JP2022066986A - Phenol resin, epoxy resin, curable resin composition, cured object, fiber reinforced composite material and fiber reinforced resin molded product - Google Patents
Phenol resin, epoxy resin, curable resin composition, cured object, fiber reinforced composite material and fiber reinforced resin molded product Download PDFInfo
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- JP2022066986A JP2022066986A JP2020175624A JP2020175624A JP2022066986A JP 2022066986 A JP2022066986 A JP 2022066986A JP 2020175624 A JP2020175624 A JP 2020175624A JP 2020175624 A JP2020175624 A JP 2020175624A JP 2022066986 A JP2022066986 A JP 2022066986A
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- resin
- epoxy resin
- carbon atoms
- resin composition
- Prior art date
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- 239000003822 epoxy resin Substances 0.000 title claims abstract description 115
- 229920000647 polyepoxide Polymers 0.000 title claims abstract description 115
- 239000005011 phenolic resin Substances 0.000 title claims abstract description 70
- 239000011342 resin composition Substances 0.000 title claims description 70
- 229920005989 resin Polymers 0.000 title claims description 51
- 239000011347 resin Substances 0.000 title claims description 51
- -1 cured object Substances 0.000 title claims description 46
- 239000000463 material Substances 0.000 title claims description 30
- 239000003733 fiber-reinforced composite Substances 0.000 title claims description 15
- 239000000835 fiber Substances 0.000 title description 12
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 46
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims abstract description 34
- 150000001875 compounds Chemical class 0.000 claims abstract description 31
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 22
- 125000003545 alkoxy group Chemical group 0.000 claims abstract description 16
- 125000005843 halogen group Chemical group 0.000 claims abstract description 14
- 150000002430 hydrocarbons Chemical group 0.000 claims abstract description 14
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 11
- AAAQKTZKLRYKHR-UHFFFAOYSA-N triphenylmethane Chemical group C1=CC=CC=C1C(C=1C=CC=CC=1)C1=CC=CC=C1 AAAQKTZKLRYKHR-UHFFFAOYSA-N 0.000 claims abstract description 10
- YCIMNLLNPGFGHC-UHFFFAOYSA-N o-dihydroxy-benzene Natural products OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 claims description 54
- 238000006243 chemical reaction Methods 0.000 claims description 36
- 125000004432 carbon atom Chemical group C* 0.000 claims description 31
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 claims description 17
- 125000002485 formyl group Chemical group [H]C(*)=O 0.000 claims description 16
- 239000012783 reinforcing fiber Substances 0.000 claims description 16
- 150000001491 aromatic compounds Chemical class 0.000 claims description 15
- 229920001568 phenolic resin Polymers 0.000 claims description 14
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 11
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical group C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 claims description 9
- 239000000203 mixture Substances 0.000 abstract description 10
- 239000000047 product Substances 0.000 description 68
- 238000005452 bending Methods 0.000 description 37
- 238000001723 curing Methods 0.000 description 35
- 238000000034 method Methods 0.000 description 33
- 230000015572 biosynthetic process Effects 0.000 description 21
- 239000010410 layer Substances 0.000 description 21
- 238000003786 synthesis reaction Methods 0.000 description 21
- 239000000155 melt Substances 0.000 description 19
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 16
- 239000003795 chemical substances by application Substances 0.000 description 16
- 229920003986 novolac Polymers 0.000 description 16
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 15
- 238000004519 manufacturing process Methods 0.000 description 15
- 239000004593 Epoxy Substances 0.000 description 14
- 238000005259 measurement Methods 0.000 description 14
- 239000004065 semiconductor Substances 0.000 description 13
- 239000002904 solvent Substances 0.000 description 13
- 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 11
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 10
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 10
- 238000010030 laminating Methods 0.000 description 10
- 239000003960 organic solvent Substances 0.000 description 10
- 239000000243 solution Substances 0.000 description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 9
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 9
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 9
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 9
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 9
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- 238000010438 heat treatment Methods 0.000 description 9
- 125000003118 aryl group Chemical group 0.000 description 8
- 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 8
- 239000011256 inorganic filler Substances 0.000 description 8
- 229910003475 inorganic filler Inorganic materials 0.000 description 8
- 239000000523 sample Substances 0.000 description 8
- 239000002966 varnish Substances 0.000 description 8
- 229920000049 Carbon (fiber) Polymers 0.000 description 7
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 7
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 7
- 239000004917 carbon fiber Substances 0.000 description 7
- 230000001681 protective effect Effects 0.000 description 7
- 239000002994 raw material Substances 0.000 description 7
- 125000001424 substituent group Chemical group 0.000 description 7
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 6
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 6
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 6
- 239000002313 adhesive film Substances 0.000 description 6
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 6
- 239000003063 flame retardant Substances 0.000 description 6
- 239000011521 glass Substances 0.000 description 6
- 230000009477 glass transition Effects 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- 238000002156 mixing Methods 0.000 description 6
- 239000000758 substrate Substances 0.000 description 6
- 238000004448 titration Methods 0.000 description 6
- KJCVRFUGPWSIIH-UHFFFAOYSA-N 1-naphthol Chemical compound C1=CC=C2C(O)=CC=CC2=C1 KJCVRFUGPWSIIH-UHFFFAOYSA-N 0.000 description 5
- 239000002585 base Substances 0.000 description 5
- 239000012490 blank solution Substances 0.000 description 5
- 239000006227 byproduct Substances 0.000 description 5
- 239000002131 composite material Substances 0.000 description 5
- 238000002788 crimping Methods 0.000 description 5
- WSFSSNUMVMOOMR-UHFFFAOYSA-N formaldehyde Natural products O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 5
- 239000005350 fused silica glass Substances 0.000 description 5
- 230000006872 improvement Effects 0.000 description 5
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 5
- 230000009257 reactivity Effects 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 5
- 238000005406 washing Methods 0.000 description 5
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 4
- JWAZRIHNYRIHIV-UHFFFAOYSA-N 2-naphthol Chemical compound C1=CC=CC2=CC(O)=CC=C21 JWAZRIHNYRIHIV-UHFFFAOYSA-N 0.000 description 4
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 4
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 4
- 239000000853 adhesive Substances 0.000 description 4
- 230000001070 adhesive effect Effects 0.000 description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 4
- 239000011889 copper foil Substances 0.000 description 4
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 4
- 238000011049 filling Methods 0.000 description 4
- 239000011810 insulating material Substances 0.000 description 4
- 150000002989 phenols Chemical class 0.000 description 4
- 150000003018 phosphorus compounds Chemical class 0.000 description 4
- 230000003014 reinforcing effect Effects 0.000 description 4
- 239000000377 silicon dioxide Substances 0.000 description 4
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 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
- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- 229910052581 Si3N4 Inorganic materials 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 3
- 239000004305 biphenyl Substances 0.000 description 3
- 235000010290 biphenyl Nutrition 0.000 description 3
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 description 3
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 239000004020 conductor Substances 0.000 description 3
- 229930003836 cresol Natural products 0.000 description 3
- 229910002026 crystalline silica Inorganic materials 0.000 description 3
- 239000008393 encapsulating agent Substances 0.000 description 3
- 238000005538 encapsulation Methods 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 3
- 239000004744 fabric Substances 0.000 description 3
- 239000011888 foil Substances 0.000 description 3
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 3
- 230000003993 interaction Effects 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- 230000007935 neutral effect Effects 0.000 description 3
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 description 3
- 229910052698 phosphorus Inorganic materials 0.000 description 3
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 239000012488 sample solution Substances 0.000 description 3
- 235000012239 silicon dioxide Nutrition 0.000 description 3
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 3
- FYGHSUNMUKGBRK-UHFFFAOYSA-N 1,2,3-trimethylbenzene Chemical compound CC1=CC=CC(C)=C1C FYGHSUNMUKGBRK-UHFFFAOYSA-N 0.000 description 2
- GWHJZXXIDMPWGX-UHFFFAOYSA-N 1,2,4-trimethylbenzene Chemical compound CC1=CC=C(C)C(C)=C1 GWHJZXXIDMPWGX-UHFFFAOYSA-N 0.000 description 2
- 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 2
- BSYJHYLAMMJNRC-UHFFFAOYSA-N 2,4,4-trimethylpentan-2-ol Chemical compound CC(C)(C)CC(C)(C)O BSYJHYLAMMJNRC-UHFFFAOYSA-N 0.000 description 2
- FPZWZCWUIYYYBU-UHFFFAOYSA-N 2-(2-ethoxyethoxy)ethyl acetate Chemical compound CCOCCOCCOC(C)=O FPZWZCWUIYYYBU-UHFFFAOYSA-N 0.000 description 2
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 229910015900 BF3 Inorganic materials 0.000 description 2
- 229930185605 Bisphenol Natural products 0.000 description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 2
- MQJKPEGWNLWLTK-UHFFFAOYSA-N Dapsone Chemical compound C1=CC(N)=CC=C1S(=O)(=O)C1=CC=C(N)C=C1 MQJKPEGWNLWLTK-UHFFFAOYSA-N 0.000 description 2
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 239000002841 Lewis acid Substances 0.000 description 2
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 description 2
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- 241000209094 Oryza Species 0.000 description 2
- 235000007164 Oryza sativa Nutrition 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 150000008065 acid anhydrides Chemical class 0.000 description 2
- 239000003377 acid catalyst Substances 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- 150000001408 amides Chemical class 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 229910000148 ammonium phosphate Inorganic materials 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 239000004760 aramid Substances 0.000 description 2
- 229920003235 aromatic polyamide Polymers 0.000 description 2
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 2
- 238000007664 blowing Methods 0.000 description 2
- 125000004106 butoxy group Chemical group [*]OC([H])([H])C([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 125000001309 chloro group Chemical group Cl* 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 239000004643 cyanate ester Substances 0.000 description 2
- 150000007973 cyanuric acids Chemical class 0.000 description 2
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 description 2
- ZZTCPWRAHWXWCH-UHFFFAOYSA-N diphenylmethanediamine Chemical compound C=1C=CC=CC=1C(N)(N)C1=CC=CC=C1 ZZTCPWRAHWXWCH-UHFFFAOYSA-N 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 239000000428 dust Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 125000001153 fluoro group Chemical group F* 0.000 description 2
- SLGWESQGEUXWJQ-UHFFFAOYSA-N formaldehyde;phenol Chemical compound O=C.OC1=CC=CC=C1 SLGWESQGEUXWJQ-UHFFFAOYSA-N 0.000 description 2
- 238000013007 heat curing Methods 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 150000002460 imidazoles Chemical class 0.000 description 2
- 230000001771 impaired effect Effects 0.000 description 2
- 150000007517 lewis acids Chemical class 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 2
- 238000001471 micro-filtration Methods 0.000 description 2
- DNIAPMSPPWPWGF-UHFFFAOYSA-N monopropylene glycol Natural products CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 2
- 150000007524 organic acids Chemical class 0.000 description 2
- ZRSNZINYAWTAHE-UHFFFAOYSA-N p-methoxybenzaldehyde Chemical compound COC1=CC=C(C=O)C=C1 ZRSNZINYAWTAHE-UHFFFAOYSA-N 0.000 description 2
- FXLOVSHXALFLKQ-UHFFFAOYSA-N p-tolualdehyde Chemical compound CC1=CC=C(C=O)C=C1 FXLOVSHXALFLKQ-UHFFFAOYSA-N 0.000 description 2
- 239000003444 phase transfer catalyst Substances 0.000 description 2
- 239000010452 phosphate Substances 0.000 description 2
- 125000004437 phosphorous atom Chemical group 0.000 description 2
- 229920002239 polyacrylonitrile Polymers 0.000 description 2
- 229920000139 polyethylene terephthalate Polymers 0.000 description 2
- 239000005020 polyethylene terephthalate Substances 0.000 description 2
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- 229920001296 polysiloxane Polymers 0.000 description 2
- 229920002223 polystyrene Polymers 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 125000002572 propoxy group Chemical group [*]OC([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 2
- 150000004053 quinones Chemical class 0.000 description 2
- 235000009566 rice Nutrition 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 150000003512 tertiary amines Chemical class 0.000 description 2
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 2
- 239000002759 woven fabric Substances 0.000 description 2
- 239000008096 xylene Substances 0.000 description 2
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 2
- LTVUCOSIZFEASK-MPXCPUAZSA-N (3ar,4s,7r,7as)-3a-methyl-3a,4,7,7a-tetrahydro-4,7-methano-2-benzofuran-1,3-dione Chemical compound C([C@H]1C=C2)[C@H]2[C@H]2[C@]1(C)C(=O)OC2=O LTVUCOSIZFEASK-MPXCPUAZSA-N 0.000 description 1
- MUTGBJKUEZFXGO-OLQVQODUSA-N (3as,7ar)-3a,4,5,6,7,7a-hexahydro-2-benzofuran-1,3-dione Chemical compound C1CCC[C@@H]2C(=O)OC(=O)[C@@H]21 MUTGBJKUEZFXGO-OLQVQODUSA-N 0.000 description 1
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- VSWALKINGSNVAR-UHFFFAOYSA-N naphthalen-1-ol;phenol Chemical compound OC1=CC=CC=C1.C1=CC=C2C(O)=CC=CC2=C1 VSWALKINGSNVAR-UHFFFAOYSA-N 0.000 description 1
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- YLLIGHVCTUPGEH-UHFFFAOYSA-M potassium;ethanol;hydroxide Chemical compound [OH-].[K+].CCO YLLIGHVCTUPGEH-UHFFFAOYSA-M 0.000 description 1
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- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 1
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- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
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- KCNSDMPZCKLTQP-UHFFFAOYSA-N tetraphenylen-1-ol Chemical compound C12=CC=CC=C2C2=CC=CC=C2C2=CC=CC=C2C2=C1C=CC=C2O KCNSDMPZCKLTQP-UHFFFAOYSA-N 0.000 description 1
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Images
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
- Phenolic Resins Or Amino Resins (AREA)
- Epoxy Resins (AREA)
Abstract
Description
本発明は、特定構造のフェノール性水酸基含有化合物を含むフェノール樹脂、前記フェノール樹脂より得られるエポキシ樹脂、前記エポキシ樹脂を含有する硬化性樹脂組成物、前記硬化性樹脂組成物より得られる硬化物、繊維強化複合材料、及び、繊維強化樹脂成形品に関する。 The present invention relates to a phenol resin containing a phenolic hydroxyl group-containing compound having a specific structure, an epoxy resin obtained from the phenol resin, a curable resin composition containing the epoxy resin, and a cured product obtained from the curable resin composition. The present invention relates to a fiber-reinforced composite material and a fiber-reinforced resin molded product.
エポキシ樹脂及びその硬化剤を必須成分とする硬化性樹脂組成物は、その硬化物において優れた機械的強度、耐熱性、耐水性、耐薬品性、及び、絶縁性等を有することから、その用途は幅広く、繊維強化複合材料のマトリックス、放熱部材、塗料、半導体、プリント配線基板等、広く用いられている。 A curable resin composition containing an epoxy resin and a curing agent thereof as an essential component has excellent mechanical strength, heat resistance, water resistance, chemical resistance, insulating property, etc. in the cured product, and therefore its use. Is widely used in a matrix of fiber-reinforced composite materials, heat-dissipating members, paints, semiconductors, printed wiring boards, and the like.
中でも、強化繊維で強化した繊維強化樹脂成形品は、軽量でありながら、機械的強度に優れる特徴が注目され、自動車や航空機、船舶等の筐体或いは各種部材をはじめ、様々な構造体用途での利用が拡大しており、特に、炭素繊維複合材料（ＣＦＲＰ）は、航空機や自動車分野への適用が拡大していることに伴い、そのマトリックス樹脂としてのエポキシ樹脂の使用量は増加の一途をたどっている。 Among them, fiber-reinforced resin molded products reinforced with reinforced fibers are attracting attention for their light weight and excellent mechanical strength, and are used in various structural applications such as housings and various members of automobiles, aircraft, ships, etc. In particular, carbon fiber composite material (CFRP) is expanding its application to the aircraft and automobile fields, and the amount of epoxy resin used as its matrix resin is steadily increasing. I'm following.
現在、炭素繊維複合材料の用途で主に使用されているエポキシ樹脂としては、ビスフェノールＡのジグリシジルエーテルや、ジアミノジフェニルメタンのテトラグリシジルアミン（ＴＧＤＤＭ）等が挙げられる（例えば、特許文献１参照）。これらのエポキシ樹脂は、ある程度、機械的強度（破壊強度）や耐熱性等、炭素繊維複合材料の用途の要求特性を満足している。 Currently, examples of the epoxy resin mainly used in the use of carbon fiber composite materials include diglycidyl ether of bisphenol A and tetraglycidylamine (TGDDM) of diaminodiphenylmethane (see, for example, Patent Document 1). To some extent, these epoxy resins satisfy the required characteristics of carbon fiber composite materials such as mechanical strength (breaking strength) and heat resistance.
しかしながら、現在、市場から、更なる破壊強度の向上や高耐熱化の要求があり、高曲げ特性（曲げ強度、曲げ弾性率等）や高ガラス転移温度（高耐熱性）を有するエポキシ樹脂が求められているが、これらを満足するまでには至っていない。 However, at present, there is a demand from the market for further improvement of fracture strength and high heat resistance, and an epoxy resin having high bending characteristics (bending strength, flexural modulus, etc.) and high glass transition temperature (high heat resistance) is required. However, they have not been satisfied with these.
従って、本発明が解決しようとする課題は、特定構造を有するフェノール樹脂を用いて得られるエポキシ樹脂を含有する硬化性樹脂組成物を用いることで、優れた高曲げ特性、及び、高耐熱性を有する硬化物を提供することにある。 Therefore, the problem to be solved by the present invention is to obtain excellent high bending characteristics and high heat resistance by using a curable resin composition containing an epoxy resin obtained by using a phenol resin having a specific structure. The purpose is to provide a cured product having.
そこで、本発明者は、上記課題を解決すべく、鋭意検討を重ねた結果、硬化性樹脂組成物に特定構造を有するフェノール樹脂を用いて得られるエポキシ樹脂を用いることにより得られる硬化物が、優れた高曲げ特性、及び、高耐熱性を発現することを見出し、本発明を完成するに至った。 Therefore, as a result of diligent studies to solve the above problems, the present inventor has obtained a cured product obtained by using an epoxy resin obtained by using a phenol resin having a specific structure in the curable resin composition. They have found that they exhibit excellent high bending properties and high heat resistance, and have completed the present invention.
即ち、本発明は、下記一般式（１）で表されるトリフェニルメタン骨格を有するフェノール性水酸基含有化合物を含有することを特徴とするフェノール樹脂に関する。
本発明のフェノール樹脂は、前記フェノール性水酸基含有化合物が、カテコール化合物（ａ）、及び、ホルミル基含有芳香族化合物（ｂ）を反応させて得られることが好ましい。 The phenolic resin of the present invention is preferably obtained by reacting the phenolic hydroxyl group-containing compound with the catechol compound (a) and the formyl group-containing aromatic compound (b).
本発明は、下記一般式（２）で表され、前記フェノール樹脂、及び、エピハロヒドリンを反応させて得られるグリシジルエーテル基含有化合物を含有することを特徴とするエポキシ樹脂に関する。
本発明は、前記エポキシ樹脂を含有することを特徴とする硬化性樹脂組成物に関する。 The present invention relates to a curable resin composition comprising the epoxy resin.
本発明は、前記硬化性樹脂組成物を硬化反応させて得られることを特徴とする硬化物に関する。 The present invention relates to a cured product obtained by subjecting the curable resin composition to a curing reaction.
本発明は、前記硬化性樹脂組成物と、強化繊維を含有することを特徴とする繊維強化複合材料に関する。 The present invention relates to the curable resin composition and a fiber-reinforced composite material characterized by containing reinforcing fibers.
本発明は、前記硬化物と、強化繊維を含有することを特徴とする繊維強化樹脂成形品に関する。 The present invention relates to a fiber-reinforced resin molded product characterized by containing the cured product and reinforcing fibers.
本発明によれば、得られるエポキシ樹脂は低溶融粘度であるため、ハンドリング性に優れ、前記エポキシ樹脂を含有するエポキシ樹脂を使用して得られる硬化物は、優れた高曲げ特性、及び、高耐熱性を発現することができ、有用である。 According to the present invention, since the obtained epoxy resin has a low melt viscosity, it is excellent in handleability, and a cured product obtained by using the epoxy resin containing the epoxy resin has excellent high bending characteristics and high bending property. It is useful because it can develop heat resistance.
［フェノール樹脂］
本発明は、下記一般式（１）で表されるトリフェニルメタン骨格を有するフェノール性水酸基含有化合物を含有することを特徴とするフェノール樹脂に関する。
The present invention relates to a phenol resin comprising a phenolic hydroxyl group-containing compound having a triphenylmethane skeleton represented by the following general formula (1).
上記式（１）中、Ｒ１は、水素原子、炭素数１～４のアルキル基を表し、硬化物の曲げ特性の観点から、好ましくは、Ｒ１は、水素原子、メチル基、エチル基、プロピル基、ブチル基で表され、好ましくは、水素原子、または、メチル基であり、より好ましくは、水素原子である。前記Ｒ１が、水素原子等であることにより、硬化物の耐熱性と曲げ特性をバランスよく有するため好ましく、中でも、前記Ｒ１が、水素原子であることで、
溶融粘度が低く、ハンドリング性が向上することとなり、好ましい態様となる。
In the above formula (1), R 1 represents a hydrogen atom and an alkyl group having 1 to 4 carbon atoms, and from the viewpoint of bending characteristics of the cured product, R 1 is preferably a hydrogen atom, a methyl group and an ethyl group. It is represented by a propyl group or a butyl group, preferably a hydrogen atom or a methyl group, and more preferably a hydrogen atom. Since R 1 is a hydrogen atom or the like, it is preferable because it has a good balance between heat resistance and bending characteristics of the cured product. Above all, when R 1 is a hydrogen atom, it is preferable.
The melt viscosity is low and the handleability is improved, which is a preferable embodiment.
上記式（１）中、Ｒ２は、水素原子、炭素原子数１～４の炭化水素基、炭素原子数１～４のアルコキシ基、または、ハロゲン原子で表され、原料として使用する際の反応性や硬化物の曲げ特性の観点から、好ましくは、前記炭素原子数１～４の炭化水素基は、メチル基、エチル基、プロピル基、ブチル基、t－ブチル基等が挙げられる。また、前記炭素原子数１～４のアルコキシ基は、メトキシ基、エトキシ基、プロピルオキシ基、ブトキシ基等が挙げられる。更に、前記ハロゲン原子は、フッ素原子、塩素原子、臭素原子等が挙げられる。中でも、前記Ｒ２が、水素原子であることで、溶融粘度が低く、ハンドリング性に優れ、曲げ特性と耐熱性のバランスに優れることとなり、好ましい態様となる。 In the above formula (1), R 2 is represented by a hydrogen atom, a hydrocarbon group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or a halogen atom, and is a reaction when used as a raw material. From the viewpoint of properties and bending characteristics of the cured product, preferably, the hydrocarbon group having 1 to 4 carbon atoms includes a methyl group, an ethyl group, a propyl group, a butyl group, a t-butyl group and the like. Examples of the alkoxy group having 1 to 4 carbon atoms include a methoxy group, an ethoxy group, a propyloxy group, a butoxy group and the like. Further, examples of the halogen atom include a fluorine atom, a chlorine atom and a bromine atom. Above all, since R 2 is a hydrogen atom, the melt viscosity is low, the handleability is excellent, and the balance between bending characteristics and heat resistance is excellent, which is a preferable embodiment.
上記式（１）中、Ｒ３は、水素原子、炭素原子数１～４の炭化水素基、炭素原子数１～４のアルコキシ基、水酸基、または、ハロゲン原子で表され、原料として使用する際の反応性や硬化物の曲げ特性の観点から、好ましくは、前記炭素原子数１～４の炭化水素基は、メチル基、エチル基、プロピル基、ブチル基、t－ブチル基等が挙げられる。また、前記炭素原子数１～４のアルコキシ基は、メトキシ基、エトキシ基、プロピルオキシ基、ブトキシ基等が挙げられる。更に、前記ハロゲン原子は、フッ素原子、塩素原子、臭素原子等が挙げられる。中でも、前記Ｒ３が、水素原子であることで、溶融粘度が低く、ハンドリング性に優れ、曲げ特性と耐熱性のバランスに優れることとなり、好ましい態様となる。 In the above formula (1), R 3 is represented by a hydrogen atom, a hydrocarbon group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a hydroxyl group, or a halogen atom, and is used as a raw material. From the viewpoint of the reactivity of the cured product and the bending property of the cured product, preferably, the hydrocarbon group having 1 to 4 carbon atoms includes a methyl group, an ethyl group, a propyl group, a butyl group, a t-butyl group and the like. Examples of the alkoxy group having 1 to 4 carbon atoms include a methoxy group, an ethoxy group, a propyloxy group, a butoxy group and the like. Further, examples of the halogen atom include a fluorine atom, a chlorine atom and a bromine atom. Above all, since the R 3 is a hydrogen atom, the melt viscosity is low, the handleability is excellent, and the balance between bending characteristics and heat resistance is excellent, which is a preferable embodiment.
上記式（１）中、ｍは、０～３の整数を示し、原料として使用する際の反応性や硬化物の曲げ特性の観点から、好ましくは、０又は１の整数である。 In the above formula (1), m represents an integer of 0 to 3, and is preferably an integer of 0 or 1 from the viewpoint of reactivity when used as a raw material and bending characteristics of the cured product.
上記式（１）中、ｎは、０～５の整数を示し、原料として使用する際の反応性や硬化物の曲げ特性の観点から、好ましくは、０又は１の整数である。 In the above formula (1), n represents an integer of 0 to 5, and is preferably an integer of 0 or 1 from the viewpoint of reactivity when used as a raw material and bending characteristics of the cured product.
特に、前記フェノール樹脂を用いて得られるエポキシ樹脂の溶融粘度と、得られる硬化物における耐熱性とのバランスに優れるエポキシ樹脂を合成できることから、ｍ及びｎが共に０であり、置換基を有しない（水素原子である）ことが好ましい。 In particular, since an epoxy resin having an excellent balance between the melt viscosity of the epoxy resin obtained by using the phenol resin and the heat resistance of the obtained cured product can be synthesized, both m and n are 0 and there is no substituent. It is preferably (hydrogen atom).
本発明のフェノール樹脂が、上記一般式（１）で表されるトリフェニルメタン骨格を有するフェノール性水酸基含有化合物を含有することにより、前記フェノール性水酸基含有化合物の分子鎖が屈曲構造をとるため、高弾性となると推定され、また、前記トリフェニルメタン骨格を有することにより、分子間のπ－π相互作用により分子間密度が高まることも推定され、得られる硬化物は、高耐熱性、及び、高曲げ特性（曲げ強度や曲げ弾性率などの向上）を有することができ、好ましい。なお、本発明における「フェノール樹脂」とは、前記フェノール性水酸基含有化合物を少なくとも含有する樹脂を指す。 Since the phenolic resin of the present invention contains a phenolic hydroxyl group-containing compound having a triphenylmethane skeleton represented by the above general formula (1), the molecular chain of the phenolic hydroxyl group-containing compound has a bent structure. It is presumed to have high elasticity, and it is also presumed that having the triphenylmethane skeleton increases the intermolecular density due to the π-π interaction between molecules, and the obtained cured product has high heat resistance and high heat resistance. It is preferable because it can have high bending characteristics (improvement of bending strength, bending elasticity, etc.). The "phenolic resin" in the present invention refers to a resin containing at least the phenolic hydroxyl group-containing compound.
また、本発明のフェノール樹脂は、前記フェノール性水酸基含有化合物が、カテコール化合物（ａ）、及び、ホルミル基含有芳香族化合物（ｂ）を反応させて得られることが好ましい。前記フェノール性水酸基含有化合物は、前記カテコール化合物（ａ）、及び、前記ホルミル基含有芳香族化合物（ｂ）を反応させることで、トリフェニルメタン骨格、及び、前記トリフェニルメタン骨格中に、カテコール骨格（芳香環に置換基として水酸基を２個有し、２個の水酸基が互いにオルト位の位置関係にある）を包含することになり、分子内に適度な空隙を有することが可能であると推定され、かつ、多官能となるため、低溶融粘度を示し、かつ、得られる硬化物が高耐熱性を示すため、好ましい。 Further, the phenolic resin of the present invention is preferably obtained by reacting the phenolic hydroxyl group-containing compound with the catechol compound (a) and the formyl group-containing aromatic compound (b). The phenolic hydroxyl group-containing compound has a triphenylmethane skeleton and a catechol skeleton in the triphenylmethane skeleton by reacting the catechol compound (a) and the formyl group-containing aromatic compound (b). It is presumed that it is possible to have an appropriate void in the molecule by including (the aromatic ring has two hydroxyl groups as substituents and the two hydroxyl groups are in a positional relationship with each other at the ortho position). It is preferable because it is polyfunctional and exhibits low melt viscosity, and the obtained cured product exhibits high heat resistance.
［カテコール化合物（ａ）］
前記フェノール性水酸基含有化合物は、カテコール化合物（ａ）を反応させて得られることが好ましい。前記フェノール性水酸基含有化合物は、前記カテコール化合物（ａ）に基づき、トリフェニルメタン骨格中にカテコール骨格（芳香環に置換基として水酸基を２個有し、２個の水酸基が互いにオルト位の位置関係にある）が包含されることで、後述するグリシジルエーテル基含有化合物中のグリシジルエーテル基が近接することになり、前記近接したグリシジルエーテル基と、硬化剤との硬化反応時に生成する水酸基も近接することになり、その結果として、水素結合がより強く作用すると推定され、弾性率が高く、機械強度に優れた硬化物を得ることができ、好ましい。
[Catechol compound (a)]
The phenolic hydroxyl group-containing compound is preferably obtained by reacting the catechol compound (a). Based on the catechol compound (a), the phenolic hydroxyl group-containing compound has a catechol skeleton (two hydroxyl groups as substituents on the aromatic ring in the triphenylmethane skeleton, and the two hydroxyl groups have an ortho-position positional relationship with each other. By including), the glycidyl ether groups in the glycidyl ether group-containing compound described later are close to each other, and the hydroxyl groups generated during the curing reaction between the close glycidyl ether groups and the curing agent are also close to each other. As a result, it is presumed that the hydrogen bond acts more strongly, and a cured product having a high elastic coefficient and excellent mechanical strength can be obtained, which is preferable.
前記カテコール化合物（ａ）とは、１位と２位とに水酸基を有するジヒドロキシベンゼンであり、芳香環上にメチル基やtert－ブチル基などのアルキル基を置換基として有していてもよい。 The catechol compound (a) is dihydroxybenzene having hydroxyl groups at the 1-position and 2-position, and may have an alkyl group such as a methyl group or a tert-butyl group as a substituent on the aromatic ring.
前記置換基として、メチル基を有する場合、その位置及び置換基の数としては特に制限されるものではないが、機械特性や、耐熱性や疎水性に優れた硬化物が得られることから、カテコールの場合には、４位に１つのメチル基やtert－ブチル基を有することが好ましいが、置換基を有していないもの(カテコール)であることが曲げ特性の観点から、最も好ましい。また、前記アルキル基として、立体障害の大きなアルキル基を有することで、耐吸水性の向上に寄与することができ、中でも、４－メチルカテコールや４－tert－ブチルカテコールなどの使用も好ましい。なお、前記アルキル基の炭素数としては、１～４が好ましい。前記炭素数が４を超えると、立体障害が大きくなりすぎ、前記フェノール樹脂の合成時に反応性が低くなりすぎたり、硬化物の機械強度が低下するため、好ましくない。 When the substituent has a methyl group, its position and the number of substituents are not particularly limited, but catechol can be obtained because a cured product having excellent mechanical properties, heat resistance and hydrophobicity can be obtained. In the case of, it is preferable to have one methyl group or tert-butyl group at the 4-position, but one having no substituent (catechol) is most preferable from the viewpoint of bending characteristics. Further, as the alkyl group, having an alkyl group having a large steric hindrance can contribute to the improvement of water absorption resistance, and among them, the use of 4-methylcatechol, 4-tert-butylcatechol or the like is also preferable. The number of carbon atoms of the alkyl group is preferably 1 to 4. If the number of carbon atoms exceeds 4, the steric hindrance becomes too large, the reactivity becomes too low during the synthesis of the phenol resin, and the mechanical strength of the cured product decreases, which is not preferable.
前記カテコール化合物（ａ）は、単独で用いてもよく、メチル基等のアルキル基の位置が異なる複数の化合物を併用してもよい。 The catechol compound (a) may be used alone, or a plurality of compounds having different positions of alkyl groups such as a methyl group may be used in combination.
［ホルミル基含有芳香族化合物（ｂ）］
前記フェノール性水酸基含有化合物は、ホルミル基含有芳香族化合物（ｂ）を反応させて得られることが好ましい。前記フェノール樹脂中に、前記カテコール化合物（ａ）と前記ホルミル基含有芳香族化合物（ｂ）との反応に基づくトリフェニルメタン骨格を導入することにより、３つの芳香環が３級炭素を介して、歪んだ構造（一平面上にない構造）となるため、分子間相互作用が適度に弱まることになり、低溶融粘度で、ハンドリング性に優れたフェノール樹脂となる。また、芳香環に基づく分子間のπ－π相互作用により、分子間密度が高まることで、機械強度や耐熱性に優れた硬化物を得ることができ、好ましい。
[Formyl group-containing aromatic compound (b)]
The phenolic hydroxyl group-containing compound is preferably obtained by reacting the formyl group-containing aromatic compound (b). By introducing a triphenylmethane skeleton based on the reaction between the catechol compound (a) and the formyl group-containing aromatic compound (b) into the phenol resin, three aromatic rings are mediated by tertiary carbon. Since the structure is distorted (a structure that is not on one plane), the interaction between molecules is moderately weakened, and the phenol resin has a low melt viscosity and excellent handleability. Further, the π-π interaction between molecules based on the aromatic ring increases the intramolecular density, so that a cured product having excellent mechanical strength and heat resistance can be obtained, which is preferable.
前記ホルミル基含有芳香族化合物（ｂ）としては、たとえば、ベンズアルデヒド、４－メチルベンズアルデヒド、４－メトキシベンズアルデヒド等のアルデヒド基が少なくとも１つ置換されたベンゼン環を有する化合物であることが好ましい。中でも、エポキシ樹脂合成時の反応性や、ハンドリング性の観点から、ベンズアルデヒドがより好ましい。 The formyl group-containing aromatic compound (b) is preferably a compound having a benzene ring in which at least one aldehyde group such as benzaldehyde, 4-methylbenzaldehyde, or 4-methoxybenzaldehyde is substituted. Of these, benzaldehyde is more preferable from the viewpoint of reactivity during epoxy resin synthesis and handleability.
本発明のフェノール樹脂に含有される前記フェノール性水酸基含有化合物は、例えば、下記一般式（３）で表されるカテコール化合物（ａ）と、下記一般式（４）で表されるホルミル基含有芳香族化合物（ｂ）とを反応させることにより得ることができる。
なお、上記一般式（３）及び（４）中の、Ｒ２及びＲ３は上記一般式（１）中と同様である。 In addition, R2 and R3 in the general formula ( 3 ) and (4) are the same as in the above general formula (1).
前記カテコール化合物（ａ）と前記ホルミル基含有芳香族化合物（ｂ）との反応比率は、溶融粘度と硬化物における耐熱性とのバランスに優れるエポキシ樹脂が得られることから、前記カテコール化合物（ａ）１モルに対し、前記ホルミル基含有芳香族化合物（ｂ）が０．０１～０．９モルの範囲であることが好ましい。 The reaction ratio between the catechol compound (a) and the formyl group-containing aromatic compound (b) is such that an epoxy resin having an excellent balance between melt viscosity and heat resistance in a cured product can be obtained. Therefore, the catechol compound (a) The amount of the formyl group-containing aromatic compound (b) is preferably in the range of 0.01 to 0.9 mol with respect to 1 mol.
前記カテコール化合物（ａ）と前記ホルミル基含有芳香族化合物（ｂ）との反応は、効率的に反応が進むことから、酸触媒の存在下で行うことが好ましい。前記酸触媒は、例えば、塩酸、硫酸、リン酸などの無機酸、メタンスルホン酸、パラトルエンスルホン酸、シュウ酸などの有機酸、三フッ化ホウ素、無水塩化アルミニウム、塩化亜鉛などのルイス酸などが挙げられる。このとき、反応触媒の使用量は、反応原料の総質量に対して、０．０１～５質量％の範囲であることが好ましい。 The reaction between the catechol compound (a) and the formyl group-containing aromatic compound (b) is preferably carried out in the presence of an acid catalyst because the reaction proceeds efficiently. The acid catalyst includes, for example, inorganic acids such as hydrochloric acid, sulfuric acid and phosphoric acid, organic acids such as methanesulfonic acid, paratoluenesulfonic acid and oxalic acid, and Lewis acids such as boron trifluoride, anhydrous aluminum chloride and zinc chloride. Can be mentioned. At this time, the amount of the reaction catalyst used is preferably in the range of 0.01 to 5% by mass with respect to the total mass of the reaction raw materials.
前記カテコール化合物（ａ）と前記ホルミル基含有芳香族化合物（ｂ）との反応は、通常、８０～２００℃の温度条件下、１～２０時間で行うことができる。該反応は必要に応じて有機溶剤中で行っても良い。ここで用いる有機溶剤は、前記温度条件下で使用可能な有機溶剤であれば特に限定されるものではなく、具体的には、メチルセロソルブ、エチルセロソルブ、トルエン、キシレン、メチルイソブチルケトン等が挙げられる。これら有機溶剤を用いる場合には反応原料の総質量に対して、１０～５００質量％の範囲で用いることが好ましい。 The reaction between the catechol compound (a) and the formyl group-containing aromatic compound (b) can usually be carried out under temperature conditions of 80 to 200 ° C. for 1 to 20 hours. The reaction may be carried out in an organic solvent, if necessary. The organic solvent used here is not particularly limited as long as it can be used under the above temperature conditions, and specific examples thereof include methyl cellosolve, ethyl cellosolve, toluene, xylene, and methyl isobutyl ketone. .. When these organic solvents are used, it is preferable to use them in the range of 10 to 500% by mass with respect to the total mass of the reaction raw materials.
前記カテコール化合物（ａ）と前記ホルミル基含有芳香族化合物（ｂ）との反応終了後は、未反応の反応原料や副生成物等を留去することにより、前記フェノール性水酸基含有化合物を含む前記フェノール樹脂が得られる。
なお、前記カテコール化合物（ａ）と前記ホルミル基含有芳香族化合物（ｂ）との反応終了後、前記カテコール化合物（ａ）の一部が未反応のまま残留した場合、反応に使用する反応炉の汚染や、周囲環境に悪影響を与えたり、化学量論的に誤差が生じて物性低下を招く懸念があり、さらに、残留した前記カテコール化合物（ａ）が硬化物の製造時などにおいて、揮発することで、ボイドの発生原因となるなど、前記カテコール化合物（ａ）の残留量が多くなることは好ましくない。そのため、ＧＰ測定により算出される残留した（未反応の）前記カテコール化合物（ａ）の含有割合としては、ＧＰＣ面積％において、５面積％以下であることが好ましい。前記フェノール性水酸基含有化合物以外の副生成物としては、例えば、下記一般式（５）で表される化合物等が挙げられる。また、前記副生成物は、本発明の効果を阻害しない程度に含んでいても良く、具体的には、ＧＰＣ面積％で、前記副生成物の合計値が３０％未満であることが好ましい。なお、ここでのＧＰＣ面積％とは、副生成物のＧＰＣピーク面積値を全成分のＧＰＣピーク面積値の合計で除した値を指す。
If a part of the catechol compound (a) remains unreacted after the reaction between the catechol compound (a) and the formyl group-containing aromatic compound (b) is completed, the reaction furnace used for the reaction There is a concern that the catechol compound (a) may be contaminated, adversely affect the surrounding environment, or cause a stoichiometric error to deteriorate the physical properties, and the residual catechol compound (a) may volatilize during the production of the cured product. Therefore, it is not preferable that the residual amount of the catechol compound (a) is large, for example, it causes the generation of voids. Therefore, the content ratio of the residual (unreacted) catechol compound (a) calculated by GP measurement is preferably 5 area% or less in terms of GPC area%. Examples of by-products other than the phenolic hydroxyl group-containing compound include compounds represented by the following general formula (5). Further, the by-products may be contained to such an extent that the effects of the present invention are not impaired, and specifically, it is preferable that the total value of the by-products is less than 30% in terms of GPC area%. The GPC area% here refers to a value obtained by dividing the GPC peak area value of the by-product by the total of the GPC peak area values of all the components.
前記フェノール樹脂の水酸基当量は、６０～１１０ｇ／ｅｑであることが好ましく、７０～１００ｇ／ｅｑであることがより好ましく、７５～９０ｇ／ｅｑであることが更に好ましい。前記フェノール樹脂の水酸基当量が前記範囲内であると、硬化物中の官能基密度が高まることとなり、得られる硬化物の耐熱性や機械強度も優れることから好ましい。ここでの前記フェノール樹脂の水酸基当量は、下記実施例における「フェノール樹脂の水酸基当量」の測定方法に基づいたものである。 The hydroxyl group equivalent of the phenol resin is preferably 60 to 110 g / eq, more preferably 70 to 100 g / eq, and even more preferably 75 to 90 g / eq. When the hydroxyl group equivalent of the phenol resin is within the above range, the functional group density in the cured product is increased, and the heat resistance and mechanical strength of the obtained cured product are also excellent, which is preferable. The hydroxyl group equivalent of the phenol resin here is based on the measuring method of "hydroxyl equivalent of the phenol resin" in the following examples.
前記フェノール樹脂の溶融粘度（１５０℃）は、５．０ｄＰａ・ｓ以下であることが好ましく、０．１～４．５ｄＰａ・ｓであることがより好ましく、１．０～４．０ｄＰａ・ｓであることが更に好ましい。前記エポキシ樹脂の溶融粘度が前記範囲内であると、低粘度で流動性、ハンドリング性に優れるため、エポキシ樹脂合成時のハンドリング性や、硬化物作製時のハンドリング性などにも優れることから好ましい。ここでの溶融粘度（１５０℃）は、ＡＳＴＭ Ｄ４２８７に準拠し、ＩＣＩ粘度計にて測定されるものである。 The melt viscosity (150 ° C.) of the phenol resin is preferably 5.0 dPa · s or less, more preferably 0.1 to 4.5 dPa · s, and 1.0 to 4.0 dPa · s. It is more preferable to have. When the melt viscosity of the epoxy resin is within the above range, it is preferable because it has a low viscosity and is excellent in fluidity and handleability, and is also excellent in handleability at the time of synthesizing an epoxy resin and at the time of producing a cured product. The melt viscosity (150 ° C.) here is measured by an ICI viscometer in accordance with ASTM D4287.
前記フェノール樹脂の軟化点としては、５０～１１０℃であることが好ましく、６０～１００℃であることがより好ましい。前記フェノール樹脂の軟化点が前記範囲内であると、ハンドリング性や貯蔵安定性に優れることから好ましい。ここでの軟化点は、ＪＩＳ Ｋ ７２３４（環球法）に基づき測定されるものである。 The softening point of the phenol resin is preferably 50 to 110 ° C, more preferably 60 to 100 ° C. When the softening point of the phenol resin is within the above range, it is preferable because it is excellent in handleability and storage stability. The softening point here is measured based on JIS K 7234 (ring ball method).
＜エポキシ樹脂＞
本発明は、下記一般式（２）で表され、前記フェノール樹脂、及び、エピハロヒドリンを反応させて得られるグリシジルエーテル基含有化合物を含有することを特徴とするエポキシ樹脂に関する。前記フェノール樹脂に、エピハロヒドリンを反応させることにより、グリシジルエーテル基が導入されたグリシジルエーテル基含有化合物するエポキシ樹脂を得ることができ、低溶融粘度で曲げ特性に優れた硬化物が得られるためとなり、好ましい。
The present invention relates to an epoxy resin represented by the following general formula (2) and containing the phenol resin and a glycidyl ether group-containing compound obtained by reacting with epihalohydrin. By reacting the phenol resin with epihalohydrin, an epoxy resin containing a glycidyl ether group into which a glycidyl ether group has been introduced can be obtained, and a cured product having a low melt viscosity and excellent bending characteristics can be obtained. preferable.
上記一般式（２）中、Ｒ４は、水素原子、または、メチル基を表すことが好ましく、より好ましくは水素原子である。前記Ｒ４が、水素原子等であることにより、曲げ特性と耐熱性に優れることとなり、好ましい。中でも水素原子であることにより、溶融粘度が低くなり、特に好ましい態様となる。
なお、上記一般式（２）中、Ｒ１、Ｒ２、Ｒ３、ｍ、及び、ｎは、上記一般式（１）と同様である。
In the above general formula (2), R4 preferably represents a hydrogen atom or a methyl group, and more preferably a hydrogen atom. Since R 4 is a hydrogen atom or the like, it is preferable because it has excellent bending characteristics and heat resistance. Among them, the hydrogen atom has a low melt viscosity, which is a particularly preferable embodiment.
In the general formula (2), R 1 , R 2 , R 3 , m, and n are the same as those in the general formula (1).
前記フェノール樹脂とエピハロヒドリンとを反応させ、目的のエポキシ樹脂を得ることができる。該反応は、例えば、前記フェノール樹脂中のフェノール性水酸基の１モルに対し、エピハロヒドリンが２～１０モルの範囲となる割合で両者を用い、フェノール性水酸基１モルに対し、０．９～２．０モルの塩基性触媒を一括又は分割添加しながら、２０～１２０℃の温度で０．５～１０時間反応させる方法などが挙げられる。 The desired epoxy resin can be obtained by reacting the phenol resin with epihalohydrin. In the reaction, for example, both were used at a ratio of epihalohydrin in the range of 2 to 10 mol with respect to 1 mol of the phenolic hydroxyl group in the phenol resin, and 0.9 to 2. Examples thereof include a method of reacting at a temperature of 20 to 120 ° C. for 0.5 to 10 hours while adding 0 mol of a basic catalyst in a batch or in portions.
なお、工業生産を行う際、エポキシ樹脂生産の初バッチでは仕込みに用いるエピハロヒドリン類の全てが新しいものであるが、次バッチ以降は、粗反応生成物から回収されたエピハロヒドリンと、反応で消費される分で消失する分に相当する新しいエピハロヒドリンとを併用することが好ましい。この時、使用するエピハロヒドリンは特に限定されないが、例えば、エピクロルヒドリン、エピブロモヒドリン、β－メチルエピクロルヒドリン等が挙げられる。なかでも工業的入手が容易なことからエピクロルヒドリンが好ましい。 In the first batch of epoxy resin production, all of the epihalohydrins used for preparation are new during industrial production, but after the next batch, the epihalohydrins recovered from the crude reaction product are consumed in the reaction. It is preferable to use in combination with a new epihalohydrin corresponding to the amount that disappears in minutes. At this time, the epichlorohydrin used is not particularly limited, and examples thereof include epichlorohydrin, epibromohydrin, and β-methylepichlorohydrin. Of these, epichlorohydrin is preferable because it is easily available industrially.
前記塩基性触媒は、具体的には、アルカリ土類金属水酸化物、アルカリ金属炭酸塩及びアルカリ金属水酸化物等が挙げられる。中でも、触媒活性に優れる点からアルカリ金属水酸化物が好ましく、具体的には、水酸化ナトリウムや水酸化カリウム等が好ましい。 Specific examples of the basic catalyst include alkaline earth metal hydroxides, alkali metal carbonates and alkali metal hydroxides. Of these, alkali metal hydroxides are preferable from the viewpoint of excellent catalytic activity, and specifically, sodium hydroxide, potassium hydroxide and the like are preferable.
反応終了後は、反応混合物を水洗した後、加熱減圧下での蒸留によって未反応のエピハロヒドリンや有機溶媒を留去する。また、加水分解性ハロゲンの一層少ないエポキシ樹脂とするために、得られたエポキシ樹脂を再び有機溶媒に溶解し、水酸化ナトリウム、水酸化カリウムなどのアルカリ金属水酸化物の水溶液を加えてさらに反応を行うこともできる。この際、反応速度の向上を目的として、４級アンモニウム塩やクラウンエーテル等の相関移動触媒を存在させてもよい。相関移動触媒を使用する場合の使用量はエポキシ樹脂１００質量部に対して０．１～３．０質量部となる割合であることが好ましい。反応終了後、生成した塩を濾過や水洗等により除去し、加熱減圧下で有機溶媒を留去することにより、目的とする本発明のエポキシ樹脂を得ることができる。 After completion of the reaction, the reaction mixture is washed with water, and then unreacted epihalohydrin and an organic solvent are distilled off by distillation under heating and reduced pressure. Further, in order to obtain an epoxy resin having a lower amount of hydrolyzable halogen, the obtained epoxy resin is dissolved again in an organic solvent, and an aqueous solution of an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide is added for further reaction. Can also be done. At this time, a phase transfer catalyst such as a quaternary ammonium salt or crown ether may be present for the purpose of improving the reaction rate. When the phase transfer catalyst is used, the amount used is preferably 0.1 to 3.0 parts by mass with respect to 100 parts by mass of the epoxy resin. After completion of the reaction, the produced salt is removed by filtration, washing with water or the like, and the organic solvent is distilled off under heating and reduced pressure to obtain the desired epoxy resin of the present invention.
前記エポキシ樹脂のエポキシ当量は、１２０～４００ｇ／ｅｑであることが好ましく、１３０～３００ｇ／ｅｑであることがより好ましく、１４０～２００ｇ／ｅｑであることが更に好ましい。前記エポキシ樹脂のエポキシ当量が前記範囲内であると、硬化物の架橋密度が高まり、得られる硬化物の耐熱性に優れることから好ましい。ここでのエポキシ当量の測定は、ＪＩＳ Ｋ ７２３６に基づいて測定されるものである。 The epoxy equivalent of the epoxy resin is preferably 120 to 400 g / eq, more preferably 130 to 300 g / eq, and even more preferably 140 to 200 g / eq. When the epoxy equivalent of the epoxy resin is within the above range, the crosslink density of the cured product is increased and the heat resistance of the obtained cured product is excellent, which is preferable. The measurement of epoxy equivalent here is based on JIS K 7236.
前記エポキシ樹脂の溶融粘度（１５０℃）は、２.０ｄＰａ・ｓ以下であることが好ましく、０．０１～１．０ｄＰａ・ｓであることがより好ましく、０．１～０．６ｄＰａ・ｓであることが更に好ましい。前記エポキシ樹脂の溶融粘度が前記範囲内であると、低粘度で流動性、ハンドリング性に優れるため、得られる硬化物の成形性にも優れることから好ましい。ここでの溶融粘度（１５０℃）は、ＡＳＴＭ Ｄ４２８７に準拠し、ＩＣＩ粘度計にて測定されるものである。 The melt viscosity (150 ° C.) of the epoxy resin is preferably 2.0 dPa · s or less, more preferably 0.01 to 1.0 dPa · s, and 0.1 to 0.6 dPa · s. It is more preferable to have. When the melt viscosity of the epoxy resin is within the above range, it is preferable because it has a low viscosity and is excellent in fluidity and handleability, and is also excellent in moldability of the obtained cured product. The melt viscosity (150 ° C.) here is measured by an ICI viscometer in accordance with ASTM D4287.
＜硬化性樹脂組成物＞
本発明は、前記エポキシ樹脂を含有することを特徴とする硬化性樹脂組成物に関する。前記硬化性樹脂組成物は、前記エポキシ樹脂を含有することにより、ハンドリング性に優れ、得られる硬化物は、高曲げ特性、及び、高耐熱性となり、有用である。
<Curable resin composition>
The present invention relates to a curable resin composition comprising the epoxy resin. The curable resin composition is excellent in handleability by containing the epoxy resin, and the obtained cured product has high bending characteristics and high heat resistance, which is useful.
本発明の硬化性樹脂組成物は、前記エポキシ樹脂以外にも、本発明の効果を損なわない範囲において、他の樹脂(その他のエポキシ樹脂を含む)、硬化剤、添加剤、溶剤等をさらに含んでいてもよい。 In addition to the epoxy resin, the curable resin composition of the present invention further contains other resins (including other epoxy resins), curing agents, additives, solvents and the like as long as the effects of the present invention are not impaired. You may be.
［その他エポキシ樹脂］
前記その他のエポキシ樹脂としては、種々のエポキシ樹脂を用いることができるが、例えば、２，７－ジグリシジルオキシナフタレン、α－ナフトールノボラック型エポキシ樹脂、β－ナフトールノボラック型エポキシ樹脂、α－ナフトール／β－ナフトール共縮合型ノボラックのポリグリシジルエーテル、ナフトールアラルキル型エポキシ樹脂、１，１－ビス（２，７－ジグリシジルオキシ－１－ナフチル）アルカン等のナフタレン骨格含有エポキシ樹脂；ビスフェノールＡ型エポキシ樹脂、ビスフェノールＦ型エポキシ樹脂等のビスフェノール型エポキシ樹脂；ビフェニル型エポキシ樹脂、テトラメチルビフェニル型エポキシ樹脂等のビフェニル型エポキシ樹脂；フェノールノボラック型エポキシ樹脂、クレゾールノボラック型エポキシ樹脂、ビスフェノールＡノボラック型エポキシ樹脂、ビフェニルノボラック型エポキシ樹脂等のノボラック型エポキシ樹脂；テトラフェニルエタン型エポキシ樹脂；ジシクロペンタジエン－フェノール付加反応型エポキシ樹脂；フェノールアラルキル型エポキシ樹脂；リン原子含有エポキシ樹脂等が挙げられる。前記リン原子含有エポキシ樹脂は、９，１０－ジヒドロ－９－オキサ－１０－ホスファフェナントレン－１０－オキサイド（以下、「ＨＣＡ」と略記する。）のエポキシ化物、ＨＣＡとキノン類とを反応させて得られるフェノール樹脂のエポキシ化物、フェノールノボラック型エポキシ樹脂をＨＣＡで変性したエポキシ樹脂、クレゾールノボラック型エポキシ樹脂をＨＣＡで変性したエポキシ樹脂、ビスフェノールＡ型エポキシ樹脂を及びＨＣＡとキノン類とを反応させて得られるフェノール樹脂で変成して得られるエポキシ樹脂等が挙げられる。これらはそれぞれ単独で用いても良いし、２種類以上を併用しても良い。
[Other epoxy resins]
As the other epoxy resin, various epoxy resins can be used, and for example, 2,7-diglycidyloxynaphthalene, α-naphthol novolac type epoxy resin, β-naphthol novolak type epoxy resin, α-naphthol / β-naphthol cocondensation type novolak polyglycidyl ether, naphthol aralkyl type epoxy resin, naphthalene skeleton-containing epoxy resin such as 1,1-bis (2,7-diglycidyloxy-1-naphthyl) alkane; bisphenol A type epoxy resin , Bisphenol type epoxy resin such as bisphenol F type epoxy resin; Biphenyl type epoxy resin such as biphenyl type epoxy resin, tetramethyl biphenyl type epoxy resin; Examples thereof include a novolak type epoxy resin such as a biphenyl novolak type epoxy resin; a tetraphenylethane type epoxy resin; a dicyclopentadiene-phenol addition reaction type epoxy resin; a phenol aralkyl type epoxy resin; and a phosphorus atom-containing epoxy resin. The phosphorus atom-containing epoxy resin is an epoxy of 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (hereinafter abbreviated as "HCA"), which is a reaction between HCA and quinones. Epoxy product of phenol resin obtained above, epoxy resin obtained by modifying phenol novolac type epoxy resin with HCA, epoxy resin obtained by modifying cresol novolac type epoxy resin with HCA, bisphenol A type epoxy resin, and reaction of HCA with quinones. Examples thereof include an epoxy resin obtained by modifying with the obtained phenol resin. These may be used alone or in combination of two or more.
［他の樹脂］
本発明の硬化性樹脂組成物は、前記エポキシ樹脂や、前記その他のエポキシ樹脂に加えて、他の樹脂を含んでいてもよい。なお、本明細書において、「他の樹脂」とは、エポキシ樹脂以外の樹脂を意味する。
[Other resins]
The curable resin composition of the present invention may contain other resins in addition to the epoxy resin and other epoxy resins. In addition, in this specification, "other resin" means a resin other than an epoxy resin.
前記他の樹脂の具体例としては、特に制限されないが、活性エステル、マレイミド樹脂、ビスマレイミド樹脂、ポリマレイミド樹脂、ポリフェニレンエーテル樹脂、ポリイミド樹脂、シアネートエステル樹脂、ベンゾオキサジン樹脂、トリアジン含有クレゾールノボラック樹脂、シアン酸エステル樹脂、スチレン－無水マレイン酸樹脂、ジアリルビスフェノールやトリアリルイソシアヌレート等のアリル基含有樹脂、ポリリン酸エステル、リン酸エステル－カーボネート共重合体等が挙げられる。これらの他の樹脂は単独で用いても、２種以上を組み合わせて用いてもよい。 Specific examples of the other resins include, but are not limited to, active esters, maleimide resins, bismaleimide resins, polymerimide resins, polyphenylene ether resins, polyimide resins, cyanate ester resins, benzoxazine resins, triazine-containing cresol novolak resins, and the like. Examples thereof include cyanate ester resin, styrene-maleic anhydride resin, allyl group-containing resin such as diallyl bisphenol and triallyl isocyanurate, polyphosphate ester, phosphate ester-carbonate copolymer and the like. These other resins may be used alone or in combination of two or more.
［硬化剤］
本発明のエポキシ樹脂組成物は、前記エポキシ樹脂と共に、硬化剤を含有することができる。前記硬化剤を含むことにより、耐熱性に優れた硬化物を得ることができる。
[Curing agent]
The epoxy resin composition of the present invention can contain a curing agent together with the epoxy resin. By containing the curing agent, a cured product having excellent heat resistance can be obtained.
ここで用いる硬化剤としては、アミン化合物、アミド化合物、酸無水物、フェノ－ル樹脂等が挙げられ、これらはそれぞれ単独で用いても良いし、２種類以上を併用しても良い。 Examples of the curing agent used here include amine compounds, amide compounds, acid anhydrides, phenolic resins and the like, and these may be used alone or in combination of two or more.
前記アミン化合物としては、例えば、ジアミノジフェニルメタン、ジエチレントリアミン、トリエチレンテトラミン、ジアミノジフェニルスルホン、イソホロンジアミン、イミダゾ－ル、ＢＦ３－アミン錯体、グアニジン誘導体等が挙げられる。 Examples of the amine compound include diaminodiphenylmethane, diethylenetriamine, triethylenetetramine, diaminodiphenylsulfone, isophoronediamine, imidazole, BF3 -amine complex, guanidine derivative and the like.
前記アミド系化合物としては、例えば、ジシアンジアミド、脂肪族二塩基酸やダイマー酸、脂肪酸のカルボン酸化合物とエチレンジアミン等のアミンとより合成されるポリアミド樹脂等が挙げられる。 Examples of the amide-based compound include dicyandiamide, aliphatic dibasic acids and dimer acids, and polyamide resins synthesized from carboxylic acid compounds of fatty acids and amines such as ethylenediamine.
前記酸無水物としては、例えば、無水フタル酸、無水トリメリット酸、無水ピロメリット酸、無水マレイン酸、テトラヒドロ無水フタル酸、メチルテトラヒドロ無水フタル酸、無水メチルナジック酸、ヘキサヒドロ無水フタル酸、メチルヘキサヒドロ無水フタル酸等が挙げられる。 Examples of the acid anhydride include phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, maleic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylnadic anhydride, hexahydrophthalic anhydride, and methylhexa. Examples include hydrophthalic anhydride.
前記フェノール樹脂としては、例えば、フェノールノボラック樹脂、クレゾールノボラック樹脂、芳香族炭化水素ホルムアルデヒド樹脂変性フェノール樹脂、ジシクロペンタジエンフェノール付加型樹脂、フェノールアラルキル樹脂（ザイロック樹脂）、レゾルシンノボラック樹脂に代表される多価ヒドロキシ化合物とホルムアルデヒドから合成される多価フェノールノボラック樹脂、ナフトールアラルキル樹脂、トリメチロールメタン樹脂、テトラフェニロールエタン樹脂、ナフトールノボラック樹脂、ナフトール－フェノール共縮ノボラック樹脂、ナフトール－クレゾール共縮ノボラック樹脂、ビフェニル変性フェノール樹脂（ビスメチレン基でフェノール核が連結された多価フェノール化合物）、ビフェニル変性ナフトール樹脂（ビスメチレン基でフェノール核が連結された多価ナフトール化合物）、アミノトリアジン変性フェノール樹脂（メラミン、ベンゾグアナミンなどでフェノール核が連結された多価フェノール化合物）やアルコキシ基含有芳香環変性ノボラック樹脂（ホルムアルデヒドでフェノール核及びアルコキシ基含有芳香環が連結された多価フェノール化合物）等の多価フェノール化合物等が挙げられる。 Examples of the phenol resin include phenol novolac resin, cresol novolak resin, aromatic hydrocarbon formaldehyde resin-modified phenol resin, dicyclopentadienephenol-added resin, phenol aralkyl resin (Zyroc resin), and resorcin novolac resin. Polyvalent phenol novolac resin synthesized from valent hydroxy compounds and formaldehyde, naphthol aralkyl resin, trimethylolmethane resin, tetraphenylol ethane resin, naphthol novolak resin, naphthol-phenol co-condensed novolak resin, naphthol-cresol co-condensed novolak resin, Biphenyl-modified phenolic resin (polyvalent phenolic compound in which phenolic nuclei are linked by bismethylene group), biphenyl-modified naphthol resin (polyvalent naphthol compound in which phenolic nucleus is linked by bismethylene group), aminotriazine-modified phenolic resin (melamine, benzoguanamine, etc.) Polyhydric phenol compounds in which phenol nuclei are linked in) and polyhydric phenol compounds such as alkoxy group-containing aromatic ring-modified novolak resin (polyhydric phenol compounds in which phenol nuclei and alkoxy group-containing aromatic rings are linked with formaldehyde) are listed. Is done.
これらの硬化剤はそれぞれ単独で用いても良いし、２種類以上を併用しても良い。 Each of these curing agents may be used alone, or two or more kinds may be used in combination.
本発明の硬化性樹脂組成物において、エポキシ樹脂成分と硬化剤との配合割合は、硬化性に優れ、耐熱性や靭性に優れる硬化物が得られることから、エポキシ樹脂成分中のエポキシ基の合計１当量に対して、硬化剤中の活性基が０．７～１．５当量になる量が好ましい。 In the curable resin composition of the present invention, the mixing ratio of the epoxy resin component and the curing agent is such that a cured product having excellent curability and excellent heat resistance and toughness can be obtained. The amount of the active group in the curing agent is preferably 0.7 to 1.5 equivalents with respect to 1 equivalent.
前記添加剤としては、例えば、硬化促進剤、難燃剤、無機充填剤、シランカップリング剤、離型剤、顔料、乳化剤、溶剤等の各種添加剤が挙げられ、必要に応じて、前記構成樹脂組成物に含有することができる。 Examples of the additive include various additives such as a curing accelerator, a flame retardant, an inorganic filler, a silane coupling agent, a mold release agent, a pigment, an emulsifier, and a solvent, and if necessary, the constituent resin. It can be contained in the composition.
［硬化促進剤］
前記硬化促進剤は、例えば、リン系化合物、第３級アミン、イミダゾール、有機酸金属塩、ルイス酸、アミン錯塩等が挙げられる。中でも、硬化性、耐熱性、電気特性、耐湿信頼性等に優れる点から、イミダゾール化合物では２－エチル－４－メチルイミダゾール、リン系化合物ではトリフェニルホスフィン、第３級アミンでは１，８－ジアザビシクロ－［５．４．０］－ウンデセン（ＤＢＵ）が好ましい。
[Curing accelerator]
Examples of the curing accelerator include phosphorus compounds, tertiary amines, imidazoles, organic acid metal salts, Lewis acids, amine complex salts and the like. Among them, 2-ethyl-4-methylimidazole for imidazole compounds, triphenylphosphine for phosphorus compounds, and 1,8-diazabicyclo for tertiary amines are excellent in curability, heat resistance, electrical properties, moisture resistance reliability, etc. -[5.4.0]-Undecen (DBU) is preferred.
［難燃剤］
前記難燃剤は、例えば、赤リン、リン酸一アンモニウム、リン酸二アンモニウム、リン酸三アンモニウム、ポリリン酸アンモニウム等のリン酸アンモニウム、リン酸アミド等の無機リン化合物；リン酸エステル化合物、ホスホン酸化合物、ホスフィン酸化合物、ホスフィンオキシド化合物、ホスホラン化合物、有機系含窒素リン化合物、９，１０－ジヒドロ－９－オキサ－１０－ホスファフェナントレン－１０－オキシド、１０－（２，５－ジヒドロオキシフェニル）－１０Ｈ－９－オキサ－１０－ホスファフェナントレン－１０－オキシド、１０－（２，７－ジヒドロオキシナフチル）－１０Ｈ－９－オキサ－１０－ホスファフェナントレン－１０－オキシド等の環状有機リン化合物、及びそれをエポキシ樹脂やフェノール樹脂等の化合物と反応させた誘導体等の有機リン化合物；トリアジン化合物、シアヌル酸化合物、イソシアヌル酸化合物、フェノチアジン等の窒素系難燃剤；シリコーンオイル、シリコーンゴム、シリコーン樹脂等のシリコーン系難燃剤；金属水酸化物、金属酸化物、金属炭酸塩化合物、金属粉、ホウ素化合物、低融点ガラス等の無機難燃剤等が挙げられる。これら難燃剤を用いる場合は、硬化性樹脂組成物中０．１～２０質量％の範囲であることが好ましい。
[Flame retardants]
The flame retardant may be, for example, red phosphorus, monoammonium phosphate, diammonium phosphate, triammonium phosphate, ammonium phosphate such as ammonium polyphosphate, inorganic phosphorus compounds such as phosphate amide; phosphoric acid ester compounds, phosphonic acid. Compounds, phosphinic acid compounds, phosphin oxide compounds, phosphoran compounds, organonitrous phosphorus compounds, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 10- (2,5-dihydrooxyphenyl) ) -10H-9-Oxa-10-phosphaphenanthrene-10-oxide, 10- (2,7-dihydrooxynaphthyl) -10H-9-oxa-10-phosphaphenanthrene-10-oxide, etc. Cyclic organic phosphorus Organophosphorus compounds such as compounds and derivatives obtained by reacting them with compounds such as epoxy resins and phenol resins; nitrogen-based flame retardants such as triazine compounds, cyanuric acid compounds, isocyanuric acid compounds and phenothiazine; silicone oils, silicone rubbers and silicones. Silicone-based flame retardants such as resins; examples thereof include metal hydroxides, metal oxides, metal carbonate compounds, metal powders, boron compounds, and inorganic flame retardants such as low melting point glass. When these flame retardants are used, it is preferably in the range of 0.1 to 20% by mass in the curable resin composition.
［無機充填剤］
前記無機充填剤は、例えば、本発明の硬化性樹脂組成物を半導体封止材料用途に用いる場合などに配合される。前記無機充填剤は、例えば、溶融シリカ、結晶シリカ、アルミナ、窒化珪素、水酸化アルミ等が挙げられる。中でも、無機充填剤をより多く配合することが可能となることから、前記溶融シリカが好ましい。前記溶融シリカは破砕状、球状のいずれでも使用可能であるが、溶融シリカの配合量を高め、且つ、硬化性樹脂組成物の溶融粘度の上昇を抑制するためには、球状のものを主に用いることが好ましい。更に、球状シリカの配合量を高めるためには、球状シリカの粒度分布を適当に調整することが好ましい。その充填率は硬化性樹脂組成物１００質量部中、０．５～９５質量部の範囲で配合することが好ましい。
[Inorganic filler]
The inorganic filler is blended, for example, when the curable resin composition of the present invention is used for semiconductor encapsulation material applications. Examples of the inorganic filler include fused silica, crystalline silica, alumina, silicon nitride, aluminum hydroxide and the like. Above all, the molten silica is preferable because it is possible to add a larger amount of the inorganic filler. The fused silica can be used in either a crushed form or a spherical shape, but in order to increase the blending amount of the fused silica and suppress the increase in the melt viscosity of the curable resin composition, a spherical one is mainly used. It is preferable to use it. Further, in order to increase the blending amount of spherical silica, it is preferable to appropriately adjust the particle size distribution of spherical silica. The filling rate is preferably in the range of 0.5 to 95 parts by mass in 100 parts by mass of the curable resin composition.
本発明の硬化性樹脂組成物は、無溶剤で調製しても構わないし、溶媒を含んでいてもよい。前記溶媒は、硬化性樹脂組成物の粘度を調整する機能等を有する。前記溶媒の具体例としては、特に制限されないが、アセトン、メチルエチルケトン、メチルイソブチルケトン、シクロヘキサノン等のケトン系溶剤；ジエチルエーテル、テトラヒドロフラン等のエーテル系溶剤；酢酸エチル、酢酸ブチル、セロソルブアセテート、プロピレングリコールモノメチルエーテルアセテート、カルビトールアセテート等のエステル系溶剤；セロソルブ、ブチルカルビトール等のカルビトール類、トルエン、キシレン、エチルベンゼン、メシチレン、１,２,３－トリメチルベンゼン、１,２,４－トリメチルベンゼン等の芳香族炭化水素、ジメチルホルムアミド、ジメチルアセトアミド、Ｎ－メチルピロリドン等のアミド系溶剤等が挙げられる。これらの溶媒は単独で用いても、２種以上を組み合わせて用いてもよい。 The curable resin composition of the present invention may be prepared without a solvent, or may contain a solvent. The solvent has a function of adjusting the viscosity of the curable resin composition and the like. Specific examples of the solvent are not particularly limited, but are ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone; ether solvents such as diethyl ether and tetrahydrofuran; ethyl acetate, butyl acetate, cellosolve acetate and propylene glycol monomethyl. Ester solvents such as ether acetate and carbitol acetate; carbitols such as cellosolve and butyl carbitol, toluene, xylene, ethylbenzene, mecitylene, 1,2,3-trimethylbenzene, 1,2,4-trimethylbenzene and the like. Examples thereof include amide-based solvents such as aromatic hydrocarbons, dimethylformamide, dimethylacetamide, and N-methylpyrrolidone. These solvents may be used alone or in combination of two or more.
この他、本発明の硬化性樹脂組成物を導電ペーストなどの用途に使用する場合は、銀粉や銅粉等の導電性充填剤を用いることができる。 In addition, when the curable resin composition of the present invention is used for applications such as conductive paste, a conductive filler such as silver powder or copper powder can be used.
＜硬化物＞
本発明は、前記硬化性樹脂組成物を硬化反応させて得られることを特徴とする硬化物に関する。前記硬化物は、前記エポキシ樹脂を含有する前記硬化性樹脂組成物により得られるため、高耐熱性、及び、高曲げ特性（曲げ強度や曲げ弾性率などの向上）を発現することができ、好ましい。
<Curing product>
The present invention relates to a cured product obtained by subjecting the curable resin composition to a curing reaction. Since the cured product is obtained from the curable resin composition containing the epoxy resin, it is preferable because it can exhibit high heat resistance and high bending characteristics (improvement of bending strength, bending elastic modulus, etc.). ..
本発明の硬化性樹脂組成物は、上記した各成分を均一に混合することにより得られる。エポキシ樹脂成分、硬化剤、更に必要により硬化促進剤などが配合され、これを用いて、従来公知の方法と同様の方法にて、容易に硬化物を得ることができる。得られた硬化物は、積層物、注型物、接着層、塗膜、フィルム等の成形硬化物が挙げられる。 The curable resin composition of the present invention is obtained by uniformly mixing each of the above-mentioned components. An epoxy resin component, a curing agent, and if necessary, a curing accelerator and the like are blended, and by using this, a cured product can be easily obtained by the same method as a conventionally known method. Examples of the obtained cured product include molded products such as laminates, cast products, adhesive layers, coating films, and films.
前記硬化性樹脂組成物を硬化反応させてなる硬化物を得る方法としては、例えば、加熱硬化する際の加熱温度は、特に制限されないが、１００～３００℃であり、加熱時間としては、１～２４時間であることが好ましい。 As a method for obtaining a cured product obtained by subjecting the curable resin composition to a curing reaction, for example, the heating temperature at the time of heat curing is not particularly limited, but is 100 to 300 ° C., and the heating time is 1 to 1 to 1. It is preferably 24 hours.
＜硬化性樹脂組成物の用途＞
前記硬化性樹脂組成物が用いられる用途としては、プリント配線板材料、フレキシルブル配線基板用樹脂組成物、ビルドアップ基板用層間絶縁材料、ビルドアップ用接着フィルム等の回路基板用絶縁材料、樹脂注型材料、接着剤、半導体封止材料、半導体装置、プリプレグ、導電ペースト、ビルドアップフィルム、ビルドアップ基板、繊維強化複合材料、前記複合材料を硬化させてなる成形品等が挙げられる。これら各種用途のうち、プリント配線板材料、回路基板用絶縁材料、ビルドアップ用接着フィルム用途では、コンデンサ等の受動部品やＩＣチップ等の能動部品を基板内に埋め込んだ所謂電子部品内蔵用基板用の絶縁材料として用いることができる。さらに、上記の中でも、硬化物が優れた耐熱性、低誘電特性、及び、高弾性率等を有するといった特性を生かし、本発明の硬化性樹脂組成物は、半導体封止材料、半導体装置、プリプレグ、フレキシルブル配線基板、回路基板、及び、ビルドアップフィルム、ビルドアップ基板、多層プリント配線板、繊維強化複合材料、前記複合材料を硬化させてなる成形品に用いることが好ましい。以下に、硬化性樹脂組成物から、前記繊維強化複合材料などを製造する方法について説明する。
<Use of curable resin composition>
Applications in which the curable resin composition is used include printed wiring board materials, resin compositions for flexible wiring boards, interlayer insulating materials for build-up boards, insulating materials for circuit boards such as adhesive films for build-up, and resin injection. Examples thereof include mold materials, adhesives, semiconductor encapsulant materials, semiconductor devices, prepregs, conductive pastes, build-up films, build-up substrates, fiber-reinforced composite materials, and molded products obtained by curing the composite materials. Among these various applications, printed wiring board materials, insulating materials for circuit boards, and adhesive films for build-up are for so-called electronic component built-in boards in which passive components such as capacitors and active components such as IC chips are embedded in the substrate. Can be used as an insulating material. Further, among the above, the curable resin composition of the present invention is a semiconductor encapsulating material, a semiconductor device, and a prepreg, taking advantage of the characteristics that the cured product has excellent heat resistance, low dielectric property, high elastic coefficient, and the like. , Flexible wiring boards, circuit boards, and build-up films, build-up boards, multilayer printed wiring boards, fiber-reinforced composite materials, and molded products obtained by curing the composite materials. Hereinafter, a method for producing the fiber-reinforced composite material or the like from the curable resin composition will be described.
１．半導体封止材料
上記硬化性樹脂組成物から半導体封止材料を得る方法としては、上記硬化性樹脂組成物、及び硬化促進剤、及び無機充填剤等の配合剤とを必要に応じて押出機、ニ－ダ、ロ－ル等を用いて均一になるまで充分に溶融混合する方法が挙げられる。その際、無機充填剤としては、通常、溶融シリカが用いられるが、パワートランジスタ、パワーＩＣ用高熱伝導半導体封止材として用いる場合は、溶融シリカよりも熱伝導率の高い結晶シリカ、アルミナ、窒化ケイ素などの高充填化、又は溶融シリカ、結晶性シリカ、アルミナ、窒化ケイ素などを用いるとよい。その充填率は硬化性樹脂組成物１００質量部当たり、無機充填剤を３０～９５質量部の範囲で用いることが好ましく、中でも、難燃性や耐湿性や耐ハンダクラック性の向上、線膨張係数の低下を図るためには、７０質量部以上がより好ましく、８０質量部以上であることがさらに好ましい。
1. 1. Semiconductor encapsulation material As a method for obtaining a semiconductor encapsulation material from the curable resin composition, an extruder such as the curable resin composition, a curing accelerator, and a compounding agent such as an inorganic filler is used as necessary. Examples thereof include a method of sufficiently melting and mixing until uniform using a feeder, a roll or the like. At that time, fused silica is usually used as the inorganic filler, but when used as a high thermal conductivity semiconductor encapsulant for power transistors and power ICs, crystalline silica, alumina, and silicon nitride having higher thermal conductivity than fused silica are used. It is preferable to increase the filling of silicon or the like, or to use molten silica, crystalline silica, alumina, silicon nitride or the like. It is preferable to use an inorganic filler in the range of 30 to 95 parts by mass per 100 parts by mass of the curable resin composition, and above all, improvement of flame retardancy, moisture resistance and solder crack resistance, and a coefficient of linear expansion. 70 parts by mass or more is more preferable, and 80 parts by mass or more is further preferable.
２．半導体装置
上記硬化性樹脂組成物から半導体装置を得る方法としては、上記半導体封止材料を注型、或いはトランスファー成形機、射出成形機などを用いて成形し、さらに５０～２００℃で２～１０時間の間、加熱する方法が挙げられる。
2. 2. Semiconductor device As a method of obtaining a semiconductor device from the curable resin composition, the semiconductor encapsulant material is cast or molded using a transfer molding machine, an injection molding machine, or the like, and further, 2 to 10 at 50 to 200 ° C. Examples include methods of heating for hours.
３．プリプレグ
上記硬化性樹脂組成物からプリプレグを得る方法としては、下記有機溶媒を配合してワニス化した硬化性樹脂組成物を、補強基材（紙、ガラス布、ガラス不織布、アラミド紙、アラミド布、ガラスマット、ガラスロービング布など）に含浸したのち、用いた溶媒種に応じた加熱温度、好ましくは５０～１７０℃で加熱することによって、得る方法が挙げられる。この時用いる樹脂組成物と補強基材の質量割合としては、特に限定されないが、通常、プリプレグ中の樹脂分が２０～６０質量％となるように調製することが好ましい。
3. 3. Prepreg As a method for obtaining a prepreg from the above curable resin composition, a curable resin composition obtained by blending the following organic solvent to form a varnish is used as a reinforcing base material (paper, glass cloth, glass non-woven fabric, aramid paper, aramid cloth, etc.). A method obtained by impregnating a glass mat, a glass roving cloth, etc.) and then heating at a heating temperature according to the solvent type used, preferably 50 to 170 ° C. can be mentioned. The mass ratio of the resin composition and the reinforcing base material used at this time is not particularly limited, but it is usually preferable to prepare the resin composition in the prepreg so as to have a mass ratio of 20 to 60% by mass.
ここで用いる有機溶媒としては、メチルエチルケトン、アセトン、ジメチルホルムアミド、メチルイソブチルケトン、メトキシプロパノール、シクロヘキサノン、メチルセロソルブ、エチルジグリコールアセテート、プロピレングリコールモノメチルエーテルアセテート等が挙げられ、その選択や適正な使用量は用途によって適宜選択し得るが、例えば、下記のようにプリプレグからプリント回路基板をさらに製造する場合には、メチルエチルケトン、アセトン、ジメチルホルムアミド等の沸点が１６０℃以下の極性溶媒を用いることが好ましく、また、不揮発分が４０～８０質量％となる割合で用いることが好ましい。 Examples of the organic solvent used here include methyl ethyl ketone, acetone, dimethylformamide, methyl isobutyl ketone, methoxypropanol, cyclohexanone, methyl cellosolve, ethyl diglycol acetate, propylene glycol monomethyl ether acetate and the like. It can be appropriately selected depending on the application, but for example, when further producing a printed circuit board from prepylene as described below, it is preferable to use a polar solvent having a boiling point of 160 ° C. or lower, such as methyl ethyl ketone, acetone, or dimethylformamide. , It is preferable to use the non-volatile content at a ratio of 40 to 80% by mass.
４．回路基板
上記硬化性樹脂組成物からプリント回路基板を得る方法としては、上記プリプレグを、常法により積層し、適宜銅箔を重ねて、１～１０ＭＰａの加圧下に１７０～３００℃で１０分～３時間、加熱圧着させる方法が挙げられる
4. Circuit board As a method of obtaining a printed circuit board from the curable resin composition, the prepregs are laminated by a conventional method, copper foils are appropriately laminated, and the pressure of 1 to 10 MPa is applied at 170 to 300 ° C. for 10 minutes. A method of heat-bonding for 3 hours can be mentioned.
５．フレキシルブル配線基板
上記硬化性樹脂組成物からフレキシルブル配線基板を製造する方法としては、以下に示す３つの工程からなる方法で製造されるものが挙げられる。第１の工程は、活性エステル、エポキシ樹脂、及び有機溶媒を配合した硬化性樹脂組成物を、リバースロールコータ、コンマコータ等の塗布機を用いて、電気絶縁性フィルムに塗布する工程であり、第２の工程は、加熱機を用いて６０～１７０℃で１～１５分間の間、硬化性樹脂組成物が塗布された電気絶縁性フィルム加熱し、電気絶縁性フィルムから溶媒を揮発させて、硬化性樹脂組成物をＢ－ステージ化する工程であり、第３の工程は、硬化性樹脂組成物がＢ－ステージ化された電気絶縁性フィルムに、加熱ロール等を用いて、接着剤に金属箔を熱圧着（圧着圧力は２～２００Ｎ／ｃｍ、圧着温度は４０～２００℃が好ましい）する工程である。なお、上記３つの工程を経ることで、十分な接着性能が得られれば、ここで終えても構わないが、完全接着性能が必要な場合は、さらに１００～２００℃で１～２４時間の条件で後硬化させることが好ましい。最終的に硬化させた後の硬化性樹脂組成物膜の厚みは、５～１００μｍの範囲が好ましい。
5. Flexible wiring board As a method for manufacturing a flexible wiring board from the curable resin composition, there is a method manufactured by a method consisting of the following three steps. The first step is a step of applying a curable resin composition containing an active ester, an epoxy resin, and an organic solvent to an electrically insulating film using a coating machine such as a reverse roll coater or a comma coater. In step 2, the electrically insulating film coated with the curable resin composition is heated at 60 to 170 ° C. for 1 to 15 minutes using a heater, and the solvent is volatilized from the electrically insulating film to cure. The step is to B-stage the sex resin composition, and the third step is to use a heating roll or the like on an electrically insulating film in which the curable resin composition is B-staged, and to use a metal foil as an adhesive. Is a step of thermal crimping (preferably a crimping pressure of 2 to 200 N / cm and a crimping temperature of 40 to 200 ° C.). If sufficient adhesive performance can be obtained by going through the above three steps, the process may be completed here, but if complete adhesive performance is required, the condition is 1 to 24 hours at 100 to 200 ° C. It is preferable to post-cure with. The thickness of the curable resin composition film after the final curing is preferably in the range of 5 to 100 μm.
６．ビルドアップ基板
上記硬化性樹脂組成物からビルドアップ基板を製造する方法としては、以下に示す３つの工程からなる方法で製造されるものが挙げられる。第１の工程は、ゴム、フィラーなどを適宜配合した上記硬化性樹脂組成物を、回路を形成した回路基板にスプレーコーティング法、カーテンコーティング法等を用いて塗布した後、硬化させる工程であり、第２の工程は、その後、必要に応じて所定のスルーホール部等の穴あけを行った後、粗化剤により処理し、その表面を湯洗することによって、凹凸を形成させ、銅などの金属をめっき処理する工程であり、第３の工程は、このような操作を所望に応じて順次繰り返し、樹脂絶縁層及び所定の回路パターンの導体層を交互にビルドアップして形成する工程である。なお、スルーホール部の穴あけは、最外層の樹脂絶縁層の形成後に行うことが好ましい。第一の工程は、上述の溶液塗布によるもの以外にも、あらかじめ所望の厚みに塗工して乾燥したビルドアップフィルムのラミネートによる方法でも行うことができる。また、本発明のビルドアップ基板は、銅箔上で当該樹脂組成物を半硬化させた樹脂付き銅箔を、回路を形成した配線基板上に、１７０～２５０℃で加熱圧着することで、粗化面を形成、メッキ処理の工程を省き、ビルドアップ基板を製造することも可能である。
6. Build-up Substrate As a method for producing a build-up substrate from the curable resin composition, a method comprising the following three steps can be mentioned. The first step is a step of applying the above-mentioned curable resin composition appropriately blended with rubber, filler, etc. to the circuit board on which the circuit is formed by using a spray coating method, a curtain coating method, or the like, and then curing the curable resin composition. In the second step, after that, if necessary, a predetermined through hole or the like is drilled, treated with a roughening agent, and the surface thereof is washed with hot water to form irregularities, and a metal such as copper is formed. The third step is a step of sequentially repeating such an operation as desired to alternately build up and form a resin insulating layer and a conductor layer having a predetermined circuit pattern. It is preferable that the through-hole portion is drilled after the resin insulating layer of the outermost layer is formed. In addition to the above-mentioned solution coating, the first step can also be performed by laminating a build-up film that has been previously coated to a desired thickness and dried. Further, the build-up substrate of the present invention is coarsely formed by heat-pressing a copper foil with a resin, which is a semi-cured resin composition on a copper foil, onto a wiring board on which a circuit is formed at 170 to 250 ° C. It is also possible to manufacture a build-up substrate by forming a chemical surface and omitting the plating process.
７．ビルドアップフィルム
上記硬化性樹脂組成物からビルドアップフィルムを製造する方法としては、上記硬化性樹脂組成物を、支持フィルム上に塗布し、硬化性樹脂組成物層を形成させて多層プリント配線板用の接着フィルムとすることにより製造する方法が挙げられる。
7. Build-up film As a method for producing a build-up film from the curable resin composition, the curable resin composition is applied onto a support film to form a curable resin composition layer for a multilayer printed wiring board. A method of manufacturing by using the adhesive film of the above can be mentioned.
硬化性樹脂組成物からビルドアップフィルムを製造する場合、該フィルムは、真空ラミネート法におけるラミネートの温度条件（通常７０～１４０℃）で軟化し、回路基板のラミネートと同時に、回路基板に存在するビアホール、あるいは、スルーホール内の樹脂充填が可能な流動性（樹脂流れ）を示すことが肝要であり、このような特性を発現するよう上記各成分を配合することが好ましい。 When a build-up film is produced from a curable resin composition, the film is softened under the temperature conditions of laminating (usually 70 to 140 ° C.) in the vacuum laminating method, and the via holes existing in the circuit board are present at the same time as laminating the circuit board. Alternatively, it is important to show fluidity (resin flow) capable of filling the through hole with the resin, and it is preferable to add each of the above components so as to exhibit such characteristics.
ここで、多層プリント配線板のスルーホールの直径は、通常０．１～０．５ｍｍ、深さは通常０．１～１．２ｍｍであり、通常この範囲で樹脂充填を可能とするのが好ましい。なお回路基板の両面をラミネートする場合はスルーホールの１／２程度充填されることが望ましい。 Here, the diameter of the through hole of the multilayer printed wiring board is usually 0.1 to 0.5 mm, and the depth is usually 0.1 to 1.2 mm, and it is usually preferable to enable resin filling in this range. .. When laminating both sides of the circuit board, it is desirable to fill about 1/2 of the through hole.
上記した接着フィルムを製造する方法は、具体的には、ワニス状の上記硬化性樹脂組成物を調製した後、支持フィルム（Ｙ）の表面に、このワニス状の組成物を塗布し、更に加熱、あるいは熱風吹きつけ等により有機溶媒を乾燥させて硬化性樹脂組成物からなる組成物層（Ｘ）を形成させることにより製造することができる。 Specifically, in the method for producing the adhesive film described above, after preparing the varnish-like curable resin composition, the varnish-like composition is applied to the surface of the support film (Y) and further heated. Alternatively, it can be produced by drying an organic solvent by blowing hot air or the like to form a composition layer (X) made of a curable resin composition.
形成される組成物層（Ｘ）の厚さは、通常、導体層の厚さ以上とすることが好ましい。回路基板が有する導体層の厚さは通常５～７０μｍの範囲であるので、樹脂組成物層の厚さは１０～１００μｍの厚みを有するのが好ましい。 The thickness of the composition layer (X) to be formed is usually preferably equal to or greater than the thickness of the conductor layer. Since the thickness of the conductor layer of the circuit board is usually in the range of 5 to 70 μm, the thickness of the resin composition layer is preferably 10 to 100 μm.
なお、本発明における組成物層（Ｘ）は、後述する保護フィルムで保護されていてもよい。保護フィルムで保護することにより、樹脂組成物層表面へのゴミ等の付着やキズを防止することができる。 The composition layer (X) in the present invention may be protected by a protective film described later. By protecting with a protective film, it is possible to prevent dust and the like from adhering to the surface of the resin composition layer and scratches.
上記した支持フィルム及び保護フィルムは、ポリエチレン、ポリプロピレン、ポリ塩化ビニル等のポリオレフィン、ポリエチレンテレフタレート（以下「ＰＥＴ」と略称することがある。）、ポリエチレンナフタレート等のポリエステル、ポリカーボネート、ポリイミド、更には離型紙や銅箔、アルミニウム箔等の金属箔などを挙げることができる。なお、支持フィルム及び保護フィルムはマッド処理、コロナ処理の他、離型処理を施してあってもよい。 The above-mentioned support film and protective film include polyolefins such as polyethylene, polypropylene and polyvinyl chloride, polyethylene terephthalate (hereinafter, may be abbreviated as "PET"), polyesters such as polyethylene naphthalate, polycarbonate, polyimide, and further release. Examples include metal foils such as molds, copper foils, and aluminum foils. The support film and the protective film may be subjected to a mold release treatment in addition to the mud treatment and the corona treatment.
支持フィルムの厚さは特に限定されないが、通常１０～１５０μｍであり、好ましくは２５～５０μｍの範囲で用いられる。また保護フィルムの厚さは１～４０μｍとするのが好ましい。 The thickness of the support film is not particularly limited, but is usually 10 to 150 μm, and is preferably used in the range of 25 to 50 μm. The thickness of the protective film is preferably 1 to 40 μm.
上記した支持フィルム（Ｙ）は、回路基板にラミネートした後に、或いは加熱硬化することにより絶縁層を形成した後に、剥離される。接着フィルムを加熱硬化した後に支持フィルム（Ｙ）を剥離すれば、硬化工程でのゴミ等の付着を防ぐことができる。硬化後に剥離する場合、通常、支持フィルムには予め離型処理が施される。 The above-mentioned support film (Y) is peeled off after being laminated on a circuit board or after forming an insulating layer by heat curing. If the support film (Y) is peeled off after the adhesive film is heat-cured, it is possible to prevent dust and the like from adhering in the curing step. When peeling after curing, the support film is usually subjected to a mold release treatment in advance.
８．多層プリント配線板
なお、上記のようして得られたフィルムを用いて多層プリント配線板を製造することもできる。そのような多層プリント配線板の製造方法は、例えば、組成物層（Ｘ）が保護フィルムで保護されている場合はこれらを剥離した後、組成物層（Ｘ）を回路基板に直接、回路基板の片面又は両面に、例えば真空ラミネート法によりラミネートする。ラミネートの方法はバッチ式であってもロールでの連続式であってもよい。またラミネートを行う前に接着フィルム及び回路基板を必要により加熱（プレヒート）しておいてもよい。
8. Multi-layer printed wiring board It is also possible to manufacture a multi-layer printed wiring board using the film obtained as described above. In the method of manufacturing such a multilayer printed wiring board, for example, when the composition layer (X) is protected by a protective film, the composition layer (X) is directly attached to the circuit board after peeling off the protective film. It is laminated on one side or both sides of the above, for example, by a vacuum laminating method. The laminating method may be a batch method or a continuous method using a roll. Further, the adhesive film and the circuit board may be preheated if necessary before laminating.
ラミネートの条件は、圧着温度（ラミネート温度）を好ましくは７０～１４０℃、圧着圧力を好ましくは１～１１ｋｇｆ／ｃｍ２（９．８×１０４～１０７．９×１０４Ｎ／ｍ２）とし、空気圧２０ｍｍＨｇ（２６．７ｈＰａ）以下の減圧下でラミネートすることが好ましい。 The laminating conditions were preferably a crimping temperature (laminating temperature) of 70 to 140 ° C. and a crimping pressure of 1 to 11 kgf / cm 2 (9.8 × 10 4 to 107.9 × 10 4 N / m 2 ). , It is preferable to laminate under a reduced pressure of 20 mmHg (26.7 hPa) or less.
９．繊維強化複合材料
本発明は、前記硬化性樹脂組成物と、強化繊維を含有することを特徴とする繊維強化複合材料に関する。前記硬化性樹脂組成物から繊維強化複合材料を製造する方法としては、硬化性樹脂組成物を構成する各成分を均一に混合してワニスを調整し、次いでこれを強化繊維からなる強化基材に含浸した後、重合反応させることにより製造することができる。特に本発明のエポキシ樹脂は、低溶融粘度であるため、ハンドリング性に優れるため、前記繊維強化複合材料の製造に適しており、好ましい。
9. Fiber Reinforced Composite Material The present invention relates to the curable resin composition and a fiber reinforced composite material containing reinforcing fibers. As a method for producing a fiber-reinforced composite material from the curable resin composition, each component constituting the curable resin composition is uniformly mixed to prepare a varnish, and then this is used as a reinforcing base material made of reinforcing fibers. It can be produced by impregnating and then polymerizing. In particular, since the epoxy resin of the present invention has a low melt viscosity and is excellent in handleability, it is suitable for producing the fiber-reinforced composite material and is preferable.
かかる重合反応を行う際の硬化温度は、具体的には、５０～２５０℃の温度範囲であることが好ましく、特に、５０～１００℃で硬化させ、タックフリー状の硬化物にした後、更に、１２０～２００℃の温度条件で処理することが好ましい。 Specifically, the curing temperature at the time of carrying out such a polymerization reaction is preferably in the temperature range of 50 to 250 ° C., and in particular, after curing at 50 to 100 ° C. to form a tack-free cured product, further , It is preferable to treat at a temperature condition of 120 to 200 ° C.
ここで、強化繊維は、有撚糸、解撚糸、又は無撚糸などいずれでも良いが、解撚糸や無撚糸が、繊維強化プラスチック製部材の成形性と機械強度を両立することから、好ましい。さらに、強化繊維の形態は、繊維方向が一方向に引き揃えたものや、織物が使用できる。織物では、平織り、朱子織りなどから、使用する部位や用途に応じて自由に選択することができる。具体的には、機械強度や耐久性に優れることから、炭素繊維、ガラス繊維、アラミド繊維、ボロン繊維、アルミナ繊維、炭化ケイ素繊維などが挙げられ、これらの２種以上を併用することもできる。これらの中でもとりわけ成形品の強度が良好なものとなる点から炭素繊維が好ましく、かかる、炭素繊維は、ポリアクリロニトリル系、ピッチ系、レーヨン系などの各種のものが使用できる。中でも、容易に高強度の炭素繊維が得られるポリアクリロニトリル系のものが好ましい。ここで、ワニスを強化繊維からなる強化基材に含浸して繊維強化複合材料とする際の強化繊維の使用量は、該繊維強化複合材料中の強化繊維の体積含有率が４０～８５％の範囲となる量であることが好ましい。 Here, the reinforcing fiber may be twisted yarn, untwisted yarn, untwisted yarn, or the like, but untwisted yarn or untwisted yarn is preferable because it has both formability and mechanical strength of the fiber-reinforced plastic member. Further, as the form of the reinforcing fiber, a fiber whose fiber direction is aligned in one direction or a woven fabric can be used. For woven fabrics, plain weaves, satin weaves, and the like can be freely selected according to the part to be used and the intended use. Specific examples thereof include carbon fiber, glass fiber, aramid fiber, boron fiber, alumina fiber, silicon carbide fiber and the like because of their excellent mechanical strength and durability, and two or more of these can be used in combination. Among these, carbon fiber is particularly preferable from the viewpoint of improving the strength of the molded product, and various carbon fibers such as polyacrylonitrile-based, pitch-based, and rayon-based can be used. Of these, polyacrylonitrile-based ones, which can easily obtain high-strength carbon fibers, are preferable. Here, the amount of the reinforcing fiber used when the varnish is impregnated into the reinforcing base material made of the reinforcing fiber to form a fiber-reinforced composite material is such that the volume content of the reinforcing fiber in the fiber-reinforced composite material is 40 to 85%. The amount is preferably in the range.
１０．繊維強化樹脂成形品
本発明は、前記硬化物と、強化繊維を含有することを特徴とする繊維強化樹脂成形品に関する。前記硬化性樹脂組成物から繊維強化樹脂成形品を製造する方法としては、型に繊維骨材を敷き、上記ワニスを多重積層してゆくハンドレイアップ法やスプレーアップ法、オス型・メス型のいずれかを使用し、強化繊維からなる基材にワニスを含浸させながら積み重ねて成形、圧力を成形物に作用させることのできるフレキシブルな型をかぶせ、気密シールしたものを真空（減圧）成型する真空バッグ法、あらかじめ強化繊維を含有するワニスをシート状にしたものを金型で圧縮成型するＳＭＣプレス法、繊維を敷き詰めた合わせ型に上記ワニスを注入するＲＴＭ法などにより、強化繊維に上記ワニスを含浸させたプリプレグを製造し、これを大型のオートクレーブで焼き固める方法などが挙げられる。特に本発明のエポキシ樹脂は、低溶融粘度であるため、ハンドリング性に優れるため、前記繊維強化樹脂成形品の製造に適しており、好ましい。なお、上記で得られた繊維強化樹脂成形品は、強化繊維と硬化性樹脂組成物の硬化物とを有する成形品であり、具体的には、繊維強化樹脂成形品中の強化繊維の量は、４０～７０質量％の範囲であることが好ましく、強度の点から５０～７０質量％の範囲であることが特に好ましい。
10. Fiber Reinforced Resin Molded Product The present invention relates to a fiber reinforced resin molded product characterized by containing the cured product and reinforcing fibers. As a method for producing a fiber-reinforced resin molded product from the curable resin composition, a hand lay-up method, a spray-up method, in which a fiber aggregate is laid on a mold and the varnish is laminated in multiple layers, and a male / female mold are used. Using either of them, the base material made of reinforced fibers is impregnated with varnish and stacked to form, covered with a flexible mold that can apply pressure to the molded product, and the airtightly sealed one is vacuum (decompressed) molded. The varnish is applied to the reinforcing fibers by the bag method, the SMC press method in which a sheet of varnish containing reinforcing fibers is previously compression-molded with a mold, and the RTM method in which the varnish is injected into a combined mold in which fibers are spread. Examples include a method of producing an impregnated prepreg and baking it in a large autoclave. In particular, since the epoxy resin of the present invention has a low melt viscosity and is excellent in handleability, it is suitable for producing the fiber-reinforced resin molded product and is preferable. The fiber-reinforced resin molded product obtained above is a molded product having a reinforcing fiber and a cured product of a curable resin composition. Specifically, the amount of the reinforcing fiber in the fiber-reinforced resin molded product is , 40 to 70% by mass is preferable, and 50 to 70% by mass is particularly preferable from the viewpoint of strength.
１１．その他
上記で半導体封止材料や繊維強化複合材料等を製造する方法について説明したが、硬化性樹脂組成物からその他の硬化物を製造することもできる。その他の硬化物の製造方法としては、一般的な硬化性樹脂組成物の硬化方法に準拠することにより製造することができる。例えば加熱温度条件は、組み合わせる硬化剤の種類や用途等によって、適宜選択すればよい。
11. Others Although the method for producing a semiconductor encapsulating material, a fiber-reinforced composite material, or the like has been described above, other cured products can also be produced from the curable resin composition. As another method for producing a cured product, it can be produced by complying with a general curing method for a curable resin composition. For example, the heating temperature conditions may be appropriately selected depending on the type and application of the curing agent to be combined.
以下に、本発明を実施例、及び、比較例により具体的に説明するが、これらに限定解釈されるものではない。また、以下において、「部」及び「％」について、特に断わりのない限り質量基準である。なお、以下に得られたフェノール樹脂やエポキシ樹脂、前記エポキシ樹脂を用いて得られる硬化物については、以下の条件等にて測定・評価を行った。 Hereinafter, the present invention will be specifically described with reference to Examples and Comparative Examples, but the present invention is not limited thereto. In the following, "parts" and "%" are based on mass unless otherwise specified. The phenol resin and epoxy resin obtained below, and the cured product obtained by using the epoxy resin were measured and evaluated under the following conditions and the like.
＜フェノール樹脂の水酸基当量＞
以下に示す手順、及び、計算式により、フェノール樹脂の水酸基当量（ｇ／ｅｑ）を測定した。
５００ｍＬ三角フラスコに、以下に得られたフェノール樹脂を試料とし、これを２．５ｇ、トリフェニルホスフィン７．５ｇ、ピリジン７．５ｇ、無水酢酸２．５ｇを精秤し、１２０℃にて２．５時間処理した後、５ｍＬの蒸留水を加え反応を停止した。その後、テトラヒドロフラン１５０ｍＬ、プリピレングリコールモノメチルエーテル２００ｍＬに溶解することで、試料溶液を調製した。
前記試料溶液とは別に、１０ｍＬ蒸留水、２．５ｇの無水酢酸を精秤し、ピリジン１０ｇを入れ、１０分間攪拌し、２０分静置した後、テトラヒドロフラン１５０ｍＬ、プリピレングリコールモノメチルエーテル２００ｍＬと混合することで、ブランク溶液を調製した。
得られた試料溶液、及び、ブランク溶液について、電位差自動滴定装置ＡＴ－５１０（京都電子工業社製）を使用し、０．５ｍｏｌ／Ｌエタノール性水酸化カリウム溶液（滴定液）を用いて、滴定を行った後、以下の計算式を用いて、水酸基当量を算出した。
<Hydroxyvalent equivalent of phenol resin>
The hydroxyl group equivalent (g / eq) of the phenol resin was measured by the procedure shown below and the calculation formula.
Using the phenol resin obtained below as a sample in a 500 mL Erlenmeyer flask, weigh 2.5 g of it, 7.5 g of triphenylphosphine, 7.5 g of pyridine, and 2.5 g of anhydrous acetic acid, and weigh them at 120 ° C. After treatment for 5 hours, 5 mL of distilled water was added to stop the reaction. Then, a sample solution was prepared by dissolving in 150 mL of tetrahydrofuran and 200 mL of prepyrene glycol monomethyl ether.
Separately from the sample solution, 10 mL distilled water and 2.5 g of anhydrous acetic acid are precisely weighed, 10 g of pyridine is added, the mixture is stirred for 10 minutes, allowed to stand for 20 minutes, and then mixed with 150 mL of tetrahydrofuran and 200 mL of prepyrene glycol monomethyl ether. To prepare a blank solution.
The obtained sample solution and blank solution are titrated using an automatic potential difference titrator AT-510 (manufactured by Kyoto Denshi Kogyo Co., Ltd.) and a 0.5 mol / L ethanolic potassium hydroxide solution (titration solution). After that, the hydroxyl equivalent was calculated using the following formula.
［ブランクの計算式］
ＢＬ＝（ブランク溶液の滴定量）×（２．５ｇの無水酢酸の理論滴定量）／（ブランク溶液の理論滴定量）
＝Ｙ×[（２．５／１０２．０９）×２×（１０００／５）]／［（Ｗ／１０２．０９）×２×（１０００／５）］
ＢＬ：ブランク値（ｍＬ）
Ｙ：ブランク溶液の滴定量（ｍＬ）
Ｗ：ブランク測定の無水酢酸の量（ｇ）
[Blank calculation formula]
BL = (Titration of blank solution) x (Theoretical titration of 2.5 g anhydrous acetic acid) / (Theoretical titration of blank solution)
= Y × [(2.5 / 102.09) × 2 × (1000/5)] / [(W / 102.09) × 2 × (1000/5)]
BL: Blank value (mL)
Y: Titration of blank solution (mL)
W: Amount of acetic anhydride measured in blank (g)
［試料の水酸基当量を計算するための式］
水酸基当量（ｇ／ｅｑ）
＝Ｓ×１０００／［｛（ＢＬ×ＦＡ３／ＦＡ５）－ＥＰ１｝×ＦＡ４］
Ｓ：サンプル量（ｇ）
ＦＡ３：試料測定時の無水酢酸の量（ｇ）
ＦＡ４：滴定液（エタノール性ＫＯＨ溶液）の濃度（ｍｏｌ／Ｌ）
ＦＡ５：試料測定時の無水酢酸の量（ｇ）
ＥＰ１：試料の滴定量（ｍＬ）
[Formula for calculating the hydroxyl group equivalent of a sample]
Hydroxy group equivalent (g / eq)
= S × 1000 / [{(BL × FA3 / FA5) -EP1} × FA4]
S: Sample amount (g)
FA3: Amount of acetic anhydride at the time of sample measurement (g)
FA4: Concentration of titrant solution (ethanol KOH solution) (mol / L)
FA5: Amount of acetic anhydride at the time of sample measurement (g)
EP1: Titration of sample (mL)
＜フェノール樹脂の軟化点＞
ＪＩＳ Ｋ ７２３４（環球法）に準拠して、以下に得られたフェノール樹脂の軟化点（℃）を測定した。
<Softening point of phenolic resin>
The softening point (° C.) of the phenol resin obtained below was measured according to JIS K 7234 (ring ball method).
＜フェノール樹脂、及び、エポキシ樹脂の溶融粘度測定（１５０℃）＞
ＡＳＴＭ Ｄ４２８７に準拠して、ＩＣＩ粘度計にて、１５０℃における溶融粘度（ｄＰａ・ｓ）測定した。
<Measurement of melt viscosity of phenolic resin and epoxy resin (150 ° C)>
Melt viscosity (dPa · s) at 150 ° C. was measured with an ICI viscometer according to ASTM D4287.
＜エポキシ樹脂（Ａ－１）及び（Ａ－２）の粘度測定（２５℃）＞
Ｅ型粘度計（東機産業株式会社製 ＴＶ－２２）を用いて、２５℃における粘度（ｍＰａ・ｓ）測定した。
<Viscosity measurement of epoxy resins (A-1) and (A-2) (25 ° C)>
The viscosity (mPa · s) at 25 ° C. was measured using an E-type viscometer (TV-22 manufactured by Toki Sangyo Co., Ltd.).
＜エポキシ樹脂のエポキシ当量＞
ＪＩＳ Ｋ ７２３６に準拠して、以下に得られたエポキシ樹脂のエポキシ当量（ｇ／ｅｑ）を測定した。
<Epoxy equivalent of epoxy resin>
The epoxy equivalent (g / eq) of the epoxy resin obtained below was measured according to JIS K 7236.
＜ＧＰＣの測定＞
以下の測定装置、測定条件を用いて測定し、以下に示す合成方法で得られたフェノール樹脂、及び前記フェノール樹脂を用いて得られたエポキシ樹脂の合成確認をＧＰＣ測定に基づき行った。
測定装置：東ソー株式会社製「ＨＬＣ－８３２０ ＧＰＣ」、
カラム：東ソー株式会社製ガードカラム「ＨＸＬ－Ｌ」
＋東ソー株式会社製「ＴＳＫ－ＧＥＬ Ｇ２０００ＨＸＬ」
＋東ソー株式会社製「ＴＳＫ－ＧＥＬ Ｇ２０００ＨＸＬ」
＋東ソー株式会社製「ＴＳＫ－ＧＥＬ Ｇ３０００ＨＸＬ」
＋東ソー株式会社製「ＴＳＫ－ＧＥＬ Ｇ４０００ＨＸＬ」
検出器：ＲＩ（示差屈折計）
データ処理：東ソー株式会社製「ＧＰＣワークステーション ＥｃｏＳＥＣ－ＷｏｒｋＳｔａｔｉｏｎ」
測定条件：カラム温度 ４０℃
展開溶媒 テトラヒドロフラン
流速 １．０ｍｌ／分
標準 ：前記「ＧＰＣワークステーション ＥｃｏＳＥＣ―ＷｏｒｋＳｔａｔｉｏｎ」の測定マニュアルに準拠して、分子量が既知の下記の単分散ポリスチレンを用いた。
（使用ポリスチレン）
東ソー株式会社製「Ａ－５００」
東ソー株式会社製「Ａ－１０００」
東ソー株式会社製「Ａ－２５００」
東ソー株式会社製「Ａ－５０００」
東ソー株式会社製「Ｆ－１」
東ソー株式会社製「Ｆ－２」
東ソー株式会社製「Ｆ－４」
東ソー株式会社製「Ｆ－１０」
東ソー株式会社製「Ｆ－２０」
東ソー株式会社製「Ｆ－４０」
東ソー株式会社製「Ｆ－８０」
東ソー株式会社製「Ｆ－１２８」
試料：エポキシ樹脂固形分換算で１．０質量％であり、のテトラヒドロフラン溶液をマイクロフィルターでろ過したもの（５０μｌ）。
なお、前記フェノール樹脂中の残留した（未反応の）カテコール化合物の含有割合（面積％）については、硬化時の揮発分を低減する観点から、残留カテコール化合物の含有割合が、５．０面積％以下であることが好ましい。
<Measurement of GPC>
The measurement was carried out using the following measuring device and measurement conditions, and the synthesis confirmation of the phenol resin obtained by the synthesis method shown below and the epoxy resin obtained by using the phenol resin was performed based on the GPC measurement.
Measuring device: "HLC-8320 GPC" manufactured by Tosoh Corporation,
Column: Guard column "HXL-L" manufactured by Tosoh Corporation
+ "TSK-GEL G2000HXL" manufactured by Tosoh Corporation
+ "TSK-GEL G2000HXL" manufactured by Tosoh Corporation
+ "TSK-GEL G3000HXL" manufactured by Tosoh Corporation
+ "TSK-GEL G4000HXL" manufactured by Tosoh Corporation
Detector: RI (Differential Refractometer)
Data processing: "GPC Workstation EcoSEC-WorkStation" manufactured by Tosoh Corporation
Measurement conditions: Column temperature 40 ° C
Developing solvent Tetrahydrofuran
Flow rate 1.0 ml / min Standard: The following monodisperse polystyrene with a known molecular weight was used in accordance with the measurement manual of the above-mentioned "GPC workstation EcoSEC-WorkStation".
(Polystyrene used)
"A-500" manufactured by Tosoh Corporation
"A-1000" manufactured by Tosoh Corporation
"A-2500" manufactured by Tosoh Corporation
"A-5000" manufactured by Tosoh Corporation
"F-1" manufactured by Tosoh Corporation
"F-2" manufactured by Tosoh Corporation
"F-4" manufactured by Tosoh Corporation
"F-10" manufactured by Tosoh Corporation
"F-20" manufactured by Tosoh Corporation
"F-40" manufactured by Tosoh Corporation
"F-80" manufactured by Tosoh Corporation
"F-128" manufactured by Tosoh Corporation
Sample: 1.0% by mass in terms of epoxy resin solid content, obtained by filtering a tetrahydrofuran solution of the sample with a microfilter (50 μl).
Regarding the content ratio (area%) of the residual (unreacted) catechol compound in the phenol resin, the content ratio of the residual catechol compound is 5.0 area% from the viewpoint of reducing the volatile content at the time of curing. The following is preferable.
［実施例１］
フェノール樹脂（Ｐ－１）の合成
温度計、冷却管、攪拌機を取り付けた２Ｌフラスコにカテコール３３０．３質量部（３．００ｍｏｌ）、トルエン３２８．３質量部、パラトルエンスルホン酸０．９５質量部（０．０５ｍｏｌ）を仕込み、溶解しながら１００℃まで昇温した。その温度を保ったままベンズアルデヒド１０６．１質量部（１．００ｍｏｌ）を１時間かけて滴下した後、さらに３時間反応させた。反応後、メチルイソブチルケトン６１６．２質量部を仕込み、中性になるまで水洗を行った後、１５０℃減圧下で濃縮し、さらに水蒸気を吹き込みながら未反応カテコールを留去することで、主成分とするフェノール樹脂（Ｐ－１）２６１質量部を得た。
前記フェノール樹脂（Ｐ－１）の水酸基当量は８６ｇ／ｅｑであり、軟化点は９６℃、１５０℃における溶融粘度は３．６ｄＰａ・ｓ、残留カテコール量はＧＰＣにて０．９面積％であった。前記フェノール樹脂（Ｐ－１）のＧＰＣチャートを図１に示した。ピークトップ３４．１ｍｉｎのメインピークにより生成を確認した。
なお、ここで言う「主成分」とは、ＧＰＣ面積％で５０面積％以上含むことであり、各成分のＧＰＣ面積％は、各成分のＧＰＣピーク面積値を全成分のＧＰＣピーク面積値の合計で除した値を指す。
[Example 1]
Synthesis of phenolic resin (P-1) 330.3 parts by mass (3.00 mol) of catechol, 328.3 parts by mass of toluene, 0.95 parts by mass of paratoluenesulfonic acid in a 2 L flask equipped with a thermometer, a cooling tube and a stirrer. (0.05 mol) was charged and the temperature was raised to 100 ° C. while dissolving. While maintaining the temperature, 106.1 parts by mass (1.00 mol) of benzaldehyde was added dropwise over 1 hour, and then the reaction was carried out for another 3 hours. After the reaction, 616.2 parts by mass of methyl isobutyl ketone was charged, washed with water until neutral, concentrated under reduced pressure at 150 ° C., and unreacted catechol was distilled off while blowing steam to distill off the main component. 261 parts by mass of the phenol resin (P-1) to be used was obtained.
The hydroxyl group equivalent of the phenol resin (P-1) was 86 g / eq, the softening point was 96 ° C., the melt viscosity at 150 ° C. was 3.6 dPa · s, and the residual catechol amount was 0.9 area% in GPC. rice field. The GPC chart of the phenolic resin (P-1) is shown in FIG. Generation was confirmed by the main peak of peak top 34.1 min.
The "main component" here means that the GPC area% includes 50 area% or more, and the GPC area% of each component is the sum of the GPC peak area values of each component and the GPC peak area values of all components. Refers to the value divided by.
［実施例２］
フェノール樹脂（Ｐ－２）の合成
カテコールの仕込み量を４４０．４質量部（４．００ｍｏｌ）に変更した以外は、実施例１と同様に合成し、フェノール樹脂（Ｐ－２）を２７５質量部得た。
前記フェノール樹脂（Ｐ－２）の水酸基当量は８２ｇ／ｅｑであり、軟化点は８９℃、１５０℃における溶融粘度は１．９ｄＰａ・ｓ、残留カテコール量はＧＰＣにて２．３面積％であった。また、実施例１と同様にＧＰＣを測定し、合成できたことを確認した。
[Example 2]
Synthesis of Phenol Resin (P-2) Synthesis was carried out in the same manner as in Example 1 except that the amount of catechol charged was changed to 440.4 parts by mass (4.00 mol), and 275 parts by mass of phenol resin (P-2) was added. Obtained.
The hydroxyl group equivalent of the phenol resin (P-2) was 82 g / eq, the softening point was 89 ° C., the melt viscosity at 150 ° C. was 1.9 dPa · s, and the residual catechol amount was 2.3 area% in GPC. rice field. In addition, GPC was measured in the same manner as in Example 1 and it was confirmed that the synthesis was possible.
［実施例３］
フェノール樹脂（Ｐ－３）の合成
カテコールの仕込み量を５５０．６質量部（５．００ｍｏｌ）に変更した以外は、実施例１と同様に合成し、フェノール樹脂（Ｐ－３）有量の水酸基当量は８０ｇ／ｅｑであり、軟化点は９２℃、１５０℃における溶融粘度は２．６ｄＰａ・ｓ、残留カテコール量はＧＰＣにて１．２面積％であった。また、実施例１と同様にＧＰＣを測定し、合成できたことを確認した。
[Example 3]
Synthesis of Phenol Formaldehyde (P-3) Synthetic in the same manner as in Example 1 except that the amount of catechol charged was changed to 550.6 parts by mass (5.00 mol), and a large amount of hydroxyl group of phenol resin (P-3) was synthesized. The equivalent was 80 g / eq, the softening point was 92 ° C., the melt viscosity at 150 ° C. was 2.6 dPa · s, and the amount of residual catechol was 1.2 area% by GPC. In addition, GPC was measured in the same manner as in Example 1 and it was confirmed that the synthesis was possible.
［実施例４］
フェノール樹脂（Ｐ－４）の合成
カテコールの仕込み量を６６０．７質量部（６．００ｍｏｌ）に変更した以外は、実施例１と同様に合成し、フェノール樹脂（Ｐ－４）を２６０質量部得た。
前記フェノール樹脂（Ｐ－４）のカテコール含有量の水酸基当量は８２ｇ／ｅｑであり、軟化点は９１℃、１５０℃における溶融粘度は２．３ｄＰａ・ｓ、残留カテコール量はＧＰＣにて１．１面積％であった。また、実施例１と同様にＧＰＣを測定し、合成できたことを確認した。
[Example 4]
Synthesis of phenol resin (P-4) The synthesis was carried out in the same manner as in Example 1 except that the amount of catechol charged was changed to 660.7 parts by mass (6.00 mol), and the phenol resin (P-4) was 260 parts by mass. Obtained.
The hydroxyl group equivalent of the catechol content of the phenol resin (P-4) is 82 g / eq, the softening point is 91 ° C., the melt viscosity at 150 ° C. is 2.3 dPa · s, and the residual catechol amount is 1.1 in GPC. The area was%. In addition, GPC was measured in the same manner as in Example 1 and it was confirmed that the synthesis was possible.
［実施例５］
エポキシ樹脂（Ｅ－１）の合成
温度計、冷却管、攪拌機を取り付けた２Ｌフラスコにフェノール樹脂（Ｐ－１）１８０．０質量部、エピクロルヒドリン７７４．２質量部（８．３７ｍｏｌ）を仕込み、攪拌溶解しながら５０℃に昇温した。次いで、５０％テトラメチルアンモニウムクロライド水溶液９．１８質量部を仕込み、５０℃の温度のまま２４時間反応させた。さらに、４９％水酸化ナトリウム水溶液１８７．９質量部（水酸基に対して１．１０当量）を３時間かけて滴下し、さらに５０℃で１時間反応させた。反応終了後、イソプロピルアルコール２３２．３質量部添加し、攪拌を停止して、下層に溜まった水層を除去し、攪拌を再開し１５０℃減圧下で未反応エピクロルヒドリンを留去した。得られた粗エポキシ樹脂にメチルイソブチルケトン５０５．３質量部を加え溶解し、洗浄液のｐＨが中性となるまで水１４８．６質量部で水洗を繰り返した。次いで、共沸によって系内を脱水し、精密ろ過を経た後に、溶媒を減圧下にて留去し目的のエポキシ樹脂（Ｅ－１）２７３．０質量部を得た。
得られたエポキシ樹脂（Ｅ－１）のエポキシ当量は１５９ｇ／ｅｑであり、１５０℃における溶融粘度は０．５２ｄＰａ・ｓであった。前記エポキシ樹脂（Ｅ－１）のＧＰＣチャートを図２に示した。ピークトップ３２．４ｍｉｎのメインピークにより生成を確認した。
[Example 5]
Synthesis of epoxy resin (E-1) 180.0 parts by mass of phenol resin (P-1) and 774.2 parts by mass (8.37 mol) of epichlorohydrin are charged in a 2 L flask equipped with a thermometer, a cooling tube and a stirrer, and stirred. The temperature was raised to 50 ° C. while melting. Then, 9.18 parts by mass of a 50% tetramethylammonium chloride aqueous solution was charged, and the reaction was carried out at a temperature of 50 ° C. for 24 hours. Further, 187.9 parts by mass (1.10 equivalents with respect to the hydroxyl group) of a 49% aqueous sodium hydroxide solution was added dropwise over 3 hours, and the reaction was further carried out at 50 ° C. for 1 hour. After completion of the reaction, 232.3 parts by mass of isopropyl alcohol was added, stirring was stopped, the aqueous layer accumulated in the lower layer was removed, stirring was restarted, and unreacted epichlorohydrin was distilled off under reduced pressure at 150 ° C. 505.3 parts by mass of methyl isobutyl ketone was added to the obtained crude epoxy resin to dissolve it, and washing with 148.6 parts by mass of water was repeated until the pH of the washing liquid became neutral. Then, the inside of the system was dehydrated by azeotrope, and after undergoing microfiltration, the solvent was distilled off under reduced pressure to obtain 273.0 parts by mass of the target epoxy resin (E-1).
The epoxy equivalent of the obtained epoxy resin (E-1) was 159 g / eq, and the melt viscosity at 150 ° C. was 0.52 dPa · s. The GPC chart of the epoxy resin (E-1) is shown in FIG. Generation was confirmed by the main peak of the peak top 32.4 min.
［実施例６］
エポキシ樹脂（Ｅ－２）の合成
前記フェノール樹脂（Ｐ－２）の仕込み量を１７５質量部、エピクロルヒドリン７９３．４質量部（８．５８ｍｏｌ）とした以外は、実施例５と同様に合成し、エポキシ樹脂（Ｅ－２）を２５５質量部得た。
得られたエポキシ樹脂（Ｅ－２）のエポキシ当量は１６２ｇ／ｅｑであり、１５０℃における溶融粘度は０．５０ｄＰａ・ｓであった。また、実施例５と同様にＧＰＣを測定し、合成できたことを確認した。
[Example 6]
Synthesis of Epoxy Resin (E-2) The phenol resin (P-2) was synthesized in the same manner as in Example 5 except that the amount of the phenol resin (P-2) charged was 175 parts by mass and 793.4 parts by mass (8.58 mol) of epichlorohydrin. 255 parts by mass of epoxy resin (E-2) was obtained.
The epoxy equivalent of the obtained epoxy resin (E-2) was 162 g / eq, and the melt viscosity at 150 ° C. was 0.50 dPa · s. In addition, GPC was measured in the same manner as in Example 5, and it was confirmed that the synthesis was possible.
［実施例７］
エポキシ樹脂（Ｅ－３）の合成
前記フェノール樹脂（Ｐ－３）の仕込み量を１８０質量部、エピクロルヒドリン８３２．５質量部（９ｍｏｌ）とした以外は、実施例５と同様に合成し、エポキシ樹脂（Ｅ－３）を２７１質量部得た。
得られたエポキシ樹脂（Ｅ－３）のエポキシ当量は１５４ｇ／ｅｑであり、１５０℃における溶融粘度は０．４８ｄＰａ・ｓであった。また、実施例５と同様にＧＰＣを測定し、合成できたことを確認した。
[Example 7]
Synthesis of Epoxy Resin (E-3) The epoxy resin was synthesized in the same manner as in Example 5 except that the amount of the phenol resin (P-3) charged was 180 parts by mass and 832.5 parts by mass (9 mol) of epichlorohydrin. 271 parts by mass of (E-3) was obtained.
The epoxy equivalent of the obtained epoxy resin (E-3) was 154 g / eq, and the melt viscosity at 150 ° C. was 0.48 dPa · s. In addition, GPC was measured in the same manner as in Example 5, and it was confirmed that the synthesis was possible.
［実施例８］
エポキシ樹脂（Ｅ－４）の合成
前記フェノール樹脂（Ｐ－４）の仕込み量を１７５質量部、エピクロルヒドリン７９４．５質量部（８．５９ｍｏｌ）とした以外は、実施例５と同様に合成し、エポキシ樹脂（Ｅ－４）を２６６質量部得た。
得られたエポキシ樹脂（Ｅ－４）のエポキシ当量は１６１ｇ／ｅｑであり、１５０℃における溶融粘度は０．４８ｄＰａ・ｓであった。また、実施例５と同様にＧＰＣを測定し、合成できたことを確認した。
[Example 8]
Synthesis of Epoxy Resin (E-4) The phenol resin (P-4) was synthesized in the same manner as in Example 5 except that the amount of the phenol resin (P-4) charged was 175 parts by mass and 794.5 parts by mass (8.59 mol) of epichlorohydrin. 266 parts by mass of epoxy resin (E-4) was obtained.
The epoxy equivalent of the obtained epoxy resin (E-4) was 161 g / eq, and the melt viscosity at 150 ° C. was 0.48 dPa · s. In addition, GPC was measured in the same manner as in Example 5, and it was confirmed that the synthesis was possible.
［比較例１］
エポキシ樹脂（Ａ－１）の合成
温度計、冷却管、攪拌機を取り付けた２Ｌフラスコにカテコール１６５．０質量部（１．５ｍｏｌ）、エピクロルヒドリン１１１０質量部（１２ｍｏｌ）を仕込み、攪拌溶解しながら５０℃に昇温した。次いで、塩化ベンジルトリメチルアンモニウムを１１．２質量部仕込み、５０℃の温度のまま２４時間反応させた。さらに４９％水酸化ナトリウム水溶液２６９．４質量部（水酸基に対して１．１０ｍｏｌ）を３時間かけて滴下し、さらに５０℃で１時間反応させた。反応終了後、ｎ－ブタノール２２２．０質量部添加し、攪拌を停止して、下層に溜まった水層を除去し、攪拌を再開し１５０℃減圧下で未反応エピクロルヒドリンを留去した。それで得られた粗エポキシ樹脂にメチルイソブチルケトン５６６．１質量部とｎ－ブタノール９４．５質量部を加え溶解した。さらにこの溶液に１０％水酸化ナトリウム水溶液１４．２質量部を添加して８０℃２時間反応させた後に洗浄液のｐＨが中性となるまで水１８５．０質量部で水洗を繰り返した。次いで、共沸によって系内を脱水し、精密ろ過を経た後に、溶媒を減圧下にて留去し、エポキシ樹脂（Ａ－１）を３２３．０質量部得た。
得られたエポキシ樹脂（Ａ－１）のエポキシ当量は１３９ｇ／ｅｑであり、２５℃における粘度は１９０ｍＰａ・ｓであった。
[Comparative Example 1]
Synthesis of epoxy resin (A-1) 165.0 parts by mass (1.5 mol) of catechol and 1110 parts by mass (12 mol) of epichlorohydrin were placed in a 2 L flask equipped with a thermometer, a condenser, and a stirrer, and the temperature was 50 ° C. while stirring and dissolving. The temperature was raised to. Then, 11.2 parts by mass of benzyltrimethylammonium chloride was charged and reacted at a temperature of 50 ° C. for 24 hours. Further, 269.4 parts by mass (1.10 mol with respect to the hydroxyl group) of a 49% aqueous sodium hydroxide solution was added dropwise over 3 hours, and the reaction was further carried out at 50 ° C. for 1 hour. After completion of the reaction, 222.0 parts by mass of n-butanol was added, stirring was stopped, the aqueous layer accumulated in the lower layer was removed, stirring was restarted, and unreacted epichlorohydrin was distilled off under reduced pressure at 150 ° C. 566.1 parts by mass of methyl isobutyl ketone and 94.5 parts by mass of n-butanol were added to the obtained crude epoxy resin and dissolved. Further, 14.2 parts by mass of a 10% aqueous sodium hydroxide solution was added to this solution and reacted at 80 ° C. for 2 hours, and then washing with 185.0 parts by mass of water was repeated until the pH of the washing solution became neutral. Then, the inside of the system was dehydrated by azeotrope, and after undergoing microfiltration, the solvent was distilled off under reduced pressure to obtain 323.0 parts by mass of epoxy resin (A-1).
The epoxy equivalent of the obtained epoxy resin (A-1) was 139 g / eq, and the viscosity at 25 ° C. was 190 mPa · s.
［比較例２］
エポキシ樹脂（Ａ－２）の合成
ビスフェノールＡ型エポキシ樹脂（ＤＩＣ社製、ＥＰＩＣＬＯＮ ８５０Ｓ、エポキシ当量は１８８ｇ／ｅｑ、２５℃における粘度は１３５００ｍＰａ・ｓ）をエポキシ樹脂（Ａ－２）とした。
[Comparative Example 2]
Synthesis of Epoxy Resin (A-2) Bisphenol A type epoxy resin (manufactured by DIC Corporation, EPICLON 850S, epoxy equivalent is 188 g / eq, viscosity at 25 ° C. is 13500 mPa · s) was used as the epoxy resin (A-2).
［実施例９～１２、比較例１～２］
＜硬化物の作製＞
得られたエポキシ樹脂、及び、硬化剤として４，４’－ジアミノジフェニルスルホンをエポキシ当量(エポキシ樹脂)／活性水素当量(硬化剤)が１／１となるように配合し、１２０℃で溶融混合して、硬化性樹脂組成物を得た。
さらに、前記硬化性樹脂組成物を、２ｍｍおよび４ｍｍのスペーサーを挟んだガラス板の間に流し込み、１５０℃で１時間、次いで１８０℃で３時間硬化反応を行い、硬化物を作製した。
[Examples 9 to 12, Comparative Examples 1 to 2]
<Preparation of cured product>
The obtained epoxy resin and 4,4'-diaminodiphenyl sulfone as a curing agent were blended so that the epoxy equivalent (epoxy resin) / active hydrogen equivalent (curing agent) was 1/1, and melt-mixed at 120 ° C. Then, a curable resin composition was obtained.
Further, the curable resin composition was poured between glass plates sandwiching 2 mm and 4 mm spacers, and a curing reaction was carried out at 150 ° C. for 1 hour and then at 180 ° C. for 3 hours to prepare a cured product.
＜ガラス転移温度（Ｔｇ）＞
得られた硬化物を厚さ２ｍｍ、幅５ｍｍ、長さ２０ｍｍのサイズに切り出し、これを試験片とした。この試験片を粘弾性測定装置（ＤＭＡ：日立ハイテクサイエンス社製固体粘弾性測定装置「ＤＭＳ６１００」、変形モード：両持ち曲げ、測定モード：正弦波振動、周波数１Ｈｚ、昇温速度３℃／分）を用いて、弾性率変化が最大となる（ｔａｎδ変化率が最も大きい）温度をガラス転移温度として評価した。
なお、前記ガラス転移温度（Ｔｇ）としては、好ましくは、２５０℃以上であり、より好ましくは、２８０℃以上である。前記範囲内にあれば、高耐熱性を発現でき、有用である。
<Glass transition temperature (Tg)>
The obtained cured product was cut into a size having a thickness of 2 mm, a width of 5 mm, and a length of 20 mm, and this was used as a test piece. This test piece is used as a viscoelasticity measuring device (DMA: Hitachi High-Tech Science solid viscoelasticity measuring device "DMS6100", deformation mode: double-sided bending, measurement mode: sinusoidal vibration, frequency 1 Hz, temperature rise rate 3 ° C./min). The temperature at which the change in viscoelasticity was maximum (the rate of change in tan δ was the largest) was evaluated as the glass transition temperature.
The glass transition temperature (Tg) is preferably 250 ° C. or higher, more preferably 280 ° C. or higher. If it is within the above range, high heat resistance can be exhibited, which is useful.
＜曲げ強度、曲げ弾性率、曲げ歪の測定＞
得られた硬化物を厚さ２ｍｍ、幅１０ｍｍ、長さ８０ｍｍの大きさに切り出し、これを試験片とした。
精密万能試験機（島津製作所株式会社製「ＡＵＴＯＧＲＡＰＨ ＡＧ－Ｉ」）を用いて、前記試験片の曲げ強度、曲げ弾性率、曲げ歪をＪＩＳ Ｋ６９１１に従って、測定した。
なお、前記曲げ弾性率としては、好ましくは、３０００ＭＰａ以上であり、より好ましくは、３５００ＭＰａ以上である。また、前記曲げ強度としては、好ましくは、１００ＭＰａ以上であり、より好ましくは、１２０ＭＰａ以上である。前記曲げ歪みとしては、好ましくは、３％以上であり、より好ましくは、４％以上である。前記範囲内にあれば、高曲げ特性を発現でき、有用である。
<Measurement of bending strength, flexural modulus, and bending strain>
The obtained cured product was cut into a size of 2 mm in thickness, 10 mm in width, and 80 mm in length, and used as a test piece.
The bending strength, flexural modulus, and bending strain of the test piece were measured according to JIS K6911 using a precision universal testing machine (“AUTOGRAPH AG-I” manufactured by Shimadzu Corporation).
The flexural modulus is preferably 3000 MPa or more, and more preferably 3500 MPa or more. The bending strength is preferably 100 MPa or more, and more preferably 120 MPa or more. The bending strain is preferably 3% or more, more preferably 4% or more. If it is within the above range, high bending characteristics can be exhibited, which is useful.
上記表１の評価結果より、実施例９～１２においては、実施例１～４で得られた所望のフェノール樹脂を用いて得られるエポキシ樹脂を使用したことで、高曲げ特性、及び、高耐熱性の硬化物を得られることが確認できた。
一方、比較例１においては、実施例９等の様に、カテコール化合物とホルミル基含有芳香族化合物を反応させて得られるフェノール性水酸基含有化合物を使用するのではなく、カテコール化合物のみを使用して合成したエポキシ樹脂を使用したため、ガラス転移温度が非常に低く、曲げ強度は実施例と比べて低く、曲げ歪みは所望の範囲よりも低く、耐熱性及び曲げ特性の両立を図ることができなかった。
また、比較例２においては、一般的に使用されるビスフェノールＡ型エポキシ樹脂を使用したが、実施例９等に比べて、ガラス転移温度や曲げ弾性率が低く、耐熱性及び曲げ特性の両立を図ることができなかった。
From the evaluation results in Table 1 above, in Examples 9 to 12, high bending characteristics and high heat resistance were obtained by using the epoxy resin obtained by using the desired phenol resin obtained in Examples 1 to 4. It was confirmed that a cured product of sex could be obtained.
On the other hand, in Comparative Example 1, the phenolic hydroxyl group-containing compound obtained by reacting the catechol compound with the formyl group-containing aromatic compound as in Example 9 and the like is not used, but only the catechol compound is used. Since the synthesized epoxy resin was used, the glass transition temperature was very low, the bending strength was lower than that of the examples, the bending strain was lower than the desired range, and it was not possible to achieve both heat resistance and bending characteristics. ..
Further, in Comparative Example 2, a commonly used bisphenol A type epoxy resin was used, but the glass transition temperature and flexural modulus were lower than those of Example 9 and the like, and both heat resistance and bending characteristics were compatible. I couldn't plan.
Claims (7)
A fiber-reinforced resin molded product comprising the cured product according to claim 5 and reinforcing fibers.
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