TW201529728A - Polyimide precursor composition, method of manufacturing polyimide, polyimide, polyimide film, and substrate - Google Patents
Polyimide precursor composition, method of manufacturing polyimide, polyimide, polyimide film, and substrate Download PDFInfo
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- TW201529728A TW201529728A TW103141244A TW103141244A TW201529728A TW 201529728 A TW201529728 A TW 201529728A TW 103141244 A TW103141244 A TW 103141244A TW 103141244 A TW103141244 A TW 103141244A TW 201529728 A TW201529728 A TW 201529728A
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- Prior art keywords
- polyimine
- polyimide
- precursor
- chemical formula
- film
- Prior art date
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- 229920001721 polyimide Polymers 0.000 title claims abstract description 218
- 239000002243 precursor Substances 0.000 title claims abstract description 216
- 239000004642 Polyimide Substances 0.000 title claims abstract description 100
- 239000000203 mixture Substances 0.000 title claims abstract description 82
- 239000000758 substrate Substances 0.000 title claims description 87
- 238000004519 manufacturing process Methods 0.000 title claims description 29
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims abstract description 91
- 239000000126 substance Substances 0.000 claims description 113
- -1 imidazole compound Chemical class 0.000 claims description 65
- 238000010438 heat treatment Methods 0.000 claims description 32
- 238000002834 transmittance Methods 0.000 claims description 26
- GIWQSPITLQVMSG-UHFFFAOYSA-N 1,2-dimethylimidazole Chemical compound CC1=NC=CN1C GIWQSPITLQVMSG-UHFFFAOYSA-N 0.000 claims description 23
- 125000003118 aryl group Chemical group 0.000 claims description 19
- 125000004432 carbon atom Chemical group C* 0.000 claims description 13
- 125000000217 alkyl group Chemical group 0.000 claims description 11
- 150000001412 amines Chemical class 0.000 claims description 8
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims description 8
- 239000001257 hydrogen Substances 0.000 claims description 7
- 229910052739 hydrogen Inorganic materials 0.000 claims description 7
- MCTWTZJPVLRJOU-UHFFFAOYSA-N 1-methyl-1H-imidazole Chemical compound CN1C=CN=C1 MCTWTZJPVLRJOU-UHFFFAOYSA-N 0.000 claims description 6
- 239000011248 coating agent Substances 0.000 claims description 6
- 238000000576 coating method Methods 0.000 claims description 6
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 6
- HYZJCKYKOHLVJF-UHFFFAOYSA-N 1H-benzimidazole Chemical compound C1=CC=C2NC=NC2=C1 HYZJCKYKOHLVJF-UHFFFAOYSA-N 0.000 claims description 5
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 claims description 5
- 125000002947 alkylene group Chemical group 0.000 claims description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N benzene Substances C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims 1
- 150000001875 compounds Chemical class 0.000 abstract description 11
- 150000004985 diamines Chemical class 0.000 description 77
- 239000010408 film Substances 0.000 description 66
- 239000002966 varnish Substances 0.000 description 53
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 47
- 239000011521 glass Substances 0.000 description 40
- 239000005340 laminated glass Substances 0.000 description 38
- 230000015572 biosynthetic process Effects 0.000 description 32
- 238000006243 chemical reaction Methods 0.000 description 29
- 150000000000 tetracarboxylic acids Chemical class 0.000 description 29
- 239000002904 solvent Substances 0.000 description 28
- 238000003786 synthesis reaction Methods 0.000 description 27
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 21
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 20
- 238000000034 method Methods 0.000 description 20
- 239000001301 oxygen Substances 0.000 description 20
- 229910052760 oxygen Inorganic materials 0.000 description 20
- 238000005259 measurement Methods 0.000 description 19
- 239000012528 membrane Substances 0.000 description 19
- 239000012299 nitrogen atmosphere Substances 0.000 description 19
- 239000004810 polytetrafluoroethylene Substances 0.000 description 19
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 19
- 230000000052 comparative effect Effects 0.000 description 18
- 239000012456 homogeneous solution Substances 0.000 description 17
- 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 description 16
- 229910052727 yttrium Inorganic materials 0.000 description 15
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 14
- 239000003795 chemical substances by application Substances 0.000 description 13
- 125000006158 tetracarboxylic acid group Chemical group 0.000 description 12
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 10
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 description 9
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 9
- 239000002253 acid Substances 0.000 description 9
- 238000003756 stirring Methods 0.000 description 9
- DLFVBJFMPXGRIB-UHFFFAOYSA-N Acetamide Chemical compound CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 8
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 7
- 239000007789 gas Substances 0.000 description 7
- 239000004973 liquid crystal related substance Substances 0.000 description 7
- 229910052707 ruthenium Inorganic materials 0.000 description 7
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 6
- HLBLWEWZXPIGSM-UHFFFAOYSA-N 4-Aminophenyl ether Chemical compound C1=CC(N)=CC=C1OC1=CC=C(N)C=C1 HLBLWEWZXPIGSM-UHFFFAOYSA-N 0.000 description 6
- NVKGJHAQGWCWDI-UHFFFAOYSA-N 4-[4-amino-2-(trifluoromethyl)phenyl]-3-(trifluoromethyl)aniline Chemical compound FC(F)(F)C1=CC(N)=CC=C1C1=CC=C(N)C=C1C(F)(F)F NVKGJHAQGWCWDI-UHFFFAOYSA-N 0.000 description 6
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 6
- 229960000978 cyproterone acetate Drugs 0.000 description 6
- 239000000178 monomer Substances 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- 238000006116 polymerization reaction Methods 0.000 description 6
- QUPKCFBHJFNUEW-UHFFFAOYSA-N 2-ethyl-4,5-dihydro-1h-imidazole Chemical compound CCC1=NCCN1 QUPKCFBHJFNUEW-UHFFFAOYSA-N 0.000 description 5
- HYDATEKARGDBKU-UHFFFAOYSA-N 4-[4-[4-(4-aminophenoxy)phenyl]phenoxy]aniline Chemical group C1=CC(N)=CC=C1OC1=CC=C(C=2C=CC(OC=3C=CC(N)=CC=3)=CC=2)C=C1 HYDATEKARGDBKU-UHFFFAOYSA-N 0.000 description 5
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 5
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 5
- 235000010290 biphenyl Nutrition 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- DHKHKXVYLBGOIT-UHFFFAOYSA-N 1,1-Diethoxyethane Chemical compound CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 description 4
- ZCUJYXPAKHMBAZ-UHFFFAOYSA-N 2-phenyl-1h-imidazole Chemical compound C1=CNC(C=2C=CC=CC=2)=N1 ZCUJYXPAKHMBAZ-UHFFFAOYSA-N 0.000 description 4
- JJYPMNFTHPTTDI-UHFFFAOYSA-N 3-methylaniline Chemical compound CC1=CC=CC(N)=C1 JJYPMNFTHPTTDI-UHFFFAOYSA-N 0.000 description 4
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 4
- OZJPLYNZGCXSJM-UHFFFAOYSA-N 5-valerolactone Chemical compound O=C1CCCCO1 OZJPLYNZGCXSJM-UHFFFAOYSA-N 0.000 description 4
- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Chemical compound CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 4
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Chemical compound C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 description 4
- 230000004888 barrier function Effects 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 4
- 239000004020 conductor Substances 0.000 description 4
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 4
- BGTOWKSIORTVQH-UHFFFAOYSA-N cyclopentanone Chemical compound O=C1CCCC1 BGTOWKSIORTVQH-UHFFFAOYSA-N 0.000 description 4
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 description 4
- JBFHTYHTHYHCDJ-UHFFFAOYSA-N gamma-caprolactone Chemical compound CCC1CCC(=O)O1 JBFHTYHTHYHCDJ-UHFFFAOYSA-N 0.000 description 4
- GAEKPEKOJKCEMS-UHFFFAOYSA-N gamma-valerolactone Chemical compound CC1CCC(=O)O1 GAEKPEKOJKCEMS-UHFFFAOYSA-N 0.000 description 4
- 238000006358 imidation reaction Methods 0.000 description 4
- RLSSMJSEOOYNOY-UHFFFAOYSA-N m-cresol Chemical compound CC1=CC=CC(O)=C1 RLSSMJSEOOYNOY-UHFFFAOYSA-N 0.000 description 4
- QWVGKYWNOKOFNN-UHFFFAOYSA-N o-cresol Chemical compound CC1=CC=CC=C1O QWVGKYWNOKOFNN-UHFFFAOYSA-N 0.000 description 4
- 230000003287 optical effect Effects 0.000 description 4
- 239000003960 organic solvent Substances 0.000 description 4
- IWDCLRJOBJJRNH-UHFFFAOYSA-N p-cresol Chemical compound CC1=CC=C(O)C=C1 IWDCLRJOBJJRNH-UHFFFAOYSA-N 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- 238000003860 storage Methods 0.000 description 4
- GEYOCULIXLDCMW-UHFFFAOYSA-N 1,2-phenylenediamine Chemical compound NC1=CC=CC=C1N GEYOCULIXLDCMW-UHFFFAOYSA-N 0.000 description 3
- 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 3
- 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 3
- JCRRFJIVUPSNTA-UHFFFAOYSA-N 4-[4-(4-aminophenoxy)phenoxy]aniline Chemical compound C1=CC(N)=CC=C1OC(C=C1)=CC=C1OC1=CC=C(N)C=C1 JCRRFJIVUPSNTA-UHFFFAOYSA-N 0.000 description 3
- PJWQLRKRVISYPL-UHFFFAOYSA-N 4-[4-amino-3-(trifluoromethyl)phenyl]-2-(trifluoromethyl)aniline Chemical compound C1=C(C(F)(F)F)C(N)=CC=C1C1=CC=C(N)C(C(F)(F)F)=C1 PJWQLRKRVISYPL-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 3
- HYZLYRGDKCMKOK-UHFFFAOYSA-N NC1=CC=C(C(=O)C2=C(C=CC=C2)C2=CC=C(C=C2)N)C=C1 Chemical compound NC1=CC=C(C(=O)C2=C(C=CC=C2)C2=CC=C(C=C2)N)C=C1 HYZLYRGDKCMKOK-UHFFFAOYSA-N 0.000 description 3
- 125000003277 amino group Chemical group 0.000 description 3
- 238000005452 bending Methods 0.000 description 3
- 239000004305 biphenyl Substances 0.000 description 3
- ZLSMCQSGRWNEGX-UHFFFAOYSA-N bis(4-aminophenyl)methanone Chemical compound C1=CC(N)=CC=C1C(=O)C1=CC=C(N)C=C1 ZLSMCQSGRWNEGX-UHFFFAOYSA-N 0.000 description 3
- 238000009835 boiling Methods 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- 150000005690 diesters Chemical class 0.000 description 3
- 150000002009 diols Chemical class 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 229910052731 fluorine Inorganic materials 0.000 description 3
- 125000001153 fluoro group Chemical group F* 0.000 description 3
- 125000000524 functional group Chemical group 0.000 description 3
- 238000004817 gas chromatography Methods 0.000 description 3
- 150000002460 imidazoles Chemical class 0.000 description 3
- MTNDZQHUAFNZQY-UHFFFAOYSA-N imidazoline Chemical compound C1CN=CN1 MTNDZQHUAFNZQY-UHFFFAOYSA-N 0.000 description 3
- 150000002466 imines Chemical class 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 3
- 150000002923 oximes Chemical class 0.000 description 3
- XNGIFLGASWRNHJ-UHFFFAOYSA-L phthalate(2-) Chemical compound [O-]C(=O)C1=CC=CC=C1C([O-])=O XNGIFLGASWRNHJ-UHFFFAOYSA-L 0.000 description 3
- 229920002098 polyfluorene Polymers 0.000 description 3
- 238000007639 printing Methods 0.000 description 3
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 3
- 238000007363 ring formation reaction Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 238000007740 vapor deposition Methods 0.000 description 3
- UGCMFUQMPWJOON-UHFFFAOYSA-N (1-cycloheptylcycloheptyl)methanediamine Chemical compound C1CCCCCC1C1(C(N)N)CCCCCC1 UGCMFUQMPWJOON-UHFFFAOYSA-N 0.000 description 2
- GWNMOARSGRXJMV-UHFFFAOYSA-N (1-cycloheptylcycloheptyl)oxymethanediamine Chemical compound C1CCCCCC1C1(OC(N)N)CCCCCC1 GWNMOARSGRXJMV-UHFFFAOYSA-N 0.000 description 2
- DIIIISSCIXVANO-UHFFFAOYSA-N 1,2-Dimethylhydrazine Chemical compound CNNC DIIIISSCIXVANO-UHFFFAOYSA-N 0.000 description 2
- CYSGHNMQYZDMIA-UHFFFAOYSA-N 1,3-Dimethyl-2-imidazolidinon Chemical compound CN1CCN(C)C1=O CYSGHNMQYZDMIA-UHFFFAOYSA-N 0.000 description 2
- MNKDMOZTFOSBSA-UHFFFAOYSA-N 1-(1-aminocycloheptyl)cycloheptan-1-amine Chemical compound C1CCCCCC1(N)C1(N)CCCCCC1 MNKDMOZTFOSBSA-UHFFFAOYSA-N 0.000 description 2
- SPJXZYLLLWOSLQ-UHFFFAOYSA-N 1-[(1-aminocyclohexyl)methyl]cyclohexan-1-amine Chemical compound C1CCCCC1(N)CC1(N)CCCCC1 SPJXZYLLLWOSLQ-UHFFFAOYSA-N 0.000 description 2
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical compound CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 description 2
- NRKYWOKHZRQRJR-UHFFFAOYSA-N 2,2,2-trifluoroacetamide Chemical compound NC(=O)C(F)(F)F NRKYWOKHZRQRJR-UHFFFAOYSA-N 0.000 description 2
- YTPFRRRNIYVFFE-UHFFFAOYSA-N 2,2,3,3,5,5-hexamethyl-1,4-dioxane Chemical compound CC1(C)COC(C)(C)C(C)(C)O1 YTPFRRRNIYVFFE-UHFFFAOYSA-N 0.000 description 2
- BEBVJSBFUZVWMS-UHFFFAOYSA-N 2-(2-methylpropyl)cyclohexane-1,4-diamine Chemical compound CC(C)CC1CC(N)CCC1N BEBVJSBFUZVWMS-UHFFFAOYSA-N 0.000 description 2
- PTTPXKJBFFKCEK-UHFFFAOYSA-N 2-Methyl-4-heptanone Chemical compound CC(C)CC(=O)CC(C)C PTTPXKJBFFKCEK-UHFFFAOYSA-N 0.000 description 2
- HIEBSORULQQANM-UHFFFAOYSA-N 2-butylcyclohexane-1,4-diamine Chemical compound CCCCC1CC(N)CCC1N HIEBSORULQQANM-UHFFFAOYSA-N 0.000 description 2
- FMZFBOHWVULQIY-UHFFFAOYSA-N 2-ethylcyclohexane-1,4-diamine Chemical compound CCC1CC(N)CCC1N FMZFBOHWVULQIY-UHFFFAOYSA-N 0.000 description 2
- SFHLLWPKGUSQIK-UHFFFAOYSA-N 2-methylcyclohexane-1,4-diamine Chemical compound CC1CC(N)CCC1N SFHLLWPKGUSQIK-UHFFFAOYSA-N 0.000 description 2
- ALBWHZWLFAHNRI-UHFFFAOYSA-N 2-propan-2-ylcyclohexane-1,4-diamine Chemical compound CC(C)C1CC(N)CCC1N ALBWHZWLFAHNRI-UHFFFAOYSA-N 0.000 description 2
- WNRDZWNCHXTBTQ-UHFFFAOYSA-N 2-propylcyclohexane-1,4-diamine Chemical compound CCCC1CC(N)CCC1N WNRDZWNCHXTBTQ-UHFFFAOYSA-N 0.000 description 2
- RKBNPLYPKZRNEF-UHFFFAOYSA-N 2-tert-butylcyclohexane-1,4-diamine Chemical compound CC(C)(C)C1CC(N)CCC1N RKBNPLYPKZRNEF-UHFFFAOYSA-N 0.000 description 2
- HUWXDEQWWKGHRV-UHFFFAOYSA-N 3,3'-Dichlorobenzidine Chemical group C1=C(Cl)C(N)=CC=C1C1=CC=C(N)C(Cl)=C1 HUWXDEQWWKGHRV-UHFFFAOYSA-N 0.000 description 2
- JRBJSXQPQWSCCF-UHFFFAOYSA-N 3,3'-Dimethoxybenzidine Chemical group C1=C(N)C(OC)=CC(C=2C=C(OC)C(N)=CC=2)=C1 JRBJSXQPQWSCCF-UHFFFAOYSA-N 0.000 description 2
- RNLHGQLZWXBQNY-UHFFFAOYSA-N 3-(aminomethyl)-3,5,5-trimethylcyclohexan-1-amine Chemical compound CC1(C)CC(N)CC(C)(CN)C1 RNLHGQLZWXBQNY-UHFFFAOYSA-N 0.000 description 2
- HORNXRXVQWOLPJ-UHFFFAOYSA-N 3-chlorophenol Chemical compound OC1=CC=CC(Cl)=C1 HORNXRXVQWOLPJ-UHFFFAOYSA-N 0.000 description 2
- FWOLORXQTIGHFX-UHFFFAOYSA-N 4-(4-amino-2,3,5,6-tetrafluorophenyl)-2,3,5,6-tetrafluoroaniline Chemical compound FC1=C(F)C(N)=C(F)C(F)=C1C1=C(F)C(F)=C(N)C(F)=C1F FWOLORXQTIGHFX-UHFFFAOYSA-N 0.000 description 2
- LVNPGQZSPDFZNC-UHFFFAOYSA-N 4-(4-amino-3-fluorophenyl)-2-fluoroaniline Chemical group C1=C(F)C(N)=CC=C1C1=CC=C(N)C(F)=C1 LVNPGQZSPDFZNC-UHFFFAOYSA-N 0.000 description 2
- ASNOFHCTUSIHOM-UHFFFAOYSA-N 4-[10-(4-aminophenyl)anthracen-9-yl]aniline Chemical compound C1=CC(N)=CC=C1C(C1=CC=CC=C11)=C(C=CC=C2)C2=C1C1=CC=C(N)C=C1 ASNOFHCTUSIHOM-UHFFFAOYSA-N 0.000 description 2
- BEKFRNOZJSYWKZ-UHFFFAOYSA-N 4-[2-(4-aminophenyl)-1,1,1,3,3,3-hexafluoropropan-2-yl]aniline Chemical compound C1=CC(N)=CC=C1C(C(F)(F)F)(C(F)(F)F)C1=CC=C(N)C=C1 BEKFRNOZJSYWKZ-UHFFFAOYSA-N 0.000 description 2
- HHLMWQDRYZAENA-UHFFFAOYSA-N 4-[4-[2-[4-(4-aminophenoxy)phenyl]-1,1,1,3,3,3-hexafluoropropan-2-yl]phenoxy]aniline Chemical compound C1=CC(N)=CC=C1OC1=CC=C(C(C=2C=CC(OC=3C=CC(N)=CC=3)=CC=2)(C(F)(F)F)C(F)(F)F)C=C1 HHLMWQDRYZAENA-UHFFFAOYSA-N 0.000 description 2
- WXNZTHHGJRFXKQ-UHFFFAOYSA-N 4-chlorophenol Chemical compound OC1=CC=C(Cl)C=C1 WXNZTHHGJRFXKQ-UHFFFAOYSA-N 0.000 description 2
- WOYZXEVUWXQVNV-UHFFFAOYSA-N 4-phenoxyaniline Chemical compound C1=CC(N)=CC=C1OC1=CC=CC=C1 WOYZXEVUWXQVNV-UHFFFAOYSA-N 0.000 description 2
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 2
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- 239000007788 liquid Substances 0.000 description 1
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- 238000010525 oxidative degradation reaction Methods 0.000 description 1
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- 239000002245 particle Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
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- 239000011734 sodium Substances 0.000 description 1
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- 229910001220 stainless steel Inorganic materials 0.000 description 1
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Classifications
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- H01L31/0248—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1042—Copolyimides derived from at least two different tetracarboxylic compounds or two different diamino compounds
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- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1046—Polyimides containing oxygen in the form of ether bonds in the main chain
- C08G73/105—Polyimides containing oxygen in the form of ether bonds in the main chain with oxygen only in the diamino moiety
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1075—Partially aromatic polyimides
- C08G73/1078—Partially aromatic polyimides wholly aromatic in the diamino moiety
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Abstract
Description
本發明係關於一種溶液組成物(聚醯亞胺前驅體組成物),含有可獲得透明性更優異、線熱膨脹係數小、機械特性也優良之聚醯亞胺的聚醯亞胺前驅體,並係關於聚醯亞胺之製造方法。又,本發明也係關於透明性優異、線熱膨脹係數小、機械特性也優良的聚醯亞胺、聚醯亞胺膜、及基板。The present invention relates to a solution composition (polyimine precursor composition) containing a polyimine precursor which can obtain a polyimine which is more excellent in transparency, has a small coefficient of thermal expansion, and excellent in mechanical properties, and It relates to a method for producing polyimine. Further, the present invention relates to a polyimide, a polyimide film, and a substrate which are excellent in transparency, have a small linear thermal expansion coefficient, and are excellent in mechanical properties.
近年伴隨高度資訊化社會的到來,於光通訊領域之光纖或光波導等顯示裝置領域之液晶配向膜或彩色濾光片用保護膜等光學材料之開發已有進展。尤其,於顯示裝置領域,已有人探討替代玻璃基板之質輕且可撓性優異之塑膠基板、或開發可彎、可圓化的顯示器正在積極進行中。所以,尋求可用在如此的用途中的更高性能的光學材料。In recent years, with the advent of a highly information society, development of optical materials such as liquid crystal alignment films or protective films for color filters in the field of display devices such as optical fibers and optical waveguides in the field of optical communication has progressed. In particular, in the field of display devices, it has been actively explored that plastic substrates having superior lightness and flexibility in replacing glass substrates, or development of bendable and roundable displays are being actively carried out. Therefore, a higher performance optical material that can be used in such applications is sought.
芳香族聚醯亞胺,由於形成分子內共軛或電荷移動錯合物而固有地著色為黃褐色。為了抑制著色之方法,有人提出例如對於分子內導入氟原子、對於主鏈賦予彎曲性、導入體積大的基團作為側鏈等以妨礙分子內共軛或電荷移動錯合物形成並且使其展現透明性之方法。The aromatic polyimine is inherently colored yellowish due to the formation of intramolecular conjugates or charge transport complexes. In order to suppress the coloring, for example, a fluorine atom is introduced intramolecularly, a bending property is imparted to the main chain, and a bulky group is introduced as a side chain or the like to hinder the formation of an intramolecular conjugate or a charge transport complex and to exhibit it. The method of transparency.
又,也有人提出使用理論上不形成電荷移動錯合物的半脂環族或全脂環族聚醯亞胺以使其展現透明性之方法。例如:專利文獻1~4揭示使用脂環族四羧酸二酐作為四羧酸成分、使用芳香族二胺作為二胺成分之高透明性之半脂環族聚醯亞胺。Further, it has also been proposed to use a semi-alicyclic or full-aliphatic polyimine which theoretically does not form a charge transporting complex to exhibit transparency. For example, Patent Documents 1 to 4 disclose a highly transparent semi-alicyclic polyamidene using an alicyclic tetracarboxylic dianhydride as a tetracarboxylic acid component and an aromatic diamine as a diamine component.
專利文獻5、專利文獻6揭示使用十氫-1,4:5,8-二甲橋萘-2,3,6,7-四羧酸類作為四羧酸成分的聚醯亞胺。非專利文獻1揭示使用(4arH,8acH)-十氫-1t,4t:5c,8c-二甲橋萘-2t,3t,6c,7c-四羧酸類作為四羧酸成分之聚醯亞胺,非專利文獻2揭示使用(4arH,8acH)-十氫-1t,4t:5c,8c-二甲橋萘-2c,3c,6c,7c-四羧酸類作為四羧酸成分之聚醯亞胺。Patent Document 5 and Patent Document 6 disclose a polyimide using tetrahydro-1,4:5,8-dimethylnaphthalene-2,3,6,7-tetracarboxylic acid as a tetracarboxylic acid component. Non-Patent Document 1 discloses the use of (4arH, 8acH)-decahydro-1t, 4t:5c, 8c-dimethylnaphthalene-2t, 3t, 6c, 7c-tetracarboxylic acid as a polycarboxylic acid of a tetracarboxylic acid component, Non-Patent Document 2 discloses a polyimine which uses (4arH, 8acH)-decahydro-1t, 4t:5c, 8c-dimethylnaphthalene-2c, 3c, 6c, 7c-tetracarboxylic acid as a tetracarboxylic acid component.
但是尤其是在顯示裝置等領域,需要透明性更高的聚醯亞胺。又,使用脂環族四羧酸二酐作為四羧酸成分、芳香族二胺作為二胺成分的半脂環族聚醯亞胺,雖兼具高透明性、彎折耐性、高耐熱性,但一般有線熱膨脹係數大的傾向。若聚醯亞胺之線熱膨脹係數大,和金屬等導體間的線熱膨脹係數差距大,會有形成電路基板時的翹曲增大等不良現象,尤其會有在顯示器用途等微細電路形成處理不容易進行的情形。However, in particular, in the field of display devices and the like, a polyimide having a higher transparency is required. Further, a semialicyclic polyimine which uses an alicyclic tetracarboxylic dianhydride as a tetracarboxylic acid component and an aromatic diamine as a diamine component has high transparency, bending resistance, and high heat resistance. However, the general linear thermal expansion coefficient tends to be large. If the coefficient of thermal expansion of the polyimine is large and the difference in linear thermal expansion coefficient between the conductors such as metal is large, there is a problem that warpage increases when the circuit board is formed, and in particular, fine circuit formation processing such as display use is not performed. Easy to carry out.
另一方面,專利文獻7揭示將於聚醯亞胺前驅體(聚醯胺酸) 摻合咪唑啉系化合物及/或咪唑系化合物而成的塗液予以加熱而形成的聚醯亞胺。更具體而言,實施例1中,係將於由3,3’,4,4’-二苯基酮四羧酸二酐與4,4’-二胺基聯苯醚獲得之聚醯胺酸之溶液中加有2,4-二甲基咪唑啉而得的溶液塗佈在基板上,於200℃加熱1小時,而獲得膜厚1000埃(0.1μm)之芳香族聚醯亞胺皮膜。實施例2中,將於由苯均四酸二酐與4,4’-二胺基聯苯醚獲得之聚醯胺酸之溶液中加有2-乙基咪唑啉及1,2-二甲基咪唑而得的溶液塗佈在基板上,於150℃加熱1小時,而獲得膜厚800埃(0.08μm)之芳香族聚醯亞胺皮膜。專利文獻7記載:藉由添加咪唑啉系化合物及/或咪唑系化合物可避免茶褐色之顯著著色,可獲得高透光率的透明性優異之液晶顯示元件。但是使用實施例1之聚醯亞胺皮膜(液晶配向膜)獲得之液晶顯示元件,波長400nm之透光率為82%(聚醯亞胺膜厚:0.1μm),使用實施例2之聚醯亞胺皮膜(液晶配向膜)獲得之液晶顯示元件之波長400nm之透光率為83%(聚醯亞胺膜厚:0.08μm),此聚醯亞胺未有充足的透明性。On the other hand, Patent Document 7 discloses a polyimide which is formed by heating a coating liquid obtained by blending an imidazoline-based compound (poly-proline) with an imidazoline-based compound and/or an imidazole-based compound. More specifically, in Example 1, a polyamine obtained from 3,3',4,4'-diphenyl ketone tetracarboxylic dianhydride and 4,4'-diaminodiphenyl ether A solution obtained by adding 2,4-dimethylimidazoline to the acid solution was coated on the substrate and heated at 200 ° C for 1 hour to obtain an aromatic polyimide film having a film thickness of 1000 Å (0.1 μm). . In Example 2, 2-ethylimidazoline and 1,2-dimethyl are added to a solution of polyamic acid obtained from pyromellitic dianhydride and 4,4'-diaminodiphenyl ether. The solution obtained by imidazole was coated on a substrate and heated at 150 ° C for 1 hour to obtain an aromatic polyimide film having a film thickness of 800 Å (0.08 μm). Patent Document 7 discloses that by adding an imidazoline-based compound and/or an imidazole-based compound, significant coloration of brownish brown can be avoided, and a liquid crystal display element having excellent transparency and high transparency can be obtained. However, the liquid crystal display element obtained by using the polyimide film (liquid crystal alignment film) of Example 1 had a light transmittance of 82% at a wavelength of 400 nm (polyimine film thickness: 0.1 μm), and the polyfluorene of Example 2 was used. The light transmittance of the liquid crystal display element obtained by the imine film (liquid crystal alignment film) at a wavelength of 400 nm was 83% (polyimine film thickness: 0.08 μm), and the polyimide did not have sufficient transparency.
又,作為低透明性之芳香族聚醯亞胺之製造方法,專利文獻8揭示:把將聚醯亞胺前驅體樹脂、及咪唑、N-甲基咪唑等聚醯亞胺前驅體樹脂之硬化促進劑溶於有機極性溶劑而得的含聚醯亞胺前驅體樹脂的溶液塗佈在基材上,然後利用熱處理進行乾燥及利用醯亞胺化形成聚醯亞胺樹脂層的步驟於280~380℃之範圍內完成的聚醯亞胺樹脂層的形成方法,並有記載:藉由使用該等硬化促進劑,能控制熱線膨脹係數為低。專利文獻8尚記載:硬化促進劑宜使用沸點超過120℃者較佳,宜選擇沸點不超過熱處理之上限溫度者較佳,並記載:沸點為例如400℃以上之硬化促進劑,在醯亞胺化後之聚醯亞胺樹脂層中殘存的比例高,有影響聚醯亞胺樹脂層之機能的傾向。 【先前技術文獻】 【專利文獻】Further, as a method for producing a low-transparency aromatic polyimine, Patent Document 8 discloses that a polyimide polyimide precursor resin and a polyimide resin such as imidazole or N-methylimidazole are hardened. The solution containing the polyamidiamine precursor resin obtained by dissolving the accelerator in an organic polar solvent is coated on a substrate, and then dried by heat treatment and formed into a polyimide layer by yttrium imidation at 280~ A method of forming a polyimine resin layer which is completed in the range of 380 ° C, and it is described that the coefficient of thermal linear expansion can be controlled to be low by using the curing accelerator. Patent Document 8 discloses that it is preferable to use a curing accelerator having a boiling point of more than 120 ° C, and it is preferred to select a boiling point not exceeding the upper limit temperature of the heat treatment, and it is described that a hardening accelerator having a boiling point of, for example, 400 ° C or more is used in the imine. The proportion of the polyimine resin layer remaining in the layer is high, and there is a tendency to affect the function of the polyimide layer. [Prior Art Literature] [Patent Literature]
【專利文獻1】日本特開2003-168800號公報 【專利文獻2】國際公開第2008/146637號 【專利文獻3】日本特開2002-69179號公報 【專利文獻4】日本特開2002-146021號公報 【專利文獻5】日本特開2007-2023號公報 【專利文獻6】日本特開平6-51316號公報 【專利文獻7】日本特開昭61-267030號公報 【專利文獻8】日本特開2008-115378號公報 【非專利文獻】[Patent Document 1] Japanese Patent Laid-Open Publication No. JP-A-2002-146-A No. 2002-146. [Patent Document 5] Japanese Patent Laid-Open Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. -115378 [Non-patent literature]
【非專利文獻1】Macromolecules,Vol.27,No.5,P1117-1123,1994 【非專利文獻2】Macromolecules,Vol.32,No.15,P4933-4939,1999[Non-Patent Document 1] Macromolecules, Vol. 27, No. 5, P1117-1123, 1994 [Non-Patent Document 2] Macromolecules, Vol. 32, No. 15, P4933-4939, 1999
【發明欲解決之課題】[The subject to be solved by the invention]
本發明係有鑑於如以上的狀況而生,目的在於提供一種: 聚醯亞胺前驅體組成物(含聚醯亞胺前驅體之溶液組成物),可獲得即使是相同組成之聚醯亞胺,但為透明性更優異、低線熱膨脹係數之聚醯亞胺、或可獲得透明性優異、低線熱膨脹係數且機械特性也優良的聚醯亞胺;並提供聚醯亞胺之製造方法。 【解決課題之方式】The present invention has been made in view of the above circumstances, and an object thereof is to provide a polyiminoimine precursor composition (a solution composition containing a polyimide precursor), and a polyimine of the same composition can be obtained. However, it is a polyimine which is more excellent in transparency and has a low coefficient of thermal expansion, or a polyimide which is excellent in transparency, a low coefficient of thermal expansion, and excellent in mechanical properties, and a method for producing a polyimide. [How to solve the problem]
本發明係關於以下各項。 1.一種聚醯亞胺前驅體組成物,其特徵為: 包含含有下列化學式(1-1)表示之重複單元之聚醯亞胺前驅體、及咪唑系化合物, 咪唑系化合物之含量相對於聚醯亞胺前驅體之重複單元1莫耳為未達4莫耳;The present invention relates to the following. A polyimine precursor composition comprising: a polyimine precursor comprising a repeating unit represented by the following chemical formula (1-1), and an imidazole compound, wherein the content of the imidazole compound is relative to the poly The repeating unit 1 of the quinone imine precursor is less than 4 moles;
【化1】(式中,A為有芳香族環之2價基,X1 、X2 各自獨立地為氫、碳數1~6之烷基、或碳數3~9之烷矽基。) 2.如1.之聚醯亞胺前驅體組成物,其中,該聚醯亞胺前驅體含有下列化學式(1-2)表示之重複單元;【化1】 (In the formula, A is a divalent group having an aromatic ring, and X 1 and X 2 are each independently hydrogen, an alkyl group having 1 to 6 carbon atoms, or an alkanoyl group having 3 to 9 carbon atoms.) 1. The polyimine precursor composition, wherein the polyimine precursor contains a repeating unit represented by the following chemical formula (1-2);
【化2】(式中,A為有芳香族環之2價基,X1 、X2 各自獨立地為氫、碳數1~6之烷基、或碳數3~9之烷矽基。) 3.如1.或2.之聚醯亞胺前驅體組成物,其中,該化學式(1-1)或該化學式(1-2)中之A為下列化學式(1-A)表示之基;[Chemical 2] (In the formula, A is a divalent group having an aromatic ring, and X 1 and X 2 are each independently hydrogen, an alkyl group having 1 to 6 carbon atoms, or an alkanoyl group having 3 to 9 carbon atoms.) 1. The polyimine precursor composition of 1. or 2. wherein A in the chemical formula (1-1) or the chemical formula (1-2) is a group represented by the following chemical formula (1-A);
【化3】(式中,m表示0~3之整數、n表示0~3之整數,m、n各自獨立;Y1 、Y2 、Y3 各自獨立地表示選自於由氫原子、甲基、三氟甲基構成之群組中之1種,Q、R各自獨立地表示直接鍵結、或選自於由式:-NHCO-、-CONH-、-COO-、-OCO-表示之基構成之群組中之1種)。 4.如1.至3.中任一項之聚醯亞胺前驅體組成物,其中,由此聚醯亞胺前驅體組成物獲得之聚醯亞胺,厚度10μm之膜於波長400nm之透光率為75%以上。 5.如1.至4.中任一項之聚醯亞胺前驅體組成物,其中,該咪唑系化合物之含量相對於聚醯亞胺前驅體之重複單元1莫耳為0.05莫耳以上2莫耳以下。 6.如1.至5.中任一項之聚醯亞胺前驅體組成物,其中,該咪唑系化合物為1,2-二甲基咪唑、1-甲基咪唑、2-甲基咪唑、2-苯基咪唑、咪唑、或苯并咪唑中之任一者。 7.一種聚醯亞胺之製造方法,其特徵為:係將如1.至6.中任一項之聚醯亞胺前驅體組成物於最高加熱溫度超過350℃進行加熱處理,而將聚醯亞胺前驅體予以醯亞胺化。 8.如7.之聚醯亞胺之製造方法,包括以下步驟: 將如1.至6.中任一項之聚醯亞胺前驅體組成物塗佈在基材上; 將基材上之聚醯亞胺前驅體組成物於最高加熱溫度超過350℃進行加熱處理而將聚醯亞胺前驅體予以醯亞胺化。 9.如7.或8.之聚醯亞胺之製造方法,其中,該加熱處理之最高加熱溫度超過400℃。 10.一種聚醯亞胺,係利用如7.至9.中任一項之聚醯亞胺之製造方法製造。 11.如10.之聚醯亞胺,其中,厚度10μm之膜於波長400nm之透光率為75%以上。 12.一種聚醯亞胺膜,係利用如7.至9.中任一項之聚醯亞胺之製造方法製造。 13.一種顯示器用、觸控面板用、或太陽能電池用之基板,其特徵為含有如10.或11.之聚醯亞胺、或如12.之聚醯亞胺膜。 【發明之效果】[化3] (wherein m represents an integer of 0 to 3, n represents an integer of 0 to 3, and m and n are each independently; and Y 1 , Y 2 , and Y 3 each independently represent a hydrogen atom, a methyl group, and a trifluoro group. In the group consisting of methyl groups, Q and R each independently represent a direct bond or a group selected from the group consisting of: -NHCO-, -CONH-, -COO-, -OCO- One of the groups). 4. The polyimine precursor composition according to any one of items 1 to 3, wherein the polyimine obtained from the polyimide precursor precursor composition has a thickness of 10 μm and is transparent at a wavelength of 400 nm. The light rate is 75% or more. 5. The polyimine precursor composition according to any one of items 1 to 4, wherein the content of the imidazole-based compound is 0.05 mol or more relative to the repeating unit 1 of the polyimine precursor. Moel below. 6. The polyimine precursor composition according to any one of items 1 to 5, wherein the imidazole compound is 1,2-dimethylimidazole, 1-methylimidazole, 2-methylimidazole, Any of 2-phenylimidazole, imidazole, or benzimidazole. A method for producing a polyimine, which is characterized in that the polyimide composition precursor composition according to any one of 1. to 6. is heat-treated at a maximum heating temperature of more than 350 ° C, and is polymerized. The quinone imine precursor is imidized. 8. The method for producing a polyimine according to 7., comprising the steps of: coating a polyimide composition precursor composition according to any one of 1. to 6. on a substrate; The polyimine precursor composition is subjected to heat treatment at a maximum heating temperature of more than 350 ° C to imidize the polyimine precursor. 9. The method for producing a polyimine of 7, or 8. wherein the heat treatment has a maximum heating temperature of more than 400 °C. A polyimine which is produced by the method for producing a polyimine according to any one of items 7. to 9. 11. The polyimine of 10., wherein the film having a thickness of 10 μm has a light transmittance of 75% or more at a wavelength of 400 nm. A polyimine film produced by the method for producing a polyimine according to any one of items 7. to 9. A substrate for a display, a touch panel, or a solar cell, which comprises a polyimine such as 10. or 11. or a polyimide film such as 12. [Effects of the Invention]
依本發明可提供能獲得即使是同一組成之聚醯亞胺,仍有較優良透明性、低線熱膨脹係數之聚醯亞胺、或透明性更優異、低線熱膨脹係數且機械特性也優良之聚醯亞胺的聚醯亞胺前驅體組成物(含聚醯亞胺前驅體之溶液組成物)、及聚醯亞胺之製造方法。According to the present invention, it is possible to obtain a polyimine having excellent transparency and a low coefficient of thermal expansion even if it is a polyimide having the same composition, or having superior transparency, a low coefficient of thermal expansion, and excellent mechanical properties. A polyimine precursor composition of polyimine (a solution composition containing a polyimide precursor) and a method for producing a polyimide.
由本發明之聚醯亞胺前驅體組成物獲得之聚醯亞胺(本發明之聚醯亞胺)的透明性高、且為低線熱膨脹係數,易形成微細電路,可適用於形成顯示器用途等的基板。又,本發明之聚醯亞胺也可理想地使用於形成觸控面板用、太陽能電池用之基板。The polyimine (the polyimine of the present invention) obtained from the polyimine precursor composition of the present invention has high transparency and a low coefficient of thermal expansion, and is easy to form a fine circuit, and can be suitably used for forming a display. The substrate. Moreover, the polyimine of the present invention can also be suitably used for forming a substrate for a touch panel or a solar cell.
本發明之聚醯亞胺前驅體組成物包含含有前述化學式(1-1)表示之重複單元至少1種之聚醯亞胺前驅體、與咪唑系化合物,咪唑系化合物之含量相對於聚醯亞胺前驅體之重複單元1莫耳未達4莫耳。The polyimine precursor composition of the present invention comprises a polyimine precursor containing at least one of the repeating units represented by the above formula (1-1), and an imidazole compound, and the content of the imidazole compound is relative to the polyazide. The repeating unit 1 of the amine precursor is less than 4 moles.
由含有前述化學式(1-1)表示之重複單元至少1種之聚醯亞胺前驅體獲得之聚醯亞胺,亦即半脂環族聚醯亞胺,有高透明性。為如此的透明性高的聚醯亞胺的情形,不宜使用會成為著色原因之添加物。但是藉由將咪唑系化合物以相對於聚醯亞胺前驅體之重複單元1莫耳為未達4莫耳,較佳為0.05莫耳以上2莫耳以下的比例加到聚醯亞胺前驅體組成物,獲得之聚醯亞胺的透明性會進一步提高,且獲得之聚醯亞胺的線熱膨脹係數減小。亦即,依照本發明,可由同一組成之聚醯亞胺前驅體獲得透明性更高、線熱膨脹係數低的聚醯亞胺。The polyimine obtained from the polyimine precursor containing at least one of the repeating units represented by the above formula (1-1), that is, the semialicyclic polyimine, has high transparency. In the case of such a highly transparent polyimine, it is not preferable to use an additive which causes coloring. However, the imidazole compound is added to the polyimine precursor by a ratio of less than 4 moles, preferably 0.05 moles to 2 moles, relative to the repeating unit 1 mole of the polyimide precursor. The composition, the transparency of the obtained polyimine, is further improved, and the linear thermal expansion coefficient of the obtained polyimine is reduced. That is, according to the present invention, a polyimine having a higher transparency and a lower coefficient of linear thermal expansion can be obtained from a polyimide intermediate precursor of the same composition.
再者,為了獲得高透明性的聚醯亞胺,一般認為宜將聚醯亞胺前驅體於比較低的溫度進行加熱處理而完成醯亞胺化,但是依照本發明,即使利用最高加熱溫度超過350℃,尤佳為超過400℃之加熱處理將聚醯亞胺前驅體予以醯亞胺化,仍可製造高透明性的聚醯亞胺。其結果用以醯亞胺化之加熱處理之最高加熱溫度可為超過350℃之高溫,尤佳為超過400℃之高溫,所以獲得之聚醯亞胺之機械特性提高。亦即,依照本發明可獲得高透明性、線熱膨脹係數低、機械特性也優良的聚醯亞胺。Further, in order to obtain a highly transparent polyimine, it is generally considered that the polyimine precursor is heat-treated at a relatively low temperature to complete the oxime imidization, but according to the present invention, even if the maximum heating temperature is exceeded The heat treatment of 350 ° C, and more preferably more than 400 ° C, the ruthenium imide of the polyimide precursor can still produce a highly transparent polyimide. As a result, the maximum heating temperature for the heat treatment of the hydrazine imidation may be a high temperature exceeding 350 ° C, and particularly preferably a high temperature exceeding 400 ° C, so that the mechanical properties of the obtained polyimine are improved. That is, according to the present invention, a polyimide having high transparency, a low coefficient of thermal expansion coefficient, and excellent mechanical properties can be obtained.
如前述,本發明之聚醯亞胺前驅體組成物包括含有前述化學式(1-1)表示之重複單元至少1種之聚醯亞胺前驅體。作為聚醯亞胺前驅體,宜為含有前述化學式(1-2)表示之重複單元之聚醯亞胺前驅體為較佳。As described above, the polyimine precursor composition of the present invention includes a polyimine precursor containing at least one of the repeating units represented by the above formula (1-1). As the polyimine precursor, a polyimine precursor containing a repeating unit represented by the above formula (1-2) is preferred.
惟前述化學式(1-1)及前述化學式(1-2),十氫-1,4:5,8-二甲橋萘環之2位或3位的其中一酸基和胺基反應而形成醯胺鍵(-CONH-),另一者為未形成醯胺鍵之-COOX1 表示之基,6位或7位的其中一酸基和胺基反應而形成醯胺鍵(-CONH-),另一者為未形成醯胺鍵之-COOX2 表示之基。亦即,前述化學式(1-1)及前述化學式(1-2)有4種結構異構物,亦即以下全部包括:(i)2位具有-COOX1 表示之基、3位有-CONH-表示之基,且6位有-COOX2 表示之基、7位有-CONH-A-表示之基者;(ii)3位有-COOX1 表示之基、2位有-CONH-表示之基,且6位有-COOX2 表示之基、7位有-CONH-A-表示之基者; (iii)2位有-COOX1 表示之基、3位有-CONH-表示之基,且7位有-COOX2 表示之基、6位有-CONH-A-表示之基者;(iv)3位有-COOX1 表示之基、2位有-CONH-表示之基,且7位有-COOX2 表示之基、6位有-CONH-A-表示之基者。However, the above chemical formula (1-1) and the aforementioned chemical formula (1-2), one of the acid groups and the amine group at the 2- or 3-position of the decahydro-1,4:5,8-dimethylnaphthalene ring are reacted to form a guanamine bond (-CONH-), the other is a group represented by COOX 1 which does not form a guanamine bond, and one of the acid groups at the 6 or 7 position reacts with an amine group to form a guanamine bond (-CONH-) The other is the group represented by -COOX 2 which does not form a guanamine bond. That is, the above chemical formula (1-1) and the above chemical formula (1-2) have four structural isomers, that is, all of the following include: (i) the 2-position has a group represented by -COOX 1 , and the 3-position has -CONH - indicates the base, and 6 has a base represented by -COOX 2 , 7 has a base represented by -CONH-A-; (ii) 3 has a base represented by -COOX 1 , and 2 has a -CONH- And 6 positions have a base represented by -COOX 2 , and 7 positions have a base represented by -CONH-A-; (iii) 2 positions have a base represented by -COOX 1 , and 3 positions have a base represented by -CONH-, and The 7-position has a base represented by -COOX 2 , and the 6-position has a base represented by -CONH-A-; (iv) 3 positions have a base represented by -COOX 1 , 2 have a base represented by -CONH-, and 7 have -COOX 2 represents the base and 6 bits have the base of -CONH-A-.
作為前述化學式(1-1)及前述化學式(1-2)中之A,宜為碳數6~40之有芳香族環之2價基為較佳。The A in the chemical formula (1-1) and the chemical formula (1-2) is preferably a divalent group having an aromatic ring having 6 to 40 carbon atoms.
再者,聚醯亞胺前驅體宜含有A係前述化學式(1-A)表示之基的化學式(1-1),更佳為化學式(1-2)表示之重複單元至少1種較佳。Further, the polyimine precursor preferably contains the chemical formula (1-1) of the group represented by the above formula (1-A), and more preferably at least one of the repeating units represented by the chemical formula (1-2).
換言之,聚醯亞胺前驅體係由包括十氫-1,4:5,8-二甲橋萘-2,3,6,7-四羧酸類等,更佳為(4arH,8acH)-十氫-1t,4t:5c,8c-二甲橋萘-2t,3t,6c,7c-四羧酸類等(四羧酸類等,係代表四羧酸、及四羧酸二酐、四羧酸矽酯、四羧酸酯、四羧醯氯等四羧酸衍生物)之四羧酸成分、與包括有芳香族環之二胺成分,更佳為賦予A係前述化學式(1-A)表示之基之化學式(1-1)或化學式(1-2)之重複單元的二胺成分的二胺成分獲得之聚醯亞胺前驅體。In other words, the polyimine precursor system includes trihydro-1,4:5,8-dimethylnaphthalene-2,3,6,7-tetracarboxylic acid, etc., more preferably (4arH, 8acH)-decahydrogen. -1t, 4t: 5c, 8c-dimethyl bridge naphthalene-2t, 3t, 6c, 7c-tetracarboxylic acid, etc. (tetracarboxylic acid, etc., representing tetracarboxylic acid, and tetracarboxylic dianhydride, tetracarboxylic acid decyl ester a tetracarboxylic acid component of a tetracarboxylic acid derivative such as a tetracarboxylic acid ester or a tetracarboxylic cerium chloride, and a diamine component including an aromatic ring, more preferably a group represented by the chemical formula (1-A) of the A system. A polyimine precursor obtained from a diamine component of a diamine component of a repeating unit of the chemical formula (1-1) or the chemical formula (1-2).
作為賦予前述化學式(1-1)之重複單元的四羧酸成分,可使用十氫-1,4:5,8-二甲橋萘-2,3,6,7-四羧酸類等中的單獨1種,也可組合使用多種。作為賦予前述化學式(1-2)之重複單元之四羧酸成分,可使用(4arH,8acH)-十氫-1t,4t:5c,8c-二甲橋萘-2t,3t,6c,7c-四羧酸類等的單獨也可組合使用多種。As the tetracarboxylic acid component which imparts the repeating unit of the above chemical formula (1-1), decahydro-1,4:5,8-dimethylnaphthalene-2,3,6,7-tetracarboxylic acid or the like can be used. A single type can also be used in combination. As the tetracarboxylic acid component imparting the repeating unit of the above chemical formula (1-2), (4arH, 8acH)-decahydro-1t, 4t: 5c, 8c-dimethylnaphthalene-2t, 3t, 6c, 7c- can be used. A plurality of tetracarboxylic acids and the like may be used alone or in combination.
賦予前述化學式(1-1)或前述化學式(1-2)之重複單元之二胺成分,宜包括賦予A係前述化學式(1-A)表示之基者的二胺較佳。The diamine component to which the repeating unit of the above chemical formula (1-1) or the above chemical formula (1-2) is added preferably contains a diamine which imparts a base represented by the above formula (1-A).
賦予A係前述化學式(1-A)表示之基的化學式(1-1)或化學式(1-2)之重複單元的二胺成分,係有芳香環,且於有多個芳香環的情形,芳香環彼此各自獨立地直接鍵結、以醯胺鍵、或酯鍵連結。芳香環彼此之連結位置不特別限定,有時藉由以胺基或相對於芳香環彼此之連結基於4位鍵結而成為直線結構,獲得之聚醯亞胺會變成低線熱膨脹。又,芳香環也可以有甲基、三氟甲基取代。又,取代位置不特別限定。The diamine component of the repeating unit of the chemical formula (1-1) or the chemical formula (1-2) which is a group represented by the above-mentioned chemical formula (1-A) is an aromatic ring, and when a plurality of aromatic rings are present, The aromatic rings are directly bonded to each other independently, and are linked by a guanamine bond or an ester bond. The position at which the aromatic rings are bonded to each other is not particularly limited, and a linear structure is obtained by bonding with an amine group or an aromatic ring based on a 4-position bond, and the obtained polyimine will become a low-line thermal expansion. Further, the aromatic ring may be substituted with a methyl group or a trifluoromethyl group. Further, the substitution position is not particularly limited.
作為賦予A係前述化學式(1-A)表示之基的化學式(1-1)或化學式(1-2)之重複單元的二胺成分無特殊限定,例如:對苯二胺、間苯二胺、鄰聯甲苯胺、聯苯胺、3,3’-二胺基-聯苯、2,2’-雙(三氟甲基)聯苯胺、3,3’-雙(三氟甲基)聯苯胺、間聯甲苯胺、4,4’-二胺基苯醯替苯胺、3,4’-二胺基苯醯替苯胺、N,N’-雙(4-胺基苯基)對苯二甲醯胺、N,N’-對伸苯基雙(對胺基苯甲醯胺)、4-胺基苯氧基-4-二胺基苯甲酸酯、雙(4-胺基苯基)對苯二甲酸酯、聯苯-4,4’-二羧酸雙(4-胺基苯基)酯、對伸苯基雙(對胺基苯甲酸酯)、雙(4-胺基苯基)-[1,1’-聯苯]-4,4’-二羧酸酯、[1,1’-聯苯]-4,4’-二基雙(4-胺基苯甲酸酯)等,可以單獨使用也可組合使用多種。該等之中,對苯二胺、間聯甲苯胺、4,4’-二胺基苯醯替苯胺、4-胺基苯氧基-4-二胺基苯甲酸酯、2,2’-雙(三氟甲基)聯苯胺、聯苯胺、N,N’-雙(4-胺基苯基)對苯二甲醯胺、聯苯-4,4’-二羧酸雙(4-胺基苯基)酯較理想,對苯二胺、4,4’-二胺基苯醯替苯胺、2,2’-雙(三氟甲基)聯苯胺更理想。藉由使用對苯二胺、4,4’-二胺基苯醯替苯胺、2,2’-雙(三氟甲基)聯苯胺作為二胺成分,獲得之聚醯亞胺兼顧高耐熱性與高透光率。該等二胺可以單獨使用也可組合使用多種。The diamine component of the repeating unit of the chemical formula (1-1) or the chemical formula (1-2) which imparts the group represented by the above formula (1-A) is not particularly limited, and examples thereof include p-phenylenediamine and m-phenylenediamine. , o-toluidine, benzidine, 3,3'-diamino-biphenyl, 2,2'-bis(trifluoromethyl)benzidine, 3,3'-bis(trifluoromethyl)benzidine , m-toluidine, 4,4'-diaminobenzophenone, 3,4'-diaminophenyl benzophenone, N,N'-bis(4-aminophenyl)-p-xylylene Indoleamine, N,N'-p-phenylene bis(p-aminobenzamide), 4-aminophenoxy-4-diaminobenzoate, bis(4-aminophenyl) Terephthalate, biphenyl (4-aminophenyl) ester of biphenyl-4,4'-dicarboxylate, p-phenylene bis(p-aminobenzoate), bis(4-amino group) Phenyl)-[1,1'-biphenyl]-4,4'-dicarboxylate, [1,1'-biphenyl]-4,4'-diylbis(4-aminobenzoic acid Ester) and the like may be used singly or in combination of two or more. Among these, p-phenylenediamine, m-toluidine, 4,4'-diaminobenzidine, 4-aminophenoxy-4-diaminobenzoate, 2,2' - bis(trifluoromethyl)benzidine, benzidine, N,N'-bis(4-aminophenyl)terephthalamide, biphenyl-4,4'-dicarboxylic acid bis(4- Aminophenyl) esters are preferred, and p-phenylenediamine, 4,4'-diaminophenylbenzophenone, and 2,2'-bis(trifluoromethyl)benzidine are more preferred. By using p-phenylenediamine, 4,4'-diaminobenzoquinone and 2,2'-bis(trifluoromethyl)benzidine as the diamine component, the polyimine obtained has high heat resistance. With high light transmittance. These diamines may be used singly or in combination of two or more.
作為賦予前述化學式(1-1)或前述化學式(1-2)中之A之二胺成分(亦即,賦予前述化學式(1-1)或前述化學式(1-2)之重複單元之二胺成分),可以併用賦予A係前述化學式(1-A)之結構者的二胺成分以外的其他二胺。作為其他二胺成分,可使用其他芳香族或脂肪族二胺類。例如:4,4’-氧基二苯胺、3,4’-氧基二苯胺、3,3’-氧基二苯胺、對亞甲基雙(苯二胺)、1,3-雙(4-胺基苯氧基)苯、1,3-雙(3-胺基苯氧基)苯、1,4-雙(4-胺基苯氧基)苯、4,4’-雙(4-胺基苯氧基)聯苯、4,4’-雙(3-胺基苯氧基)聯苯、2,2-雙(4-(4-胺基苯氧基)苯基)六氟丙烷、2,2-雙(4-胺基苯基)六氟丙烷、雙(4-胺基苯基)碸、3,3’-雙(三氟甲基)聯苯胺、3,3’-雙((胺基苯氧基)苯基)丙烷、2,2’-雙(3-胺基-4-羥基苯基)六氟丙烷、雙(4-(4-胺基苯氧基)二苯基)碸、雙(4-(3-胺基苯氧基)二苯基)碸、八氟聯苯胺、3,3’-二甲氧基-4,4’-二胺基聯苯、3,3’-二氯-4,4’-二胺基聯苯、3,3’-二氟-4,4’-二胺基聯苯、1,4-二胺基環己烷、1,4-二胺基-2-甲基環己烷、1,4-二胺基-2-乙基環己烷、1,4-二胺基-2-正丙基環己烷、1,4-二胺基-2-異丙基環己烷、1,4-二胺基-2-正丁基環己烷、1,4-二胺基-2-異丁基環己烷、1,4-二胺基-2―第二丁基環己烷、1,4-二胺基-2―第三丁基環己烷、1,2-二胺基環己烷、1,3-二胺基環丁烷、1,4-雙(胺基甲基)環己烷、1,3-雙(胺基甲基)環己烷、二胺基雙環庚烷、二胺基甲基雙環庚烷、二胺基氧雙環庚烷、二胺基甲氧基雙環庚烷、異佛爾酮二胺、二胺基三環癸烷、二胺基甲基三環癸烷、雙(胺基環己基)甲烷、雙(胺基環己基)異亞丙基6,6'-雙(3-胺基苯氧基)-3,3,3',3'-四甲基-1,1'-螺聯茚滿、6,6'-雙(4-胺基苯氧基)-3,3,3',3'-四甲基-1,1'-螺聯茚滿等、該等之衍生物,可以單獨使用也可組合使用多種。該等之中, 4,4’-氧基二苯胺、3,4’-氧基二苯胺、3,3’-氧基二苯胺、對亞甲基雙(苯二胺)、1,3-雙(4-胺基苯氧基)苯、1,3-雙(3-胺基苯氧基)苯、1,4-雙(4-胺基苯氧基)苯、4,4’-雙(4-胺基苯氧基)聯苯、4,4’-雙(3-胺基苯氧基)聯苯較理想,尤其4,4’-雙(4-胺基苯氧基)聯苯為較佳。a diamine which imparts a diamine component of A in the above chemical formula (1-1) or the above chemical formula (1-2) (that is, a repeating unit which imparts the above chemical formula (1-1) or the aforementioned chemical formula (1-2) As the component, a diamine other than the diamine component of the structure of the above-mentioned chemical formula (1-A) of the A system may be used in combination. As the other diamine component, other aromatic or aliphatic diamines can be used. For example: 4,4'-oxydiphenylamine, 3,4'-oxydiphenylamine, 3,3'-oxydiphenylamine, p-methylenebis(phenylenediamine), 1,3-double (4 -aminophenoxy)benzene, 1,3-bis(3-aminophenoxy)benzene, 1,4-bis(4-aminophenoxy)benzene, 4,4'-bis(4- Aminophenoxy)biphenyl, 4,4'-bis(3-aminophenoxy)biphenyl, 2,2-bis(4-(4-aminophenoxy)phenyl)hexafluoropropane , 2,2-bis(4-aminophenyl)hexafluoropropane, bis(4-aminophenyl)anthracene, 3,3'-bis(trifluoromethyl)benzidine, 3,3'-double ((Aminophenoxy)phenyl)propane, 2,2'-bis(3-amino-4-hydroxyphenyl)hexafluoropropane, bis(4-(4-aminophenoxy)diphenyl碸, bis(4-(3-aminophenoxy)diphenyl)anthracene, octafluorobenzidine, 3,3'-dimethoxy-4,4'-diaminobiphenyl, 3 , 3'-dichloro-4,4'-diaminobiphenyl, 3,3'-difluoro-4,4'-diaminobiphenyl, 1,4-diaminocyclohexane, 1, 4-Diamino-2-methylcyclohexane, 1,4-diamino-2-ethylcyclohexane, 1,4-diamino-2-n-propylcyclohexane, 1,4 -diamino-2-isopropylcyclohexane, 1,4-diamino-2-n-butylcyclohexane, 1,4-diamino-2-isobutylcyclohexane, 1, 4-two Base-2-t-butylcyclohexane, 1,4-diamino-2-t-butylcyclohexane, 1,2-diaminocyclohexane, 1,3-diaminocyclobutane Alkane, 1,4-bis(aminomethyl)cyclohexane, 1,3-bis(aminomethyl)cyclohexane, diaminobicycloheptane, diaminomethylbicycloheptane, diamine Oxyxybicycloheptane, diaminomethoxybicycloheptane, isophoronediamine, diaminotricyclodecane, diaminomethyltricyclodecane, bis(aminocyclohexyl)methane, Bis(Aminocyclohexyl)isopropylidene 6,6'-bis(3-aminophenoxy)-3,3,3',3'-tetramethyl-1,1'-spiroindane 6,6'-bis(4-aminophenoxy)-3,3,3',3'-tetramethyl-1,1'-spiropyrene, etc., such derivatives, may be used alone A variety of combinations can also be used. Among these, 4,4'-oxydiphenylamine, 3,4'-oxydiphenylamine, 3,3'-oxydiphenylamine, p-methylenebis(phenylenediamine), 1,3- Bis(4-aminophenoxy)benzene, 1,3-bis(3-aminophenoxy)benzene, 1,4-bis(4-aminophenoxy)benzene, 4,4'-double (4-Aminophenoxy)biphenyl, 4,4'-bis(3-aminophenoxy)biphenyl is preferred, especially 4,4'-bis(4-aminophenoxy)biphenyl It is better.
本發明之聚醯亞胺前驅體,在前述化學式(1-1)或前述化學式(1-2)表示之重複單元100莫耳%中,A係前述化學式(1-A)表示之基的化學式(1-1)或化學式(1-2)表示之重複單元之合計比例較佳為50莫耳%以上,更佳為70莫耳%以上,又更佳為90莫耳%以上,尤佳為100莫耳%。A係前述化學式(1-A)表示之基的化學式(1-1)或化學式(1-2)表示之重複單元的比例比50莫耳%小的情形,有時獲得之聚醯亞胺的線熱膨脹係數增大。The polyimine precursor of the present invention is a chemical formula represented by the above formula (1-A) in the repeating unit 100 mol% represented by the above chemical formula (1-1) or the above chemical formula (1-2). The total ratio of the repeating unit represented by (1-1) or the chemical formula (1-2) is preferably 50% by mole or more, more preferably 70% by mole or more, still more preferably 90% by mole or more, and particularly preferably 100% by mole. In the case where the ratio of the repeating unit represented by the chemical formula (1-1) or the chemical formula (1-2) represented by the above formula (1-A) is smaller than 50 mol%, the polyimine obtained may be obtained. The coefficient of linear thermal expansion increases.
在某實施態樣中,考量獲得之聚醯亞胺之特性,賦予前述化學式(1-1)或前述化學式(1-2)之重複單元之二胺成分100莫耳%中,賦予前述化學式(1-A)之結構之二胺成分之合計比例有時較佳為70莫耳%以下,更佳為80莫耳%以下,又更佳為90莫耳%以下較佳。例如:4,4’-氧基二苯胺、4,4’-雙(4-胺基苯氧基)聯苯等有醚鍵(-O-)之二胺等其他二胺類在賦予前述化學式(1-1)或前述化學式(1-2)之重複單元之二胺成分100莫耳%中,有時宜以例如40莫耳%以下,較佳為30莫耳%以下,更佳為20莫耳%以下,又更佳為10莫耳%以下的量使用較佳。In an embodiment, the properties of the obtained polyimine are given to 100 mol% of the diamine component of the repeating unit of the above chemical formula (1-1) or the above chemical formula (1-2), and the above chemical formula is imparted ( The total proportion of the diamine component of the structure of 1-A) is preferably 70 mol% or less, more preferably 80 mol% or less, still more preferably 90 mol% or less. For example, other diamines such as a diamine having an ether bond (-O-) such as 4,4'-oxydiphenylamine or 4,4'-bis(4-aminophenoxy)biphenyl are given the above chemical formula. (1-1) or 100 parts by mole of the diamine component of the repeating unit of the above chemical formula (1-2), for example, preferably 40 mol% or less, preferably 30 mol% or less, more preferably 20 mol. It is preferably used in an amount of less than or equal to 0%, more preferably less than 10% by mole.
如前述,本發明之包含前述化學式(1-1)或前述化學式(1-2)表示之重複單元之聚醯亞胺前驅體中,前述化學式(1-1)或前述化學式(1-2)中之A宜為前述化學式(1-A)較佳。換言之,賦予前述化學式(1-1)或前述化學式(1-2)之重複單元之二胺成分,宜為賦予A係前述化學式(1-A)表示之基之化學式(1-1)或化學式(1-2)之重複單元的二胺成分較佳。藉由使賦予前述化學式(1-1)或前述化學式(1-2)中之A之二胺成分(亦即,賦予前述化學式(1-1)或前述化學式(1-2)之重複單元之二胺成分)為賦予A係前述化學式(1-A)表示之基化學式(1-1)或化學式(1-2)之重複單元之二胺成分,獲得之聚醯亞胺之耐熱性提高。As described above, in the polyimine precursor of the present invention comprising the repeating unit represented by the above chemical formula (1-1) or the above chemical formula (1-2), the above chemical formula (1-1) or the aforementioned chemical formula (1-2) A of A is preferably the above chemical formula (1-A). In other words, the diamine component to which the repeating unit of the above chemical formula (1-1) or the above chemical formula (1-2) is imparted is preferably a chemical formula (1-1) or a chemical formula which imparts a group represented by the above-mentioned chemical formula (1-A) of the A system. The diamine component of the repeating unit of (1-2) is preferred. By giving the diamine component of the above formula (1-1) or A in the above chemical formula (1-2) (that is, giving a repeating unit of the above chemical formula (1-1) or the aforementioned chemical formula (1-2) The diamine component is a diamine component which imparts a repeating unit of the formula (1-1) or the chemical formula (1-2) represented by the above formula (1-A), and the heat resistance of the obtained polyimine is improved.
在某實施態樣中,本發明之包含前述化學式(1-1)或前述化學式(1-2)表示之重複單元之聚醯亞胺前驅體,有時宜含有A係前述化學式(1-A)表示之基的化學式(1-1)或化學式(1-2)之重複單元至少2種較佳。換言之,賦予前述化學式(1-1)或前述化學式(1-2)之重複單元之二胺成分,有時宜含有賦予A係前述化學式(1-A)表示之基的化學式(1-1)或化學式(1-2)之重複單元的二胺成分至少2種較佳。藉由賦予前述化學式(1-1)或前述化學式(1-2)中之A之二胺成分(亦即,賦予前述化學式(1-1)或前述化學式(1-2)之重複單元之二胺成分)含有賦予A係前述化學式(1-A)之結構者的二胺成分至少2種,獲得之聚醯亞胺可取得高透明性與低線熱膨脹性的均衡性(亦即,可獲得透明性高、且低線熱膨脹係數的聚醯亞胺)。In a certain embodiment, the polyimine precursor of the present invention comprising the repeating unit represented by the above chemical formula (1-1) or the above chemical formula (1-2) may preferably contain the above-mentioned chemical formula (1-A) of the A system. At least two kinds of repeating units of the chemical formula (1-1) or the chemical formula (1-2) which are represented are preferred. In other words, the diamine component which imparts the repeating unit of the above chemical formula (1-1) or the above chemical formula (1-2) may preferably contain the chemical formula (1-1) which imparts a group represented by the above formula (1-A). At least two kinds of diamine components of the repeating unit of the chemical formula (1-2) are preferred. By giving the diamine component of the above chemical formula (1-1) or A in the above chemical formula (1-2) (that is, giving the repeating unit of the above chemical formula (1-1) or the aforementioned chemical formula (1-2) The amine component) contains at least two kinds of diamine components which impart a structure of the above-mentioned chemical formula (1-A) of the A system, and the obtained polyimine can achieve a balance between high transparency and low-line thermal expansion property (that is, it can be obtained) Polyimine with high transparency and low coefficient of thermal expansion.
在此實施態樣中,例如:本發明之包含前述化學式(1-1)或前述化學式(1-2)表示之重複單元之聚醯亞胺前驅體,其賦予前述化學式(1-1)或前述化學式(1-2)中之A之二胺成分(亦即,賦予前述化學式(1-1)或前述化學式(1-2)之重複單元之二胺成分)含有賦予A係前述化學式(1-A)之結構者的二胺成分至少2種,且其中1種為4,4’-二胺基苯醯替苯胺較佳。藉由賦予前述化學式(1-1)或前述化學式(1-2)中之A之二胺成分含有賦予前述化學式(1-A)之結構之二胺成分至少2種,且其中1種為4,4’-二胺基苯醯替苯胺,可獲得除了有高透明性與低線熱膨脹性,尚兼顧高耐熱性的聚醯亞胺。In this embodiment, for example, the polyimine precursor of the present invention comprising the repeating unit represented by the above chemical formula (1-1) or the above chemical formula (1-2), which gives the aforementioned chemical formula (1-1) or The diamine component of A in the above chemical formula (1-2) (that is, the diamine component which imparts the repeating unit of the above chemical formula (1-1) or the above chemical formula (1-2)) contains the above-mentioned chemical formula (1). The structure of the -A) has at least two kinds of diamine components, and one of them is preferably 4,4'-diaminobenzophenone. The diamine component which imparts A to the above chemical formula (1-1) or the above chemical formula (1-2) contains at least two kinds of diamine components which impart the structure of the above chemical formula (1-A), and one of them is 4 4'-diaminophenyl benzophenone can obtain a polyimine which has high heat resistance and high heat resistance in addition to high transparency and low linear thermal expansion.
在某實施態樣中,本發明之包含前述化學式(1-1)或前述化學式(1-2)表示之重複單元之聚醯亞胺前驅體,其賦予前述化學式(1-1)或前述化學式(1-2)中之A之二胺成分(亦即,賦予前述化學式(1-1)或前述化學式(1-2)之重複單元之二胺成分)宜含有選自於2,2’-雙(三氟甲基)聯苯胺及對苯二胺中之至少1種、及4,4’-二胺基苯醯替苯胺較佳。藉由組合該等二胺成分,可獲得兼顧高透明性、低線熱膨脹性、耐熱性的聚醯亞胺。In one embodiment, the polyimine precursor of the present invention comprising the repeating unit represented by the above chemical formula (1-1) or the above chemical formula (1-2), which imparts the aforementioned chemical formula (1-1) or the aforementioned chemical formula The diamine component of A in (1-2) (that is, the diamine component which imparts the repeating unit of the above chemical formula (1-1) or the above chemical formula (1-2)) preferably contains a selected from 2, 2'- It is preferred that at least one of bis(trifluoromethyl)benzidine and p-phenylenediamine and 4,4'-diaminobenzophenone are preferred. By combining these diamine components, polyimine which achieves both high transparency, low-line thermal expansion property, and heat resistance can be obtained.
在此實施態樣中,作為賦予前述化學式(1-1)或前述化學式(1-2)中之A之二胺成分(亦即,賦予前述化學式(1-1)或前述化學式(1-2)之重複單元之二胺成分)較佳為含有4,4’-二胺基苯醯替苯胺20莫耳%以上、80莫耳%以下,且含有對苯二胺與2,2’-雙(三氟甲基)聯苯胺中任一者或兩者20莫耳%以上、80莫耳%以下較佳,更佳為含有4,4’-二胺基苯醯替苯胺30莫耳%以上、70莫耳%以下,且含有對苯二胺與2,2’-雙(三氟甲基)聯苯胺中任一者或兩者30莫耳%以上、70莫耳%以下較佳,尤佳為含有4,4’-二胺基苯醯替苯胺40莫耳%以上、60莫耳%以下,且含有對苯二胺與2,2’-雙(三氟甲基)聯苯胺中任一者或兩者40莫耳%以上、60莫耳%以下更佳。In this embodiment, the diamine component which imparts A to the above chemical formula (1-1) or the above chemical formula (1-2) (that is, gives the aforementioned chemical formula (1-1) or the aforementioned chemical formula (1-2) The diamine component of the repeating unit) preferably contains 4,4'-diaminophenylbenzophenone 20 mol% or more, 80 mol% or less, and contains p-phenylenediamine and 2,2'-double Any one or both of (trifluoromethyl)benzidine is preferably 20 mol% or more and 80 mol% or less, more preferably 30 mol% or more of 4,4'-diaminobenzophenidine. 70 mol% or less, and more preferably 30 mol% or more and 70 mol% or less of either or both of p-phenylenediamine and 2,2'-bis(trifluoromethyl)benzidine, especially Preferably, it contains 4,4'-diaminophenylbenzophenone 40 mol% or more, 60 mol% or less, and contains p-phenylenediamine and 2,2'-bis(trifluoromethyl)benzidine. One or both of them are 40% or more and 60% by mole or less.
本發明之聚醯亞胺前驅體可含有前述化學式(1-1)或前述化學式(1-2)表示之重複單元以外的其他重複單元。The polyimine precursor of the present invention may contain a repeating unit other than the repeating unit represented by the above chemical formula (1-1) or the above chemical formula (1-2).
作為賦予其他重複單元之四羧酸成分,可以使用其他芳香族或脂肪族四羧酸類。例如:2,2-雙(3,4-二羧基苯基)六氟丙烷、4-(2,5-二側氧基四氫呋喃-3-基)-1,2,3,4-四氫萘-1,2-二羧酸、苯均四酸、3,3’,4,4’-二苯基酮四羧酸、3,3’,4,4’-聯苯四羧酸、2,3,3’,4’-聯苯四羧酸、4,4’-氧基二鄰苯二甲酸、雙(3,4-二羧基苯基)碸二無水物、間聯三苯-3,4,3’,4’-四羧酸二酐、對聯三苯-3,4,3’,4’-四羧酸二酐、雙羧基苯基二甲基矽烷、雙二羧基苯氧基二苯基硫醚、磺醯基二鄰苯二甲酸、1,2,3,4-環丁烷四羧酸、異亞丙基二苯氧基雙鄰苯二甲酸、環己烷-1,2,4,5-四羧酸、[1,1’-聯(環己烷)]-3,3’,4,4’-四羧酸、[1,1’-聯(環己烷)]-2,3,3’,4’-四羧酸、[1,1’-聯(環己烷)]-2,2’,3,3’-四羧酸、4,4’-亞甲基雙(環己烷-1,2-二羧酸)、4,4’-(丙烷-2,2-二基)雙(環己烷-1,2-二羧酸)、4,4’-氧基雙(環己烷-1,2-二羧酸)、4,4’-硫雙(環己烷-1,2-二羧酸)、4,4’-磺醯基雙(環己烷-1,2-二羧酸)、4,4’-(二甲基矽烷二基)雙(環己烷-1,2-二羧酸)、4,4’-(四氟丙烷-2,2-二基)雙(環己烷-1,2-二羧酸)、八氫戊搭烯-1,3,4,6-四羧酸、雙環[2.2.1]庚烷-2,3,5,6-四羧酸、6-(羧基甲基)雙環[2.2.1]庚烷-2,3,5-三羧酸、雙環[2.2.2]辛烷-2,3,5,6-四羧酸、雙環[2.2.2]辛-5-烯-2,3,7,8-四羧酸、三環[4.2.2.02,5]癸烷-3,4,7,8-四羧酸、三環[4.2.2.02,5]癸-7-烯-3,4,9,10-四羧酸、9-氧雜三環[4.2.1.02,5]壬烷-3,4,7,8-四羧酸、降莰烷-2-螺-α-環戊酮-α’-螺-2’’-降莰烷5,5’’,6,6’’-四羧酸、(4arH,8acH)-十氫-1t,4t:5c,8c-二甲橋萘-2c,3c,6c,7c-四羧酸等衍生物、該等之酸二酐,可以單獨使用也可組合使用多種。該等之中,雙環[2.2.1]庚烷-2,3,5,6-四羧酸、雙環[2.2.2]辛烷-2,3,5,6-四羧酸、降莰烷-2-螺-α-環戊酮-α’-螺-2’’-降莰烷5,5’’,6,6’’-四羧酸、(4arH,8acH)-十氫-1t,4t:5c,8c-二甲橋萘-2c,3c,6c,7c-四羧酸等衍生物、該等之酸二酐,考量聚醯亞胺之製造容易且獲得之聚醯亞胺之耐熱性優異之觀點,較為理想。該等酸二酐可以單獨使用也可組合使用多種。As the tetracarboxylic acid component to be imparted to other repeating units, other aromatic or aliphatic tetracarboxylic acids can be used. For example: 2,2-bis(3,4-dicarboxyphenyl)hexafluoropropane, 4-(2,5-di-oxytetrahydrofuran-3-yl)-1,2,3,4-tetrahydronaphthalene -1,2-dicarboxylic acid, pyromellitic acid, 3,3',4,4'-diphenyl ketone tetracarboxylic acid, 3,3',4,4'-biphenyltetracarboxylic acid, 2, 3,3',4'-biphenyltetracarboxylic acid, 4,4'-oxydiphthalic acid, bis(3,4-dicarboxyphenyl)phosphonium anhydrate, meta-triphenyl-3, 4,3',4'-tetracarboxylic dianhydride, conjugated triphenyl-3,4,3',4'-tetracarboxylic dianhydride, biscarboxyphenyldimethyl decane, bisdicarboxyphenoxy Phenyl sulfide, sulfonyl diphthalic acid, 1,2,3,4-cyclobutane tetracarboxylic acid, isopropylidene diphenoxy diphthalic acid, cyclohexane-1,2 , 4,5-tetracarboxylic acid, [1,1'-linked (cyclohexane)]-3,3',4,4'-tetracarboxylic acid, [1,1'-linked (cyclohexane)] -2,3,3',4'-tetracarboxylic acid, [1,1'-bi(cyclohexane)]-2,2',3,3'-tetracarboxylic acid, 4,4'-methylene Bis(cyclohexane-1,2-dicarboxylic acid), 4,4'-(propane-2,2-diyl)bis(cyclohexane-1,2-dicarboxylic acid), 4,4' -oxybis(cyclohexane-1,2-dicarboxylic acid), 4,4'-thiobis(cyclohexane-1,2-dicarboxylic acid), 4,4'-sulfonyl bis(cyclo) Hexane-1,2-dicarboxylic acid), 4, 4'-(Dimethyldecanediyl)bis(cyclohexane-1,2-dicarboxylic acid), 4,4'-(tetrafluoropropane-2,2-diyl)bis(cyclohexane-1 ,2-dicarboxylic acid), octahydropentene-1,3,4,6-tetracarboxylic acid, bicyclo[2.2.1]heptane-2,3,5,6-tetracarboxylic acid, 6-( Carboxymethyl)bicyclo[2.2.1]heptane-2,3,5-tricarboxylic acid, bicyclo[2.2.2]octane-2,3,5,6-tetracarboxylic acid, bicyclo[2.2.2] Oct-5-ene-2,3,7,8-tetracarboxylic acid, tricyclo[4.2.2.02,5]decane-3,4,7,8-tetracarboxylic acid, tricyclo[4.2.2.02,5癸-7-ene-3,4,9,10-tetracarboxylic acid, 9-oxatricyclo[4.2.1.02,5]nonane-3,4,7,8-tetracarboxylic acid, norbornane -2-spiro-α-cyclopentanone-α'-spiro-2''-norbornane 5,5'',6,6''-tetracarboxylic acid, (4arH,8acH)-decahydro-1t, 4t: 5c, 8c-dimethylnaphthalene-2c, 3c, 6c, 7c-tetracarboxylic acid and the like, and the acid dianhydride may be used singly or in combination. Among these, bicyclo [2.2.1] heptane-2,3,5,6-tetracarboxylic acid, bicyclo[2.2.2]octane-2,3,5,6-tetracarboxylic acid, norbornane -2-spiro-α-cyclopentanone-α'-spiro-2''-norbornane 5,5'',6,6''-tetracarboxylic acid, (4arH,8acH)-decahydro-1t, 4t: 5c, 8c-dimethylnaphthalene-2c, 3c, 6c, 7c-tetracarboxylic acid and other derivatives, such acid dianhydride, considering the easy production of polyimine and the heat resistance of the obtained polyimine The idea of excellent sex is ideal. These acid dianhydrides may be used singly or in combination of two or more.
賦予其他重複單元之二胺成分,也可為就賦予A係前述化學式(1-A)表示之基之化學式(1-1)或化學式(1-2)之重複單元的二胺成分例示的二胺。The diamine component to which the other repeating unit is added may be exemplified as the diamine component which imparts a repeating unit of the chemical formula (1-1) or the chemical formula (1-2) represented by the above formula (1-A). amine.
作為賦予其他重複單元之二胺成分,可以使用其他芳香族或脂肪族二胺類。例如:4,4’-氧基二苯胺、3,4’-氧基二苯胺、3,3’-氧基二苯胺、對亞甲基雙(苯二胺)、1,3-雙(4-胺基苯氧基)苯、1,3-雙(3-胺基苯氧基)苯、1,4-雙(4-胺基苯氧基)苯、4,4’-雙(4-胺基苯氧基)聯苯、4,4’-雙(3-胺基苯氧基)聯苯、2,2-雙(4-(4-胺基苯氧基)苯基)六氟丙烷、2,2-雙(4-胺基苯基)六氟丙烷、雙(4-胺基苯基)碸、3,3’-雙(三氟甲基)聯苯胺、3,3’-雙((胺基苯氧基)苯基)丙烷、2,2’-雙(3-胺基-4-羥基苯基)六氟丙烷、雙(4-(4-胺基苯氧基)二苯基)碸、雙(4-(3-胺基苯氧基)二苯基)碸、八氟聯苯胺、3,3’-二甲氧基-4,4’-二胺基聯苯、3,3’-二氯-4,4’-二胺基聯苯、3,3’-二氟-4,4’-二胺基聯苯、1,4-二胺基環己烷、1,4-二胺基-2-甲基環己烷、1,4-二胺基-2-乙基環己烷、1,4-二胺基-2-正丙基環己烷、1,4-二胺基-2-異丙基環己烷、1,4-二胺基-2-正丁基環己烷、1,4-二胺基-2-異丁基環己烷、1,4-二胺基-2―第二丁基環己烷、1,4-二胺基-2―第三丁基環己烷、1,2-二胺基環己烷、1,3-二胺基環丁烷、1,4-雙(胺基甲基)環己烷、1,3-雙(胺基甲基)環己烷、二胺基雙環庚烷、二胺基甲基雙環庚烷、二胺基氧雙環庚烷、二胺基甲氧基雙環庚烷、異佛爾酮二胺、二胺基三環癸烷、二胺基甲基三環癸烷、雙(胺基環己基)甲烷、雙(胺基環己基)異亞丙基6,6'-雙(3-胺基苯氧基)-3,3,3',3'-四甲基-1,1'-螺聯茚滿、6,6'-雙(4-胺基苯氧基)-3,3,3',3'-四甲基-1,1'-螺聯茚滿等、該等之衍生物,可以單獨使用也可組合使用多種。As the diamine component to which other repeating units are imparted, other aromatic or aliphatic diamines can be used. For example: 4,4'-oxydiphenylamine, 3,4'-oxydiphenylamine, 3,3'-oxydiphenylamine, p-methylenebis(phenylenediamine), 1,3-double (4 -aminophenoxy)benzene, 1,3-bis(3-aminophenoxy)benzene, 1,4-bis(4-aminophenoxy)benzene, 4,4'-bis(4- Aminophenoxy)biphenyl, 4,4'-bis(3-aminophenoxy)biphenyl, 2,2-bis(4-(4-aminophenoxy)phenyl)hexafluoropropane , 2,2-bis(4-aminophenyl)hexafluoropropane, bis(4-aminophenyl)anthracene, 3,3'-bis(trifluoromethyl)benzidine, 3,3'-double ((Aminophenoxy)phenyl)propane, 2,2'-bis(3-amino-4-hydroxyphenyl)hexafluoropropane, bis(4-(4-aminophenoxy)diphenyl碸, bis(4-(3-aminophenoxy)diphenyl)anthracene, octafluorobenzidine, 3,3'-dimethoxy-4,4'-diaminobiphenyl, 3 , 3'-dichloro-4,4'-diaminobiphenyl, 3,3'-difluoro-4,4'-diaminobiphenyl, 1,4-diaminocyclohexane, 1, 4-Diamino-2-methylcyclohexane, 1,4-diamino-2-ethylcyclohexane, 1,4-diamino-2-n-propylcyclohexane, 1,4 -diamino-2-isopropylcyclohexane, 1,4-diamino-2-n-butylcyclohexane, 1,4-diamino-2-isobutylcyclohexane, 1, 4-two Base-2-t-butylcyclohexane, 1,4-diamino-2-t-butylcyclohexane, 1,2-diaminocyclohexane, 1,3-diaminocyclobutane Alkane, 1,4-bis(aminomethyl)cyclohexane, 1,3-bis(aminomethyl)cyclohexane, diaminobicycloheptane, diaminomethylbicycloheptane, diamine Oxyxybicycloheptane, diaminomethoxybicycloheptane, isophoronediamine, diaminotricyclodecane, diaminomethyltricyclodecane, bis(aminocyclohexyl)methane, Bis(Aminocyclohexyl)isopropylidene 6,6'-bis(3-aminophenoxy)-3,3,3',3'-tetramethyl-1,1'-spiroindane 6,6'-bis(4-aminophenoxy)-3,3,3',3'-tetramethyl-1,1'-spiropyrene, etc., such derivatives, may be used alone A variety of combinations can also be used.
在某實施態樣中,聚醯亞胺前驅體,其前述化學式(1-1)或前述化學式(1-2)表示之重複單元合計在全部重複單元中較佳為含有50莫耳%以上,更佳為70莫耳%以上,又更佳為90莫耳%以上,尤佳為100莫耳%。前述化學式(1-1)或前述化學式(1-2)表示之重複單元的比例為50莫耳%以上的情形,製膜性提高且獲得之聚醯亞胺之線熱膨脹係數極小。又,考量全光透射率之觀點,可將前述化學式(1-1)或前述化學式(1-2)表示之重複單元於全部重複單元100莫耳%中以較佳為50莫耳%以上至99莫耳%以下,更佳為60莫耳%以上至95莫耳%以下,尤佳為70莫耳%以上至95莫耳%以下的量使用。In one embodiment, the polyimine precursor preferably has a repeating unit represented by the above chemical formula (1-1) or the above chemical formula (1-2) in an amount of 50 mol% or more in all repeating units. More preferably, it is 70 mol% or more, more preferably 90 mol% or more, and particularly preferably 100 mol%. When the ratio of the repeating unit represented by the above chemical formula (1-1) or the above chemical formula (1-2) is 50 mol% or more, the film formability is improved and the linear thermal expansion coefficient of the obtained polyimine is extremely small. Further, from the viewpoint of the total light transmittance, the repeating unit represented by the above chemical formula (1-1) or the above chemical formula (1-2) may be preferably 50 mol% or more in all the repeating unit 100 mol%. 99 mol% or less, more preferably 60 mol% or more to 95 mol% or less, and particularly preferably 70 mol% or more to 95 mol% or less.
四羧酸成分及二胺成分包括異構物的情形,可將其異構物單離後使用於聚合等,又,也可將異構物以混合物的形式用於聚合等。When the tetracarboxylic acid component and the diamine component include an isomer, the isomer may be used for polymerization or the like, or the isomer may be used in the form of a mixture for polymerization or the like.
本發明之聚醯亞胺前驅體中,前述化學式(1-1)及前述化學式(1-2)之X1 、X2 各自獨立地為氫、碳數1~6,較佳為碳數1~3之烷基、或碳數3~9之烷矽基中任一者。X1 及X2 可藉由後述製造方法改變其官能基種類、及官能基之導入率。In the polyimine precursor of the present invention, X 1 and X 2 of the above chemical formula (1-1) and the above chemical formula (1-2) are each independently hydrogen, and have a carbon number of 1 to 6, preferably a carbon number of 1. Any of an alkyl group of ~3 or an alkylene group of 3 to 9 carbon atoms. X 1 and X 2 can change the type of the functional group and the introduction ratio of the functional group by the production method described later.
X1 及X2 為氫的情形,聚醯亞胺之製造有容易的傾向。When X 1 and X 2 are hydrogen, the production of polyimine is likely to be easy.
又,X1 及X2 為碳數1~6,較佳為碳數1~3之烷基的情形,聚醯亞胺前驅體有保存安定性優異的傾向。於此情形,X1 及X2 宜為甲基或乙基更佳。Further, when X 1 and X 2 are carbon atoms of 1 to 6, preferably an alkyl group having 1 to 3 carbon atoms, the polyimide precursor has a tendency to be excellent in storage stability. In this case, X 1 and X 2 are preferably a methyl group or an ethyl group.
又,X1 及X2 為碳數3~9之烷矽基的情形,聚醯亞胺前驅體之溶解性有優良的傾向。於此情形,X1 及X2 宜為三甲基矽基或第三丁基二甲基矽基更佳。Further, when X 1 and X 2 are alkanofluorene having 3 to 9 carbon atoms, the solubility of the polyimine precursor tends to be excellent. In this case, X 1 and X 2 are preferably a trimethylindenyl group or a tert-butyldimethylindenyl group.
官能基之導入率不特別限定,於導入烷基或烷矽基的情形,X1 及X2 可各有25%以上,較佳為50%以上,更佳為75%以上為烷基或烷矽基。The introduction ratio of the functional group is not particularly limited, and in the case of introducing an alkyl group or an alkyl fluorenyl group, X 1 and X 2 may each be 25% or more, preferably 50% or more, and more preferably 75% or more of an alkyl group or an alkyl group.矽基.
本發明之聚醯亞胺前驅體,取決於X1 及X2 採取的化學結構,可分類成:1)聚醯胺酸(X1 及X2 為氫)、2)聚醯胺酸酯(X1 及X2 之至少一部分為烷基)、3)4)聚醯胺酸矽酯(X1 及X2 之至少一部分為烷矽基)。並且,本發明之聚醯亞胺前驅體可就其分類依以下之製造方法輕易地製造。惟本發明之聚醯亞胺前驅體之製造方法不限於以下之製造方法。The polyimine precursor of the present invention, depending on the chemical structure taken by X 1 and X 2 , can be classified into: 1) poly-proline (X 1 and X 2 are hydrogen), 2) polyphthalate ( At least a portion of X 1 and X 2 are alkyl groups, and 3) 4) polydecyl phthalate (at least a portion of X 1 and X 2 is an alkane group). Further, the polyimine precursor of the present invention can be easily produced in terms of its classification according to the following production method. However, the method for producing the polyimine precursor of the present invention is not limited to the following production methods.
1)聚醯胺酸 本發明之聚醯亞胺前驅體,可藉由於溶劑中使作為四羧酸成分之四羧酸二酐、與二胺成分,以略等莫耳,較佳為二胺成分相對於四羧酸成分之莫耳比[二胺成分之莫耳數/四羧酸成分之莫耳數]為0.90~1.10,更佳為0.95~1.05之比例,於例如120℃以下之較低溫於抑制醯亞胺化之狀態進行反應,以聚醯亞胺前驅體溶液組成物的形式理想地獲得。1) Polylysine The polyimine precursor of the present invention may be a slightly more molar, preferably a diamine, by using a tetracarboxylic dianhydride as a tetracarboxylic acid component and a diamine component in a solvent. The molar ratio of the component to the tetracarboxylic acid component [molar number of the diamine component / mole number of the tetracarboxylic acid component] is from 0.90 to 1.10, more preferably from 0.95 to 1.05, for example, below 120 ° C. The reaction is carried out at a low temperature in a state in which hydrazine imidation is inhibited, and is preferably obtained in the form of a composition of a polyimide precursor solution.
並不限定,更具體而言,可藉由於有機溶劑溶解二胺,並於此溶液中於攪拌狀態緩慢添加四羧酸二酐,於0~120℃,較佳為5~80℃之範圍攪拌1~72小時而獲得聚醯亞胺前驅體。於80℃以上反應時,分子量會依存於聚合時之溫度歷程而變動且因熱而進行醯亞胺化,故可能無法穩定製造聚醯亞胺前驅體。上述製造方法中之二胺與四羧酸二酐之添加順序,容易提高聚醯亞胺前驅體之分子量,故較理想。又,上述製造方法中之二胺與四羧酸二酐之添加順序也可顛倒,從析出物減少之觀點,為較理想。It is not limited, and more specifically, the diamine may be dissolved in an organic solvent, and tetracarboxylic dianhydride may be slowly added in a stirred state in the solution, and stirred at 0 to 120 ° C, preferably 5 to 80 ° C. A polybendimimine precursor is obtained from 1 to 72 hours. When the reaction is carried out at 80 ° C or higher, the molecular weight changes depending on the temperature history at the time of polymerization, and the oxime imidization proceeds due to heat, so that the polyimide precursor may not be stably produced. The order of addition of the diamine and the tetracarboxylic dianhydride in the above production method tends to increase the molecular weight of the polyimide precursor, which is preferable. Further, the order of addition of the diamine and the tetracarboxylic dianhydride in the above production method may be reversed, and it is preferable from the viewpoint of reducing precipitates.
又,四羧酸成分與二胺成分之莫耳比為二胺成分過量時,視需要,可添加大致相當於二胺成分之過量莫耳數之量的羧酸衍生物,並使四羧酸成分與二胺成分之莫耳比接近大致的當量。在此作為羧酸衍生物,宜為實質上不使聚醯亞胺前驅體溶液之黏度增加,即實質上不涉及分子鏈延長之四羧酸、或作為末端停止劑之三羧酸及其酐、二羧酸及其酐等較理想。Further, when the molar ratio of the tetracarboxylic acid component to the diamine component is an excess of the diamine component, a carboxylic acid derivative in an amount corresponding to an excess of the molar amount of the diamine component may be added as needed, and the tetracarboxylic acid may be added. The molar ratio of the component to the diamine component is approximately equal to the equivalent. Here, the carboxylic acid derivative is preferably a tetracarboxylic acid which does not substantially increase the viscosity of the polyimide precursor solution, that is, does not substantially involve molecular chain elongation, or a tricarboxylic acid and an anhydride thereof as a terminal stopper. Dicarboxylic acid and its anhydride are ideal.
2)聚醯胺酸酯 使四羧酸二酐與任意之醇反應,獲得二酯二羧酸後,與氯化試藥(亞硫醯氯、草醯氯等)反應,獲得二酯二羧醯氯。將此二酯二羧醯氯與二胺於-20~120℃,較佳為-5~80℃之範圍攪拌1~72小時,獲得聚醯亞胺前驅體。於80℃以上反應時,分子量會依存於聚合時之溫度歷程而變動且因熱而進行醯亞胺化,可能無法穩定製造聚醯亞胺前驅體。又,將二酯二羧酸與二胺使用磷系縮合劑、碳二醯亞胺縮合劑等進行脱水縮合,也能簡便地獲得聚醯亞胺前驅體。2) Polyphthalate causes tetracarboxylic dianhydride to react with any alcohol to obtain a diester dicarboxylic acid, and then reacts with a chlorination reagent (sulfurium chloride, grass chloroform, etc.) to obtain a diester dicarboxylate. Chlorine. The diester dicarboxyfluorene chloride and the diamine are stirred at -20 to 120 ° C, preferably at -5 to 80 ° C for 1 to 72 hours to obtain a polyimine precursor. When the reaction is carried out at 80 ° C or higher, the molecular weight changes depending on the temperature history at the time of polymerization, and the ruthenium is imidized by heat, and the polyimide precursor may not be stably produced. Further, the diester dicarboxylic acid and the diamine can be easily dehydrated and condensed using a phosphorus-based condensing agent or a carbodiimide condensing agent, and the polyimine precursor can be easily obtained.
以此方法獲得之聚醯亞胺前驅體為安定,故也可加入水或醇等溶劑進行再沉澱等精製。Since the polyimide precursor obtained by this method is stable, it can also be reprecipitated by adding a solvent such as water or alcohol.
3)聚醯胺酸矽酯(間接法) 預先使二胺與矽基化劑反應,獲得經矽基化之二胺。視需要,利用蒸餾等進行經矽基化之二胺之精製。並於已脱水之溶劑中使已矽基化之二胺先溶解,並邊攪拌邊添加四羧酸二酐,於0~120℃,較佳為5~80℃之範圍進行1~72小時攪拌,可獲得聚醯亞胺前驅體。於80℃以上反應時,分子量會依存於聚合時之溫度歷程而變動且因熱而進行醯亞胺化,可能無法穩定製造聚醯亞胺前驅體。3) Polydecyl phthalate (indirect method) The diamine is previously reacted with a guanylating agent to obtain a guanidinated diamine. The thiolated diamine is purified by distillation or the like as needed. And dissolving the fluorinated diamine in a dehydrated solvent, adding tetracarboxylic dianhydride while stirring, stirring at 0 to 120 ° C, preferably 5 to 80 ° C for 1 to 72 hours. A polyimine precursor can be obtained. When the reaction is carried out at 80 ° C or higher, the molecular weight changes depending on the temperature history at the time of polymerization, and the ruthenium is imidized by heat, and the polyimide precursor may not be stably produced.
在此使用之矽基化劑,使用不含氯之矽基化劑則不須將已矽基化之二胺精製,為較理想。不含氯原子之矽基化劑,例如N,O-雙(三甲基矽基)三氟乙醯胺、N,O-雙(三甲基矽基)乙醯胺、六甲基二矽氮烷。不含氟原子,為低成本之觀點,N,O-雙(三甲基矽基)乙醯胺、六甲基二矽氮烷尤佳。The thiolating agent to be used herein is preferably a non-chlorinated thiolizing agent, which does not require purification of the fluorinated diamine. A sulfhydrylating agent free of chlorine atoms, such as N,O-bis(trimethyldecyl)trifluoroacetamide, N,O-bis(trimethyldecyl)acetamide, hexamethyldifluorene Azane. From the viewpoint of not containing a fluorine atom, N, O-bis(trimethyldecyl)acetamide or hexamethyldioxane is preferred.
又,二胺之矽基化反應中,為了促進反應,可使用吡啶、哌啶、三乙胺等胺系觸媒。此觸媒可直接使用於作為聚醯亞胺前驅體之聚合觸媒。Further, in the thiolation reaction of a diamine, an amine-based catalyst such as pyridine, piperidine or triethylamine may be used to promote the reaction. This catalyst can be directly used as a polymerization catalyst as a polyimide precursor.
4)聚醯胺酸矽酯(直接法) 將1)之方法獲得之聚醯胺酸溶液與矽基化劑混合,於0~120℃,較佳為5~80℃之範圍攪拌1~72小時,可獲得聚醯亞胺前驅體。於80℃以上使其反應時,分子量會依存於聚合時之溫度歷程而變動且因熱而進行醯亞胺化,可能無法穩定製造聚醯亞胺前驅體。4) Polydecyl phthalate (direct method) The polyphthalic acid solution obtained by the method of 1) is mixed with a thiolizing agent, and stirred at 0 to 120 ° C, preferably 5 to 80 ° C for 1 to 72. In a few hours, a polyimide precursor can be obtained. When the reaction is carried out at 80 ° C or higher, the molecular weight changes depending on the temperature history at the time of polymerization, and the ruthenium imidization due to heat may not stably produce the polyimide precursor.
在此使用之矽基化劑,使用不含氯之矽基化劑,則無須將經矽基化之聚醯胺酸、或獲得之聚醯亞胺精製,較理想。作為不含氯原子之矽基化劑,可列舉N,O-雙(三甲基矽基)三氟乙醯胺、N,O-雙(三甲基矽基)乙醯胺、六甲基二矽氮烷。不含氟原子,為低成本之觀點,N,O-雙(三甲基矽基)乙醯胺、六甲基二矽氮烷尤佳。When the thiolating agent to be used herein is a chlorine-free thiolating agent, it is not necessary to refine the thiolated polyamic acid or the obtained polyimine. Examples of the sulfhydrylating agent containing no chlorine atom include N,O-bis(trimethyldecyl)trifluoroacetamide, N,O-bis(trimethyldecyl)acetamide, hexamethyl group. Dioxane. From the viewpoint of not containing a fluorine atom, N, O-bis(trimethyldecyl)acetamide or hexamethyldioxane is preferred.
前述製造方法均可於有機溶劑中理想地進行,其結果可輕易獲得含有聚醯亞胺前驅體之溶液或溶液組成物。The above production method can be suitably carried out in an organic solvent, and as a result, a solution or a solution composition containing a polyimide precursor can be easily obtained.
製備聚醯亞胺前驅體時使用之溶劑,例如N,N-二甲基甲醯胺、N,N-二甲基乙醯胺、N-甲基-2-吡咯烷酮、1,3-二甲基-2-咪唑啶酮、二甲基亞碸等非質子性溶劑較理想,尤其N,N-二甲基乙醯胺較佳,但只要原料單體成分與生成之聚醯亞胺前驅體能溶解即可,何種種類之溶劑都能無問題地使用,其結構不特別限定。作為溶劑,採用N,N-二甲基甲醯胺、N,N-二甲基乙醯胺、N-甲基吡咯烷酮等醯胺溶劑、γ-丁內酯、γ-戊內酯、δ-戊內酯、γ-己內酯、ε-己內酯、α-甲基-γ-丁內酯等環狀酯溶劑、碳酸伸乙酯、碳酸伸丙酯等碳酸酯溶劑、三乙二醇等二醇系溶劑、間甲酚、對甲酚、3-氯苯酚、4-氯苯酚等苯酚系溶劑、苯乙酮、1,3-二甲基-2-咪唑啶酮、環丁碸、二甲基亞碸等較理想。再者,其他一般的有機溶劑,亦即苯酚、鄰甲酚、乙酸丁酯、乙酸乙酯、乙酸異丁酯、丙二醇甲基乙酸酯、乙基賽珞蘇、丁基賽珞蘇、2-甲基賽珞蘇乙酸酯、乙基賽珞蘇乙酸酯、丁基賽珞蘇乙酸酯、四氫呋喃、二甲氧基乙烷、二乙氧基乙烷、二丁醚、二乙二醇二甲醚、甲基異丁基酮、二異丁基酮、環戊酮、環己酮、甲乙酮、丙酮、丁醇、乙醇、二甲苯、甲苯、氯苯、萜烯、礦精、石油腦系溶劑等也可使用。又,溶劑也可組合多種使用。a solvent used in the preparation of a polyimide precursor, such as N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, 1,3-dimethyl Aprotic solvents such as acetyl-2-imidazolidone and dimethyl hydrazine are preferred, especially N,N-dimethylacetamide, but only the raw material monomer component and the resulting polyimine precursor can It can be dissolved, and any kind of solvent can be used without problems, and the structure is not particularly limited. As the solvent, a decylamine solvent such as N,N-dimethylformamide, N,N-dimethylacetamide or N-methylpyrrolidone, γ-butyrolactone, γ-valerolactone, δ- is used. a cyclic ester solvent such as valerolactone, γ-caprolactone, ε-caprolactone, α-methyl-γ-butyrolactone, a carbonate solvent such as ethyl carbonate or propylene carbonate, or triethylene glycol a diol solvent such as a diol solvent, m-cresol, p-cresol, 3-chlorophenol or 4-chlorophenol, acetophenone, 1,3-dimethyl-2-imidazolidinone, or cyclopentane, Dimethyl hydrazine and the like are preferred. Furthermore, other common organic solvents, namely phenol, o-cresol, butyl acetate, ethyl acetate, isobutyl acetate, propylene glycol methyl acetate, ethyl cyanidin, butyl cycas, 2 -Methyl cyproterone acetate, ethyl cyproterone acetate, butyl cyproterone acetate, tetrahydrofuran, dimethoxyethane, diethoxyethane, dibutyl ether, diethyl Diol dimethyl ether, methyl isobutyl ketone, diisobutyl ketone, cyclopentanone, cyclohexanone, methyl ethyl ketone, acetone, butanol, ethanol, xylene, toluene, chlorobenzene, decene, ore, Petroleum brain solvents and the like can also be used. Further, the solvent may be used in combination of a plurality of types.
本發明中,聚醯亞胺前驅體之對數黏度不特別限定,於30℃之濃度0.5g/dL之N,N-二甲基乙醯胺溶液中之對數黏度為0.2dL/g以上,更佳為0.3dL/g以上,尤佳為0.4dL/g以上較佳。對數黏度為0.2dL/g以上時,聚醯亞胺前驅體之分子量高,獲得之聚醯亞胺之機械強度、耐熱性優異。In the present invention, the logarithmic viscosity of the polyimide precursor is not particularly limited, and the logarithmic viscosity in the N,N-dimethylacetamide solution at a concentration of 0.5 g/dL at 30 ° C is 0.2 dL/g or more. Preferably, it is 0.3 dL/g or more, and more preferably 0.4 dL/g or more. When the logarithmic viscosity is 0.2 dL/g or more, the molecular weight of the polyimine precursor is high, and the obtained polyimine is excellent in mechanical strength and heat resistance.
本發明之聚醯亞胺前驅體組成物含有聚醯亞胺前驅體與咪唑系化合物,可於依前述製造方法獲得之聚醯亞胺前驅體溶液或溶液組成物中加入咪唑系化合物以製備。又,視需要也可去除或加入溶劑,也可添加咪唑系化合物以外的所望成分。又,也可於溶劑中加入四羧酸成分(四羧酸二酐等)與二胺成分與咪唑系化合物,於咪唑系化合物存在下使四羧酸成分與二胺成分反應,而獲得本發明之聚醯亞胺前驅體組成物(含有聚醯亞胺前驅體與咪唑系化合物之溶液組成物)。The polyimine precursor composition of the present invention contains a polyimide intermediate and an imidazole compound, and can be prepared by adding an imidazole compound to a polyamidene precursor solution or solution composition obtained by the above production method. Further, a solvent may be removed or added as needed, and a desired component other than the imidazole compound may be added. Further, the tetracarboxylic acid component (such as tetracarboxylic dianhydride) and the diamine component and the imidazole compound may be added to the solvent, and the tetracarboxylic acid component and the diamine component may be reacted in the presence of the imidazole compound to obtain the present invention. The polyimide precursor composition (containing a solution composition of a polyimide precursor and an imidazole compound).
本發明使用之咪唑系化合物,只要有咪唑骨架即可,無特殊限定。可藉由添加咪唑系化合物,獲得透明性更高、線熱膨脹係數低的聚醯亞胺。The imidazole compound used in the present invention is not particularly limited as long as it has an imidazole skeleton. By adding an imidazole-based compound, a polyimine having a higher transparency and a lower coefficient of linear thermal expansion can be obtained.
本發明使用之咪唑系化合物不特別限定,可以列舉1,2-二甲基咪唑、1-甲基咪唑、2-甲基咪唑、2-苯基咪唑、咪唑、苯并咪唑等。咪唑系化合物可單獨使用1種也可組合使用多種。The imidazole compound used in the present invention is not particularly limited, and examples thereof include 1,2-dimethylimidazole, 1-methylimidazole, 2-methylimidazole, 2-phenylimidazole, imidazole, and benzimidazole. The imidazole compound may be used alone or in combination of two or more.
本發明中,聚醯亞胺前驅體組成物之咪唑系化合物之含量,相對於聚醯亞胺前驅體之重複單元1莫耳未達4莫耳。咪唑系化合物之含量若相對聚醯亞胺前驅體之重複單元1莫耳成為4莫耳以上,聚醯亞胺前驅體組成物之保存安定性會變差。咪唑系化合物之含量宜相對於聚醯亞胺前驅體之重複單元1莫耳為0.05莫耳以上較佳,又,宜相對於聚醯亞胺前驅體之重複單元1莫耳為2莫耳以下較佳。又,在此,聚醯亞胺前驅體之重複單元1莫耳對應於四羧酸成分1莫耳。In the present invention, the content of the imidazole compound of the polyimide precursor composition is less than 4 moles relative to the repeating unit 1 of the polyimide intermediate. When the content of the imidazole-based compound is 4 mol or more with respect to the repeating unit 1 of the polyimine precursor, the storage stability of the polyimine precursor composition is deteriorated. The content of the imidazole compound is preferably 0.05 mol or more with respect to the repeating unit 1 molar of the polyimide precursor, and is preferably 2 mol or less with respect to the repeating unit 1 of the polyimine precursor. Preferably. Here, the repeating unit 1 of the polyimine precursor is corresponding to the tetracarboxylic acid component 1 mole.
本發明之聚醯亞胺前驅體組成物通常含有溶劑。本發明之聚醯亞胺前驅體組成物使用之溶劑,只要聚醯亞胺前驅體能夠溶解即無問題,其結構無特別限定。作為溶劑,使用N,N-二甲基甲醯胺、N,N-二甲基乙醯胺、N-甲基-2-吡咯烷酮等醯胺溶劑、γ-丁內酯、γ-戊內酯、δ-戊內酯、γ-己內酯、ε-己內酯、α-甲基-γ-丁內酯等環狀酯溶劑、碳酸伸乙酯、碳酸伸丙酯等碳酸酯溶劑、三乙二醇等二醇系溶劑、間甲酚、對甲酚、3-氯苯酚、4-氯苯酚等苯酚系溶劑、苯乙酮、1,3-二甲基-2-咪唑啶酮、環丁碸、二甲基亞碸等較理想。再者,也可使用其他一般的有機溶劑,亦即苯酚、鄰甲酚、乙酸丁酯、乙酸乙酯、乙酸異丁酯、丙二醇甲基乙酸酯、乙基賽珞蘇、丁基賽珞蘇、2-甲基賽珞蘇乙酸酯、乙基賽珞蘇乙酸酯、丁基賽珞蘇乙酸酯、四氫呋喃、二甲氧基乙烷、二乙氧基乙烷、二丁醚、二乙二醇二甲醚、甲基異丁基酮、二異丁基酮、環戊酮、環己酮、甲乙酮、丙酮、丁醇、乙醇、二甲苯、甲苯、氯苯、萜烯、礦精、石油腦系溶劑等。又,也可將此等組合多種使用。又,聚醯亞胺前驅體組成物之溶劑,可直接使用在製備聚醯亞胺前驅體時使用的溶劑。The polyimine precursor composition of the present invention usually contains a solvent. The solvent used in the composition of the polyimine precursor of the present invention is not particularly limited as long as the polyimide precursor can be dissolved without any problem. As the solvent, a decylamine solvent such as N,N-dimethylformamide, N,N-dimethylacetamide or N-methyl-2-pyrrolidone, γ-butyrolactone or γ-valerolactone is used. , a cyclic ester solvent such as δ-valerolactone, γ-caprolactone, ε-caprolactone, α-methyl-γ-butyrolactone, a carbonate solvent such as ethyl carbonate or propyl carbonate, and the like a diol solvent such as ethylene glycol, a phenol solvent such as m-cresol, p-cresol, 3-chlorophenol or 4-chlorophenol, acetophenone or 1,3-dimethyl-2-imidazolidinone, or a ring Ding, dimethyl adenine, etc. are ideal. Furthermore, other general organic solvents can also be used, namely phenol, o-cresol, butyl acetate, ethyl acetate, isobutyl acetate, propylene glycol methyl acetate, ethyl cyanidin, butyl cyanobacteria. Sodium, 2-methyl cyproterone acetate, ethyl cyproterone acetate, butyl cyproterone acetate, tetrahydrofuran, dimethoxyethane, diethoxyethane, dibutyl ether , diethylene glycol dimethyl ether, methyl isobutyl ketone, diisobutyl ketone, cyclopentanone, cyclohexanone, methyl ethyl ketone, acetone, butanol, ethanol, xylene, toluene, chlorobenzene, decene, Mineral concentrate, petroleum brain solvent, etc. Also, these combinations can be used in various combinations. Further, as the solvent of the polyimine precursor composition, a solvent used in the preparation of the polyimide precursor can be used as it is.
本發明中,四羧酸成分與二胺成分之合計量,相對於溶劑與四羧酸成分與二胺成分之合計量,為5質量%以上,較佳為10質量%以上,更佳為15質量%以上的比例較理想。又,通常四羧酸成分與二胺成分之合計量,相對於溶劑與四羧酸成分與二胺成分之合計量宜為60質量%以下,較佳為50質量%以下較理想。此濃度大致接近起因於聚醯亞胺前驅體之固體成分濃度,若此濃度太低,當例如製造聚醯亞胺膜時獲得之聚醯亞胺膜的膜厚有時會變得難控制。In the present invention, the total amount of the tetracarboxylic acid component and the diamine component is 5% by mass or more, preferably 10% by mass or more, and more preferably 15% based on the total amount of the solvent and the tetracarboxylic acid component and the diamine component. The ratio of mass% or more is ideal. In addition, the total amount of the tetracarboxylic acid component and the diamine component is preferably 60% by mass or less, preferably 50% by mass or less, based on the total amount of the solvent and the tetracarboxylic acid component and the diamine component. This concentration is approximately close to the solid content concentration of the polyimide precursor, and if the concentration is too low, the film thickness of the polyimide film obtained when, for example, a polyimide film is sometimes difficult to control.
本發明中,聚醯亞胺前驅體之清漆之黏度(旋轉黏度)不特別限定,使用E型旋轉黏度計,於溫度25℃、剪切速度20sec-1 測定之旋轉黏度為0.01~1000Pa・sec較理想,0.1~100Pa・sec更理想。又,視需要,也可賦予觸變性。上述範圍之黏度,於進行塗覆或製膜時,容易操作,又,眼孔(eye hole)受抑制,勻塗性優異,可獲得良好之被覆膜。In the present invention, the viscosity (rotational viscosity) of the varnish of the polyimide precursor is not particularly limited, and the rotational viscosity measured at a temperature of 25 ° C and a shear rate of 20 sec -1 is 0.01 to 1000 Pa·sec using an E-type rotational viscometer. Ideally, 0.1 to 100 Pa·sec is more desirable. Further, thixotropy can also be imparted as needed. The viscosity in the above range is easy to handle when coating or film formation, and the eye hole is suppressed, and the leveling property is excellent, and a good coating film can be obtained.
本發明之聚醯亞胺前驅體之清漆,視需要,可添加化學醯亞胺化劑(乙酸酐等酸酐、或吡啶、異喹啉等胺化合物)、抗氧化劑、填料(二氧化矽等無機粒子等)、染料、顏料、矽烷偶聯劑等偶聯劑、底塗劑、阻燃材、消泡劑、塗平劑、流變性控制劑(流動輔助劑)、剝離劑等。The varnish of the polyimide precursor of the present invention may be added with a chemical sulfhydrylating agent (an acid anhydride such as acetic anhydride or an amine compound such as pyridine or isoquinoline), an antioxidant, or a filler (such as cerium oxide), if necessary. Coupling agents such as particles, dyes, pigments, decane coupling agents, primers, flame retardants, defoamers, leveling agents, rheology control agents (flow aids), strippers, and the like.
本發明之聚醯亞胺可藉由將如前述本發明之聚醯亞胺前驅體組成物予以醯亞胺化(亦即,將聚醯亞胺前驅體進行脱水閉環反應)而得。醯亞胺化的方法不特別限定,可理想地使用公知之熱醯亞胺化、或化學醯亞胺化方法。獲得之聚醯亞胺之形態,可列舉膜、聚醯亞胺膜與其他基材之疊層體、塗覆膜、粉末、珠粒、成型體、發泡體及清漆等較理想。The polyimine of the present invention can be obtained by subjecting a polybendimimine precursor composition of the present invention to the ruthenium imidization (that is, subjecting the polyimine precursor to a dehydration ring-closure reaction). The method for the imidization of hydrazine is not particularly limited, and a known thermal hydrazine imidation or chemical hydrazylation method can be preferably used. The form of the obtained polyimine is preferably a film, a laminate of a polyimide film and another substrate, a coating film, a powder, a bead, a molded body, a foam, a varnish, or the like.
本發明中,宜將聚醯亞胺前驅體組成物於最高加熱溫度超過350℃進行加熱處理而將聚醯亞胺前驅體予以醯亞胺化較佳。用以醯亞胺化之加熱處理之最高加熱溫度宜超過380℃更佳,超過400℃尤佳。藉由使用以醯亞胺化之加熱處理之最高加熱溫度設為超過350℃之溫度,更佳為超過380℃之溫度,尤佳為超過400℃之溫度,獲得之聚醯亞胺之機械特性提高。加熱處理之最高加熱溫度之上限不特別限定,通常宜為500℃以下較佳。In the present invention, it is preferred that the polyimide precursor composition is heat-treated at a maximum heating temperature of more than 350 ° C to impart a ruthenium imide to the polyimide precursor. The maximum heating temperature for the heat treatment of hydrazine imidization is preferably more than 380 ° C, more preferably more than 400 ° C. The mechanical properties of the polyimine obtained by setting the maximum heating temperature by heat treatment with hydrazide to a temperature exceeding 350 ° C, more preferably more than 380 ° C, and particularly preferably more than 400 ° C. improve. The upper limit of the maximum heating temperature of the heat treatment is not particularly limited, and is usually preferably 500 ° C or less.
例如:將本發明之聚醯亞胺前驅體組成物流延・塗佈在基材上,將此基材上的聚醯亞胺前驅體組成物以最高加熱溫度超過350℃,更佳為超過380℃,尤佳為超過400℃的溫度進行加熱處理而將聚醯亞胺前驅體予以醯亞胺化,可理想地製造聚醯亞胺。又,加熱曲線不特別限定,可適當選擇,但考量生產性,加熱處理的時間宜短較佳。For example, the polyimine precursor composition of the present invention is further coated and coated on a substrate, and the polyamidene precursor composition on the substrate is heated at a maximum temperature of more than 350 ° C, more preferably more than 380. It is preferable to carry out heat treatment at a temperature of more than 400 ° C at a temperature of more than 400 ° C to imidize the polyimide precursor to ruthenium, and it is preferable to produce a polyimide. Further, the heating curve is not particularly limited and may be appropriately selected, but the productivity is considered, and the time of the heat treatment is preferably short.
又,將本發明之聚醯亞胺前驅體組成物流延・塗佈在基材上,較佳為於180℃以下的溫度範圍進行乾燥,在基材上形成聚醯亞胺前驅體組成物的膜,並將獲得之聚醯亞胺前驅體組成物的膜從基材上剝離,於固定此膜的端部的狀態,於最高加熱溫度超過350℃,更佳為超過380℃,尤佳為超過400℃的溫度進行加熱處理,以將聚醯亞胺前驅體予以醯亞胺化,也能理想地製造聚醯亞胺。Further, the polyimine precursor composition of the present invention is further coated on a substrate, preferably dried at a temperature of 180 ° C or lower, and a polyimide composition precursor composition is formed on the substrate. a film, and the film of the obtained polyimide precursor composition is peeled off from the substrate, and the state of fixing the end of the film is at a maximum heating temperature of more than 350 ° C, more preferably more than 380 ° C, particularly preferably The polyimine is also preferably produced by heat treatment at a temperature exceeding 400 ° C to imidize the polyimine precursor.
更具體的本發明之聚醯亞胺(聚醯亞胺膜/基材疊層體、或聚醯亞胺膜)之製造方法的一例將於後述。More specifically, an example of a method for producing a polyimine (polyimine film/substrate laminate or polyimide film) of the present invention will be described later.
由本發明之聚醯亞胺前驅體組成物獲得之聚醯亞胺(本發明之聚醯亞胺)不特別限定,製成膜時,150℃至250℃的線熱膨脹係數能較佳為40ppm/K以下,更佳為35ppm/K以下,又更佳為30ppm/K以下,尤佳為25ppm/K以下。線熱膨脹係數若大,和金屬等導體間的線熱膨脹係數差距大,形成電路基板時有時會出現翹曲增大等不良現象。The polyimine (the polyimine of the present invention) obtained from the polyimine precursor composition of the present invention is not particularly limited, and when it is formed into a film, the linear thermal expansion coefficient at 150 ° C to 250 ° C can preferably be 40 ppm / Below K, it is more preferably 35 ppm/K or less, still more preferably 30 ppm/K or less, and particularly preferably 25 ppm/K or less. If the coefficient of thermal expansion of the wire is large, and the coefficient of thermal expansion coefficient between the conductors such as metal is large, a problem such as an increase in warpage may occur when the circuit board is formed.
由本發明之聚醯亞胺前驅體組成物獲得之聚醯亞胺(本發明之聚醯亞胺)不特別限定,厚度10μm的膜的全光透射率(波長380nm~780nm之平均透光率)能較佳為86%以上,更佳為87%以上,又更佳為88%以上。在顯示器用途等使用時,若全光透射率低,則須加強光源,會有耗費能量的問題等發生。The polyimine (the polyimine of the present invention) obtained from the polyimine precursor composition of the present invention is not particularly limited, and the total light transmittance (average transmittance of a wavelength of 380 nm to 780 nm) of a film having a thickness of 10 μm. It is preferably 86% or more, more preferably 87% or more, and still more preferably 88% or more. When it is used for a display or the like, if the total light transmittance is low, the light source must be reinforced, and there is a problem that energy is consumed.
尤其使用在顯示器用途等聚醯亞胺膜透光的用途時,希望聚醯亞胺膜的透明性高較理想。由本發明之聚醯亞胺前驅體組成物獲得之聚醯亞胺(本發明之聚醯亞胺)不特別限定,厚度10μm之膜於波長400nm的透光率能較佳為75%以上,更佳為80%以上,又更佳為超過80%,再更佳為81%以上,尤佳為82%以上。In particular, when it is used for light transmission of a polyimide film such as a display, it is desirable that the polyimide film has high transparency. The polyimine (the polyimine of the present invention) obtained from the polyimine precursor composition of the present invention is not particularly limited, and the film having a thickness of 10 μm can preferably have a light transmittance of at least 75% at a wavelength of 400 nm. Preferably, the amount is more than 80%, more preferably more than 80%, and even more preferably 81% or more, and particularly preferably 82% or more.
又,由本發明之聚醯亞胺前驅體組成物獲得之聚醯亞胺(本發明之聚醯亞胺)構成的膜,取決於用途,膜厚度較佳為0.1μm~250μm,更佳為1μm~150μm,又更佳為1μm~50μm,尤佳為1μm~30μm。聚醯亞胺膜使用在透光的用途時,聚醯亞胺膜若過厚,會有透光率減低之虞。Further, the film composed of the polyimine (the polyimine of the present invention) obtained from the polyimine precursor composition of the present invention preferably has a film thickness of from 0.1 μm to 250 μm, more preferably 1 μm, depending on the use. ~150 μm, more preferably 1 μm to 50 μm, and particularly preferably 1 μm to 30 μm. When the polyimide film is used for light transmission, if the polyimide film is too thick, the light transmittance is lowered.
由本發明之聚醯亞胺前驅體組成物獲得之聚醯亞胺(本發明之聚醯亞胺)不特別限定,為聚醯亞胺膜之耐熱性之指標的1%重量減少溫度能較佳為470℃以上,更佳為480℃以上,又更佳為485℃以上,尤佳為490℃以上。當於聚醯亞胺上形成電晶體等在聚醯亞胺上形成氣體阻隔膜等的情形,若耐熱性低,有時在聚醯亞胺與阻隔膜之間會引起伴隨聚醯亞胺分解的散逸氣體造成的膨起。The polyimine (the polyimine of the present invention) obtained from the polyimine precursor composition of the present invention is not particularly limited, and a 1% weight loss temperature which is an index of heat resistance of the polyimide film is preferred. It is 470 ° C or higher, more preferably 480 ° C or higher, and even more preferably 485 ° C or higher, and particularly preferably 490 ° C or higher. When a gas barrier film or the like is formed on a polyimide, such as a crystal on a polyimine, if the heat resistance is low, a decomposition of the polyimide may be caused between the polyimide and the barrier film. The swelling caused by the fugitive gas.
由本發明之聚醯亞胺前驅體組成物獲得之聚醯亞胺,亦即本發明之聚醯亞胺,有高透明性、彎折耐性、高耐熱性等優良特性且有極低線熱膨脹係數,所以在顯示器用透明基板、觸控面板用透明基板、或太陽能電池用基板的用途可理想地使用。The polyimine obtained from the polyimine precursor composition of the present invention, that is, the polyimine of the present invention, has excellent properties such as high transparency, bending resistance, high heat resistance and has a very low coefficient of thermal expansion. Therefore, it is preferably used for a transparent substrate for a display, a transparent substrate for a touch panel, or a substrate for a solar cell.
以下就使用本發明之聚醯亞胺前驅體組成物之聚醯亞胺膜/基材疊層體、或聚醯亞胺膜之製造方法之一例敘述。惟不限於以下方法。Hereinafter, an example of a method for producing a polyimine film/substrate laminate or a polyimide film using the polyimide composition of the present invention will be described. However, it is not limited to the following methods.
將本發明之聚醯亞胺前驅體組成物(清漆)流延於例如於陶瓷(玻璃、矽、氧化鋁)、金屬(銅、鋁、不銹鋼)、耐熱塑膠膜(聚醯亞胺)等基材,並於真空中,氮等鈍性氣體中,或空氣中使用熱風或紅外線於20~180℃,較佳為20~150℃之溫度範圍進行乾燥。其次,將獲得之聚醯亞胺前驅體膜於基材上、或將聚醯亞胺前驅體膜從基材上剝離,於固定此膜之端部的狀態,於真空中,氮氣等鈍性氣體中,或空氣中,使用熱風或紅外線於約200~500℃,更佳為於最高加熱溫度超過350℃,更佳為超過380℃,尤佳為超過400℃的溫度進行加熱醯亞胺化,可製造聚醯亞胺膜/基材疊層體、或聚醯亞胺膜。又,為了防止獲得之聚醯亞胺膜氧化劣化,加熱醯亞胺化於真空中,或鈍性氣體中進行較理想。在此聚醯亞胺膜(聚醯亞胺膜/基材疊層體時,為聚醯亞胺膜層) 之厚度,為了以後步驟之運送性,較佳為1~250μm,更佳為1~150μm。The polyimine precursor composition (varnish) of the present invention is cast on a base such as ceramic (glass, bismuth, alumina), metal (copper, aluminum, stainless steel), heat-resistant plastic film (polyimine), and the like. The material is dried in a vacuum, a passive gas such as nitrogen, or a hot air or infrared light in the air at a temperature of 20 to 180 ° C, preferably 20 to 150 ° C. Next, the obtained polyimide precursor precursor film is peeled off from the substrate on the substrate, or the polyimide film precursor film is peeled off from the substrate, and the end portion of the film is fixed, and a vacuum such as nitrogen is blunt. In the gas, or in the air, hot air or infrared rays are used at about 200 to 500 ° C, more preferably at a maximum heating temperature of more than 350 ° C, more preferably more than 380 ° C, and more preferably at a temperature exceeding 400 ° C. A polyimide film/substrate laminate or a polyimide film can be produced. Further, in order to prevent oxidative degradation of the obtained polyimide film, it is preferred to heat the oxime in a vacuum or in a passive gas. The thickness of the polyimide film (polyimine film layer in the case of the polyimide film/substrate laminate) is preferably from 1 to 250 μm, more preferably 1 for the transportability of the subsequent step. ~150μm.
又,聚醯亞胺前驅體之醯亞胺化反應,也可將如前述加熱處理所為之加熱醯亞胺化,替換為利用將聚醯亞胺前驅體於吡啶或三乙胺等3級胺存在下浸漬於含有乙酸酐等脱水環化試藥之溶液等化學性處理進行。又,也可將該等脱水環化試藥預先投入聚醯亞胺前驅體組成物(清漆)中並攪拌,並將其在基材上流延・乾燥,以製作部分醯亞胺化之聚醯亞胺前驅體,藉由將其進一步進行如前述加熱處理,可獲得聚醯亞胺膜/基材疊層體、或聚醯亞胺膜。Further, the hydrazine imidization reaction of the polyimine precursor may be carried out by heating the hydrazine as described above by heating, instead of using the polyimine precursor to a quaternary amine such as pyridine or triethylamine. In the presence of a chemical treatment such as immersion in a solution containing a dehydrating cyclization reagent such as acetic anhydride. Further, the dehydrated cyclization reagent may be previously introduced into a polyamidene precursor composition (varnish) and stirred, and cast and dried on a substrate to prepare a partially yttrium-polymerized polypene. The imine precursor is further subjected to heat treatment as described above to obtain a polyimide film/substrate laminate or a polyimide film.
以如此方式獲得之聚醯亞胺膜/基材疊層體、或聚醯亞胺膜,藉由於其單面或兩面形成導電性層,可獲得可撓性導電性基板。The polyimide film/substrate laminate or the polyimide film obtained in this manner can form a flexible conductive substrate by forming a conductive layer on one or both sides.
可撓性導電性基板,例如可依以下方法獲得。亦即,作為第一之方法,不從聚醯亞胺膜/基材疊層體之基材剝離聚醯亞胺膜,而於其聚醯亞胺膜表面利用濺鍍、蒸鍍、印刷等形成導電性物質(金屬或金屬氧化物、導電性有機物、導電性碳等)之導電層,並製造導電性層/聚醯亞胺膜/基材之導電性疊層體。之後視需要從基材剝離導電性層/聚醯亞胺膜疊層體,可獲得由導電性層/聚醯亞胺膜疊層體構成之透明且可撓性的導電性基板。The flexible conductive substrate can be obtained, for example, by the following method. That is, as a first method, the polyimide film is not peeled off from the substrate of the polyimide film/substrate laminate, and sputtering, vapor deposition, printing, etc. are used on the surface of the polyimide film. A conductive layer of a conductive material (metal, metal oxide, conductive organic substance, conductive carbon, or the like) is formed, and a conductive layer/polyimine film/substrate conductive laminate is produced. Then, if necessary, the conductive layer/polyimine film laminate is peeled off from the substrate, and a transparent and flexible conductive substrate composed of a conductive layer/polyimine film laminate can be obtained.
作為第二之方法,可從聚醯亞胺膜/基材疊層體之基材將聚醯亞胺膜剝離,獲得聚醯亞胺膜,並於此聚醯亞胺膜表面以和第一方法同樣地形成導電性物質(金屬或金屬氧化物、導電性有機物、導電性碳等)之導電層,獲得由導電性層/聚醯亞胺膜疊層體、或導電性層/聚醯亞胺膜疊層體/導電性層構成之透明且可撓性之導電性基板。As a second method, the polyimide film can be peeled off from the substrate of the polyimide film/substrate laminate to obtain a polyimide film, and the surface of the polyimide film is first and In the same manner, a conductive layer of a conductive material (metal, metal oxide, conductive organic substance, conductive carbon, or the like) is formed, and a conductive layer/polyimine film laminate or a conductive layer/polyfluorene is obtained. A transparent and flexible conductive substrate composed of an amine film laminate/conductive layer.
又,第一、第二之方法中,視需要在聚醯亞胺膜表面形成導電層之前,也可利用濺鍍、蒸鍍或凝膠-溶膠法等形成水蒸氣、氧等氣體阻隔層、光調整層等無機層。Further, in the first and second methods, a gas barrier layer such as water vapor or oxygen may be formed by sputtering, vapor deposition, gel-sol method or the like before forming a conductive layer on the surface of the polyimide film. An inorganic layer such as a light adjustment layer.
又,導電層可利用光微影法或各種印刷法、噴墨法等方法適當地形成電路。Further, the conductive layer can be appropriately formed by a photolithography method, a method such as various printing methods, or an inkjet method.
本發明之基板,係於由本發明之聚醯亞胺構成之聚醯亞胺膜之表面視需要介隔氣體阻隔層或無機層而具有導電層之電路者。此基板為可撓性,且高透明性、彎折性、耐熱性優良,且於直到高溫有極低線熱膨脹係數或兼具優良的耐溶劑性,所以容易形成微細電路。因此此基板可理想地作為顯示器用、觸控面板用、或太陽能電池用之基板。The substrate of the present invention is a circuit having a conductive layer by interposing a gas barrier layer or an inorganic layer on the surface of the polyimide film composed of the polyimine of the present invention as needed. This substrate is flexible, has high transparency, bendability, and heat resistance, and has an extremely low linear thermal expansion coefficient up to a high temperature or an excellent solvent resistance, so that a fine circuit can be easily formed. Therefore, the substrate can be suitably used as a substrate for a display, a touch panel, or a solar cell.
亦即,可理想地於此基板利用蒸鍍、各種印刷法、或噴墨法等進一步形成電晶體(無機電晶體、有機電晶體)並製造可撓性薄膜電晶體,並且作為顯示裝置用液晶元件、EL元件、光電元件。 【實施例】In other words, it is preferable to further form a transistor (inorganic transistor, organic transistor) by vapor deposition, various printing methods, or an inkjet method, and to manufacture a flexible thin film transistor, and to use it as a liquid crystal for a display device. Element, EL element, photoelectric element. [Examples]
以下依實施例及比較例對於本發明更進一步説明。又本發明不限於以下實施例。The present invention will be further described below by way of examples and comparative examples. Further, the present invention is not limited to the following embodiments.
以下各例之評價依以下方法進行。The evaluation of the following examples was carried out in the following manner.
<聚醯亞胺前驅體溶液(清漆)之評價> [保存安定性] 於23℃保存清漆,於3日後若為有流動性的均勻狀態則評為○、 3日後為白濁、或凝膠化則評為×。<Evaluation of Polyimine Precursor Solution (Varnish)> [Storage Stability] The varnish was stored at 23 ° C, and it was evaluated as ○ after 3 days, and it was white turbid or gelled after 3 days. Then rated as ×.
<聚醯亞胺膜之評價> [400nm透光率、全光透射率] 使用紫外可見分光光度計/V-650DS(日本分光製),測定膜厚約10μm之聚醯亞胺膜於400nm之透光率與全光透射率(於380nm~780nm之平均透過率)。將測得之400nm之透光率、全光透射率令反射率為10%,使用Lambert-Beer law法則,計算厚10μm時於400nm之透光率、全光透射率。算式如下。<Evaluation of Polyimine Film> [400 nm Transmittance, Total Light Transmittance] Using a UV-visible spectrophotometer/V-650DS (manufactured by JASCO Corporation), a polyimide film having a film thickness of about 10 μm was measured at 400 nm. Light transmittance and total light transmittance (average transmittance from 380 nm to 780 nm). The transmittance at 400 nm and the total light transmittance were measured to have a reflectance of 10%, and the light transmittance at 400 nm and the total light transmittance at a thickness of 10 μm were calculated using the Lambert-Beer law. The formula is as follows.
Log10 ((T1 +10)/100)=10/L×(Log10 ((T1 ’+10)/100)) Log10 ((T2 +10)/100)=10/L×(Log10 ((T2 ’+10)/100)) T1 :令反射率為10%時厚10μm之聚醯亞胺膜於400nm之透光率(%) T1 ’:測得之400nm之透光率(%) T2 :令反射率為10%時厚10μm之聚醯亞胺膜之全光透射率(%) T2 ’:測得之全光透射率(%) L:測得之聚醯亞胺膜之膜厚(μm)Log 10 ((T 1 +10)/100)=10/L×(Log 10 ((T 1 '+10)/100)) Log 10 ((T 2 +10)/100)=10/L×(Log 10 ( (T 2 '+10)/100)) T 1 : Transmittance (%) of a polyimide film having a thickness of 10 μm at a reflectance of 10% at 400 nm T 1 ': measured transmittance at 400 nm ( %) T 2 : total light transmittance (%) of a polyimide film having a reflectance of 10% and a thickness of 10 μm T 2 ': measured total light transmittance (%) L: measured polyfluorene Film thickness of amine film (μm)
[彈性係數、斷裂點伸長度] 將膜厚約10μm之聚醯亞胺膜衝壓成IEC450規格之啞鈴形狀,當作試驗片,使用ORIENTEC公司製TENSILON,以夾頭間長30mm、拉伸速度2mm/min,測定起始彈性係數、斷裂點伸長度。[Elasticity coefficient, elongation at break point] A polyimide film having a film thickness of about 10 μm was punched into a dumbbell shape of IEC450, and used as a test piece. TENSILON manufactured by ORIENTEC Co., Ltd. was used, and the length between the chucks was 30 mm, and the stretching speed was 2 mm. /min, the initial elastic modulus and the elongation at break were measured.
[線熱膨脹係數(CTE)] 將膜厚約10μm之聚醯亞胺膜切成寬4mm的條狀,當作試驗片,並使用TMA/SS6100(SII TECHNOLOGY(股)公司製),以夾頭間長15mm、負荷2g、升溫速度20℃/min,升溫至500℃。從獲得之TMA曲線,求取150℃至250℃之線膨脹係數。[Linear thermal expansion coefficient (CTE)] A polyimine film having a film thickness of about 10 μm was cut into strips having a width of 4 mm, and used as a test piece, and TMA/SS6100 (manufactured by SII TECHNOLOGY Co., Ltd.) was used as a chuck. The length was 15 mm, the load was 2 g, the temperature increase rate was 20 ° C/min, and the temperature was raised to 500 °C. From the obtained TMA curve, a linear expansion coefficient of 150 ° C to 250 ° C was obtained.
[1%重量減少溫度] 以膜厚10μm之聚醯亞胺膜當作試驗片,使用TA INSTRUMENT公司製熱量計測定裝置(Q5000IR),於氮氣氣流中,以升溫速度10℃/min從25℃升溫至600℃。從獲得之重量曲線求取1%重量減少溫度。[1% weight reduction temperature] A polyimide film having a film thickness of 10 μm was used as a test piece, and a calorimeter measuring device (Q5000IR) manufactured by TA INSTRUMENT Co., Ltd. was used in a nitrogen gas stream at a temperature rising rate of 10 ° C/min from 25 ° C. Warm up to 600 °C. A 1% weight reduction temperature was obtained from the obtained weight curve.
以下各例使用之原材料之簡稱、純度等如下。The abbreviations, purity, etc. of the raw materials used in the following examples are as follows.
[二胺成分] DABAN:4,4’-二胺基苯醯替苯胺[純度:99.90%(GC分析)] PPD:對苯二胺[純度:99.9%(GC分析)] BAPB:4,4’-雙(4-胺基苯氧基)聯苯[純度:99.93%(HPLC分析)] [四羧酸成分] DNDAxx:(4arH,8acH)-十氫-1t,4t:5c,8c-二甲橋萘-2t,3t,6c,7c-四羧酸二酐[就DNDAxx而言之純度:99.2%(GC分析)][Diamine component] DABAN: 4,4'-diaminobenzoquinone [Purification: 99.90% (GC analysis)] PPD: p-phenylenediamine [Purity: 99.9% (GC analysis)] BAPB: 4, 4 '-bis(4-aminophenoxy)biphenyl [purity: 99.93% (HPLC analysis)] [tetracarboxylic acid component] DNDAxx: (4arH, 8acH)-decahydro-1t, 4t: 5c, 8c-two A bridge naphthalene-2t, 3t, 6c, 7c-tetracarboxylic dianhydride [purity in the case of DNDAxx: 99.2% (GC analysis)]
[咪唑・咪唑啉化合物] 1,2-二甲基咪唑 1- 甲基咪唑 2-甲基咪唑 2-苯基咪唑 咪唑 苯并咪唑 2- 乙基-2-咪唑啉[Imidazole/Imidazoline Compound] 1,2-Dimethylimidazole 1-Methylimidazole 2-Methylimidazole 2-Phenylimidazole Imidazole Benzimidazole 2-Ethyl-2-imidazoline
[溶劑] NMP:N-甲基-2-吡咯烷酮 DMAc:N,N-二甲基乙醯胺[Solvent] NMP: N-methyl-2-pyrrolidone DMAc: N,N-dimethylacetamide
表1-1記載實施例、比較例使用之四羧酸成分、表1-2記載實施例、比較例使用之二胺成分、表1-3記載實施例、比較例使用之咪唑・咪唑啉化合物之結構式。Table 1-1 shows the tetracarboxylic acid components used in the examples and comparative examples, the diamine components used in the examples and comparative examples in Table 1-2, and the imidazole/imidazoline compounds used in the examples and comparative examples in Table 1-3. The structural formula.
【表1-1】 【Table 1-1】
【表1-2】 [Table 1-2]
【表1-3】 [Table 1-3]
[合成例1] 於經氮氣取代之反應容器中加入DABAN 11.36g(0.050莫耳)與PPD 5.41g(0.050莫耳);加入N-甲基-2-吡咯烷酮187.99g,此量係使進料單體總質量(二胺成分與羧酸成分之總和)成為20質量%之量,於室溫攪拌1小時。於此溶液中將DNDAxx 30.23g(0.100莫耳)緩慢加入。於室溫攪拌12小時,獲得均勻且黏稠的聚醯亞胺前驅體溶液(清漆A)。[Synthesis Example 1] To a reaction vessel substituted with nitrogen, DABAN 11.36 g (0.050 mol) and PPD 5.41 g (0.050 mol) were added; and N-methyl-2-pyrrolidone 187.99 g was added, which was such that the feed was made. The total mass of the monomer (the sum of the diamine component and the carboxylic acid component) was 20% by mass, and the mixture was stirred at room temperature for 1 hour. DNDAxx 30.23 g (0.100 mol) was slowly added to this solution. Stir at room temperature for 12 hours to obtain a homogeneous and viscous polyimide precursor solution (varnish A).
[合成例2] 於經氮氣取代之反應容器中加入DABAN 11.36g(0.050莫耳)與PPD 5.41g(0.050莫耳);加入N,N-二甲基乙醯胺187.99g,此量係使進料單體總質量(二胺成分與羧酸成分之總和)成為20質量%之量,於室溫攪拌1小時。於此溶液中將DNDAxx 30.23g(0.100莫耳)緩慢加入。於室溫攪拌12小時,獲得均勻且黏稠的聚醯亞胺前驅體溶液(清漆B)。[Synthesis Example 2] To a reaction vessel substituted with nitrogen, DABAN 11.36 g (0.050 mol) and PPD 5.41 g (0.050 mol) were added; and N,N-dimethylacetamide was added to 187.99 g, which was The total mass of the feed monomer (the sum of the diamine component and the carboxylic acid component) was 20% by mass, and the mixture was stirred at room temperature for 1 hour. DNDAxx 30.23 g (0.100 mol) was slowly added to this solution. Stir at room temperature for 12 hours to obtain a homogeneous and viscous polyimide precursor solution (varnish B).
[合成例3] 於經氮氣取代之反應容器中加入DABAN 6.82g(0.030莫耳)與PPD 4.33g(0.040莫耳)與BAPB 11.05g(0.030莫耳);加入N-甲基-2-吡咯烷酮209.70g,此量係使進料單體總質量(二胺成分與羧酸成分之總和)成為20質量%之量,於室溫攪拌1小時。於此溶液中將DNDAxx 30.23g(0.100莫耳)緩慢加入。於室溫攪拌12小時,獲得均勻且黏稠的聚醯亞胺前驅體溶液(清漆C)。[Synthesis Example 3] DABAN 6.82 g (0.030 mol) and PPD 4.33 g (0.040 mol) and BAPB 11.05 g (0.030 mol) were added to a nitrogen-substituted reaction vessel; N-methyl-2-pyrrolidone was added thereto. 209.70 g, which is an amount of the total mass of the feed monomer (the sum of the diamine component and the carboxylic acid component) of 20% by mass, and stirred at room temperature for 1 hour. DNDAxx 30.23 g (0.100 mol) was slowly added to this solution. Stir at room temperature for 12 hours to obtain a homogeneous and viscous polyimide precursor solution (varnish C).
[合成例4] 於經氮氣取代之反應容器中加入DABAN 15.91g(0.070莫耳)與BAPB 11.05g(0.030莫耳);添加N-甲基-2-吡咯烷酮228.76g,此量係使進料單體總質量(二胺成分與羧酸成分之總和)成為20質量%之量,於室溫攪拌1小時。於此溶液中將DNDAxx 30.23g(0.100莫耳)緩慢加入。於室溫攪拌12小時,獲額均勻且黏稠的聚醯亞胺前驅體溶液(清漆D)。[Synthesis Example 4] DABAN 15.91 g (0.070 mol) and BAPB 11.05 g (0.030 mol) were added to a nitrogen-substituted reaction vessel; N-methyl-2-pyrrolidone 228.76 g was added, which was used to feed The total mass of the monomer (the sum of the diamine component and the carboxylic acid component) was 20% by mass, and the mixture was stirred at room temperature for 1 hour. DNDAxx 30.23 g (0.100 mol) was slowly added to this solution. After stirring at room temperature for 12 hours, a uniform and viscous polyimide precursor solution (varnish D) was obtained.
[合成例5] 於經氮氣取代之反應容器中加入DABAN 9.09g(0.040莫耳)與PPD 4.33g(0.040莫耳)與BAPB 7.37g(0.020莫耳);加入N-甲基-2-吡咯烷酮204.06g,此量係使進料單體總質量(二胺成分與羧酸成分之總和)成為20質量%之量,於室溫攪拌1小時。於此溶液中將DNDAxx 30.23g(0.100莫耳)緩慢加入。於室溫攪拌12小時,獲得均勻且黏稠的聚醯亞胺前驅體溶液(清漆E)。[Synthesis Example 5] In a reaction vessel substituted with nitrogen, DABAN 9.09 g (0.040 mol) and PPD 4.33 g (0.040 mol) and BAPB 7.37 g (0.020 mol) were added; N-methyl-2-pyrrolidone was added. 204.06g, which is an amount of the total mass of the feed monomer (the sum of the diamine component and the carboxylic acid component) of 20% by mass, and stirred at room temperature for 1 hour. DNDAxx 30.23 g (0.100 mol) was slowly added to this solution. Stir at room temperature for 12 hours to obtain a homogeneous and viscous polyimide precursor solution (varnish E).
[實施例1] 將1,2-二甲基咪唑 0.10g(1.0毫莫耳)與N-甲基-2-吡咯烷酮 0.10g加到反應容器中,獲得均勻的溶液。於此溶液中加入合成例1獲得之清漆A 23.50g(相對於清漆A中之聚醯亞胺前驅體之重複單元之分子量,為10毫莫耳),於室溫攪拌3小時,獲得均勻且黏稠的聚醯亞胺前驅體溶液。若從進料量計算,相對於聚醯亞胺前驅體之重複單元1莫耳,1,2-二甲基咪唑之莫耳數為0.1當量。[Example 1] 0.10 g (1.0 mmol) of 1,2-dimethylimidazole and 0.10 g of N-methyl-2-pyrrolidone were added to a reaction vessel to obtain a homogeneous solution. To the solution, 23.50 g of the varnish A obtained in Synthesis Example 1 (molecular weight of the repeating unit of the polyimine precursor in the varnish A, 10 mmol) was added, and the mixture was stirred at room temperature for 3 hours to obtain uniformity. A viscous polyimide precursor solution. The molar number of 1,2-dimethylimidazole relative to the repeating unit of the polyimine precursor was 0.1 equivalent, based on the amount of feed.
將經PTFE製濾膜過濾的聚醯亞胺前驅體溶液塗佈在玻璃基板,於氮氣環境下(氧濃度200ppm以下),直接在玻璃基板上從室溫加熱到440℃而進行熱醯亞胺化,獲得無色透明的聚醯亞胺膜/玻璃疊層體。其次將獲得之聚醯亞胺膜/玻璃疊層體浸於水後剝離並乾燥,獲得膜厚約10μm之聚醯亞胺膜。The polyimine precursor solution filtered through the PTFE filter membrane is coated on a glass substrate, and heated to a temperature of 440 ° C on a glass substrate under a nitrogen atmosphere (oxygen concentration: 200 ppm or less) to carry out thermal yttrium imine. The colorless transparent polyimide film/glass laminate was obtained. Next, the obtained polyimide film/glass laminate was immersed in water, peeled off, and dried to obtain a polyimide film having a film thickness of about 10 μm.
此聚醯亞胺膜之特性的測定結果示於表2-1。The measurement results of the properties of this polyimide film are shown in Table 2-1.
[實施例2] 將1,2-二甲基咪唑 0.38g(4.0毫莫耳)與N-甲基-2-吡咯烷酮 0.38g加到反應容器中,獲得均勻的溶液。於此溶液中合成例1加入獲得之清漆A 23.50g(相對於清漆A中之聚醯亞胺前驅體之重複單元之分子量,為10毫莫耳),於室溫攪拌3小時,獲得均勻且黏稠的聚醯亞胺前驅體溶液。若從進料量計算,相對於聚醯亞胺前驅體之重複單元1莫耳,1,2-二甲基咪唑之莫耳數為0.4當量。[Example 2] 0.38 g (4.0 mmol) of 1,2-dimethylimidazole and 0.38 g of N-methyl-2-pyrrolidone were added to a reaction vessel to obtain a homogeneous solution. In this solution, Synthesis Example 1 was added to 23.2 g of the obtained varnish A (molecular weight of 10 mmol of the repeating unit of the polyimine precursor in varnish A), and stirred at room temperature for 3 hours to obtain uniformity. A viscous polyimide precursor solution. The molar number of 1,2-dimethylimidazole relative to the repeating unit of the polyimine precursor was calculated to be 0.4 equivalents based on the amount of the feed.
將經PTFE製濾膜過濾的聚醯亞胺前驅體溶液塗佈在玻璃基板,於氮氣環境下(氧濃度200ppm以下),直接在玻璃基板上從室溫加熱到440℃而進行熱醯亞胺化,獲得無色透明的聚醯亞胺膜/玻璃疊層體。其次將獲得之聚醯亞胺膜/玻璃疊層體浸於水後剝離並乾燥,獲得膜厚約10μm之聚醯亞胺膜。The polyimine precursor solution filtered through the PTFE filter membrane is coated on a glass substrate, and heated to a temperature of 440 ° C on a glass substrate under a nitrogen atmosphere (oxygen concentration: 200 ppm or less) to carry out thermal yttrium imine. The colorless transparent polyimide film/glass laminate was obtained. Next, the obtained polyimide film/glass laminate was immersed in water, peeled off, and dried to obtain a polyimide film having a film thickness of about 10 μm.
此聚醯亞胺膜之特性的測定結果示於表2-1。The measurement results of the properties of this polyimide film are shown in Table 2-1.
[實施例3] 將1,2-二甲基咪唑 0.96g(10.0毫莫耳)與N-甲基-2-吡咯烷酮 0.48g加到反應容器,獲得均勻的溶液。於此溶液中加入合成例1獲得之清漆A 23.50g(相對於清漆A中之聚醯亞胺前驅體之重複單元之分子量,為10毫莫耳),於室溫攪拌3小時,獲得均勻且黏稠的聚醯亞胺前驅體溶液。若從進料量計算,相對於聚醯亞胺前驅體之重複單元1莫耳,1,2-二甲基咪唑之莫耳數為1.0當量。[Example 3] 1,6 g (10.0 mmol) of 1,2-dimethylimidazole and 0.48 g of N-methyl-2-pyrrolidone were added to a reaction vessel to obtain a homogeneous solution. To the solution, 23.50 g of the varnish A obtained in Synthesis Example 1 (molecular weight of the repeating unit of the polyimine precursor in the varnish A, 10 mmol) was added, and the mixture was stirred at room temperature for 3 hours to obtain uniformity. A viscous polyimide precursor solution. The molar number of 1,2-dimethylimidazole relative to the repeating unit of the polyimine precursor was 1.0 equivalent, based on the amount of feed.
將經PTFE製濾膜過濾的聚醯亞胺前驅體溶液塗佈在玻璃基板,於氮氣環境下(氧濃度200ppm以下),直接在玻璃基板上從室溫加熱到440℃而進行熱醯亞胺化,獲得無色透明的聚醯亞胺膜/玻璃疊層體。其次將獲得之聚醯亞胺膜/玻璃疊層體浸於水後剝離並乾燥,獲得膜厚約10μm之聚醯亞胺膜。The polyimine precursor solution filtered through the PTFE filter membrane is coated on a glass substrate, and heated to a temperature of 440 ° C on a glass substrate under a nitrogen atmosphere (oxygen concentration: 200 ppm or less) to carry out thermal yttrium imine. The colorless transparent polyimide film/glass laminate was obtained. Next, the obtained polyimide film/glass laminate was immersed in water, peeled off, and dried to obtain a polyimide film having a film thickness of about 10 μm.
此聚醯亞胺膜之特性的測定結果示於表2-1。The measurement results of the properties of this polyimide film are shown in Table 2-1.
[實施例4] 將1,2-二甲基咪唑 1.92g(20.0毫莫耳)與N-甲基-2-吡咯烷酮 0.48g加到反應容器,獲得均勻的溶液。於此溶液中加入合成例1獲得之清漆A 23.50g(相對於清漆A中之聚醯亞胺前驅體之重複單元之分子量,為10毫莫耳),於室溫攪拌3小時,獲得均勻且黏稠的聚醯亞胺前驅體溶液。若從進料量計算,相對於聚醯亞胺前驅體之重複單元1莫耳,1,2-二甲基咪唑之莫耳數為2.0當量。[Example 4] 1.92 g (20.0 mmol) of 1,2-dimethylimidazole and 0.48 g of N-methyl-2-pyrrolidone were added to a reaction vessel to obtain a homogeneous solution. To the solution, 23.50 g of the varnish A obtained in Synthesis Example 1 (molecular weight of the repeating unit of the polyimine precursor in the varnish A, 10 mmol) was added, and the mixture was stirred at room temperature for 3 hours to obtain uniformity. A viscous polyimide precursor solution. The molar number of 1,2-dimethylimidazole relative to the repeating unit of the polyimine precursor was 2.0 equivalents, calculated from the amount of feed.
將經PTFE製濾膜過濾的聚醯亞胺前驅體溶液塗佈在玻璃基板,於氮氣環境下(氧濃度200ppm以下),直接在玻璃基板上從室溫加熱到440℃而進行熱醯亞胺化,獲得無色透明的聚醯亞胺膜/玻璃疊層體。其次將獲得之聚醯亞胺膜/玻璃疊層體浸於水後剝離並乾燥,獲得膜厚約10μm之聚醯亞胺膜。The polyimine precursor solution filtered through the PTFE filter membrane is coated on a glass substrate, and heated to a temperature of 440 ° C on a glass substrate under a nitrogen atmosphere (oxygen concentration: 200 ppm or less) to carry out thermal yttrium imine. The colorless transparent polyimide film/glass laminate was obtained. Next, the obtained polyimide film/glass laminate was immersed in water, peeled off, and dried to obtain a polyimide film having a film thickness of about 10 μm.
此聚醯亞胺膜之特性的測定結果示於表2-1。The measurement results of the properties of this polyimide film are shown in Table 2-1.
[比較例1] 將經PTFE製濾膜過濾的合成例1獲得之清漆A塗佈在玻璃基板,於氮氣環境下(氧濃度200ppm以下),直接在玻璃基板上從室溫加熱到440℃而進行熱醯亞胺化,獲得無色透明的聚醯亞胺膜/玻璃疊層體。其次將獲得之聚醯亞胺膜/玻璃疊層體浸於水後剝離並乾燥,獲得膜厚約10μm之聚醯亞胺膜。[Comparative Example 1] The varnish A obtained in Synthesis Example 1 filtered through a PTFE filter membrane was applied onto a glass substrate, and heated directly from room temperature to 440 ° C on a glass substrate under a nitrogen atmosphere (oxygen concentration: 200 ppm or less). The enthalpy imidization was carried out to obtain a colorless transparent polyimide film/glass laminate. Next, the obtained polyimide film/glass laminate was immersed in water, peeled off, and dried to obtain a polyimide film having a film thickness of about 10 μm.
此聚醯亞胺膜之特性的測定結果示於表2-1。The measurement results of the properties of this polyimide film are shown in Table 2-1.
[實施例5] 將1,2-二甲基咪唑 0.10g(1.0毫莫耳)與N,N-二甲基乙醯胺 0.10g加到反應容器中,獲得均勻的溶液。於此溶液中加入合成例2獲得之清漆B 23.50g(相對於清漆B中之聚醯亞胺前驅體之重複單元之分子量,為10毫莫耳),於室溫攪拌3小時,獲得均勻且黏稠的聚醯亞胺前驅體溶液。若從進料量計算,相對於聚醯亞胺前驅體之重複單元1莫耳,1,2-二甲基咪唑之莫耳數為0.1當量。[Example 5] 0.10 g (1.0 mmol) of 1,2-dimethylimidazole and 0.10 g of N,N-dimethylacetamide were added to a reaction vessel to obtain a homogeneous solution. To the solution, 23.50 g of the varnish B obtained in Synthesis Example 2 (molecular weight of 10 ppm of the repeating unit of the polyimine precursor in the varnish B) was added, and the mixture was stirred at room temperature for 3 hours to obtain uniformity. A viscous polyimide precursor solution. The molar number of 1,2-dimethylimidazole relative to the repeating unit of the polyimine precursor was 0.1 equivalent, based on the amount of feed.
將經PTFE製濾膜過濾的聚醯亞胺前驅體溶液塗佈在玻璃基板,於氮氣環境下(氧濃度200ppm以下),直接在玻璃基板上從室溫加熱到440℃而進行熱醯亞胺化,獲得無色透明的聚醯亞胺膜/玻璃疊層體。其次將獲得之聚醯亞胺膜/玻璃疊層體浸於水後剝離並乾燥,獲得膜厚約10μm之聚醯亞胺膜。The polyimine precursor solution filtered through the PTFE filter membrane is coated on a glass substrate, and heated to a temperature of 440 ° C on a glass substrate under a nitrogen atmosphere (oxygen concentration: 200 ppm or less) to carry out thermal yttrium imine. The colorless transparent polyimide film/glass laminate was obtained. Next, the obtained polyimide film/glass laminate was immersed in water, peeled off, and dried to obtain a polyimide film having a film thickness of about 10 μm.
此聚醯亞胺膜之特性的測定結果示於表2-1。The measurement results of the properties of this polyimide film are shown in Table 2-1.
[實施例6] 將1,2-二甲基咪唑 0.38g(4.0毫莫耳)與N,N-二甲基乙醯胺 0.38g加到反應容器中,獲得均勻的溶液。於此溶液中加入合成例2獲得之清漆B 23.50g(相對於清漆B中之聚醯亞胺前驅體之重複單元之分子量,為10毫莫耳),於室溫攪拌3小時,獲得均勻且黏稠的聚醯亞胺前驅體溶液。若從進料量計算,相對於聚醯亞胺前驅體之重複單元1莫耳,1,2-二甲基咪唑之莫耳數為0.4當量。[Example 6] 0.38 g (4.0 mmol) of 1,2-dimethylimidazole and 0.38 g of N,N-dimethylacetamide were added to a reaction vessel to obtain a homogeneous solution. To the solution, 23.50 g of the varnish B obtained in Synthesis Example 2 (molecular weight of 10 ppm of the repeating unit of the polyimine precursor in the varnish B) was added, and the mixture was stirred at room temperature for 3 hours to obtain uniformity. A viscous polyimide precursor solution. The molar number of 1,2-dimethylimidazole relative to the repeating unit of the polyimine precursor was calculated to be 0.4 equivalents based on the amount of the feed.
將經PTFE製濾膜過濾的聚醯亞胺前驅體溶液塗佈在玻璃基板,於氮氣環境下(氧濃度200ppm以下),直接在玻璃基板上從室溫加熱到440℃而進行熱醯亞胺化,獲得無色透明的聚醯亞胺膜/玻璃疊層體。其次將獲得之聚醯亞胺膜/玻璃疊層體浸於水後剝離並乾燥,獲得膜厚約10μm之聚醯亞胺膜。The polyimine precursor solution filtered through the PTFE filter membrane is coated on a glass substrate, and heated to a temperature of 440 ° C on a glass substrate under a nitrogen atmosphere (oxygen concentration: 200 ppm or less) to carry out thermal yttrium imine. The colorless transparent polyimide film/glass laminate was obtained. Next, the obtained polyimide film/glass laminate was immersed in water, peeled off, and dried to obtain a polyimide film having a film thickness of about 10 μm.
此聚醯亞胺膜之特性的測定結果示於表2-1。The measurement results of the properties of this polyimide film are shown in Table 2-1.
[比較例2] 將經PTFE製濾膜過濾的合成例2獲得之清漆B塗佈在玻璃基板,於氮氣環境下(氧濃度200ppm以下),直接在玻璃基板上從室溫加熱到440℃而進行熱醯亞胺化,獲得無色透明的聚醯亞胺膜/玻璃疊層體。其次將獲得之聚醯亞胺膜/玻璃疊層體浸於水後剝離並乾燥,獲得膜厚約10μm之聚醯亞胺膜。[Comparative Example 2] The varnish B obtained in Synthesis Example 2 filtered through a PTFE filter membrane was applied onto a glass substrate, and heated directly from room temperature to 440 ° C on a glass substrate under a nitrogen atmosphere (oxygen concentration: 200 ppm or less). The enthalpy imidization was carried out to obtain a colorless transparent polyimide film/glass laminate. Next, the obtained polyimide film/glass laminate was immersed in water, peeled off, and dried to obtain a polyimide film having a film thickness of about 10 μm.
此聚醯亞胺膜之特性的測定結果示於表2-1。The measurement results of the properties of this polyimide film are shown in Table 2-1.
[實施例7] 將1,2-二甲基咪唑 0.19g(2.0毫莫耳)與N-甲基-2-吡咯烷酮 0.19g加到反應容器中,獲得均勻的溶液。於此溶液中加入合成例3獲得之清漆C 26.21g(相對於清漆C中之聚醯亞胺前驅體之重複單元之分子量,為10毫莫耳),於室溫攪拌3小時,獲得均勻且黏稠的聚醯亞胺前驅體溶液。若從進料量計算,相對於聚醯亞胺前驅體之重複單元1莫耳,1,2-二甲基咪唑之莫耳數為0.2當量。[Example 7] 0.19 g (2.0 mmol) of 1,2-dimethylimidazole and 0.19 g of N-methyl-2-pyrrolidone were added to a reaction vessel to obtain a homogeneous solution. To the solution, 26.21 g of the varnish C obtained in Synthesis Example 3 (molecular weight with respect to the repeating unit of the polyimine precursor in varnish C, 10 mmol) was added, and stirred at room temperature for 3 hours to obtain uniformity. A viscous polyimide precursor solution. The molar number of 1,2-dimethylimidazole relative to the repeating unit of the polyimide intermediate precursor was 0.2 equivalents based on the amount of the feed.
將經PTFE製濾膜過濾的聚醯亞胺前驅體溶液塗佈在玻璃基板,於氮氣環境下(氧濃度200ppm以下),直接在玻璃基板上從室溫加熱到440℃而進行熱醯亞胺化,獲得無色透明的聚醯亞胺膜/玻璃疊層體。其次將獲得之聚醯亞胺膜/玻璃疊層體浸於水後剝離並乾燥,獲得膜厚約10μm之聚醯亞胺膜。The polyimine precursor solution filtered through the PTFE filter membrane is coated on a glass substrate, and heated to a temperature of 440 ° C on a glass substrate under a nitrogen atmosphere (oxygen concentration: 200 ppm or less) to carry out thermal yttrium imine. The colorless transparent polyimide film/glass laminate was obtained. Next, the obtained polyimide film/glass laminate was immersed in water, peeled off, and dried to obtain a polyimide film having a film thickness of about 10 μm.
此聚醯亞胺膜之特性的測定結果示於表2-1。The measurement results of the properties of this polyimide film are shown in Table 2-1.
[比較例3] 將經PTFE製濾膜過濾的合成例3獲得之清漆C塗佈在玻璃基板,於氮氣環境下(氧濃度200ppm以下),直接在玻璃基板上從室溫加熱到440℃而進行熱醯亞胺化,獲得無色透明的聚醯亞胺膜/玻璃疊層體。其次將獲得之聚醯亞胺膜/玻璃疊層體浸於水後剝離並乾燥,獲得膜厚約10μm之聚醯亞胺膜。[Comparative Example 3] The varnish C obtained in Synthesis Example 3 filtered through a PTFE filter membrane was applied onto a glass substrate, and heated directly from room temperature to 440 ° C on a glass substrate under a nitrogen atmosphere (oxygen concentration: 200 ppm or less). The enthalpy imidization was carried out to obtain a colorless transparent polyimide film/glass laminate. Next, the obtained polyimide film/glass laminate was immersed in water, peeled off, and dried to obtain a polyimide film having a film thickness of about 10 μm.
此聚醯亞胺膜之特性的測定結果示於表2-1。The measurement results of the properties of this polyimide film are shown in Table 2-1.
[實施例8] 將1,2-二甲基咪唑 0.19g(2.0毫莫耳)與N-甲基-2-吡咯烷酮 0.19g加到反應容器中,獲得均勻的溶液。於此溶液中加入合成例4獲得之清漆D 28.60g(相對於清漆D中之聚醯亞胺前驅體之重複單元之分子量,為10毫莫耳),於室溫攪拌3小時,獲得均勻且黏稠的聚醯亞胺前驅體溶液。若從進料量計算,相對於聚醯亞胺前驅體之重複單元1莫耳,1,2-二甲基咪唑之莫耳數為0.2當量。[Example 8] 0.19 g (2.0 mmol) of 1,2-dimethylimidazole and 0.19 g of N-methyl-2-pyrrolidone were added to a reaction vessel to obtain a homogeneous solution. To the solution was added 28.60 g of the varnish D obtained in Synthesis Example 4 (molecular weight of 10 ppm with respect to the repeating unit of the polyimine precursor in varnish D), and stirred at room temperature for 3 hours to obtain uniformity. A viscous polyimide precursor solution. The molar number of 1,2-dimethylimidazole relative to the repeating unit of the polyimide intermediate precursor was 0.2 equivalents based on the amount of the feed.
將經PTFE製濾膜過濾的聚醯亞胺前驅體溶液塗佈在玻璃基板,於氮氣環境下(氧濃度200ppm以下),直接在玻璃基板上從室溫加熱到440℃而進行熱醯亞胺化,獲得無色透明的聚醯亞胺膜/玻璃疊層體。其次將獲得之聚醯亞胺膜/玻璃疊層體浸於水後剝離並乾燥,獲得膜厚約10μm之聚醯亞胺膜。The polyimine precursor solution filtered through the PTFE filter membrane is coated on a glass substrate, and heated to a temperature of 440 ° C on a glass substrate under a nitrogen atmosphere (oxygen concentration: 200 ppm or less) to carry out thermal yttrium imine. The colorless transparent polyimide film/glass laminate was obtained. Next, the obtained polyimide film/glass laminate was immersed in water, peeled off, and dried to obtain a polyimide film having a film thickness of about 10 μm.
此聚醯亞胺膜之特性的測定結果示於表2-1。The measurement results of the properties of this polyimide film are shown in Table 2-1.
[比較例4] 將經PTFE製濾膜過濾的合成例4獲得之清漆D塗佈在玻璃基板,於氮氣環境下(氧濃度200ppm以下),直接在玻璃基板上從室溫加熱到440℃而進行熱醯亞胺化,獲得無色透明的聚醯亞胺膜/玻璃疊層體。其次將獲得之聚醯亞胺膜/玻璃疊層體浸於水後剝離並乾燥,獲得膜厚約10μm之聚醯亞胺膜。[Comparative Example 4] The varnish D obtained in Synthesis Example 4 filtered through a PTFE filter membrane was applied onto a glass substrate, and heated directly from room temperature to 440 ° C on a glass substrate under a nitrogen atmosphere (oxygen concentration: 200 ppm or less). The enthalpy imidization was carried out to obtain a colorless transparent polyimide film/glass laminate. Next, the obtained polyimide film/glass laminate was immersed in water, peeled off, and dried to obtain a polyimide film having a film thickness of about 10 μm.
此聚醯亞胺膜之特性的測定結果示於表2-1。The measurement results of the properties of this polyimide film are shown in Table 2-1.
[實施例9] 將1,2-二甲基咪唑 0.19g(2.0毫莫耳)與N-甲基-2-吡咯烷酮 0.19g加到反應容器中,獲得均勻的溶液。於此溶液中加入合成例5獲得之清漆E 25.51g(相對於清漆E中之聚醯亞胺前驅體之重複單元之分子量,為10毫莫耳),於室溫攪拌3小時,獲得均勻且黏稠的聚醯亞胺前驅體溶液。若從進料量計算,相對於聚醯亞胺前驅體之重複單元1莫耳,1,2-二甲基咪唑之莫耳數為0.2當量。[Example 9] 0.19 g (2.0 mmol) of 1,2-dimethylimidazole and 0.19 g of N-methyl-2-pyrrolidone were added to a reaction vessel to obtain a homogeneous solution. The varnish E 25.51 g obtained in Synthesis Example 5 (molecular weight of the repeating unit of the polyimine precursor in varnish E was 10 mmol) was added to the solution, and stirred at room temperature for 3 hours to obtain uniformity. A viscous polyimide precursor solution. The molar number of 1,2-dimethylimidazole relative to the repeating unit of the polyimide intermediate precursor was 0.2 equivalents based on the amount of the feed.
將經PTFE製濾膜過濾的聚醯亞胺前驅體溶液塗佈在玻璃基板,於氮氣環境下(氧濃度200ppm以下),直接在玻璃基板上從室溫加熱到440℃而進行熱醯亞胺化,獲得無色透明的聚醯亞胺膜/玻璃疊層體。其次將獲得之聚醯亞胺膜/玻璃疊層體浸於水後剝離並乾燥,獲得膜厚約10μm之聚醯亞胺膜。The polyimine precursor solution filtered through the PTFE filter membrane is coated on a glass substrate, and heated to a temperature of 440 ° C on a glass substrate under a nitrogen atmosphere (oxygen concentration: 200 ppm or less) to carry out thermal yttrium imine. The colorless transparent polyimide film/glass laminate was obtained. Next, the obtained polyimide film/glass laminate was immersed in water, peeled off, and dried to obtain a polyimide film having a film thickness of about 10 μm.
此聚醯亞胺膜之特性的測定結果示於表2-2。The measurement results of the properties of this polyimide film are shown in Table 2-2.
[實施例10] 將1-甲基咪唑 0.16g(2.0毫莫耳)與N-甲基-2-吡咯烷酮 0.16g加到反應容器,獲得均勻的溶液。於此溶液中加入合成例5獲得之清漆E 25.51g(相對於清漆E中之聚醯亞胺前驅體之重複單元之分子量,為10毫莫耳),於室溫攪拌3小時,獲得均勻且黏稠的聚醯亞胺前驅體溶液。若從進料量計算,相對於聚醯亞胺前驅體之重複單元1莫耳,1-甲基咪唑之莫耳數為0.2當量。[Example 10] 0.16 g (2.0 mmol) of 1-methylimidazole and 0.16 g of N-methyl-2-pyrrolidone were added to a reaction vessel to obtain a homogeneous solution. The varnish E 25.51 g obtained in Synthesis Example 5 (molecular weight of the repeating unit of the polyimine precursor in varnish E was 10 mmol) was added to the solution, and stirred at room temperature for 3 hours to obtain uniformity. A viscous polyimide precursor solution. The molar number of 1-methylimidazole is 0.2 equivalents based on the amount of the feed, relative to the repeat unit of the polyimine precursor.
將經PTFE製濾膜過濾的聚醯亞胺前驅體溶液塗佈在玻璃基板,於氮氣環境下(氧濃度200ppm以下),直接在玻璃基板上從室溫加熱到440℃而進行熱醯亞胺化,獲得無色透明的聚醯亞胺膜/玻璃疊層體。其次將獲得之聚醯亞胺膜/玻璃疊層體浸於水後剝離並乾燥,獲得膜厚約10μm之聚醯亞胺膜。The polyimine precursor solution filtered through the PTFE filter membrane is coated on a glass substrate, and heated to a temperature of 440 ° C on a glass substrate under a nitrogen atmosphere (oxygen concentration: 200 ppm or less) to carry out thermal yttrium imine. The colorless transparent polyimide film/glass laminate was obtained. Next, the obtained polyimide film/glass laminate was immersed in water, peeled off, and dried to obtain a polyimide film having a film thickness of about 10 μm.
此聚醯亞胺膜之特性的測定結果示於表2-2。The measurement results of the properties of this polyimide film are shown in Table 2-2.
[實施例11] 將2-甲基咪唑 0.16g(2.0毫莫耳)與N-甲基-2-吡咯烷酮 0.16g加到反應容器,獲得均勻的溶液。於此溶液中加入合成例5獲得之清漆E 25.51g(相對於清漆E中之聚醯亞胺前驅體之重複單元之分子量,為10毫莫耳),於室溫攪拌3小時,獲得均勻且黏稠的聚醯亞胺前驅體溶液。若從進料量計算,相對於聚醯亞胺前驅體之重複單元1莫耳,2-甲基咪唑之莫耳數為0.2當量。[Example 11] 0.16 g (2.0 mmol) of 2-methylimidazole and 0.16 g of N-methyl-2-pyrrolidone were added to a reaction vessel to obtain a homogeneous solution. The varnish E 25.51 g obtained in Synthesis Example 5 (molecular weight of the repeating unit of the polyimine precursor in varnish E was 10 mmol) was added to the solution, and stirred at room temperature for 3 hours to obtain uniformity. A viscous polyimide precursor solution. The molar number of 2-methylimidazole is 0.2 equivalents based on the amount of the feed, relative to the repeat unit of the polyimine precursor.
將經PTFE製濾膜過濾的聚醯亞胺前驅體溶液塗佈在玻璃基板,於氮氣環境下(氧濃度200ppm以下),直接在玻璃基板上從室溫加熱到440℃而進行熱醯亞胺化,獲得無色透明的聚醯亞胺膜/玻璃疊層體。其次將獲得之聚醯亞胺膜/玻璃疊層體浸於水後剝離並乾燥,獲得膜厚約10μm之聚醯亞胺膜。The polyimine precursor solution filtered through the PTFE filter membrane is coated on a glass substrate, and heated to a temperature of 440 ° C on a glass substrate under a nitrogen atmosphere (oxygen concentration: 200 ppm or less) to carry out thermal yttrium imine. The colorless transparent polyimide film/glass laminate was obtained. Next, the obtained polyimide film/glass laminate was immersed in water, peeled off, and dried to obtain a polyimide film having a film thickness of about 10 μm.
此聚醯亞胺膜之特性的測定結果示於表2-2。The measurement results of the properties of this polyimide film are shown in Table 2-2.
[實施例12] 將咪唑 0.14g(2.0毫莫耳)與N-甲基-2-吡咯烷酮 0.14g加到反應容器中,獲得均勻的溶液。於此溶液中加入合成例5獲得之清漆E 25.51g(相對於清漆E中之聚醯亞胺前驅體之重複單元之分子量,為10毫莫耳),於室溫攪拌3小時,獲得均勻且黏稠的聚醯亞胺前驅體溶液。若從進料量計算,相對於聚醯亞胺前驅體之重複單元1莫耳,咪唑之莫耳數為0.2當量。[Example 12] 0.14 g (2.0 mmol) of imidazole and 0.14 g of N-methyl-2-pyrrolidone were added to a reaction vessel to obtain a homogeneous solution. The varnish E 25.51 g obtained in Synthesis Example 5 (molecular weight of the repeating unit of the polyimine precursor in varnish E was 10 mmol) was added to the solution, and stirred at room temperature for 3 hours to obtain uniformity. A viscous polyimide precursor solution. The molar number of imidazoles was 0.2 equivalents relative to the repeating unit of the polyamidene precursor, 1 mole, calculated from the amount of feed.
將經PTFE製濾膜過濾的聚醯亞胺前驅體溶液塗佈在玻璃基板,於氮氣環境下(氧濃度200ppm以下),直接在玻璃基板上從室溫加熱到440℃而進行熱醯亞胺化,獲得無色透明的聚醯亞胺膜/玻璃疊層體。其次將獲得之聚醯亞胺膜/玻璃疊層體浸於水後剝離並乾燥,獲得膜厚約10μm之聚醯亞胺膜。The polyimine precursor solution filtered through the PTFE filter membrane is coated on a glass substrate, and heated to a temperature of 440 ° C on a glass substrate under a nitrogen atmosphere (oxygen concentration: 200 ppm or less) to carry out thermal yttrium imine. The colorless transparent polyimide film/glass laminate was obtained. Next, the obtained polyimide film/glass laminate was immersed in water, peeled off, and dried to obtain a polyimide film having a film thickness of about 10 μm.
此聚醯亞胺膜之特性的測定結果示於表2-2。The measurement results of the properties of this polyimide film are shown in Table 2-2.
[實施例13] 將2-苯基咪唑 0.29g(2.0毫莫耳)與N-甲基-2-吡咯烷酮 0.29g加到反應容器,獲得均勻的溶液。於此溶液中加入合成例5獲得之清漆E 25.51g(相對於清漆E中之聚醯亞胺前驅體之重複單元之分子量,為10毫莫耳),於室溫攪拌3小時,獲得均勻且黏稠的聚醯亞胺前驅體溶液。若從進料量計算,相對於聚醯亞胺前驅體之重複單元1莫耳,2-苯基咪唑之莫耳數為0.2當量。[Example 13] 0.29 g (2.0 mmol) of 2-phenylimidazole and 0.29 g of N-methyl-2-pyrrolidone were added to a reaction vessel to obtain a homogeneous solution. The varnish E 25.51 g obtained in Synthesis Example 5 (molecular weight of the repeating unit of the polyimine precursor in varnish E was 10 mmol) was added to the solution, and stirred at room temperature for 3 hours to obtain uniformity. A viscous polyimide precursor solution. The molar number of 2-phenylimidazole is 0.2 equivalents based on the amount of the feed, relative to the repeat unit of the polyimine precursor.
將經PTFE製濾膜過濾的聚醯亞胺前驅體溶液塗佈在玻璃基板,於氮氣環境下(氧濃度200ppm以下),直接在玻璃基板上從室溫加熱到440℃而進行熱醯亞胺化,獲得無色透明的聚醯亞胺膜/玻璃疊層體。其次將獲得之聚醯亞胺膜/玻璃疊層體浸於水後剝離並乾燥,獲得膜厚約10μm之聚醯亞胺膜。The polyimine precursor solution filtered through the PTFE filter membrane is coated on a glass substrate, and heated to a temperature of 440 ° C on a glass substrate under a nitrogen atmosphere (oxygen concentration: 200 ppm or less) to carry out thermal yttrium imine. The colorless transparent polyimide film/glass laminate was obtained. Next, the obtained polyimide film/glass laminate was immersed in water, peeled off, and dried to obtain a polyimide film having a film thickness of about 10 μm.
此聚醯亞胺膜之特性的測定結果示於表2-2。The measurement results of the properties of this polyimide film are shown in Table 2-2.
[實施例14] 將苯并咪唑 0.24g(2.0毫莫耳)與N-甲基-2-吡咯烷酮 0.24g加到反應容器中,獲得均勻的溶液。於此溶液中加入合成例5獲得之清漆E 25.51g(相對於清漆E中之聚醯亞胺前驅體之重複單元之分子量,為10毫莫耳),於室溫攪拌3小時,獲得均勻且黏稠的聚醯亞胺前驅體溶液。若從進料量計算,相對於聚醯亞胺前驅體之重複單元1莫耳,苯并咪唑之莫耳數為0.2當量。[Example 14] 0.24 g (2.0 mmol) of benzimidazole and 0.24 g of N-methyl-2-pyrrolidone were added to a reaction vessel to obtain a homogeneous solution. The varnish E 25.51 g obtained in Synthesis Example 5 (molecular weight of the repeating unit of the polyimine precursor in varnish E was 10 mmol) was added to the solution, and stirred at room temperature for 3 hours to obtain uniformity. A viscous polyimide precursor solution. The molar number of benzimidazole is 0.2 equivalents relative to the repeating unit of the polyamidene precursor, 1 mole, calculated from the amount of feed.
將經PTFE製濾膜過濾的聚醯亞胺前驅體溶液塗佈在玻璃基板,於氮氣環境下(氧濃度200ppm以下),直接在玻璃基板上從室溫加熱到440℃而進行熱醯亞胺化,獲得無色透明的聚醯亞胺膜/玻璃疊層體。其次將獲得之聚醯亞胺膜/玻璃疊層體浸於水後剝離並乾燥,獲得膜厚約10μm之聚醯亞胺膜。The polyimine precursor solution filtered through the PTFE filter membrane is coated on a glass substrate, and heated to a temperature of 440 ° C on a glass substrate under a nitrogen atmosphere (oxygen concentration: 200 ppm or less) to carry out thermal yttrium imine. The colorless transparent polyimide film/glass laminate was obtained. Next, the obtained polyimide film/glass laminate was immersed in water, peeled off, and dried to obtain a polyimide film having a film thickness of about 10 μm.
此聚醯亞胺膜之特性的測定結果示於表2-2。The measurement results of the properties of this polyimide film are shown in Table 2-2.
[比較例5] 將經PTFE製濾膜過濾的合成例5獲得之清漆E塗佈在玻璃基板,於氮氣環境下(氧濃度200ppm以下),直接在玻璃基板上從室溫加熱到440℃而進行熱醯亞胺化,獲得無色透明的聚醯亞胺膜/玻璃疊層體。其次將獲得之聚醯亞胺膜/玻璃疊層體浸於水後剝離並乾燥,獲得膜厚約10μm之聚醯亞胺膜。[Comparative Example 5] The varnish E obtained in Synthesis Example 5 filtered through a PTFE filter membrane was applied onto a glass substrate, and heated directly from room temperature to 440 ° C on a glass substrate under a nitrogen atmosphere (oxygen concentration: 200 ppm or less). The enthalpy imidization was carried out to obtain a colorless transparent polyimide film/glass laminate. Next, the obtained polyimide film/glass laminate was immersed in water, peeled off, and dried to obtain a polyimide film having a film thickness of about 10 μm.
此聚醯亞胺膜之特性的測定結果示於表2-2。The measurement results of the properties of this polyimide film are shown in Table 2-2.
[比較例6] 將2-乙基-2-咪唑啉 0.10g(1.0毫莫耳)與N-甲基-2-吡咯烷酮 0.90g加到反應容器,獲得均勻的溶液。於此溶液中加入合成例5獲得之清漆E 25.51g(相對於清漆E中之聚醯亞胺前驅體之重複單元之分子量,為10毫莫耳),則清漆凝膠化。即使維持在室溫攪拌3小時,仍未獲得均勻的聚醯亞胺前驅體溶液。若從進料量計算,相對於聚醯亞胺前驅體之重複單元1莫耳,2-乙基-2-咪唑啉之莫耳數為0.1當量。[Comparative Example 6] 0.10 g (1.0 mmol) of 2-ethyl-2-imidazoline and 0.90 g of N-methyl-2-pyrrolidone were added to a reaction vessel to obtain a homogeneous solution. To the solution, the varnish E 25.51 g obtained in Synthesis Example 5 (molecular weight of 10 mmol of the repeating unit of the polyimine precursor in the varnish E) was added, and the varnish was gelated. Even after stirring at room temperature for 3 hours, a uniform polyimide precursor solution was not obtained. The molar number of 2-ethyl-2-imidazoline was 0.1 equivalent based on the amount of the feed, relative to the repeat unit of the polyimine precursor.
[比較例7] 將2-乙基-2-咪唑啉 0.20g(2.0毫莫耳)與N-甲基-2-吡咯烷酮 1.80g加到反應容器中,獲得均勻的溶液。於此溶液中加入合成例5獲得之清漆E 25.51g(相對於清漆E中之聚醯亞胺前驅體之重複單元之分子量,為10毫莫耳),則清漆凝膠化。即使維持在室溫攪拌3小時,仍未獲得均勻的聚醯亞胺前驅體溶液。若從進料量計算,相對於聚醯亞胺前驅體之重複單元1莫耳,2-乙基-2-咪唑啉之莫耳數為0.2當量。[Comparative Example 7] 0.20 g (2.0 mmol) of 2-ethyl-2-imidazoline and 1.80 g of N-methyl-2-pyrrolidone were added to a reaction vessel to obtain a homogeneous solution. To the solution, the varnish E 25.51 g obtained in Synthesis Example 5 (molecular weight of 10 mmol of the repeating unit of the polyimine precursor in the varnish E) was added, and the varnish was gelated. Even after stirring at room temperature for 3 hours, a uniform polyimide precursor solution was not obtained. The molar number of 2-ethyl-2-imidazoline was 0.2 equivalents based on the amount of the feed, relative to the repeat unit of the polyimine precursor.
[比較例8] 將1,2-二甲基咪唑 3.85g(40.0毫莫耳)與N-甲基-2-吡咯烷酮 0.50g加到反應容器中,獲得均勻的溶液。於此溶液中加入合成例5獲得之清漆E 25.51g(相對於清漆E中之聚醯亞胺前驅體之重複單元之分子量,為10毫莫耳),於室溫攪拌3小時,獲得均勻且黏稠的聚醯亞胺前驅體溶液。若從進料量計算,相對於聚醯亞胺前驅體之重複單元1莫耳,1,2-二甲基咪唑之莫耳數為4.0當量。若將獲得之聚醯亞胺前驅體溶液保存在23℃,在直到第3日,聚醯亞胺前驅體溶液凝膠化。[Comparative Example 8] 1.85 g (40.0 mmol) of 1,2-dimethylimidazole and 0.50 g of N-methyl-2-pyrrolidone were added to a reaction vessel to obtain a homogeneous solution. The varnish E 25.51 g obtained in Synthesis Example 5 (molecular weight of the repeating unit of the polyimine precursor in varnish E was 10 mmol) was added to the solution, and stirred at room temperature for 3 hours to obtain uniformity. A viscous polyimide precursor solution. The molar number of 1,2-dimethylimidazole relative to the repeating unit of the polyimine precursor was calculated to be 4.0 equivalents based on the amount of the feed. If the obtained polyimide intermediate precursor solution was stored at 23 ° C, the polyimine precursor solution gelled until the third day.
【表2-2】
由表2-1~2-2所示結果可知:由含有咪唑系化合物之聚醯亞胺前驅體組成物獲得之聚醯亞胺,透明性較優異、線熱膨脹係數小(實施例1~4與比較例1、實施例5~6與比較例2、實施例7與比較例3、實施例8與比較例4、實施例9~14與比較例5)。又,可知:咪唑系化合物之含量相對於聚醯亞胺前驅體之重複單元1莫耳若未達4莫耳,保存安定性亦優良(實施例9與比較例8)。From the results shown in Tables 2-1 to 2-2, it is understood that the polyimine obtained from the polyimide composition containing the imidazole compound has excellent transparency and a small coefficient of thermal expansion (Examples 1-4). Comparative Example 1, Examples 5 to 6 and Comparative Example 2, Example 7 and Comparative Example 3, Example 8 and Comparative Example 4, Examples 9 to 14 and Comparative Example 5). Further, it was found that the content of the imidazole-based compound was not more than 4 mol with respect to the repeating unit 1 of the polyimine precursor, and the storage stability was also excellent (Example 9 and Comparative Example 8).
如前述,由本發明之聚醯亞胺前驅體組成物獲得之聚醯亞胺,有優良的透光性、機械特性,而且有低線熱膨脹係數,本發明之聚醯亞胺膜可理想地作為顯示器用途等的無色透明且能形成微細電路的透明基板。 【產業利用性】As described above, the polyimine obtained from the polyimine precursor composition of the present invention has excellent light transmittance, mechanical properties, and a low linear thermal expansion coefficient, and the polyimine film of the present invention can be suitably used as A transparent substrate that is colorless and transparent and can form a fine circuit for display purposes. [Industry Utilization]
依本發明,可提供能獲得即使為同一組成之聚醯亞胺仍有更優良透明性、低線熱膨脹係數之聚醯亞胺、或有更透明性優異、低線熱膨脹係數且機械特性亦優良之聚醯亞胺之聚醯亞胺前驅體組成物(含有聚醯亞胺前驅體之溶液組成物)、及聚醯亞胺之製造方法。由此聚醯亞胺前驅體組成物獲得之聚醯亞胺,透明性高且為低線熱膨脹係數,易形成微細電路,尤其適於用在顯示器用、觸控面板用、太陽能電池用等的基板的形成。According to the present invention, it is possible to provide a polyimine which has better transparency and a low coefficient of thermal expansion even if it is a polyimide of the same composition, or has excellent transparency, a low coefficient of thermal expansion, and excellent mechanical properties. A polyimine precursor composition of a polyimine (a solution composition containing a polyimide precursor) and a method for producing a polyimide. The polyimine obtained by the polyimine precursor composition has high transparency and a low coefficient of thermal expansion, and is easy to form a fine circuit, and is particularly suitable for use in displays, touch panels, solar cells, and the like. Formation of a substrate.
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CN105254884B (en) * | 2011-03-11 | 2018-05-29 | 宇部兴产株式会社 | Polyimide precursor and polyimides |
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