JP5940096B2 - エポキシ樹脂のための高潜在性硬化剤 - Google Patents
エポキシ樹脂のための高潜在性硬化剤 Download PDFInfo
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- JP5940096B2 JP5940096B2 JP2013554899A JP2013554899A JP5940096B2 JP 5940096 B2 JP5940096 B2 JP 5940096B2 JP 2013554899 A JP2013554899 A JP 2013554899A JP 2013554899 A JP2013554899 A JP 2013554899A JP 5940096 B2 JP5940096 B2 JP 5940096B2
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- Prior art keywords
- curing agent
- nhc
- acid
- alkyl
- dimethylurea
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- 239000003795 chemical substances by application Substances 0.000 title claims description 114
- 229920000647 polyepoxide Polymers 0.000 title claims description 64
- 239000003822 epoxy resin Substances 0.000 title claims description 63
- 239000000203 mixture Substances 0.000 claims description 92
- 239000007788 liquid Substances 0.000 claims description 78
- 150000003672 ureas Chemical class 0.000 claims description 45
- 239000003381 stabilizer Substances 0.000 claims description 34
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 31
- XZMCDFZZKTWFGF-UHFFFAOYSA-N Cyanamide Chemical compound NC#N XZMCDFZZKTWFGF-UHFFFAOYSA-N 0.000 claims description 30
- 239000002131 composite material Substances 0.000 claims description 23
- 125000006732 (C1-C15) alkyl group Chemical group 0.000 claims description 22
- 239000001257 hydrogen Substances 0.000 claims description 21
- 229910052739 hydrogen Inorganic materials 0.000 claims description 21
- 125000003118 aryl group Chemical group 0.000 claims description 20
- 239000000835 fiber Substances 0.000 claims description 18
- 150000007522 mineralic acids Chemical class 0.000 claims description 18
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 16
- 150000002431 hydrogen Chemical class 0.000 claims description 16
- 125000000217 alkyl group Chemical group 0.000 claims description 14
- 150000007524 organic acids Chemical class 0.000 claims description 14
- 239000002904 solvent Substances 0.000 claims description 14
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 13
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 claims description 13
- 235000005985 organic acids Nutrition 0.000 claims description 12
- 239000002253 acid Substances 0.000 claims description 11
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 11
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 10
- YGSDEFSMJLZEOE-UHFFFAOYSA-N salicylic acid Chemical compound OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 claims description 10
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 claims description 8
- YBBLOADPFWKNGS-UHFFFAOYSA-N 1,1-dimethylurea Chemical compound CN(C)C(N)=O YBBLOADPFWKNGS-UHFFFAOYSA-N 0.000 claims description 6
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 6
- 150000008064 anhydrides Chemical class 0.000 claims description 6
- 239000004202 carbamide Substances 0.000 claims description 6
- 239000000463 material Substances 0.000 claims description 6
- 239000002657 fibrous material Substances 0.000 claims description 5
- FJKROLUGYXJWQN-UHFFFAOYSA-N papa-hydroxy-benzoic acid Natural products OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 claims description 5
- 229960004889 salicylic acid Drugs 0.000 claims description 5
- 229910052736 halogen Inorganic materials 0.000 claims description 4
- 150000002367 halogens Chemical class 0.000 claims description 4
- LBLYYCQCTBFVLH-UHFFFAOYSA-N 2-Methylbenzenesulfonic acid Chemical compound CC1=CC=CC=C1S(O)(=O)=O LBLYYCQCTBFVLH-UHFFFAOYSA-N 0.000 claims description 3
- KDQTUCKOAOGTLT-UHFFFAOYSA-N 3-[3-(dimethylcarbamoylamino)-4-methylphenyl]-1,1-dimethylurea Chemical compound CN(C)C(=O)NC1=CC=C(C)C(NC(=O)N(C)C)=C1 KDQTUCKOAOGTLT-UHFFFAOYSA-N 0.000 claims description 3
- XMTQQYYKAHVGBJ-UHFFFAOYSA-N 3-(3,4-DICHLOROPHENYL)-1,1-DIMETHYLUREA Chemical compound CN(C)C(=O)NC1=CC=C(Cl)C(Cl)=C1 XMTQQYYKAHVGBJ-UHFFFAOYSA-N 0.000 claims description 2
- NEVYNAFJLYYHPR-UHFFFAOYSA-N 3-[3-(dimethylcarbamoylamino)-2-methylphenyl]-1,1-dimethylurea Chemical compound CN(C)C(=O)NC1=CC=CC(NC(=O)N(C)C)=C1C NEVYNAFJLYYHPR-UHFFFAOYSA-N 0.000 claims description 2
- MOAPNXVHLARBNQ-UHFFFAOYSA-N 3-[4-[[4-(dimethylcarbamoylamino)phenyl]methyl]phenyl]-1,1-dimethylurea Chemical compound C1=CC(NC(=O)N(C)C)=CC=C1CC1=CC=C(NC(=O)N(C)C)C=C1 MOAPNXVHLARBNQ-UHFFFAOYSA-N 0.000 claims description 2
- JXCGFZXSOMJFOA-UHFFFAOYSA-N chlorotoluron Chemical compound CN(C)C(=O)NC1=CC=C(C)C(Cl)=C1 JXCGFZXSOMJFOA-UHFFFAOYSA-N 0.000 claims description 2
- XXOYNJXVWVNOOJ-UHFFFAOYSA-N fenuron Chemical compound CN(C)C(=O)NC1=CC=CC=C1 XXOYNJXVWVNOOJ-UHFFFAOYSA-N 0.000 claims description 2
- RZILCCPWPBTYDO-UHFFFAOYSA-N fluometuron Chemical compound CN(C)C(=O)NC1=CC=CC(C(F)(F)F)=C1 RZILCCPWPBTYDO-UHFFFAOYSA-N 0.000 claims description 2
- BMLIZLVNXIYGCK-UHFFFAOYSA-N monuron Chemical compound CN(C)C(=O)NC1=CC=C(Cl)C=C1 BMLIZLVNXIYGCK-UHFFFAOYSA-N 0.000 claims description 2
- 230000000630 rising effect Effects 0.000 claims 1
- -1 1-methylpentyl Chemical group 0.000 description 194
- 238000002347 injection Methods 0.000 description 24
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- 238000000034 method Methods 0.000 description 23
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- 239000011347 resin Substances 0.000 description 21
- 238000009472 formulation Methods 0.000 description 15
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 14
- 239000004848 polyfunctional curative Substances 0.000 description 13
- 150000001412 amines Chemical class 0.000 description 12
- 239000002952 polymeric resin Substances 0.000 description 11
- 229920003002 synthetic resin Polymers 0.000 description 11
- 238000003860 storage Methods 0.000 description 10
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 8
- 230000008569 process Effects 0.000 description 8
- 238000002844 melting Methods 0.000 description 7
- 230000008018 melting Effects 0.000 description 7
- 235000011007 phosphoric acid Nutrition 0.000 description 7
- 239000000843 powder Substances 0.000 description 7
- 230000008901 benefit Effects 0.000 description 6
- 230000009477 glass transition Effects 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- 230000009257 reactivity Effects 0.000 description 6
- 125000006527 (C1-C5) alkyl group Chemical group 0.000 description 5
- RNLHGQLZWXBQNY-UHFFFAOYSA-N 3-(aminomethyl)-3,5,5-trimethylcyclohexan-1-amine Chemical compound CC1(C)CC(N)CC(C)(CN)C1 RNLHGQLZWXBQNY-UHFFFAOYSA-N 0.000 description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 5
- 239000000654 additive Substances 0.000 description 5
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- 239000000126 substance Substances 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 125000002947 alkylene group Chemical group 0.000 description 4
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 4
- 229920005749 polyurethane resin Polymers 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 125000004432 carbon atom Chemical group C* 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
- 150000001991 dicarboxylic acids Chemical class 0.000 description 3
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 description 3
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 3
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 229920000570 polyether Polymers 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 150000003628 tricarboxylic acids Chemical class 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 125000004493 2-methylbut-1-yl group Chemical group CC(C*)CC 0.000 description 2
- 125000003542 3-methylbutan-2-yl group Chemical group [H]C([H])([H])C([H])(*)C([H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 2
- PLIKAWJENQZMHA-UHFFFAOYSA-N 4-aminophenol Chemical compound NC1=CC=C(O)C=C1 PLIKAWJENQZMHA-UHFFFAOYSA-N 0.000 description 2
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- 239000004593 Epoxy Substances 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- RWRDLPDLKQPQOW-UHFFFAOYSA-N Pyrrolidine Chemical compound C1CCNC1 RWRDLPDLKQPQOW-UHFFFAOYSA-N 0.000 description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 2
- 229910052794 bromium Inorganic materials 0.000 description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- XPPKVPWEQAFLFU-UHFFFAOYSA-N diphosphoric acid Chemical compound OP(O)(=O)OP(O)(O)=O XPPKVPWEQAFLFU-UHFFFAOYSA-N 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 238000005470 impregnation Methods 0.000 description 2
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- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
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- 125000004433 nitrogen atom Chemical group N* 0.000 description 2
- 125000003538 pentan-3-yl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])C([H])([H])[H] 0.000 description 2
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- 238000003756 stirring Methods 0.000 description 2
- ISIJQEHRDSCQIU-UHFFFAOYSA-N tert-butyl 2,7-diazaspiro[4.5]decane-7-carboxylate Chemical compound C1N(C(=O)OC(C)(C)C)CCCC11CNCC1 ISIJQEHRDSCQIU-UHFFFAOYSA-N 0.000 description 2
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- UNXRWKVEANCORM-UHFFFAOYSA-N triphosphoric acid Chemical compound OP(O)(=O)OP(O)(=O)OP(O)(O)=O UNXRWKVEANCORM-UHFFFAOYSA-N 0.000 description 2
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- 125000006218 1-ethylbutyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000006219 1-ethylpentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C([H])([H])[H] 0.000 description 1
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 1
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- 125000003229 2-methylhexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
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- VEORPZCZECFIRK-UHFFFAOYSA-N 3,3',5,5'-tetrabromobisphenol A Chemical compound C=1C(Br)=C(O)C(Br)=CC=1C(C)(C)C1=CC(Br)=C(O)C(Br)=C1 VEORPZCZECFIRK-UHFFFAOYSA-N 0.000 description 1
- YBRVSVVVWCFQMG-UHFFFAOYSA-N 4,4'-diaminodiphenylmethane Chemical compound C1=CC(N)=CC=C1CC1=CC=C(N)C=C1 YBRVSVVVWCFQMG-UHFFFAOYSA-N 0.000 description 1
- 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
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
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- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 description 1
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- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 238000000113 differential scanning calorimetry Methods 0.000 description 1
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- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 1
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- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 238000001879 gelation Methods 0.000 description 1
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 239000003049 inorganic solvent Substances 0.000 description 1
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 1
- 239000004310 lactic acid Substances 0.000 description 1
- 235000014655 lactic acid Nutrition 0.000 description 1
- 239000007791 liquid phase Substances 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
- 230000007246 mechanism Effects 0.000 description 1
- XGEGHDBEHXKFPX-NJFSPNSNSA-N methylurea Chemical compound [14CH3]NC(N)=O XGEGHDBEHXKFPX-NJFSPNSNSA-N 0.000 description 1
- 125000002950 monocyclic group Chemical group 0.000 description 1
- DUWWHGPELOTTOE-UHFFFAOYSA-N n-(5-chloro-2,4-dimethoxyphenyl)-3-oxobutanamide Chemical compound COC1=CC(OC)=C(NC(=O)CC(C)=O)C=C1Cl DUWWHGPELOTTOE-UHFFFAOYSA-N 0.000 description 1
- SYSQUGFVNFXIIT-UHFFFAOYSA-N n-[4-(1,3-benzoxazol-2-yl)phenyl]-4-nitrobenzenesulfonamide Chemical class C1=CC([N+](=O)[O-])=CC=C1S(=O)(=O)NC1=CC=C(C=2OC3=CC=CC=C3N=2)C=C1 SYSQUGFVNFXIIT-UHFFFAOYSA-N 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 125000001971 neopentyl group Chemical group [H]C([*])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229920003986 novolac Polymers 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- KJIFKLIQANRMOU-UHFFFAOYSA-N oxidanium;4-methylbenzenesulfonate Chemical compound O.CC1=CC=C(S(O)(=O)=O)C=C1 KJIFKLIQANRMOU-UHFFFAOYSA-N 0.000 description 1
- 150000002924 oxiranes Chemical class 0.000 description 1
- 125000002080 perylenyl group Chemical group C1(=CC=C2C=CC=C3C4=CC=CC5=CC=CC(C1=C23)=C45)* 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000012744 reinforcing agent Substances 0.000 description 1
- 239000012783 reinforcing fiber Substances 0.000 description 1
- 239000012779 reinforcing material Substances 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 230000002269 spontaneous effect Effects 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000013008 thixotropic agent Substances 0.000 description 1
- 125000005425 toluyl group Chemical group 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- 238000001721 transfer moulding Methods 0.000 description 1
- 230000002485 urinary effect Effects 0.000 description 1
- 125000002256 xylenyl group Chemical group C1(C(C=CC=C1)C)(C)* 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/44—Amides
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/4007—Curing agents not provided for by the groups C08G59/42 - C08G59/66
- C08G59/4014—Nitrogen containing compounds
- C08G59/4021—Ureas; Thioureas; Guanidines; Dicyandiamides
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/44—Amides
- C08G59/46—Amides together with other curing agents
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/21—Urea; Derivatives thereof, e.g. biuret
-
- 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
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
- C08L75/04—Polyurethanes
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Epoxy Resins (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Reinforced Plastic Materials (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
R1、R2=互いに同時に又は独立に、水素、C1〜C15アルキル、C3〜C15シクロアルキル、又は一緒にC3〜C10アルキレンの環を形成し;
R3=水素、C1〜C15アルキル、C3〜C15シクロアルキル、アリール、アリールアルキル、−NHC(O)NR1R2で置換されたC1〜C15アルキル、−NHC(O)NR1R2で置換されたC3〜C15シクロアルキル、−NHC(O)NR1R2で置換されたアリール、又は−NHC(O)NR1R2で置換されたアリールアルキル;
R4、R5、R6、R7、R8=互いに同時に又は独立に、水素、ハロゲン、C1〜C15アルキル、C3〜C15シクロアルキル、アリール、アリールアルキル、−CF3、−NHC(O)NR1R2、−NHC(O)NR1R2で置換されたC1〜C15アルキル、−NHC(O)NR1R2で置換されたアリール、又は−NHC(O)NR1R2で置換されたアリールアルキル。
R4、R4’、R5、R5’、R6、R6’、R7、R7’、R8、R8’=互いに同時に又は独立に、水素、C1〜C15アルキル、C3〜C15シクロアルキル、−NHC(O)NR1R2又は−NHC(O)NR1R2で置換されたC1〜C15アルキル。
R1、R2=水素、C1〜C15アルキル;
R3=水素、C1〜C15アルキル、C3〜C15シクロアルキル、−NHC(O)NR1R2で置換されたC1〜C15アルキル、−NHC(O)NR1R2で置換されたC3〜C15シクロアルキル、又は−NHC(O)NR1R2で置換されたアリール
である、式(I)の尿素誘導体を含む液体硬化剤である。
R1、R2=互いに同時に又は独立に、メチル又はエチル;
R3=水素、C1〜C15アルキル、C3〜C15シクロアルキル、−NHC(O)NR1R2で置換されたC1〜C15アルキル、−NHC(O)NR1R2で置換されたC3〜C15シクロアルキル、又は−NHC(O)NR1R2で置換されたアリール
である、式(I)の尿素誘導体を含む液体硬化剤が好適である。
1)本発明による硬化剤の調製
(装置)
研究室の攪拌機(DISPERMAT model AE03−C1)、500mlの金属の混合容器、直径60mmの撹拌プレート、金属スパチュラ
100gの個々の成分(表1のとおり)を500mlの混合容器に量り入れ、スパチュラによって簡単に一緒に混合した。薄い結晶スラリーが形成されるまで、混合物を100〜200rpmで攪拌機を用いて撹拌した。その後、40℃の温度に達するまで、混合物を500から2000rpmで撹拌した。その後、必要であれば硬化剤100gあたり2gの安定剤(有機酸又は無機酸)を加えて、液体を安定化させた。その後、25℃の温度に達するまで、液体の撹拌を続けた。生成した残留物を濾過した。こうして得られた液相を集め、室温(23℃)で保存した。
混合に依存して、収率は75%から97%の間であった。
本発明による安定剤を加えることにより、収率は75〜90%から83〜97%に上昇した。
シアナミド:AlzChem AG
尿素 B1:1,1−ジメチル尿素 − AlzChem AG
尿素 B2:異性体の工業的混合物 1,1’−(4−メチル−m−フェニレン)−ビス(3,3−ジメチル尿素)及び1,1’−(2−メチル−m−フェニレン)−ビス−(3,3−ジメチル尿素) − AlzChem AG
尿素 B3:尿素 − Merck KGaA
尿素 B4:1−(N,N−ジメチル尿素)−3−(N,N−ジメチル尿素メチル)−3,5,5−トリメチルシクロヘキサン − CAS:39992−90−0 − AlzChem AG
E 828:Epikote 828 − Momentive Specialty Chemicals
E 828LVEL:Epikote 828 LVEL − Momentive Specialty Chemicals
安定剤 S2:[リン酸(液体) Merckによる分析により85%]
安定剤 S3:[サリチル酸(固体)&リン酸(液体)(H3PO4 Merckによる分析により85%)]、1:1の比
安定剤 S4:[Merckからのサリチル酸(固体) 超高純度]
安定剤 S5:[Merckからのフタル酸(固体) min. 99.5%]
安定剤 S6:[Merckからのフタル酸無水物(固体) >98%]
安定剤 S7:[Merckからのトルエン−4−スルホン酸一水和物(固体) >97%]
安定剤 S8:[J T Bakerからの硫酸(液体) >97%]
RIMR 135:エポキシ樹脂 − Momentive Specialty Chemicals
RIMH 137:液体アミン硬化剤 − Momentive Specialty Chemicals
Vestamin IPDA:液体アミン硬化剤 − Evonik Degussa GmbH
(粘度の測定)
HAAKE Rheostress 1での測定を、25℃、mPa・s、35mm直径及び1°で、5.0/s(毎秒)の剪断速度で行った。
融点をDSCにより測定した。
Mettler Toledo DSC 822による測定
10K/分の加熱速度におけるDyn DSC −40℃〜60℃
1)エポキシ樹脂組成物の調製
100質量部のエポキシ樹脂と、7質量部の本発明による硬化剤とを、250mlの混合容器に量り入れ、攪拌機を用いて500rpmで2分間混合した。その後、混合物を真空下で10分間脱気した。
−Dyn. DSC:標準 10K/分の加熱速度で30〜250℃
−Cold Tg:標準 10K/分の加熱速度で30〜250℃
−Final Tg:標準 Tg
20℃/分で30℃から200℃まで加熱
200℃で10.0分間維持
20℃/分で200℃から50℃まで冷却
50℃で5.0分間維持
20℃/分で50℃から200℃まで加熱
200℃で10.0分間維持
20℃/分で200℃から50℃まで冷却
50℃で5.0分間維持
20℃/分で50℃から220℃まで加熱
−Pa・sの25℃における粘度(1° コーン)
−140℃におけるゲル化時間
−80℃における加熱プレート上の注入試験
30gの、E828LVELと液体硬化剤との100:7.0の比の混合物を、直径10cmを有するペトリ皿に量り入れ(離型剤としてXTEND Release 19CMSで前処理)、蓋で閉じた。ペトリ皿を80℃の乾燥キャビネットに入れ、混合物が固化したら再び取り出した。冷却後、得られたプレートを取り、プレートの一部をコールドTg(cold Tg)及び最終Tg(final Tg)の試験のために用いた。
表4によるエポキシ樹脂組成物を混合し、加熱可能な保存容器内で予備加熱した。供給ラインを保存容器に導入して固定し、排気ライン(注入試験の構造を参照、表7)を安全弁によって真空ポンプに接続し、ポンプのスイッチを入れた。(加熱可能な成形体を刺激する)加熱プレートを注入温度にした。真空の適用時に、エポキシ樹脂組成物を繊維複合材によって引き込んだ。含浸が完了したら、供給ライン及び排気ラインを外してキャップをし、その後全体の構造物を加熱プレート上で硬化して積層体を形成した。硬化及び冷却が完了した後、積層体を構造物から取り除いた。
Claims (12)
- a)シアナミド;
b)式(I)又は式(II)の少なくとも1つの尿素誘導体:
それぞれの場合において互いに同時に又は独立に、
R1、R2=互いに同時に又は独立に、水素、C1〜C15アルキル、C3〜C15シクロアルキル、又は一緒にC3〜C10アルキルの環を形成し;
R3=水素、C1〜C15アルキル、C3〜C15シクロアルキル、アリール、アリールアルキル、−NHC(O)NR1R2で置換されたC1〜C15アルキル、−NHC(O)NR1R2で置換されたC3〜C15シクロアルキル、−NHC(O)NR1R2で置換されたアリール、又は−NHC(O)NR1R2で置換されたアリールアルキル;
R4、R5、R6、R7、R8=互いに同時に又は独立に、水素、ハロゲン、C1〜C15アルキル、C3〜C15シクロアルキル、アリール、アリールアルキル、−CF3、−NHC(O)NR1R2、−NHC(O)NR1R2で置換されたC1〜C15アルキル、−NHC(O)NR1R2で置換されたアリール、又は−NHC(O)NR1R2で置換されたアリールアルキル
が適用される);並びに
c)無機酸又は有機酸を含む群から選択される少なくとも1つの安定剤
を含む、硬化可能なエポキシ樹脂を硬化するための液体硬化剤。 - シアナミドと、式(I)又は式(II)の少なくとも1つの尿素誘導体とを、1:1から4:1のシアナミド:尿素誘導体又は尿素誘導体の混合物のモル比で含むことを特徴とする、請求項1に記載の液体硬化剤。
- シアナミド、少なくとも1つの尿素誘導体及び安定剤に加えて、溶媒又は可溶化剤を含まない、或いは溶媒フリー又は可溶化剤フリーであることを特徴とする、請求項1又は2に記載の液体硬化剤。
- 少なくとも2つの異なる尿素誘導体を含むことを特徴とする、請求項1から3のいずれか一項に記載の液体硬化剤。
- 前記基に以下:
それぞれの場合において互いに同時に又は独立に、
R1及びR2=水素、C1〜C15アルキル;
R3=水素、C1〜C15アルキル、C3〜C15シクロアルキル、−NHC(O)NR1R2で置換されたC1〜C15アルキル、−NHC(O)NR1R2で置換されたC3〜C15シクロアルキル、又は−NHC(O)NR1R2で置換されたアリール
が適用される、式(I)の尿素誘導体を含むことを特徴とする、請求項1から4のいずれか一項に記載の液体硬化剤。 - a)シアナミド、b)尿素、1,1−ジメチル尿素、3−(3−クロロ−4−メチルフェニル)−1,1−ジメチル尿素、3−(p−クロロフェニル)−1,1−ジメチル尿素、3−フェニル−1,1−ジメチル尿素、3−(3,4−ジクロロフェニル)−1,1−ジメチル尿素、1,1’−(メチレン−ジ−p−フェニレン)−ビス−(3,3−ジメチル尿素)、3−(3−トリフルオロメチルフェニル)−1,1−ジメチル尿素、1,1’−(2−メチル−m−フェニレン)−ビス−(3,3−ジメチル尿素)、及び/又は1,1’−(4−メチル−m−フェニレン)−ビス−(3,3−ジメチル尿素)を含む群から選択される尿素誘導体、並びにc)無機酸又は有機酸を含む群から選択される少なくとも1つの安定剤を含むことを特徴とする、請求項1から5のいずれか一項に記載の液体硬化剤。
- 前記無機酸又は有機酸として、サリチル酸、フタル酸、トルエンスルホン酸、硫酸、リン酸、若しくはこれらの無水物、又はこれらの混合物を含む群から選択される酸を用いることを特徴とする、請求項1から6のいずれか一項に記載の液体硬化剤。
- a)少なくとも1つの硬化可能なエポキシ樹脂、及び
b)請求項1から7のいずれか一項に記載の少なくとも1つの液体硬化剤
を含む、エポキシ樹脂組成物。 - a)支持体材料、
b)少なくとも1つの硬化可能なエポキシ樹脂、並びに
c)請求項1から7のいずれか一項に記載の少なくとも1つの液体硬化剤
を含む、複合材料。 - 少なくとも1つの硬化可能なエポキシ樹脂を含む組成物を硬化するための、請求項1から7のいずれか一項に記載の液体硬化剤の使用。
- 少なくとも1つの硬化可能なエポキシ樹脂で含浸された繊維材料又は少なくとも1つの硬化可能なエポキシ樹脂で含浸された織った繊維、編んだ繊維又はブライジングを硬化するための、請求項1から7のいずれか一項に記載の液体硬化剤の使用。
- 前記支持体材料が繊維材料である、請求項9に記載の複合材料。
Applications Claiming Priority (5)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE201110012079 DE102011012079A1 (de) | 2011-02-23 | 2011-02-23 | Neue Härter für Epoxidharze |
DE102011012079.3 | 2011-02-23 | ||
DE102012000674 | 2012-01-17 | ||
DE102012000674.8 | 2012-01-17 | ||
PCT/EP2012/053091 WO2012113878A1 (de) | 2011-02-23 | 2012-02-23 | Hochlatente härter für epoxidharze |
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JP2014506621A JP2014506621A (ja) | 2014-03-17 |
JP5940096B2 true JP5940096B2 (ja) | 2016-06-29 |
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JP2013554900A Active JP5976686B2 (ja) | 2011-02-23 | 2012-02-23 | エポキシ樹脂のための新規な硬化剤 |
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US (3) | US9296855B2 (ja) |
EP (2) | EP2678369B1 (ja) |
JP (2) | JP5940096B2 (ja) |
KR (2) | KR101926757B1 (ja) |
CN (2) | CN103261263B (ja) |
BR (2) | BR112013021411B1 (ja) |
CA (2) | CA2816725C (ja) |
DK (2) | DK2678368T3 (ja) |
ES (2) | ES2537285T3 (ja) |
HK (1) | HK1184479A1 (ja) |
PL (2) | PL2678369T3 (ja) |
RU (2) | RU2586118C2 (ja) |
SI (2) | SI2678369T1 (ja) |
WO (2) | WO2012113878A1 (ja) |
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