WO2021100649A1 - 繊維強化複合材料の成形方法、およびそれに用いられるエポキシ樹脂組成物 - Google Patents
繊維強化複合材料の成形方法、およびそれに用いられるエポキシ樹脂組成物 Download PDFInfo
- Publication number
- WO2021100649A1 WO2021100649A1 PCT/JP2020/042584 JP2020042584W WO2021100649A1 WO 2021100649 A1 WO2021100649 A1 WO 2021100649A1 JP 2020042584 W JP2020042584 W JP 2020042584W WO 2021100649 A1 WO2021100649 A1 WO 2021100649A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- epoxy resin
- fiber
- resin composition
- reinforced composite
- composite material
- Prior art date
Links
- 239000003822 epoxy resin Substances 0.000 title claims abstract description 317
- 229920000647 polyepoxide Polymers 0.000 title claims abstract description 317
- 239000000203 mixture Substances 0.000 title claims abstract description 207
- 239000000463 material Substances 0.000 title claims abstract description 187
- 239000003733 fiber-reinforced composite Substances 0.000 title claims abstract description 166
- 238000000034 method Methods 0.000 title claims abstract description 91
- 238000002835 absorbance Methods 0.000 claims abstract description 59
- 239000012783 reinforcing fiber Substances 0.000 claims abstract description 42
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 claims abstract description 30
- 239000003054 catalyst Substances 0.000 claims abstract description 26
- 239000000470 constituent Substances 0.000 claims abstract description 5
- 238000000465 moulding Methods 0.000 claims description 74
- 229920005989 resin Polymers 0.000 claims description 41
- 239000011347 resin Substances 0.000 claims description 41
- CXOFVDLJLONNDW-UHFFFAOYSA-N Phenytoin Chemical group N1C(=O)NC(=O)C1(C=1C=CC=CC=1)C1=CC=CC=C1 CXOFVDLJLONNDW-UHFFFAOYSA-N 0.000 claims description 35
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 32
- 239000002585 base Substances 0.000 claims description 31
- 239000003795 chemical substances by application Substances 0.000 claims description 23
- -1 amine compound Chemical class 0.000 claims description 22
- 230000009477 glass transition Effects 0.000 claims description 22
- 238000010521 absorption reaction Methods 0.000 claims description 20
- 229920001971 elastomer Polymers 0.000 claims description 20
- 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 claims description 17
- 150000003839 salts Chemical class 0.000 claims description 17
- 238000010438 heat treatment Methods 0.000 claims description 16
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 15
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 claims description 14
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 14
- WDGCBNTXZHJTHJ-UHFFFAOYSA-N 2h-1,3-oxazol-2-id-4-one Chemical group O=C1CO[C-]=N1 WDGCBNTXZHJTHJ-UHFFFAOYSA-N 0.000 claims description 12
- 239000007848 Bronsted acid Substances 0.000 claims description 12
- 239000002253 acid Substances 0.000 claims description 12
- 239000003341 Bronsted base Substances 0.000 claims description 11
- 238000010494 dissociation reaction Methods 0.000 claims description 11
- 230000005593 dissociations Effects 0.000 claims description 11
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical group OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 claims description 11
- 230000009467 reduction Effects 0.000 claims description 11
- 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 claims description 8
- 229930185605 Bisphenol Natural products 0.000 claims description 7
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims description 7
- 238000002411 thermogravimetry Methods 0.000 claims description 6
- 230000001590 oxidative effect Effects 0.000 claims description 4
- 150000001450 anions Chemical class 0.000 claims description 3
- 150000001735 carboxylic acids Chemical class 0.000 claims description 3
- 239000011208 reinforced composite material Substances 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 3
- 239000001257 hydrogen Substances 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 150000004714 phosphonium salts Chemical group 0.000 claims description 2
- 150000003242 quaternary ammonium salts Chemical class 0.000 claims description 2
- 150000003460 sulfonic acids Chemical class 0.000 claims description 2
- 238000002347 injection Methods 0.000 abstract description 16
- 239000007924 injection Substances 0.000 abstract description 16
- 125000000466 oxiranyl group Chemical group 0.000 abstract 1
- 239000004848 polyfunctional curative Substances 0.000 abstract 1
- 238000001723 curing Methods 0.000 description 141
- 238000005259 measurement Methods 0.000 description 34
- 239000000126 substance Substances 0.000 description 20
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 17
- GQHTUMJGOHRCHB-UHFFFAOYSA-N 2,3,4,6,7,8,9,10-octahydropyrimido[1,2-a]azepine Chemical compound C1CCCCN2CCCN=C21 GQHTUMJGOHRCHB-UHFFFAOYSA-N 0.000 description 16
- 239000012948 isocyanate Substances 0.000 description 15
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 14
- 238000000113 differential scanning calorimetry Methods 0.000 description 14
- 239000011159 matrix material Substances 0.000 description 13
- 229920000049 Carbon (fiber) Polymers 0.000 description 12
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 12
- 239000004917 carbon fiber Substances 0.000 description 12
- 239000007788 liquid Substances 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 11
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 11
- 238000006243 chemical reaction Methods 0.000 description 10
- 229920001187 thermosetting polymer Polymers 0.000 description 10
- 239000000835 fiber Substances 0.000 description 9
- 150000002513 isocyanates Chemical class 0.000 description 9
- 238000003860 storage Methods 0.000 description 9
- 238000012360 testing method Methods 0.000 description 9
- 239000002759 woven fabric Substances 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 239000004593 Epoxy Substances 0.000 description 8
- 150000001412 amines Chemical class 0.000 description 7
- 239000011162 core material Substances 0.000 description 7
- 235000011054 acetic acid Nutrition 0.000 description 6
- 238000000354 decomposition reaction Methods 0.000 description 6
- 238000005470 impregnation Methods 0.000 description 6
- 238000002360 preparation method Methods 0.000 description 6
- 238000007363 ring formation reaction Methods 0.000 description 6
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 description 5
- 238000004132 cross linking Methods 0.000 description 5
- JXTHNDFMNIQAHM-UHFFFAOYSA-N dichloroacetic acid Chemical compound OC(=O)C(Cl)Cl JXTHNDFMNIQAHM-UHFFFAOYSA-N 0.000 description 5
- 230000010354 integration Effects 0.000 description 5
- 238000002844 melting Methods 0.000 description 5
- 230000008018 melting Effects 0.000 description 5
- 229920002635 polyurethane Polymers 0.000 description 5
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 4
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 4
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 4
- 239000012346 acetyl chloride Substances 0.000 description 4
- 238000005452 bending Methods 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 238000011049 filling Methods 0.000 description 4
- 230000020169 heat generation Effects 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- IGALFTFNPPBUDN-UHFFFAOYSA-N phenyl-[2,3,4,5-tetrakis(oxiran-2-ylmethyl)phenyl]methanediamine Chemical compound C=1C(CC2OC2)=C(CC2OC2)C(CC2OC2)=C(CC2OC2)C=1C(N)(N)C1=CC=CC=C1 IGALFTFNPPBUDN-UHFFFAOYSA-N 0.000 description 4
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 239000011342 resin composition Substances 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 4
- 238000005160 1H NMR spectroscopy Methods 0.000 description 3
- IZXIZTKNFFYFOF-UHFFFAOYSA-N 2-Oxazolidone Chemical compound O=C1NCCO1 IZXIZTKNFFYFOF-UHFFFAOYSA-N 0.000 description 3
- FVCSARBUZVPSQF-UHFFFAOYSA-N 5-(2,4-dioxooxolan-3-yl)-7-methyl-3a,4,5,7a-tetrahydro-2-benzofuran-1,3-dione Chemical compound C1C(C(OC2=O)=O)C2C(C)=CC1C1C(=O)COC1=O FVCSARBUZVPSQF-UHFFFAOYSA-N 0.000 description 3
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 3
- 238000005481 NMR spectroscopy Methods 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 230000006866 deterioration Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- GPRLSGONYQIRFK-UHFFFAOYSA-N hydron Chemical compound [H+] GPRLSGONYQIRFK-UHFFFAOYSA-N 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 229920005862 polyol Polymers 0.000 description 3
- 150000003077 polyols Chemical class 0.000 description 3
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 description 3
- 229920005992 thermoplastic resin Polymers 0.000 description 3
- 230000008719 thickening Effects 0.000 description 3
- SGUVLZREKBPKCE-UHFFFAOYSA-N 1,5-diazabicyclo[4.3.0]-non-5-ene Chemical compound C1CCN=C2CCCN21 SGUVLZREKBPKCE-UHFFFAOYSA-N 0.000 description 2
- PULOARGYCVHSDH-UHFFFAOYSA-N 2-amino-3,4,5-tris(oxiran-2-ylmethyl)phenol Chemical compound C1OC1CC1=C(CC2OC2)C(N)=C(O)C=C1CC1CO1 PULOARGYCVHSDH-UHFFFAOYSA-N 0.000 description 2
- FVKFHMNJTHKMRX-UHFFFAOYSA-N 3,4,6,7,8,9-hexahydro-2H-pyrimido[1,2-a]pyrimidine Chemical compound C1CCN2CCCNC2=N1 FVKFHMNJTHKMRX-UHFFFAOYSA-N 0.000 description 2
- LJGHYPLBDBRCRZ-UHFFFAOYSA-N 3-(3-aminophenyl)sulfonylaniline Chemical compound NC1=CC=CC(S(=O)(=O)C=2C=C(N)C=CC=2)=C1 LJGHYPLBDBRCRZ-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 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
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- CPELXLSAUQHCOX-UHFFFAOYSA-N Hydrogen bromide Chemical compound Br CPELXLSAUQHCOX-UHFFFAOYSA-N 0.000 description 2
- 239000005058 Isophorone diisocyanate Substances 0.000 description 2
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-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
- WETWJCDKMRHUPV-UHFFFAOYSA-N acetyl chloride Chemical compound CC(Cl)=O WETWJCDKMRHUPV-UHFFFAOYSA-N 0.000 description 2
- KSTVMGTVOPUBDE-UHFFFAOYSA-N acetyl chloride;pyridine Chemical compound CC(Cl)=O.C1=CC=NC=C1 KSTVMGTVOPUBDE-UHFFFAOYSA-N 0.000 description 2
- RDUAHLHDEOZCAA-UHFFFAOYSA-N acetyl chloride;toluene Chemical compound CC(Cl)=O.CC1=CC=CC=C1 RDUAHLHDEOZCAA-UHFFFAOYSA-N 0.000 description 2
- 229920006231 aramid fiber Polymers 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 229910052796 boron Inorganic materials 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 238000005520 cutting process Methods 0.000 description 2
- 229960005215 dichloroacetic acid Drugs 0.000 description 2
- 125000005442 diisocyanate group Chemical group 0.000 description 2
- KIQKWYUGPPFMBV-UHFFFAOYSA-N diisocyanatomethane Chemical compound O=C=NCN=C=O KIQKWYUGPPFMBV-UHFFFAOYSA-N 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- QEWYKACRFQMRMB-UHFFFAOYSA-N fluoroacetic acid Chemical compound OC(=O)CF QEWYKACRFQMRMB-UHFFFAOYSA-N 0.000 description 2
- 239000006260 foam Chemical group 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000005227 gel permeation chromatography Methods 0.000 description 2
- 239000003365 glass fiber Substances 0.000 description 2
- 235000011187 glycerol Nutrition 0.000 description 2
- 239000008187 granular material Substances 0.000 description 2
- 150000004820 halides Chemical class 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- 238000009787 hand lay-up Methods 0.000 description 2
- 150000002460 imidazoles Chemical class 0.000 description 2
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 description 2
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- JAYXSROKFZAHRQ-UHFFFAOYSA-N n,n-bis(oxiran-2-ylmethyl)aniline Chemical compound C1OC1CN(C=1C=CC=CC=1)CC1CO1 JAYXSROKFZAHRQ-UHFFFAOYSA-N 0.000 description 2
- 238000006386 neutralization reaction Methods 0.000 description 2
- 239000005011 phenolic resin Substances 0.000 description 2
- 238000013001 point bending Methods 0.000 description 2
- 229920002223 polystyrene Polymers 0.000 description 2
- YLLIGHVCTUPGEH-UHFFFAOYSA-M potassium;ethanol;hydroxide Chemical compound [OH-].[K+].CCO YLLIGHVCTUPGEH-UHFFFAOYSA-M 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 238000004904 shortening Methods 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- NHGXDBSUJJNIRV-UHFFFAOYSA-M tetrabutylammonium chloride Chemical compound [Cl-].CCCC[N+](CCCC)(CCCC)CCCC NHGXDBSUJJNIRV-UHFFFAOYSA-M 0.000 description 2
- RKHXQBLJXBGEKF-UHFFFAOYSA-M tetrabutylphosphanium;bromide Chemical compound [Br-].CCCC[P+](CCCC)(CCCC)CCCC RKHXQBLJXBGEKF-UHFFFAOYSA-M 0.000 description 2
- 150000004992 toluidines Chemical class 0.000 description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 2
- 238000001721 transfer moulding Methods 0.000 description 2
- FWBSWSPGFNAXPP-UHFFFAOYSA-M (2,4-dichlorophenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].ClC1=CC(Cl)=CC=C1C[P+](C=1C=CC=CC=1)(C=1C=CC=CC=1)C1=CC=CC=C1 FWBSWSPGFNAXPP-UHFFFAOYSA-M 0.000 description 1
- VJVZPTPOYCJFNI-UHFFFAOYSA-M (2-ethoxy-2-oxoethyl)-triphenylphosphanium;bromide Chemical compound [Br-].C=1C=CC=CC=1[P+](C=1C=CC=CC=1)(CC(=O)OCC)C1=CC=CC=C1 VJVZPTPOYCJFNI-UHFFFAOYSA-M 0.000 description 1
- SAYKZWPCENNSDR-UHFFFAOYSA-M (n-methylanilino)-triphenylphosphanium;iodide Chemical compound [I-].C=1C=CC=CC=1[P+](C=1C=CC=CC=1)(C=1C=CC=CC=1)N(C)C1=CC=CC=C1 SAYKZWPCENNSDR-UHFFFAOYSA-M 0.000 description 1
- GFNDFCFPJQPVQL-UHFFFAOYSA-N 1,12-diisocyanatododecane Chemical compound O=C=NCCCCCCCCCCCCN=C=O GFNDFCFPJQPVQL-UHFFFAOYSA-N 0.000 description 1
- FKTHNVSLHLHISI-UHFFFAOYSA-N 1,2-bis(isocyanatomethyl)benzene Chemical compound O=C=NCC1=CC=CC=C1CN=C=O FKTHNVSLHLHISI-UHFFFAOYSA-N 0.000 description 1
- ZTNJGMFHJYGMDR-UHFFFAOYSA-N 1,2-diisocyanatoethane Chemical compound O=C=NCCN=C=O ZTNJGMFHJYGMDR-UHFFFAOYSA-N 0.000 description 1
- ZGDSDWSIFQBAJS-UHFFFAOYSA-N 1,2-diisocyanatopropane Chemical compound O=C=NC(C)CN=C=O ZGDSDWSIFQBAJS-UHFFFAOYSA-N 0.000 description 1
- GIWQSPITLQVMSG-UHFFFAOYSA-N 1,2-dimethylimidazole Chemical compound CC1=NC=CN1C GIWQSPITLQVMSG-UHFFFAOYSA-N 0.000 description 1
- RTTZISZSHSCFRH-UHFFFAOYSA-N 1,3-bis(isocyanatomethyl)benzene Chemical compound O=C=NCC1=CC=CC(CN=C=O)=C1 RTTZISZSHSCFRH-UHFFFAOYSA-N 0.000 description 1
- IKYNWXNXXHWHLL-UHFFFAOYSA-N 1,3-diisocyanatopropane Chemical compound O=C=NCCCN=C=O IKYNWXNXXHWHLL-UHFFFAOYSA-N 0.000 description 1
- FVLCBDPSQUONII-UHFFFAOYSA-N 1,4-diisocyanato-2,3-dimethylbutane Chemical compound O=C=NCC(C)C(C)CN=C=O FVLCBDPSQUONII-UHFFFAOYSA-N 0.000 description 1
- OVBFMUAFNIIQAL-UHFFFAOYSA-N 1,4-diisocyanatobutane Chemical compound O=C=NCCCCN=C=O OVBFMUAFNIIQAL-UHFFFAOYSA-N 0.000 description 1
- DFPJRUKWEPYFJT-UHFFFAOYSA-N 1,5-diisocyanatopentane Chemical compound O=C=NCCCCCN=C=O DFPJRUKWEPYFJT-UHFFFAOYSA-N 0.000 description 1
- VZXPHDGHQXLXJC-UHFFFAOYSA-N 1,6-diisocyanato-5,6-dimethylheptane Chemical compound O=C=NC(C)(C)C(C)CCCCN=C=O VZXPHDGHQXLXJC-UHFFFAOYSA-N 0.000 description 1
- XQUPVDVFXZDTLT-UHFFFAOYSA-N 1-[4-[[4-(2,5-dioxopyrrol-1-yl)phenyl]methyl]phenyl]pyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C(C=C1)=CC=C1CC1=CC=C(N2C(C=CC2=O)=O)C=C1 XQUPVDVFXZDTLT-UHFFFAOYSA-N 0.000 description 1
- FBHPRUXJQNWTEW-UHFFFAOYSA-N 1-benzyl-2-methylimidazole Chemical compound CC1=NC=CN1CC1=CC=CC=C1 FBHPRUXJQNWTEW-UHFFFAOYSA-N 0.000 description 1
- XZKLXPPYISZJCV-UHFFFAOYSA-N 1-benzyl-2-phenylimidazole Chemical compound C1=CN=C(C=2C=CC=CC=2)N1CC1=CC=CC=C1 XZKLXPPYISZJCV-UHFFFAOYSA-N 0.000 description 1
- DCYGAPKNVCQNOE-UHFFFAOYSA-N 2,2,2-triphenylacetic acid Chemical compound C=1C=CC=CC=1C(C=1C=CC=CC=1)(C(=O)O)C1=CC=CC=C1 DCYGAPKNVCQNOE-UHFFFAOYSA-N 0.000 description 1
- YIIHEMGEQQWSMA-UHFFFAOYSA-M 2-(dimethylamino)ethyl-triphenylphosphanium;bromide Chemical compound [Br-].C=1C=CC=CC=1[P+](C=1C=CC=CC=1)(CCN(C)C)C1=CC=CC=C1 YIIHEMGEQQWSMA-UHFFFAOYSA-M 0.000 description 1
- HHRACYLRBOUBKM-UHFFFAOYSA-N 2-[(4-tert-butylphenoxy)methyl]oxirane Chemical compound C1=CC(C(C)(C)C)=CC=C1OCC1OC1 HHRACYLRBOUBKM-UHFFFAOYSA-N 0.000 description 1
- MOKYFHFMPMQNOT-UHFFFAOYSA-M 2-acetyloxyethyl(trimethyl)phosphanium;bromide Chemical compound [Br-].CC(=O)OCC[P+](C)(C)C MOKYFHFMPMQNOT-UHFFFAOYSA-M 0.000 description 1
- OYRWATRYBSDCFH-UHFFFAOYSA-M 2-acetyloxyethyl(trimethyl)phosphanium;chloride Chemical compound [Cl-].CC(=O)OCC[P+](C)(C)C OYRWATRYBSDCFH-UHFFFAOYSA-M 0.000 description 1
- PQAMFDRRWURCFQ-UHFFFAOYSA-N 2-ethyl-1h-imidazole Chemical compound CCC1=NC=CN1 PQAMFDRRWURCFQ-UHFFFAOYSA-N 0.000 description 1
- YTWBFUCJVWKCCK-UHFFFAOYSA-N 2-heptadecyl-1h-imidazole Chemical compound CCCCCCCCCCCCCCCCCC1=NC=CN1 YTWBFUCJVWKCCK-UHFFFAOYSA-N 0.000 description 1
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 1
- NIPWFPYJCVZBSC-UHFFFAOYSA-M 2-hydroxyethyl(trimethyl)phosphanium;chloride Chemical compound [Cl-].C[P+](C)(C)CCO NIPWFPYJCVZBSC-UHFFFAOYSA-M 0.000 description 1
- RVEJRPJGKXTQIF-UHFFFAOYSA-M 2-oxoethyl(triphenyl)phosphanium;chloride Chemical compound [Cl-].C=1C=CC=CC=1[P+](C=1C=CC=CC=1)(CC=O)C1=CC=CC=C1 RVEJRPJGKXTQIF-UHFFFAOYSA-M 0.000 description 1
- XAMZZEBAJZJERT-UHFFFAOYSA-M 2-oxopropyl(triphenyl)phosphanium;chloride Chemical compound [Cl-].C=1C=CC=CC=1[P+](C=1C=CC=CC=1)(CC(=O)C)C1=CC=CC=C1 XAMZZEBAJZJERT-UHFFFAOYSA-M 0.000 description 1
- HACRKYQRZABURO-UHFFFAOYSA-N 2-phenylethyl isocyanate Chemical compound O=C=NCCC1=CC=CC=C1 HACRKYQRZABURO-UHFFFAOYSA-N 0.000 description 1
- LLEASVZEQBICSN-UHFFFAOYSA-N 2-undecyl-1h-imidazole Chemical compound CCCCCCCCCCCC1=NC=CN1 LLEASVZEQBICSN-UHFFFAOYSA-N 0.000 description 1
- SESYNEDUKZDRJL-UHFFFAOYSA-N 3-(2-methylimidazol-1-yl)propanenitrile Chemical compound CC1=NC=CN1CCC#N SESYNEDUKZDRJL-UHFFFAOYSA-N 0.000 description 1
- WADSJYLPJPTMLN-UHFFFAOYSA-N 3-(cycloundecen-1-yl)-1,2-diazacycloundec-2-ene Chemical compound C1CCCCCCCCC=C1C1=NNCCCCCCCC1 WADSJYLPJPTMLN-UHFFFAOYSA-N 0.000 description 1
- FLROJJGKUKLCAE-UHFFFAOYSA-N 3-amino-2-methylphenol Chemical compound CC1=C(N)C=CC=C1O FLROJJGKUKLCAE-UHFFFAOYSA-N 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- CXXSQMDHHYTRKY-UHFFFAOYSA-N 4-amino-2,3,5-tris(oxiran-2-ylmethyl)phenol Chemical compound C1=C(O)C(CC2OC2)=C(CC2OC2)C(N)=C1CC1CO1 CXXSQMDHHYTRKY-UHFFFAOYSA-N 0.000 description 1
- MLOSJPZSZWUDSK-UHFFFAOYSA-N 4-carboxybutyl(triphenyl)phosphanium;bromide Chemical compound [Br-].C=1C=CC=CC=1[P+](C=1C=CC=CC=1)(CCCCC(=O)O)C1=CC=CC=C1 MLOSJPZSZWUDSK-UHFFFAOYSA-N 0.000 description 1
- ULKLGIFJWFIQFF-UHFFFAOYSA-N 5K8XI641G3 Chemical compound CCC1=NC=C(C)N1 ULKLGIFJWFIQFF-UHFFFAOYSA-N 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- 101100481033 Arabidopsis thaliana TGA7 gene Proteins 0.000 description 1
- 239000005711 Benzoic acid Substances 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 description 1
- 241000696426 Epiclines Species 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 1
- KDXKERNSBIXSRK-YFKPBYRVSA-N L-lysine Chemical compound NCCCC[C@H](N)C(O)=O KDXKERNSBIXSRK-YFKPBYRVSA-N 0.000 description 1
- 239000004472 Lysine Substances 0.000 description 1
- KDXKERNSBIXSRK-UHFFFAOYSA-N Lysine Natural products NCCCCC(N)C(O)=O KDXKERNSBIXSRK-UHFFFAOYSA-N 0.000 description 1
- OMRDSWJXRLDPBB-UHFFFAOYSA-N N=C=O.N=C=O.C1CCCCC1 Chemical compound N=C=O.N=C=O.C1CCCCC1 OMRDSWJXRLDPBB-UHFFFAOYSA-N 0.000 description 1
- INWVTRVMRQMCCM-UHFFFAOYSA-N N=C=O.N=C=O.C=1C=CC=CC=1C(C)(C)C1=CC=CC=C1 Chemical compound N=C=O.N=C=O.C=1C=CC=CC=1C(C)(C)C1=CC=CC=C1 INWVTRVMRQMCCM-UHFFFAOYSA-N 0.000 description 1
- HDONYZHVZVCMLR-UHFFFAOYSA-N N=C=O.N=C=O.CC1CCCCC1 Chemical compound N=C=O.N=C=O.CC1CCCCC1 HDONYZHVZVCMLR-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- 240000007182 Ochroma pyramidale Species 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- 102220569696 Pyridoxal-dependent decarboxylase domain-containing protein 1_M11S_mutation Human genes 0.000 description 1
- VBIIFPGSPJYLRR-UHFFFAOYSA-M Stearyltrimethylammonium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCCCC[N+](C)(C)C VBIIFPGSPJYLRR-UHFFFAOYSA-M 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 1
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 description 1
- GKXVJHDEWHKBFH-UHFFFAOYSA-N [2-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=CC=C1CN GKXVJHDEWHKBFH-UHFFFAOYSA-N 0.000 description 1
- 125000000218 acetic acid group Chemical group C(C)(=O)* 0.000 description 1
- ZEHGKSPCAMLJDC-UHFFFAOYSA-M acetylcholine bromide Chemical compound [Br-].CC(=O)OCC[N+](C)(C)C ZEHGKSPCAMLJDC-UHFFFAOYSA-M 0.000 description 1
- JUGOREOARAHOCO-UHFFFAOYSA-M acetylcholine chloride Chemical compound [Cl-].CC(=O)OCC[N+](C)(C)C JUGOREOARAHOCO-UHFFFAOYSA-M 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical group [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- SWLVFNYSXGMGBS-UHFFFAOYSA-N ammonium bromide Chemical compound [NH4+].[Br-] SWLVFNYSXGMGBS-UHFFFAOYSA-N 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000004760 aramid Chemical group 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 229920003235 aromatic polyamide Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000005102 attenuated total reflection Methods 0.000 description 1
- SRSXLGNVWSONIS-UHFFFAOYSA-N benzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-N 0.000 description 1
- 229940092714 benzenesulfonic acid Drugs 0.000 description 1
- 235000010233 benzoic acid Nutrition 0.000 description 1
- UUZYBYIOAZTMGC-UHFFFAOYSA-M benzyl(trimethyl)azanium;bromide Chemical compound [Br-].C[N+](C)(C)CC1=CC=CC=C1 UUZYBYIOAZTMGC-UHFFFAOYSA-M 0.000 description 1
- KXHPPCXNWTUNSB-UHFFFAOYSA-M benzyl(trimethyl)azanium;chloride Chemical compound [Cl-].C[N+](C)(C)CC1=CC=CC=C1 KXHPPCXNWTUNSB-UHFFFAOYSA-M 0.000 description 1
- VTQLZQMNJYFXIZ-UHFFFAOYSA-M benzyl(trimethyl)phosphanium;bromide Chemical compound [Br-].C[P+](C)(C)CC1=CC=CC=C1 VTQLZQMNJYFXIZ-UHFFFAOYSA-M 0.000 description 1
- TXXACRDXEHKXKD-UHFFFAOYSA-M benzyl(trimethyl)phosphanium;chloride Chemical compound [Cl-].C[P+](C)(C)CC1=CC=CC=C1 TXXACRDXEHKXKD-UHFFFAOYSA-M 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 239000001273 butane Substances 0.000 description 1
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- DVBJBNKEBPCGSY-UHFFFAOYSA-M cetylpyridinium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+]1=CC=CC=C1 DVBJBNKEBPCGSY-UHFFFAOYSA-M 0.000 description 1
- YMKDRGPMQRFJGP-UHFFFAOYSA-M cetylpyridinium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCC[N+]1=CC=CC=C1 YMKDRGPMQRFJGP-UHFFFAOYSA-M 0.000 description 1
- FOCAUTSVDIKZOP-UHFFFAOYSA-N chloroacetic acid Chemical compound OC(=O)CCl FOCAUTSVDIKZOP-UHFFFAOYSA-N 0.000 description 1
- SGMZJAMFUVOLNK-UHFFFAOYSA-M choline chloride Chemical compound [Cl-].C[N+](C)(C)CCO SGMZJAMFUVOLNK-UHFFFAOYSA-M 0.000 description 1
- 235000015165 citric acid Nutrition 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000009841 combustion method Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- XLJMAIOERFSOGZ-UHFFFAOYSA-M cyanate Chemical compound [O-]C#N XLJMAIOERFSOGZ-UHFFFAOYSA-M 0.000 description 1
- UURSXESKOOOTOV-UHFFFAOYSA-N dec-5-ene Chemical compound CCCCC=CCCCC UURSXESKOOOTOV-UHFFFAOYSA-N 0.000 description 1
- 230000002542 deteriorative effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 229940120124 dichloroacetate Drugs 0.000 description 1
- KORSJDCBLAPZEQ-UHFFFAOYSA-N dicyclohexylmethane-4,4'-diisocyanate Chemical compound C1CC(N=C=O)CCC1CC1CCC(N=C=O)CC1 KORSJDCBLAPZEQ-UHFFFAOYSA-N 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- CCIVGXIOQKPBKL-UHFFFAOYSA-M ethanesulfonate Chemical compound CCS([O-])(=O)=O CCIVGXIOQKPBKL-UHFFFAOYSA-M 0.000 description 1
- 238000009730 filament winding Methods 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 238000013007 heat curing Methods 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 229910000042 hydrogen bromide Inorganic materials 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 1
- 229910000039 hydrogen halide Inorganic materials 0.000 description 1
- 239000012433 hydrogen halide Substances 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 1
- 229910000043 hydrogen iodide Inorganic materials 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 150000004693 imidazolium salts Chemical class 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 239000004310 lactic acid Substances 0.000 description 1
- 235000014655 lactic acid Nutrition 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 229940098779 methanesulfonic acid Drugs 0.000 description 1
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- RGHXWDVNBYKJQH-UHFFFAOYSA-N nitroacetic acid Chemical compound OC(=O)C[N+]([O-])=O RGHXWDVNBYKJQH-UHFFFAOYSA-N 0.000 description 1
- 238000007500 overflow downdraw method Methods 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- AEHDSYHVTDJGDN-UHFFFAOYSA-M phenacyl(triphenyl)phosphanium;bromide Chemical compound [Br-].C=1C=CC=CC=1C(=O)C[P+](C=1C=CC=CC=1)(C=1C=CC=CC=1)C1=CC=CC=C1 AEHDSYHVTDJGDN-UHFFFAOYSA-M 0.000 description 1
- XNGIFLGASWRNHJ-UHFFFAOYSA-L phthalate(2-) Chemical compound [O-]C(=O)C1=CC=CC=C1C([O-])=O XNGIFLGASWRNHJ-UHFFFAOYSA-L 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 229920003192 poly(bis maleimide) Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 239000005056 polyisocyanate Substances 0.000 description 1
- 229920001228 polyisocyanate Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 230000002040 relaxant effect Effects 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000011975 tartaric acid Substances 0.000 description 1
- 235000002906 tartaric acid Nutrition 0.000 description 1
- IBWGNZVCJVLSHB-UHFFFAOYSA-M tetrabutylphosphanium;chloride Chemical compound [Cl-].CCCC[P+](CCCC)(CCCC)CCCC IBWGNZVCJVLSHB-UHFFFAOYSA-M 0.000 description 1
- BRKFQVAOMSWFDU-UHFFFAOYSA-M tetraphenylphosphanium;bromide Chemical compound [Br-].C1=CC=CC=C1[P+](C=1C=CC=CC=1)(C=1C=CC=CC=1)C1=CC=CC=C1 BRKFQVAOMSWFDU-UHFFFAOYSA-M 0.000 description 1
- YNJBWRMUSHSURL-UHFFFAOYSA-N trichloroacetic acid Chemical compound OC(=O)C(Cl)(Cl)Cl YNJBWRMUSHSURL-UHFFFAOYSA-N 0.000 description 1
- PPUSAUHBQQGYQC-UHFFFAOYSA-N triethyl(2-methoxyethoxymethyl)azanium Chemical compound CC[N+](CC)(CC)COCCOC PPUSAUHBQQGYQC-UHFFFAOYSA-N 0.000 description 1
- MQGXELHDPFXZHF-UHFFFAOYSA-M triethyl(2-methoxyethoxymethyl)azanium;bromide Chemical compound [Br-].CC[N+](CC)(CC)COCCOC MQGXELHDPFXZHF-UHFFFAOYSA-M 0.000 description 1
- OFMVXJJITSZRJO-UHFFFAOYSA-N triethyl(2-methoxyethoxymethyl)phosphanium Chemical compound CC[P+](CC)(CC)COCCOC OFMVXJJITSZRJO-UHFFFAOYSA-N 0.000 description 1
- BRNRUXYQLSAFEJ-UHFFFAOYSA-M triethyl(2-methoxyethoxymethyl)phosphanium;bromide Chemical compound [Br-].CC[P+](CC)(CC)COCCOC BRNRUXYQLSAFEJ-UHFFFAOYSA-M 0.000 description 1
- ITMCEJHCFYSIIV-UHFFFAOYSA-N triflic acid Chemical compound OS(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-N 0.000 description 1
- SZEMGTQCPRNXEG-UHFFFAOYSA-M trimethyl(octadecyl)azanium;bromide Chemical compound [Br-].CCCCCCCCCCCCCCCCCC[N+](C)(C)C SZEMGTQCPRNXEG-UHFFFAOYSA-M 0.000 description 1
- CVFVQXOZIJNRLO-UHFFFAOYSA-M trimethyl(octadecyl)phosphanium;chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCCCC[P+](C)(C)C CVFVQXOZIJNRLO-UHFFFAOYSA-M 0.000 description 1
- CMSYDJVRTHCWFP-UHFFFAOYSA-N triphenylphosphane;hydrobromide Chemical compound Br.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 CMSYDJVRTHCWFP-UHFFFAOYSA-N 0.000 description 1
- 238000000870 ultraviolet spectroscopy Methods 0.000 description 1
- 229920006337 unsaturated polyester resin Polymers 0.000 description 1
- 229920001567 vinyl ester resin Polymers 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- 239000013585 weight reducing agent Substances 0.000 description 1
- 238000004804 winding Methods 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/16—Catalysts
- C08G18/161—Catalysts containing two or more components to be covered by at least two of the groups C08G18/166, C08G18/18 or C08G18/22
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/16—Catalysts
- C08G18/166—Catalysts not provided for in the groups C08G18/18 - C08G18/26
- C08G18/168—Organic compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/16—Catalysts
- C08G18/18—Catalysts containing secondary or tertiary amines or salts thereof
- C08G18/1875—Catalysts containing secondary or tertiary amines or salts thereof containing ammonium salts or mixtures of secondary of tertiary amines and acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/16—Catalysts
- C08G18/18—Catalysts containing secondary or tertiary amines or salts thereof
- C08G18/20—Heterocyclic amines; Salts thereof
- C08G18/2045—Heterocyclic amines; Salts thereof containing condensed heterocyclic rings
- C08G18/2063—Heterocyclic amines; Salts thereof containing condensed heterocyclic rings having two nitrogen atoms in the condensed ring system
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/16—Catalysts
- C08G18/18—Catalysts containing secondary or tertiary amines or salts thereof
- C08G18/20—Heterocyclic amines; Salts thereof
- C08G18/2045—Heterocyclic amines; Salts thereof containing condensed heterocyclic rings
- C08G18/2072—Heterocyclic amines; Salts thereof containing condensed heterocyclic rings having at least three nitrogen atoms in the condensed ring system
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/58—Epoxy resins
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
- C08G18/7657—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings
- C08G18/7664—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
- C08J5/0405—Reinforcing macromolecular compounds with loose or coherent fibrous material with inorganic fibres
- C08J5/042—Reinforcing macromolecular compounds with loose or coherent fibrous material with inorganic fibres with carbon fibres
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2363/00—Characterised by the use of epoxy resins; Derivatives of epoxy resins
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2463/00—Characterised by the use of epoxy resins; Derivatives of epoxy resins
Definitions
- the present invention relates to a method for molding a fiber-reinforced composite material suitable for aerospace applications and automobile applications, and an epoxy resin composition used therein.
- Fiber reinforced composite material consisting of reinforcing fiber and matrix resin
- FRP Fiber reinforced composite material
- the reinforcing fiber glass fiber, aramid fiber, carbon fiber, boron fiber and the like are used. Further, as the matrix resin, both a thermosetting resin and a thermoplastic resin are used, but from the viewpoint of heat resistance and productivity, a thermosetting resin is often used.
- a thermosetting resin epoxy resin, unsaturated polyester resin, vinyl ester resin, phenol resin, bismaleimide resin, cyanate resin and the like are used. Of these, epoxy resins are preferably used from the viewpoints of adhesiveness and dimensional stability between the resin and the reinforcing fiber, and mechanical properties such as strength and rigidity of the obtained composite material.
- the matrix resin used in the conventional method for molding a fiber-reinforced composite material as described above is liquid or semi-solid at room temperature, that is, low-molecular-weight thermosetting in order to sufficiently impregnate the reinforcing fiber base material.
- the toughness of the cured product of the thermosetting resin is generally lower than that of the thermoplastic resin, so that the impact resistance of the fiber-reinforced composite material is relatively low. It was a big issue to become.
- CFRP carbon fiber reinforced composite material
- Patent Documents 1 and 2 it is known that by applying a matrix resin containing a liquid isocyanate curing agent, toughness and heat resistance are improved while having a low viscosity (Patent Documents 1 and 2).
- Patent Document 1 assuming the use as a sealing agent or a coating material, 0.001 to 1% by mass of liquid isocyanate is used as a curing agent and 0.001 to 1% by mass of diazabicycloundecene is used as a catalyst, and the temperature is in a medium temperature region of 70 to 100 ° C. Disclosed is a technique for producing an epoxy resin composition having excellent heat resistance by curing with.
- an epoxy resin composition using an excessive amount of isocyanate as a curing agent contains a polyol to obtain an epoxy resin composition that cures in a short time at a low temperature and has excellent heat resistance and toughness.
- the technology to be used is disclosed.
- Patent Document 3 an isocyanate pre-reacted with a polyol with an epoxy is blended in a large excess in the range of 3 to 20 equivalents, and an oxazolidone cyclization reaction is allowed to proceed using a Lewis acid-base catalyst. It has been shown that the heat resistance of the cured product can be improved.
- Patent Document 1 favorably promotes self-polymerization of isocyanate by medium temperature curing to mainly form an isocyanurate ring having excellent heat resistance, but the ring has three bonding points and therefore has a high cross-linking density. It was easy to become a polymer and was not excellent in toughness.
- Patent Document 2 tends to cause deterioration and thickening due to hydrolysis peculiar to urethane bonds.
- it contains an excessive amount of isocyanate, it is easy to form an isocyanurate ring, and when this material is used as a fiber-reinforced composite material, a very brittle portion is formed and the balance of mechanical properties is deteriorated. There was a case that it ended up.
- An object of the present invention is to improve the drawbacks of the prior art and to provide a resin composition having excellent toughness and heat resistance, and a fiber-reinforced composite material using the same.
- the present invention is a fiber-reinforced composite composed of at least a cured product of the reinforcing fiber [A] and the epoxy resin composition [B].
- Epoxy resin having at least two oxylan groups in the molecule [b] Epoxy resin curing agent having at least two isocyanate groups in the molecule [c] Catalyst (where, the absorbance ratio is FT-IR (where, the above-mentioned absorbance ratio is FT-IR).
- a second aspect of the method for molding a fiber-reinforced composite material is a method for molding a fiber-reinforced composite material composed of at least a cured product of the reinforcing fiber [A] and the epoxy resin composition [B], wherein the epoxy resin composition.
- [B] contains the following components [a], [b], and [c], and the epoxy resin composition [B] has a relationship between the rubber state elasticity (Gr) and the glass transition temperature (Tg) in Equation 1.
- an epoxy resin composition for a fiber-reinforced composite material in which a specific degree of curing X in which the absorbance ratio Da / (Da + Db) at the degree of curing X% is in the range of 0.4 to 1 exists in the range of 85 to 95%.
- Catalyst (where, the degree of curing is obtained by DSC.
- an epoxy for a fiber-reinforced composite material in which a specific curing degree X in which the relationship between the rubber state elastic modulus (Gr) and the glass transition temperature (Tg) at the curing degree X satisfies the formula 1 exists in the range of 85 to 95%. It is a resin composition.
- Epoxy resin having at least two oxylan groups in the molecule [b] Epoxy resin curing agent having at least two isocyanate groups in the molecule [c] Catalyst Tg ⁇ 10 ⁇ Gr + 120 (Formula 1) Further, it is a cured product of these epoxy resin compositions and a fiber-reinforced composite material using the cured product.
- thermosetting resin that cures under specific conditions and by using a molding method that cures under specific conditions, toughness and heat resistance are not deteriorated without deteriorating the balance of mechanical properties.
- a fiber-reinforced composite material having excellent properties can be obtained.
- epoxy resin composition for the fiber-reinforced composite material
- the epoxy resin composition [B] is commonly used in the first aspect and the second aspect.
- Such an epoxy resin composition is an epoxy resin having at least two oxylan groups in the molecule as a component [a], an epoxy resin curing agent having at least two isocyanate groups in the molecule as a component [b], and a component [ It is essential to include a catalyst as c].
- the first aspect or the second aspect is not specified and the method of molding the fiber-reinforced composite material is described, the first aspect and the second aspect of the method for molding the fiber-reinforced composite material are described. It means that the contents are common to the above aspects. (The same applies to the epoxy resin composition for fiber-reinforced composite materials).
- the component [a] in the molding method of the fiber-reinforced composite material of the present invention is an epoxy resin having at least two oxylan groups in the molecule.
- the component [a] has a number average molecular weight of 200 to 200 or more because it has a low viscosity and is excellent in impregnation property into reinforcing fibers, and is excellent in mechanical properties such as heat resistance and elastic modulus when it is used as a fiber reinforced composite material.
- An epoxy resin in the range of 800 and containing an aromatic skeleton is preferably used.
- the number average molecular weight is determined by GPC (Gel Permeation Chromatography) using, for example, a polystyrene standard sample, but when the epoxy equivalent is known, a numerical value calculated from the product of the epoxy equivalent and the number of epoxy functional groups is used. You can also do it.
- Examples of the epoxy resin having at least two oxylan groups in the molecule used in the molding method of the fiber-reinforced composite material of the present invention include bisphenol type epoxy resin and amine type epoxy resin.
- Examples of the bisphenol type epoxy resin used in the molding method of the fiber-reinforced composite material of the present invention include bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol AD type epoxy resin, or halogens, alkyl substituents, and water thereof. Examples include accessories. Among them, the bisphenol F type epoxy resin is preferably used because it has an excellent balance between high elastic modulus and high toughness. Specific examples of such a bisphenol type epoxy resin include the following.
- Examples of commercially available bisphenol F type epoxy resins include “jER (registered trademark)” 806, “jER (registered trademark)” 807, and “jER (registered trademark)” 4004P (all manufactured by Mitsubishi Chemical Corporation).
- "EPICLON (registered trademark)” 830 manufactured by DIC Co., Ltd.
- “Epototo (registered trademark)” YD-170 is added to the resin.
- “Epototo (registered trademark)” YDF-8170C examples of commercially available bisphenol F type epoxy resins
- YDF-870GS examples of commercially available bisphenol F type epoxy resins
- Examples of commercially available bisphenol AD type epoxy resins include EPOX-MK R710 and EPOX-MK R1710 (all manufactured by Printec Co., Ltd.).
- Examples of the amine-type epoxy resin used in the molding method of the fiber-reinforced composite material of the present invention include tetraglycidyl diaminodiphenylmethane, tetraglycidyl diaminodiphenyl sulfone, triglycidyl aminophenol, triglycidyl aminocresol, diglycidyl aniline, and diglycidyl toluidine. , Tetraglycidyl xylylene diamine, or their halogens, alkyl substituents, hydrogenated products and the like. Specific examples of such an epoxy resin include the following.
- Examples of commercially available products of tetraglycidyl diaminodiphenyl sulfone include TG3DAS (manufactured by Mitsui Kagaku Fine Co., Ltd.).
- Examples of commercially available products of diglycidyl aniline include GAN (manufactured by Nippon Kayaku Co., Ltd.) and PxGAN (manufactured by Toray Fine Chemicals Co., Ltd.).
- Examples of commercially available diglycidyl toluidine include GOT (manufactured by Nippon Kayaku Co., Ltd.).
- Examples of commercially available products of tetraglycidylxylylenediamine and its hydrogenated products include "TETRAD (registered trademark)" -X and “TETRAD (registered trademark)” -C (all manufactured by Mitsubishi Gas Chemical Company, Inc.). .. Among them, tetraglycidyldiaminodiphenylmethane and triglycidyldiaminophenol are preferably used because they have both high elastic modulus and high heat resistance.
- the component [a] contains one or more types of amine-type epoxy resin and / or one or more types of bisphenol-type epoxy resin.
- the combined use of the amine type epoxy resin and the bisphenol type epoxy resin is preferable from the viewpoint of improving the balance between the high elastic modulus, high heat resistance, and high toughness.
- the component [b] in the molding method of the fiber-reinforced composite material of the present invention is an epoxy resin curing agent having at least two isocyanate groups in the molecule, and the isocyanate group is mainly composed of the oxylane group of the component [a].
- the component [b] containing an aromatic in the skeleton is preferably used because it gives higher heat resistance.
- Examples of the epoxy resin curing agent having at least two isocyanate groups in the molecule used in the method for molding the fiber-reinforced composite material of the present invention include methylene diisocyanate, ethylene diisocyanate, propylene diisocyanate, trimethylene diisocyanate, dodecamethylene diisocyanate, and hexa.
- Examples of commercially available aliphatic isocyanates include HDI (above, manufactured by Tosoh Corporation), “Duranate (registered trademark)” D101, “Duranate (registered trademark)” D201 (above, manufactured by Asahi Kasei Corporation), and the like. ..
- aromatic isocyanates include “Luplanate®” MS, “Luplanate®” MI, “Luplanate®” M20S, “Luplanate®” M11S, and “Luplanate®”. ) “M5S,” Luplanate® “T-80,” Luplanate® “MM-103,” Luplanate® “MM-102,” Luplanate® “MM-301 (above, BASF INOAC Polyurethane Co., Ltd., “Millionate (registered trademark)” MT, “Millionate (registered trademark)” MT-F, “Millionate (registered trademark)” MT-NBP, “Millionate (registered trademark)” NM, “ “Millionate (registered trademark)” MR-100, “Millionate (registered trademark)” MR-200, “Millionate (registered trademark)” MR-400, “Coronate (registered trademark)” T-80, “Coronate (registered trademark)” T-80
- Examples of commercially available alicyclic isocyanates include "Takenate (registered trademark)” 600 (manufactured by Mitsui Chemicals, Inc.) and “Fortimo (registered trademark)” 1,4-H6XDI (manufactured by Mitsui Chemicals, Inc.). Be done.
- a product obtained by pre-reacting an epoxy resin and an epoxy resin curing agent can also be blended in the epoxy resin composition. This method may be effective in adjusting the viscosity and improving the storage stability.
- the component [c] in the method for molding the fiber-reinforced composite material of the present invention is a catalyst, and is cured by oxazolidone cyclization of the oxylan group contained in the component [a] and the isocyanate group contained in the component [b]. It is a compound that can promote the reaction.
- the curing reaction proceeds under appropriate conditions, and the oxazolidone cyclization reaction proceeds preferentially over side reactions such as isocyanurate ring formation to form a rigid and low crosslink density molecular structure. As a result, a molded product having excellent moisture resistance and toughness can be obtained.
- the catalyst used in the method for forming the fiber-reinforced composite material of the present invention is not particularly limited, but is preferably a basic catalyst or an onium salt in which a salt composed of a blended acid and a base or an anion is a halide, more preferably amines or The derivative or ammonium salt, imidazoles or a derivative thereof or the imidazolium salt is used. These catalysts may be used alone or in combination of two or more.
- the epoxy resin composition [B] has an absorbance ratio of Da /. It is essential to obtain a fiber-reinforced composite material by curing so that (Da + Db) is in the range of 0.4 to 1.
- the absorbance ratio Da / (Da + Db) By setting the absorbance ratio Da / (Da + Db) in the range of 0.4 to 1, preferably in the range of 0.5 to 1, and more preferably in the range of 0.7 to 1, cross-linking while maintaining heat resistance. A structure having a low density can be formed, and a highly tough cured product can be obtained.
- the absorbance ratio Da / (Da + Db) is lower than 0.4, the crosslink density becomes too high, and the strength and toughness of the obtained fiber-reinforced composite material decrease. The closer the absorbance ratio Da / (Da + Db) is to 1, the lower the crosslink density and the better the heat resistance, which is preferable.
- the FT-IR (ATR method), resolution 4 cm -1, when measuring the number of integrations in 32 times, and Da absorbance absorption around 1760 cm -1, the absorbance of absorption around 1710 cm -1 Db It can be calculated from the above.
- the first aspect of the method for molding a fiber-reinforced composite material of the present invention is that the absorbance ratio Da / (Da + Db) of the epoxy resin composition [B] at a specific curing degree within the range of 15 to 25%. It is preferable to cure so that it is in the range of 0.01 to 1. That is, in the first aspect of the method for molding the fiber-reinforced composite material of the present invention, the absorbance ratio Da / (for example, the degree of curing is 20%) at any curing degree within the range of 15 to 25%. It is preferable to cure so that Da + Db) is in the range of 0.01 to 1.
- the absorbance ratio Da / (Da + Db) of the epoxy resin composition [B] at a specific curing degree within the curing degree range of 15 to 25% is in the range of 0.01 to 1, preferably in the range of 0.05 to 1. More preferably, the range is 0.1 to 1, which gives priority to oxazolidone ring formation over isocyanurate ring formation, that is, it is possible to suppress a reaction in which the crosslink density tends to be high, and a significant increase in the initial stage of curing. Stickiness can be avoided.
- QT the total calorific value obtained by measuring the temperature range from 30 ° C. to 350 ° C. with a DSC at a heating rate of 10 ° C./min with respect to the epoxy resin composition [B]
- QR the residual calorific value obtained by measuring the cured product of the epoxy resin composition [B].
- the same epoxy resin composition [B] as in the first aspect is used, and the epoxy resin composition [B] is subjected to a rubber state elastic modulus ( It is essential that the relationship between Gr) and the glass transition temperature (Tg) is cured so as to satisfy Equation 1 to obtain a fiber-reinforced composite material.
- the preferential formation of the oxazolidone ring during curing forms a rigid and low-crosslinking molecular structure, and as a result, the relationship between Gr and Tg is based on Formula 1, preferably Formula 1a. Preferably, the formula 1b is satisfied. As a result, a cured product having high heat resistance and excellent toughness and a fiber-reinforced composite material can be obtained.
- the relationship between Gr and Tg does not satisfy Equation 1, the balance between heat resistance and toughness of the obtained fiber-reinforced composite material is not good. It is preferable that the relationship between Gr and Tg also satisfies Equation 1'.
- the epoxy resin composition [B] is cured so that the elastic modulus in rubber state (Gr) satisfies Equation 2 to obtain a fiber-reinforced composite material. Is preferable.
- the elastic modulus in the rubber state is a value measured as follows. That is, the epoxy resin composition is heat-cured into a plate having a thickness of about 2 mm, processed into a test piece having a width of 12 ⁇ 1 mm and a length of 30 to 40 mm, and then the temperature rise rate is 5 with a dynamic viscoelasticity measuring device. Dynamic viscoelasticity is measured under the condition of ° C / min.
- the elastic modulus in the rubber state is defined as the storage elastic modulus at a temperature that exceeds the glass transition temperature obtained by the dynamic viscoelasticity measurement by 50 ° C.
- the glass transition temperature obtained by the dynamic viscoelasticity measurement is the temperature at the intersection of the tangent line drawn in the glass region and the tangent line drawn in the glass transition region in the temperature-storage elastic modulus curve.
- the epoxy resin composition [B] is cured so that the mass reduction rate ⁇ Wr in the thermogravimetric analysis (TGA) satisfies the range of 10% or less to obtain the fiber-reinforced composite material. It is preferable to obtain.
- the non-oxidizing atmosphere indicates an atmosphere that does not substantially contain oxygen, that is, an atmosphere of an inert gas such as nitrogen, helium, or argon.
- an inert gas such as nitrogen, helium, or argon.
- the epoxy resin composition [B] used in the molding method of the fiber-reinforced composite material of the present invention has the characteristics that the initial viscosity increase is small, the injection time is long, and the curing can be performed in a short time. For this reason, it is most suitable for the RTM method that keeps the mold temperature constant from injection to demolding, but the RTM method that heats up and cures after resin injection, hand lay-up, plursion, and filament other than the RTM method. It can be applied to any molding method using a liquid thermosetting resin such as winding, and any molding method is effective in shortening the molding time and improving the impregnation property of the reinforcing fiber.
- the method for molding the fiber-reinforced composite material of the present invention will be described in more detail by taking the above-mentioned RTM method as an example.
- the epoxy resin composition [B] is placed in a molding mold heated to 100 to 200 ° C. It is produced by injecting it into a base material made of reinforcing fiber [A], impregnating it, and curing it in the molding die.
- the epoxy resin composition [B] before injection is preferably heated to a constant temperature, and the heating temperature is the point of impregnation property into the base material made of the reinforcing fiber [A]. Therefore, it is determined from the relationship between the initial viscosity of the epoxy resin composition [B] and the increase in viscosity, and is preferably 30 to 80 ° C, more preferably 40 to 70 ° C.
- the molding temperature of the fiber-reinforced composite material (heat curing temperature of the epoxy resin composition [B]) can be adjusted by heating the molding mold, and the temperature of the heated molding mold is in the range of 100 to 200 ° C. It is preferably in the range of 120 to 180 ° C., and more preferably in the range of 120 to 180 ° C.
- the resin is provided in the molding die. It is preferable to inject from a plurality of locations. Specifically, a fiber-reinforced composite to be obtained is obtained by using a molding mold having a plurality of injection ports and injecting the epoxy resin composition [B] from the plurality of injection ports at the same time or sequentially with a time lag. It is preferable to select appropriate conditions according to the material because it has a degree of freedom to accommodate molded products of various shapes and sizes. There is no limit to the number and shape of such injection ports, but it is better to have more injection ports to enable injection in a short time, and the arrangement is such that the flow length of the resin can be shortened according to the shape of the molded product. Is preferable.
- the injection pressure when injecting the epoxy resin composition [B] is usually 0.1 to 1.0 MPa, preferably 0.1 to 0.6 MPa from the viewpoint of injection time and equipment economy. Further, a VaRTM (Vacum-Assisted Resin Transfer Molding) method in which the epoxy resin composition [B] is injected by vacuum suctioning the inside of the mold can also be used. Even when pressure injection is performed, it is preferable to suck the inside of the mold into a vacuum before injecting the epoxy resin composition [B] because the generation of voids is suppressed.
- VaRTM Va-Assisted Resin Transfer Molding
- glass fiber, aramid fiber, carbon fiber, boron fiber and the like are preferably used as the reinforcing fiber [A].
- carbon fiber is preferably used because it is possible to obtain a fiber-reinforced composite material which is lightweight but has excellent mechanical properties such as strength and elastic modulus.
- the carbon fiber any kind of carbon fiber can be used depending on the application, but from the viewpoint of impact resistance, it is preferable that the carbon fiber has a tensile elastic modulus of at most 400 GPa. From the viewpoint of strength, a carbon fiber having a tensile strength of 4.4 GPa or more and 6.5 GPa or less is preferable because a composite material having high rigidity and mechanical strength can be obtained. Further, the tensile elongation is also an important factor, and it is preferable that the carbon fiber has a high strength and a high elongation of 1.7% or more and 2.3% or less. Therefore, carbon fibers having the characteristics of a tensile elastic modulus of at least 230 GPa, a tensile strength of at least 4.4 GPa, and a tensile elongation of at least 1.7% are particularly suitable.
- the reinforcing fiber [A] may be either a short fiber or a continuous fiber, or both may be used in combination. In order to obtain a fiber-reinforced composite material having a high Vf, continuous fibers are preferable.
- the reinforcing fiber [A] may be used in the form of a strand, but the reinforcing fiber [A] may be used in the form of a mat, a woven fabric, a knit, a blade, a unidirectional sheet or the like.
- a base material made of the processed reinforcing fiber [A] is preferably used.
- a woven fabric in which a fiber-reinforced composite material having a high Vf is easily obtained and has excellent handleability is preferably used.
- the ratio of the net volume of the reinforcing fiber [A] to the apparent volume of the woven fabric is defined as the filling rate of the woven fabric.
- the filling rate of the woven fabric is calculated by the formula of W / (1000t ⁇ ⁇ f) from the grain W (unit: g / m 2 ), thickness t (unit: mm), and reinforcing fiber density ⁇ f (unit: g / cm 3). Be done.
- the basis weight and thickness of the woven fabric are determined in accordance with JIS R7602: 1995.
- the filling rate of the woven fabric is 0.10 to 0.85, preferably 0.40 to 0.85, and more preferably 0.50. It is preferably in the range of ⁇ 0.85.
- the fiber volume content Vf of the fiber-reinforced composite material referred to here is a value defined and measured as follows in accordance with ASTM D3171 (1999), and is a base material made of the reinforcing fiber [A]. This refers to a state after the thermosetting resin [B] is injected and cured.
- the fiber volume content Vf of the fiber-reinforced composite material can be calculated from the thickness h and the like of the fiber-reinforced composite material using the following formula.
- Vf (%) (Af ⁇ N) / ( ⁇ f ⁇ h) / 10
- Af 1 base material made of reinforcing fiber [A] , mass per 1 m 2 (g / m 2 )
- N Number of laminated base materials made of reinforcing fiber [A] (sheets)
- ⁇ f Density of reinforcing fiber [A] (g / cm 3 )
- h Thickness (mm) of the fiber-reinforced composite material (test piece).
- the base material made of the reinforcing fiber [A] may be separated from the fiber-reinforced composite material and taken out by any of a combustion method, a nitrate decomposition method, and a sulfuric acid decomposition method based on JIS K7075: 1991.
- a value measured based on JIS R7603: 1999 is used for the density of the reinforcing fiber [A] used in this case.
- the thickness h of the fiber-reinforced composite material is preferably measured with a micrometer specified in JIS B7502: 1994 or a material having an accuracy equal to or higher than that specified in JIS K7072: 1991. If the fiber-reinforced composite has a complicated shape and is difficult to measure, a sample (a sample having a certain shape and size for measurement) is cut out from the fiber-reinforced composite. , May be measured.
- One of the preferred forms of the fiber-reinforced composite material obtained by the method for molding the fiber-reinforced composite material of the present invention is a veneer.
- a sandwich structure in which a veneer-shaped fiber-reinforced composite material is arranged on both sides of a core material a hollow structure in which a veneer-shaped structure is surrounded by a veneer-shaped structure, or a veneer-shaped fiber Examples thereof include a so-called canappe structure in which a reinforced composite material is arranged on one side of a core material.
- a foam core is preferably used because a lightweight fiber-reinforced composite material can be obtained.
- the epoxy resin composition for a fiber-reinforced composite material of the present invention is an epoxy resin having at least two oxylan groups in the molecule as a component [a], and an epoxy having at least two isocyanate groups in the molecule as a component [b]. It is essential that the resin curing agent contains a catalyst as a component [c].
- the component [a] in the epoxy resin composition for a fiber-reinforced composite material of the present invention is an epoxy resin having at least two bonded oxylan groups in the molecule, and has been described in the method for molding a fiber-reinforced composite material of the present invention. The same as the one is preferably used.
- the component [b] in the epoxy resin composition for a fiber-reinforced composite material of the present invention contains at least two bonded isocyanate groups in the molecule and has an active group capable of reacting with the oxylane group of the component [a].
- the ratio of the number of mols of isocyanate groups of the component [b] to the number of mols of oxylan groups of all the epoxy resins contained in the epoxy resin composition is 0.5 to 5. It is preferably contained so as to be 1.8, more preferably contained so as to be 0.8 to 1.5, and further preferably contained so as to be 0.8 to 1.1. It is preferable that it is contained so as to be 0.95 to 1.05.
- the ratio of the mol number of the isocyanate groups to the mol number of the oxylan groups of all the epoxy resins contained in the epoxy resin composition of the present invention is less than 0.5, the self-polymerization of the component [a] by the oxylan groups. May progress easily and the heat resistance may be insufficient.
- the ratio exceeds 1.8 the viaduct density tends to be high, and the resin elongation may be insufficient. Further, if the highly reactive isocyanate group is excessive, a side reaction is likely to proceed, and in some cases, bubbles may be generated in the cured epoxy resin.
- the component [c] in the epoxy resin composition for a fiber-reinforced composite material of the present invention is a catalyst, and causes a curing reaction between an oxylan group contained in the component [a] and an isocyanate group contained in the component [b]. It is a compound that can be promoted.
- the component [c] in the epoxy resin composition those similar to those described in the method for molding the fiber-reinforced composite material of the present invention are preferably used.
- the component [c] is preferably a salt composed of a Bronsted base and a Bronsted acid having a base dissociation constant pKb of 20 or more in acetonitrile.
- the component [c] is more preferably a salt having a pKb of 24 or more and a Bronsted base and a Bronsted acid, and even more preferably a salt having a pKb of 25 or more and a Bronsted base and a Bronsted acid.
- a salt consisting of a Bronsted base having a pKb of 26 or more and a Bronsted acid is particularly preferable. By including such a component [c], excellent reactivity and reaction selectivity are exhibited. If the pKb of the Bronsted base is less than 20 in the salt composed of the Bronsted base and the Bronsted acid, the curing time may become long and the productivity may decrease.
- the base dissociation constant in acetonitrile can be calculated from, for example, a spectrum obtained by dissolving a base in acetonitrile, titrating it with an acid, and measuring it by visible ultraviolet spectroscopy.
- the Bronsted base is not particularly limited as long as it is a base capable of accepting a proton in the neutralization reaction with an acid, but it is preferably at least one selected from the group consisting of an amine compound and an imidazole compound.
- blended bases include 1,8-diazabicyclo [5.4.0] undec-7-ene, 1,5-diazabicyclo [4.3.0] -5-nonen, 7-methyl-1, Amine compounds such as 5,7-triazabicyclo [4.4.0] deca-5-ene, 1,5,7-triazabicyclo [4.4.0] deca-5-ene, imidazole (melting point 89) °C), 2-ethylimidazole (melting point 80 °C), 2-undecylimidazole (melting point 72 °C), 2-heptadecylimidazole (melting point 89 °C), 1,2-dimethylimidazole (liquid at room temperature), 2-ethyl -4-Methylimidazole (liquid at room temperature), 1-benzyl-2-phenylimidazole (liquid at room temperature), 1-benzyl-2-methylimidazole (liquid at room temperature), 1-cyanoethyl-2-methylimidazo
- the Bronsted acid in a salt composed of a Bronsted base having a base dissociation constant pKb of 20 or more and a Bronsted acid in acetonitrile is not particularly limited as long as it is an acid capable of providing a proton in a neutralization reaction with the base, but in water.
- the acid dissociation constant pKa in the above is preferably 5 or less, more preferably 3 or less, further preferably 1.5 or less, and particularly preferably 0 or less. If it exceeds 5, the reaction that tends to increase the crosslink density tends to occur in advance, and the obtained cured product and the fiber-reinforced composite material may become brittle.
- the Bronsted acid is preferably at least one selected from the group consisting of carboxylic acids, sulfonic acids and hydrogen halides.
- the acid dissociation constant can be calculated from the concentration of the corresponding substance and the hydrogen ion concentration by measuring the hydrogen ion concentration using, for example, a pH meter.
- carboxylic acids examples include formic acid, acetic acid, oxalic acid, benzoic acid, phthalic acid, maleic acid, fumaric acid, malonic acid, tartaric acid, citric acid, lactic acid, succinic acid, monochloroacetic acid, dichloroacetic acid, trichloroacetic acid, and tri. Fluoroacetic acid, nitroacetic acid, triphenylacetic acid and the like can be mentioned.
- sulfonic acid examples include methanesulfonic acid, ethanesulfonic acid, benzenesulfonic acid, p-toluenesulfonic acid, trifluoromethanesulfonic acid and the like.
- Examples of such hydrogen halide include hydrogen chloride, hydrogen bromide, hydrogen iodide and the like.
- Such a component [c] is preferable because it exhibits excellent reactivity and reaction selectivity even when the anion contains an onium salt which is a halide.
- an onium salt a quaternary ammonium salt and a quaternary phosphonium salt are preferably used.
- Examples of such quaternary ammonium halide include trimethyloctadecylammonium chloride, trimethyloctadecylammonium bromide, benzyltrimethylammonium chloride, benzyltrimethylammonium bromide, tetrabutylammonium chloride, tetrabutylammonium bromide, and (2-methoxyethoxymethyl) triethylammonium.
- Chloride (2-methoxyethoxymethyl) triethylammonium bromide, (2-acetoxyethyl) trimethylammonium chloride, (2-acetoxyethyl) trimethylammonium bromide, (2-hydroxyethyl) trimethylammonium chloride, (2-hydroxyethyl) trimethyl
- ammonium bromide bis (polyoxyethylene) dimethylammonium chloride, bis (polyoxyethylene) dimethylammonium bromide, 1-hexadecylpyridinium chloride, 1-hexadecylpyridinium bromide and the like.
- Examples of such quaternary phosphonium halide include trimethyloctadecylphosphonium chloride, trimethyloctadecilphosphonium bromide, benzyltrimethylphosphonium chloride, benzyltrimethylphosphonium bromide, tetrabutylphosphonium chloride, tetrabutylphosphonium bromide, and (2-methoxyethoxymethyl) triethylphosphonium.
- the total amount of the component [c] is preferably 1 part by mass or more and 10 parts by mass or less, and more preferably 1 part by mass or more and 5 parts by mass or less, based on 100 parts by mass of the total amount of the component [a]. It is more preferable to contain 1 part by mass or more and 3 parts by mass or less. If it is less than 1 part by mass, the curing time becomes long and the productivity may decrease. On the other hand, if it exceeds 10 parts by mass, the self-polymerization of the oxylan group contained in the component [a] may proceed and the heat resistance may be insufficient.
- the component [c] is a catalyst that can be dissolved in the epoxy resin of the component [a] in order to uniformly exhibit the catalytic action in the curing process.
- the catalyst that can be dissolved in the epoxy resin of the component [a] is a catalyst added to the epoxy resin of the component [a] by 1 part by mass with respect to 100 parts by mass of the total amount of the component [a] at room temperature or. It means that the two are uniformly compatible when the temperature is raised to near the melting point of the catalyst, the mixture is kneaded at 200 rpm for 30 minutes, and the mixture is left at room temperature for 1 hour.
- a phase-contrast microscope is used, and the presence or absence of insoluble matter in the catalyst is used for determination.
- the first aspect of the epoxy resin composition for a fiber-reinforced composite material of the present invention is.
- a specific degree of curing X in which the absorbance ratio Da / (Da + Db) at the degree of curing X is in the range of 0.4 to 1 is 85 to 95%.
- the degree of curing X is in the range of 85 to 95% when cured while raising the temperature at 30 ° C. to 10 ° C./min.
- the absorbance ratio Da / (Da + Db) at or (for example, 90% curing degree) is in the range of 0.4 to 1.
- the FT-IR ATR method
- resolution 4 cm -1 when measuring the number of integrations in 32 times
- Da absorbance absorption around 1760 cm -1 the absorbance of absorption around 1710 cm -1 Db
- the heat resistance is such that the absorbance ratio Da / (Da + Db) at the specific degree of curing X is in the range of 0.4 to 1, preferably in the range of 0.5 to 1, and more preferably in the range of 0.7 to 1. It is possible to form a structure having a low crosslink density while maintaining the property, that is, to increase the toughness.
- the absorbance ratio Da / (Da + Db) at the specific degree of curing X is lower than 0.4, the crosslink density becomes too high, and the strength and toughness of the cured product of the epoxy resin composition decrease.
- the absorbance ratio Da / at the degree of curing Y it is preferable that a specific degree of curing Y in which (Da + Db) is in the range of 0.01 to 1 is present in the range of 15 to 25%. That is, in the first aspect of the epoxy resin composition for a fiber-reinforced composite material of the present invention, when the epoxy resin composition is cured while raising the temperature at 30 ° C. to 10 ° C./min, the degree of curing is any one in the range of 15 to 25% ( For example, the absorbance ratio Da / (Da + Db) at (curing degree 20%) is preferably in the range of 0.01 to 1.
- the absorbance ratio Da / (Da + Db) at the specific degree of curing Y is in the range of 0.01 to 1, preferably in the range of 0.05 to 1, and more preferably in the range of 0.1 to 1. It is possible to suppress the reaction that tends to increase the crosslink density, and it is possible to avoid significant thickening in the initial stage of curing.
- the absorbance ratio Da / (Da + Db) at the specific degree of curing Y is lower than 0.01, a structure having high heat resistance can be expected, but the obtained fiber-reinforced composite material becomes brittle. In addition, the viscosity is not sufficient, which leads to deterioration of surface quality.
- the same epoxy resin composition [B] as in the first aspect is used and cured while raising the temperature from 30 ° C. to 10 ° C./min. It is essential that a specific degree of cure X in which the relationship between the rubber state elastic modulus (Gr) and the glass transition temperature (Tg) at the degree of cure X satisfies Equation 1 exists in the range of 85 to 95%. ..
- the preferential formation of the oxazolidone ring during curing forms a rigid and low-crosslinking molecular structure.
- the relationship between Gr and Tg is expressed in formula 1, preferably in formula 1a, more preferably in formula 1b. Will meet.
- a cured product having high heat resistance and excellent toughness and a fiber-reinforced composite material can be obtained.
- the relationship between Gr and Tg does not satisfy Equation 1, the balance between heat resistance and toughness of the obtained fiber-reinforced composite material is not good. It is preferable that the relationship between Gr and Tg also satisfies Equation 1'.
- a specific degree of curing X in the range of 5 to 15 MPa preferably exists in the range of 85 to 95%, and a specific degree of curing in which the elastic modulus in the rubber state at the degree of cure X is in the range of 0.5 to 10 MPa. More preferably, X is in the range of 85-95%. That is, in the second aspect of the epoxy resin composition for a fiber-reinforced composite material of the present invention, when cured while raising the temperature at 30 ° C. to 10 ° C./min, the degree of curing is any one in the range of 85 to 95%.
- the elastic modulus in the rubber state at (for example, 90% curing degree) is preferably in the range of 0.5 to 15 MPa.
- the crosslink density can be appropriately controlled while introducing a rigid skeleton, so that the matrix resin has both heat resistance and toughness. Can be.
- the elastic modulus in the rubber state at the specific degree of curing X is lower than 0.5 MPa, the crosslink density of the molecular chains is too low, and the obtained fiber-reinforced composite material has inferior heat resistance.
- the elastic modulus in the rubber state at the specific degree of curing X exceeds 15 MPa, the cross-linking density becomes too high, the resin elongation does not develop, and the toughness of the obtained fiber-reinforced composite material is insufficient.
- the elastic modulus in the rubber state explained here is a value measured as follows. That is, the epoxy resin composition is heat-cured into a plate having a thickness of about 2 mm, processed into a test piece having a width of 12 ⁇ 1 mm and a length of 30 to 40 mm, and then the temperature rise rate is 5 with a dynamic viscoelasticity measuring device. Dynamic viscoelasticity is measured under the condition of ° C / min.
- the elastic modulus in the rubber state is defined as the storage elastic modulus at a temperature that exceeds the glass transition temperature obtained by the dynamic viscoelasticity measurement by 50 ° C.
- the glass transition temperature obtained by the dynamic viscoelasticity measurement is the temperature at the intersection of the tangent line drawn in the glass region and the tangent line drawn in the glass transition region in the temperature-storage elastic modulus curve.
- the amount of hydroxyl groups in the epoxy resin composition is 0.20 mol / kg or less. It is more preferably 0.17 mol / kg or less, further preferably 0.13 mol / kg or less, further preferably 0.09 mol / kg or less, and 0.06 mol / kg or less. It is more preferably 0.03 mol / kg or less, and further preferably 0.03 mol / kg or less.
- the amount of hydroxyl groups in the epoxy resin composition is calculated by the following formula 3 using the equivalent of hydroxyl groups for each component of the constituent elements.
- the epoxy resin composition for a fiber-reinforced composite material of the present invention contains a component other than the constituent elements [a] to [c ⁇ and the component contains a hydroxyl group (a powder or granular material component such as a filler or a filler is also on the surface). If the component has a hydroxyl group, it is assumed that the component contains a hydroxyl group), the component shall also be included in each of the above components and used in the calculation by the following formula.
- COH ( ⁇ (wn / wnOH)) / W ⁇ 1000 ...
- Equation 3 COH: Amount of hydroxyl groups in the epoxy resin composition (mol / kg) wn: mass part of each component wnOH: hydroxyl group equivalent of each component (g / eq) W: The sum of the mass parts of all the components.
- the hydroxyl group equivalent for each component is the hydroxyl value measured by the pyridine-acetyl chloride method based on JIS K0070: 1992 (necessary for neutralizing acetic acid bonded to the hydroxyl group when 1 g of the sample is acetylated).
- the number of mg of potassium hydroxide, unit: mgKOH / g) divided by the formula amount of potassium hydroxide (56.11) is the inverse of the value, which corresponds to the molecular weight per hydroxyl group (unit). : G / eq).
- the measurement component is dissolved in pyridine (the powder and granule components are dispersed), and an acetyl chloride-toluene solution is added and heated. After cooling, it was further boiled to hydrolyze excess acetyl chloride, and then the acetic acid produced was titrated with a potassium hydroxide ethanol solution for measurement.
- the abundance ratio of urethane bonds and oxylan groups at the degree of curing Z becomes 0.10 or less. It is preferable that a specific degree of curing Z is in the range of 5 to 15%, and more preferably 0.05 or less. That is, when the epoxy resin composition for a fiber-reinforced composite material of the present invention is cured while raising the temperature at 30 ° C. to 10 ° C./min, the curing degree is any one in the range of 5 to 15% (for example, curing degree 10).
- the abundance ratio of the urethane bond and the oxylan group is preferably 0.10 or less. If the abundance ratio of the urethane bond and the oxylan group exceeds 0.10, the heat resistance and elastic modulus will be insufficient, and the viscosity will increase significantly at low temperatures, which may result in insufficient impregnation into the reinforcing fibers. ..
- the abundance ratio of the urethane bond and the oxylan group described here is the number of protons of the oxylan group and the proton of the urethane bond in the epoxy resin composition obtained by nuclear magnetic resonance of the epoxy resin composition having the specific degree of curing Z. It is a value specified by calculating with the area ratio of numbers. For example, using a high-resolution nuclear magnetic resonance analyzer (NMR measurement), using 500 MHz 1 H-NMR in a deuterated chloroform solvent, the number of integrations is 128 times, and 2.7 ppm is adjacent to the carbon in the oxylan group of the epoxy resin. It is a value that can be observed with high resolution for the protons and the protons adjacent to the urethane-bonded nitrogen at 5.4 ppm. Since the area ratio of 1 1 H-NMR reflects the number of moles thereof, the abundance ratio can be calculated.
- the epoxy resin composition for a fiber-reinforced composite material of the present invention preferably has a flexural modulus of 3.0 GPa or more and 6.0 GPa or less in any range of the curing degree of 85 to 95% (for example, the curing degree of 90%). More preferably, it is 3.4 GPa or more and 5.0 GPa or less. If the flexural modulus is less than 3.0 GPa, the compressive strength may be insufficient when the fiber-reinforced composite material is used, and when it exceeds 6.0 GPa, the cutting surface becomes rough when the fiber-reinforced composite material is used for cutting. It can be rough.
- the epoxy resin composition for a fiber-reinforced composite material of the present invention preferably contains the above-mentioned components appropriately so that the viscosity at 25 ° C. is 0.1 to 1.0 Pa ⁇ s, preferably 0.1. It is more preferable to set it to about 0.5 Pa ⁇ s.
- the viscosity at 25 ° C. is 0.1 to 1.0 Pa ⁇ s or less, the viscosity at the molding temperature can be lowered, the injection time into the reinforcing fiber base material can be shortened, and the cause of non-impregnation can be prevented. Further, by setting the viscosity at 25 ° C.
- the viscosity at the molding temperature does not become too low, and pits generated by entraining air during injection into the reinforcing fiber base material can be prevented and impregnated. It is possible to prevent the occurrence of unimpregnated regions caused by non-uniformity.
- the viscosity at 25 ° C. is measured immediately after the preparation of the epoxy resin composition.
- the reinforcing fiber to be combined with the epoxy resin composition for the fiber-reinforced composite material of the present invention is not particularly limited, but the same method as the molding method of the fiber-reinforced composite material of the present invention is preferably used.
- the form, composition, etc. of the fiber-reinforced composite material to be combined with the epoxy resin composition for the fiber-reinforced composite material of the present invention are not particularly limited, but the same method as the molding method of the fiber-reinforced composite material of the present invention is preferably used.
- Comparative Example 1 75 parts by mass of "jER (registered trademark)" 828 and 25 parts by mass of 3,3'-DAS were added as an epoxy resin and further kneaded to obtain an epoxy resin composition.
- Carbon fiber woven fabric CO6343 (carbon fiber: T300-3K, structure: plain weave, grain: 198 g / m 2) as reinforcing fibers in a mold having a plate-shaped cavity of 350 mm ⁇ 700 mm ⁇ 2 mm , Toray Industries, Inc.) was laminated in the cavity, and the mold was fastened with a press device.
- the epoxy resin composition in which the inside of the mold held at 100 ° C. (molding temperature) was depressurized to atmospheric pressure ⁇ 0.1 MPa by a vacuum pump and preheated to 50 ° C. was prepared.
- the mixture was mixed using a resin injection machine and injected at a pressure of 0.2 MPa. Then, it was cured under the curing conditions shown in Table 1 and demolded to obtain a fiber-reinforced composite material.
- Example 1 As described above, a cured product of the epoxy resin composition and a fiber-reinforced composite material were prepared under the curing conditions shown in Table 1. The cured product of such an epoxy resin composition had excellent heat resistance and ⁇ Wr levels, and had excellent toughness.
- Example 2 The curing conditions were changed from Example 1.
- the cured product of such an epoxy resin composition had a level of heat resistance without any problem, and was excellent in toughness and ⁇ Wr.
- Example 3 The curing conditions were changed from Example 1.
- the cured product of such an epoxy resin composition was excellent in heat resistance, toughness and ⁇ Wr.
- Examples 4 to 27 and Comparative Examples 2 to 8 are as described below (including Tables 2-1 to 2-4).
- Epoxy resin curing agent having at least two isocyanate groups- "Luplanate (registered trademark)" M20S (Polymeric MDI, manufactured by BASF INOC Polyurethane Co., Ltd.) -"Luplanate (registered trademark)” MI (Monomeric MDI, manufactured by BASF INOC Polyurethane Co., Ltd.).
- 2-Phenylethyl isocyanate an epoxy resin curing agent having an isocyanate group other than [b] (manufactured by Tokyo Chemical Industry Co., Ltd.).
- Epoxy Resin Composition The epoxy resin and catalyst are blended at the blending ratios (mass ratios) shown in Tables 2-1 to 2-4, and after confirming the dissolution with a retardation microscope, the epoxy resin is cured.
- An epoxy resin composition was prepared by blending the agents.
- the hydroxyl value (unit: mgKOH / g) of the component [a] is titrated by the pyridine-acetyl chloride method based on JIS K0070: 1992, and this is the formula amount of potassium hydroxide (the formula amount of potassium hydroxide).
- the amount of hydroxyl groups (unit: mmol / g) was calculated by dividing by 56.11).
- the "pyridine-acetyl chloride method" which measures the hydroxyl group equivalent of an epoxy resin, specifically dissolves the measurement resin in pyridine, adds an acetyl chloride-toluene solution, heats it, cools it, and then boil it to make excess acetyl chloride. Was hydrolyzed, and then the acetic acid produced was titrated with a potassium hydroxide ethanol solution and measured.
- the epoxy resin composition has a specific curing degree X (curing degree 90% in this example), a specific curing degree Y (curing degree 20% in this example), and a specific curing degree.
- the temperature at which Z (in this example, the degree of curing was 10%) was calculated.
- the storage elastic modulus at a temperature higher than the glass transition temperature obtained by the dynamic viscoelasticity measurement by 50 ° C. was adopted.
- the glass transition temperature obtained by the dynamic viscoelasticity measurement was defined as the temperature at the intersection of the tangent line drawn in the glass region and the tangent line drawn in the glass transition region in the temperature-storage elastic modulus curve.
- Example 4 As described above, the epoxy resin composition was prepared at the content ratio shown in Table 2-1.
- the epoxy resin composition had an excellent viscosity at 25 ° C.
- the epoxy resin composition was excellent in heat resistance, toughness, and elastic modulus at a degree of curing of 90%.
- Example 5 From Example 4, the component [a] was changed to an epoxy resin having a small amount of hydroxyl groups.
- the epoxy resin composition had a particularly excellent viscosity at 25 ° C.
- the epoxy resin composition was excellent in heat resistance and elastic modulus at a degree of curing of 90%, and was particularly excellent in toughness.
- Example 6 From Example 4, the component [a] was changed to a bisphenol F type epoxy resin.
- the epoxy resin composition had a particularly excellent viscosity at 25 ° C.
- the heat resistance of the epoxy resin composition at a curing degree of 90% was at a level without any problem, and the toughness and elastic modulus were excellent.
- Example 7 From Example 4, the component [c] was changed to a salt of Bronsted base and Bronsted acid.
- the epoxy resin composition had an excellent viscosity at 25 ° C.
- the heat resistance of the epoxy resin composition at a curing degree of 90% was at a level without any problem, and the toughness and elastic modulus were excellent.
- Example 12 From Example 4, the component [c] was changed to a halogenated onium salt.
- the epoxy resin composition had an excellent viscosity at 25 ° C.
- the heat resistance of the epoxy resin composition at a curing degree of 90% was at a level without any problem, and the toughness and elastic modulus were excellent.
- Example 14 From Example 4, the amount of the component [c] was changed to 1 part by mass.
- the epoxy resin composition had an excellent viscosity at 25 ° C.
- the heat resistance and elastic modulus of the epoxy resin composition at a curing degree of 90% were at no problem level, and the toughness was excellent.
- Example 15 From Example 4, the amount of the component [c] was changed to 10 parts by mass.
- the viscosity of the epoxy resin composition at 25 ° C. was at a level that was not a problem.
- the epoxy resin composition had excellent heat resistance and elastic modulus at a curing degree of 90%, and the toughness was at a level without any problem.
- Example 16 From Example 4, the ratio of the number of isocyanate groups of the component [b] to the number of oxylan groups of the epoxy resin composition was changed to 0.8.
- the epoxy resin composition had an excellent viscosity at 25 ° C.
- the heat resistance and elastic modulus of the epoxy resin composition at a curing degree of 90% were at no problem level, and the toughness was excellent.
- Example 17 From Example 4, the ratio of the number of isocyanate groups of the component [b] to the number of oxylan groups of the epoxy resin composition was changed to 0.5.
- the viscosity of the epoxy resin composition at 25 ° C. was at a level that was not a problem.
- the heat resistance and elastic modulus of the epoxy resin composition at a curing degree of 90% were inferior, the toughness was at a level that was not a problem.
- Example 18 From Example 4, the ratio of the number of isocyanate groups of the component [b] to the number of oxylan groups of the epoxy resin composition was changed to 1.1.
- the epoxy resin composition had an excellent viscosity at 25 ° C.
- the epoxy resin composition had excellent heat resistance and elastic modulus at a curing degree of 90%, and the toughness was at a level without any problem.
- Example 19 From Example 4, the ratio of the number of isocyanate groups of the component [b] to the number of oxylan groups of the epoxy resin composition was changed to 1.4.
- the epoxy resin composition had an excellent viscosity at 25 ° C.
- the epoxy resin composition had excellent heat resistance and elastic modulus at a degree of curing of 90%, and the toughness was at an acceptable level.
- Example 20 From Example 4, the ratio of the number of isocyanate groups of the component [b] to the number of oxylan groups of the epoxy resin composition was changed to 1.7.
- the epoxy resin composition had an excellent viscosity at 25 ° C.
- the epoxy resin composition had excellent heat resistance and elastic modulus at a degree of curing of 90%, and the toughness was at an acceptable level.
- Example 21 The type of the component [b] was changed from the fourth embodiment.
- the epoxy resin composition had an excellent viscosity at 25 ° C.
- the heat resistance and elastic modulus of the epoxy resin composition at a curing degree of 90% were at no problem level, and the toughness was excellent.
- Example 22 From Example 4, 30% of the component [a] was changed to an epoxy resin having a small amount of hydroxyl groups.
- the viscosity of the epoxy resin composition at 25 ° C. was slightly superior, and the heat resistance and toughness of the epoxy resin composition at a curing degree of 90% were also improved.
- Example 23 Compared to Example 22, the amount of epoxy resin having a small amount of hydroxyl groups in the component [a] was increased to 70%. The viscosity of the epoxy resin composition at 25 ° C. was further superior, and the heat resistance and toughness of the epoxy resin composition at a curing degree of 90% were further improved.
- Example 24 From Example 4, the component [a] was changed to a tetrafunctional amine type epoxy resin.
- the epoxy resin composition had a particularly excellent viscosity at 25 ° C.
- the heat resistance and elastic modulus of the epoxy resin composition at a curing degree of 90% were particularly excellent, and the toughness was at an acceptable level.
- Example 25 From Example 4, the component [a] was changed to a combination of a bisphenol F type epoxy and a trifunctional amine type epoxy resin.
- the epoxy resin composition had an excellent viscosity at 25 ° C.
- the heat resistance and elastic modulus of the epoxy resin composition at a curing degree of 90% were particularly excellent, and the toughness was excellent.
- Example 26 From Example 4, the component [a] was changed to a combination of a bisphenol F type epoxy and a tetrafunctional amine type epoxy resin.
- the epoxy resin composition had an excellent viscosity at 25 ° C.
- the heat resistance and elastic modulus of the epoxy resin composition at a curing degree of 90% were particularly excellent, and the toughness was excellent.
- Example 27 From Example 5, the component [a] was changed to an epoxy resin having a smaller amount of hydroxyl groups. The viscosity of the epoxy resin composition at 25 ° C. was further superior, and the heat resistance and toughness of the epoxy resin composition at a curing degree of 90% were further improved.
- Example 6 It is similar to Example I12 of Patent Document 1 (International Publication No. 2014/184882). Many isocyanurate rings were formed and the toughness was inferior.
- Example 7 It is similar to Example 1 of Patent Document 2 (International Publication No. 2016/102358).
- the amount of hydroxyl groups was significantly increased, many urethane bonds were formed, and the viscosity at 25 ° C., the heat resistance at a curing degree of 90%, and the elastic modulus were inferior.
- the present invention has viscosity stability at low temperature of the resin composition, it retains low viscosity when injected into reinforcing fibers, has excellent impregnation property, has high toughness and high heat resistance, and has a high elastic modulus. It is possible to provide an epoxy resin composition for a fiber-reinforced composite material, and a fiber-reinforced composite material using the same. As a result, the application of fiber-reinforced composite materials to aircraft and automobile applications will progress, and it is expected that further weight reduction will contribute to improved fuel efficiency and reduction of global warming gas emissions.
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Epoxy Resins (AREA)
- Reinforced Plastic Materials (AREA)
Abstract
Description
[a]分子内に少なくとも2つのオキシラン基を有するエポキシ樹脂
[b]分子内に少なくとも2つのイソシアネート基を有するエポキシ樹脂硬化剤
[c]触媒
(ここで、前記の吸光度比は、FT-IR(ATR法)において、オキサゾリドン環のカルボキシル基のC=O二重結合に起因する吸収の吸光度Daと、イソシアヌレート環のカルボキシル基のC=O二重結合に起因する吸収の吸光度Dbから吸光度比Da/(Da+Db)を算出することにより特定される。)
繊維強化複合材料の成形方法についての第2の態様として、少なくとも、強化繊維[A]およびエポキシ樹脂組成物[B]の硬化物からなる繊維強化複合材料の成形方法であって、エポキシ樹脂組成物[B]が次の構成要素[a]、[b]、[c]を含み、かつエポキシ樹脂組成物[B]をゴム状態弾性率(Gr)とガラス転移温度(Tg)の関係が式1を満たすように硬化して繊維強化複合材料を得る、繊維強化複合材料の成形方法である。
[a]分子内に少なくとも2つのオキシラン基を有するエポキシ樹脂
[b]分子内に少なくとも2つのイソシアネート基を有するエポキシ樹脂硬化剤
[c]触媒
Tg≧10×Gr+120 (式1)
繊維強化複合材料用エポキシ樹脂組成物についての第1の態様として、次の構成要素[a]、[b]、[c]を含み、30℃から10℃/分で昇温しながら硬化した際に、硬化度X%における吸光度比Da/(Da+Db)が0.4~1の範囲となるある特定の硬化度Xが85~95%の範囲に存在する、繊維強化複合材料用エポキシ樹脂組成物である。
[a]分子内に少なくとも2つのオキシラン基を有するエポキシ樹脂
[b]分子内に少なくとも2つのイソシアネート基を有するエポキシ樹脂硬化剤
[c]触媒
(ここで、前記の硬化度は、DSCにより得られるエポキシ樹脂組成物の総発熱量QTと、エポキシ樹脂組成物の硬化物の残存発熱量QRから硬化度(%)=(QT-QR)/QT×100で算出することにより特定される。)
繊維強化複合材料用エポキシ樹脂組成物についての第2の態様として、次の構成要素[a]、[b]、[c]を含み、30℃から10℃/分で昇温しながら硬化した際に、硬化度Xにおけるゴム状態弾性率(Gr)とガラス転移温度(Tg)の関係が式1を満たすある特定の硬化度Xが85~95%の範囲に存在する、繊維強化複合材料用エポキシ樹脂組成物である。
[a]分子内に少なくとも2つのオキシラン基を有するエポキシ樹脂
[b]分子内に少なくとも2つのイソシアネート基を有するエポキシ樹脂硬化剤
[c]触媒
Tg≧10×Gr+120 (式1)
さらに、これらのエポキシ樹脂組成物の硬化物、およびそれを用いた繊維強化複合材料である。
Tg≧10×Gr+120 (式1)
Tg≧10×Gr+140 (式1a)
Tg≧10×Gr+160 (式1b)
Tg≦10×Gr+230 (式1’)
本発明の繊維強化複合材料の成形方法についての第2の態様では、エポキシ樹脂組成物[B]をゴム状態弾性率(Gr)が式2を満たすように硬化して繊維強化複合材料を得ることが好ましい。
0.5≦Gr≦15 (式2)
0.5≦Gr≦10 (式2a)
0.5≦Gr≦5 (式2b)
ここでガラス転移温度は、エポキシ樹脂硬化物を、示差走査熱量測定装置を用いて、10℃/分の昇温速度で30℃から350℃まで昇温測定し、JIS K7121:1987に基づいて求めた中間点温度である。
Vf(%)=(Af×N)/(ρf×h)/10
Af:強化繊維[A]からなる基材1枚・1m2当たりの質量(g/m2)
N:強化繊維[A]からなる基材の積層枚数(枚)
ρf:強化繊維[A]の密度(g/cm3)
h:繊維強化複合材料(試験片)の厚み(mm)。
Tg≧10×Gr+120 (式1)
Tg≧10×Gr+140 (式1a)
Tg≧10×Gr+160 (式1b)
Tg≦10×Gr+230 (式1’)
また、本発明の繊維強化複合材料用エポキシ樹脂組成物についての第2の態様において、30℃から10℃/分で昇温しながら硬化した際に、硬化度Xにおけるゴム状態弾性率が0.5~15MPaの範囲となるある特定の硬化度Xが85~95%の範囲に存在することが好ましく、硬化度Xにおけるゴム状態弾性率が0.5~10MPaの範囲となるある特定の硬化度Xが85~95%の範囲に存在することがより好ましい。すなわち、本発明の繊維強化複合材料用エポキシ樹脂組成物についての第2の態様において、30℃から10℃/分で昇温しながら硬化した際に、硬化度85~95%の範囲のいずれか(例えば、硬化度90%)におけるゴム状態弾性率が0.5~15MPaの範囲となることが好ましい。
COH=(Σ(wn/wnOH))/W×1000 ・・・(式3)
COH:エポキシ樹脂組成物中の水酸基量(mol/kg)
wn:各成分の質量部
wnOH:各成分の水酸基当量(g/eq)
W:全成分の質量部の和。
実施例のエポキシ樹脂組成物を得るために、以下の原料を用いた。
・“jER(登録商標)”828(ビスフェノールA型エポキシ樹脂液状、三菱ケミカル(株)製)
・“ルプラネート(登録商標)”M20S(ポリメリックMDI、BASF INOAC ポリウレタン(株)製)
・“DBU(登録商標)”(1,8-ジアザビシクロ[5.4.0]ウンデカ-7-エン、サンアプロ(株)製))
・3,3’-DAS(3,3’-ジアミノジフェニルスルホン、三井化学ファイン(株)製)。
実施例1~3、参考例1は、エポキシ樹脂として、“jER(登録商標)”828 100質量部、“DBU(登録商標)” 4質量部を投入し、混練し、透明な粘調液を得た。その後、“ルプラネート(登録商標)”M20S 72質量部添加し、さらに混練し、エポキシ樹脂組成物を得た。
上記(2)で作製したエポキシ樹脂硬化物を真空中で脱泡した後、予備加熱したプレートに注型し、表1に記載した硬化条件で、動的粘弾性試験装置(ATD:アルファテクノロジーズLLC製)を用いてエポキシ樹脂硬化板を作製した。
上記(2)で調製したエポキシ樹脂組成物を5mg採取し、示差走査熱量測定装置(DSC2910:TAインスツルメンツ社製)を用いて、10℃/分の昇温速度で30℃から350℃まで昇温測定し、発熱カーブを取得し、その発熱ピークを積分することにより、熱硬化性樹脂の総発熱量QTを算出した。分解反応などによる発熱または吸熱のピークが見られる場合は、それらピーク以下の温度範囲で測定を行った。
上記(3)で作製したエポキシ樹脂硬化板から10mg採取し、示差走査熱量測定装置(DSC2910:TAインスツルメンツ社製)を用いて、10℃/分の昇温速度で30℃から350℃まで昇温測定し、JIS K7121:1987に基づいて求めた中間点温度をガラス転移温度Tgとし、耐熱性を評価した。
上記(3)で作製したエポキシ樹脂硬化板を#240、#800、#2000のサンドペーパーで表面を研磨させ、厚さ2mmのエポキシ樹脂硬化板を得た。次に、得られたエポキシ樹脂硬化板から、幅10mm、長さ60mmの試験片を切り出し、スパン間32mmの3点曲げを測定し、JIS K7171:1994に従い、樹脂靭性の指標となる曲げ撓み量を求めた。
上記(3)で作製したエポキシ樹脂硬化板、または硬化度15~25%の範囲内のある特定の硬化度(本実施例では、硬化度20%)のエポキシ樹脂硬化板を採取し、FT-IR装置(7000FT-IR:Varian製)を用いて、FT-IR(ATR法)を実施した。測定条件は、分解能を4cm-1、積算回数を32回とした。
上記(3)で作製したエポキシ樹脂硬化板を10mg採取し、熱重量分析機(TGA7:パーキンエルマー社製)を用いて、窒素(純度:99.99%以上)気流下、プログラム温度50℃で1分保持、プログラム温度50℃から800℃まで昇温速度20℃/分で昇温の条件にて質量減少率の測定を行った。
350mm×700mm×2mmの板状キャビティーを持つ金型に、強化繊維として炭素繊維織物CO6343(炭素繊維:T300-3K、組織:平織、目付:198g/m2、東レ(株)製)をキャビティー内に9枚積層し、プレス装置で型締めを行った。次に、100℃(成形温度)に保持した金型内を、真空ポンプにより、大気圧-0.1MPaに減圧し、あらかじめ、それぞれに50℃に加温しておいたエポキシ樹脂組成物を、樹脂注入機を用いて混合し、0.2MPaの圧力で注入した。その後、表1に記載の硬化条件で硬化し、脱型して、繊維強化複合材料を得た。
上記(9)で作製した繊維強化複合材料から10mg採取し、示差走査熱量測定装置(DSC2910:TAインスツルメンツ社製)を用いて、10℃/分の昇温速度で30℃から350℃まで昇温測定し、JIS K7121:1987に基づいて求めた中間点温度をガラス転移温度Tgとし、耐熱性を評価した。
前記のようにして、表1に記載の硬化条件でエポキシ樹脂組成物の硬化物および繊維強化複合材料を作製した。かかるエポキシ樹脂組成物の硬化物は、耐熱性とΔWrは問題ないレベルであり、靭性は優れていた。
実施例1から硬化条件を変更した。かかるエポキシ樹脂組成物の硬化物は、耐熱性は問題ないレベルであり、靭性とΔWrは優れていた。
実施例1から硬化条件を変更した。かかるエポキシ樹脂組成物の硬化物は、耐熱性、靭性とΔWrは優れていた。
実施例1から硬化条件を変更した。かかるエポキシ樹脂組成物の硬化物はDa/(Da+Db)が劣っており、耐熱性は優れているものの、靭性およびΔWrに劣っていた。
構成要素[b]以外の硬化剤として、アミン化合物を配合した。かかるエポキシ樹脂組成物の硬化物はオキサゾリドン環が形成されず、耐熱性とΔWrに劣っていた。
実施例のエポキシ樹脂組成物を得るために、以下の原料を用いた。
[a]分子内に少なくとも2つのオキシラン基を有するエポキシ樹脂
・“jER(登録商標)”828(ビスフェノールA型エポキシ樹脂、三菱ケミカル(株)製)
・“エポトート(登録商標)”YD-8125(ビスフェノールA型エポキシ樹脂、日鉄ケミカル&マテリアル(株)製)
・“EPICLON(登録商標)”830(ビスフェノールF型エポキシ樹脂、DIC(株)製)
・YD-8125変性品
100質量部の“エポトート(登録商標)”YD-8125に無水酢酸を10質量部添加し、110℃で1時間加熱撹拌し、YD-8125に少量含まれる水酸基をアセチル化した。その後、110℃で真空加熱することにより、余剰の酢酸と生成した酢酸を除去し、YD-8125変性品を得た。
・“デナコール”EX-313(グリセリン型エポキシ樹脂、1,3-ビス(オキシラニルメトキシ)プロパン-2-オール、ナガセケムテックス(株)製)
・“アラルダイド(登録商標)”MY0510(トリグリシジル-p-アミノフェノール、ハンツマン・アドバンスト・マテリアルズ社製)
・“アラルダイド(登録商標)”MY721(テトラグリシジルジアミノジフェニルメタン、ハンツマン・アドバンスト・マテリアルズ社製)。
・“ルプラネート(登録商標)”M20S(ポリメリックMDI、BASF INOAC ポリウレタン(株)製)
・“ルプラネート(登録商標)”MI(モノメリックMDI、BASF INOAC ポリウレタン(株)製)。
・“DBU(登録商標)”(1,8-ジアザビシクロ[5.4.0]ウンデカ-7-エン、サンアプロ(株)製、pKb=25)
・“DBU”/フタル酸(東京化成工業(株)製、pKa=3)塩
・“DBU”/ジクロロ酢酸(東京化成工業(株)製、pKa=1.5)塩
・“DBU”/p-トルエンスルホン酸(東京化成工業(株)製、pKa=-3)塩
・“DBN(登録商標)”(1,5-ジアザビシクロ[4.3.0]-5-ノネン、サンアプロ(株)製、pKb=24)/フタル酸塩
・TBD(1,5,7-トリアザビシクロ[4.4.0]デカ-5-エン、東京化成工業(株)製、pKb=26)/ジクロロ酢酸塩
・TBAB(テトラブチルアンモニウムブロミド、東京化成工業(株)製)
・“ホクコー TBP-BB(登録商標)”(テトラブチルホスホニウムブロミド、北興化学工業(株)製)。
・BGE(4-tert-ブチルフェニルグリシジルエーテル、東京化成工業(株)製)。
・2-フェニルエチルイソシアナート(東京化成工業(株)製)。
・ポリプロピレングリコール(富士フイルム和光純薬(株)製)。
・“ロンザキュア(登録商標)”M-DEA(ハンツマン・アドバンスト・マテリアルズ社製)。
表2-1~表2-4に記載した配合比(質量比)でエポキシ樹脂と触媒を配合し、位相差顕微鏡にて溶解を確認した後に、エポキシ樹脂硬化剤を配合してエポキシ樹脂組成物を調製した。
エポキシ樹脂組成物中の水酸基量は、構成要素の成分ごとに水酸基当量を用いて、式3で算出した。
COH=(Σ(wn/wnOH))/W×1000 ・・・(式3)
COH:エポキシ樹脂組成物中の水酸基量(mol/kg)
wn:各成分の質量部
wnOH:各成分の水酸基当量(g/eq)
W:全成分の質量部の和。
動的粘弾性測定装置(ARES:TAインスツルメント社製)を用い、直径40mmのパラレルプレートを用い、昇温速度1.5℃/minで単純昇温し、周波数1Hz、Gap 1mmの測定条件で得られた、複素粘性率η*の25℃における値を採用した。
上記(2)で調製したエポキシ樹脂組成物を真空中で脱泡した後、予備加熱したプレートに注型し、動的粘弾性試験装置(ATD:アルファテクノロジーズLLC製)を用いて、30℃から(6)項に記載の測定で得た硬化度が90%となる温度まで10℃/分で昇温することでエポキシ樹脂硬化板を作製した。
上記(2)で調製したエポキシ樹脂組成物を5mg採取し、示差走査熱量測定装置(DSC2910:TAインスツルメンツ社製)を用いて、10℃/分の昇温速度で30℃から350℃まで昇温測定し、発熱カーブを取得し、その発熱ピークを積分することにより、熱硬化性樹脂の総発熱量QTを算出した。分解反応などによる発熱または吸熱のピークが見られる場合は、それらピーク以下の温度範囲で測定を行った。
上記(5)で作製した特定の硬化度Z(本実施例では、硬化度10%)のエポキシ樹脂硬化物を採取し、重水素化クロロホルム溶媒中、500MHz 1H-NMRを用い、積算回数128回により測定した。2.7ppmにエポキシ樹脂のオキシラン基における炭素に隣接するプロトンと、5.4ppmにウレタン結合の窒素に隣接するプロトンの面積値より存在比率を算出した。
上記(5)で作製した特定の硬化度X(本実施例では、硬化度90%)および特定の硬化度Y(本実施例では、硬化度20%)のエポキシ樹脂硬化物を採取し、FT-IR装置(7000FT-IR:Varian製)を用いて、FT-IR(ATR法)を実施した。測定条件は、分解能を4cm-1、積算回数を32回とした。
上記(5)で作製した硬化度X(本実施例では、硬化度90%)のエポキシ樹脂硬化物から10mg採取し、示差走査熱量測定装置(DSC2910:TAインスツルメンツ社製)を用いて、10℃/分の昇温速度で30℃から350℃まで昇温測定し、JIS K7121:1987に基づいて求めた中間点温度をガラス転移温度Tgとし、耐熱性を評価した。
上記(5)で作製した硬化度X(本実施例では、硬化度90%)のエポキシ樹脂硬化物からから、幅10mm、長さ40mmの試験片を切り出し、動的粘弾性測定装置(ARES:TAインスツルメント社製)を用い、固体ねじり治具に試験片をセットし、昇温速度5℃/分、周波数1Hz、歪み量0.1%にて30~300℃の温度範囲について測定を行った。架橋密度の指標となるゴム状態弾性率は、動的粘弾性測定で得られるガラス転移温度を50℃上回った温度における貯蔵弾性率を採用した。なお、動的粘弾性測定で得られるガラス転移温度は、温度-貯蔵弾性率曲線において、ガラス領域に引いた接線と、ガラス転移領域に引いた接線との交点における温度とした。
上記(5)で作製した硬化度X(本実施例では、硬化度90%)のエポキシ樹脂硬化物を#240、#800、#2000のサンドペーパーで表面を研磨させ、厚さ2mmのエポキシ樹脂硬化板を得た後に、得られたエポキシ樹脂硬化板から、幅10mm、長さ60mmの試験片を切り出し、スパン間32mmの3点曲げを測定し、JIS K7171:1994に従い、曲げ弾性率と樹脂靭性の指標となる曲げ撓み量を求めた。
前記のようにして、表2-1に記載した含有割合でエポキシ樹脂組成物を調製した。かかるエポキシ樹脂組成物は25℃における粘度は優れていた。エポキシ樹脂組成物の硬化度90%における耐熱性、靭性、弾性率は優れていた。
実施例4から構成要素[a]を水酸基量の少ないエポキシ樹脂に変更した。かかるエポキシ樹脂組成物は25℃における粘度は特に優れていた。エポキシ樹脂組成物の硬化度90%における耐熱性、弾性率は優れており、靭性は特に優れていた。
実施例4から構成要素[a]をビスフェノールF型エポキシ樹脂に変更した。かかるエポキシ樹脂組成物は25℃における粘度は特に優れていた。エポキシ樹脂組成物の硬化度90%における耐熱性は問題ないレベルであり、靭性と弾性率は優れていた。
実施例4から構成要素[c]をブレンステッド塩基とブレンステッド酸の塩に変更した。かかるエポキシ樹脂組成物は25℃における粘度は優れていた。エポキシ樹脂組成物の硬化度90%における耐熱性は問題ないレベルであり、靭性と弾性率は優れていた。
実施例4から構成要素[c]をハロゲン化オニウム塩に変更した。かかるエポキシ樹脂組成物は25℃における粘度は優れていた。エポキシ樹脂組成物の硬化度90%における耐熱性は問題ないレベルであり、靭性と弾性率は優れていた。
実施例4から構成要素[c]の量を1質量部に変更した。かかるエポキシ樹脂組成物は25℃における粘度は優れていた。エポキシ樹脂組成物の硬化度90%における耐熱性と弾性率は問題ないレベルであり、靭性は優れていた。
実施例4から構成要素[c]の量を10質量部に変更した。かかるエポキシ樹脂組成物は25℃における粘度は問題ないレベルであった。エポキシ樹脂組成物の硬化度90%における耐熱性と弾性率は優れており、靭性は問題ないレベルであった。
実施例4から構成要素[b]のイソシアネート基数とエポキシ樹脂組成物のオキシラン基数の比を0.8に変更した。かかるエポキシ樹脂組成物は25℃における粘度は優れていた。エポキシ樹脂組成物の硬化度90%における耐熱性と弾性率は問題ないレベルであり、靭性は優れていた。
実施例4から構成要素[b]のイソシアネート基数とエポキシ樹脂組成物のオキシラン基数の比を0.5に変更した。かかるエポキシ樹脂組成物は25℃における粘度は問題ないレベルであった。エポキシ樹脂組成物の硬化度90%における耐熱性と弾性率は劣るものの、靭性は問題ないレベルであった。
実施例4から構成要素[b]のイソシアネート基数とエポキシ樹脂組成物のオキシラン基数の比を1.1に変更した。かかるエポキシ樹脂組成物は25℃における粘度は優れていた。エポキシ樹脂組成物の硬化度90%における耐熱性と弾性率は優れており、靭性は問題ないレベルであった。
実施例4から構成要素[b]のイソシアネート基数とエポキシ樹脂組成物のオキシラン基数の比を1.4に変更した。かかるエポキシ樹脂組成物は25℃における粘度は優れていた。エポキシ樹脂組成物の硬化度90%における耐熱性と弾性率は優れており、靭性は許容されるレベルであった。
実施例4から構成要素[b]のイソシアネート基数とエポキシ樹脂組成物のオキシラン基数の比を1.7に変更した。かかるエポキシ樹脂組成物は25℃における粘度は優れていた。エポキシ樹脂組成物の硬化度90%における耐熱性と弾性率は優れており、靭性は許容されるレベルであった。
実施例4から構成要素[b]の種類を変更した。かかるエポキシ樹脂組成物は25℃における粘度は優れていた。エポキシ樹脂組成物の硬化度90%における耐熱性と弾性率は問題ないレベルであり、靭性は優れていた。
実施例4から構成要素[a]の3割を水酸基量の少ないエポキシ樹脂に変更した。かかるエポキシ樹脂組成物は25℃における粘度はやや優位となり、エポキシ樹脂組成物の硬化度90%における耐熱性と靭性もそれぞれ向上した。
実施例22に対し、構成要素[a]の水酸基量の少ないエポキシ樹脂を7割に増量した。かかるエポキシ樹脂組成物は25℃における粘度はさらに優位となり、エポキシ樹脂組成物の硬化度90%における耐熱性と靭性もそれぞれさらに向上した。
実施例4から構成要素[a]を4官能アミン型エポキシ樹脂に変更した。かかるエポキシ樹脂組成物は25℃における粘度は特に優れていた。エポキシ樹脂組成物の硬化度90%における耐熱性と弾性率は特に優れており、靭性は許容されるレベルであった。
実施例4から構成要素[a]をビスフェノールF型エポキシと3官能アミン型エポキシ樹脂の組み合わせに変更した。かかるエポキシ樹脂組成物は25℃における粘度は優れていた。エポキシ樹脂組成物の硬化度90%における耐熱性と弾性率は特に優れており、靭性は優れていた。
実施例4から構成要素[a]をビスフェノールF型エポキシと4官能アミン型エポキシ樹脂の組み合わせに変更した。かかるエポキシ樹脂組成物は25℃における粘度は優れていた。エポキシ樹脂組成物の硬化度90%における耐熱性と弾性率は特に優れており、靭性は優れていた。
実施例5から構成要素[a]をさらに水酸基量の少ないエポキシ樹脂に変更した。かかるエポキシ樹脂組成物は25℃における粘度はさらに優位となり、エポキシ樹脂組成物の硬化度90%における耐熱性と靭性もそれぞれさらに向上した。
構成要素[a]としてグリセリン型エポキシ樹脂を配合し、25℃における粘度、硬化度90%における耐熱性、弾性率に劣っていた。
構成要素[a]として単官能エポキシ樹脂を配合し、25℃における粘度、硬化度90%における耐熱性、靭性、弾性率に劣っていた。
構成要素[b]として単官能イソシアネートを配合し、25℃における粘度、硬化度90%における耐熱性、靭性、弾性率に劣っていた。
構成要素[c]を配合しないことで、指定の条件では硬化度90%の硬化物が得られなかった。
特許文献1(国際公開第2014/184082号)の実施例I12に類似したものである。イソシアヌレート環が多く形成され、靭性に劣っていた。
特許文献2(国際公開第2016/102358号)の実施例1に類似したものである。ポリオールを配合した樹脂組成物とすることで水酸基量が大幅に増え、ウレタン結合が多く形成され、25℃における粘度、硬化度90%における耐熱性、弾性率に劣っていた。
構成要素[c]を含まず、かつ構成要素[b]の代わりにアミン硬化剤を配合した結果、25℃における粘度、硬化度90%における耐熱性、弾性率に劣っていた。
Claims (29)
- 少なくとも、強化繊維[A]およびエポキシ樹脂組成物[B]の硬化物からなる繊維強化複合材料の成形方法であって、エポキシ樹脂組成物[B]が次の構成要素[a]、[b]、[c]を含み、かつエポキシ樹脂組成物[B]を吸光度比Da/(Da+Db)が0.4~1の範囲となるように硬化して繊維強化複合材料を得る、繊維強化複合材料の成形方法。
[a]分子内に少なくとも2つのオキシラン基を有するエポキシ樹脂
[b]分子内に少なくとも2つのイソシアネート基を有するエポキシ樹脂硬化剤
[c]触媒
(ここで、前記の吸光度比は、FT-IR(ATR法)において、オキサゾリドン環のカルボキシル基のC=O二重結合に起因する吸収の吸光度Daと、イソシアヌレート環のカルボキシル基のC=O二重結合に起因する吸収の吸光度Dbから吸光度比Da/(Da+Db)を算出することにより特定される。) - エポキシ樹脂組成物[B]を硬化度15~25%の範囲内のある特定の硬化度における吸光度比Da/(Da+Db)が0.01~1の範囲となるように硬化する、請求項1に記載の繊維強化複合材料の成形方法。
(ここで、前記の硬化度は、昇温速度10℃/分でのDSCにより得られるエポキシ樹脂組成物の総発熱量QTと、その硬化物の残存発熱量QRから硬化度(%)=(QT-QR)/QT×100を算出することにより特定される。) - エポキシ樹脂組成物[B]を吸光度比が0.7~1の範囲となるように硬化して繊維強化複合材料を得る、請求項1または2に記載の繊維強化複合材料の成形方法。
- 少なくとも、強化繊維[A]およびエポキシ樹脂組成物[B]の硬化物からなる繊維強化複合材料の成形方法であって、エポキシ樹脂組成物[B]が次の構成要素[a]、[b]、[c]を含み、かつエポキシ樹脂組成物[B]をゴム状態弾性率(Gr)とガラス転移温度(Tg)の関係が式1を満たすように硬化して繊維強化複合材料を得る、繊維強化複合材料の成形方法。
[a]分子内に少なくとも2つのオキシラン基を有するエポキシ樹脂
[b]分子内に少なくとも2つのイソシアネート基を有するエポキシ樹脂硬化剤
[c]触媒
Tg≧10×Gr+120 (式1) - さらにエポキシ樹脂組成物[B]を、式2を満たすように硬化して繊維強化複合材料を得る、請求項4記載の繊維強化複合材料の成形方法。
0.5≦Gr≦15 (式2) - 繊維強化複合材料を構成するエポキシ樹脂組成物[B]の硬化物は、質量減少率△Wrが10%以下の範囲となるものである、請求項1~5のいずれかに記載の繊維強化複合材料の成形方法。
(ここで、前記の質量減少率は、常圧の非酸化性雰囲気下で50℃から800℃の温度まで昇温速度10℃/分で熱重量分析を行った際に、70℃到達時点の質量W1と、320℃到達時の試料質量W2から質量減少率△Wr(%)=(W1-W2)/W1×100を算出することにより特定される。) - エポキシ樹脂組成物[B]を、100~200℃に加熱した成形型内に配置した強化繊維[A]からなる基材に注入し、含浸させ、該成形型内で硬化する、請求項1~6のいずれかに記載の繊維強化複合材料の成形方法。
- 30~80℃に加温したエポキシ樹脂組成物[B]を、120~180℃に加熱した成形型内に配置した強化繊維[A]からなる基材に注入し、含浸させ、該成形型内で硬化する、請求項1~7のいずれかに記載の繊維強化複合材料の成形方法。
- エポキシ樹脂組成物[B]を、成形型内に配置した強化繊維[A]からなる基材に注入するに際して、該樹脂を該成形型に設けられた複数の箇所から注入する、請求項7または8に記載の繊維強化複合材料の成形方法。
- 次の構成要素[a]、[b]、[c]を含み、30℃から10℃/分で昇温しながら硬化した際に、硬化度Xにおける吸光度比Da/(Da+Db)が0.4~1の範囲となるある特定の硬化度Xが85~95%の範囲に存在する、繊維強化複合材料用エポキシ樹脂組成物。
[a]分子内に少なくとも2つのオキシラン基を有するエポキシ樹脂
[b]分子内に少なくとも2つのイソシアネート基を有するエポキシ樹脂硬化剤
[c]触媒
(ここで、前記の吸光度比は、FT-IR(ATR法)において、オキサゾリドン環のカルボキシル基のC=O二重結合に起因する吸収の吸光度Daと、イソシアヌレート環のカルボキシル基のC=O二重結合に起因する吸収の吸光度Dbから吸光度比Da/(Da+Db)を算出することにより特定される。また、前記の硬化度は、昇温速度10℃/分でのDSCにより得られるエポキシ樹脂組成物の総発熱量QTと、その硬化物の残存発熱量QRから硬化度(%)=(QT-QR)/QT×100を算出することにより特定される。) - 30℃から10℃/分で昇温しながら硬化した際に、硬化度Yにおける吸光度比Da/(Da+Db)が0.01~1の範囲となるある特定の硬化度Yが15~25%の範囲に存在する、請求項10に記載の繊維強化複合材料用エポキシ樹脂組成物。
- 次の構成要素[a]、[b]、[c]を含み、30℃から10℃/分で昇温しながら硬化した際に、硬化度Xにおけるゴム状態弾性率(Gr)とガラス転移温度(Tg)の関係が式1を満たすある特定の硬化度Xが85~95%の範囲に存在する、繊維強化複合材料用エポキシ樹脂組成物。
[a]分子内に少なくとも2つのオキシラン基を有するエポキシ樹脂
[b]分子内に少なくとも2つのイソシアネート基を有するエポキシ樹脂硬化剤
[c]触媒
Tg≧10×Gr+120 (式1) - 30℃から10℃/分で昇温しながら硬化した際に、硬化度Xにおけるゴム状態弾性率が0.5~15MPaの範囲となるある特定の硬化度Xが85~95%の範囲に存在する、請求項12に記載の繊維強化複合材料用エポキシ樹脂組成物。
- 水酸基量が0.20mol/kg以下である、請求項10~13のいずれかに記載の繊維強化複合材料用エポキシ樹脂組成物。
- 構成要素[a]として1種類以上のアミン型エポキシ樹脂を含む、請求項10~14のいずれかに記載の繊維強化複合材料用エポキシ樹脂組成物。
- 構成要素[a]として1種類以上のビスフェノール型エポキシ樹脂を含む、請求項10~15のいずれかに記載の繊維強化複合材料用エポキシ樹脂組成物。
- エポキシ樹脂組成物に含まれる全エポキシ樹脂のオキシラン基のmol数に対する、構成要素[b]のイソシアネート基のmol数の比率が0.5~1.8である、請求項10~16のいずれかに記載の繊維強化複合材料用エポキシ樹脂組成物。
- 構成要素[c]として、アセトニトリル中での塩基解離定数pKbが20以上のブレンステッド塩基とブレンステッド酸からなる塩を含む、請求項10~17のいずれかに記載の繊維強化複合材料用エポキシ樹脂組成物。
- ブレンステッド酸の水中での酸解離定数pKaが5以下である、請求項18に記載の繊維強化複合材料用エポキシ樹脂組成物。
- ブレンステッド塩基がアミン化合物およびイミダゾール化合物からなる群から選択される少なくとも1種類である、請求項18または19に記載の繊維強化複合材料用エポキシ樹脂組成物。
- ブレンステッド酸がカルボン酸、スルホン酸およびハロゲン化水素からなる群から選択される少なくとも1種類である、請求項18~20のいずれかに記載の繊維強化複合材料用エポキシ樹脂組成物。
- 構成要素[c]として、アニオンがハロゲン化物イオンであるオニウム塩を含む、請求項10~17のいずれかに記載の繊維強化複合材料用エポキシ樹脂組成物。
- オニウム塩が四級アンモニウム塩および四級ホスホニウム塩からなる群から選択される少なくとも1種類である、請求項22に記載の繊維強化複合材料用エポキシ樹脂組成物。
- 構成要素[c]が構成要素[a]の総量100質量部に対して1質量部以上10質量部以下である、請求項10~23のいずれかに記載の繊維強化複合材料用エポキシ樹脂組成物。
- 構成要素[c]は、構成要素[a]に溶解し得る、請求項10~24のいずれかに記載の繊維強化複合材料用エポキシ樹脂組成物。
- 30℃から10℃/分で昇温しながら硬化した際に、硬化度Zにおけるウレタン結合とオキシラン基の存在比率が0.10以下となるある特定の硬化度Zが5~15%の範囲に存在する、請求項10~25のいずれかに記載の繊維強化複合材料用エポキシ樹脂組成物。
- 25℃における粘度が0.1~1.0Pa・sである、請求項10~26のいずれかに記載の繊維強化複合材料用エポキシ樹脂組成物。
- 請求項10~27のいずれかに記載の繊維強化複合材料用エポキシ樹脂組成物の硬化物。
- 請求項28に記載の硬化物と、強化繊維を含んでなる繊維強化複合材料。
Priority Applications (5)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US17/775,628 US20220396696A1 (en) | 2019-11-18 | 2020-11-16 | Method for forming fiber-reinforced composite material and epoxy resin composition for use therein |
EP20890479.7A EP4063436A4 (en) | 2019-11-18 | 2020-11-16 | METHOD FOR FORMING A FIBER-REINFORCED COMPOSITE MATERIAL AND EPOXY RESIN COMPOSITION USED THEREIN |
AU2020387250A AU2020387250A1 (en) | 2019-11-18 | 2020-11-16 | Method for forming fiber-reinforced composite material and epoxy resin composition for use therein |
JP2020564680A JPWO2021100649A1 (ja) | 2019-11-18 | 2020-11-16 | |
CN202080078489.8A CN114729133A (zh) | 2019-11-18 | 2020-11-16 | 纤维增强复合材料的成型方法及其中使用的环氧树脂组合物 |
Applications Claiming Priority (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2019-207633 | 2019-11-18 | ||
JP2019207633 | 2019-11-18 | ||
JP2020-096754 | 2020-06-03 | ||
JP2020096754 | 2020-06-03 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2021100649A1 true WO2021100649A1 (ja) | 2021-05-27 |
Family
ID=75980754
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/JP2020/042584 WO2021100649A1 (ja) | 2019-11-18 | 2020-11-16 | 繊維強化複合材料の成形方法、およびそれに用いられるエポキシ樹脂組成物 |
Country Status (6)
Country | Link |
---|---|
US (1) | US20220396696A1 (ja) |
EP (1) | EP4063436A4 (ja) |
JP (1) | JPWO2021100649A1 (ja) |
CN (1) | CN114729133A (ja) |
AU (1) | AU2020387250A1 (ja) |
WO (1) | WO2021100649A1 (ja) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2022102467A1 (ja) * | 2020-11-16 | 2022-05-19 | 東レ株式会社 | 熱硬化性エポキシ樹脂組成物とその成形品、繊維強化複合材料、繊維強化複合材料用成形材料、および繊維強化複合材料の製造方法 |
WO2022124191A1 (ja) * | 2020-12-08 | 2022-06-16 | 東レ株式会社 | 熱硬化性エポキシ樹脂組成物、熱硬化性エポキシ樹脂成形品、繊維強化複合材料用成形材料、繊維強化複合材料、および繊維強化複合材料の製造方法 |
Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS6020922A (ja) * | 1983-06-27 | 1985-02-02 | シ−メンス、アクチエンゲゼルシヤフト | 成形物質の製造方法 |
JPS6069121A (ja) * | 1983-06-27 | 1985-04-19 | シ−メンス、アクチエンゲゼルシヤフト | 反応樹脂成形物質の製造方法 |
JPH04506678A (ja) * | 1989-06-06 | 1992-11-19 | ザ ダウ ケミカル カンパニー | エポキシを末端とするポリオキサゾリドン、調製方法、及びそれから作られる電気用積層板 |
WO2014184082A1 (de) | 2013-05-13 | 2014-11-20 | Basf Se | Isocyanat-epoxid-hybridharze |
WO2016102358A1 (de) | 2014-12-22 | 2016-06-30 | Henkel Ag & Co. Kgaa | Katalysator-zusammensetzung zur härtung von epoxidgruppen-haltigen harzen |
JP2018501391A (ja) * | 2014-12-22 | 2018-01-18 | ヘンケル・アクチェンゲゼルシャフト・ウント・コムパニー・コマンディットゲゼルシャフト・アウフ・アクチェンHenkel AG & Co. KGaA | 繊維強化材料用オキサゾリジノンおよびイソシアヌレート架橋マトリックス |
WO2019046382A1 (en) | 2017-09-01 | 2019-03-07 | Dow Global Technologies Llc | THERMOSETTING COMPOSITIONS |
Family Cites Families (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
ES2909123T3 (es) * | 2016-06-20 | 2022-05-05 | Henkel Ag & Co Kgaa | Composición curada con alta resistencia al impacto y estabilidad frente a la temperatura, que se basa en una resina epoxídica y un poliisocianato |
-
2020
- 2020-11-16 CN CN202080078489.8A patent/CN114729133A/zh active Pending
- 2020-11-16 AU AU2020387250A patent/AU2020387250A1/en active Pending
- 2020-11-16 WO PCT/JP2020/042584 patent/WO2021100649A1/ja unknown
- 2020-11-16 EP EP20890479.7A patent/EP4063436A4/en active Pending
- 2020-11-16 US US17/775,628 patent/US20220396696A1/en active Pending
- 2020-11-16 JP JP2020564680A patent/JPWO2021100649A1/ja active Pending
Patent Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS6020922A (ja) * | 1983-06-27 | 1985-02-02 | シ−メンス、アクチエンゲゼルシヤフト | 成形物質の製造方法 |
JPS6069121A (ja) * | 1983-06-27 | 1985-04-19 | シ−メンス、アクチエンゲゼルシヤフト | 反応樹脂成形物質の製造方法 |
JPH04506678A (ja) * | 1989-06-06 | 1992-11-19 | ザ ダウ ケミカル カンパニー | エポキシを末端とするポリオキサゾリドン、調製方法、及びそれから作られる電気用積層板 |
WO2014184082A1 (de) | 2013-05-13 | 2014-11-20 | Basf Se | Isocyanat-epoxid-hybridharze |
WO2016102358A1 (de) | 2014-12-22 | 2016-06-30 | Henkel Ag & Co. Kgaa | Katalysator-zusammensetzung zur härtung von epoxidgruppen-haltigen harzen |
JP2018501391A (ja) * | 2014-12-22 | 2018-01-18 | ヘンケル・アクチェンゲゼルシャフト・ウント・コムパニー・コマンディットゲゼルシャフト・アウフ・アクチェンHenkel AG & Co. KGaA | 繊維強化材料用オキサゾリジノンおよびイソシアヌレート架橋マトリックス |
WO2019046382A1 (en) | 2017-09-01 | 2019-03-07 | Dow Global Technologies Llc | THERMOSETTING COMPOSITIONS |
Non-Patent Citations (1)
Title |
---|
See also references of EP4063436A4 |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2022102467A1 (ja) * | 2020-11-16 | 2022-05-19 | 東レ株式会社 | 熱硬化性エポキシ樹脂組成物とその成形品、繊維強化複合材料、繊維強化複合材料用成形材料、および繊維強化複合材料の製造方法 |
WO2022124191A1 (ja) * | 2020-12-08 | 2022-06-16 | 東レ株式会社 | 熱硬化性エポキシ樹脂組成物、熱硬化性エポキシ樹脂成形品、繊維強化複合材料用成形材料、繊維強化複合材料、および繊維強化複合材料の製造方法 |
Also Published As
Publication number | Publication date |
---|---|
US20220396696A1 (en) | 2022-12-15 |
AU2020387250A1 (en) | 2022-06-02 |
EP4063436A1 (en) | 2022-09-28 |
JPWO2021100649A1 (ja) | 2021-05-27 |
CN114729133A (zh) | 2022-07-08 |
EP4063436A4 (en) | 2023-12-06 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN110088163B (zh) | 固化性树脂组合物以及使用其的膜、成型品、预浸料和纤维增强塑料 | |
EP2834308B1 (en) | Benzoxazine resin composition, prepreg, and fiber-reinforced composite material | |
JP6812671B2 (ja) | 繊維強化複合材料、成形品および圧力容器 | |
EP2551288B1 (en) | Epoxy resin composition for use in a carbon-fiber-reinforced composite material, prepreg, and carbon-fiber-reinforced composite material | |
EP3312210B1 (en) | Epoxy resin composition, prepreg, and fiber-reinforced composite material | |
JP2014520903A (ja) | 熱硬化性エポキシ系の強化剤用付加体 | |
WO2021100649A1 (ja) | 繊維強化複合材料の成形方法、およびそれに用いられるエポキシ樹脂組成物 | |
US11319435B2 (en) | Heat-curable resin composition, prepreg, and fiber-reinforced composite material | |
JPWO2017038880A1 (ja) | エポキシ樹脂組成物、プリプレグおよび炭素繊維強化複合材料 | |
US20210253808A1 (en) | Heat-curable molding material, fiber-reinforced composite, heat-curable epoxy resin composition for fiber-reinforced plastic, production method for heat-curable molding material, and fiber-reinforced plastic | |
JP2016138205A (ja) | プリプレグ及び繊維強化複合材料 | |
CN112218904A (zh) | 环氧树脂组合物、预浸体及纤维强化复合材料 | |
JP7491215B2 (ja) | エポキシ樹脂組成物、中間基材および繊維強化複合材料 | |
JP2020158716A (ja) | 硬化性樹脂組成物、及びそれを用いたトゥプリプレグ | |
EP3763765A1 (en) | Resin composition for fiber-reinforced composite materials, and fiber-reinforced composite material using same | |
JP7424990B2 (ja) | 繊維強化複合材料用樹脂組成物及びそれを用いた繊維強化複合材料 | |
EP4059975A1 (en) | Epoxy resin composition, prepreg, and fiber-reinforced composite material | |
EP4059977A1 (en) | Epoxy resin composition, prepreg, and fiber-reinforced composite material | |
EP4265664A1 (en) | Thermosetting epoxy resin composition, molded article of same, fiber-reinforced composite material, molding material for fiber-reinforced composite materials, and method for producing fiber-reinforced composite material | |
JP2016094610A (ja) | 熱硬化性エポキシ系の強化剤用付加体 | |
JP2020122047A (ja) | エポキシ樹脂組成物、プリプレグ、及び繊維強化複合樹脂成形体 | |
JPH05170862A (ja) | 多液型熱硬化性樹脂組成物及び硬化樹脂成形物の製造方法 | |
WO2023219007A1 (ja) | 熱硬化性樹脂組成物、成形品、繊維強化複合材料用成形材料および繊維強化複合材料 | |
WO2024024677A1 (ja) | プリプレグ、繊維強化複合材料、および繊維強化複合材料の製造方法 | |
EP4059974A1 (en) | Epoxy resin composition, prepreg, and fiber-reinforced composite material |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
ENP | Entry into the national phase |
Ref document number: 2020564680 Country of ref document: JP Kind code of ref document: A |
|
121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 20890479 Country of ref document: EP Kind code of ref document: A1 |
|
ENP | Entry into the national phase |
Ref document number: 2020387250 Country of ref document: AU Date of ref document: 20201116 Kind code of ref document: A |
|
NENP | Non-entry into the national phase |
Ref country code: DE |
|
ENP | Entry into the national phase |
Ref document number: 2020890479 Country of ref document: EP Effective date: 20220620 |