CN105348527A - Heat convertible resin, heat convertible resin composition with heat convertible resin, cured material, prepreg, laminated board and printed circuit board - Google Patents
Heat convertible resin, heat convertible resin composition with heat convertible resin, cured material, prepreg, laminated board and printed circuit board Download PDFInfo
- Publication number
- CN105348527A CN105348527A CN201510848759.XA CN201510848759A CN105348527A CN 105348527 A CN105348527 A CN 105348527A CN 201510848759 A CN201510848759 A CN 201510848759A CN 105348527 A CN105348527 A CN 105348527A
- Authority
- CN
- China
- Prior art keywords
- thermosetting resin
- general formula
- resin
- heat convertible
- convertible resin
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000011347 resin Substances 0.000 title claims abstract description 81
- 229920005989 resin Polymers 0.000 title claims abstract description 81
- 239000000463 material Substances 0.000 title abstract description 11
- 239000011342 resin composition Substances 0.000 title abstract description 3
- -1 diamines compounds Chemical class 0.000 claims abstract description 64
- 150000002989 phenols Chemical class 0.000 claims abstract description 25
- 238000006243 chemical reaction Methods 0.000 claims abstract description 13
- 229920001187 thermosetting polymer Polymers 0.000 claims description 68
- 239000000203 mixture Substances 0.000 claims description 34
- 238000000034 method Methods 0.000 claims description 20
- 229910052739 hydrogen Inorganic materials 0.000 claims description 10
- 239000001257 hydrogen Substances 0.000 claims description 10
- 125000004432 carbon atom Chemical group C* 0.000 claims description 7
- 150000001875 compounds Chemical class 0.000 claims description 5
- 125000000962 organic group Chemical group 0.000 claims description 5
- 125000005842 heteroatom Chemical group 0.000 claims description 4
- 238000005470 impregnation Methods 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 229910052760 oxygen Inorganic materials 0.000 claims description 2
- HBGPNLPABVUVKZ-POTXQNELSA-N (1r,3as,4s,5ar,5br,7r,7ar,11ar,11br,13as,13br)-4,7-dihydroxy-3a,5a,5b,8,8,11a-hexamethyl-1-prop-1-en-2-yl-2,3,4,5,6,7,7a,10,11,11b,12,13,13a,13b-tetradecahydro-1h-cyclopenta[a]chrysen-9-one Chemical compound C([C@@]12C)CC(=O)C(C)(C)[C@@H]1[C@H](O)C[C@]([C@]1(C)C[C@@H]3O)(C)[C@@H]2CC[C@H]1[C@@H]1[C@]3(C)CC[C@H]1C(=C)C HBGPNLPABVUVKZ-POTXQNELSA-N 0.000 claims 1
- PFRGGOIBYLYVKM-UHFFFAOYSA-N 15alpha-hydroxylup-20(29)-en-3-one Natural products CC(=C)C1CCC2(C)CC(O)C3(C)C(CCC4C5(C)CCC(=O)C(C)(C)C5CCC34C)C12 PFRGGOIBYLYVKM-UHFFFAOYSA-N 0.000 claims 1
- SOKRNBGSNZXYIO-UHFFFAOYSA-N Resinone Natural products CC(=C)C1CCC2(C)C(O)CC3(C)C(CCC4C5(C)CCC(=O)C(C)(C)C5CCC34C)C12 SOKRNBGSNZXYIO-UHFFFAOYSA-N 0.000 claims 1
- CMLFRMDBDNHMRA-UHFFFAOYSA-N 2h-1,2-benzoxazine Chemical compound C1=CC=C2C=CNOC2=C1 CMLFRMDBDNHMRA-UHFFFAOYSA-N 0.000 abstract description 30
- 230000008901 benefit Effects 0.000 abstract description 6
- 239000000178 monomer Substances 0.000 abstract description 4
- BGDOLELXXPTPFX-UHFFFAOYSA-N 3,4-dihydro-2h-1,2-benzoxazine Chemical group C1=CC=C2ONCCC2=C1 BGDOLELXXPTPFX-UHFFFAOYSA-N 0.000 abstract 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 63
- 239000000047 product Substances 0.000 description 34
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 22
- 238000002360 preparation method Methods 0.000 description 21
- 239000000126 substance Substances 0.000 description 16
- 229930040373 Paraformaldehyde Natural products 0.000 description 13
- 239000012298 atmosphere Substances 0.000 description 13
- 150000004985 diamines Chemical class 0.000 description 13
- 229920002866 paraformaldehyde Polymers 0.000 description 13
- 230000000052 comparative effect Effects 0.000 description 12
- 239000000470 constituent Substances 0.000 description 12
- 239000000243 solution Substances 0.000 description 11
- 239000002904 solvent Substances 0.000 description 11
- 239000003814 drug Substances 0.000 description 10
- 238000010992 reflux Methods 0.000 description 10
- 238000000926 separation method Methods 0.000 description 10
- 238000005406 washing Methods 0.000 description 10
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 239000003054 catalyst Substances 0.000 description 5
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 4
- 239000003063 flame retardant Substances 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 230000035484 reaction time Effects 0.000 description 4
- 229920003987 resole Polymers 0.000 description 4
- 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 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-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
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000004305 biphenyl Substances 0.000 description 3
- 235000010290 biphenyl Nutrition 0.000 description 3
- 239000006227 byproduct Substances 0.000 description 3
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 238000007711 solidification Methods 0.000 description 3
- 230000008023 solidification Effects 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 3
- POILWHVDKZOXJZ-ARJAWSKDSA-M (z)-4-oxopent-2-en-2-olate Chemical compound C\C([O-])=C\C(C)=O POILWHVDKZOXJZ-ARJAWSKDSA-M 0.000 description 2
- QDFXRVAOBHEBGJ-UHFFFAOYSA-N 3-(cyclononen-1-yl)-4,5,6,7,8,9-hexahydro-1h-diazonine Chemical compound C1CCCCCCC=C1C1=NNCCCCCC1 QDFXRVAOBHEBGJ-UHFFFAOYSA-N 0.000 description 2
- KLSLBUSXWBJMEC-UHFFFAOYSA-N 4-Propylphenol Chemical compound CCCC1=CC=C(O)C=C1 KLSLBUSXWBJMEC-UHFFFAOYSA-N 0.000 description 2
- OAHMVZYHIJQTQC-UHFFFAOYSA-N 4-cyclohexylphenol Chemical compound C1=CC(O)=CC=C1C1CCCCC1 OAHMVZYHIJQTQC-UHFFFAOYSA-N 0.000 description 2
- 125000004203 4-hydroxyphenyl group Chemical group [H]OC1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- CYYZDBDROVLTJU-UHFFFAOYSA-N 4-n-Butylphenol Chemical compound CCCCC1=CC=C(O)C=C1 CYYZDBDROVLTJU-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- ZTQSAGDEMFDKMZ-UHFFFAOYSA-N Butyraldehyde Chemical compound CCCC=O ZTQSAGDEMFDKMZ-UHFFFAOYSA-N 0.000 description 2
- 0 CC**1(CC(CCC(C)(C)CC)*2C(C)=*(C)C[C+]2)C(*C)C1 Chemical compound CC**1(CC(CCC(C)(C)CC)*2C(C)=*(C)C[C+]2)C(*C)C1 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 239000004593 Epoxy Substances 0.000 description 2
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 2
- ICXMNILZYYOUSS-UHFFFAOYSA-N O1NC=CC2=C1C=CC=C2.[Si] Chemical compound O1NC=CC2=C1C=CC=C2.[Si] ICXMNILZYYOUSS-UHFFFAOYSA-N 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- NBBJYMSMWIIQGU-UHFFFAOYSA-N Propionic aldehyde Chemical compound CCC=O NBBJYMSMWIIQGU-UHFFFAOYSA-N 0.000 description 2
- 239000002250 absorbent Substances 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- LLEMOWNGBBNAJR-UHFFFAOYSA-N biphenyl-2-ol Chemical compound OC1=CC=CC=C1C1=CC=CC=C1 LLEMOWNGBBNAJR-UHFFFAOYSA-N 0.000 description 2
- YXVFYQXJAXKLAK-UHFFFAOYSA-N biphenyl-4-ol Chemical compound C1=CC(O)=CC=C1C1=CC=CC=C1 YXVFYQXJAXKLAK-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
- 230000007812 deficiency Effects 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000003822 epoxy resin Substances 0.000 description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 2
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- KJFMBFZCATUALV-UHFFFAOYSA-N phenolphthalein Chemical compound C1=CC(O)=CC=C1C1(C=2C=CC(O)=CC=2)C2=CC=CC=C2C(=O)O1 KJFMBFZCATUALV-UHFFFAOYSA-N 0.000 description 2
- 229920000647 polyepoxide Polymers 0.000 description 2
- 229920001721 polyimide Polymers 0.000 description 2
- 239000009719 polyimide resin Substances 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 238000007151 ring opening polymerisation reaction Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 238000010189 synthetic method Methods 0.000 description 2
- 229920006337 unsaturated polyester resin Polymers 0.000 description 2
- NSGXIBWMJZWTPY-UHFFFAOYSA-N 1,1,1,3,3,3-hexafluoropropane Chemical compound FC(F)(F)CC(F)(F)F NSGXIBWMJZWTPY-UHFFFAOYSA-N 0.000 description 1
- 125000000355 1,3-benzoxazolyl group Chemical group O1C(=NC2=C1C=CC=C2)* 0.000 description 1
- MNAHQWDCXOHBHK-UHFFFAOYSA-N 1-phenylpropane-1,1-diol Chemical compound CCC(O)(O)C1=CC=CC=C1 MNAHQWDCXOHBHK-UHFFFAOYSA-N 0.000 description 1
- MQCPOLNSJCWPGT-UHFFFAOYSA-N 2,2'-Bisphenol F Chemical compound OC1=CC=CC=C1CC1=CC=CC=C1O MQCPOLNSJCWPGT-UHFFFAOYSA-N 0.000 description 1
- VXHYVVAUHMGCEX-UHFFFAOYSA-N 2-(2-hydroxyphenoxy)phenol Chemical compound OC1=CC=CC=C1OC1=CC=CC=C1O VXHYVVAUHMGCEX-UHFFFAOYSA-N 0.000 description 1
- DIZBQMTZXOUFTD-UHFFFAOYSA-N 2-(furan-2-yl)-3h-benzimidazole-5-carboxylic acid Chemical compound N1C2=CC(C(=O)O)=CC=C2N=C1C1=CC=CO1 DIZBQMTZXOUFTD-UHFFFAOYSA-N 0.000 description 1
- MVRPPTGLVPEMPI-UHFFFAOYSA-N 2-cyclohexylphenol Chemical compound OC1=CC=CC=C1C1CCCCC1 MVRPPTGLVPEMPI-UHFFFAOYSA-N 0.000 description 1
- 229940061334 2-phenylphenol Drugs 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
- KZMYFIUFUAOZHP-UHFFFAOYSA-N 4-(1-adamantyl)phenol Chemical compound C1=CC(O)=CC=C1C1(C2)CC(C3)CC2CC3C1 KZMYFIUFUAOZHP-UHFFFAOYSA-N 0.000 description 1
- NZGQHKSLKRFZFL-UHFFFAOYSA-N 4-(4-hydroxyphenoxy)phenol Chemical compound C1=CC(O)=CC=C1OC1=CC=C(O)C=C1 NZGQHKSLKRFZFL-UHFFFAOYSA-N 0.000 description 1
- GIXNHONPKYUROG-UHFFFAOYSA-N 4-(9h-fluoren-1-yl)phenol Chemical class C1=CC(O)=CC=C1C1=CC=CC2=C1CC1=CC=CC=C12 GIXNHONPKYUROG-UHFFFAOYSA-N 0.000 description 1
- QGMGHALXLXKCBD-UHFFFAOYSA-N 4-amino-n-(2-aminophenyl)benzamide Chemical compound C1=CC(N)=CC=C1C(=O)NC1=CC=CC=C1N QGMGHALXLXKCBD-UHFFFAOYSA-N 0.000 description 1
- HJSPWKGEPDZNLK-UHFFFAOYSA-N 4-benzylphenol Chemical compound C1=CC(O)=CC=C1CC1=CC=CC=C1 HJSPWKGEPDZNLK-UHFFFAOYSA-N 0.000 description 1
- HXDOZKJGKXYMEW-UHFFFAOYSA-N 4-ethylphenol Chemical compound CCC1=CC=C(O)C=C1 HXDOZKJGKXYMEW-UHFFFAOYSA-N 0.000 description 1
- FJKROLUGYXJWQN-UHFFFAOYSA-N 4-hydroxybenzoic acid Chemical compound OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 description 1
- ZSBDGXGICLIJGD-UHFFFAOYSA-N 4-phenoxyphenol Chemical compound C1=CC(O)=CC=C1OC1=CC=CC=C1 ZSBDGXGICLIJGD-UHFFFAOYSA-N 0.000 description 1
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- KUFFULVDNCHOFZ-UHFFFAOYSA-N Cc(cc1C)ccc1O Chemical compound Cc(cc1C)ccc1O KUFFULVDNCHOFZ-UHFFFAOYSA-N 0.000 description 1
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical class ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N Furan Chemical compound C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
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- 239000004640 Melamine resin Substances 0.000 description 1
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 1
- 239000004902 Softening Agent Substances 0.000 description 1
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- 239000006096 absorbing agent Substances 0.000 description 1
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- 150000007513 acids Chemical class 0.000 description 1
- 125000002252 acyl group Chemical group 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
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- REDXJYDRNCIFBQ-UHFFFAOYSA-N aluminium(3+) Chemical compound [Al+3] REDXJYDRNCIFBQ-UHFFFAOYSA-N 0.000 description 1
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- 125000003118 aryl group Chemical group 0.000 description 1
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- 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 1
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- 229910000428 cobalt oxide Inorganic materials 0.000 description 1
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- 238000000354 decomposition reaction Methods 0.000 description 1
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- 229920002521 macromolecule Polymers 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
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- 150000004706 metal oxides Chemical class 0.000 description 1
- VYQNWZOUAUKGHI-UHFFFAOYSA-N monobenzone Chemical compound C1=CC(O)=CC=C1OCC1=CC=CC=C1 VYQNWZOUAUKGHI-UHFFFAOYSA-N 0.000 description 1
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- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 description 1
- QBDSZLJBMIMQRS-UHFFFAOYSA-N p-Cumylphenol Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=CC=C1 QBDSZLJBMIMQRS-UHFFFAOYSA-N 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920003192 poly(bis maleimide) Polymers 0.000 description 1
- 229920001955 polyphenylene ether Polymers 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 239000003223 protective agent Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000000523 sample Substances 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 229920002050 silicone resin Polymers 0.000 description 1
- 239000012453 solvate Substances 0.000 description 1
- 238000000807 solvent casting Methods 0.000 description 1
- 238000000935 solvent evaporation Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 1
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- QLAGHGSFXJZWKY-UHFFFAOYSA-N triphenylborane;triphenylphosphane Chemical compound C1=CC=CC=C1B(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 QLAGHGSFXJZWKY-UHFFFAOYSA-N 0.000 description 1
- HGBOYTHUEUWSSQ-UHFFFAOYSA-N valeric aldehyde Natural products CCCCC=O HGBOYTHUEUWSSQ-UHFFFAOYSA-N 0.000 description 1
- 150000003738 xylenes Chemical class 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/28—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42
-
- 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
- C08J5/24—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs
-
- 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
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
- C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K1/00—Printed circuits
- H05K1/02—Details
Abstract
The invention provides heat convertible resin of a dihydro-benzoxazine ring structure, a heat convertible resin composition with the heat convertible resin, a cured material, prepreg, a laminated board and a printed circuit board. The heat convertible resin of the dihydro-benzoxazine ring structure is mainly prepared from multifunctional phenol compounds shown by the general formula (I) and/or the general formula (II) and diamines compounds and aldehyde compounds (c) shown by the general formula (a) and/or the general formula (b) in a reaction mode. The heat convertible resin of the dihydro-benzoxazine ring structure is compounded through two different multifunctional phenol compounds and diamines compounds, the advantages of the two kinds of monomers are effectively combined, the disadvantages of the two kinds of monomers are overcome, and the obtained benzoxazine resin has the excellent combination performances of low dielectric performance and water-absorbing performance, high heat resistance and tenacity and the like.
Description
Technical field
The present invention relates to thermosetting resin, compositions of thermosetting resin, cured article, prepreg, veneer sheet and printed circuit board containing it.
Background technology
The high speed development of electronic information technology and consumer electronics, propose its characteristic dimension of new demand-make to multifunctional integrated circuit to reduce and higher integrated level, this demand must have more strict requirement to electronic package material: as developed the raw material resin etc. had compared with low-k and low-dielectric loss.
The thermosetting resins such as epoxy resin, resol, bimaleimide resin and unsaturated polyester resin have the excellent series of advantages such as water tolerance, chemical resistant properties, thermotolerance, physical strength, are thus widely used in electronic material is capable.But these thermosetting resins also exist many deficiencies: as resol can produce volatile by product at curing reaction, the poor fire of epoxy resin, and the cost of bimaleimide resin is more high.
Therefore, the novel structure resin of the continuous research and probe excellent combination property of people.Er hydrogen benzoxazine colophony (to be called for short lower benzoxazine) has a kind ofly been proved to be the thermosetting resin had compared with low-k, the specific inductivity of common benzoxazine is about 3.5, and it has the advantages such as good thermotolerance, flame retardant resistance and low water absorbable, this makes its having a extensive future at electronic package material field tool.The general structure formula of benzoxazine ring, such as formula shown in (1) and (2), does not have the generation of volatile component during its ring-opening polymerization solidification, therefore, and good stability of the dimension, good mechanical performance.
Although the dielectric properties of above-mentioned benzoxazine compound can meet comparatively harsh requirement, for the more high performance of electronics and parts in recent years, then have too many difficulties to cope with.Such as, for the resin material of the multilager base plate of formation IC encapsulation such as storer or theoretical treatment device (ICpackage), the requirement specific inductivity of 100MHz and lGHz at envrionment temperature 23 DEG C is be less than 3.5 and be less than less than 0.015 with the dielectric dissipation factor under condition, then existing benzoxazine colophony is more difficult meets.
CN102584884A discloses a kind of containing silicon benzoxazine colophony, its specific inductivity is low, high heat-resisting and owing to having introduced a large amount of flexible unit in molecular chain, such material is made to have good toughness, but this kind is complicated containing the synthetic method of silicon benzoxazine colophony, and cost is higher, be difficult to obtain industrial applications.
Benzoxazole structure containing PBO is incorporated in benzoxazine structure as essential groups by CN103059296A, has synthesized a kind of benzoxazine of novelty.Although this invention claims that this resin has second-order transition temperature and reaches 402 DEG C, and it reaches 62% at 800 DEG C of Residual carbon, and specific inductivity is 2.1-2.3, the numerical value of dielectric loss is lower than 0.003 etc. advantage.But this invention does not provide the data such as corresponding synthesis step and embodiment, be therefore difficult to judge its application prospect.
JP2005239827 proposes to have excellent heat resistance, high tenacity and flexual benzoxazine.But it is not owing to there is free OH base in this benzoxazine product, therefore very good in water absorbability, electrical characteristic.
Summary of the invention
Based on this, an object of the present invention is to provide a kind of benzoxazine thermosetting resin with excellent heat resistance, dielectric properties, toughness and low water absorbable.The compositions of thermosetting resin, cured article, prepreg, veneer sheet and the printed circuit board that there is provided containing above-mentioned thermosetting resin are provided.
To achieve these goals, present invention employs following technical scheme:
A kind of thermosetting resin with Er hydrogen benzoxazine ring structure, it is primarily of the multifunctional phenolic compound shown in general formula (I) and/or (II), and general formula (a) and/or the diamine compounds shown in (b) and aldehyde compound (c) reaction prepare:
Wherein, n
1, n
2, n
3and n
4be the integer of 0 ~ 10 all independently, such as 0,1,2,3,4,5,6,7,8 or 9, can be identical or different.In the present invention, consider the aspect of the thermotolerance of reactivity when above-mentioned thermosetting resin synthesizes, cured body, mechanical characteristic and dielectric characteristics, n
1, n
2, n
3and n
4be the integer of preferred 0-5 all independently.
What the present inventor carried out furtheing investigate found that, improves from the view point of thermotolerance, dielectric properties, toughness and water-absorbent, uses the manufacture method of the thermosetting resin of certain aromatic diamines and particular phenolic compounds to reach above-mentioned purpose.
As the aldehyde compound of (c) composition used in the present invention, there is no particular limitation, preferred formaldehyde, as this formaldehyde, can use under as forms such as the paraformaldehyde (paraformaldehyde) of its polymkeric substance or the formalin of aqueous solution form.When using paraformaldehyde, the carrying out of reaction is more stablized.In addition, as other aldehyde compound, acetaldehyde, propionic aldehyde or butyraldehyde etc. can also be used.
There is as preferred preparation the technical scheme of the thermosetting resin of Er hydrogen benzoxazine ring structure, except the multifunctional phenolic compound shown in general formula (I) and/or (II), general formula (a) and/or the diamine compounds shown in (b) and aldehyde compound (c) are outward, also can add the mono-functional phenols compounds shown in general formula (III), it can guarantee the processibilities such as solvability.
Above-mentioned mono-functional phenols compounds is the compound that side chain molecular weight is large, Z in general formula (III) is carbonatoms is more than 4, preferred carbonatoms is more than 6, and preferably carbonatoms is the organic group of 8-20 (such as 9,10,11,12,13,14,15,16,17,18 or 19) further.When carbonatoms increases, often free volume increase, specific inductivity reduce.
Preferably, containing heteroatoms in described organic group, described heteroatoms is N, O or F.
Preferably, in the mono-functional phenols compounds shown in general formula (III), substituting group Z is combined in contraposition relative to OH base key, and substituting group Z is any one in following structure:
Wherein, n
5be the integer of 0 ~ 10, such as 1,2,3,4,5,6,7,8 or 9.
Preferably, the aspect of the dielectric characteristicies such as the non-volatility under high temperature, specific inductivity and dielectric dissipation factor, above-mentioned substituting group Z is combined in contraposition relative to OH base key, and is any one in the group shown in following formula:
As the object lesson of above-mentioned mono-functional phenols compounds, 2-cyclohexylphenol, 4-cyclohexylphenol, 2-phenylphenol, 4-phenylphenol, 2-hydroxyl phenol, 4-benzylphenol, 2-dihydroxy benaophenonel, 4-dihydroxy benaophenonel, 4-HBA phenylester, 4-phenoxy phenyl, 3-benzyloxy phenol phenol, 4-benzyloxy phenol, 4-(1 can be enumerated, 1,3,3-tetramethyl butyl) mixture of any one or at least two kinds in phenol, 4-α-cumyl phenol, 4-adamantyl phenol or 4-trityl group phenol etc.
A kind of thermosetting resin, for having the thermosetting resin shown in following general formula (IV) with Er hydrogen benzoxazine ring structure.
In formula, X
1and X
2can be identical, also can not be identical, namely in above-mentioned general formula (IV), X
1and X
2for any one or two kinds of structures following:
N
6and n
7be the integer of 0 ~ 10, such as 1,2,3,4,5,6,7,8 or 9, can identical also can not be identical;
M is the integer of 2 ~ 15, such as 3,4,5,6,7,8,9,10,11,12,13 or 14.
Preferably, in the present invention, by above-mentioned multifunctional phenolic compound, diamine compounds and aldehyde compound in suitable solvent, the heating of mono-functional phenols compounds can be also had as required, makes it react.
There is no particular limitation for the solvent of described use, as raw material phenolic compound or diamine compounds and more easily obtain high-polymerization degree as the good person of structure adaptability of product.This kind solvent such as can enumerate the aromatic series such as toluene, dimethylbenzene series solvent, the halogen such as chloroform, methylene dichloride series solvent, the ether such as THF, dioxane series solvent etc.
Temperature of reaction, reaction times are not particularly limited, usually can it are made to react 10 minutes ~ 24 hours at the temperature about room temperature ~ 120 DEG C.In the present invention, 20 minutes-9 hours (such as 1 hour, 2 hours, 3 hours, 4 hours, 5 hours, 6 hours, 7 hours or 8 hours) are reacted particularly preferably under 30-110 DEG C (such as 40 DEG C, 50 DEG C, 60 DEG C, 70 DEG C, 80 DEG C, 90 DEG C or 100 DEG C), its reason is, the polymkeric substance reacted to showing thermosetting resin function of the present invention carries out.
From at high temperature and to produce for a long time unexpected macromolecule resin or three-dimensional cross-linked polymer under reaction and occur in be the aspect of amination, preferred reduction temperature of reaction or Reaction time shorten, and cannot synthesize under low temperature and the reaction of short period of time the fully large resin of molecular weight being suitable for applying in set out, preferably increase the reaction times or improve temperature of reaction.In addition, by the water produced when reacting removing to system be also the effective ways promoting to react outward.By adding the poor solvents such as such as a large amount of methyl alcohol in solution after the reaction, polymkeric substance can be made to separate out, be isolated, dry, then can obtain subject polymer.
In the present invention, mono-functional phenols compounds or multifunctional phenolic compound can also be added further.
At this, as the mono-functional phenols compounds that can add, above-mentioned mono-functional phenols compounds etc. can be enumerated, as multifunctional phenolic compound, above-mentioned multifunctional phenol can be enumerated, or 4,4'-bis-phenol, 2,2 '-bis-phenol, 4,4'-dihydroxydiphenyl ether, 2,2'-dihydroxydiphenyl ether, 4,4'-dihydroxydiphenyl methane, 2,2'--dihydroxydiphenyl methane, two (4-hydroxy phenyl) propane of 2,2-, 4,4'-dihydroxy benaophenonel, two (4-hydroxy phenyl) ethane of 1,1-, two (4-hydroxy phenyl) propane of 1,1-, two (4-hydroxy phenyl) butane of 1,1-, two (4-hydroxy phenyl) butane of 2,2-, two (4-the hydroxy phenyl)-2-methylpropane of 1,1-, two (4-hydroxy phenyl) cyclohexane of 1,1-, two (4-hydroxy phenyl) pentamethylene of 1,1-, two (4-the hydroxy phenyl)-1-diphenylphosphino ethane of 1,1-, two (4-hydroxy phenyl) ditan, two (4-hydroxy phenyl) fluorenes of 9,9-, two (4-hydroxy phenyl) HFC-236fa of 2,2-, two (4-hydroxyphenoxy) benzene of 1,3-, Isosorbide-5-Nitrae-bis-(3-hydroxyphenoxy) benzene or 2,6-(two (2-hydroxy phenyl) methyl) phenol etc.
Be explained, in the scope not damaging thermosetting resin characteristic of the present invention, monofunctional amines compounds, tri-functional amines compounds or other diamine compounds can also be used further.When using monofunctional amines compounds, can adjusting degree of polymerization, when using tri-functional amines compounds, the polymkeric substance with side chain can be obtained.In addition, by and with other diamine compounds, can physical property be adjusted.They can use with the diamine compounds shown in necessary general formula (a) He (b) in the present invention simultaneously, but consider reaction sequence, also can add in reaction system in more late, make it react.
Said structure can use IR, NMR, GC-MS and other method to identify.
Thermosetting resin of the present invention has the characteristic that thermotolerance is excellent especially, electrical characteristic are good, water-absorbent is low and fragility is significantly improved.
A kind of thermoset composition, it is at least containing thermosetting resin as above.
Thermoset composition of the present invention at least will contain aforesaid thermosetting resin.Thermoset composition of the present invention preferably contains above-mentioned thermosetting resin as principal constituent, such as, contain above-mentioned thermosetting resin as principal constituent, and can containing other thermosetting resin as minor component.
Other thermosetting resin as minor component such as can enumerate the mixture of any one or at least two kinds in epoxy system resin, thermohardening type modified polyphenylene ether resin, thermohardening type polyimide resin, silicone resin, melamine resin, urea-formaldehyde resin, acrylic resin, resol, unsaturated polyester resin, bismaleimides system resin, Synolac, furane resin, urethane resin or aniline resin etc.In above-mentioned thermosetting resin, from the view point of the thermotolerance that can improve the cured article formed by said composition further, the mixture of any one or at least two kinds in preferred epoxy system resin, resol or thermohardening type polyimide resin.
In addition, thermoset composition of the present invention preferably using having at least 1 in the molecule recorded at known document, preferably there is in molecule the compound of 2 Er hydrogen benzoxazines use as minor component.The compound at least in above-mentioned molecule with 1 dihydrobenzene oxazines can only use a kind, can also and use two or more.
In addition, thermoset composition of the present invention can also contain fire retardant as required, make ring agent, the various additive such as antioxidant (protective agent), thermo-stabilizer, photostabilizer, UV light absorber, lubricant, flame retardant, antistatic agent, antifogging agent, weighting agent, tenderizer, softening agent or tinting material.These additives may be used alone, can also and use two or more.
In addition, when preparing thermoset composition of the present invention, reactive or non-reacted solvent can also be used.Thermosetting resin of the present invention or compositions of thermosetting resin can be dissolved in organic solvent to be cast, and solvent seasoning is formed film like.Thermosetting resin of the present invention or the compositions of thermosetting resin composition that preferably solubleness is large in the organic solvents such as toluene.This is because, when carrying out in a solvent casting and forming film, there is following advantage, that is, quantity of solvent can be reduced, and when the amount of solvent is few, energy for solvent evaporation is little, and time of drying is short, does not have the attached effect of the foaming rapidly caused by drying.
A kind of cured article, is obtained by thermoset composition as above.
Cured article of the present invention is apply to having heat cured above-mentioned thermosetting resin or resin combination the material that heat solidifies.As its curing, known any curing can be used, in general can heat a few hours under about 120-300 DEG C, but Heating temperature is too low, heat-up time, time not enough, according to circumstances different had the situation that solidification becomes insufficient, physical strength is not enough.In addition, when Heating temperature is too high, heat-up time, time long, according to circumstances different had the situation that generation decomposition waits side reaction, physical strength poorly reduces.Therefore, the felicity condition of the characteristic corresponding to heat-curable compounds used is preferably selected.
In addition, when being cured, suitable curing catalyst can be added.As this curing catalyst, can use normally used any curing catalyst during the benzoxazine compound ring-opening polymerization of Er hydrogen, such as pyrocatechol can be enumerated, the multifunctional phenols such as dihydroxyphenyl propane, tosic acid, the sulphonic acids such as p-phenolsulfonic acid, phenylformic acid, Whitfield's ointment, oxalic acid, the carboxylic-acids such as hexanodioic acid, bore (II) acetic acid acyl acetone solvate, aluminium (III) acetylacetonate, the metal complexs such as cobalt (IV) acetylacetonate, calcium oxide, cobalt oxide, magnesium oxide, the metal oxides such as ferric oxide, calcium hydroxide, imidazole and its derivants, diazabicylo undecylene (diazabicycloundecene), tertiary amine and their salt such as Diazabicyclononene (diazabicyclononene), triphenylphosphine, triphenylphosphine quinone derivatives, triphenylphosphine triphenyl-boron, phosphorus series compound and the derivatives thereof such as tetraphenyl phosphine (tetraphenylphosphonium) tetraphenyl borate salts.These materials can be used alone, and can also mix two or more and use.
The addition of curing catalyst is not particularly limited, when addition is too much, the specific inductivity of cured article or dielectric dissipation factor rise, dielectric characteristics worsens, detrimentally affect is caused to mechanical properties, therefore in general preferred to be below 5 weight parts relative to above-mentioned thermosetting resin 100 weight part, to be more preferably the ratio of below 3 weight parts interpolation curing catalyst.
As mentioned above, the cured article of the present invention that the above-mentioned thermosetting resin so obtained or above-mentioned thermoset composition are formed, owing to having specific benzoxazine structure in polymer architecture, therefore can realize excellent dielectric characteristics.
In addition, due to the heat cured character that above-mentioned thermosetting resin or above-mentioned thermoset composition have, the excellences such as cured article reliability of the present invention, flame retardant resistance and plasticity, and glass transition temperature (Tg) is high, therefore also go for being applied with the position of stress or the material at movable position, and volatile by product can not be produced due to during polymerization, thus this volatile by product can not remain in cured article, also preferred on hygiene control.
A kind of prepreg, it comprises strongthener and by the above-mentioned resin of the dry postadhesion of impregnation on strongthener or resin combination, makes its semicure or do not make it solidify and obtain.
Prepreg of the present invention passes through above-mentioned thermosetting resin or contains its thermoset composition semicure or do not solidify and obtain.Here, " semicure " to refer to that when the solidification of thermosetting resin midway stops, and then can continue the state that is cured.
A kind of veneer sheet, is obtained by thermosetting resin as above.
A kind of veneer sheet, containing prepreg as above, is obtained by heating under vacuum lamination.
Veneer sheet of the present invention preferably can be applicable to the purposes such as printed circuit board, electronics and material thereof, the multilager base plate requiring dielectric properties excellence, copper-clad laminates.
A kind of printed circuit board, containing veneer sheet as above.
The printed circuit board that the present invention mentions refers in laminate surface of the present invention, to possess conductive layer and the substrate of terminal for being electrically connected possessing flexible substrate and so on, or is provided with the substrate etc. of IC element, resistance, electrical condenser, coil.
Compared to prior art, technical scheme of the present invention at least possesses following beneficial effect:
The present invention adopts two kinds of different multifunctional phenolic compounds and diamine compounds synthesis to have the thermosetting resin of Er hydrogen benzoxazine ring structure, effectively combine the advantage of two kinds of monomers, and overcome respective shortcoming, the benzoxazine colophony obtained has the excellent over-all properties such as low-dielectric energy, high heat-resisting, high tenacity and low water absorbable simultaneously, be specially: Td (5%) is 450 ~ 472 DEG C, Dk/Df (100MHz) for 2.82-2.92/0.0028-0.0034, Dk/Df (1GHz) be 2.80-2.87/0.0039-0.0051.
In addition, method of the present invention and the product obtained avoid the deficiency in the performance of the benzoxazine colophony adopting a kind of monomer synthesize, and tool synthetic method is feasible, has broad application prospects.
Embodiment
Technical scheme of the present invention is further illustrated below by embodiment.
Embodiment 1
(the preparation of 1) benzoxazine colophony
The mixture 26.21g altogether that mass ratio is the multifunctional phenolic compound represented by formula (I) and (II) of 1/1 is dropped in chloroform, mass ratio is the mixture 30.13g of the diamine compounds represented by formula (a) and (b) of 1/1, paraformaldehyde (medicine system pure with light, 94%) 8.05g (0.25mol), makes it react 6 hours under reflux removing the moisture produced while.Reacted solution is dropped in a large amount of methyl alcohol, product is separated out.Then filter product separation, wash with methyl alcohol.By dry for the product at reduced pressure through washing, thus obtain 50.78g using the benzoxazine compound of following structure as the thermosetting resin of principal constituent.It is 20500 that GPC records its molecular weight.
(2) preparation of cured article
The polymkeric substance utilizing hot pressurization step (1) to be obtained keeps 3 hours at 220 DEG C, obtains the sheet cured article that 0.5mm is thick.The cured body obtained is that brown is transparent, even, bendability is excellent.For obtained cured article, capacity plate antenna method is utilized to measure 23 DEG C, the specific inductivity of 100MHz and lGHz and dielectric dissipation factor.5% weight minimizing temperature (Td5) under utilizing TGA to evaluate air atmosphere under the heat-up rate of 10 DEG C/min.Show the result in table 1.
Embodiment 2
(the preparation of 1) benzoxazine colophony
The mixture 21.5g altogether that mass ratio is the multifunctional phenolic compound represented by formula (I) and (II) of 1/2 is dropped in chloroform, mass ratio is the mixture 66.68g of the diamine compounds represented by formula (a) and (b) of 2/1, paraformaldehyde (medicine system pure with light, 94%) 7.36g (0.22mol), makes it react 6 hours under reflux removing the moisture produced while.Reacted solution is dropped in a large amount of methyl alcohol, product is separated out.Then filter product separation, wash with methyl alcohol.By dry for the product at reduced pressure through washing, thus obtain 91.10g using the benzoxazine compound of following structure as the thermosetting resin of principal constituent.It is 16600 that GPC records its molecular weight.
(2) preparation of cured article
The polymkeric substance utilizing hot pressurization step (1) to be obtained keeps 3 hours at 220 DEG C, obtains the sheet cured article that 0.5mm is thick.The cured body obtained is that brown is transparent, even, bendability is excellent.For obtained cured article, capacity plate antenna method is utilized to measure 23 DEG C, the specific inductivity of 100MHz and lGHz and dielectric dissipation factor.5% weight minimizing temperature (Td5) under utilizing TGA to evaluate air atmosphere under the heat-up rate of 10 DEG C/min.Show the result in table 1.
Embodiment 3
(the preparation of 1) benzoxazine colophony
The mixture 16.12g altogether that mass ratio is the multifunctional phenolic compound represented by formula (I) and (II) of 2/1 is dropped in chloroform, the diamine compounds 49.77g represented by formula (a), paraformaldehyde (medicine system pure with light, 94%) 10.64g (0.32mol), makes it react 6 hours under reflux removing the moisture produced while.Reacted solution is dropped in a large amount of methyl alcohol, product is separated out.Then filter product separation, wash with methyl alcohol.By dry for the product at reduced pressure through washing, thus obtain 62.32g using the benzoxazine compound of following structure as the thermosetting resin of principal constituent.It is 17800 that GPC records its molecular weight.
(2) preparation of cured article
The polymkeric substance utilizing hot pressurization step (1) to be obtained keeps 3 hours at 220 DEG C, obtains the sheet cured article that 0.5mm is thick.The cured body obtained is that brown is transparent, even, bendability is excellent.For obtained cured article, capacity plate antenna method is utilized to measure 23 DEG C, the specific inductivity of 100MHz and lGHz and dielectric dissipation factor.5% weight minimizing temperature (Td5) under utilizing TGA to evaluate air atmosphere under the heat-up rate of 10 DEG C/min.Show the result in table 1.
Embodiment 4
(the preparation of 1) benzoxazine colophony
The mixture 14.33g altogether that mass ratio is the multifunctional phenolic compound represented by formula (I) and (II) of 1/3 is dropped in chloroform, the diamine compounds 41.46g represented by formula (b), paraformaldehyde (medicine system pure with light, 94%) 9.96g (0.30mol), makes it react 6 hours under reflux removing the moisture produced while.Reacted solution is dropped in a large amount of methyl alcohol, product is separated out.Then filter product separation, wash with methyl alcohol.By dry for the product at reduced pressure through washing, thus obtain 52.38g using the benzoxazine compound of following structure as the thermosetting resin of principal constituent.It is 20100 that GPC records its molecular weight.
(2) preparation of cured article
The polymkeric substance utilizing hot pressurization step (1) to be obtained keeps 3 hours at 220 DEG C, obtains the sheet cured article that 0.5mm is thick.The cured body obtained is that brown is transparent, even, bendability is excellent.For obtained cured article, capacity plate antenna method is utilized to measure 23 DEG C, the specific inductivity of 100MHz and lGHz and dielectric dissipation factor.5% weight minimizing temperature (Td5) under utilizing TGA to evaluate air atmosphere under the heat-up rate of 10 DEG C/min.Show the result in table 1.
Embodiment 5
(the preparation of 1) benzoxazine colophony
The multifunctional phenolic compound 10.75g represented by formula (I) is dropped in chloroform, the diamine compounds 31.50g represented by formula (a), paraformaldehyde (medicine system pure with light, 94%) 6.65g (0.2mol), makes it react 6 hours under reflux removing the moisture produced while.Reacted solution is dropped in a large amount of methyl alcohol, product is separated out.Then filter product separation, wash with methyl alcohol.By dry for the product at reduced pressure through washing, thus obtain 41.26g using the benzoxazine compound of following structure as the thermosetting resin of principal constituent.It is 18600 that GPC records its molecular weight.
(2) preparation of cured article
The polymkeric substance utilizing hot pressurization step (1) to be obtained keeps 3 hours at 220 DEG C, obtains the sheet cured article that 0.5mm is thick.The cured body obtained is that brown is transparent, even, bendability is excellent.For obtained cured article, capacity plate antenna method is utilized to measure 23 DEG C, the specific inductivity of 100MHz and lGHz and dielectric dissipation factor.5% weight minimizing temperature (Td5) under utilizing TGA to evaluate air atmosphere under the heat-up rate of 10 DEG C/min.Show the result in table 1.
Embodiment 6
(the preparation of 1) benzoxazine colophony
The multifunctional phenolic compound 18.5g represented by formula (II) is dropped in chloroform, the diamine compounds 55.40g represented by formula (a), paraformaldehyde (medicine system pure with light, 94%) 13.29g (0.4mol), makes it react 6 hours under reflux removing the moisture produced while.Reacted solution is dropped in a large amount of methyl alcohol, product is separated out.Then filter product separation, wash with methyl alcohol.By dry for the product at reduced pressure through washing, thus obtain 79.20g using the benzoxazine compound of following structure as the thermosetting resin of principal constituent.It is 16500 that GPC records its molecular weight.
(2) preparation of cured article
The polymkeric substance utilizing hot pressurization step (1) to be obtained keeps 3 hours at 220 DEG C, obtains the sheet cured article that 0.5mm is thick.The cured body obtained is that brown is transparent, even, bendability is excellent.For obtained cured article, capacity plate antenna method is utilized to measure 23 DEG C, the specific inductivity of 100MHz and lGHz and dielectric dissipation factor.5% weight minimizing temperature (Td5) under utilizing TGA to evaluate air atmosphere under the heat-up rate of 10 DEG C/min.Show the result in table 1.
Embodiment 7
(the preparation of 1) benzoxazine colophony
The multifunctional phenolic compound 21.50g represented by formula (I) is dropped in chloroform, mass ratio is the mixture 58.20g of the diamine compounds represented by formula (a) and (b) of 2/3, paraformaldehyde (medicine system pure with light, 94%) 13.29g (0.4mol), makes it react 6 hours under reflux removing the moisture produced while.Reacted solution is dropped in a large amount of methyl alcohol, product is separated out.Then filter product separation, wash with methyl alcohol.By dry for the product at reduced pressure through washing, thus obtain 85.00g using the benzoxazine compound of following structure as the thermosetting resin of principal constituent.It is 18500 that GPC records its molecular weight.
(2) preparation of cured article
The polymkeric substance utilizing hot pressurization step (1) to be obtained keeps 3 hours at 220 DEG C, obtains the sheet cured article that 0.5mm is thick.The cured body obtained is that brown is transparent, even, bendability is excellent.For obtained cured article, capacity plate antenna method is utilized to measure 23 DEG C, the specific inductivity of 100MHz and lGHz and dielectric dissipation factor.5% weight minimizing temperature (Td5) under utilizing TGA to evaluate air atmosphere under the heat-up rate of 10 DEG C/min.Show the result in table 1.
Embodiment 8
(the preparation of 1) benzoxazine colophony
The multifunctional phenolic compound 18.5g represented by formula (II) is dropped in chloroform, mass ratio is the mixture 58.20g of the diamine compounds represented by formula (a) and (b) of 2/3, paraformaldehyde (medicine system pure with light, 94%) 13.29g (0.4mol), makes it react 6 hours under reflux removing the moisture produced while.Reacted solution is dropped in a large amount of methyl alcohol, product is separated out.Then filter product separation, wash with methyl alcohol.By dry for the product at reduced pressure through washing, thus obtain 82g using the benzoxazine compound of following structure as the thermosetting resin of principal constituent.It is 19000 that GPC records its molecular weight.
(2) preparation of cured article
The polymkeric substance utilizing hot pressurization step (1) to be obtained keeps 3 hours at 220 DEG C, obtains the sheet cured article that 0.5mm is thick.The cured body obtained is that brown is transparent, even, bendability is excellent.For obtained cured article, capacity plate antenna method is utilized to measure 23 DEG C, the specific inductivity of 100MHz and lGHz and dielectric dissipation factor.5% weight minimizing temperature (Td5) under utilizing TGA to evaluate air atmosphere under the heat-up rate of 10 DEG C/min.Show the result in table 1.
Comparative example 1
(the preparation of 1) benzoxazine colophony
The mixture 14.33g altogether that mass ratio is the multifunctional phenolic compound represented by formula (I) and (II) of 1/1 is dropped in chloroform, 2, two [4-(4-amino-benzene oxygen) phenyl] propane (Tokyo changes into) 30.16g of 2-, paraformaldehyde (medicine system pure with light, 94%) 9.57g (0.29mol), makes it react 6 hours under reflux removing the moisture produced while.Reacted solution is dropped in a large amount of methyl alcohol, product is separated out.Then filter product separation, wash with methyl alcohol.By dry for the product at reduced pressure through washing, thus obtain 48.31g using the benzoxazine compound of following structure as the thermosetting resin of principal constituent.It is 20500 that GPC records its molecular weight.
(2) preparation of cured article
The polymkeric substance utilizing hot pressurization step (1) to be obtained keeps 3 hours at 220 DEG C, obtains the sheet cured article that 0.5mm is thick.The cured body obtained is that brown is transparent, even, bendability is excellent.For obtained cured article, capacity plate antenna method is utilized to measure 23 DEG C, the specific inductivity of 100MHz and lGHz and dielectric dissipation factor.5% weight minimizing temperature (Td5) under utilizing TGA to evaluate air atmosphere under the heat-up rate of 10 DEG C/min.Show the result in table 1.
Comparative example 2
(the preparation of 1) benzoxazine colophony
The mixture 14.33g altogether that mass ratio is the multifunctional phenolic compound represented by formula (I) and (II) of 1/1 is dropped in chloroform, dianiline M (Mitsui Chemicals) 24.81g, paraformaldehyde (medicine system pure with light, 94%) 9.57g (0.29mol), makes it react 6 hours under reflux removing the moisture produced while.Reacted solution is dropped in a large amount of methyl alcohol, product is separated out.Then filter product separation, wash with methyl alcohol.By dry for the product at reduced pressure through washing, thus obtain 42.96g using the benzoxazine compound of following structure as the thermosetting resin of principal constituent.It is 17000 that GPC records its molecular weight.
(2) preparation of cured article
The polymkeric substance utilizing hot pressurization step (1) to be obtained keeps 3 hours at 220 DEG C, obtains the sheet cured article that 0.5mm is thick.The cured body obtained is that brown is transparent, even, bendability is excellent.For obtained cured article, capacity plate antenna method is utilized to measure 23 DEG C, the specific inductivity of 100MHz and lGHz and dielectric dissipation factor.5% weight minimizing temperature (Td5) under utilizing TGA to evaluate air atmosphere under the heat-up rate of 10 DEG C/min.Show the result in table 1.
Comparative example 3
Utilize hot pressurization to be kept 3 hours at 220 DEG C by bisphenol-f type benzoxazine colophony, obtain the sheet cured article that 0.5mm is thick.The cured body obtained is that brown is transparent, even, bendability is excellent.For obtained cured article, capacity plate antenna method is utilized to measure 23 DEG C, the specific inductivity of 100MHz and lGHz and dielectric dissipation factor.5% weight minimizing temperature (Td5) under utilizing TGA to evaluate air atmosphere under the heat-up rate of 10 DEG C/min.Show the result in table 1.
Comparative example 4
Utilize hot pressurization to be kept 3 hours at 220 DEG C by bisphenol A-type benzoxazine colophony, obtain the sheet cured article that 0.5mm is thick.The cured body obtained is that brown is transparent, even, bendability is excellent.For obtained cured article, capacity plate antenna method is utilized to measure 23 DEG C, the specific inductivity of 100MHz and lGHz and dielectric dissipation factor.5% weight minimizing temperature (Td5) under utilizing TGA to evaluate air atmosphere under the heat-up rate of 10 DEG C/min.Show the result in table 1.
Comparative example 5
Utilize hot pressurization to be kept 3 hours at 220 DEG C by phenolphthalein type benzoxazine resin, obtain the sheet cured article that 0.5mm is thick.The cured body obtained is that brown is transparent, even, bendability is excellent.For obtained cured article, capacity plate antenna method is utilized to measure 23 DEG C, the specific inductivity of 100MHz and lGHz and dielectric dissipation factor.5% weight minimizing temperature (Td5) under utilizing TGA to evaluate air atmosphere under the heat-up rate of 10 DEG C/min.Show the result in table 1.
Table 1
| Dk/Df(100MHz) | Dk/Df(1GHz) | Td5％(℃) | |
| Embodiment 1 | 2.90/0.0028 | 2.84/0.0045 | 450 |
| Embodiment 2 | 2.92/0.0029 | 2.87/0.005 | 472 |
| Embodiment 3 | 2.88/0.0031 | 2.83/0.0039 | 455 |
| Embodiment 4 | 2.85/0.003 | 2.86/0.0048 | 467 |
| Embodiment 5 | 2.82/0.0034 | 2.80/0.0044 | 466 |
| Embodiment 6 | 2.87/0.003 | 2.86/0.0041 | 452 |
| Embodiment 7 | 2.89/0.0028 | 2.87/0.0051 | 471 |
| Embodiment 8 | 2.83/0.003 | 2.80/0.0049 | 469 |
| Comparative example 1 | 3.14/0.0053 | 3.12/0.0065 | 415 |
| Comparative example 2 | 3.11/0.0051 | 3.11/0.007 | 421 |
| Comparative example 3 | 3.32/0.0045 | 3.30/0.007 | 385 |
| Comparative example 4 | 3.28/0.006 | 3.30/0.008 | 392 |
| Comparative example 5 | 3.35/0.0065 | 3.36/0.008 | 388 |
As seen from the data in Table 1, embodiment 1-8 shows that the macromole benzoxazine colophony cured article that the multifunctional phenols by biphenyl structural (I) and polycyclopentadiene structure (II) of the present invention and the Diamines (a) of biphenyl structural and the Diamines (II) of polycyclopentadiene structure are obtained by reacting in the presence of aldehydes has good specific inductivity, dielectric dissipation factor, and has excellent thermotolerance.The benzoxazine colophony condensate performance using the amine of non-biphenyl structural or polycyclopentadiene structure (comparative example 1-2) to obtain then has certain gap, and common benzoxazine colophony (comparative example 3-5) is that dielectric properties or thermotolerance are all poor.
Benzoxazine colophony disclosed by the present invention and the resin combination containing this resin can not be widely used in veneer sheet, copper-clad plate and printed circuit board field, have larger productive value.
Applicant states, the present invention illustrates method detailed of the present invention by above-described embodiment, but the present invention is not limited to above-mentioned method detailed, does not namely mean that the present invention must rely on above-mentioned method detailed and could implement.Person of ordinary skill in the field should understand, any improvement in the present invention, to equivalence replacement and the interpolation of ancillary component, the concrete way choice etc. of each raw material of product of the present invention, all drops within protection scope of the present invention and open scope.
Claims (10)
1. one kind has the thermosetting resin of two hydrogen benzoxazine ring structures, it is primarily of the multifunctional phenolic compound shown in general formula (I) and/or (II), and general formula (a) and/or the diamine compounds shown in (b) and aldehyde compound (c) reaction prepare:
Wherein, n
1, n
2, n
3and n
4be the integer of 0 ~ 10 all independently, can be identical or different.
2. thermosetting resin as claimed in claim 1, is characterized in that, n
1, n
2, n
3and n
4be the integer of 0 ~ 5 all independently.
3. there is the manufacture method of the thermosetting resin of Er hydrogen benzoxazine ring structure as claimed in claim 1 or 2, it is characterized in that, except the multifunctional phenolic compound shown in general formula (I) and/or (II), general formula (a) and/or the diamine compounds shown in (b) and aldehyde compound (c), also add the mono-functional phenols compounds shown in general formula (III) outward:
Described mono-functional phenols compounds is the compound that side chain molecular weight is large, wherein, Z to be carbonatoms be more than 4 organic group;
Preferably, Z is carbonatoms is more than 6, and preferred carbonatoms is the organic group of 8-20;
Preferably, containing heteroatoms in described organic group, described heteroatoms is N, O or F;
Preferably, in the simple function group phenolic compound shown in described general formula (III), substituting group Z is combined in contraposition relative to OH base key, and substituting group Z is any one in following structure:
Wherein, n
5it is the integer of 0 ~ 10;
Preferably, substituting group Z is combined in contraposition relative to OH base key, and is any one in the group shown in following formula:
4. a thermosetting resin, for having the thermosetting resin with two hydrogen benzoxazine ring structures shown in following general formula (IV):
In formula, X
1and X
2can be identical, also can not be identical, X
1and X
2for any one or two kinds of structures following:
N
6and n
7be the integer of 0 ~ 10, can be identical, also can not be identical;
M is the integer of 2 ~ 15.
5. a thermoset composition, it is at least containing, for example the thermosetting resin one of claim 1-4 Suo Shu.
6. a cured article, obtains by making thermoset composition as claimed in claim 5 solidify.
7. a prepreg, it comprises strongthener and by the as claimed in claim 5 compositions of thermosetting resin of the dry postadhesion of impregnation on strongthener.
8. a veneer sheet, is obtained by the thermosetting resin as described in one of claim 1-4.
9. a veneer sheet, is obtained by prepreg as claimed in claim 7.
10. a printed circuit board, containing, for example the veneer sheet described in claim 8 or 9.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510848759.XA CN105348527B (en) | 2015-11-27 | 2015-11-27 | Thermosetting resin, the compositions of thermosetting resin containing it, solidfied material, prepreg, laminate and printed circuit board |
| PCT/CN2016/099120 WO2017088561A1 (en) | 2015-11-27 | 2016-09-14 | Thermosetting resin, thermosetting resin composition comprising same, cured material, prepreg, laminated board, and printed circuit board |
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|---|---|---|---|
| CN201510848759.XA CN105348527B (en) | 2015-11-27 | 2015-11-27 | Thermosetting resin, the compositions of thermosetting resin containing it, solidfied material, prepreg, laminate and printed circuit board |
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|---|---|
| CN105348527A true CN105348527A (en) | 2016-02-24 |
| CN105348527B CN105348527B (en) | 2017-11-21 |
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|---|---|---|---|
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|---|---|
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| WO (1) | WO2017088561A1 (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106079723A (en) * | 2016-06-24 | 2016-11-09 | 浙江大学宁波理工学院 | Flame-retardant modified ramie fabric/benzoxazine resins laminate and preparation method thereof |
| WO2017088561A1 (en) * | 2015-11-27 | 2017-06-01 | 广东生益科技股份有限公司 | Thermosetting resin, thermosetting resin composition comprising same, cured material, prepreg, laminated board, and printed circuit board |
| CN110073560A (en) * | 2016-12-19 | 2019-07-30 | Abb瑞士股份有限公司 | Lamination type multiphase busbar connector and the method for manufacturing it |
| CN113474387A (en) * | 2019-02-26 | 2021-10-01 | 长濑化成株式会社 | Cured product of curable material, method for producing cured product, and polymer composition |
| CN113583276A (en) * | 2021-08-27 | 2021-11-02 | 中国民用航空飞行学院 | Benzoxazine toughening modification preparation method |
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| JP2009242737A (en) * | 2008-03-31 | 2009-10-22 | Sekisui Chem Co Ltd | Thermosetting resin composition, its preparation, and copper plated laminate plate |
| CN105348527B (en) * | 2015-11-27 | 2017-11-21 | 广东生益科技股份有限公司 | Thermosetting resin, the compositions of thermosetting resin containing it, solidfied material, prepreg, laminate and printed circuit board |
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| JP2003064180A (en) * | 2001-06-11 | 2003-03-05 | Nippon Steel Chem Co Ltd | Curable resin having dihydrobenzoxazine ring structure and heat-resistant cured resin |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2017088561A1 (en) * | 2015-11-27 | 2017-06-01 | 广东生益科技股份有限公司 | Thermosetting resin, thermosetting resin composition comprising same, cured material, prepreg, laminated board, and printed circuit board |
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| CN106079723B (en) * | 2016-06-24 | 2018-08-31 | 浙江大学宁波理工学院 | Flame-retardant modified ramie fabric/benzoxazine colophony laminate and preparation method thereof |
| CN110073560A (en) * | 2016-12-19 | 2019-07-30 | Abb瑞士股份有限公司 | Lamination type multiphase busbar connector and the method for manufacturing it |
| CN113474387A (en) * | 2019-02-26 | 2021-10-01 | 长濑化成株式会社 | Cured product of curable material, method for producing cured product, and polymer composition |
| CN113583276A (en) * | 2021-08-27 | 2021-11-02 | 中国民用航空飞行学院 | Benzoxazine toughening modification preparation method |
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| Publication number | Publication date |
|---|---|
| CN105348527B (en) | 2017-11-21 |
| WO2017088561A1 (en) | 2017-06-01 |
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