２−メチル−４−グリシドキシ−５−三級ブチルフ
ェニル）グロノぐン、１，１．３−）リス（３、５−ツ
メチル−４−グリシドキシフェニル）プロパン。A particularly preferable substance as the trifunctional epoxy compound represented by the above general formula (I) or (I-(1)) is, for example, 1,1.3-)lis(2-methyl-4-glycidoxy-5-trifunctional epoxy compound). butylphenyl)butane, 1-[α-methyl-α-(4′-glycidoxyphenyl)ethyl)-
4-Ca2. α'-bis(41-glycidoxyphenyl)ethyl]benzene, tris(4-glycidoxyphenyl)methane, 1.1.1-tris(4-glycidoxyphenyl)ethane, tris(2-methyl- 4-glycidoxy-5-tert-butylphenyl)methane, tris(3゜5-tmethyl-4-glycidoxyphenyl)methane, tris(3-tert-butyl-4-glycidoxyphenyl)methane, tris(3 -Methyl-4-glycidoxy-5-tert-butylphenyl)methane, tris(2,5-dimethyl-4-glycidoxy)methane, 1,1.3-)lis(4
-glycidoxyphenyl)propane, 1,1.3-)lis(2-methyl-4-glycidoxy-5-tert-butylphenyl)gulonogun, 1,1.3-)lis(3,5-tumethyl -4-glycidoxyphenyl)propane.
１．１．３−トリス（３−三級ブチル−４−グリシドキ
シフェニル）７ｓロノ量ン、１，１．３−）リス（３−
メチル−４−グリシドキシ−５−三級ブチルフェニル）
クロパン、１，１．３−）リス（２，５−ジメチル−４
−グリシドキシフェニル）プロノ辛ン、１，１．３−ト
リス（４−グリシドキシフェニル）ブタン、１，１．３
−）リス（３，５−ツメチル−４−グリシドキシフェニ
ル）ブタン、１．１．３−）リス（３−三級ブチル−４
−グリシドキシフェニル）ブタン、１，１．３−）リス
（３−メチル−４−グリシドキシ−５−三級ブチルフェ
ニル）ブタン、１，１．３−）リス（２，５−ジメチル
−４−グリシドキシフェニル）ブタン、２．２．４−）
リス（４−グリシドキシフェニル）ブタン、２，２．４
−）リス（２−メチル−４−グリシドキシ−５−三級ブ
チルフェニル）ブタン、２．２．４−）リス（３，５−
ジメチル−４−グリシドキシフェニル）ブタン、２，２
．４−）リス（３−三級プチル−４−グリシドキシフェ
ニル）ブタン、２，２．４−）リス（３−メチル−４−
グリシドキシ−５−三級ブチルフェニル）２タン。1.1.3-tris(3-tert-butyl-4-glycidoxyphenyl) 7sronon, 1,1.3-)lis(3-
Methyl-4-glycidoxy-5-tertiary butylphenyl)
Clopan, 1,1.3-)lis(2,5-dimethyl-4
-glycidoxyphenyl)pronosin, 1,1.3-tris(4-glycidoxyphenyl)butane, 1,1.3
-) Lis(3,5-tumethyl-4-glycidoxyphenyl)butane, 1.1.3-) Lis(3-tert-butyl-4
-glycidoxyphenyl)butane, 1,1.3-)lis(3-methyl-4-glycidoxy-5-tert-butylphenyl)butane, 1,1.3-)lis(2,5-dimethyl-4 -glycidoxyphenyl)butane, 2.2.4-)
Lis(4-glycidoxyphenyl)butane, 2,2.4
-) Lis(2-methyl-4-glycidoxy-5-tert-butylphenyl)butane, 2.2.4-) Lis(3,5-
dimethyl-4-glycidoxyphenyl)butane, 2,2
．． 4-) Lis(3-tertiary butyl-4-glycidoxyphenyl)butane, 2,2.4-) Lis(3-methyl-4-
Glycidoxy-5-tert-butylphenyl) ditan.
２．２，４−トリス（２，５−ジメチル−４−グリシド
キシフェニル）ブタン、１−（α−メチル−α−（２′
−メチル−４′−グリシドキシ−５′−三級ブチルフェ
ニル）エチル）−４−（α′、α−−ビス（２Ｉ−メチ
ル−４１−グリシドキシ−５１−三Ｒブｆルフェニル）
エチル〕ベンゼン、１−（α−メチル−α−（３’ 、
５’−ツメチル−４１−グリシドキシフェニル）エチル
）−４−（α′、αＩ−ビス（３＃ 、 ５１−ジメチ
ル−４Ｉ−グリシドキシフェニル）エチル〕ベンゼン、
１−（α−メチル−α−（３′−三級ブチル−４′−グ
リシドキシフェニル）エチル）−４−Ｃａ２．α′−ビ
ス（３１−三級ブチル−４Ｉ−グリシドキシフエニル）
エチル〕ベンゼン、１−〔α−メチル−α−（３′−メ
チル−４２−グリシドキシ−５′−三級ブチルフェニル
）エチル）−４−（α７．α′−ビス（３ｚ−メチル−
４１−グリシドキシ−５Ｉ−三級ブチルフェニル）エチ
ル〕ベンゼン、１−〔α−メチル−α−（２′，５′−
ジメチル−４′−グリシドキシフェニル）エチル〕−４
−〔α′、α′−ビス（２Ｎ、 ５＃ −ジメチル−
４１−グリシドキシフェニル）エチル〕ベンゼン、など
である。2.2,4-tris(2,5-dimethyl-4-glycidoxyphenyl)butane, 1-(α-methyl-α-(2′
-Methyl-4'-glycidoxy-5'-tert-butylphenyl)ethyl)-4-(α',α--bis(2I-methyl-41-glycidoxy-51-3Rbutylphenyl)
ethyl]benzene, 1-(α-methyl-α-(3',
5'-trimethyl-41-glycidoxyphenyl)ethyl)-4-(α', αI-bis(3#, 51-dimethyl-4I-glycidoxyphenyl)ethyl]benzene,
1-(α-methyl-α-(3′-tertiary butyl-4′-glycidoxyphenyl)ethyl)-4-Ca2. α′-bis(31-tert-butyl-4I-glycidoxyphenyl)
ethyl]benzene, 1-[α-methyl-α-(3'-methyl-42-glycidoxy-5'-tert-butylphenyl)ethyl)-4-(α7.α'-bis(3z-methyl-
41-Glycidoxy-5I-tert-butylphenyl)ethyl]benzene, 1-[α-methyl-α-(2′,5′-
Dimethyl-4'-glycidoxyphenyl)ethyl]-4
-[α', α'-bis(2N, 5# -dimethyl-
41-glycidoxyphenyl)ethyl]benzene, and the like.
前述した一般式（１）で表わされる３官能性エポキシ化
合物は１例えば下記一般式（１−（ＩＩ））、式中、Ｒ
１，Ｒ２，Ｒ，、Ｙおよびｎは前記した通シである、
で表わされるトリスフェノール化合物と、エピハロヒド
リンまたはβ−メチルエピハロヒドリン、好ましくはエ
ピクロルヒドリンまたはβ−メチルエピクロルヒドリン
とを、適轟なエーテル化触媒の存在下にエーテル化し、
次いで脱ハロゲン化水素することによって製造される。The trifunctional epoxy compound represented by the general formula (1) described above is 1, for example, the following general formula (1-(II)), in which R
1, R2, R, , Y and n are the same as described above. etherified in the presence of
It is then produced by dehydrohalogenation.
トリスフェノール化合物とエピハロヒドリンまたはβ−
メチルエピハロヒドリンとを反応させると、一般式（夏
）で表わされる３官能性エポキシ樹脂の他に１例えば下
記一般式（１−（ｌｉｉ） ）、式中、Ｒ１，Ｒ２，Ｒ
３，Ｚ、Ｙ、Ａおよびｎは前記した通シである。Trisphenol compounds and epihalohydrin or β-
When reacted with methyl epihalohydrin, in addition to the trifunctional epoxy resin represented by the general formula (summer), 1, for example, the following general formula (1-(lii)), in which R1, R2, R
3, Z, Y, A and n are the same as described above.
で表わされる４官能性エポキシ樹脂の如き多官能性エポ
キシ樹脂も生成する。Multifunctional epoxy resins such as the tetrafunctional epoxy resin represented by the formula are also produced.
本発明においては、一般式（１）で表わされる３官能性
エポキシ樹脂の他に一般式（１−（ＩＩ））で表わされ
るトリスフェノール化合物とエピハロヒドリンまたはβ
−メチルエピハロヒドリンとを反応させて得られる他の
多官能性エポキシ樹脂を含む多官能性エポキシ樹脂混合
物を用いても、これをハロゲン化ビスフェノール類と反
応させるととＫよって耐熱難燃性エポキシ樹脂を得るこ
とができる。In the present invention, in addition to the trifunctional epoxy resin represented by the general formula (1), a trisphenol compound represented by the general formula (1-(II)) and epihalohydrin or β
- Even if a polyfunctional epoxy resin mixture containing other polyfunctional epoxy resins obtained by reacting with methyl epihalohydrin is used, if this is reacted with halogenated bisphenols, a heat-resistant and flame-retardant epoxy resin will be produced. Obtainable.
従って、以下の説明において、本発明組成物における主
要成分である３官能性エポキシ樹脂に関することは、上
記多官能性エポキシ樹脂混合物についても同様に適用さ
れるものである。Therefore, in the following explanation, what is said regarding the trifunctional epoxy resin which is the main component in the composition of the present invention applies similarly to the above-mentioned polyfunctional epoxy resin mixture.
トリスフェノール化合物とエピハロヒドリンまたはβ−
メチルエピハロヒドリンとの反応は、従来公知のこの種
の反応にならって種々の方法で行なうことができる。そ
の一つの方法は、アルカリ化合物、例えば水酸化ナトリ
ウム、水酸化カリウム、水酸化リチウムなどのアルカリ
金属水酸化物、好ましくは水酸化ナトリウムをトリスフ
ェノール類のフェノール性水酸基１当量に対して倍モル
量１以上、好ましくは１．０２〜１．０５倍モルを用い
て、エーテル化工程と脱ハロゲン化水素化工程とを同時
に、水の存在下において約６０〜９０℃の温度で反応さ
せ、反応終了後反応混合物から未反応のハロヒドリン類
、水および生成した塩を除去し、反応生成物たる３官能
性エポキシ化合物を乾燥し、取得する方法（−投法）で
ある。Trisphenol compounds and epihalohydrin or β-
The reaction with methyl epihalohydrin can be carried out in various ways following conventionally known reactions of this type. One method is to add an alkali compound, for example, an alkali metal hydroxide such as sodium hydroxide, potassium hydroxide, lithium hydroxide, preferably sodium hydroxide, in twice the molar amount per equivalent of the phenolic hydroxyl group of trisphenol. 1 or more, preferably 1.02 to 1.05 times the mole, the etherification step and the dehydrohalogenation step are simultaneously reacted at a temperature of about 60 to 90 ° C. in the presence of water, and the reaction is completed. This is a method (-throwing method) in which unreacted halohydrins, water, and generated salts are removed from the post-reaction mixture, and a trifunctional epoxy compound as a reaction product is dried and obtained.
しかしながら、エーテル化工程と脱ハロゲン化水素化工
程とを順次行なう方法（二段法）を採用すると、安定し
た品質のエポキシ化合物を得ることができるので、よシ
好ましい方法といえる。However, a method in which the etherification step and the dehydrohalogenation step are carried out sequentially (two-stage method) is a more preferable method because an epoxy compound of stable quality can be obtained.
エーテル化工程は、トリスフェノール類のフェノール性
水酸基１当量に対して約０．００５〜５モル−のエーテ
ル化触媒、例えばトリメチルアミン、トリエチルアミン
などの第３アミン、トリフェニルホスフィン、トリブチ
ルホスフィンなどの第３ホスフイン、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、テトラエチルアンそニクムクロライド、テトラエ
チルアンモニウムブロマイド、塩化コリンなどの第４ア
ンそニウム塩、テトラメチルホスホニウムブロマイド、
テトラメチルホスホニウムアイオダイド、トリフェニル
７’０ビルホスホニウムブロマイドなどの第４ホスホニ
ウム塩、ペンジルグツチルスルホニウムクロ２イド、ベ
ンジルジメチルスルホニウムクロライドなどの第３スル
ホニウム塩など、好ましくは第４アンモニウム塩の存在
下で反応が行われる。The etherification step is carried out using an etherification catalyst of about 0.005 to 5 mol per equivalent of the phenolic hydroxyl group of trisphenols, such as a tertiary amine such as trimethylamine or triethylamine, or a tertiary amine such as triphenylphosphine or tributylphosphine. Quaternary amsonium salts such as phosphine, tetramethylammonium chloride, tetramethylammonium bromide, tetraethylammonium chloride, tetraethylammonium bromide, choline chloride, tetramethylphosphonium bromide,
Preferably in the presence of a quaternary ammonium salt, such as a quaternary phosphonium salt such as tetramethylphosphonium iodide, triphenyl 7'0ylphosphonium bromide, a tertiary sulfonium salt such as penzylbuttylsulfonium chloride, benzyldimethylsulfonium chloride, etc. The reaction takes place.
このエーテル化工程では、トリスフェノール類の水酸基
の少くとも約５０％以上、好ましくは約８０％以上がエ
ーテル化される迄反応が行われる。In this etherification step, the reaction is carried out until at least about 50% or more, preferably about 80% or more, of the hydroxyl groups of trisphenols are etherified.
この反応は、一般に約６０〜１１０℃の温度で約１〜１
２時間行われ、この除水は存在しない方が好ましく、存
在しても３．０重ｆ＃−以下となるように制御される。This reaction is generally carried out at a temperature of about 60 to 110°C and about 1 to 1
It is preferable that this water removal is not present, and even if it is present, it is controlled to be 3.0 weight f#- or less.
次の脱ハロｒン化水緊化工程には、エーテル化工程の反
応生成物がそのまま、即ち未反応のエビハロヒドリンを
含んだまま反応に供せられる。この反応の触媒としては
、上記第１の方法で使用したのと同じアルカリ化合物、
例えばアルカリ金属水酸化物、好ましくは水酸化ナトリ
ウムが、トリスフェノール類の７工ノール性水酸基１重
量に対して０，５倍七ル以上、好ましくは０．８倍モル
以上の割合で用いられる。ただし、この使用割合は、ダ
ル化などの不都合を避けるために１倍そル以下とするこ
とが望ましい。In the next dehalonization and water tightening step, the reaction product of the etherification step is subjected to the reaction as it is, ie, containing unreacted shrimp halohydrin. As a catalyst for this reaction, the same alkali compound as used in the first method above,
For example, an alkali metal hydroxide, preferably sodium hydroxide, is used in a molar ratio of 0.5 times or more, preferably 0.8 times or more, per weight of the heptanolic hydroxyl group of trisphenol. However, it is desirable that this usage ratio be less than 1:1 in order to avoid inconveniences such as dullness.
トリスフェノール化合物１モルに対して、エピハロヒド
リンマタハβ−メチルエビハロヒドリンを３〜３０屯ル
使用することが好ましい。エビハロヒドリンまたはβ−
メチルエピハロヒドリンとしては、工業的見地からエピ
クロルヒドリンまたはβ−メチルクロルヒドリンが好ま
しい。It is preferable to use 3 to 30 tons of epihalohydrin β-methylepihalohydrin per mole of the trisphenol compound. Shrimp halohydrin or β-
As the methyl epihalohydrin, epichlorohydrin or β-methylchlorohydrin is preferable from an industrial standpoint.
反応終了後は、減圧蒸留による未反応のエビハロヒドリ
ンの除去、水洗などによる副生塩の餘去および必要に応
じてリン酸、リン酸二水素ナトリウムなどの弱散による
中和がそれぞれ行われ、乾燥させて目的物たるエポキシ
化合物が取得される。After the reaction is complete, unreacted shrimp halohydrin is removed by distillation under reduced pressure, by-product salt is removed by washing with water, etc., and if necessary, neutralization is performed with weak dispersion of phosphoric acid, sodium dihydrogen phosphate, etc., and then dried. In this way, the target epoxy compound is obtained.
本発明における３官能性エポキシ化合物は、室温におい
て半固形から軟化点が１３０℃以下、エポキシ当量が１
５４乃至３８０のものである。The trifunctional epoxy compound in the present invention has a softening point ranging from semi-solid to 130°C or less at room temperature, and an epoxy equivalent of 1
54 to 380.
本発明において、前記３官能性エポキシ樹脂と反応させ
るハロゲン化ビスフェノール類としては、それ自体公知
のもの、例えばビスフェノールＡ。In the present invention, the halogenated bisphenols to be reacted with the trifunctional epoxy resin include those known per se, such as bisphenol A.
ビスフェノールＢ及びビスフェノールＦ等の各種のビス
フェノール類のハロゲン化物は全て使用し得るが、難燃
性向上効果及び工業的に容易に入手できることを考慮し
て、ブロム化ビスフェノール類、特にテトラブロムビス
フェノールＡ１テトラブロムビスフエノールＢ、テトラ
ブロムビスフェノールＦ及び１，１−ビス（３，５−ジ
ブロム−４−ヒドロキシフェニル）エタンが好適に使用
される。All of the halides of various bisphenols such as bisphenol B and bisphenol F can be used, but considering the effect of improving flame retardancy and the ease with which they can be obtained industrially, brominated bisphenols, especially tetrabromo bisphenol A1 tetra Bromobisphenol B, tetrabromobisphenol F and 1,1-bis(3,5-dibromo-4-hydroxyphenyl)ethane are preferably used.
本発明において、３官能性エポキシ樹脂とハロゲン化ビ
スフェノール類との反応は、無溶媒下或いは必要に応じ
トルエン、キシレン等の如き芳香族炭化水素類、メチル
イソブチルケトンの如きケトン類等の溶媒を使用し、触
媒の存在下で行なう。In the present invention, the reaction between the trifunctional epoxy resin and the halogenated bisphenols is carried out without a solvent or, if necessary, using a solvent such as an aromatic hydrocarbon such as toluene or xylene, or a ketone such as methyl isobutyl ketone. and in the presence of a catalyst.
上記触媒としては、エポキシ基と７エノール性水酸基と
の重付加反応に使用されるそれ自体公知の触媒のいずれ
をも使用することができる。このような触媒としては、
例えば、水酸化ナトリウム。As the catalyst, any catalyst known per se used for the polyaddition reaction between an epoxy group and a heptaenolic hydroxyl group can be used. Such a catalyst is
For example, sodium hydroxide.
炭酸ナトリウムなどの塩基性触媒、テトラアルキルアン
そニウムハライド、アラルキルトリアルキルアンモニウ
ムハライドなどの第４級アンモニウム塩触媒、トリフェ
ニルホスフィン、エチルトリフェニルホスホニウムハラ
イドなどのリン系触媒等を挙げることができる。触媒は
、使用されるエポキシ樹脂に対し、１０乃至４００ ｐ
ｐｍ程度使用することが好ましい。Examples include basic catalysts such as sodium carbonate, quaternary ammonium salt catalysts such as tetraalkylamsonium halides and aralkyl trialkylammonium halides, and phosphorus catalysts such as triphenylphosphine and ethyltriphenylphosphonium halides. The catalyst is 10 to 400 p based on the epoxy resin used.
It is preferable to use about pm.
上記反応は、約１２０乃至２００℃の温度で通常常圧下
に約３乃至２０時間、溶融状態乃至溶液状態で攪拌下に
行うことができる。The above reaction can be carried out at a temperature of about 120 to 200° C., usually under normal pressure, for about 3 to 20 hours in a molten or solution state with stirring.
上記反応において、更に、ｖスフエノールＡ型エポキシ
樹脂、ビスフェノールＦｉエポキシ樹脂、１．１−ビス
（グリシドキシフェニル）エタン等の２官能性エポキシ
化合物を併用することができる。本発明組成物における
主要成分である３官能性エポキシ樹脂とハロゲン化ビス
フェノールとを反応させて得られたエポキシ樹脂組成物
は、そのハロゲン含有量が多い場合には一般にその軟化
点が高くなシ過ぎる傾向にあるが、上記２官能性エポキ
シ樹脂を併用すると、反応後に得られるエポキシ樹脂の
難燃性を低下させることなくその軟化点を低下させるこ
とができる。従って、上記２官能性エポキシ樹脂の使用
量は、本発明のエポキシ樹脂組成物のハロゲン含有量、
所望する軟化点などによって適宜調節することができる
。しかしながら、本発明のエポキシ樹脂組成物が得られ
る硬化物のガラス転移温度を、従来公知のエポキシ樹脂
からの硬化物のそれよりも充分な効果が得られるように
するには、３官能性エポキシ化合物と２官能性工４キシ
化合物とは、５０：５０，９０：１０の重量比、特に６
０：４０乃至８０：２０の重量比で存在することが望ま
しい。In the above reaction, a bifunctional epoxy compound such as a v-sphenol A type epoxy resin, a bisphenol Fi epoxy resin, and 1,1-bis(glycidoxyphenyl)ethane can be further used in combination. The epoxy resin composition obtained by reacting the trifunctional epoxy resin and halogenated bisphenol, which are the main components in the composition of the present invention, generally has a softening point that is too high when the halogen content is high. Although there is a tendency, when the above bifunctional epoxy resin is used in combination, the softening point of the epoxy resin obtained after the reaction can be lowered without lowering the flame retardancy. Therefore, the amount of the bifunctional epoxy resin used depends on the halogen content of the epoxy resin composition of the present invention,
It can be adjusted as appropriate depending on the desired softening point. However, in order to make the glass transition temperature of the cured product obtained from the epoxy resin composition of the present invention more effective than that of the cured product from conventionally known epoxy resins, it is necessary to use a trifunctional epoxy compound. and the difunctional 4-oxy compound in a weight ratio of 50:50, 90:10, especially 6
Preferably, they are present in a weight ratio of 0:40 to 80:20.
上記ニーキシ化合物とノ・ロダン化ビスフェノール類と
の反応量割合は、反応生成エポキシ樹脂組成物中の所望
ハロゲン含有量に応じて適宜選定することができ、一般
に反応生成物である本発明のエポキシ樹脂組成物中のハ
ロゲン含有量が５乃至３０重量％、好ましくは１０乃至
２５重量％、特に好ましくは１５乃至２０重量％洗なる
ように選定することが好ましい。エポキシ樹脂組成物中
のハロゲン含有量が上記範囲よシも少ないと十分な難燃
性が発現し難い。The reaction amount ratio of the above-mentioned nixy compound and the non-rodanized bisphenol can be appropriately selected depending on the desired halogen content in the reaction product epoxy resin composition. The halogen content in the composition is preferably selected to be 5 to 30% by weight, preferably 10 to 25% by weight, particularly preferably 15 to 20% by weight. If the halogen content in the epoxy resin composition is less than the above range, it will be difficult to exhibit sufficient flame retardancy.
また、最終エポキシ樹脂は、一般に３００乃至２０００
、特に３００乃至１０００の範囲のエポキシ当量を有す
ることが、本発明の目的に望ましい。In addition, the final epoxy resin generally has a molecular weight of 300 to 2000
It is desirable for the purposes of the present invention to have an epoxy equivalent weight, especially in the range of 300 to 1000.
本発明によるエポキシ樹脂組成物は、必ずもこれに限定
されないが、下記式■、
式中、２はグリシドキシ基であり、
Ｒ１及びＲ２の各々は水素原子又は炭素数４以下のアル
キル基であシ、
Ｘはハロゲン原子であシ、
ｍは１以上の数であシ、
Ｅは、式、
（式中、Ｒ１，Ｒ２及びＲ３の各々は水素原子又は炭素
数４以下のアルキル基を示し、ｎはゼロ又は１である）
Ｙは１式、
Ｒ。Although not necessarily limited thereto, the epoxy resin composition according to the present invention has the following formula (1), where 2 is a glycidoxy group, and each of R1 and R2 is a hydrogen atom or an alkyl group having 4 or less carbon atoms. , X is a halogen atom, m is a number of 1 or more, E is the formula, (wherein each of R1, R2 and R3 represents a hydrogen atom or an alkyl group having 4 or less carbon atoms, n is zero or 1) Y is 1 formula, R.
、 ＣＨ２−Ｃ−・−（Ｉｃｅ）
薯
Ｒ７
（式中、 Ｒ４，Ｒ５，Ｒ６及びＲ２は、水素原子又は
炭素数４以下のアルキル基を示す、）で表わされる基で
ある、
で表わされる重合体を含有する。, CH2-C-.-(Ice) 薯R7 (wherein, R4, R5, R6 and R2 represent a hydrogen atom or an alkyl group having 4 or less carbon atoms), Contains union.
また、３官能性エポキシ化合物と２官能性エポキシ化合
物との組合せから誘導されるエポキシ樹脂組成物は、下
記式
％式％（［［）
式中、２はグリシドキシ基であり、
Ｒ１及びＲ２の各々は水素原子又は炭素数４以下のアル
キル基であシ、
Ｘはハロゲン原子であシ、
にはＯ又は１以上の数であシ、ｔは１以上の数であって
、３００乃至２０００のエポキシ光量と５乃至３０重量
％を有する様に選択される、Ｅは、式、
（式中、”１＊Ｒ２及びＲ５の各々は水素原子又は炭素
数４以下のアルキル基を示し、ｎはゼロ又は１である）
Ｙは、式、
Ｒ。Further, an epoxy resin composition derived from a combination of a trifunctional epoxy compound and a difunctional epoxy compound has the following formula % formula % ([[) where 2 is a glycidoxy group, and each of R1 and R2 is a hydrogen atom or an alkyl group having 4 or less carbon atoms, X is a halogen atom, is O or a number of 1 or more, t is a number of 1 or more, and 300 to 2000 epoxy E is selected to have a light intensity of 5 to 30% by weight; 1) Y is the formula, R.
又は式、
−ＣＨ２−Ｃ−＝ （Ｉｌｌｃ）
（式中、Ｒ４，Ｒ，、Ｒ４及びＲ７は、水素原子又は炭
素数４以下のアルキル基を示す、）で表わされる基を示
す、
で表わされる共重合体を含有する。or a group represented by the formula, -CH2-C-= (Illc) (wherein R4, R,, R4 and R7 represent a hydrogen atom or an alkyl group having 4 or less carbon atoms), represented by Contains a copolymer.
本発明のエポキシ樹脂組成物は、必要に応じて本発明の
目的を損なわない範囲において、それ自体公知の他のエ
ポキシ樹脂、例えばフェノールノがラック型エポキシ樹
脂、オルソクレゾールノボラック型エポキシ樹脂等と併
用することができる。The epoxy resin composition of the present invention may be used in combination with other epoxy resins known per se, such as phenolac type epoxy resins, orthocresol novolac type epoxy resins, etc., as necessary, within a range that does not impair the purpose of the present invention. can do.
エポキシ樹脂配合物には、以上の各成分以外に、７タル
酸エステル、グリコール類のエーテルまたはエステ／Ｌ
／類などの非反応性希釈剤、長鎖アルキレンオキサイド
、ブチルグリシジルエーテル、フェニルクリシジルエー
テル、ｐ−ブチルフェニルグリシジルエーテルなどの反
応性希釈剤、炭酸カルシウム、クレー、アスベスト、シ
リカ、マイカ、石英粉、アルミニウム粉末、グラファイ
ト、激化チタン、アルミナ、酸化鉄、ガラス粉末、ガラ
ス繊維などの充填剤、カーメンブラック、トルイジン赤
、ハンサイエロー、フタロシアニンブルー、フタロシア
ニングリーンなどの着色剤などが適宜配合される。In addition to the above-mentioned components, the epoxy resin formulation also contains heptalic acid ester, glycol ether or ester/L
Non-reactive diluents such as /, reactive diluents such as long chain alkylene oxide, butyl glycidyl ether, phenyl clycidyl ether, p-butylphenyl glycidyl ether, calcium carbonate, clay, asbestos, silica, mica, quartz powder , fillers such as aluminum powder, graphite, hardened titanium, alumina, iron oxide, glass powder, and glass fiber, and colorants such as carmen black, toluidine red, Hansa yellow, phthalocyanine blue, and phthalocyanine green are appropriately blended.
使用に際しては、一般に通常のエポキシ樹脂用硬化剤と
して知られている脂肪族アミン系、芳香族アミン系、ア
ミンアダクト、ジシアンジアミド、フェノールノーラッ
ク樹脂、オルトクレゾールノゲラ、り樹脂、酸無水物尋
の硬化剤を配合した組成物の形で、電気絶縁塗料、成形
材料、封止材、積層板等の製造に用いることができる。When used, aliphatic amines, aromatic amines, amine adducts, dicyandiamide, phenol Norac resins, ortho-cresol Nogera, resins, and acid anhydride resins, which are generally known as curing agents for epoxy resins, are used. In the form of a composition containing a curing agent, it can be used in the production of electrically insulating paints, molding materials, sealants, laminates, etc.
用いられる硬化剤の使用量は、硬化剤の種類によっても
異なるが１例えばボリアオン類を用いる場合には、エポ
キシ当量と活性水素当量との比を基準とする。また、硬
化促進剤も必要に応じて使用できる。The amount of the curing agent used varies depending on the type of curing agent; for example, in the case of using boriaones, it is based on the ratio of epoxy equivalent to active hydrogen equivalent. Further, a curing accelerator can also be used if necessary.
塗料として用いられる場合には、汎用の着色剤（顔料）
、充填剤、溶剤、消泡剤等を配合して調製され、成形材
料の封止材の場合には種々の充填材を使用することが出
来る。積層板用エポキシ樹脂組成物として用いられる場
合には、一般にはトルエン、キシレンなどの芳香族炭化
水床類、アセトン、メチルエチルケトン、メチルイソブ
チルケトンなどのケトン類などの溶剤を用いてフェスの
形に調製される。調製されたエポキシ樹脂組成物は、こ
れをガラスクロス、カーゲン７丁イノ々−、グラスファ
イバー、紙、石綿、Ｉリスステル繊維、芳香族ポリアミ
ド繊維（商品名ケプラー）などの補強用基材に含浸させ
、これをプリプレグとした後、プレスで加熱加圧して積
層板に成形される。When used as a paint, a general-purpose colorant (pigment)
, a filler, a solvent, an antifoaming agent, etc., and in the case of a sealant for a molding material, various fillers can be used. When used as an epoxy resin composition for laminates, it is generally prepared into a festival shape using a solvent such as aromatic hydrocarbons such as toluene and xylene, and ketones such as acetone, methyl ethyl ketone, and methyl isobutyl ketone. be done. The prepared epoxy resin composition is impregnated into a reinforcing base material such as glass cloth, Kagen 7-cho Ino-ni, glass fiber, paper, asbestos, I-lister fiber, aromatic polyamide fiber (trade name Kepler), etc. After making this prepreg, it is heated and pressed in a press to form a laminate.
実施例 １
１．１．３−）リス（２−メチル−４−グリシドキシ−
５−三級ブチルフェニル）ブタン（エポキシ当量２４Ｂ
）４００１テトラブロムビスフエノールＡ１７６．４．
Ｆおよびキシレン６０Ｉを、容積１ｔの七ツクラブルフ
ラスコに仕込み、これに更にテトラメチルアンそニウム
クルライドの１重量％水溶液１．６ ｍを添加した。こ
の混合物を窒素ガス雰囲気下で攪拌しながら加熱したと
ころ、１００℃迄で該混合物は完蚕に均一になった。引
続き反応系を減圧にし、１４０″Ｃｔで昇温しながらキ
シレンと水とを除去した。その後反応系を常圧に戻し窒
素ガス雰囲気下で１５０℃で６時間加熱を継続した。Example 1 1.1.3-)lis(2-methyl-4-glycidoxy-
5-tertiary butylphenyl)butane (epoxy equivalent weight 24B
) 4001 Tetrabromobisphenol A176.4.
F and xylene 60I were placed in a 1 t capacity seven crab flask, and 1.6 ml of a 1% by weight aqueous solution of tetramethylanthonium chloride was added thereto. When this mixture was heated under a nitrogen gas atmosphere while stirring, the mixture became homogeneous into complete silkworms at a temperature of 100°C. Subsequently, the pressure of the reaction system was reduced, and xylene and water were removed while raising the temperature to 140''Ct.The reaction system was then returned to normal pressure, and heating was continued at 150°C for 6 hours under a nitrogen gas atmosphere.
その結果、エポキシ当量が６０５、ブロム含量約１８３
ｉ量チのニーキシ樹脂組成物５７６．４！Ｉが得られた
。このニーキシ樹脂組成物はメチルエチルケトンに可溶
であった。As a result, the epoxy equivalent was 605 and the bromine content was approximately 183.
I amount of Nixi resin composition 576.4! I was obtained. This Nixie resin composition was soluble in methyl ethyl ketone.
実施例 ２
仕込原料のうち、１，１．３−）リス（２−メチル−４
−グリシドキシ−５−三級ブチルフェニル）ブタン４０
０Ｉを、１，１，３−トリス（２−メチル−４−グリシ
ドキシ−５−三級ブチルフェニルブタン（エポキシ当量
２７１）２８０ｊとビスフェノールＡ型エポキシ樹脂（
エポキシ当量１８９、三片石油化学工業■製、登録商標
エポミ、りＲ−１４０）１２０１１との混合物に変えた
ほかは、実施例１におけると同様に処理して、エポキシ
当量５７３、ブロム含有量約１８重量−のエポキシ樹脂
組成物５７６．４Ｉｉを得た。このエポキシ樹脂組成物
はメチルエチルケトンに可溶でありた。Example 2 Among the raw materials, 1,1.3-)lis(2-methyl-4
-glycidoxy-5-tertiary butylphenyl)butane 40
0I, 1,1,3-tris(2-methyl-4-glycidoxy-5-tertiary butylphenylbutane (epoxy equivalent weight 271) 280j and bisphenol A type epoxy resin (
The treatment was carried out in the same manner as in Example 1, except that the epoxy equivalent was 189, the registered trademark Epomi, manufactured by Mikata Petrochemical Industry ■, and the mixture with R-140) 12011, and the epoxy equivalent was 573 and the bromine content was approx. An epoxy resin composition 576.4Ii with a weight of 18% was obtained. This epoxy resin composition was soluble in methyl ethyl ketone.
実施例 ３
仕込原料のうち、１，１．３−トリス（２−メチル−４
−グリシドキシ−５−三級ブチルフェニル）ブタン４０
０Ｉを、１−〔α−メチル−α−（４′−グリシドキシ
フェニル）エチル］−４−〔α′、α′−ビス（４１−
グリシドキシフェニル）エチル〕ベンゼン（エポキシ当
１２０９）４００．９に変えたほかは、実施例１におけ
ると同様に処理して、エポキシ当量４８６、ブロム含有
量約１８重量−のエポキシ樹脂組成物５７６．４．５Ｉ
ｔ−得た。Example 3 Among the raw materials, 1,1,3-tris(2-methyl-4
-glycidoxy-5-tertiary butylphenyl)butane 40
0I to 1-[α-methyl-α-(4′-glycidoxyphenyl)ethyl]-4-[α′, α′-bis(41-
An epoxy resin composition having an epoxy equivalent of 486 and a bromine content of about 18 by weight was prepared in the same manner as in Example 1, except that glycidoxyphenyl)ethyl]benzene (epoxy equivalent: 1209) was changed to 400.9. .4.5I
t- got it.
このエポキシ樹脂組成物はメチルエチルケトンに可溶で
あった。This epoxy resin composition was soluble in methyl ethyl ketone.
実施例 ４
仕込原料のうち、１，１．３−）リス（２−メチル−４
−グリシドキシ−５−三級ブチルフェニル）ブタン４０
０Ｉｉを、１−〔α−メチル−α−（４′轡 グリシド
キシフェニル）エチル）−４−〔α′、α′ −ビス（
４Ｉ−グリシドキシフェニル）エチル〕ベンゼン（エポ
キシ当量２１７）２８０ＩとビスフェノールＡ型エポキ
シ樹脂（ニーキシ当量１８９、三片石油化学工業■製、
登録商標エポミックＲ−１４０）１２０ＪＩとの混合物
に変えたほかは、実施例１におけると同様に処理して、
エポキシ当量４５３、ブロム含有量約１８重量−のエポ
キシ樹脂組成物５７６．４１ｉを得た。このエポキシ樹
脂組成物はメチルエチルケトンに可溶であった。Example 4 Among the raw materials, 1,1.3-)lis(2-methyl-4
-glycidoxy-5-tertiary butylphenyl)butane 40
0Ii, 1-[α-methyl-α-(4′轡 glycidoxyphenyl)ethyl)-4-[α′, α′-bis(
4I-glycidoxyphenyl)ethyl]benzene (epoxy equivalent: 217) 280I and bisphenol A type epoxy resin (epoxy equivalent: 189, manufactured by Mikata Petrochemical Industry ■),
The process was carried out in the same manner as in Example 1, except that the mixture was changed to a mixture with registered trademark Epomic R-140) 120JI.
An epoxy resin composition 576.41i having an epoxy equivalent weight of 453 and a bromine content of about 18 weight was obtained. This epoxy resin composition was soluble in methyl ethyl ketone.
実施例 ５
仕込み原料のうち、１，１．３−）リス（２−メチル−
４−グリシドキシ−５−三級ブチルフェニル）ブタン４
００ｊを、１−〔α−メチル−α−（３’ 、５’
−ジメチル−４１−グリシドキシフェニル）エチル）−
４−（αＩ、α′−ビス（３″，５″−ジメチル−４１
−グリシドキシフェニル）エチル〕ベンゼン（エポキシ
当量２４０）４００ＩＩに変えたほかは、実施例ＩＫお
けると同様に処理して、エポキシ当量４５１、ブロム含
量約１８重量％のエポキシ樹脂組成物５７６．４Ｊ’を
得た。このエポキシ樹脂組成物はメチルエチルケトンに
可溶であった・
実施例 ６
仕込み原料のうち、１，１．３−）リス（２−メチル−
４−グリシドキシ−５−三級ブチルフェニル）ブタン４
００Ｊｌをトリス（４−グリシドキシフェニル）メタン
（エポキシ当量１６２ ） ４００ＩｉＫ変えたほかは
、実施例１におけると同様に処理して、エポキシ当量３
３０、ブロム含量約１８重量−のエポキシ樹脂組成物５
７６．４．９を得た。Example 5 Among the raw materials, 1,1.3-)lis(2-methyl-
4-glycidoxy-5-tertiary butylphenyl)butane 4
00j, 1-[α-methyl-α-(3', 5'
-dimethyl-41-glycidoxyphenyl)ethyl)-
4-(αI, α′-bis(3″,5″-dimethyl-41
-glycidoxyphenyl)ethyl]benzene (epoxy equivalent weight 240) The same procedure as in Example IK was carried out except that 400 II of benzene (epoxy equivalent weight 240) was used, and 576.4 J of an epoxy resin composition having an epoxy equivalent weight of 451 and a bromine content of about 18% by weight was prepared. got '. This epoxy resin composition was soluble in methyl ethyl ketone.
4-glycidoxy-5-tertiary butylphenyl)butane 4
The same procedure as in Example 1 was carried out except that 00Jl was changed to tris(4-glycidoxyphenyl)methane (epoxy equivalent: 162) 400IiK, and the epoxy equivalent was 3.
30, epoxy resin composition 5 having a bromine content of about 18% by weight
76.4.9 was obtained.
このエポキシ樹脂組成物はメチルエチルケトンに可溶で
あった。This epoxy resin composition was soluble in methyl ethyl ketone.
実施例 ７
仕込み原料のうち、１，１．３−）リス（２−メチル−
４−グリシドキシ−５−三級ブチルフェニル）ブタン４
００Ｆを１．１．３−）リス（４−グリシドキシフェニ
ル）グ四パン（エポキシ当量１８６）４００ＩＩＫ変え
たほかは、実施例１におけると同様に処理して、エポキ
シ当量３９４、ブロム含量約１８重量−のエポキシ樹脂
組成物５７６．４Ｎを得た。このエポキシ樹脂組成物は
メチルエチルケトンに可溶であった。Example 7 Among the raw materials, 1,1.3-)lis(2-methyl-
4-glycidoxy-5-tertiary butylphenyl)butane 4
The process was carried out in the same manner as in Example 1 except that 00F was changed to 1.1.3-)lis(4-glycidoxyphenyl)glypane (epoxy equivalent: 186) 400IIK, and the epoxy equivalent was 394 and the bromine content was approx. An epoxy resin composition of 576.4N with a weight of 18% was obtained. This epoxy resin composition was soluble in methyl ethyl ketone.
実施例 ８
仕込み原料のうち、１，１．３−）リス（２−メチル−
４−グリシドキシ−５−三級ブチルフェニル）ブタン４
００Ｊを１．１．３−）リス（３，５−ジメチ／ｌ／
−４−グリシドキシフェニル）プロ／母ン（エポキシ当
量２０６）４００ＪＩに変えたほかは実施例１における
と同様の処理をして工Ｉキシ当ｆｔ４４６．ブロム含量
約１８重量−のエポキシ樹脂組成物５７６．４Ｊを得た
。このエポキシ樹脂組成物はメチルエチルケトンに可溶
であった。Example 8 Among the raw materials, 1,1.3-)lis(2-methyl-
4-glycidoxy-5-tertiary butylphenyl)butane 4
00J to 1.1.3-)lith(3,5-dimethy/l/
-4-Glycidoxyphenyl)pro/mathane (epoxy equivalent weight 206) was treated in the same manner as in Example 1, except that the epoxy equivalent weight was changed to 400 JI. 576.4 J of an epoxy resin composition having a bromine content of about 18 weight was obtained. This epoxy resin composition was soluble in methyl ethyl ketone.
比較例
１．１．３−）リス（２−メチル−４−グリシドキシ−
５−三級ブチルフェニル）ブタンの代わシに、オルソク
レゾールノ？う、り型ニーキシ樹脂（エポキシ当１−２
１２、日本化薬■製、ＥＯＣＮ１０２）４００Ｊを使用
した他は、実施例１におけると同様に処理したとζろ、
数時間の反応によって反応物がｒル化し、反応生成物は
メチルエチルケトンに可溶であった。Comparative Example 1.1.3-) Lis(2-methyl-4-glycidoxy-
Ortho-cresol instead of 5-tertiary butylphenyl) butane? U, Ri type Nixi resin (epoxy 1-2
12. The treatment was carried out in the same manner as in Example 1 except that EOCN102) 400J manufactured by Nippon Kayaku ■ was used.
After several hours of reaction, the reaction product was converted to chloride, and the reaction product was soluble in methyl ethyl ketone.
応用例 ｌ
実施例１で得られたエポキシ樹脂組成物をメチルエチル
ケトンに溶解して、エポキシ樹脂濃度７５重量−の溶液
を調製した。このエポキシ樹脂溶液（固形分として１０
０重量部）と、メチル七ロソル２１５重量部、ジメチル
ホルムアミド１５重量部、ジシアンジアミド３．１重量
部および２−エチル−４−メチルイミダゾール（四国化
成工業■製、２Ｅ４ＭＺ）０．２重量部の溶液とを混合
し、ワニス状のエポキシ樹脂組成物を調製した。Application Example 1 The epoxy resin composition obtained in Example 1 was dissolved in methyl ethyl ketone to prepare a solution with an epoxy resin concentration of 75 weight. This epoxy resin solution (solid content: 10
0 parts by weight), 215 parts by weight of methyl heptarosol, 15 parts by weight of dimethylformamide, 3.1 parts by weight of dicyandiamide and 0.2 parts by weight of 2-ethyl-4-methylimidazole (manufactured by Shikoku Kasei Kogyo ■, 2E4MZ). A varnish-like epoxy resin composition was prepared.
この組成物をガラスクロス（日東紡績■製、ＷＥ−１８
に−ＢＺ２）Ｋ含浸させ、１５０ｔｌ：で６分間加熱し
Ｂステージ化され九含浸率約４５重量％のグリプレグを
得た。このグリプレグを９グライ重ねて１８０℃、１０
ｋＩＩｆ／ｍ 、 ９０分間の成形条件下でガラスクロ
ス積層板を作製した。This composition was applied to a glass cloth (manufactured by Nitto Boseki, WE-18).
-BZ2) was impregnated with K and heated at 150 tl for 6 minutes to obtain a B-stage Gripreg with an impregnation rate of about 45% by weight. Layer 9 pieces of this Gripreg and heat at 180℃ for 10 minutes.
Glass cloth laminates were produced under molding conditions of kIIf/m for 90 minutes.
成形された積層板の硬化樹脂のガラス転移温度（Ｔｇ）
を、示差走査熱量計（ＤｓＣ）で測定した結果、１８５
℃であった。また難燃性はＵＬ法で９４Ｖ−０であった
。Glass transition temperature (Tg) of cured resin of molded laminate
As a result of measuring with a differential scanning calorimeter (DsC), it was found that 185
It was ℃. Moreover, the flame retardancy was 94V-0 according to the UL method.
応用例 ２
実施例１で得られたエポキシ樹脂組成物の代わシに実施
例２で得られたエポキシ樹脂組成物を使用し、ジシアン
ジアミドの使用量を３．３重量部に変えた他は応用例Ｉ
Ｋおけると同様に実施して、ガラスクロス積層板を作製
した。Application example 2 Application example except that the epoxy resin composition obtained in Example 2 was used instead of the epoxy resin composition obtained in Example 1, and the amount of dicyandiamide used was changed to 3.3 parts by weight. I
A glass cloth laminate was produced in the same manner as in K.
この積層板の硬化樹脂のＴ、は１７０℃であった。The T of the cured resin of this laminate was 170°C.
また、難燃性はＵＬ法で９４Ｖ−０であった。Moreover, the flame retardancy was 94V-0 according to the UL method.
応用例 ３
実施例１で得られたエポキシ樹脂の代わシに実施例３で
得られたエポキシ樹脂を使用し、ジシアンジアミドの使
用量を３．９重量部に変えた他は応用例１におけると同
様に実施して、ガラスクロス積層板を作製した。Application Example 3 Same as in Application Example 1 except that the epoxy resin obtained in Example 3 was used instead of the epoxy resin obtained in Example 1, and the amount of dicyandiamide used was changed to 3.9 parts by weight. A glass cloth laminate was produced by carrying out the following steps.
この積層板の硬化樹脂のＴｇは１８８℃であった。The Tg of the cured resin of this laminate was 188°C.
応用例 ４
実施例１で得られたエポキシ樹脂組成物の代ゎ）Ｋ実施
例４で得られたエポキシ樹脂組成物を使用し、ジシアン
ジアミドの使用量を４．２重量部に変えた他は応用例１
におけると同様に実施して、ガラスクロス積層板を作製
した。Application example 4 Example of the epoxy resin composition obtained in Example 1) The epoxy resin composition obtained in Example 4 was used, except that the amount of dicyandiamide used was changed to 4.2 parts by weight. Example 1
A glass cloth laminate was produced in the same manner as in .
この積層板の硬化樹脂のＴｇは１７５℃であった。The Tg of the cured resin of this laminate was 175°C.
また、難燃性はＵＬ法で９４Ｖ−０であった。Moreover, the flame retardancy was 94V-0 according to the UL method.
比較応用例 １
実施例１で得られたエポキシ樹脂組成物の代わシに、ブ
ロム化ビスフェノールＡ型エポキシ樹脂（エポキシ当量
４０８、ブロム含量１８重量％）１００重量部を使用し
、ジシアンジアミドの使用量を４．７重量部に変えた他
は応用例ＩＫおけると同様に実施して、ガラスクロス積
層板を作製し九〇この積層板の硬化樹脂のＴｇは１２７
℃であった。Comparative Application Example 1 Instead of the epoxy resin composition obtained in Example 1, 100 parts by weight of a brominated bisphenol A epoxy resin (epoxy equivalent: 408, bromine content: 18% by weight) was used, and the amount of dicyandiamide used was A glass cloth laminate was prepared in the same manner as in Application Example IK except that the amount was changed to 4.7 parts by weight.90 The Tg of the cured resin of this laminate was 127.
It was ℃.
応用例 ５
実施例１で得られたエポキシ樹脂組成物の代わシに実施
例５で得られたエポキシ樹脂組成物を使用し、ジシアン
ジアミドの使用量を４．２重量部に変えた他は応用例１
におけると同様に実施して、ガラスクロス積層板を作製
した。Application example 5 Application example except that the epoxy resin composition obtained in Example 5 was used instead of the epoxy resin composition obtained in Example 1, and the amount of dicyandiamide used was changed to 4.2 parts by weight. 1
A glass cloth laminate was produced in the same manner as in .
この積層板の硬化樹脂のＴｇは１９０’Ｃであった。The Tg of the cured resin of this laminate was 190'C.
また難燃性はＵＬ法で９４Ｖ−０であった。Moreover, the flame retardancy was 94V-0 according to the UL method.
応用例 ６
実施例１で得られたエポキシ樹脂組成物の代わシに実施
例６で得られたエポキシ樹脂組成物を使用し、ジシアン
ジアミドの使用量を５．８重量部に変えた他は応用例１
におけると同様に実施して、ガラスクロス積層板を作製
した。Application example 6 Application example except that the epoxy resin composition obtained in Example 6 was used instead of the epoxy resin composition obtained in Example 1, and the amount of dicyandiamide used was changed to 5.8 parts by weight. 1
A glass cloth laminate was produced in the same manner as in .
との積層板の硬化樹脂のＴｇは１８６℃であった。The Tg of the cured resin of the laminate was 186°C.
また難燃性はＵＬ法で９４Ｖ−０であった。Moreover, the flame retardancy was 94V-0 according to the UL method.
応用例 ７
実施例１で得られたエポキシ樹脂組成物の代わシに実施
例７で得られたエポキシ樹脂組成物を使用し、ジシアン
ジアミドの使用量を４．８ｉ量部に変えた他は応用例１
におけると同様に実施して、ガラスクロス積層板を作製
した。Application example 7 Application example except that the epoxy resin composition obtained in Example 7 was used instead of the epoxy resin composition obtained in Example 1, and the amount of dicyandiamide used was changed to 4.8 parts. 1
A glass cloth laminate was produced in the same manner as in .
この積層板の硬化樹脂のＴｇは１８１℃であった。The Tg of the cured resin of this laminate was 181°C.
また難燃性はＵＬ法で９４Ｖ−０であった。Moreover, the flame retardancy was 94V-0 according to the UL method.
応用例 ８
実施例１で得られたエポキシ樹脂組成物の代わシに実施
例８で得られたエポキシ樹脂組成物を使用し、ジシアン
ジアミドの使用量を４．３重量に変えた他は応用例１に
おけると同様に実施して、ガラスクロス積層板を作製し
た。Application example 8 Application example 1 except that the epoxy resin composition obtained in Example 8 was used instead of the epoxy resin composition obtained in Example 1, and the amount of dicyandiamide used was changed to 4.3 weight. A glass cloth laminate was produced in the same manner as in .
この積層板の硬化樹脂のＴｇは１８３℃であった。The Tg of the cured resin of this laminate was 183°C.
また難燃性はＵＬ法で９４Ｖ−０でありた。Moreover, the flame retardancy was 94V-0 according to the UL method.
比較応用例 ２
実施例１で得られたエポキシ樹脂組成物の代わりに、ブ
ロム化ビスフェノールＡ型エポキシ樹脂（エポキシ当量
４７９、ブロム含量２１重量％）８６重量部とオルソク
レゾールノがう、り型エポキシ樹脂（エポキシ当量２１
０、日本化系■製、ｗｏｃＮ １０３Ｓ ）１４重量部
との混合物（ブロム含量的１８重量チ）を使用し、ジシ
アンシアミドの使用量を４．７重量部に変えた他は応用
例１におけると同様に実施して、ガラスクロス積層板を
作製した。Comparative Application Example 2 Instead of the epoxy resin composition obtained in Example 1, 86 parts by weight of brominated bisphenol A epoxy resin (epoxy equivalent: 479, bromine content 21% by weight) and ortho-cresol-type epoxy were used. Resin (epoxy equivalent weight 21
Same as in Application Example 1, except that a mixture with 14 parts by weight of WOCN 103S (manufactured by Nippon Kaikai ■) (18 parts by weight in terms of bromine content) was used, and the amount of dicyancyamide used was changed to 4.7 parts by weight. A glass cloth laminate was produced by carrying out the following steps.
この積層板の硬化樹脂のＴｇは１３７℃であった。The Tg of the cured resin of this laminate was 137°C.
実施例 ９
仕込原料のうち、テトラブロムビスフェノールＡを１，
１−ビス（３，５−レゾロム−４−ヒドロキシフェニル
）エタン（臭素含有量５９．２］ｉ量チ）１７６．４Ｉ
Ｉに変えたにか、実施例１におけると同様に処理して、
エポキシ当量６１０、ブロム含有量約１８重量−の樹脂
組成物５７６．４Ｆを得た。このエポキシ樹脂組成物は
メチルエチルケトンに可溶であった。Example 9 Among the raw materials, 1% of tetrabromobisphenol A was
1-bis(3,5-resolom-4-hydroxyphenyl)ethane (bromine content 59.2) i amount 176.4I
I, but treated in the same manner as in Example 1,
Resin composition 576.4F having an epoxy equivalent of 610 and a bromine content of about 18 weight was obtained. This epoxy resin composition was soluble in methyl ethyl ketone.
実施例 １０
実施例３の仕込み原料のうちテトラブロムビスフェノー
ルＡを１，１−ビス（３，５−ジブロム−４−ヒドロキ
シフェニル）エタン１７６．４＃に変えたほか、実施例
１におけると同様に処理してエポキシ当量４７２、プシ
ム含有量約１８重量％のエポキシ樹脂組成物５７６．４
Ｆを得た。このエポキシ樹脂組成物は、メチルエチルケ
トンに可溶であった。Example 10 The same procedure as in Example 1 was carried out except that tetrabromobisphenol A of the raw materials used in Example 3 was changed to 1,1-bis(3,5-dibromo-4-hydroxyphenyl)ethane 176.4#. Processed to produce an epoxy resin composition with an epoxy equivalent weight of 472 and a psym content of approximately 18% by weight 576.4
I got an F. This epoxy resin composition was soluble in methyl ethyl ketone.
実施例 １１
実施例６の仕込み原料とうちテトラブロムビスフェノー
ルＡを１．１−ビス（３，５−グツロム−４−ヒドロキ
シフェニル）エタン１７６．１に変えたほか、実施例１
におけると同様に処理してエポキシ当量３２２、ブロム
含量約１８重量％のエポキシ樹脂組成物５７６．４ＩＩ
を得た。このエポキシ樹脂組成物はメチルエチルケトン
に可溶であった。Example 11 Among the raw materials used in Example 6, tetrabromobisphenol A was changed to 1,1-bis(3,5-guturom-4-hydroxyphenyl)ethane 176.1, and Example 1
An epoxy resin composition 576.4II having an epoxy equivalent weight of 322 and a bromine content of about 18% by weight was prepared in the same manner as in
I got it. This epoxy resin composition was soluble in methyl ethyl ketone.
実施例 １２
実施例７の仕込み原料のうちテトラブロムビスフェノー
ルＡを１，１−ビス（３，５−ジブロム−４−ヒドロキ
シフェニル）エタン１７６．４．９に変えたほか、実施
例１におけると同様に処理して、エポキシ当量３９１．
ブロム含量約１８重量−のエポキシ樹脂組成物５７６．
４１１を得た。このエポキシ樹脂組成物はメチルエチル
ケトンに可溶であった。Example 12 Same as in Example 1 except that tetrabromobisphenol A of the raw materials used in Example 7 was changed to 1,1-bis(3,5-dibromo-4-hydroxyphenyl)ethane 176.4.9. The epoxy equivalent weight was 391.
Epoxy resin composition with a bromine content of about 18% by weight 576.
I got 411. This epoxy resin composition was soluble in methyl ethyl ketone.
応用例 ９
実施例１で得られたエポキシ樹脂組成物の代わシに１実
施例９で得られたエポキシ樹脂組成物を使用した他応用
例１におけると同様に実施して、ガラスクロス積層板を
作製した。Application Example 9 In place of the epoxy resin composition obtained in Example 1, the epoxy resin composition obtained in Example 9 was used, and in the same manner as in Application Example 1, a glass cloth laminate was made. Created.
この積層板の硬化樹脂のＴｇは１７６℃であった。The Tg of the cured resin of this laminate was 176°C.
また難燃性はＵＬ法で９４Ｖ−０であった。Moreover, the flame retardancy was 94V-0 according to the UL method.
応用例 １０
実施例１で得られたエポキシ樹脂組成物の代わシに実施
例１０で得られたエポキシ樹脂組成物を使用し、ジシア
ンジアミドの使用量を３．９重量部に変えた他は応用例
１におけると同様に実施してガラスクロス積層板を作製
した。Application example 10 Application example except that the epoxy resin composition obtained in Example 10 was used instead of the epoxy resin composition obtained in Example 1, and the amount of dicyandiamide used was changed to 3.9 parts by weight. A glass cloth laminate was produced in the same manner as in Example 1.
この積層板の硬化樹脂のＴｇは１８１℃であった。The Tg of the cured resin of this laminate was 181°C.
また難燃性はＵＬ法で９４Ｖ−０であった。Moreover, the flame retardancy was 94V-0 according to the UL method.
応用例 １１
実施例１で得られたエポキシ樹脂組成物の代わシに実施
例１１で得られたエポキシ樹脂組成物を使用し、ジシア
ンジアミドの使用量を５．８重量部に変えた他は応用例
ＩＫおけると同様に実施して、ガラスクロス積層板を作
製した。Application example 11 Application example except that the epoxy resin composition obtained in Example 11 was used instead of the epoxy resin composition obtained in Example 1, and the amount of dicyandiamide used was changed to 5.8 parts by weight. A glass cloth laminate was produced in the same manner as in IK.
この積層板の硬化樹脂のＴｇは１７７℃であった。The Tg of the cured resin of this laminate was 177°C.
また難燃性はＵＬ法で９４Ｖ−０であった。Moreover, the flame retardancy was 94V-0 according to the UL method.
応用例 １２
実施例１で得られたエポキシ樹脂組成物の代わシに実施
例１２で得られたエポキシ樹脂組成物を使用し、ジシア
ンジアミドの使用量を４．８重量部に変えた他は応用例
１におけると同様に実施してガラスクロス積層板を作製
した。Application example 12 Application example except that the epoxy resin composition obtained in Example 12 was used instead of the epoxy resin composition obtained in Example 1, and the amount of dicyandiamide used was changed to 4.8 parts by weight. A glass cloth laminate was produced in the same manner as in Example 1.
この積層板の硬化樹脂のＴｇは１７２℃でありた。The Tg of the cured resin of this laminate was 172°C.
また難燃性はＵＬ法で９４Ｖ−０でおった。Moreover, the flame retardancy was 94V-0 according to the UL method.
Claims (16)
１２のアルキル基、アリール基 または炭素原子数３〜６のシクロアルキル基であり、 Ｒ＿３は水素原子または炭素原子数１〜１０のアルキル
基であり、 ｎは０又は１の数であり、 Ｚは一般式（ I ａ） ▲数式、化学式、表等があります▼（ I ａ） ここで、Ａは水素原子またはメチル基である で表わされる基であり、 Ｙは一般式（ I ｂ） ▲数式、化学式、表等があります▼（ I ｂ） または一般式（ I ｃ） ▲数式、化学式、表等があります▼（ I ｃ） ここで、Ｒ＿４、Ｒ＿５、Ｒ＿６及びＲ＿７は、夫々独
立に水素原子または炭素原子１〜４個から成るアルキル
基である、 で表わされる３官能性エポキシ化合物、又は該３官能性
エポキシ化合物及びビスフェノール類とエピクロルヒド
リンとの縮合により得られた２官能性エポキシ化合物の
組み合わせと、 （Ｂ）ハロゲン化ビスフェノール類、 とを触媒の存在下で反応させて得られたハロゲン含有エ
ポキシ樹脂から成る耐熱難燃性エポキシ樹脂組成物。(1) (A) The following general formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(I) In the formula, R_1 and R_2 are hydrogen atoms, and the number of carbon atoms is 1~
12 alkyl group, aryl group or cycloalkyl group having 3 to 6 carbon atoms, R_3 is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, n is a number of 0 or 1, and Z is General formula (I a) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (I a) Here, A is a hydrogen atom or a methyl group, and Y is a general formula (I b) ▲Mathematical formula, There are chemical formulas, tables, etc. ▼ ( I b) or general formulas ( I c) ▲ Numerical formulas, chemical formulas, tables, etc. ▼ ( I c) Here, R_4, R_5, R_6 and R_7 each independently represent a hydrogen atom or A trifunctional epoxy compound represented by, which is an alkyl group having 1 to 4 carbon atoms, or a combination of the trifunctional epoxy compound and a bifunctional epoxy compound obtained by condensation of bisphenols and epichlorohydrin; (B) A heat-resistant and flame-retardant epoxy resin composition comprising a halogen-containing epoxy resin obtained by reacting halogenated bisphenols with the following in the presence of a catalyst.
のエポキシ当量を有するものである特許請求の範囲第１
項記載の組成物。(2) Halogen-containing epoxy resin is 300 to 2000
Claim 1 has an epoxy equivalent of
Compositions as described in Section.
ハロゲン含有量を有するものである特許請求の範囲第１
項記載の組成物。(3) Claim 1, wherein the halogen-containing epoxy resin has a halogen content of 5 to 30% by weight.
Compositions as described in Section.
フェノールＡである特許請求の範囲第１項記載の組成物
。(4) The composition according to claim 1, wherein the halogenated bisphenol is halogenated bisphenol A.
ェノール類である特許請求の範囲第１項記載の組成物。(5) The composition according to claim 1, wherein the halogenated bisphenol is a brominated bisphenol.
スフェノールＡ、テトラブロム化ビスフェノールＢ、テ
トラブロム化ビスフェノールＦ、又は１，１−ビス（３
，５−ジブロム−４−ヒドロキシフェニル）エタンの何
れかである特許請求の範囲第１項記載の組成物。(6) The halogenated bisphenol is tetrabrominated bisphenol A, tetrabrominated bisphenol B, tetrabrominated bisphenol F, or 1,1-bis(3
, 5-dibromo-4-hydroxyphenyl)ethane.
４以下のアルキル基であり、 ｎ及びＹは前述した意味を有する、 で表わされる化合物である特許請求の範囲第１項記載の
組成物。(7) The trifunctional epoxy compound has the following formula ( I - (i)) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ ( I - (i)) In the formula, Z is a glycidoxy group, R_1, R_2 and The composition according to claim 1, wherein each of R_3 is a hydrogen atom or an alkyl group having 4 or less carbon atoms, and n and Y have the meanings described above.
求の範囲第７項記載の組成物。(8) The composition according to claim 7, wherein n in the formula (I-(i)) is 1.
−（４′−グリシドキシフェニル）エチル〕−４−〔α
′，α′−ビス（４″−グリシドキシフェニル）エチル
〕ベンゼンである特許請求の範囲第１項記載の組成物。(9) The trifunctional epoxy compound is 1-[α-methyl-α
-(4'-glycidoxyphenyl)ethyl]-4-[α
The composition according to claim 1, which is ',α'-bis(4''-glycidoxyphenyl)ethyl]benzene.
ス（２−メチル−４−グリシドキシ−５−三級ブチルフ
ェニル）ブタンである特許請求の範囲１項記載の組成物
。(10) The composition according to claim 1, wherein the trifunctional epoxy compound is 1,1,3-tris(2-methyl-4-glycidoxy-5-tertiary butylphenyl)butane.
α−（３′，５′−ジメチル−４′−グリシドキシフェ
ニル）エチル〕−４′−〔α′，α′−ビス（３″，５
″−ジメチル−４″−グリシドキシフェニル）エチル〕
ベンゼンである特許請求の範囲第１項記載の組成物。(11) The trifunctional epoxy compound is 1-[α-methyl-
α-(3′,5′-dimethyl-4′-glycidoxyphenyl)ethyl]-4′-[α′,α′-bis(3″,5
″-dimethyl-4″-glycidoxyphenyl)ethyl]
The composition according to claim 1, which is benzene.
合物とが、５０：５０乃至９０：１０の重量比の範囲内
にある特許請求の範囲第１項記載の組成物。(12) The composition according to claim 1, wherein the trifunctional epoxy compound and the difunctional epoxy compound are in a weight ratio of 50:50 to 90:10.
合物とが、６０：４０乃至８０：２０の範囲内にある特
許請求の範囲第１２項記載の組成物。(13) The composition according to claim 12, wherein the ratio of the trifunctional epoxy compound and the difunctional epoxy compound is in the range of 60:40 to 80:20.
囲第１項記載の組成物。(14) The composition according to claim 1, which is soluble in methyl ethyl ketone.
アルキル基であり、 Ｘはハロゲン原子であり、 ｍは１以上の数であり、 Ｅは、式、 ▲数式、化学式、表等があります▼・・・（IIａ） （式中、Ｒ＿１、Ｒ＿２及びＲ＿３の各々は水素原子又
は炭素数４以下のアルキル基を示し、 ｎはゼロ又は１である） ここでＹは式、 ▲数式、化学式、表等があります▼・・・（IIｂ） 又は式、 ▲数式、化学式、表等があります▼・・・（IIｃ） （式中、Ｒ＿４、Ｒ＿５、Ｒ＿６及びＲ＿７は、水素原
子又は炭素数４以下のアルキル基を示す、）で表わされ
る基である、 で表わされ、３００乃至２０００のエポキシ当量と５乃
至３０重量％のハロゲン含有量を有するハロゲン含有エ
ポキシ樹脂から成る耐熱難燃性エポキシ樹脂組成物。(15) Formula (II) below, ▲Mathematical formulas, chemical formulas, tables, etc.▼...(II) In the formula, Z is a glycidoxy group, and each of R_1 and R_2 is a hydrogen atom or an alkyl having 4 or less carbon atoms. group, X is a halogen atom, m is a number of 1 or more, E is a formula, ▲ Numerical formula, chemical formula, table, etc. ▼... (IIa) (In the formula, R_1, R_2 and R_3 each represents a hydrogen atom or an alkyl group having 4 or less carbon atoms, and n is zero or 1) where Y is a formula, ▲There are mathematical formulas, chemical formulas, tables, etc.▼...(IIb) or formula, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼... (IIc) (In the formula, R_4, R_5, R_6 and R_7 represent a hydrogen atom or an alkyl group having 4 or less carbon atoms), A heat-resistant flame-retardant epoxy resin composition comprising a halogen-containing epoxy resin having an epoxy equivalent weight of 300 to 2000 and a halogen content of 5 to 30% by weight.
アルキル基であり、 Ｘはハロゲン原子であり、 ｋは０又は１以上の数であり、ｌは１以上の数であって
、３００乃至２０００のエポキシ当量と５乃至３０重量
％を有する様に選択される、 Ｅは、式、 ▲数式、化学式、表等があります▼・・・（IIIａ） （式中、Ｒ＿１、Ｒ＿２及びＲ＿３の各々は水素原子又
は炭素数４以下のアルキル基を示し、 ｎはゼロ又は１である） Ｙは、式、 ▲数式、化学式、表等があります▼・・・（IIIｂ） 又は式、 ▲数式、化学式、表等があります▼・・・（IIIｃ） （式中、Ｒ＿４、Ｒ＿５、Ｒ＿６及びＲ＿７は、水素原
子又は炭素数４以下のアルキル基を示す、）で表わされ
る基を示す、 で表わされるハロゲン含有エポキシ樹脂から成る耐熱難
燃性エポキシ樹脂組成物。(16) Formula (III) below ▲Mathematical formulas, chemical formulas, tables, etc.▼...(III) In the formula, Z is a glycidoxy group, and each of R_1 and R_2 is a hydrogen atom or an alkyl group having 4 or less carbon atoms. , X is a halogen atom, k is 0 or a number greater than or equal to 1, and l is a number greater than or equal to 1 and is selected to have an epoxy equivalent weight of 300 to 2000 and an epoxy equivalent of 5 to 30% by weight. , E is a formula, ▲Mathematical formula, chemical formula, table, etc.▼...(IIIa) (In the formula, each of R_1, R_2 and R_3 represents a hydrogen atom or an alkyl group having 4 or less carbon atoms, and n is zero or 1) Y is a formula, ▲There are mathematical formulas, chemical formulas, tables, etc.▼...(IIIb) Or formulas, ▲There are mathematical formulas, chemical formulas, tables, etc.▼...(IIIc) (In the formula, R_4 , R_5, R_6 and R_7 represent a hydrogen atom or an alkyl group having 4 or less carbon atoms. A heat-resistant and flame-retardant epoxy resin composition comprising a halogen-containing epoxy resin represented by
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP16112787A JPH0784510B2 (en) | 1986-12-24 | 1987-06-30 | Heat and flame retardant epoxy resin composition |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61-306561 | 1986-12-24 | ||
| JP30656186 | 1986-12-24 | ||
| JP16112787A JPH0784510B2 (en) | 1986-12-24 | 1987-06-30 | Heat and flame retardant epoxy resin composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS63264623A true JPS63264623A (en) | 1988-11-01 |
| JPH0784510B2 JPH0784510B2 (en) | 1995-09-13 |
Family
ID=26487377
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP16112787A Expired - Lifetime JPH0784510B2 (en) | 1986-12-24 | 1987-06-30 | Heat and flame retardant epoxy resin composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0784510B2 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS63301219A (en) * | 1987-05-30 | 1988-12-08 | Mitsui Petrochem Ind Ltd | Epoxy resin composition |
| JPH0317117A (en) * | 1989-06-15 | 1991-01-25 | Mitsui Petrochem Ind Ltd | Heat-resistant epoxy resin composition |
| JP2005330475A (en) * | 2004-04-20 | 2005-12-02 | Nippon Kayaku Co Ltd | Crystalline epoxy resin, epoxy resin composition, and its cured product |
-
1987
- 1987-06-30 JP JP16112787A patent/JPH0784510B2/en not_active Expired - Lifetime
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS63301219A (en) * | 1987-05-30 | 1988-12-08 | Mitsui Petrochem Ind Ltd | Epoxy resin composition |
| JPH0317117A (en) * | 1989-06-15 | 1991-01-25 | Mitsui Petrochem Ind Ltd | Heat-resistant epoxy resin composition |
| JP2005330475A (en) * | 2004-04-20 | 2005-12-02 | Nippon Kayaku Co Ltd | Crystalline epoxy resin, epoxy resin composition, and its cured product |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0784510B2 (en) | 1995-09-13 |
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