CN105348527B - Thermosetting resin, the compositions of thermosetting resin containing it, solidfied material, prepreg, laminate and printed circuit board - Google Patents
Thermosetting resin, the compositions of thermosetting resin containing it, solidfied material, prepreg, laminate and printed circuit board Download PDFInfo
- Publication number
- CN105348527B CN105348527B CN201510848759.XA CN201510848759A CN105348527B CN 105348527 B CN105348527 B CN 105348527B CN 201510848759 A CN201510848759 A CN 201510848759A CN 105348527 B CN105348527 B CN 105348527B
- Authority
- CN
- China
- Prior art keywords
- thermosetting resin
- formula
- ring structures
- benzoxazine ring
- phenolic compound
- 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.)
- Expired - Fee Related
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- 229920005989 resin Polymers 0.000 title claims abstract description 86
- 239000011347 resin Substances 0.000 title claims abstract description 86
- 229920001187 thermosetting polymer Polymers 0.000 title claims abstract description 79
- 239000000463 material Substances 0.000 title claims abstract description 57
- 239000000203 mixture Substances 0.000 title claims abstract description 34
- -1 diamine compounds Chemical class 0.000 claims abstract description 44
- 150000002989 phenols Chemical class 0.000 claims abstract description 35
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 19
- 239000001257 hydrogen Substances 0.000 claims abstract description 19
- 238000006243 chemical reaction Methods 0.000 claims abstract description 17
- 150000001875 compounds Chemical class 0.000 claims description 17
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 7
- 229910052799 carbon Inorganic materials 0.000 claims description 7
- 125000001424 substituent group Chemical group 0.000 claims description 6
- 125000005842 heteroatom Chemical group 0.000 claims description 4
- 125000000962 organic group Chemical group 0.000 claims description 4
- 239000012779 reinforcing material Substances 0.000 claims description 4
- 229910052760 oxygen Inorganic materials 0.000 claims description 3
- 125000002485 formyl group Chemical class [H]C(*)=O 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 33
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 8
- 230000015572 biosynthetic process Effects 0.000 abstract description 6
- 238000003786 synthesis reaction Methods 0.000 abstract description 5
- 239000000178 monomer Substances 0.000 abstract description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 63
- 238000002360 preparation method Methods 0.000 description 23
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 22
- 238000000034 method Methods 0.000 description 19
- 229920000642 polymer Polymers 0.000 description 17
- 229930040373 Paraformaldehyde Natural products 0.000 description 13
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 13
- 239000012298 atmosphere Substances 0.000 description 13
- 238000011156 evaluation Methods 0.000 description 13
- 229920002866 paraformaldehyde Polymers 0.000 description 13
- 230000000052 comparative effect Effects 0.000 description 12
- 238000010438 heat treatment Methods 0.000 description 12
- 239000002904 solvent Substances 0.000 description 12
- 230000006870 function Effects 0.000 description 11
- 239000000243 solution Substances 0.000 description 11
- 239000003814 drug Substances 0.000 description 10
- 238000005406 washing Methods 0.000 description 10
- 125000004203 4-hydroxyphenyl group Chemical group [H]OC1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 9
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 8
- 238000010992 reflux Methods 0.000 description 8
- 239000000126 substance Substances 0.000 description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 description 6
- 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
- 150000004985 diamines Chemical class 0.000 description 5
- 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 5
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 239000004615 ingredient Substances 0.000 description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 4
- 229920001568 phenolic resin Polymers 0.000 description 4
- 239000005011 phenolic resin Substances 0.000 description 4
- 239000001294 propane Substances 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-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
- 239000004305 biphenyl Substances 0.000 description 3
- 235000010290 biphenyl Nutrition 0.000 description 3
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical class OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 230000007812 deficiency Effects 0.000 description 3
- 230000005611 electricity Effects 0.000 description 3
- 238000005213 imbibition Methods 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
- 230000035484 reaction time Effects 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
- 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
- ZTQSAGDEMFDKMZ-UHFFFAOYSA-N Butyraldehyde Chemical compound CCCC=O ZTQSAGDEMFDKMZ-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
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 2
- NBBJYMSMWIIQGU-UHFFFAOYSA-N Propionic aldehyde Chemical compound CCC=O NBBJYMSMWIIQGU-UHFFFAOYSA-N 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 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
- 239000001273 butane Substances 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000003822 epoxy resin Substances 0.000 description 2
- 239000003063 flame retardant Substances 0.000 description 2
- 230000009477 glass transition Effects 0.000 description 2
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 2
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-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
- 238000007151 ring opening polymerisation reaction Methods 0.000 description 2
- YGSDEFSMJLZEOE-UHFFFAOYSA-N salicylic acid Chemical compound OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 238000010189 synthetic method Methods 0.000 description 2
- 229920006337 unsaturated polyester resin Polymers 0.000 description 2
- 0 *CCC=CC=CC(P1COC(C=CCC2)=C2C1)=* Chemical compound *CCC=CC=CC(P1COC(C=CCC2)=C2C1)=* 0.000 description 1
- 125000000355 1,3-benzoxazolyl group Chemical group O1C(=NC2=C1C=CC=C2)* 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical group C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-N 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
- DIZBQMTZXOUFTD-UHFFFAOYSA-N 2-(furan-2-yl)-3h-benzimidazole-5-carboxylic acid Chemical class N1C2=CC(C(=O)O)=CC=C2N=C1C1=CC=CO1 DIZBQMTZXOUFTD-UHFFFAOYSA-N 0.000 description 1
- MVRPPTGLVPEMPI-UHFFFAOYSA-N 2-cyclohexylphenol Chemical class OC1=CC=CC=C1C1CCCCC1 MVRPPTGLVPEMPI-UHFFFAOYSA-N 0.000 description 1
- ZMLHBBXPXZXTSP-UHFFFAOYSA-N 2-fluoropropane Chemical compound C[C](C)F ZMLHBBXPXZXTSP-UHFFFAOYSA-N 0.000 description 1
- 150000005351 2-phenylphenols Chemical class 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
- FOTVZLOJAIEAOY-UHFFFAOYSA-N 3-phenylmethoxyphenol Chemical class OC1=CC=CC(OCC=2C=CC=CC=2)=C1 FOTVZLOJAIEAOY-UHFFFAOYSA-N 0.000 description 1
- HJSPWKGEPDZNLK-UHFFFAOYSA-N 4-benzylphenol Chemical class C1=CC(O)=CC=C1CC1=CC=CC=C1 HJSPWKGEPDZNLK-UHFFFAOYSA-N 0.000 description 1
- OAHMVZYHIJQTQC-UHFFFAOYSA-N 4-cyclohexylphenol Chemical class C1=CC(O)=CC=C1C1CCCCC1 OAHMVZYHIJQTQC-UHFFFAOYSA-N 0.000 description 1
- ZYUVGYBAPZYKSA-UHFFFAOYSA-N 5-(3-hydroxybutan-2-yl)-4-methylbenzene-1,3-diol Chemical compound CC(O)C(C)C1=CC(O)=CC(O)=C1C ZYUVGYBAPZYKSA-UHFFFAOYSA-N 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 1
- 239000005711 Benzoic acid Substances 0.000 description 1
- 229930185605 Bisphenol Natural products 0.000 description 1
- JHMKSWHTELMUGO-UHFFFAOYSA-N C1(=NNCCCCCC1)C1=CCCCCCCC1.C1(=NNCCCCCC1)C1=CCCCCCCC1 Chemical compound C1(=NNCCCCCC1)C1=CCCCCCCC1.C1(=NNCCCCCC1)C1=CCCCCCCC1 JHMKSWHTELMUGO-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N Furan Chemical compound C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 239000004640 Melamine resin Substances 0.000 description 1
- 229920000877 Melamine resin Polymers 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
- DLKQCLIBMWAKOH-UHFFFAOYSA-N [Co+4] Chemical compound [Co+4] DLKQCLIBMWAKOH-UHFFFAOYSA-N 0.000 description 1
- IKHGUXGNUITLKF-XPULMUKRSA-N acetaldehyde Chemical compound [14CH]([14CH3])=O IKHGUXGNUITLKF-XPULMUKRSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 125000002252 acyl group Chemical group 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 229920000180 alkyd Polymers 0.000 description 1
- REDXJYDRNCIFBQ-UHFFFAOYSA-N aluminium(3+) Chemical compound [Al+3] REDXJYDRNCIFBQ-UHFFFAOYSA-N 0.000 description 1
- 238000005576 amination reaction Methods 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 150000004984 aromatic diamines Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 235000010233 benzoic acid Nutrition 0.000 description 1
- IMHDGJOMLMDPJN-UHFFFAOYSA-N biphenyl-2,2'-diol Chemical compound OC1=CC=CC=C1C1=CC=CC=C1O IMHDGJOMLMDPJN-UHFFFAOYSA-N 0.000 description 1
- VCCBEIPGXKNHFW-UHFFFAOYSA-N biphenyl-4,4'-diol Chemical compound C1=CC(O)=CC=C1C1=CC=C(O)C=C1 VCCBEIPGXKNHFW-UHFFFAOYSA-N 0.000 description 1
- YXVFYQXJAXKLAK-UHFFFAOYSA-N biphenyl-4-ol Chemical class C1=CC(O)=CC=C1C1=CC=CC=C1 YXVFYQXJAXKLAK-UHFFFAOYSA-N 0.000 description 1
- 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
- 150000001642 boronic acid derivatives Chemical class 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- 239000003990 capacitor Substances 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- STLZCUYBVPNYED-UHFFFAOYSA-N chlorbetamide Chemical compound OCCN(C(=O)C(Cl)Cl)CC1=CC=C(Cl)C=C1Cl STLZCUYBVPNYED-UHFFFAOYSA-N 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 229910000428 cobalt oxide Inorganic materials 0.000 description 1
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- NHADDZMCASKINP-HTRCEHHLSA-N decarboxydihydrocitrinin Natural products C1=C(O)C(C)=C2[C@H](C)[C@@H](C)OCC2=C1O NHADDZMCASKINP-HTRCEHHLSA-N 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 1
- 125000006840 diphenylmethane group Chemical class 0.000 description 1
- 239000012776 electronic material Substances 0.000 description 1
- 238000004100 electronic packaging Methods 0.000 description 1
- WUOIAOOSKMHJOV-UHFFFAOYSA-N ethyl(diphenyl)phosphane Chemical class C=1C=CC=CC=1P(CC)C1=CC=CC=C1 WUOIAOOSKMHJOV-UHFFFAOYSA-N 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 150000002220 fluorenes Chemical class 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 235000011194 food seasoning agent Nutrition 0.000 description 1
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 239000012760 heat stabilizer Substances 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 125000004464 hydroxyphenyl group Chemical group 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000004611 light stabiliser Substances 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- HZVOZRGWRWCICA-UHFFFAOYSA-N methanediyl Chemical compound [CH2] HZVOZRGWRWCICA-UHFFFAOYSA-N 0.000 description 1
- VYQNWZOUAUKGHI-UHFFFAOYSA-N monobenzone Chemical class C1=CC(O)=CC=C1OCC1=CC=CC=C1 VYQNWZOUAUKGHI-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N o-dimethylbenzene Natural products CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 235000010292 orthophenyl phenol Nutrition 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 239000001301 oxygen Substances 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
- 239000005022 packaging material Substances 0.000 description 1
- FJKROLUGYXJWQN-UHFFFAOYSA-N papa-hydroxy-benzoic acid Natural products OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 description 1
- RGSFGYAAUTVSQA-UHFFFAOYSA-N pentamethylene Natural products C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 description 1
- 125000004817 pentamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- GJLNWLVPAHNBQN-UHFFFAOYSA-N phenyl 4-hydroxybenzoate Chemical compound C1=CC(O)=CC=C1C(=O)OC1=CC=CC=C1 GJLNWLVPAHNBQN-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
- 125000004193 piperazinyl group Chemical group 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920003192 poly(bis maleimide) Polymers 0.000 description 1
- 229920001955 polyphenylene ether Polymers 0.000 description 1
- 229920005749 polyurethane resin Polymers 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 229960004889 salicylic acid Drugs 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
- 239000012453 solvate Substances 0.000 description 1
- 238000000935 solvent evaporation Methods 0.000 description 1
- 230000035882 stress Effects 0.000 description 1
- 150000003512 tertiary amines Chemical class 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
- MXSVLWZRHLXFKH-UHFFFAOYSA-N triphenylborane Chemical compound C1=CC=CC=C1B(C=1C=CC=CC=1)C1=CC=CC=C1 MXSVLWZRHLXFKH-UHFFFAOYSA-N 0.000 description 1
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 1
- HGBOYTHUEUWSSQ-UHFFFAOYSA-N valeric aldehyde Natural products CCCCC=O HGBOYTHUEUWSSQ-UHFFFAOYSA-N 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
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- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
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- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
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Abstract
The invention provides a kind of thermosetting resin, the compositions of thermosetting resin containing it, solidfied material, prepreg, laminate and printed circuit board with Er hydrogen benzoxazine ring structures.The thermosetting resin with Er hydrogen benzoxazine ring structures,, mainly as leading to formula (I) and/or the multifunctional phenolic compound shown in (II), formula (a) and/or diamine compounds shown in (b) and aldehyde compound (c) reaction are prepared for it.The present invention is using the two kinds of different thermosetting resins of multifunctional phenolic compound and diamine compounds synthesis with Er hydrogen benzoxazine ring structures, effective the advantages of combining two kinds of monomers, and the shortcomings that respective is overcome, obtained benzoxazine colophony while there is the excellent combination property of low-dielectric energy, high heat-resisting, high tenacity and low water absorbable etc..
Description
Technical field
The present invention relates to thermosetting resin, the compositions of thermosetting resin containing it, solidfied material, prepreg, laminate with
And printed circuit board.
Background technology
The high speed development of electronic information technology and consumer electronics, new demand-make is proposed to multifunctional integrated circuit
Its characteristic size reduces and higher integrated level, this demand necessarily have more strict requirements to electronic package material：Such as
Exploitation has compared with raw material resin of low-k and low-dielectric loss etc..
The thermosetting resins such as epoxy resin, phenolic resin, bimaleimide resin and unsaturated polyester resin have excellent
The series of advantages such as different water resistance, chemical resistance, heat resistance, mechanical strength, thus obtained in electronic material row comes wide
General application.But there is many deficiencies for these thermosetting resins：As phenolic resin can produce in curing reaction it is volatile
Accessory substance, the poor fire of epoxy resin, and the cost of bimaleimide resin is higher etc..
Therefore, the novel structure resin of the continuous research and probe excellent combination property of people.Er hydrogen benzoxazine colophonies are (with letter
Claim lower benzoxazine) it is a kind of thermosetting resin for being proved to have compared with low-k, the dielectric of common benzoxazine is normal
Number is 3.5 or so, and it has the advantages that good heat resistance, anti-flammability and low water absorbable, and this causes it in Electronic Packaging material
Material field tool has a extensive future.Shown in the general structure formula such as formula (1) of benzoxazine ring and (2), its ring-opening polymerisation solidification
When there is no the generation of volatile ingredient, therefore, good stability of the dimension, good mechanical performance.
Although the dielectric properties of above-mentioned benzoxazine compound can meet more harsh requirement, near
The higher performance of electronic equipment and part over year, then it is awkward.Such as forming memory or theoretical treatment device
For resin material etc. the multilager base plate of IC package (IC package), 100MHz the and l GHz at 23 DEG C of environment temperature
Requirement dielectric constant be less than less than 0.015 for the dielectric dissipation factor less than 3.5 and with the conditions of, then existing Ben Bing Evil
The more difficult satisfaction of piperazine resin.
The A of CN 102584884 disclose a kind of benzoxazine colophony containing silicon, its dielectric constant is low, height is heat-resisting and due to
Substantial amounts of flexible unit is introduced in strand so that such material has preferable toughness, but such a benzoxazine containing silicon tree
The synthetic method of fat is complicated, and cost is higher, it is difficult to obtains industrial applications.
Benzoxazole structure containing PBO is incorporated into benzoxazine structure by the A of CN 103059296 as essential groups,
A kind of novel benzoxazine is synthesized.Although the invention claims that the resin has glass transition temperature up to 402 DEG C, and its
In 800 DEG C of Residual carbons up to 62%, dielectric constant 2.1-2.3, the advantages that numerical value of dielectric loss is less than 0.003 grade.But the hair
It is bright that the data such as corresponding synthesis step and embodiment are not provided, therefore be difficult to be applied to prospect to be judged.
JP2005239827 proposes the benzoxazine with excellent heat resistance, high tenacity and pliability.But the Ben Bing Evil
Due to free OH bases be present in piperazine product, thus it is not very good in terms of hygroscopicity, electrical characteristics.
The content of the invention
Based on this, an object of the present invention, which is to provide, a kind of has excellent heat resistance, dielectric properties, toughness and low
The benzoxazine thermosetting resin of water imbibition.Another object of the present invention is to provide the thermosetting containing above-mentioned thermosetting resin
Resin combination, solidfied material, prepreg, laminate and printed circuit board.
To achieve these goals, present invention employs following technical scheme：
A kind of thermosetting resin with two hydrogen benzoxazine ring structures, it is mainly as shown in logical formula (I) and/or (II)
Multifunctional phenolic compound, formula (a) and/or diamine compounds shown in (b) and aldehyde compound (c) reaction are prepared into
Arrive：
Wherein, n1、n2、n3And n4It independently is 0~10 integer, such as 0,1,2,3,4,5,6,7,8 or 9, Ke Yixiang
It is same or different.In the present invention, reactivity, the heat resistance of firming body, mechanical characteristic when considering the synthesis of above-mentioned thermosetting resin and
The aspect of dielectric property, n1、n2、n3And n4It independently is preferred 0-5 integer.
The result that the present inventor is furtherd investigate is found, is improved from heat resistance, dielectric properties, toughness and water imbibition
Viewpoint is set out, and can be reached using the manufacture method of certain aromatic diamines and the thermosetting resin of particular phenolic compounds above-mentioned
Purpose.
As the aldehyde compound of (c) composition used in the present invention, there is no particular limitation, preferably formaldehyde, is used as this
Formaldehyde, can be in the shape such as the paraformaldehyde (paraformaldehyde) as its polymer or the formalin of aqueous solution form
Used under state.During using paraformaldehyde, the progress of reaction is more stable.In addition, as other aldehyde compounds, can also make
With acetaldehyde, propionic aldehyde or butyraldehyde etc..
As the preferable technical scheme for preparing the thermosetting resin with two hydrogen benzoxazine ring structures, except logical formula (I)
And/or the multifunctional phenolic compound shown in (II), formula (a) and/or diamine compounds and aldehyde compound shown in (b)
(c) outside, the simple function phenolic compound shown in logical formula (III) can be also added, it can ensure that the processabilities such as dissolubility.
Above-mentioned simple function phenolic compound is the big compound of side chain molecular weight, and the Z led in formula (III) is that carbon number is
More than 4, preferably carbon number be more than 6, further preferred carbon number be 8-20 (such as 9,10,11,12,13,14,15,
16th, 17,18 or organic group 19).When carbon number increases, often free volume increase, dielectric constant reduce.
Preferably, hetero atom is contained in the organic group, the hetero atom is N, O or F.
Preferably, in the simple function phenolic compound shown in logical formula (III), substituent Z is bonded in pair relative to OH bases
Position, and substituent Z is any one in following structure：
Wherein, n5For 0~10 integer, such as 1,2,3,4,5,6,7,8 or 9.
Preferably, from the dielectric property aspect such as the fixedness under high temperature, dielectric constant and dielectric dissipation factor,
Above-mentioned substituent Z is bonded in contraposition relative to OH bases, and is any one in the group shown in following formula：
As the specific example of above-mentioned simple function phenolic compound, can enumerate 2- cyclohexylphenols, 4- cyclohexylphenols,
2- phenylphenols, 4- phenylphenols, 2- hydroxyl phenols, 4- benzylphenols, 2- dihydroxy benaophenonels, 4- dihydroxy benaophenonels, 4-
Hydroxybenzoic acid phenylester, 4- phenoxy phenyls, 3- benzyloxy phenols phenol, 4- benzyloxy phenols, 4- (1,1,3,3- tetramethyl fourths
Base) in phenol, 4- α-cumyl phenol, 4- adamantyls phenol or 4- trityl group phenol etc. any one or at least two
The mixture of kind.
A kind of thermosetting resin, for the thermosetting tree with two hydrogen benzoxazine ring structures shown in following logical formula (IV)s
Fat.
In formula, X1And X2Can be identical, it can also differ, i.e., in above-mentioned logical formula (IV), X1And X2To be following any
Or two kinds of structures：
n6And n7For 0~10 integer, such as 1,2,3,4,5,6,7,8 or 9, identical can also differ；
M is 2~15 integer, such as 3,4,5,6,7,8,9,10,11,12,13 or 14.
Preferably, in the present invention, can be in appropriate solvent by above-mentioned multifunctional phenolic compound, Diamines chemical combination
Thing and aldehyde compound, there is the heating of simple function phenolic compound as needed, make its reaction.
There is no particular limitation for the solvent used, as the phenolic compound or diamine compounds of raw material and conduct
The favorable solubility person of the polymer of product is more easy to obtain high polymerization degree.Such solvent is such as can enumerate toluene, dimethylbenzene
Ether series solvents such as the halogen system solvent such as fragrant family solvent, chloroform, dichloromethane, THF, dioxane etc..
Reaction temperature, reaction time are not particularly limited, generally can make it at a temperature of room temperature~120 DEG C or so
Reaction 10 minutes~24 hours or so.In the present invention, particularly preferably 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) under react -9 hours 20 minutes (such as 1 hour, 2 hours, 3 hours, 4 hours, 5 hours, 6 hours, it is 7 small
When or 8 hours), the reason is that react to can show the present invention thermosetting resin function polymer carry out.
Unexpected macromolecule resin or three-dimensional cross-linked height can be produced under high temperature and prolonged reaction
Molecule and occur to set out in terms of being amination, preferably reduce reaction temperature or shorten the reaction time, and in low temperature and in short-term
Between reaction under can not synthesize the molecular weight fully big resin suitable for coating in terms of set out, preferably increase the reaction time or carry
High reaction temperature.In addition, caused water when reacting is removed to system outside and promotes the effective ways of reaction.By anti-
The poor solvent such as substantial amounts of methanol is added in solution after answering, polymer can be separated out, is isolated, dries, then may be used
Obtain subject polymer.
In the present invention, simple function phenolic compound or multifunctional phenolic compound can also further be added.
Here, as the simple function phenolic compound that can be added, above-mentioned simple function phenolic compound etc. can be enumerated, is made
For multifunctional phenolic compound, above-mentioned multifunctional phenol or 4,4'- bis-phenol, 2,2 '-bis-phenol, 4,4'- dihydroxy two can be enumerated
Phenyl ether, 2,2'- dihydroxydiphenyl ethers, 4,4'- dihydroxydiphenyls methane, 2,2'-- dihydroxydiphenyls methane, 2,2-
Double (4- hydroxy phenyls) ethane of double (4- hydroxy phenyls) propane, 4,4'- dihydroxy benaophenonels, 1,1-, double (the 4- hydroxy benzenes of 1,1-
Base) propane, double (4- hydroxy phenyls) butane of 1,1-, double (4- hydroxy phenyls) butane of 2,2-, double (4- the hydroxy phenyls) -2- first of 1,1-
Double (4- hydroxy phenyls) thiacyclohexanes of base propane, 1,1-, double (4- hydroxy phenyls) pentamethylene of 1,1-, 1,1- double (4- hydroxy phenyls)-
Double (4- hydroxy phenyls) fluorenes of 1- diphenylphosphino ethanes, double (4- hydroxy phenyls) diphenyl methanes, 9,9-, double (the 4- hydroxy phenyls) six of 2,2-
Fluoro-propane, 1,3- double (4- hydroxyphenoxies) benzene, Isosorbide-5-Nitrae-bis- (3- hydroxyphenoxies) benzene or 2,6- (double (2- hydroxy phenyls) first
Base) phenol etc..
It is explained, in the range of thermosetting resin characteristic of the present invention is not damaged, can also further uses simple function
Aminated compounds, trifunctional aminated compounds or other diamine compounds., can be with during using simple function aminated compounds
The degree of polymerization is adjusted, during using trifunctional aminated compounds, the polymer with side chain can be obtained.In addition, by and with other
Diamine compounds, physical property can be adjusted.They can be with the Diamines shown in necessary formula (a) and (b) in the present invention
Compound uses simultaneously, but considers reaction sequence, can also be added in reaction system later when, makes its reaction.
Said structure can be identified using IR, NMR, GC-MS and other methods.
The thermosetting resin of the present invention has that heat resistance is especially excellent, electrical characteristics are good, water imbibition is low and fragility is big
The characteristic improved greatly.
A kind of thermoset composition, it at least contains thermosetting resin as described above.
The thermoset composition of the present invention will at least contain foregoing thermosetting resin.The thermoset composition of the present invention is excellent
Choosing contains above-mentioned thermosetting resin as principal component, such as contains above-mentioned thermosetting resin as principal component, and can contain other
Thermosetting resin as accessory ingredient.
Other thermosetting resins as accessory ingredient can for example enumerate epoxy system resin, thermohardening type is modified polyphenylene
Ether resin, thermohardening type polyimide resin, organic siliconresin, melamine resin, Lauxite, acrylic resin, phenolic resin,
In unsaturated polyester resin, bismaleimide amine system resin, alkyd resin, furane resins, polyurethane resin or anline resin etc.
Any one or at least two mixture.In above-mentioned thermosetting resin, from can further improve by said composition
From the viewpoint of the heat resistance of the solidfied material of formation, preferably epoxy system resin, phenolic resin or thermohardening type polyimide resin
In any one or at least two mixture.
In addition, the intramolecular recorded in known document is preferably had at least one, preferably by the thermoset composition of the present invention
The compound that intramolecular has 2 Er hydrogen benzoxazines uses as accessory ingredient.Above-mentioned intramolecular at least there is 1 dihydrobenzene to dislike
The compound of piperazine can be used only a kind, and can also use two or more.
In addition, the present invention thermoset composition can also contain as needed fire retardant, make ring agent, antioxidant (prevent
Aging agent), heat stabilizer, light stabilizer, ultra-violet absorber, lubricant, flame retardant, antistatic agent, antifoggant, filling
The various additives such as agent, softening agent, plasticizer or colouring agent.These additives may be used alone, can also and with 2
More than kind.
In addition, when preparing the thermoset composition of the present invention, reactive or non-reacted solvent can also be used.This hair
Bright thermosetting resin or compositions of thermosetting resin, which can be dissolved in organic solvent, to be cast, and solvent seasoning is formed
Film-form.Thermosetting resin or the compositions of thermosetting resin big group of solubility preferably in the organic solvents such as toluene of the present invention
Compound.This is because, when being cast in a solvent and forming film, have the following advantages that, i.e. quantity of solvent can be reduced,
And solvent amount it is few when, small for the energy required for solvent evaporation, drying time is short, caused by rapidly drying
Foaming attached effect.
A kind of solidfied material, obtained by thermoset composition as described above.
The solidfied material of the present invention is to consolidating with heat cured above-mentioned thermosetting resin or resin combination application heat
The material of change.As its curing, known any curing can be used, in general can be in 120-300
DEG C or so under be heated for a period of hours, but when heating-up temperature is too low, the heat time is insufficient, according to circumstances difference has solidification to become not
Fully, the situation of mechanical strength deficiency.In addition, when heating-up temperature is too high, the heat time is long, according to circumstances difference has generation
The situation that side reaction, the mechanical strengths such as decomposition poorly reduce.It is therefore preferable that selection corresponds to the spy of heat-curable compounds used
The felicity condition of property.
In addition, when being solidified, appropriate curing accelerator can be added.As the curing accelerator, can use will
Usually used any curing accelerator during Er hydrogen benzoxazine compound ring-opening polymerisations, such as catechol, double can be enumerated
The carboxylic acid such as sulphonic acids, benzoic acid, salicylic acid, oxalic acid, adipic acid such as the multifunctional phenols such as phenol A, p-methyl benzenesulfonic acid, p-phenolsulfonic acid
Class, bore the metal complexs such as (II) acetic acid acyl acetone solvate, aluminium (III) acetylacetonate, cobalt (IV) acetylacetonate, oxygen
Change the metal oxides such as calcium, cobalt oxide, magnesia, iron oxide, calcium hydroxide, imidazole and its derivants, diazabicylo 11
The tertiary amines such as carbene (diazabicycloundecene), Diazabicyclononene (diazabicyclononene) and they
Salt, triphenylphosphine, triphenylphosphine quinone derivatives, triphenylphosphine triphenyl borine, tetraphenyl phosphine
(tetraphenylphosphonium) phosphorus series compound such as tetraphenyl borate salts and its derivative.These materials can individually make
With two or more use can also be mixed.
The addition of curing accelerator is not particularly limited, when addition is excessive, the dielectric constant or dielectric of solidfied material
Loss factor rises, and dielectric property deteriorates, and mechanical properties are had undesirable effect, therefore in general preferably with relative to above-mentioned
The parts by weight of thermosetting resin 100 are that the ratio below 5 parts by weight, more preferably below 3 parts by weight adds curing accelerator.
As described above, of the invention consolidating of being formed of the above-mentioned thermosetting resin or above-mentioned thermoset composition that so obtain
Compound can realize excellent dielectric property due to having specific benzoxazine structure in polymer architecture.
Further, since heat cured property possessed by above-mentioned thermosetting resin or above-mentioned thermoset composition, the present invention
Solidfied material reliability, anti-flammability and formability etc. it is excellent, and glass transition temperature (Tg) is high, therefore is readily applicable to apply
The material at the position of stress or movable position, and due to during polymerization volatile accessory substance, thus this volatilization will not be produced
The accessory substance of property will not be remained in solidfied material, on administration of health it is also preferred that.
A kind of prepreg, it include reinforcing material and by be impregnated with dry after be attached to above-mentioned resin on reinforcing material or
Resin combination, make its semi-solid preparation or it is solidified and is obtained.
The prepreg of the present invention passes through by above-mentioned thermosetting resin or thermoset composition semi-solid preparation containing it or not solid
Change and obtain.Here, " semi-solid preparation " refers to that midway stops in the solidification of thermosetting resin, and then can continue to the shape being cured
State.
A kind of laminate, obtained by thermosetting resin as described above.
A kind of laminate, containing prepreg as described above, it is laminated by heating in vacuum to obtain.
The laminate of the present invention can be preferably applied to printed circuit board, electronic equipment and its material, require dielectric properties
The purposes such as excellent multilager base plate, copper-clad laminates.
A kind of printed circuit board, contain laminate as described above.
The printed circuit board that the present invention mentions refers to possess conductive layer in the laminate surface of the present invention and possessed flexible
The substrate of the terminal for being used to electrically connect of substrate etc, or the substrate of IC elements, resistance, capacitor, coil is installed etc..
Compared to prior art, technical scheme at least possesses following beneficial effect：
The present invention has Er hydrogen Ben Bing Evil using two kinds of different multifunctional phenolic compound and diamine compounds synthesis
The thermosetting resin of piperazine ring structure, the advantages of effectively combining two kinds of monomers, and the shortcomings that respective is overcome, obtained benzo
Oxazine resin has the excellent combination property of low-dielectric energy, high heat-resisting, high tenacity and low water absorbable etc. simultaneously, is specially：
Td (5%) is 450~472 DEG C, and Dk/Df (100MHz) is 2.82-2.92/0.0028-0.0034, and Dk/Df (1GHz) is 2.80-
2.87/0.0039-0.0051。
In addition, the method for the present invention and obtained product avoid the property of the benzoxazine colophony using a kind of synthesis of monomer
Deficiency on energy, tool synthetic method is feasible, has broad application prospects.
Embodiment
Technical scheme is further illustrated below by embodiment.
Embodiment 1
(the preparation of 1) benzoxazine colophonies
The mixture for the multifunctional phenolic compound represented by formula (I) and (II) that mass ratio is 1/1 is put into chloroform
Common 26.21g, the mixture 30.13g for the diamine compounds represented by formula (a) and (b) that mass ratio is 1/1, paraformaldehyde
(and pure medicine system of light, 94%) 8.05g (0.25mol), it is set to react under reflux 6 hours simultaneously in moisture caused by removing.
Reacted solution is put into substantial amounts of methanol, separates out product.Then filter and separate product, washed with methanol.
Product at reduced pressure by washing is dried, principal component is used as using the benzoxazine compound of following structures so as to obtain 50.78g
Thermosetting resin.GPC measures its molecular weight as 20500.
(2) preparation of solidfied material
The polymer obtained by step (1) is kept for 3 hours at 220 DEG C using hot pressurization, obtains the thick pieces of 0.5mm
Shape solidfied material.Resulting firming body is that brown is transparent, uniform, bendability is excellent.For resulting solidfied material, flat board is utilized
The dielectric constant and dielectric dissipation factor of 23 DEG C of capacitance method measure, 100MHz and lGHz.It is fast using heatings of the TGA in 10 DEG C/min
5% weight under the lower evaluation air atmosphere of degree reduces temperature (Td5).Show the result in table 1.
Embodiment 2
(the preparation of 1) benzoxazine colophonies
The mixture for the multifunctional phenolic compound represented by formula (I) and (II) that mass ratio is 1/2 is put into chloroform
Common 21.5g, the mixture 66.68g for the diamine compounds represented by formula (a) and (b) that mass ratio is 2/1, paraformaldehyde (and
The pure medicine system of light, 94%) 7.36g (0.22mol), it is reacted under reflux 6 hours simultaneously in moisture caused by removing.Will be anti-
Solution after answering is put into substantial amounts of methanol, separates out product.Then filter and separate product, washed with methanol.Will be through
The product at reduced pressure for crossing washing is dried, so as to obtain thermosettings of the 91.10g using the benzoxazine compound of following structures as principal component
Property resin.GPC measures its molecular weight as 16600.
(2) preparation of solidfied material
The polymer obtained by step (1) is kept for 3 hours at 220 DEG C using hot pressurization, obtains the thick pieces of 0.5mm
Shape solidfied material.Resulting firming body is that brown is transparent, uniform, bendability is excellent.For resulting solidfied material, flat board is utilized
The dielectric constant and dielectric dissipation factor of 23 DEG C of capacitance method measure, 100MHz and lGHz.It is fast using heatings of the TGA in 10 DEG C/min
5% weight under the lower evaluation air atmosphere of degree reduces temperature (Td5).Show the result in table 1.
Embodiment 3
(the preparation of 1) benzoxazine colophonies
The mixture for the multifunctional phenolic compound represented by formula (I) and (II) that mass ratio is 2/1 is put into chloroform
Common 16.12g, the diamine compounds 49.77g, paraformaldehyde (and pure medicine system of light, 94%) 10.64g represented by formula (a)
(0.32mol), it is set to react under reflux 6 hours simultaneously in moisture caused by removing.Reacted solution input is a large amount of
Methanol in, separate out product.Then filter and separate product, washed with methanol.Product at reduced pressure by washing is done
It is dry, so as to obtain thermosetting resins of the 62.32g using the benzoxazine compound of following structures as principal component.GPC measures its point
Son amount is 17800.
(2) preparation of solidfied material
The polymer obtained by step (1) is kept for 3 hours at 220 DEG C using hot pressurization, obtains the thick pieces of 0.5mm
Shape solidfied material.Resulting firming body is that brown is transparent, uniform, bendability is excellent.For resulting solidfied material, flat board is utilized
The dielectric constant and dielectric dissipation factor of 23 DEG C of capacitance method measure, 100MHz and lGHz.It is fast using heatings of the TGA in 10 DEG C/min
5% weight under the lower evaluation air atmosphere of degree reduces temperature (Td5).Show the result in table 1.
Embodiment 4
(the preparation of 1) benzoxazine colophonies
The mixture for the multifunctional phenolic compound represented by formula (I) and (II) that mass ratio is 1/3 is put into chloroform
Common 14.33g, the diamine compounds 41.46g, paraformaldehyde (and pure medicine system of light, 94%) 9.96g represented by formula (b)
(0.30mol), it is set to react under reflux 6 hours simultaneously in moisture caused by removing.Reacted solution input is a large amount of
Methanol in, separate out product.Then filter and separate product, washed with methanol.Product at reduced pressure by washing is done
It is dry, so as to obtain thermosetting resins of the 52.38g using the benzoxazine compound of following structures as principal component.GPC measures its point
Son amount is 20100.
(2) preparation of solidfied material
The polymer obtained by step (1) is kept for 3 hours at 220 DEG C using hot pressurization, obtains the thick pieces of 0.5mm
Shape solidfied material.Resulting firming body is that brown is transparent, uniform, bendability is excellent.For resulting solidfied material, flat board is utilized
The dielectric constant and dielectric dissipation factor of 23 DEG C of capacitance method measure, 100MHz and lGHz.It is fast using heatings of the TGA in 10 DEG C/min
5% weight under the lower evaluation air atmosphere of degree reduces temperature (Td5).Show the result in table 1.
Embodiment 5
(the preparation of 1) benzoxazine colophonies
The multifunctional phenolic compound 10.75g that input is represented by formula (I) in chloroform, the Diamines represented by formula (a)
Compound 31.50g, paraformaldehyde (and pure medicine system of light, 94%) 6.65g (0.2mol), returned simultaneously in moisture caused by removing
Flowing down makes it react 6 hours.Reacted solution is put into substantial amounts of methanol, separates out product.Then filter product point
From being washed with methanol.Product at reduced pressure by washing is dried, so as to obtain 41.26g with the benzoxazine of following structures
Thermosetting resin of the compound as principal component.GPC measures its molecular weight as 18600.
(2) preparation of solidfied material
The polymer obtained by step (1) is kept for 3 hours at 220 DEG C using hot pressurization, obtains the thick pieces of 0.5mm
Shape solidfied material.Resulting firming body is that brown is transparent, uniform, bendability is excellent.For resulting solidfied material, flat board is utilized
The dielectric constant and dielectric dissipation factor of 23 DEG C of capacitance method measure, 100MHz and lGHz.It is fast using heatings of the TGA in 10 DEG C/min
5% weight under the lower evaluation air atmosphere of degree reduces temperature (Td5).Show the result in table 1.
Embodiment 6
(the preparation of 1) benzoxazine colophonies
The multifunctional phenolic compound 18.5g that input is represented by formula (II) in chloroform, the Diamines represented by formula (a)
Compound 55.40g, paraformaldehyde (and pure medicine system of light, 94%) 13.29g (0.4mol), returned simultaneously in moisture caused by removing
Flowing down makes it react 6 hours.Reacted solution is put into substantial amounts of methanol, separates out product.Then filter product point
From being washed with methanol.Product at reduced pressure by washing is dried, so as to obtain 79.20g with the benzoxazine of following structures
Thermosetting resin of the compound as principal component.GPC measures its molecular weight as 16500.
(2) preparation of solidfied material
The polymer obtained by step (1) is kept for 3 hours at 220 DEG C using hot pressurization, obtains the thick pieces of 0.5mm
Shape solidfied material.Resulting firming body is that brown is transparent, uniform, bendability is excellent.For resulting solidfied material, flat board is utilized
The dielectric constant and dielectric dissipation factor of 23 DEG C of capacitance method measure, 100MHz and lGHz.It is fast using heatings of the TGA in 10 DEG C/min
5% weight under the lower evaluation air atmosphere of degree reduces temperature (Td5).Show the result in table 1.
Embodiment 7
(the preparation of 1) benzoxazine colophonies
The multifunctional phenolic compound 21.50g that input is represented by formula (I) in chloroform, mass ratio are 2/3 by formula (a)
The mixture 58.20g, paraformaldehyde (and light pure medicine system, 94%) 13.29g of the diamine compounds that represent (b)
(0.4mol), it is set to react under reflux 6 hours simultaneously in moisture caused by removing.Reacted solution input is substantial amounts of
In methanol, separate out product.Then filter and separate product, washed with methanol.Product at reduced pressure by washing is dried,
So as to obtain thermosetting resins of the 85.00g using the benzoxazine compound of following structures as principal component.GPC measures its molecule
Measure as 18500.
(2) preparation of solidfied material
The polymer obtained by step (1) is kept for 3 hours at 220 DEG C using hot pressurization, obtains the thick pieces of 0.5mm
Shape solidfied material.Resulting firming body is that brown is transparent, uniform, bendability is excellent.For resulting solidfied material, flat board is utilized
The dielectric constant and dielectric dissipation factor of 23 DEG C of capacitance method measure, 100MHz and lGHz.It is fast using heatings of the TGA in 10 DEG C/min
5% weight under the lower evaluation air atmosphere of degree reduces temperature (Td5).Show the result in table 1.
Embodiment 8
(the preparation of 1) benzoxazine colophonies
The multifunctional phenolic compound 18.5g that input is represented by formula (II) in chloroform, mass ratio are 2/3 by formula (a)
The mixture 58.20g, paraformaldehyde (and light pure medicine system, 94%) 13.29g of the diamine compounds that represent (b)
(0.4mol), it is set to react under reflux 6 hours simultaneously in moisture caused by removing.Reacted solution input is substantial amounts of
In methanol, separate out product.Then filter and separate product, washed with methanol.Product at reduced pressure by washing is dried,
So as to obtain thermosetting resins of the 82g using the benzoxazine compound of following structures as principal component.GPC measures its molecular weight
19000。
(2) preparation of solidfied material
The polymer obtained by step (1) is kept for 3 hours at 220 DEG C using hot pressurization, obtains the thick pieces of 0.5mm
Shape solidfied material.Resulting firming body is that brown is transparent, uniform, bendability is excellent.For resulting solidfied material, flat board is utilized
The dielectric constant and dielectric dissipation factor of 23 DEG C of capacitance method measure, 100MHz and lGHz.It is fast using heatings of the TGA in 10 DEG C/min
5% weight under the lower evaluation air atmosphere of degree reduces temperature (Td5).Show the result in table 1.
Comparative example 1
(the preparation of 1) benzoxazine colophonies
The mixture for the multifunctional phenolic compound represented by formula (I) and (II) that mass ratio is 1/1 is put into chloroform
Common 14.33g, 2,2- double [4- (4- amino-benzene oxygens) phenyl] propane (Tokyo chemical conversion) 30.16g, paraformaldehyde (and the pure medicine of light
System, 94%) 9.57g (0.29mol), it is reacted under reflux 6 hours simultaneously in moisture caused by removing.Will be reacted
Solution is put into substantial amounts of methanol, separates out product.Then filter and separate product, washed with methanol.Washing will be passed through
Product at reduced pressure dry, so as to obtain thermosetting trees of the 48.31g using the benzoxazine compound of following structures as principal component
Fat.GPC measures its molecular weight as 20500.
(2) preparation of solidfied material
The polymer obtained by step (1) is kept for 3 hours at 220 DEG C using hot pressurization, obtains the thick pieces of 0.5mm
Shape solidfied material.Resulting firming body is that brown is transparent, uniform, bendability is excellent.For resulting solidfied material, flat board is utilized
The dielectric constant and dielectric dissipation factor of 23 DEG C of capacitance method measure, 100MHz and lGHz.It is fast using heatings of the TGA in 10 DEG C/min
5% weight under the lower evaluation air atmosphere of degree reduces temperature (Td5).Show the result in table 1.
Comparative example 2
(the preparation of 1) benzoxazine colophonies
The mixture for the multifunctional phenolic compound represented by formula (I) and (II) that mass ratio is 1/1 is put into chloroform
Common 14.33g, dianil M (Mitsui Chemicals) 24.81g, paraformaldehyde (and pure medicine system of light, 94%) 9.57g (0.29mol), except
Remove caused moisture while it is reacted under reflux 6 hours.Reacted solution is put into substantial amounts of methanol, makes product
Separate out.Then filter and separate product, washed with methanol.Product at reduced pressure by washing is dried, so as to obtain
Thermosetting resins of the 42.96g using the benzoxazine compound of following structures as principal component.GPC measures its molecular weight
17000。
(2) preparation of solidfied material
The polymer obtained by step (1) is kept for 3 hours at 220 DEG C using hot pressurization, obtains the thick pieces of 0.5mm
Shape solidfied material.Resulting firming body is that brown is transparent, uniform, bendability is excellent.For resulting solidfied material, flat board is utilized
The dielectric constant and dielectric dissipation factor of 23 DEG C of capacitance method measure, 100MHz and lGHz.It is fast using heatings of the TGA in 10 DEG C/min
5% weight under the lower evaluation air atmosphere of degree reduces temperature (Td5).Show the result in table 1.
Comparative example 3
Bisphenol-f type benzoxazine colophony is kept for 3 hours at 220 DEG C using hot pressurization, obtains the thick sheets of 0.5mm
Solidfied material.Resulting firming body is that brown is transparent, uniform, bendability is excellent.For resulting solidfied material, flat board electricity is utilized
The dielectric constant and dielectric dissipation factor of 23 DEG C of appearance method measure, 100MHz and lGHz.Using TGA 10 DEG C/min programming rate
5% weight under lower evaluation air atmosphere reduces temperature (Td5).Show the result in table 1.
Comparative example 4
Bisphenol A-type benzoxazine colophony is kept for 3 hours at 220 DEG C using hot pressurization, obtains the thick sheets of 0.5mm
Solidfied material.Resulting firming body is that brown is transparent, uniform, bendability is excellent.For resulting solidfied material, flat board electricity is utilized
The dielectric constant and dielectric dissipation factor of 23 DEG C of appearance method measure, 100MHz and lGHz.Using TGA 10 DEG C/min programming rate
5% weight under lower evaluation air atmosphere reduces temperature (Td5).Show the result in table 1.
Comparative example 5
Phenolphthalein type benzoxazine resin is kept for 3 hours at 220 DEG C using hot pressurization, obtains the thick sheets of 0.5mm
Solidfied material.Resulting firming body is that brown is transparent, uniform, bendability is excellent.For resulting solidfied material, flat board electricity is utilized
The dielectric constant and dielectric dissipation factor of 23 DEG C of appearance method measure, 100MHz and lGHz.Using TGA 10 DEG C/min programming rate
5% weight under lower evaluation air atmosphere reduces temperature (Td5).Show the result in table 1.
Table 1
| Dk/Df(100MHz) | Dk/Df(1GHz) | Td5% (DEG C) | |
| 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 show the present invention by biphenyl structural (I) and dicyclopentadiene structure (II)
Multifunctional phenols and biphenyl structural Diamines (a) and dicyclopentadiene structure Diamines (II) it is anti-in the presence of aldehydes
The macromolecular benzoxazine colophony solidfied material that should be obtained has good dielectric constant, dielectric dissipation factor, and with excellent
Heat resistance.Consolidated using the benzoxazine colophony obtained by non-biphenyl structural or the amine (comparative example 1-2) of dicyclopentadiene structure
Compound performance then has certain gap, and common benzoxazine colophony (comparative example 3-5) either dielectric properties or heat resistance
It is all poor.
Disclosed herein benzoxazine colophony and resin combination containing the resin without can be widely applied to be laminated
Plate, copper-clad plate and printed circuit board field, there is larger productive value.
Applicant states that the present invention illustrates the method detailed of the present invention, but not office of the invention by above-described embodiment
It is limited to above-mentioned method detailed, that is, does not mean that the present invention has to rely on above-mentioned method detailed and could implemented.Art
Technical staff it will be clearly understood that any improvement in the present invention, equivalence replacement and auxiliary element to each raw material of product of the present invention
Addition, selection of concrete mode etc., within the scope of all falling within protection scope of the present invention and disclosing.
Claims (15)
1. a kind of thermosetting resin with two hydrogen benzoxazine ring structures, it is mainly as more shown in logical formula (I) and/or (II)
Function phenolic compound, formula (a) and/or diamine compounds shown in (b) and aldehyde compound (c) reaction are prepared：
Wherein, n1、n2、n3And n40~10 integer independently is, can be with identical or different.
2. there is the thermosetting resin of Er hydrogen benzoxazine ring structures as claimed in claim 1, it is characterised in that n1、n2、n3
And n4It independently is 0~5 integer.
3. there is the thermosetting resin of Er hydrogen benzoxazine ring structures as claimed in claim 1 or 2, it is characterised in that except logical
Formula (I) and/or the multifunctional phenolic compound shown in (II), formula (a) and/or diamine compounds and aldehydes shown in (b)
Compound (c) outside, is additionally added the simple function phenolic compound shown in logical formula (III)：
The simple function phenolic compound is the big compound of side chain molecular weight, wherein, Z be carbon number be more than 4 it is organic
Group.
4. there is the thermosetting resin of Er hydrogen benzoxazine ring structures as claimed in claim 3, it is characterised in that Z is carbon original
Subnumber is more than 6.
5. there is the thermosetting resin of Er hydrogen benzoxazine ring structures as claimed in claim 4, it is characterised in that Z is carbon original
Subnumber is 8-20 organic group.
6. there is the thermosetting resin of Er hydrogen benzoxazine ring structures as claimed in claim 4, it is characterised in that described organic
Contain hetero atom in group, the hetero atom is N, O or F.
7. there is the thermosetting resin of Er hydrogen benzoxazine ring structures as claimed in claim 4, it is characterised in that described logical
In simple function group phenolic compound shown in formula (III), substituent Z is bonded in contraposition relative to OH bases, and substituent Z is as follows
Any one in structure：
Wherein, n5For 0~10 integer.
8. there is the thermosetting resin of Er hydrogen benzoxazine ring structures as claimed in claim 4, it is characterised in that substituent Z
Contraposition is bonded in relative to OH bases, and is any one in the group shown in following formula：
A kind of 9. thermosetting resin, for the thermosetting tree with two hydrogen benzoxazine ring structures shown in following logical formula (IV)s
Fat：
In formula, X1And X2Can be identical, it can also differ, X1And X2For following any one or two kinds of structures：
n6And n7, can be identical for 0~10 integer, it can also differ；
M is 2~15 integer.
10. a kind of thermoset composition, it is at least containing the thermosetting resin as described in one of claim 1-9.
11. a kind of solidfied material, obtained by solidifying thermoset composition as claimed in claim 10.
12. a kind of prepreg, it include reinforcing material and by be impregnated with dry after be attached on reinforcing material such as claim
Compositions of thermosetting resin described in 10.
13. a kind of laminate, obtained as the thermosetting resin as described in one of claim 1-9.
14. a kind of laminate, obtained by prepreg as claimed in claim 12.
15. a kind of printed circuit board, contain the laminate as described in claim 13 or 14.
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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| 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 |
| PL3336990T3 (en) * | 2016-12-19 | 2021-11-08 | Abb Schweiz Ag | Laminated multi-phase busbar and method of manufacturing the same |
| 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 |
| CN113583276B (en) * | 2021-08-27 | 2023-04-28 | 中国民用航空飞行学院 | Benzoxazine toughening modification method |
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| CN101273081A (en) * | 2005-09-29 | 2008-09-24 | 积水化学工业株式会社 | Thermosetting resin, thermosetting composition containing same, and molded body obtained from same |
| CN101421324A (en) * | 2006-02-20 | 2009-04-29 | 积水化学工业株式会社 | Method for producing thermosetting resin, thermosetting resin, thermosetting composition containing same, molded body, cured body, and electronic device containing those |
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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 |
| JP2004010839A (en) * | 2002-06-10 | 2004-01-15 | Nippon Steel Chem Co Ltd | Thermosetting resin having benzoxazine structure, resin composition and cured material |
| JP2008291070A (en) * | 2007-05-22 | 2008-12-04 | Sekisui Chem Co Ltd | Manufacturing method for thermosetting resin, and thermosetting resin |
| JP5421630B2 (en) * | 2008-03-26 | 2014-02-19 | 積水化学工業株式会社 | Thermosetting resin, thermosetting composition containing thermosetting resin, molded body thereof, cured body, cured molded body, and electronic device including them |
| JP2009242737A (en) * | 2008-03-31 | 2009-10-22 | Sekisui Chem Co Ltd | Thermosetting resin composition, its preparation, and copper plated laminate plate |
| US9005761B2 (en) * | 2011-12-22 | 2015-04-14 | Elite Material Co., Ltd. | Halogen-free resin composition and its application for copper clad laminate and printed circuit board |
| 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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| CN101273081A (en) * | 2005-09-29 | 2008-09-24 | 积水化学工业株式会社 | Thermosetting resin, thermosetting composition containing same, and molded body obtained from same |
| CN101421324A (en) * | 2006-02-20 | 2009-04-29 | 积水化学工业株式会社 | Method for producing thermosetting resin, thermosetting resin, thermosetting composition containing same, molded body, cured body, and electronic device containing those |
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