TWI342323B - Thermoset resin modified polyimide resin composition - Google Patents
Thermoset resin modified polyimide resin composition Download PDFInfo
- Publication number
- TWI342323B TWI342323B TW096102257A TW96102257A TWI342323B TW I342323 B TWI342323 B TW I342323B TW 096102257 A TW096102257 A TW 096102257A TW 96102257 A TW96102257 A TW 96102257A TW I342323 B TWI342323 B TW I342323B
- Authority
- TW
- Taiwan
- Prior art keywords
- group
- bismaleimide
- hydrazine
- component
- resin composition
- Prior art date
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- 239000000203 mixture Substances 0.000 title claims description 15
- 229920001721 polyimide Polymers 0.000 title description 10
- 239000009719 polyimide resin Substances 0.000 title description 6
- 239000004634 thermosetting polymer Substances 0.000 title 1
- 229920005989 resin Polymers 0.000 claims description 31
- 239000011347 resin Substances 0.000 claims description 31
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 claims description 18
- GTDPSWPPOUPBNX-UHFFFAOYSA-N ac1mqpva Chemical compound CC12C(=O)OC(=O)C1(C)C1(C)C2(C)C(=O)OC1=O GTDPSWPPOUPBNX-UHFFFAOYSA-N 0.000 claims description 18
- 229920003192 poly(bis maleimide) Polymers 0.000 claims description 15
- -1 derived from benzene Chemical compound 0.000 claims description 13
- 239000011342 resin composition Substances 0.000 claims description 13
- 125000003118 aryl group Chemical group 0.000 claims description 12
- XQUPVDVFXZDTLT-UHFFFAOYSA-N 1-[4-[[4-(2,5-dioxopyrrol-1-yl)phenyl]methyl]phenyl]pyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C(C=C1)=CC=C1CC1=CC=C(N2C(C=CC2=O)=O)C=C1 XQUPVDVFXZDTLT-UHFFFAOYSA-N 0.000 claims description 10
- 238000006243 chemical reaction Methods 0.000 claims description 10
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 10
- 229920001187 thermosetting polymer Polymers 0.000 claims description 9
- 125000004432 carbon atom Chemical group C* 0.000 claims description 8
- 150000004985 diamines Chemical class 0.000 claims description 8
- 125000002723 alicyclic group Chemical group 0.000 claims description 7
- 229910052757 nitrogen Inorganic materials 0.000 claims description 7
- 125000000962 organic group Chemical group 0.000 claims description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 6
- 125000001931 aliphatic group Chemical group 0.000 claims description 5
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 claims description 5
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- 239000004305 biphenyl Substances 0.000 claims description 4
- 239000004643 cyanate ester Substances 0.000 claims description 4
- KZTYYGOKRVBIMI-UHFFFAOYSA-N diphenyl sulfone Chemical compound C=1C=CC=CC=1S(=O)(=O)C1=CC=CC=C1 KZTYYGOKRVBIMI-UHFFFAOYSA-N 0.000 claims description 4
- 239000000945 filler Substances 0.000 claims description 4
- 150000002466 imines Chemical class 0.000 claims description 4
- 239000000843 powder Substances 0.000 claims description 4
- 235000010290 biphenyl Nutrition 0.000 claims description 3
- 150000002430 hydrocarbons Chemical group 0.000 claims description 3
- 150000001412 amines Chemical class 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims description 2
- 125000001624 naphthyl group Chemical group 0.000 claims description 2
- 125000006839 xylylene group Chemical group 0.000 claims description 2
- 239000002585 base Substances 0.000 claims 6
- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Chemical compound C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 claims 4
- BBEAQIROQSPTKN-UHFFFAOYSA-N pyrene Chemical compound C1=CC=C2C=CC3=CC=CC4=CC=C1C2=C43 BBEAQIROQSPTKN-UHFFFAOYSA-N 0.000 claims 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims 3
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 claims 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims 2
- 125000004429 atom Chemical group 0.000 claims 2
- DMBHHRLKUKUOEG-UHFFFAOYSA-N diphenylamine Chemical compound C=1C=CC=CC=1NC1=CC=CC=C1 DMBHHRLKUKUOEG-UHFFFAOYSA-N 0.000 claims 2
- GVEPBJHOBDJJJI-UHFFFAOYSA-N fluoranthrene Natural products C1=CC(C2=CC=CC=C22)=C3C2=CC=CC3=C1 GVEPBJHOBDJJJI-UHFFFAOYSA-N 0.000 claims 2
- 125000004430 oxygen atom Chemical group O* 0.000 claims 2
- HVLLSGMXQDNUAL-UHFFFAOYSA-N triphenyl phosphite Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)OC1=CC=CC=C1 HVLLSGMXQDNUAL-UHFFFAOYSA-N 0.000 claims 2
- 229910052582 BN Inorganic materials 0.000 claims 1
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 claims 1
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 claims 1
- 229910002588 FeOOH Inorganic materials 0.000 claims 1
- 108010022355 Fibroins Proteins 0.000 claims 1
- 206010061218 Inflammation Diseases 0.000 claims 1
- YKTSYUJCYHOUJP-UHFFFAOYSA-N [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] Chemical compound [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] YKTSYUJCYHOUJP-UHFFFAOYSA-N 0.000 claims 1
- 229910052783 alkali metal Inorganic materials 0.000 claims 1
- 125000005037 alkyl phenyl group Chemical group 0.000 claims 1
- 125000002947 alkylene group Chemical group 0.000 claims 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims 1
- 229910000323 aluminium silicate Inorganic materials 0.000 claims 1
- 125000003277 amino group Chemical group 0.000 claims 1
- PYKYMHQGRFAEBM-UHFFFAOYSA-N anthraquinone Natural products CCC(=O)c1c(O)c2C(=O)C3C(C=CC=C3O)C(=O)c2cc1CC(=O)OC PYKYMHQGRFAEBM-UHFFFAOYSA-N 0.000 claims 1
- 150000004056 anthraquinones Chemical class 0.000 claims 1
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 claims 1
- 125000006267 biphenyl group Chemical group 0.000 claims 1
- 239000005388 borosilicate glass Substances 0.000 claims 1
- 229910000019 calcium carbonate Inorganic materials 0.000 claims 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 claims 1
- 229910000420 cerium oxide Inorganic materials 0.000 claims 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 claims 1
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 claims 1
- LTYMSROWYAPPGB-UHFFFAOYSA-N diphenyl sulfide Chemical compound C=1C=CC=CC=1SC1=CC=CC=C1 LTYMSROWYAPPGB-UHFFFAOYSA-N 0.000 claims 1
- CZZYITDELCSZES-UHFFFAOYSA-N diphenylmethane Chemical compound C=1C=CC=CC=1CC1=CC=CC=C1 CZZYITDELCSZES-UHFFFAOYSA-N 0.000 claims 1
- 229910000248 eudialyte Inorganic materials 0.000 claims 1
- 125000004404 heteroalkyl group Chemical group 0.000 claims 1
- 125000005842 heteroatom Chemical group 0.000 claims 1
- 230000004054 inflammatory process Effects 0.000 claims 1
- AJBQAIDJQOJYFQ-UHFFFAOYSA-N methane;pyrrole-2,5-dione Chemical compound C.O=C1NC(=O)C=C1.O=C1NC(=O)C=C1 AJBQAIDJQOJYFQ-UHFFFAOYSA-N 0.000 claims 1
- 229910052664 nepheline Inorganic materials 0.000 claims 1
- 239000010434 nepheline Substances 0.000 claims 1
- 238000005121 nitriding Methods 0.000 claims 1
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 claims 1
- 239000002245 particle Substances 0.000 claims 1
- 229940067157 phenylhydrazine Drugs 0.000 claims 1
- 229910021420 polycrystalline silicon Inorganic materials 0.000 claims 1
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims 1
- 125000000475 sulfinyl group Chemical group [*:2]S([*:1])=O 0.000 claims 1
- 125000000472 sulfonyl group Chemical group *S(*)(=O)=O 0.000 claims 1
- 229910052717 sulfur Inorganic materials 0.000 claims 1
- 125000004434 sulfur atom Chemical group 0.000 claims 1
- 239000010435 syenite Substances 0.000 claims 1
- 239000000454 talc Substances 0.000 claims 1
- 229910052623 talc Inorganic materials 0.000 claims 1
- 239000004408 titanium dioxide Substances 0.000 claims 1
- 239000011787 zinc oxide Substances 0.000 claims 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 10
- 239000002253 acid Substances 0.000 description 10
- 230000015572 biosynthetic process Effects 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 9
- 238000003786 synthesis reaction Methods 0.000 description 9
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 6
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 5
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 5
- WKDNYTOXBCRNPV-UHFFFAOYSA-N bpda Chemical compound C1=C2C(=O)OC(=O)C2=CC(C=2C=C3C(=O)OC(C3=CC=2)=O)=C1 WKDNYTOXBCRNPV-UHFFFAOYSA-N 0.000 description 5
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 229910001873 dinitrogen Inorganic materials 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000011889 copper foil Substances 0.000 description 3
- 239000011888 foil Substances 0.000 description 3
- 239000001294 propane Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 239000002966 varnish Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- VLDPXPPHXDGHEW-UHFFFAOYSA-N 1-chloro-2-dichlorophosphoryloxybenzene Chemical compound ClC1=CC=CC=C1OP(Cl)(Cl)=O VLDPXPPHXDGHEW-UHFFFAOYSA-N 0.000 description 2
- QQGYZOYWNCKGEK-UHFFFAOYSA-N 5-[(1,3-dioxo-2-benzofuran-5-yl)oxy]-2-benzofuran-1,3-dione Chemical compound C1=C2C(=O)OC(=O)C2=CC(OC=2C=C3C(=O)OC(C3=CC=2)=O)=C1 QQGYZOYWNCKGEK-UHFFFAOYSA-N 0.000 description 2
- ZHBXLZQQVCDGPA-UHFFFAOYSA-N 5-[(1,3-dioxo-2-benzofuran-5-yl)sulfonyl]-2-benzofuran-1,3-dione Chemical compound C1=C2C(=O)OC(=O)C2=CC(S(=O)(=O)C=2C=C3C(=O)OC(C3=CC=2)=O)=C1 ZHBXLZQQVCDGPA-UHFFFAOYSA-N 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- HFACYLZERDEVSX-UHFFFAOYSA-N benzidine Chemical group C1=CC(N)=CC=C1C1=CC=C(N)C=C1 HFACYLZERDEVSX-UHFFFAOYSA-N 0.000 description 2
- XLJMAIOERFSOGZ-UHFFFAOYSA-M cyanate Chemical compound [O-]C#N XLJMAIOERFSOGZ-UHFFFAOYSA-M 0.000 description 2
- MWKFXSUHUHTGQN-UHFFFAOYSA-N decan-1-ol Chemical compound CCCCCCCCCCO MWKFXSUHUHTGQN-UHFFFAOYSA-N 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 230000009477 glass transition Effects 0.000 description 2
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 2
- 210000004185 liver Anatomy 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 description 2
- 239000002798 polar solvent Substances 0.000 description 2
- 229920000767 polyaniline Polymers 0.000 description 2
- 108010026466 polyproline Proteins 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- KIDHWZJUCRJVML-UHFFFAOYSA-N putrescine Chemical compound NCCCCN KIDHWZJUCRJVML-UHFFFAOYSA-N 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- 229920001169 thermoplastic Polymers 0.000 description 2
- 229920006259 thermoplastic polyimide Polymers 0.000 description 2
- 239000004416 thermosoftening plastic Substances 0.000 description 2
- XFNJVJPLKCPIBV-UHFFFAOYSA-N trimethylenediamine Chemical compound NCCCN XFNJVJPLKCPIBV-UHFFFAOYSA-N 0.000 description 2
- 235000021419 vinegar Nutrition 0.000 description 2
- 239000000052 vinegar Substances 0.000 description 2
- OURODNXVJUWPMZ-UHFFFAOYSA-N 1,2-diphenylanthracene Chemical compound C1=CC=CC=C1C1=CC=C(C=C2C(C=CC=C2)=C2)C2=C1C1=CC=CC=C1 OURODNXVJUWPMZ-UHFFFAOYSA-N 0.000 description 1
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- YFOOEYJGMMJJLS-UHFFFAOYSA-N 1,8-diaminonaphthalene Chemical compound C1=CC(N)=C2C(N)=CC=CC2=C1 YFOOEYJGMMJJLS-UHFFFAOYSA-N 0.000 description 1
- HMUNWXXNJPVALC-UHFFFAOYSA-N 1-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)C(CN1CC2=C(CC1)NN=N2)=O HMUNWXXNJPVALC-UHFFFAOYSA-N 0.000 description 1
- AVFZOVWCLRSYKC-UHFFFAOYSA-N 1-methylpyrrolidine Chemical compound CN1CCCC1 AVFZOVWCLRSYKC-UHFFFAOYSA-N 0.000 description 1
- SXAMGRAIZSSWIH-UHFFFAOYSA-N 2-[3-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]-1,2,4-oxadiazol-5-yl]-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C1=NOC(=N1)CC(=O)N1CC2=C(CC1)NN=N2 SXAMGRAIZSSWIH-UHFFFAOYSA-N 0.000 description 1
- SSKKLVFYNOPNCW-UHFFFAOYSA-N 3-(4-ethylphenoxy)aniline Chemical compound C1=CC(CC)=CC=C1OC1=CC=CC(N)=C1 SSKKLVFYNOPNCW-UHFFFAOYSA-N 0.000 description 1
- UCFMKTNJZCYBBJ-UHFFFAOYSA-N 3-[1-(2,3-dicarboxyphenyl)ethyl]phthalic acid Chemical compound C=1C=CC(C(O)=O)=C(C(O)=O)C=1C(C)C1=CC=CC(C(O)=O)=C1C(O)=O UCFMKTNJZCYBBJ-UHFFFAOYSA-N 0.000 description 1
- DKKYOQYISDAQER-UHFFFAOYSA-N 3-[3-(3-aminophenoxy)phenoxy]aniline Chemical compound NC1=CC=CC(OC=2C=C(OC=3C=C(N)C=CC=3)C=CC=2)=C1 DKKYOQYISDAQER-UHFFFAOYSA-N 0.000 description 1
- LBPVOEHZEWAJKQ-UHFFFAOYSA-N 3-[4-(3-aminophenoxy)phenoxy]aniline Chemical compound NC1=CC=CC(OC=2C=CC(OC=3C=C(N)C=CC=3)=CC=2)=C1 LBPVOEHZEWAJKQ-UHFFFAOYSA-N 0.000 description 1
- XUSNPFGLKGCWGN-UHFFFAOYSA-N 3-[4-(3-aminopropyl)piperazin-1-yl]propan-1-amine Chemical compound NCCCN1CCN(CCCN)CC1 XUSNPFGLKGCWGN-UHFFFAOYSA-N 0.000 description 1
- UQHPRIRSWZEGEK-UHFFFAOYSA-N 3-[4-[1-[4-(3-aminophenoxy)phenyl]ethyl]phenoxy]aniline Chemical compound C=1C=C(OC=2C=C(N)C=CC=2)C=CC=1C(C)C(C=C1)=CC=C1OC1=CC=CC(N)=C1 UQHPRIRSWZEGEK-UHFFFAOYSA-N 0.000 description 1
- NYRFBMFAUFUULG-UHFFFAOYSA-N 3-[4-[2-[4-(3-aminophenoxy)phenyl]propan-2-yl]phenoxy]aniline Chemical compound C=1C=C(OC=2C=C(N)C=CC=2)C=CC=1C(C)(C)C(C=C1)=CC=C1OC1=CC=CC(N)=C1 NYRFBMFAUFUULG-UHFFFAOYSA-N 0.000 description 1
- UCQABCHSIIXVOY-UHFFFAOYSA-N 3-[4-[4-(3-aminophenoxy)phenyl]phenoxy]aniline Chemical group NC1=CC=CC(OC=2C=CC(=CC=2)C=2C=CC(OC=3C=C(N)C=CC=3)=CC=2)=C1 UCQABCHSIIXVOY-UHFFFAOYSA-N 0.000 description 1
- YBRVSVVVWCFQMG-UHFFFAOYSA-N 4,4'-diaminodiphenylmethane Chemical compound C1=CC(N)=CC=C1CC1=CC=C(N)C=C1 YBRVSVVVWCFQMG-UHFFFAOYSA-N 0.000 description 1
- IBOFVQJTBBUKMU-UHFFFAOYSA-N 4,4'-methylene-bis-(2-chloroaniline) Chemical compound C1=C(Cl)C(N)=CC=C1CC1=CC=C(N)C(Cl)=C1 IBOFVQJTBBUKMU-UHFFFAOYSA-N 0.000 description 1
- UITKHKNFVCYWNG-UHFFFAOYSA-N 4-(3,4-dicarboxybenzoyl)phthalic acid Chemical compound C1=C(C(O)=O)C(C(=O)O)=CC=C1C(=O)C1=CC=C(C(O)=O)C(C(O)=O)=C1 UITKHKNFVCYWNG-UHFFFAOYSA-N 0.000 description 1
- AIVVXPSKEVWKMY-UHFFFAOYSA-N 4-(3,4-dicarboxyphenoxy)phthalic acid Chemical compound C1=C(C(O)=O)C(C(=O)O)=CC=C1OC1=CC=C(C(O)=O)C(C(O)=O)=C1 AIVVXPSKEVWKMY-UHFFFAOYSA-N 0.000 description 1
- TZQVSGOOKNNDFU-UHFFFAOYSA-N 4-phenylsulfanylaniline Chemical compound C1=CC(N)=CC=C1SC1=CC=CC=C1 TZQVSGOOKNNDFU-UHFFFAOYSA-N 0.000 description 1
- CTVZMQGPAVURPB-UHFFFAOYSA-N C(=O)(O)C=1C=C(C=CC1C(=O)O)C1C(C(=O)OC1=O)C1=CC(=C(C=C1)C(=O)O)C(=O)O Chemical compound C(=O)(O)C=1C=C(C=CC1C(=O)O)C1C(C(=O)OC1=O)C1=CC(=C(C=C1)C(=O)O)C(=O)O CTVZMQGPAVURPB-UHFFFAOYSA-N 0.000 description 1
- UNOFIEIELCIRFO-UHFFFAOYSA-N CCCCCCCCC(CCCN)C(C)(C)C1=CC=C(C=C1)C(C)(C)C(CCCCCCCC)CCCN Chemical compound CCCCCCCCC(CCCN)C(C)(C)C1=CC=C(C=C1)C(C)(C)C(CCCCCCCC)CCCN UNOFIEIELCIRFO-UHFFFAOYSA-N 0.000 description 1
- 241000238366 Cephalopoda Species 0.000 description 1
- 101150065749 Churc1 gene Proteins 0.000 description 1
- MQJKPEGWNLWLTK-UHFFFAOYSA-N Dapsone Chemical compound C1=CC(N)=CC=C1S(=O)(=O)C1=CC=C(N)C=C1 MQJKPEGWNLWLTK-UHFFFAOYSA-N 0.000 description 1
- 241000237858 Gastropoda Species 0.000 description 1
- MKYBYDHXWVHEJW-UHFFFAOYSA-N N-[1-oxo-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propan-2-yl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(C(C)NC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 MKYBYDHXWVHEJW-UHFFFAOYSA-N 0.000 description 1
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Classifications
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- 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
- H05K1/03—Use of materials for the substrate
- H05K1/0313—Organic insulating material
- H05K1/0353—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement
- H05K1/0373—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement containing additives, e.g. fillers
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- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
- C08K3/013—Fillers, pigments or reinforcing additives
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/34—Heterocyclic compounds having nitrogen in the ring
- C08K5/3412—Heterocyclic compounds having nitrogen in the ring having one nitrogen atom in the ring
- C08K5/3415—Five-membered rings
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- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
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- H05K1/02—Details
- H05K1/03—Use of materials for the substrate
- H05K1/0313—Organic insulating material
- H05K1/032—Organic insulating material consisting of one material
- H05K1/0346—Organic insulating material consisting of one material containing N
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- 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
- C08L79/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
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- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
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- H05K2201/01—Dielectrics
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Description
1342323 九、發明說明: 【發明所屬之技術領域】 本發明有關一種熱固性樹脂改質之聚醯 【先前技術】
聚醯亞胺薄膜顯現良好高溫抗性、良好化學性質絕緣 性及高機械髓,因此廣泛用於各種技術領域。例如,聚酿亞 胺薄膜有利地以連續聚醯亞_膜/金屬義複合片之形式使 =用^製造軟性印刷板(FPC)、用於膠帶自動黏合之承載勝 帶(TAB)及晶片表面引腳(L0C)結構膠帶,尤其軟性印刷電路板 已廣泛應驗筆記難腦、㈣性電子產品、行動電話通訊設 借姑斜蓉。 在,造印職路板巾’主要使用高溫接著繼佈於聚醯亞 胺絕緣薄膜上,再與金屬箔例如銅箔壓合,而製成軟 路板,而可應用於筆記型電腦、消費性電子產i成:= 訊設備材料等。 一目前所使用之接著劑為熱塑性聚醯亞胺系統,其熱膨脹係 數,、耐熱性不佳且尺寸安定性亦不佳,況且在使雜亞胺絕 緣薄膜與金屬箔壓合時,需在高溫進行。
亞胺樹脂組成物。 鑑於上述介以熱塑性黏著劑製造軟板之缺點,需要有一種 可解決熱塑性聚醯亞胺熱膨脹係數過高之問題,同時改善耐熱 性及尺寸安定性且不需高溫即可與金屬箔貼合之接著劑'… 為此本發明人者對聚醯亞胺樹脂構造進行進一步研究而 發展出可克服上述問題之聚酿亞胺樹脂組成物,因而完成本 明。 【發明内容】 本發明有關一種熱固性樹脂改質之聚醯亞胺樹脂組成 物,其包括(a)聚醯亞胺樹脂、(b)氰酸酯、(c)雙馬來醯亞'胺、 以及(d)奈米填充劑。 依據本發明之熱固性樹脂改質之聚醯亞胺樹脂組成物,可解 5 TP060316
1342323 決熱塑性聚醯亞胺熱膨脹係數過高的問題,並可改善耐熱性增 加樹脂之熱穩定性,並可使用於與銅羯低溫貼合而製造印刷電 路板。 據此,本發明提供一種熱固性樹脂改質之聚醯亞胺樹脂組 成物’包括下列成份·(a)聚酿亞胺樹脂、(b)氣酸醋、(c)雙 馬來醯亞胺、以及(d)奈米填充劑,其中以組成物總重計,上 述成份(a)聚醯亞胺樹脂為60〜95重量% ;成份(b)氰酸醋重量 為0·卜10重量% ;成份(c)雙馬來醯亞胺為〇.卜重量% ;且 成份(d)奈米填充劑為1〜40重量%。
依據本發明之熱固性樹脂改質之聚醯亞胺樹脂組成物,藉 由雙馬來醯亞胺及氰酸酯在加熱條件下,其自身以及彼此間產 生熱交聯’得以降低聚醯亞胺之熱膨脹係數以及增加樹脂之埶 穩定性,且可於低溫下進行與金屬笛之貼合獲得軟性印刷電^ 板。 【實施方式】 依據本發明之成份(a)聚醯亞胺樹脂係由下式(I)之二胺: H2N-Ri-NH2 (I) J其中Ri為⑴共價鍵;(i i )G_I2脂族烴基;(i i i )G4 3。脂環族基;
其族基;之基(其中R2代表伸苯 c 之基且X代表共價鍵、可經齒素取代之 ^伸烧基、-〇-本基-m、暑 2 iCH(tPt(Si^SiRVR3~(其* R3 為概^ 2 s (⑶2)S-G—’ m 為 1 至 igg 之整數.s 為1至4之整數;尺4為α6燒基 數’ 與下式(11)之二_反應所得者:本4^6絲本基)],
〇 I C Ο Λ 〇 \ 〇
C C \\ 〇 (II) Τρ〇6〇316 1342323 中/代彳ίΐ 2至12個碳原子之哺脂族基、含4至8個碳 原子之四價職祕、“單環❹_合 ^ Γ、=Γ:Χ 代= 卷 υ 本基-0-、—〇—、|、—s_、_s〇 或|基)]。 心tiT巾収靠職㈣之二紐_可_如(但不 3彳,酸二' 4’4’ _氧基二___、 3,3 ,4,4 -聯苯四羧酸二酐(BPDA)、3 3,,4 4,—二 四竣酸二SKBTDA)、伸乙基四練二酐、了烧四賊 戊烷四羧酸二酐、2,2,,3,3, _二苯甲酮四羧酸'二酐、 2.2 ’3’3’ -聯苯四紐二軒、2,2_雙(3,4_二絲笨基)丙烧 二酐、2’ 2-雙(2, 3-二羧基苯基)丙烷二酐、雙(3,4_二羧基苯 醚二酐、雙(3, 4_二羧基苯基)硬二酐、1,1-雙(2, 3-二羧基 苯基)乙烷二酐、雙(2, 3-二羧基笨基)甲烷二酐、雙(3, 4—二^ 基苯基)甲烷二酐、4,4,-(對-苯二氧基)二酞酸’二酐、 4, 4 (間-本一氧基)二敝酸軒、2, 3, 6, 7-萘四繞酸二肝、 1,4, 5,8-萘四叛酸二軒、1,2, 5, 6-萘四叛酸二軒、12,3 苯四羧酸二酐、3, 4, 9,10-二萘嵌苯四羧酸二酐、2, 3,’ 6,’ /蒽 四羧酸二酐及1,2, 7, 8-菲四羧酸二酐等。該等二酸酐可單^ 使用一種或以多種之混合物使用。其中較好為苯均四酸二酐 (PMDA)、4,4’ -氧基二酞酸針⑽pA)、3,3’,4,4,-聯苯四羧 酸一針(BPDA)、3, 3’,4, 4’ -二苯甲 _四叛酸二肝(btda)、 3.3 ,4,4 -聯苯基石風四缓酸二針(DSDA)。 本發明中製備聚醯胺酸之二胺實例可舉例如(但不限於) 對本基一胺(PDA)、4, 4’-二胺基二苯基謎、4, 4’-二胺基二苯 基甲烷、4, 4’-二胺基二笨基砜、4, 4,-二胺基二苯基硫醚、4, 4,-二(間-胺基苯氧基)二苯基颯、4, 4’-二(對-胺基苯氧基)二苯 基砜、鄰-伸苯基二胺、間-伸苯基二胺、對—伸笨基二胺、聯 苯胺、2, 2’-二胺基二笨甲嗣、4, 4’-二胺基二笨甲嗣、4, 4,- TP060316 7 1342323 二胺基二苯基—2,2’-丙烷、1,5-二胺基萘、1,8-二胺基萘、三 亞甲基二胺、四亞甲基二胺、六亞甲基二胺、4,4-二曱基七亞 曱基二胺、2,11-十二烷二胺、雙(對-胺基苯氧基)二甲基矽 烷、1,4-雙(3-胺基丙基二甲基矽烷基)苯、丨,4—二胺基環己 炫、鄰-一甲苯二胺、間-二曱苯二胺、乙胍(acetoguanamine)、 ^胍、1,3-雙(3-胺基苯氧基)笨(APB)、雙[4-(3-胺基笨氧基) 苯基]曱烷、1,1-雙[4-(3-胺基苯氧基)苯基]乙烷、i,2一雙 [4-(3-胺基苯氧基)苯基]乙烷、丨,2_雙[4_(3_胺基苯氧’基)苯 基]乙,、2, 2-雙[4-(3-胺基苯氧基)苯基]丙烧、2, 2-雙[4-(3-胺基苯氧基)苯基]丁烷、2, 2-雙[4-(3-胺基苯氧基)苯 基]-1,1,1,3, 3, 3-六氟丙烷、4, 4’-雙(3-胺基苯氧基)聯笨、 雙[4-(3-胺基苯氧基)苯基]甲酮、雙[4—(3_胺基苯氧基)苯基] =醚、雙[4-(3-胺基苯氧基)苯基]亞颯、雙[4_(3_胺基苯氧基) 本基]礙、雙[4-(3-胺基笨氧基)苯基]_等。上述雙胺可單獨 使用一種或以多種混合使用。
該二酸酐與二胺之反應可在非質子極性溶劑中進行,非質 子極性溶劑之種類並無特別限制,只要不與反應物及產物反應 即可。具體實例可舉例如N,N-二甲基乙酿胺⑽c)、N_甲基 吡咯烷酮(NMP)、N,N-二甲基甲醯胺(DMF)、四氫呋喃(THF)、 二噁烷、氣仿(CHCh)、二氣甲烷等。其中較好使用N_甲基吡 咯烷酮(NMP)及N,N-二曱基乙醯胺(DMAc)。 。該二酸酐與二胺之反應一般在室溫至90〇C,較好30至 75J:之溫度範圍㈣行’且料族雙驗芳族雙酐之當量比 (芳族雙胺/芳族雙酐)介於〇·5至2 〇之範圍, 0.75〜1.25之範圍。 仕 依據本發明之成份(b)氰酸酯係以下式(in)表示: 咗(ο-C,n (m) 其中η為至少為2且不大於5之整數,且r5為: TP0603I6
1342323
Hi:<y
Ai〇C> L-10'* C1U Cih (X.N
其中P為0〜20之整數。 根據本發明之成份(c)之雙馬來酿亞胺係由下式(IV)所示 之化合物:
N-R-N 0
(IV) 0 其中R7為(i)含6至16個碳原子之二價芳族或脂環族有機基, 如伸苯基、伸萘基、伸二甲苯基(xylylene)、伸環己基或伸六 氫二甲苯基(hexahydroxylylene) ; (ii)下式⑴所示之基:
其中〇及R6如前述定義 ⑴ m上述式(IV)中之R7基所示之有機基當為芳族有機基或脂 環族有機基時’在該芳族環或該脂環族上可含有不參與反靡之 有機基,如含1至4個碳原子之烷基(如曱基或乙基)^ f 4個碳原子之烷氧基(如曱氧基或乙氧基)。 本發明之成份(c)之雙馬來醯亞胺可藉本身已知之方法 備,包括使馬來酸Sf與二胺類反應,接著使所得雙馬來 脫氫環化而獲得。該二胺由反應性之觀點而言,較好為一級二 TP060316 5 1342323 氮氣烘箱中在例如260至30(TC之溫度進行固化’可獲得高耐 熱性、高尺寸安定性之軟性印刷電路板 本發明將以下列實施例更進一步詳細說明,惟該等實施例 目的僅用以說明本發明而非用以限制本發明之範圍。 實施例 A·合成例1-聚醯胺酸之合成 於附有攪拌機及氮氣導管之四頸反應瓶中,在氮氣流量為 20cc/分鐘吹拂下’於反應瓶中置入41克(〇· 1莫耳)之2, 2-雙[4-(4-胺基苯氧基)苯基]丙烷(BAPP)並以302克N-甲基吡 略烧鲷(NMP)進行溶解’攪拌溶解後維持在15°C。取三個分別 具有攪拌子之燒瓶,各燒瓶中分別加入2· 94克(0.01莫耳)之 3,3’,4,4’ -聯笨四羧酸二酐(BPDA)以及10克NMP,第二燒 瓶加入22. 54克(0. 07莫耳)之3, 3’,4,4’-二苯甲綱四竣酸二 酐(BTDA),第三燒瓶加入6.2克(〇.〇2莫耳)之雙(3,4-二羧 基苯基)醚二酐(ODPA) ’攪拌使其溶解。將第一燒瓶之溶液加 入反應釜中,持續導入氮氣,攪拌使其反應丨小時後,倒入第 二燒瓶之溶液,再反應1小時,接著倒入第三燒瓶之溶液,持 續導入氮氣,進行反應4小時後,獲得聚醯胺酸樹脂。停止導 入氮氣,使反應釜裝配Dean Stack除水。取87克甲苯加入反 應蚤中,將溫度升至185 C進行閉環脫水反應,使聚酿胺酸樹 脂醯亞胺化形成聚醯亞胺樹脂。利用甲笨共沸持續將水帶出, 直到確認不在有水被帶出後,將溫度降至室溫。接著加入甲 使聚醯亞胺樹脂沉澱’過濾沉澱物,利用曱醇清洗沉澱物 次,於烘箱中烘乾,得到聚醯亞胺樹脂粉末。取〇. 5克之 聚酿胺酸樹脂溶於100毫升NMP於25t測量特性黏产 0. 65dl/g。後文中合成例1所得之聚酿亞胺樹脂 p :、 且其組成列於表1。 Λ 合成例2至5 類似合成例1所述之方法’以下表i所列之二胺及二酸軒 12 TP060316 1342323 及組成合成聚醯亞胺,所得聚醯亞胺樹脂分別稱為PI_2(合成 例2)〜PI-5(合成例5)。 σ
BPDA BTDA ODPA DSDA ΒΑΡΡ ΒΑΡΒ 3, 3’,4,4’-聯苯四羧酸二酐 3, 3’,4,4’-二苯甲嗣四叛酸二肝 雙(3, 4-二羧基苯基)醚二酐 3,3’,4,4’ -聯苯基礙四羧酸二酐 2, 2雙[4-(4-胺基苯氧基)苯基]丙烷 4,4’-雙(4-胺基苯氧基)聯苯 BAPS :雙[4-(4-胺基笨氧基)笨基]颯 TPE-R: 1,4-雙(3-胺基笨氧基)苯 APB: 1,3-雙(3-胺基苯氧基)苯 B, 聚醯亞胺樹脂清漆之調製 將上述各合成例反應所得之各聚醯亞胺樹脂粉末 別置於150毫升燒杯中,加入85克刚p難使其溶解^ 成固成份15%之聚醯亞胺樹脂清漆。 ° C. 奈米填充劑之調製 f Degussa股份有限公司生產銷售之%η〇 &〇2(平 為〇不米)2克置入30克NMP中,利用高速均質機轉速] ΠΜ分散,麟含2. 5%層狀氧化奴絲。㈣增速侧丨 D·熱固性樹脂改質之聚醯亞胺樹脂組成物之調製 TP060316 13 1342323
‘表其2中所百 二1= 酸基笨基)丙錄.6克先與5克ΝΜΡ· 刀鐘’倒入上述步驟(a)製備之固成份15%之聚酿亞胺樹脂 清漆中攪拌1小時’隨後另將N,N_4,4,_二苯基甲烷—雙馬來醯 亞胺(BMI)2. 4克溶於15克NMP後,添加至上述混合物中,接 著添加步驟(b)所製備之填充劑分散液(32克)’獲得最終組成 物,其固成份為12· 9%,黏度為2300 cp。 TP060316 14 1342323
比較例 5 〇〇 〇〇 <=) CO CO 05 <=> in s CO CM 比較例 4 ο o CO <x> CD LO § CO Csl 比較例 3 1 5s <=> CD CD CO 〇 isi s 寸 03 比較例 2 LO 〇〇 (ΝΙ CO c=> g C5 ud cva CV3 比較例 1 , g r—Η 〇> ο CD g —— c=> LO <=> OJ 實例7 —_1 LO CNI CO 〇 LO CO W 1 c^' <=> CO CM 實例6 LO CO c=> LO CO 05 oi CO ΙΛ CO 03 實例5 LO οα CO C=5 m CO c^> 2674 實例4 LO οα CO <〇 LO CO cn oi 2453 實例3 § (Ν1 CO LO LO CO H 0¾ oi S oa 實例2 οο CT) CO C3 LT3 CO 0¾ OJ § 00 實例1 LO OJ CO CZ5 LO CO 0¾ 〇si g CO <>J 1 Ρΐ-Κ%) 1 ΡΙ-2(%) ΡΙ-3(°/〇) 1 ΡΙ-4(%) ΡΙ-5(°/〇) 饍牮^ «C g 韌商5 氡酸酯 (B-10X%) 填充劑⑻ 溶 劑 NMP(%) 1固成份(¾) 1 P LTD OJ 0 掃w
鍩亞嬉^ttIr^-^fi-硪械 M-bYNz: mCQ ^¢¾ 械 fwwt-s^clacsi: OToalsww Π 9—odl 1342323 Ε·軟性印刷電路板之製造 將上述製得之本發明之熱固性樹脂改質之聚醯亞胺樹脂 組成物,藉線棒以3微米厚度均勻塗佈在厚度1/2密耳之 Apical聚酿亞胺薄膜(得自Kanegafuchi股份有限公司)上, 在烘箱中以200°C烘乾0. 5小時除去溶劑。將已烘乾的聚醯亞 胺薄膜利用平板壓合機或輥壓合機,在溫度32〇<t及壓力 i〇〇Kgf下與銅箔貼合’貼合後再進入氮氣烘箱中在28(rc進行 後固化1小時’製成高耐熱性、高尺寸安定性之軟性印刷電路 板。或者’亦可將本發明之熱固性樹脂改質之聚醯亞胺樹脂組 成物塗佈於聚醯亞胺薄膜兩面,並以兩面分別與銅箔壓合,而 製造雙面印刷電路板。 ° 對所得印刷電路板以IPC-TM650 2. 2. 9進行剝離強度測 試’以kgf/cm表示剝離強度;以熱比重分析儀測定印刷電路 板總體之熱膨脹係數(CTE) ’其中〇;1代表低於組成物玻璃轉 移溫度(Tg)所測付之熱膨脹儀數,α2代表高於組成物玻璃轉 移溫度(Tg)所測得之熱膨脹係數,以ppm/°c表示;耐熱性測 試係於340°C、360°C錫爐中停留1〇分鐘後,印刷電路板表面 是否有皺摺或熔解’表面保持平整者視為通過;以及以 IPC-TM650 2. 2.4測定尺寸安定性,以處理後之電路板相對於 處理前之尺寸變化比表示。該等結果列於表3。 16 TP060316 (5 ) 1342323
co^ 比較例 5 Ln g <=> g 29900 通過 1 1 比較例1 4 _1 CO Η g <=> c=j Cvl LO 29793 通過 1通過 1 - 1 比較例 3 卜 CD τ Η OJ C3 CO ! 38609 1_ 通過 比較例 2 g <=> 0.09 1 oo 22537 通過 通過 比較例 1 卜 0.12 LO <=5 LO L〇 35908 通過 實例7 CO s <r> s CD 寸 寸 17432 通過 通過 實例6 LO o s 〇 οα 14689 通過 通過 實例5 1_ LO 名 o o* CO 16573 通過 通過 實例4 1_ 1 一 0.01 g c> 15637 通過 通過 實例3 L in s C5 g o 15320 通過 通過 實例2 寸 ◦· s o LO 呀 1 16774 1_____ 丨通過 通過 1 實例I ! m <=> s o (N1 I 15320 1_____ 通過 1 |通過 1 靶 镣1 尺寸安定性| (%,MD) 1 尺寸安定性 (%,TO) CTE(al) (ppm/°C) CTE(a2) (DDm/°C) 对熱試驗 (340 °C, 10min) 财熱試驗 (360 °C,10min) P 囊g s
Claims (1)
1342323 丨公告本丨 1. 第0961〇2257號專利申請案未劃線修正頁-、申請專利範圍: 一種熱固性樹脂改質之聚SI亞胺樹脂組成物,包括下列成份:(a) 聚醯亞胺樹脂、(b)氰酸酯、(C)雙馬來醯亞胺、以及(d)奈米填 充劑,其中以組成物總重計,上述成份(a)聚醯亞胺樹脂為〜 重量% ;成份(b)氰酸酯重量為〇. M0重量% ;成份(c)雙馬來醯 亞胺,0.卜1〇重量% ;且成份(d)奈米填充劑為M〇重量%。 如申請專利範圍第1項之聚醯亞胺樹脂組成物,並中該成份Γ ) 聚醯亞胺樹脂係由下式(1)之二胺: 八 H2N-R1-NH2 (I) ;其中Ri,(i)共價鍵;(H)C2M2脂族烴基;(出)。3。脂環族基; iv)(V3。芳族基;(v)式_Ph_〇_R2—〇_ph_之基(其中沁代表伸苯基 ^-P^-X-Ph-之基且X代表共價鍵、可經齒素取代之& 4伸烷基、 Μ 3 , 〇4~、_〇—、_C0—、—S_、-S0_"或 _S〇2_ 基);或 (v)-R KSiR2-〇)ra-SiRVR3-(^ t R3 ^-(CH2)s- . -(CHOs-Ph- ^ P4炎V ◦ Ph—或~Ph_ ’m為1至100之整數;s為1至4之整數; K為Cl—6烧基、苯基或〇_6烧基苯基)]; 與下式(II)之二酸酐反應所得者: 妁年||月y日修正本 畔年11月5曰) Ό II c 〇 11 C 〇 Υ 〇、/ \ / € C \1 〇 〇 (II) 個碳原子之四價脂族基、含4至8個碳原 之、^4早喊々細合四财族基、>Ph—x-ph< 氰 R~(0~C=Nf) (ΠΙ) ΤΡ060316 i9 1342323 第096102257號專利申請案未劃線修正頁 (99年II月5日) 其中η為至少為2且不大於5之整數,且R5 (i)具有至少2價且衍生自αΙ6芳放树々宜' 萘、惠或祐(pyrene)之基;$ 4之基,例如衍生自苯、 (i i)由複數個芳族環直接鍵結或姑由 機基,例如衍生自下式⑴所示之橋接軒絲鍵結之有
, ⑴ 六〇 ί!心且P為二價脂族、芳族或芳脂族烴基、氧原子 k原子、㉟基、雜基、亞雜基、伸絲基伸絲、亞絲 〇 I15 Ό-R- Ο 〇c6h5 基 (ill)衍生自酚醛清漆型盼樹脂(nov〇lac__type phen〇l resin) 之基。 如申tf專利範圍第3項之聚醯亞胺樹脂組成物,其中式(ΙΠ)中 Rj所示之(ii)有機基係衍生自聯苯、二苯基甲烷α_二甲基 笨基曱烧、一苯基醚、二苯基二亞曱基趟、二苯基硫醚、二苯基 酮、二苯基胺、二苯基亞硬、二笨基砜、亞磷酸三苯酯或磷酸三 苯酯之基。 如申請專利範圍第1項之聚醯亞胺樹脂組成物,其中該成份 之雙馬來醯亞胺係由下式(IV)所示之化合物: V
N—R—N 0 V
(IV) 其中R7為(i)含6至16個碳原子之二價芳香族或脂環族有機基; (ii)下式(1)所示之基: TP060316 20 1342323 弟096102257號專利申請案未劃線修正頁 (99年11月5曰)
(1) 其中0為0或1且R6為二價脂族、芳族或芳脂族烴基、氧原子、 硫原子、羰基、磺醯基、亞磺醯基、伸烷氧基伸烷基、亞胺基、 9 0-R-0- 〇 _〇~R-〇-〇C6H5 oc6h5 如申請專利範圍第5項之聚醯亞胺樹脂組成物,其中以R7所示之 該含6至16個碳原子之二價芳族或脂環族有機基係伸笨基、伸 萘基、伸二曱苯基(xylylene)、伸環己基或伸六氫二甲苯基 (hexahydroxylylene)者。 如申請專利範圍第5項之聚醯亞胺樹脂組成物,其中該成份(c) 之雙馬來醯亞胺係選自N,N,-伸乙基-雙馬來醯亞胺、n,N,-伸丁 基-雙馬來酿亞胺、N,N’〜伸笨基-雙馬來酿亞胺、Ν,Ν’-六亞曱基-雙馬來醯亞胺、Ν,Ν’-4, 4’-二笨基甲烷-雙馬來醯亞胺、Ν,Ν,_4, 4,-二笨基醚-雙馬來醯亞胺、Ν,Ν’-4, 4’-二苯基颯-雙馬來醯亞胺、 Ν, Ν -4, 4 -一環己基曱烧-雙馬來酿亞胺、ν,Ν’-伸二曱苯-雙馬來 醯亞胺及Ν,Ν’-二苯基環己烧-雙馬來醯亞胺所組成之組群。 如申請專利範圍第1項之聚醯亞胺樹脂組成物,其中該成份 奈米填充劑為經矽烷改質之有機粉體或無機粉體或其混合物,且 其粒徑為10nm〜10/zm。 如申請專利範圍第8項之聚酿亞胺樹脂組成物,其中該成份(己) 係選自氧化鋁、矽酸鋁、氧化矽氧化鋁、鹼金屬鋁矽酸鹽、硼矽 酸鹽玻璃、二氧化鈦、氧化鋅、氮化硼、氮化梦、霞石(nepheline)、黑花崗石(syenite)、斜鉛石(buddeluyite)、異 性石(eudialyte)、Zr〇2 ' Fe2〇3、NiO、CnOs、3Mg0 . 4Si〇2 · H2O、 Al2〇3 . Si〇2 . xH2〇、FeOOH、滑石及 CaC〇3所組成之組群。 或 基 ΊΡ060316 21
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| TW096102257A TWI342323B (en) | 2007-01-22 | 2007-01-22 | Thermoset resin modified polyimide resin composition |
| US11/798,154 US7816437B2 (en) | 2007-01-22 | 2007-05-10 | Polymide resin composition modified with bismaleimide and cyanate |
| JP2007132451A JP2008174708A (ja) | 2007-01-22 | 2007-05-18 | 熱硬化性樹脂変性のポリイミド樹脂組成物 |
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| DE102007023557B4 (de) * | 2007-05-21 | 2010-11-25 | Siemens Ag | Schutzbeschichtung und Verwendung davon für Fahrleitungsisolatoren |
| KR100925758B1 (ko) * | 2007-11-23 | 2009-11-11 | 삼성전기주식회사 | 인쇄회로기판 제조방법 |
| US8319299B2 (en) * | 2009-11-20 | 2012-11-27 | Auman Brian C | Thin film transistor compositions, and methods relating thereto |
| US20130040517A1 (en) * | 2011-03-07 | 2013-02-14 | Mitsubishi Gas Chemical Company, Inc. | Resin composition for printed circuit board |
| US9141157B2 (en) * | 2011-10-13 | 2015-09-22 | Texas Instruments Incorporated | Molded power supply system having a thermally insulated component |
| ES2629379T3 (es) * | 2013-03-28 | 2017-08-09 | Evonik Degussa Gmbh | Mezclas curables a base de bismaleimida de xilileno |
| JP5976588B2 (ja) * | 2013-03-29 | 2016-08-23 | 新日鉄住金化学株式会社 | フレキシブル銅張積層板の製造方法 |
| WO2016010033A1 (ja) | 2014-07-18 | 2016-01-21 | 三菱瓦斯化学株式会社 | 樹脂組成物、プリプレグ、金属箔張積層板、及びプリント配線板 |
| CN108137924B (zh) * | 2015-09-30 | 2021-08-13 | 日产化学工业株式会社 | 树脂薄膜形成用组合物 |
| US10920018B2 (en) | 2016-05-09 | 2021-02-16 | Mitsubishi Gas Chemical Company, Inc. | Polyimide resin and polyimide resin composition |
| TWI588193B (zh) * | 2016-08-18 | 2017-06-21 | 臻鼎科技股份有限公司 | 樹脂組合物及應用該樹脂組合物的膠片及覆銅板 |
| KR102138704B1 (ko) * | 2018-05-14 | 2020-07-29 | 피아이첨단소재 주식회사 | 비스말레이미드계 수지 및 카본 블랙을 포함하는 폴리이미드 필름 및 이의 제조방법 |
| CN114015349B (zh) * | 2021-12-21 | 2022-04-15 | 东莞宇隆电工材料有限公司 | 一种漆包线抗老化涂层 |
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| US20080176984A1 (en) | 2008-07-24 |
| TW200831610A (en) | 2008-08-01 |
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