JP6905227B2 - Diamines and polyimides, and their use - Google Patents
Diamines and polyimides, and their use Download PDFInfo
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- JP6905227B2 JP6905227B2 JP2017099643A JP2017099643A JP6905227B2 JP 6905227 B2 JP6905227 B2 JP 6905227B2 JP 2017099643 A JP2017099643 A JP 2017099643A JP 2017099643 A JP2017099643 A JP 2017099643A JP 6905227 B2 JP6905227 B2 JP 6905227B2
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- polyimide
- bis
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- solvent
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- 229920001721 polyimide Polymers 0.000 title claims description 141
- 239000004642 Polyimide Substances 0.000 title claims description 125
- 150000004985 diamines Chemical class 0.000 title claims description 42
- 125000003118 aryl group Chemical group 0.000 claims description 23
- 239000000758 substrate Substances 0.000 claims description 23
- 239000002966 varnish Substances 0.000 claims description 23
- 125000001424 substituent group Chemical group 0.000 claims description 21
- 125000001931 aliphatic group Chemical group 0.000 claims description 19
- 238000001035 drying Methods 0.000 claims description 14
- 239000007787 solid Substances 0.000 claims description 13
- 125000004432 carbon atom Chemical group C* 0.000 claims description 10
- 125000003545 alkoxy group Chemical group 0.000 claims description 9
- 125000000217 alkyl group Chemical group 0.000 claims description 9
- 239000004033 plastic Substances 0.000 claims description 4
- 229920003023 plastic Polymers 0.000 claims description 4
- 239000000243 solution Substances 0.000 description 54
- 239000010408 film Substances 0.000 description 47
- 239000002904 solvent Substances 0.000 description 47
- 238000000034 method Methods 0.000 description 34
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 27
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 25
- -1 dinitro compound Chemical class 0.000 description 25
- 239000002243 precursor Substances 0.000 description 25
- 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 22
- 238000006243 chemical reaction Methods 0.000 description 19
- 239000000126 substance Substances 0.000 description 19
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 17
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 17
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical class C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 15
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 15
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 13
- 239000003795 chemical substances by application Substances 0.000 description 13
- 229920005575 poly(amic acid) Polymers 0.000 description 13
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 12
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 12
- 238000010438 heat treatment Methods 0.000 description 12
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 12
- 239000000843 powder Substances 0.000 description 11
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 10
- 238000000576 coating method Methods 0.000 description 10
- 239000000203 mixture Substances 0.000 description 10
- 125000006158 tetracarboxylic acid group Chemical group 0.000 description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- WVOLTBSCXRRQFR-SJORKVTESA-N Cannabidiolic acid Natural products OC1=C(C(O)=O)C(CCCCC)=CC(O)=C1[C@@H]1[C@@H](C(C)=C)CCC(C)=C1 WVOLTBSCXRRQFR-SJORKVTESA-N 0.000 description 9
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 9
- WVOLTBSCXRRQFR-DLBZAZTESA-M cannabidiolate Chemical group OC1=C(C([O-])=O)C(CCCCC)=CC(O)=C1[C@H]1[C@H](C(C)=C)CCC(C)=C1 WVOLTBSCXRRQFR-DLBZAZTESA-M 0.000 description 9
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- 239000000463 material Substances 0.000 description 9
- 239000000047 product Substances 0.000 description 9
- 150000001408 amides Chemical class 0.000 description 8
- 239000003054 catalyst Substances 0.000 description 8
- 239000003960 organic solvent Substances 0.000 description 8
- 230000000704 physical effect Effects 0.000 description 8
- 238000003756 stirring Methods 0.000 description 8
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 description 8
- 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 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 7
- 239000002244 precipitate Substances 0.000 description 7
- 238000011282 treatment Methods 0.000 description 7
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 6
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 6
- 230000008018 melting Effects 0.000 description 6
- 238000002844 melting Methods 0.000 description 6
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 5
- 238000000862 absorption spectrum Methods 0.000 description 5
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- 238000006116 polymerization reaction Methods 0.000 description 5
- 239000010409 thin film Substances 0.000 description 5
- 238000002834 transmittance Methods 0.000 description 5
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 4
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 4
- 230000015572 biosynthetic process Effects 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
- KZTYYGOKRVBIMI-UHFFFAOYSA-N diphenyl sulfone Chemical compound C=1C=CC=CC=1S(=O)(=O)C1=CC=CC=C1 KZTYYGOKRVBIMI-UHFFFAOYSA-N 0.000 description 4
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 4
- 239000010419 fine particle Substances 0.000 description 4
- 238000005227 gel permeation chromatography Methods 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 150000002576 ketones Chemical class 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 150000007524 organic acids Chemical class 0.000 description 4
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 4
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 3
- XDTTUTIFWDAMIX-UHFFFAOYSA-N 3-methyl-4-nitrobenzoic acid Chemical compound CC1=CC(C(O)=O)=CC=C1[N+]([O-])=O XDTTUTIFWDAMIX-UHFFFAOYSA-N 0.000 description 3
- JPZRPCNEISCANI-UHFFFAOYSA-N 4-(4-aminophenyl)-3-(trifluoromethyl)aniline Chemical compound C1=CC(N)=CC=C1C1=CC=C(N)C=C1C(F)(F)F JPZRPCNEISCANI-UHFFFAOYSA-N 0.000 description 3
- 150000005443 4-nitrobenzoic acid derivatives Chemical class 0.000 description 3
- YGYCECQIOXZODZ-UHFFFAOYSA-N 4415-87-6 Chemical compound O=C1OC(=O)C2C1C1C(=O)OC(=O)C12 YGYCECQIOXZODZ-UHFFFAOYSA-N 0.000 description 3
- IAZDPXIOMUYVGZ-WFGJKAKNSA-N Dimethyl sulfoxide Chemical compound [2H]C([2H])([2H])S(=O)C([2H])([2H])[2H] IAZDPXIOMUYVGZ-WFGJKAKNSA-N 0.000 description 3
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 230000002776 aggregation Effects 0.000 description 3
- 238000004220 aggregation Methods 0.000 description 3
- 125000006267 biphenyl group Chemical group 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 230000018044 dehydration Effects 0.000 description 3
- 238000006297 dehydration reaction Methods 0.000 description 3
- 230000006866 deterioration Effects 0.000 description 3
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 3
- 150000002605 large molecules Chemical class 0.000 description 3
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 description 3
- 229920000139 polyethylene terephthalate Polymers 0.000 description 3
- 239000005020 polyethylene terephthalate Substances 0.000 description 3
- 239000013557 residual solvent Substances 0.000 description 3
- 150000003384 small molecules Chemical class 0.000 description 3
- 150000003512 tertiary amines Chemical class 0.000 description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 3
- WNXJIVFYUVYPPR-UHFFFAOYSA-N 1,3-dioxolane Chemical compound C1COCO1 WNXJIVFYUVYPPR-UHFFFAOYSA-N 0.000 description 2
- JCEZOHLWDIONSP-UHFFFAOYSA-N 3-[2-[2-(3-aminopropoxy)ethoxy]ethoxy]propan-1-amine Chemical compound NCCCOCCOCCOCCCN JCEZOHLWDIONSP-UHFFFAOYSA-N 0.000 description 2
- OZJPLYNZGCXSJM-UHFFFAOYSA-N 5-valerolactone Chemical compound O=C1CCCCO1 OZJPLYNZGCXSJM-UHFFFAOYSA-N 0.000 description 2
- 0 CC(C(Cc(ccc(C(*(c(cc1)cc(*)c1-c1ccc(*)cc1*)=*)=O)c1)c1N=C)C(C)=O)=O Chemical compound CC(C(Cc(ccc(C(*(c(cc1)cc(*)c1-c1ccc(*)cc1*)=*)=O)c1)c1N=C)C(C)=O)=O 0.000 description 2
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- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 2
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 2
- JLTDJTHDQAWBAV-UHFFFAOYSA-N N,N-dimethylaniline Chemical compound CN(C)C1=CC=CC=C1 JLTDJTHDQAWBAV-UHFFFAOYSA-N 0.000 description 2
- 241000209094 Oryza Species 0.000 description 2
- 235000007164 Oryza sativa Nutrition 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 235000002597 Solanum melongena Nutrition 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 125000004018 acid anhydride group Chemical group 0.000 description 2
- 125000002723 alicyclic group Chemical group 0.000 description 2
- ZIXLDMFVRPABBX-UHFFFAOYSA-N alpha-methylcyclopentanone Natural products CC1CCCC1=O ZIXLDMFVRPABBX-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 125000002490 anilino group Chemical group [H]N(*)C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 2
- 125000006367 bivalent amino carbonyl group Chemical group [H]N([*:1])C([*:2])=O 0.000 description 2
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- VKIRRGRTJUUZHS-UHFFFAOYSA-N cyclohexane-1,4-diamine Chemical compound NC1CCC(N)CC1 VKIRRGRTJUUZHS-UHFFFAOYSA-N 0.000 description 2
- 238000007033 dehydrochlorination reaction Methods 0.000 description 2
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 description 2
- 239000004205 dimethyl polysiloxane Substances 0.000 description 2
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 2
- 239000003759 ester based solvent Substances 0.000 description 2
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- LZDKZFUFMNSQCJ-UHFFFAOYSA-N 1,2-diethoxyethane Chemical compound CCOCCOCC LZDKZFUFMNSQCJ-UHFFFAOYSA-N 0.000 description 1
- GEYOCULIXLDCMW-UHFFFAOYSA-N 1,2-phenylenediamine Chemical compound NC1=CC=CC=C1N GEYOCULIXLDCMW-UHFFFAOYSA-N 0.000 description 1
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- 125000001140 1,4-phenylene group Chemical group [H]C1=C([H])C([*:2])=C([H])C([H])=C1[*:1] 0.000 description 1
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- KZVBBTZJMSWGTK-UHFFFAOYSA-N 1-[2-(2-butoxyethoxy)ethoxy]butane Chemical compound CCCCOCCOCCOCCCC KZVBBTZJMSWGTK-UHFFFAOYSA-N 0.000 description 1
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- YMDMDDUYDDFCSX-UHFFFAOYSA-N 2,3-bis(trifluoromethyl)benzene-1,4-diamine Chemical compound NC1=CC=C(N)C(C(F)(F)F)=C1C(F)(F)F YMDMDDUYDDFCSX-UHFFFAOYSA-N 0.000 description 1
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- XFWCWQUDUPQGKG-UHFFFAOYSA-N 2,6-difluorobenzene-1,4-diamine Chemical compound NC1=CC(F)=C(N)C(F)=C1 XFWCWQUDUPQGKG-UHFFFAOYSA-N 0.000 description 1
- GXVUZYLYWKWJIM-UHFFFAOYSA-N 2-(2-aminoethoxy)ethanamine Chemical compound NCCOCCN GXVUZYLYWKWJIM-UHFFFAOYSA-N 0.000 description 1
- WMDZKDKPYCNCDZ-UHFFFAOYSA-N 2-(2-butoxypropoxy)propan-1-ol Chemical compound CCCCOC(C)COC(C)CO WMDZKDKPYCNCDZ-UHFFFAOYSA-N 0.000 description 1
- CUDYYMUUJHLCGZ-UHFFFAOYSA-N 2-(2-methoxypropoxy)propan-1-ol Chemical compound COC(C)COC(C)CO CUDYYMUUJHLCGZ-UHFFFAOYSA-N 0.000 description 1
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- 125000002510 isobutoxy group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])O* 0.000 description 1
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- 239000002245 particle Substances 0.000 description 1
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- 239000004417 polycarbonate Substances 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 239000011112 polyethylene naphthalate Substances 0.000 description 1
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- WGYKZJWCGVVSQN-UHFFFAOYSA-N propylamine Chemical group CCCN WGYKZJWCGVVSQN-UHFFFAOYSA-N 0.000 description 1
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- 125000005920 sec-butoxy group Chemical group 0.000 description 1
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- 125000004213 tert-butoxy group Chemical group [H]C([H])([H])C(O*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Paints Or Removers (AREA)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
Description
本発明は、ジアミンおよびポリイミド、並びにそれらの利用に関する。 The present invention relates to diamines and polyimides, and their use.
現在、液晶ディスプレイおよび有機ELディスプレイ等の各種表示機器において、ガラス基板が用いられている。ガラス基板は耐熱性が高く、線熱膨張係数が低く、透明性が高いという点において優れた材料である。一方、これらのディスプレイに対しては、軽量化およびフレキシブル化が求められており、ガラスに代わる材料が強く求められている。これらの要求を満足する材料として種々のポリイミド材料が検討されている。 Currently, glass substrates are used in various display devices such as liquid crystal displays and organic EL displays. The glass substrate is an excellent material in that it has high heat resistance, a low coefficient of linear thermal expansion, and high transparency. On the other hand, these displays are required to be lighter and more flexible, and there is a strong demand for a material to replace glass. Various polyimide materials have been studied as materials that satisfy these requirements.
さて、ポリイミドはその化学構造ゆえに高い耐熱性を有する。しかしながら、ポリイミドの多くは、溶媒に不溶であり、ポリイミド溶液の塗工プロセスを用いての均一なフィルム化が困難である。それゆえ、溶媒に可溶なポリイミド前駆体であるポリアミド酸を均一にフィルム化し、ポリイミドフィルムへと変換する方法が広く採用されている。 By the way, polyimide has high heat resistance due to its chemical structure. However, most of the polyimides are insoluble in solvents, and it is difficult to form a uniform film by using a polyimide solution coating process. Therefore, a method of uniformly filming polyamic acid, which is a polyimide precursor soluble in a solvent, and converting it into a polyimide film is widely adopted.
しかし、かかる方法によれば、ポリアミド酸からポリイミドへと変換する工程は、300℃以上での加熱を必要とし、大きな反応収縮を伴う。そのため、かかる方法では、無機材料基板とポリイミドフィルムとの線熱膨張係数のミスマッチにより反りが生じるばかりでなく、場合によっては副生する水によりフィルム欠陥が生じるという問題があった。 However, according to this method, the step of converting polyamic acid to polyimide requires heating at 300 ° C. or higher, and is accompanied by a large reaction shrinkage. Therefore, this method has a problem that not only warpage occurs due to a mismatch in the coefficient of linear thermal expansion between the inorganic material substrate and the polyimide film, but also film defects occur due to water produced as a by-product in some cases.
上記の課題に対し、例えば、特許文献1および2には、可溶性であり、かつ、透明なポリイミドが開示されている。
For the above problems, for example,
しかしながら、特許文献1および2に記載のポリイミドとは別の構造を有するポリイミドであって、溶液加工性に優れるポリイミドが求められていた。
However, a polyimide having a structure different from that of the polyimides described in
本発明の一態様は、溶液加工性に優れるポリイミドを提供することを課題とする。 One aspect of the present invention is to provide a polyimide having excellent solution processability.
上記の課題を解決するために、本発明者が鋭意研究を行った結果、特定の構造を有するジアミンを用いることによって、溶液加工性に優れるポリイミドを調製できることを見出し、本発明を完成させるに至った。 As a result of diligent research conducted by the present inventor in order to solve the above problems, it was found that a polyimide having excellent solution processability can be prepared by using a diamine having a specific structure, and the present invention has been completed. rice field.
すなわち、本発明の一態様に係るジアミンは、下記式(1): That is, the diamine according to one aspect of the present invention has the following formula (1):
で表される(式(1)中、置換基Rは独立して、炭素数1〜4のアルキル基またはアルコキシ基を表し、nは置換基Rの数を表し、1〜4の整数である)。 (In the formula (1), the substituent R independently represents an alkyl group or an alkoxy group having 1 to 4 carbon atoms, and n represents the number of substituents R and is an integer of 1 to 4. ).
また、本発明の一態様に係るポリイミドは、下記式(3): Further, the polyimide according to one aspect of the present invention has the following formula (3):
で表される繰り返し単位を有する(式(3)中、置換基Rは独立して、炭素数1〜4のアルキル基またはアルコキシ基を表し、nは置換基Rの数を表し、1〜4の整数であり、X1は4価の脂肪族基および芳香族基の少なくともいずれか一方を表す)。 It has a repeating unit represented by (in formula (3), the substituent R independently represents an alkyl group or an alkoxy group having 1 to 4 carbon atoms, and n represents the number of substituents R, 1 to 4 X 1 represents at least one of a tetravalent aliphatic group and an aromatic group).
本発明の一態様によれば、溶液加工性に優れるポリイミドを提供することができるという効果を奏する。 According to one aspect of the present invention, it is possible to provide a polyimide having excellent solution processability.
以下に本発明の実施形態について詳細に説明するが、これらは本発明の一態様であり、本発明はこれらの内容に限定されない。 Hereinafter, embodiments of the present invention will be described in detail, but these are aspects of the present invention, and the present invention is not limited to these contents.
なお、本明細書において「溶液加工性」とは、有機溶媒への溶解性が優れるため加工性に優れることをいう。例えばポリイミドをフィルム化する際、ポリイミドを任意の有機溶媒に溶解して得られた溶液を支持体に塗布し、乾燥するという方法などが取られるため、溶液加工性に優れることは非常に重要な特性である。 In addition, in this specification, "solution processability" means excellent processability because it is excellent in solubility in an organic solvent. For example, when forming a polyimide into a film, a method of dissolving the polyimide in an arbitrary organic solvent, applying the solution to the support, and drying the polyimide is adopted, so that it is very important to have excellent solution processability. It is a characteristic.
<1.ジアミン>
本発明の一実施形態に係るジアミンは、下記式(1):
<1. Diamine>
The diamine according to the embodiment of the present invention has the following formula (1):
で表される(式(1)中、置換基Rは独立して、炭素数1〜4のアルキル基またはアルコキシ基を表し、nは置換基Rの数を表し、1〜4の整数である)。 (In the formula (1), the substituent R independently represents an alkyl group or an alkoxy group having 1 to 4 carbon atoms, and n represents the number of substituents R and is an integer of 1 to 4. ).
上記ジアミンは、分子内にアミド結合を有する。そのため、上記ジアミンを用いて得られるポリイミドは、主鎖構造が直線状になりやすく、且つ、分子間水素結合が形成されやすい。よって、当該ポリイミドから、線熱膨張係数が低いフィルムを得ることができると考えられる。 The diamine has an amide bond in the molecule. Therefore, the polyimide obtained by using the diamine tends to have a linear main chain structure and easily form intermolecular hydrogen bonds. Therefore, it is considered that a film having a low coefficient of linear thermal expansion can be obtained from the polyimide.
また、上記ジアミンは、トリフルオロメチル基を有する。トリフルオロメチル基は立体的に嵩高いため、トリフルオロメチル基の導入により、高分子鎖の凝集および結晶化が妨げられる。これにより、ポリイミドの分子鎖間に溶媒分子が容易に侵入することができ、その結果、溶媒に可溶なポリイミドを得ることができると考えられる。 In addition, the diamine has a trifluoromethyl group. Since the trifluoromethyl group is sterically bulky, the introduction of the trifluoromethyl group prevents the aggregation and crystallization of the polymer chain. It is considered that this allows solvent molecules to easily penetrate between the molecular chains of the polyimide, and as a result, a polyimide that is soluble in the solvent can be obtained.
さらに、当該ジアミンを用いて得られたポリイミドは、後述の実施例にて示すように、置換基Rを含まないジアミンを用いて得られたポリイミドと比べて、有機溶媒に対する溶解性が顕著に改善される。これは、ポリマー鎖の緻密な凝集が妨害されるためであると推測される。 Further, as shown in Examples described later, the polyimide obtained by using the diamine has significantly improved solubility in an organic solvent as compared with the polyimide obtained by using a diamine containing no substituent R. Will be done. It is presumed that this is because the dense aggregation of the polymer chains is hindered.
各置換基Rは同一であってもよく、異なっていてもよい。炭素数1〜4のアルキル基としては、メチル基、エチル基、n−プロピル基、イソプロピル基、n−ブチル基、イソブチル基、sec−ブチル基およびtert−ブチル基等が挙げられる。炭素数1〜4のアルコキシ基としては、メトキシ基、エトキシ基、n−プロポキシ基、イソプロポキシ基、n−ブトキシ基、イソブトキシ基、sec−ブトキシ基およびtert−ブトキシ基等が挙げられる。なかでも、置換基Rがメチル基である場合、溶液加工性および耐熱性の両立が可能となるため好ましい。 Each substituent R may be the same or different. Examples of the alkyl group having 1 to 4 carbon atoms include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group and a tert-butyl group. Examples of the alkoxy group having 1 to 4 carbon atoms include a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, an n-butoxy group, an isobutoxy group, a sec-butoxy group and a tert-butoxy group. Among them, when the substituent R is a methyl group, it is preferable because both solution processability and heat resistance can be achieved at the same time.
上記ジアミンは、下記式(2): The diamine is based on the following formula (2):
で表されるものであってもよい。当該ジアミンを用いて得られるポリイミドは、トリフルオロメチル基の結合位置に起因し、透明性がより向上したフィルムを提供できる。また、置換基Rがメチル基である場合、溶液加工性および耐熱性の両立が可能となる観点から、好ましい。 It may be represented by. The polyimide obtained by using the diamine can provide a film having more improved transparency due to the bonding position of the trifluoromethyl group. Further, when the substituent R is a methyl group, it is preferable from the viewpoint that both solution processability and heat resistance can be achieved at the same time.
当該ジアミンの合成方法は、これに限定されないが、一例として、前駆体となるジニトロ化合物を得て、当該ジニトロ化合物を触媒存在下において水素還元する方法などが挙げられる。例えば、式(7)で示される方法によって、上記式(1)で表されるジアミンを得ることができる。 The method for synthesizing the diamine is not limited to this, and examples thereof include a method of obtaining a dinitro compound as a precursor and hydrogen-reducing the dinitro compound in the presence of a catalyst. For example, the diamine represented by the above formula (1) can be obtained by the method represented by the formula (7).
前駆体となるジニトロ化合物は、例えば、2,2’−ビス(トリフルオロメチル)ベンジジンと、置換基Rを有する4−ニトロ安息香酸誘導体の塩素化体とを反応させることにより得ることができる。例えば、式(2)のジアミンを得る場合は、4−ニトロ安息香酸誘導体として、3−メチル−4−ニトロ安息香酸を用いることができる。上記塩素化体は、例えば、3−メチル−4−ニトロ安息香酸を塩化チオニルに加え、さらに触媒としてN,N−ジメチルホルムアミドを加えて還流を行った後、ベンゼンを加えて過剰の塩化チオニルを共沸留去することによって得ることができる。 The precursor dinitro compound can be obtained, for example, by reacting 2,2'-bis (trifluoromethyl) benzidine with a chlorinated product of a 4-nitrobenzoic acid derivative having a substituent R. For example, when the diamine of the formula (2) is obtained, 3-methyl-4-nitrobenzoic acid can be used as the 4-nitrobenzoic acid derivative. For the chlorinated product, for example, 3-methyl-4-nitrobenzoic acid is added to thionyl chloride, N, N-dimethylformamide is added as a catalyst to reflux, and then benzene is added to add excess thionyl chloride. It can be obtained by azeotropic distillation.
2,2’−ビス(トリフルオロメチル)ベンジジンと、4−ニトロ安息香酸誘導体の塩素化体との反応は、例えば、これらを脱水済のテトラヒドロフランに溶かして混合することによって行うことができる。この際、脱塩化水素剤としてピリジンまたはトリエチルアミン等の塩基を共存させることにより、反応時に発生する塩化水素を除去できる。 The reaction of 2,2'-bis (trifluoromethyl) benzidine with a chlorinated product of a 4-nitrobenzoic acid derivative can be carried out, for example, by dissolving them in dehydrated tetrahydrofuran and mixing them. At this time, by coexisting a base such as pyridine or triethylamine as a dehydrochlorination agent, hydrogen chloride generated during the reaction can be removed.
得られたジニトロ化合物をジアミンに還元するには様々な手法があり、特に限定されるものではないが、Pd/CまたはNi等の金属触媒存在下に水素ガスを反応させる接触還元法が簡便である。その際に用いる溶媒としては1,4−ジオキサン、エタノールおよびテトラヒドロフラン等が挙げられる。 There are various methods for reducing the obtained dinitro compound to diamine, and the method is not particularly limited, but a catalytic reduction method in which hydrogen gas is reacted in the presence of a metal catalyst such as Pd / C or Ni is simple. be. Examples of the solvent used at that time include 1,4-dioxane, ethanol and tetrahydrofuran.
<2.ポリイミド>
本発明の一実施形態に係るポリイミドは、下記式(3):
<2. Polyimide>
The polyimide according to one embodiment of the present invention has the following formula (3):
で表される繰り返し単位を有する(式(3)中、置換基Rは独立して、炭素数1〜4のアルキル基またはアルコキシ基を表し、nは置換基Rの数を表し、1〜4の整数であり、X1は4価の脂肪族基および芳香族基の少なくともいずれか一方を表す)。換言すれば、X1は、4価の脂肪族基であってもよく、4価の芳香族基であってもよく、4価の脂肪族基および芳香族基を両方含む構造(例えば、4価の脂肪族基と4価の芳香族基とが連結した構造)であってもよい。 It has a repeating unit represented by (in formula (3), the substituent R independently represents an alkyl group or an alkoxy group having 1 to 4 carbon atoms, and n represents the number of substituents R, 1 to 4 X 1 represents at least one of a tetravalent aliphatic group and an aromatic group). In other words, X 1 may be a tetravalent aliphatic group or a tetravalent aromatic group, and may be a structure containing both a tetravalent aliphatic group and an aromatic group (for example, 4). It may be a structure in which a valent aliphatic group and a tetravalent aromatic group are linked).
当該ポリイミドは、上述のように式(1)で表されるジアミンに由来する構造を有するために、溶液加工性に優れ、且つ、フィルムにした場合に線熱膨張係数が低い。また、当該ポリイミドは、その化学構造に起因して高い耐熱性を示す。 Since the polyimide has a structure derived from the diamine represented by the formula (1) as described above, it is excellent in solution processability and has a low coefficient of linear thermal expansion when formed into a film. In addition, the polyimide exhibits high heat resistance due to its chemical structure.
上記ポリイミドは、下記式(4): The polyimide has the following formula (4):
で表される繰り返し単位を有するものであってもよい(式(4)中、X1は4価の脂肪族基および芳香族基の少なくともいずれか一方を表す)。 It may have a repeating unit represented by (in formula (4), X 1 represents at least one of a tetravalent aliphatic group and an aromatic group).
4価の脂肪族基は、例えば、下記の脂環式テトラカルボン酸二無水物に由来する構造であり得る:(1S,2R,4S,5R)−シクロヘキサンテトラカルボン酸二無水物(シス、シス、シス−1,2,4,5−シクロヘキサンテトラカルボン酸二無水物)、(1S,2S,4R,5R)−シクロヘキサンテトラカルボン酸二無水物、(1R,2S,4S,5R)−シクロヘキサンテトラカルボン酸二無水物、ビシクロ[2.2.2]オクタン−2,3,5,6−テトラカルボン酸二無水物、ビシクロ[2.2.2]オクト−7−エン−2,3,5,6−テトラカルボン酸二無水物、5−(ジオキソテトラヒドロフリル−3−メチル)−3−シクロヘキセン−1,2−ジカルボン酸無水物、4−(2,5−ジオキソテトラヒドロフラン−3−イル)−テトラリン−1,2−ジカルボン酸無水物、テトラヒドロフラン−2,3,4,5−テトラカルボン酸二無水物、ビシクロ−3,3’,4,4’−テトラカルボン酸二無水物、1,2,3,4−シクロペンタンテトラカルボン酸二無水物、1,2,3,4−シクロブタンテトラカルボン酸二無水物、1,3−ジメチル−1,2,3,4−シクロブタンテトラカルボン酸二無水物または1,4−ジメチル−1,2,3,4−シクロブタンテトラカルボン酸二無水物等。すなわち、4価の脂肪族基は、これらの脂環式テトラカルボン酸二無水物の酸無水物基に挟まれた構造に由来し得る。 The tetravalent aliphatic group can be, for example, a structure derived from the following alicyclic tetracarboxylic dianhydride: (1S, 2R, 4S, 5R) -cyclohexanetetracarboxylic dianhydride (cis, cis). , Sis-1,2,4,5-cyclohexanetetracarboxylic dianhydride), (1S, 2S, 4R, 5R) -cyclohexanetetracarboxylic dianhydride, (1R, 2S, 4S, 5R) -cyclohexanetetra Vicarboxylic dianhydride, bicyclo [2.2.2] octane-2,3,5,6-tetracarboxylic dianhydride, bicyclo [2.2.2] octo-7-ene-2,3,5 , 6-Tetetracarboxylic dianhydride, 5- (dioxotetrahydrofuryl-3-methyl) -3-cyclohexene-1,2-dicarboxylic dianhydride, 4- (2,5-dioxotetraxethylene-3-yl) )-Tetraline-1,2-dicarboxylic dianhydride, tetrahydrofuran-2,3,4,5-tetracarboxylic dianhydride, bicyclo-3,3', 4,4'-tetracarboxylic dianhydride, 1 , 2,3,4-cyclopentanetetracarboxylic dianhydride, 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,3-dimethyl-1,2-2,3,4-cyclobutanetetracarboxylic acid Dihydride or 1,4-dimethyl-1,2-2,3,4-cyclobutanetetracarboxylic dianhydride and the like. That is, the tetravalent aliphatic group can be derived from the structure sandwiched between the acid anhydride groups of these alicyclic tetracarboxylic dianhydrides.
ポリイミドが黄色または茶色に着色する原因は、ポリイミド分子内および/または分子間の電荷移動相互作用である。透明なポリイミドを得るためには、これらの電荷移動相互作用を抑制する必要がある。そのための一つの手段として、式(4)中、X1として、4価の脂肪族基を選択することが有効である。 The cause of the polyimide coloring yellow or brown is the intramolecular and / or intermolecular charge transfer interaction of the polyimide. In order to obtain a transparent polyimide, it is necessary to suppress these charge transfer interactions. As a means therefor, in the formula (4), as X 1, it is effective to select a tetravalent aliphatic group.
なかでも、ポリイミドの主鎖をより剛直な構造とすることができるという観点からは、X1が下記式(5): Above all, from the viewpoint that the main chain of polyimide can have a more rigid structure, X 1 is expressed by the following equation (5):
で表される4価の脂肪族基であることが好ましい。式(5)で表される構造は、1,2,3,4−シクロブタンテトラカルボン酸二無水物を用いることにより、ポリイミドに導入することができる。 It is preferably a tetravalent aliphatic group represented by. The structure represented by the formula (5) can be introduced into polyimide by using 1,2,3,4-cyclobutanetetracarboxylic dianhydride.
4価の芳香族基は、例えば、下記の芳香族テトラカルボン酸二無水物に由来する構造であり得る:4,4’−(ヘキサフルオロイソプロピリデン)ジフタル酸二無水物または1,4−ビス(フロロメチル−2,3,5,6−ベンゼンテトラカルボン酸二無水物)等。すなわち、4価の芳香族基は、これらの芳香族テトラカルボン酸二無水物の酸無水物基に挟まれた構造に由来し得る。4価の芳香族基としては、例えば、芳香環と、ヘキサフルオロイソプロピリデン基、スルホニル基、エーテル結合およびエステル結合からなる群より選択される少なくとも1種とを含むものが挙げられる。ポリイミドが4価の芳香族基を含む場合、溶液加工性を向上させることができる。 The tetravalent aromatic group can be, for example, a structure derived from the following aromatic tetracarboxylic dianhydrides: 4,4'-(hexafluoroisopropyridene) diphthalic acid dianhydride or 1,4-bis. (Fluoromethyl-2,3,5,6-benzenetetracarboxylic dianhydride) and the like. That is, the tetravalent aromatic group can be derived from the structure sandwiched between the acid anhydride groups of these aromatic tetracarboxylic dianhydrides. Examples of the tetravalent aromatic group include those containing an aromatic ring and at least one selected from the group consisting of a hexafluoroisopropylidene group, a sulfonyl group, an ether bond and an ester bond. When the polyimide contains a tetravalent aromatic group, the solution processability can be improved.
なかでも、耐熱性を損なわずに溶液加工性をより向上させることができるという観点からは、X1が下記式(6): Above all, from the viewpoint that the solution processability can be further improved without impairing the heat resistance, X 1 is expressed by the following formula (6):
で表される4価の芳香族基であることが好ましい。式(6)で表される構造は、4,4’−(ヘキサフルオロイソプロピリデン)ジフタル酸二無水物を用いることにより、ポリイミドに導入することができる。 It is preferably a tetravalent aromatic group represented by. The structure represented by the formula (6) can be introduced into the polyimide by using 4,4'-(hexafluoroisopropyridene) diphthalic acid dianhydride.
当該ポリイミドにおいて、総繰り返し単位を100mol%とした場合に、式(3)で表される繰り返し単位の含有量は、70mol%以上であることが好ましく、80molル%以上であることがより好ましく、90mol%以上であることがさらに好ましく、100mol%であること(当該ポリイミドが式(3)で表される繰り返し単位からなること)が特に好ましい。式(3)で表される繰り返し単位の含有量が70mol%以上であれば、より溶液加工性が優れ、透明で耐熱性が高く、線熱膨張係数の低いポリイミドを提供することができる。 In the polyimide, when the total repeating unit is 100 mol%, the content of the repeating unit represented by the formula (3) is preferably 70 mol% or more, more preferably 80 mol% or more. It is more preferably 90 mol% or more, and particularly preferably 100 mol% (the polyimide is composed of a repeating unit represented by the formula (3)). When the content of the repeating unit represented by the formula (3) is 70 mol% or more, it is possible to provide a polyimide having more excellent solution processability, transparency, high heat resistance, and a low coefficient of linear thermal expansion.
上記ポリイミドは、上記式(3)で表される繰り返し単位であって、X1が式(5)で表される4価の脂肪族基である繰り返し単位(以下、繰り返し単位(a)とも称する)と、上記式(3)で表される繰り返し単位であって、X1が式(6)で表される4価の芳香族基である繰り返し単位(以下、繰り返し単位(b)とも称する)との少なくとも2種類の繰り返し単位を含むものであってもよい。この場合、繰り返し単位(a)の4価の脂肪族基に基づいて透明性を向上させることができるとともに、繰り返し単位(b)の4価の芳香族基に基づいて溶液加工性を向上させることができるため、好ましい。 The polyimide is a repeating unit represented by the above formula (3), and a repeating unit in which X 1 is a tetravalent aliphatic group represented by the formula (5) (hereinafter, also referred to as a repeating unit (a)). ) And a repeating unit represented by the above formula (3), wherein X 1 is a tetravalent aromatic group represented by the formula (6) (hereinafter, also referred to as a repeating unit (b)). It may contain at least two kinds of repeating units of. In this case, the transparency can be improved based on the tetravalent aliphatic group of the repeating unit (a), and the solution processability can be improved based on the tetravalent aromatic group of the repeating unit (b). It is preferable because it can be used.
繰り返し単位(a)と繰り返し単位(b)との総モル数を100mol%とした場合に、繰り返し単位(a)と繰り返し単位(b)との組成比(モル比)、すなわち、[(a)]/[(b)]は、95/5〜5/95であることが好ましく、90/10〜10/90であることがより好ましく、80/20〜20/80であることがさらに好ましく、70/30〜50/50であることが特に好ましい。上記組成比であれば、繰り返し単位(a)の4価の脂肪族基に起因する透明性の向上と、繰り返し単位(b)の4価の芳香族基に起因する溶液加工性の向上とのバランスが良い。また、例えば、透明性の向上を優先させる場合は、[(a)]/[(b)]は、95/5〜55/45であることが好ましく、90/10〜60/40であることがより好ましく、85/15〜65/35であることがさらに好ましい。一方、溶液加工性の向上を優先させる場合は、[(a)]/[(b)]は、5/95〜50/50であることが好ましく、10/90〜40/60であることがより好ましく、15/85〜35/65であることがさらに好ましい。 When the total number of moles of the repeating unit (a) and the repeating unit (b) is 100 mol%, the composition ratio (molar ratio) of the repeating unit (a) and the repeating unit (b), that is, [(a)). ] / [(B)] is preferably 95/5 to 5/95, more preferably 90/10 to 10/90, and even more preferably 80/20 to 20/80. It is particularly preferably 70/30 to 50/50. With the above composition ratio, the improvement in transparency due to the tetravalent aliphatic group of the repeating unit (a) and the improvement in solution processability due to the tetravalent aromatic group of the repeating unit (b). Good balance. Further, for example, when giving priority to improving transparency, [(a)] / [(b)] is preferably 95/5 to 55/45, and is 90/10 to 60/40. Is more preferable, and 85/15 to 65/35 is even more preferable. On the other hand, when giving priority to improving the solution processability, [(a)] / [(b)] is preferably 5/95 to 50/50, and preferably 10/90 to 40/60. More preferably, it is 15/85 to 35/65.
上記ポリイミドを製造する際、式(1)で表されるジアミン以外にその他のジアミンを用いてもよい。その他のジアミンとしては、例えば、p−フェニレンジアミン、m−フェニレンジアミン、o−フェニレンジアミン、3,3'−ジアミノジフェニルエーテル、3,4'−ジアミノジフェニルエーテル、4,4'−ジアミノジフェニルエーテル、3,3'−ジアミノジフェニルスルフィド、3,4'−ジアミノジフェニルスルフィド、4,4'−ジアミノジフェニルスルフィド、3,3'−ジアミノジフェニルスルホン、3,4'−ジアミノジフェニルスルホン、4,4'−ジアミノジフェニルスルホン、3,3'−ジアミノベンゾフェノン、4,4'−ジアミノベンゾフェノン、3,4'−ジアミノベンゾフェノン、3,3'−ジアミノジフェニルメタン、4,4'−ジアミノジフェニルメタン、3,4'−ジアミノジフェニルメタン、2,2−ジ(3−アミノフェニル)プロパン、2,2−ジ(4−アミノフェニル)プロパン、2−(3−アミノフェニル)−2−(4−アミノフェニル)プロパン、1,1−ジ(3−アミノフェニル)−1−フェニルエタン、1,1−ジ(4−アミノフェニル)−1−フェニルエタン、1−(3−アミノフェニル)−1−(4−アミノフェニル)−1−フェニルエタン、1,3−ビス(3−アミノフェノキシ)ベンゼン、1,3−ビス(4−アミノフェノキシ)ベンゼン、1,4−ビス(3−アミノフェノキシ)ベンゼン、1,4−ビス(4−アミノフェノキシ)ベンゼン、1,3−ビス(3−アミノベンゾイル)ベンゼン、1,3−ビス(4−アミノベンゾイル)ベンゼン、1,4−ビス(3−アミノベンゾイル)ベンゼン、1,4−ビス(4−アミノベンゾイル)ベンゼン、1,3−ビス(3−アミノ−α,α−ジメチルベンジル)ベンゼン、1,3−ビス(4−アミノ−α,α−ジメチルベンジル)ベンゼン、1,4−ビス(3−アミノ−α,α−ジメチルベンジル)ベンゼン、1,4−ビス(4−アミノ−α,α−ジメチルベンジル)ベンゼン、2,6−ビス(3−アミノフェノキシ)ベンゾニトリル、2,6−ビス(3−アミノフェノキシ)ピリジン、4,4'−ビス(3−アミノフェノキシ)ビフェニル、4,4'−ビス(4−アミノフェノキシ)ビフェニル、ビス[4−(3−アミノフェノキシ)フェニル]ケトン、ビス[4−(4−アミノフェノキシ)フェニル]ケトン、ビス[4−(3−アミノフェノキシ)フェニル]スルフィド、ビス[4−(4−アミノフェノキシ)フェニル]スルフィド、ビス[4−(3−アミノフェノキシ)フェニル]スルホン、ビス[4−(4−アミノフェノキシ)フェニル]スルホン、ビス[4−(3−アミノフェノキシ)フェニル]エーテル、ビス[4−(4−アミノフェノキシ)フェニル]エーテル、2,2−ビス[4−(3−アミノフェノキシ)フェニル]プロパン、2,2−ビス[4−(4−アミノフェノキシ)フェニル]プロパン、1,3−ビス[4−(3−アミノフェノキシ)ベンゾイル]ベンゼン、1,3−ビス[4−(4−アミノフェノキシ)ベンゾイル]ベンゼン、1,4−ビス[4−(3−アミノフェノキシ)ベンゾイル]ベンゼン、1,4−ビス[4−(4−アミノフェノキシ)ベンゾイル]ベンゼン、1,3−ビス[4−(3−アミノフェノキシ)−α,α−ジメチルベンジル]ベンゼン、1,3−ビス[4−(4−アミノフェノキシ)−α,α−ジメチルベンジル]ベンゼン、1,4−ビス[4−(3−アミノフェノキシ)−α,α−ジメチルベンジル]ベンゼン、1,4−ビス[4−(4−アミノフェノキシ)−α,α−ジメチルベンジル]ベンゼン、4,4'−ビス[4−(4−アミノフェノキシ)ベンゾイル]ジフェニルエーテル、4,4'−ビス[4−(4−アミノ−α,α−ジメチルベンジル)フェノキシ]ベンゾフェノン、4,4'−ビス[4−(4−アミノ−α,α−ジメチルベンジル)フェノキシ]ジフェニルスルホン、4,4'−ビス[4−(4−アミノフェノキシ)フェノキシ]ジフェニルスルホン、3,3'−ジアミノ−4,4'−ジフェノキシベンゾフェノン、3,3'−ジアミノ−4,4'−ジビフェノキシベンゾフェノン、3,3'−ジアミノ−4−フェノキシベンゾフェノン、3,3'−ジアミノ−4−ビフェノキシベンゾフェノン、6,6'−ビス(3−アミノフェノキシ)−3,3,3',3'−テトラメチル−1,1'−スピロビインダン、6,6'−ビス(4−アミノフェノキシ)−3,3,3',3'−テトラメチル−1,1'−スピロビインダン、1,3−ビス(3−アミノプロピル)テトラメチルジシロキサン、1,3−ビス(4−アミノブチル)テトラメチルジシロキサン、α,ω−ビス(3−アミノプロピル)ポリジメチルシロキサン、α,ω−ビス(3−アミノブチル)ポリジメチルシロキサン、ビス(アミノメチル)エーテル、ビス(2−アミノエチル)エーテル、ビス(3−アミノプロピル)エーテル、ビス[(2−アミノメトキシ)エチル]エーテル、ビス[2−(2−アミノエトキシ)エチル]エーテル、ビス[2−(3−アミノプロポキシ)エチル]エーテル、1,2−ビス(アミノメトキシ)エタン、1,2−ビス(2−アミノエトキシ)エタン、1,2−ビス[2−(アミノメトキシ)エトキシ]エタン、1,2−ビス[2−(2−アミノエトキシ)エトキシ]エタン、エチレングリコールビス(3−アミノプロピル)エーテル、ジエチレングリコールビス(3−アミノプロピル)エーテル、トリエチレングリコールビス(3−アミノプロピル)エーテル、エチレンジアミン、1,3−ジアミノプロパン、1,4−ジアミノブタン、1,5−ジアミノペンタン、1,6−ジアミノヘキサン、1,7−ジアミノヘプタン、1,8−ジアミノオクタン、1,9−ジアミノノナン、1,10−ジアミノデカン、1,11−ジアミノウンデカン、1,12−ジアミノドデカン、1,2−ジアミノシクロヘキサン、1,3−ジアミノシクロヘキサン、1,4−ジアミノシクロヘキサン、trans−1,4−ジアミノシクロヘキサン、1,2−ジ(2−アミノエチル)シクロヘキサン、1,3−ジ(2−アミノエチル)シクロヘキサン、1,4−ジ(2−アミノエチル)シクロヘキサン、ビス(4−アミノシクロへキシル)メタン、2,6−ビス(アミノメチル)ビシクロ[2.2.1]ヘプタン、2,5−ビス(アミノメチル)ビシクロ[2.2.1]ヘプタン、1,4−ジアミノ−2−フルオロベンゼン、1,4−ジアミノ−2,3−ジフルオロベンゼン、1,4−ジアミノ−2,5−ジフルオロベンゼン、1,4−ジアミノ−2,6−ジフルオロベンゼン、1,4−ジアミノ−2,3,5−トリフルオロベンゼン、1,4−ジアミノ−2,3,5,6−テトラフルオロベンゼン、1,4−ジアミノ−2−(トリフルオロメチル)ベンゼン、1,4−ジアミノ−2,3−ビス(トリフルオロメチル)ベンゼン、1,4−ジアミノ−2,5−ビス(トリフルオロメチル)ベンゼン、1,4−ジアミノ−2,6−ビス(トリフルオロメチル)ベンゼン、1,4−ジアミノ−2,3,5−トリス(トリフルオロメチル)ベンゼン、1,4−ジアミノ−2,3,5,6−テトラキス(トリフルオロメチル)ベンゼン、2−フルオロベンジジン、3−フルオロベンジジン、2,3−ジフルオロベンジジン、2,5−ジフルオロベンジジン、2,6−ジフルオロベンジジン、2,3,5−トリフルオロベンジジン、2,3,6−トリフルオロベンジジン、2,3,5,6−テトラフルオロベンジジン、2,2’−ジフルオロベンジジン、3,3’−ジフルオロベンジジン、2,3’−ジフルオロベンジジン、2,2’,3−トリフルオロベンジジン、2,3,3’−トリフルオロベンジジン、2,2’,5−トリフルオロベンジジン、2,2’,6−トリフルオロベンジジン、2,3’,5−トリフルオロベンジジン、2,3’,6,−トリフルオロベンジジン、2,2’,3,3’−テトラフルオロベンジジン、2,2’,5,5’−テトラフルオロベンジジン、2,2’,6,6’−テトラフルオロベンジジン、2,2’,3,3’,6,6’−ヘキサフルオロベンジジン、2,2’,3,3’,5,5’、6,6’−オクタフルオロベンジジン、2−(トリフルオロメチル)ベンジジン、3−(トリフルオロメチル)ベンジジン、2,3−ビス(トリフルオロメチル)ベンジジン、2,5−ビス(トリフルオロメチル)ベンジジン、2、6−ビス(トリフルオロメチル)ベンジジン、2,3,5−トリス(トリフルオロメチル)ベンジジン、2,3,6−トリス(トリフルオロメチル)ベンジジン、2,3,5,6−テトラキス(トリフルオロメチル)ベンジジン、2,3’−ビス(トリフルオロメチル)ベンジジン、2,2’,3−ビス(トリフルオロメチル)ベンジジン、2,3,3’−トリス(トリフルオロメチル)ベンジジン、2,2’,5−トリス(トリフルオロメチル)ベンジジン、2,2’,6−トリス(トリフルオロメチル)ベンジジン、2,3’,5−トリス(トリフルオロメチル)ベンジジン、2,3’,6−トリス(トリフルオロメチル)ベンジジン、2,2’,3,3’−テトラキス(トリフルオロメチル)ベンジジン、2,2’,5,5’−テトラキス(トリフルオロメチル)ベンジジンおよび2,2’,6,6’−テトラキス(トリフルオロメチル)ベンジジン等が挙げられるが、これらに限定されるものではない。 When producing the above-mentioned polyimide, other diamines may be used in addition to the diamine represented by the formula (1). Examples of other diamines include p-phenylenediamine, m-phenylenediamine, o-phenylenediamine, 3,3'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl ether, 3,3. '-Diaminodiphenylsulfide, 3,4'-diaminodiphenylsulfide, 4,4'-diaminodiphenylsulfide, 3,3'-diaminodiphenylsulfone, 3,4'-diaminodiphenylsulfone, 4,4'-diaminodiphenylsulfone , 3,3'-diaminobenzophenone, 4,4'-diaminobenzophenone, 3,4'-diaminobenzophenone, 3,3'-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, 3,4'-diaminodiphenylmethane, 2 , 2-di (3-aminophenyl) propane, 2,2-di (4-aminophenyl) propane, 2- (3-aminophenyl) -2- (4-aminophenyl) propane, 1,1-di ( 3-Aminophenyl) -1-phenylethane, 1,1-di (4-aminophenyl) -1-phenylethane, 1- (3-aminophenyl) -1- (4-aminophenyl) -1-phenylethane , 1,3-bis (3-aminophenoxy) benzene, 1,3-bis (4-aminophenoxy) benzene, 1,4-bis (3-aminophenoxy) benzene, 1,4-bis (4-aminophenoxy) ) Benzene, 1,3-bis (3-aminobenzoyl) benzene, 1,3-bis (4-aminobenzoyl) benzene, 1,4-bis (3-aminobenzoyl) benzene, 1,4-bis (4-) Aminobenzoyl) benzene, 1,3-bis (3-amino-α, α-dimethylbenzyl) benzene, 1,3-bis (4-amino-α, α-dimethylbenzyl) benzene, 1,4-bis (3) -Amino-α, α-dimethylbenzyl) benzene, 1,4-bis (4-amino-α, α-dimethylbenzyl) benzene, 2,6-bis (3-aminophenoxy) benzonitrile, 2,6-bis (3-Aminophenoxy) pyridine, 4,4'-bis (3-aminophenoxy) biphenyl, 4,4'-bis (4-aminophenoxy) biphenyl, bis [4- (3-aminophenoxy) phenyl] ketone, Bis [4- (4-aminophenoxy) phenyl] ketone, bis [4- (3-aminophenoxy) phenyl] sulfide, bis [4- (4-aminophenoki) Si) phenyl] sulfide, bis [4- (3-aminophenoxy) phenyl] sulfone, bis [4- (4-aminophenoxy) phenyl] sulfone, bis [4- (3-aminophenoxy) phenyl] ether, bis [ 4- (4-Aminophenoxy) phenyl] ether, 2,2-bis [4- (3-aminophenoxy) phenyl] propane, 2,2-bis [4- (4-aminophenoxy) phenyl] propane, 1, 3-Bis [4- (3-aminophenoxy) benzoyl] benzene, 1,3-bis [4- (4-aminophenoxy) benzoyl] benzene, 1,4-bis [4- (3-aminophenoxy) benzoyl] Benzene, 1,4-bis [4- (4-aminophenoxy) benzoyl] benzene, 1,3-bis [4- (3-aminophenoxy) -α, α-dimethylbenzyl] benzene, 1,3-bis [ 4- (4-Aminophenoxy) -α, α-dimethylbenzyl] benzene, 1,4-bis [4- (3-aminophenoxy) -α, α-dimethylbenzyl] benzene, 1,4-bis [4- (4-Aminophenoxy) -α, α-dimethylbenzyl] benzene, 4,4'-bis [4- (4-aminophenoxy) benzoyl] diphenyl ether, 4,4'-bis [4- (4-amino-α) , Α-dimethylbenzyl) phenoxy] benzophenone, 4,4'-bis [4- (4-amino-α, α-dimethylbenzyl) phenoxy] diphenylsulfone, 4,4'-bis [4- (4-aminophenoxy) ) Phenoxy] diphenylsulfone, 3,3'-diamino-4,4'-diphenyloxybenzophenone, 3,3'-diamino-4,4'-dibiphenoxybenzophenone, 3,3'-diamino-4-phenoxybenzophenone, 3,3'-diamino-4-biphenyloxybenzophenone, 6,6'-bis (3-aminophenoxy) -3,3,3', 3'-tetramethyl-1,1'-spirobiindane, 6,6' -Bis (4-aminophenoxy) -3,3,3', 3'-tetramethyl-1,1'-spirobiindan, 1,3-bis (3-aminopropyl) tetramethyldisiloxane, 1,3-bis (4-Aminobutyl) tetramethyldisiloxane, α, ω-bis (3-aminopropyl) polydimethylsiloxane, α, ω-bis (3-aminobutyl) polydimethylsiloxane, bis (aminomethyl) ether, bis ( 2-aminoethyl) ether, bis ( 3-Aminopropyl) ether, bis [(2-aminomethoxy) ethyl] ether, bis [2- (2-aminoethoxy) ethyl] ether, bis [2- (3-aminopropoxy) ethyl] ether, 1, 2 -Bis (aminomethoxy) ethane, 1,2-bis (2-aminoethoxy) ethane, 1,2-bis [2- (aminomethoxy) ethoxy] ethane, 1,2-bis [2- (2-aminoethoxy) ethane ) Ethane] ethane, ethylene glycol bis (3-aminopropyl) ether, diethylene glycol bis (3-aminopropyl) ether, triethylene glycol bis (3-aminopropyl) ether, ethylenediamine, 1,3-diaminopropane, 1,4 -Diaminobutane, 1,5-diaminopentane, 1,6-diaminohexane, 1,7-diaminoheptane, 1,8-diaminooctane, 1,9-diaminononane, 1,10-diaminodecane, 1,11-diamino Benzene, 1,12-diaminododecane, 1,2-diaminocyclohexane, 1,3-diaminocyclohexane, 1,4-diaminocyclohexane, trans-1,4-diaminocyclohexane, 1,2-di (2-aminoethyl) Cyclohexane, 1,3-di (2-aminoethyl) cyclohexane, 1,4-di (2-aminoethyl) cyclohexane, bis (4-aminocyclohexyl) methane, 2,6-bis (aminomethyl) bicyclo [ 2.2.1] Heptane, 2,5-bis (aminomethyl) bicyclo [2.2.1] Heptane, 1,4-diamino-2-fluorobenzene, 1,4-diamino-2,3-difluorobenzene , 1,4-diamino-2,5-difluorobenzene, 1,4-diamino-2,6-difluorobenzene, 1,4-diamino-2,3,5-trifluorobenzene, 1,4-diamino-2 , 3,5,6-Tetrafluorobenzene, 1,4-diamino-2- (trifluoromethyl) benzene, 1,4-diamino-2,3-bis (trifluoromethyl) benzene, 1,4-diamino- 2,5-bis (trifluoromethyl) benzene, 1,4-diamino-2,6-bis (trifluoromethyl) benzene, 1,4-diamino-2,3,5-tris (trifluoromethyl) benzene, 1,4-Diamino-2,3,5,6-tetrakis (trifluoromethyl) benzene, 2-fluorobenzidine, 3-fluorobenzidine, 2,3-difluorobenze Zin, 2,5-difluorobenzidine, 2,6-difluorobenzidine, 2,3,5-trifluorobenzidine, 2,3,6-trifluorobenzidine, 2,3,5,6-tetrafluorobenzidine, 2, 2'-difluorobenzidine, 3,3'-difluorobenzidine, 2,3'-difluorobenzidine, 2,2', 3-trifluorobenzidine, 2,3,3'-trifluorobenzidine, 2,2', 5 -Trifluorobenzidine, 2,2', 6-trifluorobenzidine, 2,3', 5-trifluorobenzidine, 2,3', 6,-trifluorobenzidine, 2,2', 3,3'-tetra Fluorobenzidine, 2,2', 5,5'-tetrafluorobenzidine, 2,2', 6,6'-tetrafluorobenzidine, 2,2', 3,3', 6,6'-hexafluorobenzidine, 2,2', 3,3', 5,5', 6,6'-octafluorobenzidine, 2- (trifluoromethyl) benzidine, 3- (trifluoromethyl) benzidine, 2,3-bis (trifluoro) Methyl) benzidine, 2,5-bis (trifluoromethyl) benzidine, 2,6-bis (trifluoromethyl) benzidine, 2,3,5-tris (trifluoromethyl) benzidine, 2,3,6-tris ( Trifluoromethyl) benzidine, 2,3,5,6-tetrakis (trifluoromethyl) benzidine, 2,3'-bis (trifluoromethyl) benzidine, 2,2', 3-bis (trifluoromethyl) benzidine, 2,3,3'-tris (trifluoromethyl) benzidine, 2,2', 5-tris (trifluoromethyl) benzidine, 2,2', 6-tris (trifluoromethyl) benzidine, 2,3', 5-tris (trifluoromethyl) benzidine, 2,3', 6-tris (trifluoromethyl) benzidine, 2,2', 3,3'-tetrakis (trifluoromethyl) benzidine, 2,2', 5, Examples include, but are not limited to, 5'-tetrakis (trifluoromethyl) benzidine and 2,2', 6,6'-tetrakis (trifluoromethyl) benzidine.
上記ポリイミドの重量平均分子量は、その用途にもよるが、20,000〜500,000の範囲であることが好ましく、30,000〜300,000の範囲であることがより好ましく、40,000〜200,000の範囲であることがさらに好ましい。重量平均分子量が20,000以上であれば、十分な強度のフィルムを得ることができる。一方、重量平均分子量が500,000以下であれば、溶液粘度の上昇に伴う塗工時のハンドリングの著しい悪化もなく、良好な溶液加工性を保つことができるため、表面が平滑で膜厚が均一なフィルムを得ることができる。本明細書において、重量平均分子量分子量とは、ゲルパーミレーションクロマトグラフィー(GPC)によるポリエチレングリコール換算の値のことをいう。またポリイミドがGPC測定に用いる溶媒に不溶である場合は、ポリイミドそのものの分子量の代わりにその前駆体であるポリアミド酸の分子量を用いることができる。 The weight average molecular weight of the polyimide is preferably in the range of 20,000 to 500,000, more preferably in the range of 30,000 to 300,000, and more preferably in the range of 40,000 to 300,000, although it depends on the intended use. It is more preferably in the range of 200,000. When the weight average molecular weight is 20,000 or more, a film having sufficient strength can be obtained. On the other hand, when the weight average molecular weight is 500,000 or less, good solution processability can be maintained without significant deterioration in handling during coating due to an increase in solution viscosity, so that the surface is smooth and the film thickness is high. A uniform film can be obtained. In the present specification, the weight average molecular weight molecular weight means a value in terms of polyethylene glycol by gel permeation chromatography (GPC). When the polyimide is insoluble in the solvent used for GPC measurement, the molecular weight of polyamic acid, which is a precursor thereof, can be used instead of the molecular weight of the polyimide itself.
また、ポリイミドの固有粘度は、0.3〜10dL/gであることが好ましく、0.5〜10dL/gであることがより好ましい。固有粘度が0.3dL/g以上であれば、十分な分子量を有するため、十分な強度のフィルムを得ることができる。一方、固有粘度が10dL/g以下であれば、溶液粘度の上昇に伴う塗工時のハンドリングの著しい悪化もなく、良好な溶液加工性を保つことができるため、表面が平滑で膜厚が均一なフィルムを得ることができる。なお、固有粘度は、後述の実施例に記載の方法にて測定することができる。 The intrinsic viscosity of the polyimide is preferably 0.3 to 10 dL / g, more preferably 0.5 to 10 dL / g. When the intrinsic viscosity is 0.3 dL / g or more, it has a sufficient molecular weight, so that a film having sufficient strength can be obtained. On the other hand, when the intrinsic viscosity is 10 dL / g or less, good solution processability can be maintained without significant deterioration in handling during coating due to an increase in solution viscosity, so that the surface is smooth and the film thickness is uniform. Film can be obtained. The intrinsic viscosity can be measured by the method described in Examples described later.
上記ポリイミドの製造方法は、特に限定されず、公知の方法を用いて得ることができる。例えば式(8)で表されるテトラカルボン酸二無水物と式(1)で表されるジアミンとを溶媒中において撹拌して重合させることによって前駆体であるポリアミド酸を得て、さらにイミド化することによって上記ポリイミドを得ることができる。 The method for producing the polyimide is not particularly limited, and can be obtained by using a known method. For example, the tetracarboxylic dianhydride represented by the formula (8) and the diamine represented by the formula (1) are stirred and polymerized in a solvent to obtain a polyamic acid as a precursor, which is further imidized. By doing so, the above-mentioned polyimide can be obtained.
式(8)で表されるテトラカルボン酸二無水物としては、例えば、上述の脂環式テトラカルボン酸二無水物および/または芳香族テトラカルボン酸二無水物が挙げられる。 Examples of the tetracarboxylic dianhydride represented by the formula (8) include the above-mentioned alicyclic tetracarboxylic dianhydride and / or aromatic tetracarboxylic dianhydride.
式(1)で表されるジアミンと他のジアミンとを併用(すなわち、共重合)する場合は、ジアミンの総量を100mol%としたときに、式(1)で表されるジアミンの含有量は、10mol%以上、50mol%以上、70mol%以上、80mol%以上、90mol%以上、95mol%以上、100mol%の順に、含有量が高いほど好ましい。 When the diamine represented by the formula (1) is used in combination with another diamine (that is, copolymerization), the content of the diamine represented by the formula (1) is when the total amount of the diamine is 100 mol%. The higher the content, the more preferable, in the order of 10 mol% or more, 50 mol% or more, 70 mol% or more, 80 mol% or more, 90 mol% or more, 95 mol% or more, and 100 mol%.
重合時の溶媒は、ポリアミド酸およびポリイミドが均一に溶解できるものであればよく、反応を阻害するものでなければ、限定されるものではない。当該溶媒としては、例えば、アミド系溶媒および環状エステル系溶媒が挙げられる。アミド系溶媒としては、N−メチル−2−ピロリドン、N,N−ジメチルホルムアミド、N,N−ジメチルアセトアミドおよびヘキサメチルホスホルアミド等が挙げられる。環状エステル系溶媒としては、γ−ブチロラクトン、γ−バレロラクトン、δ−バレロラクトン、γ−カプロラクトン、ε−カプロラクトンおよびα−メチル−γ−ブチロラクトン等が挙げられる。 The solvent at the time of polymerization may be any one as long as the polyamic acid and the polyimide can be uniformly dissolved, and is not limited as long as it does not inhibit the reaction. Examples of the solvent include amide-based solvents and cyclic ester-based solvents. Examples of the amide solvent include N-methyl-2-pyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide and hexamethylphosphoramide. Examples of the cyclic ester solvent include γ-butyrolactone, γ-valerolactone, δ-valerolactone, γ-caprolactone, ε-caprolactone and α-methyl-γ-butyrolactone.
イミド化の方法は特に限定されず、公知の方法(化学イミド化法および熱イミド化法)を適用することが出来る。 The imidization method is not particularly limited, and known methods (chemical imidization method and thermal imidization method) can be applied.
まず化学イミド化によるポリイミドの製造方法について説明する。重合して得られたポリイミド前駆体ワニス、または重合時に用いる溶媒と同一の溶媒で適度に希釈したポリイミド前駆体ワニスに、攪拌下で、有機酸無水物と、触媒としての3級アミンとからなる化学イミド化剤を滴下する。そして、このワニスを0〜100℃、好ましくは20〜50℃で0.5時間〜48時間攪拌することで容易にイミド化反応を完結することができる。 First, a method for producing polyimide by chemical imidization will be described. The polyimide precursor varnish obtained by polymerization or the polyimide precursor varnish appropriately diluted with the same solvent as the solvent used at the time of polymerization is composed of an organic acid anhydride and a tertiary amine as a catalyst under stirring. The chemical imidizing agent is added dropwise. Then, the imidization reaction can be easily completed by stirring the varnish at 0 to 100 ° C., preferably 20 to 50 ° C. for 0.5 to 48 hours.
有機酸無水物としては特に限定されないが、無水酢酸、無水プロピオン酸、無水マレイン酸および無水フタル酸等が挙げられる。このうち、コストおよび後処理(除去)のしやすさの観点から無水酢酸が好適に用いられる。また3級アミンとしては特に限定されず、ピリジン、トリエチルアミンおよびN,N−ジメチルアニリン等が挙げられる。このうち、安全性の観点から好ましくはピリジンが用いられる。 The organic acid anhydride is not particularly limited, and examples thereof include acetic anhydride, propionic anhydride, maleic anhydride, and phthalic anhydride. Of these, acetic anhydride is preferably used from the viewpoint of cost and ease of post-treatment (removal). The tertiary amine is not particularly limited, and examples thereof include pyridine, triethylamine, N, N-dimethylaniline and the like. Of these, pyridine is preferably used from the viewpoint of safety.
投入する化学イミド化剤中の有機酸無水物量は、特に限定されないが、ポリイミド前駆体の理論脱水量の1〜10倍モルの範囲であり、反応の完結、反応速度および後処理の観点から2〜5倍モルの範囲であることが好ましい。また触媒としての3級アミンの使用量は、特に限定されないが、反応の完結、反応速度および後処理(除去のしやすさ)の観点から有機酸無水物量に対して0.1〜1倍モルの範囲であることが好ましい。 The amount of the organic acid anhydride in the chemical imidizing agent to be added is not particularly limited, but is in the range of 1 to 10 times the molar amount of the theoretical dehydration of the polyimide precursor, and is 2 from the viewpoint of reaction completion, reaction rate and post-treatment. It is preferably in the range of ~ 5 times the molar amount. The amount of the tertiary amine used as a catalyst is not particularly limited, but is 0.1 to 1 times the molar amount of the organic acid anhydride from the viewpoint of reaction completion, reaction rate and post-treatment (easiness of removal). It is preferably in the range of.
上記ポリイミドは、熱的手法によるイミド化(熱イミド化)によっても得ることができる。熱的手法によるイミド化は、ポリアミド酸溶液を加熱して行えばよい。あるいは、ガラス板、金属板またはPET(ポリエチレンテレフタレート)等の支持体に、ポリアミド酸溶液を流延または塗布した後、80℃〜500℃の範囲内で熱処理を行えばよい。さらに、フッ素系樹脂によるコーティング等の離型処理を施した容器に直接ポリアミド酸溶液を入れ、減圧下で加熱乾燥することによって、ポリアミド酸の脱水閉環を行うこともできる。このような熱的手法によるポリアミド酸の脱水閉環により、ポリイミド樹脂を得ることができる。なお、上記各処理の加熱時間は、脱水閉環を行うポリアミド酸溶液の処理量および加熱温度により異なるが、一般的には、処理温度が最高温度に達してから1分〜5時間の範囲で行うことが好ましい。 The polyimide can also be obtained by imidization (thermal imidization) by a thermal method. Imidization by a thermal method may be carried out by heating a polyamic acid solution. Alternatively, a polyamic acid solution may be cast or applied to a support such as a glass plate, a metal plate or PET (polyethylene terephthalate), and then heat treatment may be performed in the range of 80 ° C. to 500 ° C. Further, the polyamic acid can be dehydrated and ring-closed by putting the polyamic acid solution directly into a container that has been subjected to a mold release treatment such as coating with a fluororesin and heating and drying under reduced pressure. A polyimide resin can be obtained by dehydrating and ring-closing the polyamic acid by such a thermal method. The heating time of each of the above treatments varies depending on the treatment amount and the heating temperature of the polyamic acid solution for dehydration and ring closure, but is generally performed in the range of 1 minute to 5 hours after the treatment temperature reaches the maximum temperature. Is preferable.
また、共沸溶媒を用いた共沸法を用いる場合は、ポリアミド酸溶液にトルエンまたはキシレン等の水と共沸する溶媒を加え、170〜200℃に昇温して、脱水閉環により生成する水を積極的に系外へ除去しながら、1時間〜5時間程度反応させればよい。反応終了後、反応溶液をアルコール等の貧溶媒中に滴下して、ポリイミドを沈殿させ、必要に応じてアルコール等で洗浄を行ったのち、乾燥を行ってポリイミド樹脂を得ることができる。 When the azeotropic method using an azeotropic solvent is used, water produced by dehydration ring closure by adding a solvent azeotropically with water such as toluene or xylene to the polyamic acid solution and raising the temperature to 170 to 200 ° C. It may be allowed to react for about 1 hour to 5 hours while actively removing the water from the system. After completion of the reaction, the reaction solution is added dropwise to a poor solvent such as alcohol to precipitate the polyimide, and if necessary, the polyimide is washed with alcohol or the like and then dried to obtain a polyimide resin.
上記の沈殿析出操作で使用する貧溶媒としては、ポリイミドを溶解しないものであれば特に限定されない。貧溶媒としては、例えば、反応溶媒および化学イミド化剤との混和性および乾燥による除去のしやすさの観点から水、メタノール、エタノール、n−プロパノールもしくはイソプロパノール等、またはこれらの混合溶媒が好適に用いられる。 The poor solvent used in the above-mentioned precipitation-precipitation operation is not particularly limited as long as it does not dissolve the polyimide. As the poor solvent, for example, water, methanol, ethanol, n-propanol or isopropanol or the like, or a mixed solvent thereof is preferable from the viewpoint of miscibility with the reaction solvent and the chemical imidizing agent and ease of removal by drying. Used.
ポリイミド、化学イミド化剤または共沸剤を含有するポリイミド溶液を貧溶媒中に滴下する際、ポリイミド溶液の固形分濃度は、撹拌が可能な粘度であるならば特に制限されないが、粒径を小さくするという観点から濃度は希薄である方が好ましい。しかし、当該濃度が希薄すぎる場合、ポリイミドを析出させるために、大量の貧溶媒を使用することとなり、好ましくない。これらの観点より、ポリイミド溶液の固形分濃度が15重量%以下、好ましくは10重量%以下の濃度になるように希釈を行った後に、ポリイミド溶液に貧溶媒を滴下することが好ましい。使用する貧溶媒量はポリイミド溶液の等量以上の量を使用することが好ましく、2〜3倍量がより好ましい。ここで得られたポリイミドは、少量の化学イミド化剤および/または共沸剤を含んでいるため、上記貧溶媒で数回洗浄することが好ましい。 When a polyimide solution containing polyimide, a chemical imidizing agent or an azeotropic agent is dropped into a poor solvent, the solid content concentration of the polyimide solution is not particularly limited as long as it has a viscous structure that allows stirring, but the particle size is reduced. It is preferable that the concentration is dilute from the viewpoint of However, if the concentration is too dilute, a large amount of poor solvent is used to precipitate the polyimide, which is not preferable. From these viewpoints, it is preferable to dilute the polyimide solution so that the solid content concentration is 15% by weight or less, preferably 10% by weight or less, and then add a poor solvent to the polyimide solution. The amount of the poor solvent to be used is preferably equal to or more than the amount of the polyimide solution, and more preferably 2 to 3 times the amount. Since the polyimide obtained here contains a small amount of a chemical imidizing agent and / or an azeotropic agent, it is preferable to wash it several times with the above-mentioned poor solvent.
こうして化学イミド化法または熱イミド化法で得られたポリイミドの乾燥方法は、真空乾燥でも、熱風乾燥でもよい。樹脂に含まれる溶媒を完全に乾燥させるためには、真空乾燥が望ましい。乾燥温度は、残留溶媒の分解および残留溶媒による樹脂の劣化を防ぐ観点から80〜200℃の範囲が好ましい。また乾燥時間は樹脂に含まれる溶媒を完全に乾燥できる時間であれば任意であるが、製造プロセスコストの観点から15時間以下であることが好ましく、残留溶媒を十分に乾燥させるという観点から8時間以上であることが好ましい。 The method for drying the polyimide thus obtained by the chemical imidization method or the thermal imidization method may be vacuum drying or hot air drying. Vacuum drying is desirable in order to completely dry the solvent contained in the resin. The drying temperature is preferably in the range of 80 to 200 ° C. from the viewpoint of preventing decomposition of the residual solvent and deterioration of the resin due to the residual solvent. The drying time is arbitrary as long as the solvent contained in the resin can be completely dried, but it is preferably 15 hours or less from the viewpoint of manufacturing process cost, and 8 hours from the viewpoint of sufficiently drying the residual solvent. The above is preferable.
<3.ワニス>
本発明の一実施形態に係るワニスは、本発明の一実施形態に係るポリイミドを固形分濃度5重量%以上含む。固形分濃度が5重量%以上であれば、ワニスの塗工によって得られるフィルムの平滑性を確保することができる。上記固形分濃度は、5〜40重量%が好ましく、10〜25重量%であることがさらに好ましい。
<3. Varnish>
The varnish according to the embodiment of the present invention contains the polyimide according to the embodiment of the present invention in a solid content concentration of 5% by weight or more. When the solid content concentration is 5% by weight or more, the smoothness of the film obtained by coating the varnish can be ensured. The solid content concentration is preferably 5 to 40% by weight, more preferably 10 to 25% by weight.
当該ワニスは、上述のポリイミドを有機溶媒に均一に溶解させることによって得ることができる。当該有機溶媒は特に限定されないが、アミド系溶媒、ケトン系溶媒、エーテル系溶媒、エステル系溶媒、ジメチルスルホキシド、対称グリコールジエーテル類およびエーテル類等を挙げることができる。また、これらの有機溶媒は混合して用いられてもよい。 The varnish can be obtained by uniformly dissolving the above-mentioned polyimide in an organic solvent. The organic solvent is not particularly limited, and examples thereof include amide-based solvents, ketone-based solvents, ether-based solvents, ester-based solvents, dimethyl sulfoxide, symmetric glycol diethers, and ethers. Moreover, these organic solvents may be used in mixture.
アミド系溶媒としては、N,N−ジメチルホルムアミド、N,N−ジメチルアセトアミドおよびN−メチル−2−ピロリドン等が挙げられる。ケトン系溶媒としては、アセトン、メチルエチルケトン、メチルイソブチルケトン、シクロペンタノンおよびシクロヘキサノン等が挙げられる。エーテル系溶媒としては、テトラヒドロフラン、1,3−ジオキソランおよび1,4−ジオキサン等が挙げられる。エステル系溶媒としては、酢酸メチル、酢酸エチル、酢酸ブチル、γ−ブチロラクトン、α−アセトラクトン、β−プロピオラクトンおよびδ−バレロラクトン等が挙げられる。対称グリコールジエーテル類としては、メチルモノグライム(1,2−ジメトキシエタン)、メチルジグライム(ビス(2−メトキシエチル)エーテル)、メチルトリグライム(1,2−ビス(2−メトキシエトキシ)エタン)、メチルテトラグライム(ビス[2−(2−メトキシエトキシエチル)]エーテル)、エチルモノグライム(1,2−ジエトキシエタン)、エチルジグライム(ビス(2−エトキシエチル)エーテル)およびブチルジグライム(ビス(2−ブトキシエチル)エーテル)等が挙げられる。エーテル類としては、ジプロピレングリコールメチルエーテル、トリプロピレングリコールメチルエーテル、プロピレングリコールn−プロピルエーテル、ジプロピレングリコールn−プロピルエーテル、プロピレングリコールn−ブチルエーテル、ジプロピレングリコールn−ブチルエーテル、トリピレングリコールn−プロピルエーテル、プロピレングリコールフェニルエーテル、ジプロピレングリコールジメチルエーテル、1,3−ジオキソラン、エチレングリコールモノブチルエーテル、ジエチレングリコールモノエチルエーテル、ジエチレングリコールモノブチルエーテルおよびエチレングリコールモノエチルエーテル等が挙げられる。 Examples of the amide solvent include N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone and the like. Examples of the ketone solvent include acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone and cyclohexanone. Examples of the ether solvent include tetrahydrofuran, 1,3-dioxolane, 1,4-dioxane and the like. Examples of the ester solvent include methyl acetate, ethyl acetate, butyl acetate, γ-butyrolactone, α-acetolactone, β-propiolactone and δ-valerolactone. Symmetrical glycol diethers include methyl monoglime (1,2-dimethoxyethane), methyl diglime (bis (2-methoxyethyl) ether), and methyl triglime (1,2-bis (2-methoxyethoxy) ethane). ), Methyltetraglime (bis [2- (2-methoxyethoxyethyl)] ether), ethyl monoglime (1,2-diethoxyethane), ethyl diglime (bis (2-ethoxyethyl) ether) and butyl jig Examples thereof include lime (bis (2-butoxyethyl) ether). Examples of ethers include dipropylene glycol methyl ether, tripropylene glycol methyl ether, propylene glycol n-propyl ether, dipropylene glycol n-propyl ether, propylene glycol n-butyl ether, dipropylene glycol n-butyl ether, and tripylene glycol n-. Examples thereof include propyl ether, propylene glycol phenyl ether, dipropylene glycol dimethyl ether, 1,3-dioxolane, ethylene glycol monobutyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether and ethylene glycol monoethyl ether.
有機溶媒はこれらの中から少なくとも1つ選択されることが好ましい。またさらに、上記ポリイミドは、アミド系溶媒、ケトン系溶媒およびエーテル系溶媒の全てに溶解することが、塗工する基板に合わせた溶媒を都度選定できるという点で特に好ましい。この中で、有機溶媒としては、塗工中、乾燥途上の塗膜が吸湿することにより、白化、不均一化および固化等の不具合が生じることを防止するという観点から、アミド系溶媒と、ケトン系溶媒またはエーテル系溶媒との混合溶媒が好ましく、更には、ケトン系溶媒またはエーテル系溶媒単体か、またはそれらの混合溶媒での使用がより好ましい。その中でも特に好ましいアミド系溶媒としては、ジメチルホルムアミド、ジメチルアセトアミドおよびN−メチルピロリドンが挙げられる。特に好ましいケトン系溶媒としては、メチルエチルケトン、メチルイソブチルケトン、シクロペンタノンおよびシクロヘキサノンが挙げられる。特に好ましいエーテル系溶媒としてはメチルモノグライム(1,2−ジメトキシエタン)、メチルジグライム(ビス(2−メトキシエチル)エーテル)およびメチルトリグライム(1,2−ビス(2−メトキシエトキシ)エタン)等が挙げられる。 It is preferable that at least one organic solvent is selected from these. Furthermore, it is particularly preferable that the polyimide is dissolved in all of the amide solvent, the ketone solvent and the ether solvent, because the solvent suitable for the substrate to be coated can be selected each time. Among these, as organic solvents, amide-based solvents and ketones are used from the viewpoint of preventing problems such as whitening, non-uniformity and solidification due to moisture absorption of the coating film during coating and drying. A mixed solvent with a system solvent or an ether solvent is preferable, and further, it is more preferable to use a ketone solvent or an ether solvent alone, or a mixed solvent thereof. Among them, particularly preferable amide-based solvents include dimethylformamide, dimethylacetamide and N-methylpyrrolidone. Particularly preferred ketone solvents include methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone and cyclohexanone. Particularly preferred ether solvents are methyl monoglime (1,2-dimethoxyethane), methyl diglime (bis (2-methoxyethyl) ether) and methyl triglime (1,2-bis (2-methoxyethoxy) ethane). And so on.
ワニスの粘度は塗工する厚みおよび塗工環境に応じて、随時選択されるが、0.1〜50Pa・sであることが好ましく、0.5〜30Pa・sであることがさらに好ましい。ワニスの粘度が0.1Pa・s以上であれば、十分な粘度を確保でき、その結果、十分な膜厚精度を確保することができる。また、ワニスの粘度が50Pa・s以下であれば、膜厚精度を確保できるとともに、塗工後すぐに乾燥する部分が発生することによるゲル欠陥等の外観欠陥の発生をより確実に防ぐことができる。上記粘度は、23℃における動粘度を、E型粘度計を用いて測定したものである。 The viscosity of the varnish is selected at any time according to the coating thickness and the coating environment, but is preferably 0.1 to 50 Pa · s, and more preferably 0.5 to 30 Pa · s. When the viscosity of the varnish is 0.1 Pa · s or more, a sufficient viscosity can be secured, and as a result, a sufficient film thickness accuracy can be ensured. Further, if the viscosity of the varnish is 50 Pa · s or less, the film thickness accuracy can be ensured, and the occurrence of appearance defects such as gel defects due to the occurrence of a portion that dries immediately after coating can be more reliably prevented. can. The above viscosity is a kinematic viscosity at 23 ° C. measured using an E-type viscometer.
上記ワニスは、さらに、光硬化性成分もしくは熱硬化性成分、ポリイミド以外の非重合性バインダー樹脂、またはその他の成分が配合されていてもよい。 The varnish may further contain a photocurable component or a thermosetting component, a non-polymerizable binder resin other than polyimide, or other components.
上記ワニスに加工特性または各種機能性を付与するために、様々な有機または無機の低分子化合物または高分子化合物を配合してもよい。例えば、染料、界面活性剤、レベリング剤、可塑剤、微粒子、または増感剤等を用いることができる。微粒子には、ポリスチレンおよびポリテトラフルオロエチレン等の有機微粒子、コロイダルシリカ、カーボンおよび層状珪酸塩等の無機微粒子等が包含される。それらは多孔質または中空構造であってもよい。また、上記低分子または高分子化合物の機能としては、顔料またはフィラーが挙げられる。上記低分子または高分子化合物の形態は繊維であってもよい。 Various organic or inorganic low molecular weight compounds or high molecular weight compounds may be blended in order to impart processing characteristics or various functionalities to the varnish. For example, dyes, surfactants, leveling agents, plasticizers, fine particles, sensitizers and the like can be used. The fine particles include organic fine particles such as polystyrene and polytetrafluoroethylene, and inorganic fine particles such as colloidal silica, carbon and layered silicate. They may be porous or hollow. Further, as a function of the low molecular weight or high molecular weight compound, a pigment or a filler can be mentioned. The form of the low molecular weight or high molecular weight compound may be a fiber.
<4.フィルム>
本発明の一実施形態に係るフィルム(ポリイミドフィルム)は、本発明の一実施形態に係るワニス(ポリイミドワニス)を乾燥して得られる。上記フィルムは、基板上にワニスを塗工し、乾燥することで製造することができる。また、ポリイミド前駆体であるポリアミド酸を基板に塗工し、得られた膜を加熱してイミド化および乾燥することでもフィルムを得ることができる。得られるフィルムの熱膨張特性および寸法安定性の観点から、上述のポリイミドワニスを塗工し、乾燥する方法がより好ましい。
<4. Film>
The film (polyimide film) according to the embodiment of the present invention is obtained by drying the varnish (polyimide varnish) according to the embodiment of the present invention. The film can be produced by applying a varnish on a substrate and drying the film. A film can also be obtained by applying a polyamic acid, which is a polyimide precursor, to a substrate and heating the obtained film to imidize and dry it. From the viewpoint of thermal expansion characteristics and dimensional stability of the obtained film, the method of applying the above-mentioned polyimide varnish and drying it is more preferable.
上記ワニスを塗工する基板としては、ガラス基板;SUS等の金属基板あるいは金属ベルト;ポリエチレンテレフタレート、ポリカーボネート、ポリアクリレート、ポリエチレンナフタレートおよびトリアセチルセルロース等のプラスチックフィルム等が使用されるが、これらに限定されるものではない。現行のバッチタイプのデバイス製造プロセスに適応させるためには、ガラス基板を用いることが好ましい。 As the substrate to which the varnish is applied, a glass substrate; a metal substrate such as SUS or a metal belt; a plastic film such as polyethylene terephthalate, polycarbonate, polyacrylate, polyethylene naphthalate and triacetyl cellulose is used. It is not limited. In order to adapt to the current batch type device manufacturing process, it is preferable to use a glass substrate.
フィルム製造時の乾燥温度に関しては、プロセスに合わせた条件を選択することが可能であり、特性に影響を与えない限り、特に制限されない。 The drying temperature during film production can be selected according to the process, and is not particularly limited as long as it does not affect the characteristics.
上記フィルムの表面には、金属酸化物または透明電極等の各種無機薄膜が形成されていてもよい。これら無機薄膜の製膜方法は特に限定されるものではなく、例えばCVD法、並びに、スパッタリング法、真空蒸着法およびイオンプレーティング法等のPVD法等が挙げられる。 Various inorganic thin films such as metal oxides and transparent electrodes may be formed on the surface of the film. The method for forming these inorganic thin films is not particularly limited, and examples thereof include a CVD method and a PVD method such as a sputtering method, a vacuum deposition method, and an ion plating method.
<5.ポリイミドの利用>
本発明の一実施形態に係るポリイミドは、耐熱性および絶縁性等のポリイミド本来の特性に加えて、線熱膨張係数が低く、しかも溶液加工性および透明性に優れるという極めて有用な特性を示す。
<5. Use of polyimide>
The polyimide according to one embodiment of the present invention exhibits extremely useful properties such as low linear thermal expansion coefficient and excellent solution processability and transparency, in addition to the original properties of polyimide such as heat resistance and insulation.
そのため、本発明の一実施形態に係るポリイミドは、これらの特性が有効とされる分野および製品、例えば、基板、カラーフィルター、印刷物、光学材料、電子デバイス、画像表示装置などに使用されることが好ましく、さらには現在ガラスまたは透明材料が使用されている部分の代替材料とすることがさらに好ましい。これにより、ガラスにはない軽量性およびフレキシブル性を示し、かつ高精細であるという特性を備えた基板、画像表示装置、光学材料、電子デバイスを提供することができる。 Therefore, the polyimide according to one embodiment of the present invention may be used in fields and products in which these characteristics are effective, for example, substrates, color filters, printed matter, optical materials, electronic devices, image display devices, and the like. It is preferable, and even more preferably, it is used as a substitute material for the portion where glass or a transparent material is currently used. This makes it possible to provide a substrate, an image display device, an optical material, and an electronic device, which are lightweight and flexible, which glass does not have, and have the characteristics of high definition.
上記基板は、画像表示装置用プラスチック基板(例えば、フレキシブルディスプレイ基板)、TFT基板および透明導電膜基板などである。画像表示装置は、フレキシブルディスプレイ、液晶表示装置、有機EL、電子ペーパーおよび3−Dディスプレイ等である。光学材料は、光学フィルム等である。電子デバイスは、タッチパネルおよび太陽電池等である。例えば、本発明の一実施形態に係る画像表示装置用プラスチック基板は、本発明の一実施形態に係るフィルムを含むものであってもよく、本発明の一実施形態に係るフィルムからなるものであってもよい。 The substrate is a plastic substrate for an image display device (for example, a flexible display substrate), a TFT substrate, a transparent conductive film substrate, or the like. The image display device is a flexible display, a liquid crystal display device, an organic EL, an electronic paper, a 3-D display, or the like. The optical material is an optical film or the like. Electronic devices include touch panels and solar cells. For example, the plastic substrate for an image display device according to an embodiment of the present invention may include a film according to an embodiment of the present invention, or is composed of a film according to an embodiment of the present invention. You may.
本発明は上述した各実施形態に限定されるものではなく、請求項に示した範囲で種々の変更が可能であり、異なる実施形態にそれぞれ開示された技術的手段を適宜組み合わせて得られる実施形態についても本発明の技術的範囲に含まれる。 The present invention is not limited to the above-described embodiments, and various modifications can be made within the scope of the claims, and the embodiments obtained by appropriately combining the technical means disclosed in the different embodiments. Is also included in the technical scope of the present invention.
本発明は、以下のように構成することも可能である。 The present invention can also be configured as follows.
<1>下記式(1): <1> The following formula (1):
で表されるジアミン
(式(1)中、置換基Rは独立して、炭素数1〜4のアルキル基またはアルコキシ基を表し、nは置換基Rの数を表し、1〜4の整数である)。
Diamine represented by (in the formula (1), the substituent R independently represents an alkyl group or an alkoxy group having 1 to 4 carbon atoms, n represents the number of substituents R, and is an integer of 1 to 4 be).
<2>下記式(2): <2> The following formula (2):
で表される<1>に記載のジアミン。 The diamine according to <1> represented by.
<3>下記式(3): <3> The following formula (3):
で表される繰り返し単位を有するポリイミド
(式(3)中、置換基Rは独立して、炭素数1〜4のアルキル基またはアルコキシ基を表し、nは置換基Rの数を表し、1〜4の整数であり、X1は4価の脂肪族基および芳香族基の少なくともいずれか一方を表す)。
In a polyimide having a repeating unit represented by (3), the substituent R independently represents an alkyl group or an alkoxy group having 1 to 4 carbon atoms, and n represents the number of substituents R, 1 to 1. It is an integer of 4 and X 1 represents at least one of a tetravalent aliphatic group and an aromatic group).
<4>下記式(4): <4> The following formula (4):
で表される繰り返し単位を有する<3>に記載のポリイミド
(式(4)中、X1は4価の脂肪族基および芳香族基の少なくともいずれか一方を表す)。
The polyimide according to <3> having a repeating unit represented by (X 1 represents at least one of a tetravalent aliphatic group and an aromatic group in the formula (4)).
<5>X1が下記式(5): <5> X 1 is the following formula (5):
で表される4価の脂肪族基であることを特徴とする<3>または<4>に記載のポリイミド。 The polyimide according to <3> or <4>, which is a tetravalent aliphatic group represented by.
<6>X1が下記式(6): <6> X 1 is the following formula (6):
で表される4価の芳香族基であることを特徴とする<3>または<4>に記載のポリイミド。 The polyimide according to <3> or <4>, which is a tetravalent aromatic group represented by.
<7><3>〜<6>のいずれか1つに記載のポリイミドを固形分濃度5重量%以上にて含むワニス。 <7> A varnish containing the polyimide according to any one of <3> to <6> at a solid content concentration of 5% by weight or more.
<8><7>に記載のワニスを乾燥して得られるフィルム。 <8> A film obtained by drying the varnish according to <7>.
<9><8>に記載のフィルムを含む画像表示装置用プラスチック基板。 <9> A plastic substrate for an image display device including the film according to <8>.
〔物性の評価〕
以下、本発明を実施例により具体的に説明するが、これら実施例に限定されるものではない。なお、以下の例における物性値は、次の方法により測定した。
[Evaluation of physical properties]
Hereinafter, the present invention will be specifically described with reference to Examples, but the present invention is not limited to these Examples. The physical property values in the following examples were measured by the following methods.
<赤外線吸収(FT−IR)スペクトル>
ジアミンの赤外線吸収スペクトルは、フーリエ変換赤外分光光度計(日本分光社製、FT−IR4100)を用い、KBr法で測定した。またポリイミド前駆体およびポリイミドの赤外線吸収スペクトルは、別途約4〜5μm厚の薄膜を作製し、透過法で測定した。
<Infrared absorption (FT-IR) spectrum>
The infrared absorption spectrum of diamine was measured by the KBr method using a Fourier transform infrared spectrophotometer (FT-IR4100, manufactured by JASCO Corporation). The infrared absorption spectra of the polyimide precursor and the polyimide were separately prepared as a thin film having a thickness of about 4 to 5 μm and measured by a transmission method.
<1H−NMRスペクトル>
ジアミンおよびポリイミド粉末の1H−NMRスペクトルは、重水素化ジメチルスルホキシド(DMSO−d6)を溶媒として、NMR分光光度計(日本電子社製、ECP400)を用いて測定した。
< 1 1 H-NMR spectrum>
The 1 H-NMR spectra of the diamine and the polyimide powder were measured using an NMR spectrophotometer (ECP400, manufactured by JEOL Ltd.) using deuterated dimethyl sulfoxide (DMSO-d 6) as a solvent.
<示差走査熱量分析(融点および融解曲線)>
ジアミンの融点および融解曲線は、示差走査熱量分析装置(ネッチ・ジャパン社製、DSC3100)を用い、窒素雰囲気中、昇温速度5℃/分で測定した。
<Differential scanning calorimetry (melting point and melting curve)>
The melting point and melting curve of the diamine were measured using a differential scanning calorimeter (DSC3100, manufactured by Netch Japan Co., Ltd.) in a nitrogen atmosphere at a heating rate of 5 ° C./min.
<固有粘度(ηinh)>
ポリイミド前駆体(PAA)およびポリイミド(PI)の還元粘度は、固形分濃度0.5重量%、30℃においてオストワルド粘度計を用いて測定した。この値は固有粘度と見なすことができ、この値が高い程分子量が高いことを表す。
<Intrinsic viscosity (η inh )>
The reduced viscosities of the polyimide precursor (PAA) and the polyimide (PI) were measured using an Ostwald viscometer at a solid content concentration of 0.5% by weight and 30 ° C. This value can be regarded as the intrinsic viscosity, and the higher this value, the higher the molecular weight.
<ガラス転移温度(Tg)>
ポリイミドフィルム(約20μm厚)のガラス転移温度(Tg)は、熱機械分析装置(ネッチ・ジャパン社製、TMA4000)を用い、周波数0.1Hz、昇温速度5℃/分における損失エネルギー曲線のピーク温度から求めた。Tgが高いほど、物理的耐熱性が高いことを表す。
<Glass transition temperature (T g )>
The glass transition temperature (T g ) of the polyimide film (about 20 μm thick) was determined by using a thermomechanical analyzer (TMA4000, manufactured by Netch Japan Co., Ltd.) with a frequency of 0.1 Hz and a heating rate of 5 ° C./min. Obtained from the peak temperature. The higher the T g , the higher the physical heat resistance.
<線熱膨張係数(CTE)>
ポリイミドフィルム(約20μm厚)のCTEは、熱機械分析装置(ネッチ・ジャパン社製、TMA4000)を用い、荷重0.5g/膜厚1μm当たり、昇温速度5℃/分における試験片の伸びより、100〜200℃の範囲での平均値として求めた。CTE値が0に近いほど熱寸法安定性に優れていることを表す。
<Coefficient of linear thermal expansion (CTE)>
For the CTE of the polyimide film (about 20 μm thickness), a thermomechanical analyzer (TMA4000, manufactured by Netch Japan Co., Ltd.) was used, and the elongation of the test piece at a heating rate of 5 ° C./min per load of 0.5 g / film thickness of 1 μm was obtained. , As an average value in the range of 100 to 200 ° C. The closer the CTE value is to 0, the better the thermal dimensional stability.
<5%重量減少温度(Td 5)>
ポリイミドフィルム(約20μm厚)の5%重量減少温度(Td 5)は、ネッチ・ジャパン社製熱重量分析装置(TG−DTA2000)を用いて、窒素中(N2)および空気中(air)、昇温速度10℃/分での昇温過程において、ポリイミドフィルム(20μm厚)の重量が、初期重量の5%減少した時の温度から求めた。Td 5値が高いほど化学的耐熱性(熱安定性)が高いことを表す。
<5% weight loss temperature (T d 5 )>
The 5% weight loss temperature (T d 5 ) of the polyimide film (about 20 μm thickness) was set in nitrogen (N 2 ) and in air (air) using a thermogravimetric analyzer (TG-DTA2000) manufactured by Netch Japan Co., Ltd. In the heating process at a heating rate of 10 ° C./min, the weight of the polyimide film (20 μm thickness) was determined from the temperature when the initial weight was reduced by 5%. The higher the T d 5 value, the higher the chemical heat resistance (thermal stability).
<引張弾性率、破断伸び、破断強度>
ポリイミドフィルム(約20μm厚)の機械的特性はエー・アンド・ディー社製引張試験機(テンシロンUTM−II)を用いて評価した。試験片(30mm長×3mm幅×約20μm厚)を作製し、引張試験(延伸速度:8mm/分)を実施して、応力−歪曲線の初期勾配から引張弾性率(E)、破断点応力から破断強度(σb)、破断時の伸び率から破断伸び(εb)を求めた。破断伸びが高いほどフィルムの靭性が高いことを表す。なお、破断伸びは、平均値(ave)と最大値(max)とを示した。
<Tension modulus, elongation at break, strength at break>
The mechanical properties of the polyimide film (thickness of about 20 μm) were evaluated using a tensile tester (Tensilon UTM-II) manufactured by A & D Co., Ltd. A test piece (30 mm length x 3 mm width x about 20 μm thickness) was prepared, and a tensile test (stretching speed: 8 mm / min) was performed. From the initial gradient of the stress-strain curve, the tensile elastic modulus (E) and the breaking point stress from breaking strength (σ b), it was determined breaking elongation (epsilon b) from elongation at break. The higher the elongation at break, the higher the toughness of the film. The elongation at break showed an average value (ave) and a maximum value (max).
<ポリイミドフィルムの透明性:光透過率、カット・オフ波長、黄色度指数、ヘイズ>
ポリイミドフィルムの透明性は以下の光学特性から評価した。日本分光社製紫外−可視分光光度計(V−530)を用いて波長200〜800nmの範囲でポリイミドフィルム(約20μm厚)の光透過率曲線を測定し、波長400nmにおける光透過率(T400)、および、光透過率が事実上ゼロとなる波長(カット・オフ波長(λcut))を求めた。またこのスペクトルを基に、色彩計算プログラム(日本分光)を用い、ASTM E313規格に基づいて黄色度指数(YI値)を求めた。更に、ヘイズメーター(日本電色工業社製、NDH4000)を用い、JIS K7361−1およびJIS K7136規格に基づき、全光線透過率(Ttot)および濁度(ヘイズ)を求めた。
<Transparency of polyimide film: light transmittance, cut-off wavelength, yellowness index, haze>
The transparency of the polyimide film was evaluated from the following optical characteristics. The light transmittance curve of the polyimide film (about 20 μm thickness) was measured in the wavelength range of 200 to 800 nm using an ultraviolet-visible spectrophotometer (V-530) manufactured by Nippon Kogaku Co., Ltd., and the light transmittance (T 400) at a wavelength of 400 nm was measured. ), And the wavelength (cut-off wavelength (λ cut )) at which the light transmittance is practically zero was determined. Based on this spectrum, a color calculation program (JASCO Corporation) was used to determine the yellowness index (YI value) based on the ASTM E313 standard. Further, using a haze meter (NDH4000, manufactured by Nippon Denshoku Industries Co., Ltd.), the total light transmittance (T tot ) and turbidity (haze) were determined based on JIS K7361-1 and JIS K7136 standards.
<厚み方向複屈折(Δnth)>
偏光板付接眼鏡付Abbe屈折計4T(ATAGO社製)を用い、光源としてNaD線(589.3nm)、中間液としてヨウ化メチレン溶液に硫黄を飽和させた溶液(nD=1.72〜1.80)、および、テストピース(nD=1.72)を用いて、ポリイミドフィルムの面内屈折率ninと面外屈折率noutとを測定し、厚み方向複屈折Δnth(=nin−nout)を求めた。
<Thickness direction birefringence (Δn th)>
Using an Abbe refractometer 4T (manufactured by ATAGO) with a polarizing plate and an eyepiece, a NaD line (589.3 nm) was used as the light source, and a methylene iodide solution saturated with sulfur was used as the intermediate solution (n D = 1.72-1). Using the .80) and the test piece (n D = 1.72), the in- plane refractive index n in and the out-of-plane refractive index n out of the polyimide film were measured, and the birefringence Δn th (= n) in the thickness direction was measured. in −n out ) was obtained.
<溶液加工性>
溶液加工性を、溶媒への溶解性に基づいて評価した。ポリイミドの粉末を99倍重量の溶媒に加え、試験管ミキサーを用いて5分間撹拌して溶解状態を目視で確認した。ここで、ポリイミドの粉末が溶媒に均一に溶解した場合、「優れた溶解性を示す」と評価した。
<Solution processability>
Solution processability was evaluated based on solubility in solvents. The polyimide powder was added to a solvent having a weight of 99 times, and the mixture was stirred for 5 minutes using a test tube mixer to visually confirm the dissolved state. Here, when the polyimide powder was uniformly dissolved in the solvent, it was evaluated as "exhibiting excellent solubility".
〔略称〕
3−メチル−4−ニトロ安息香酸=3M4NB
3M4NB塩素化体=3M4NBC
N,N−ジメチルホルムアミド=DMF
テトラヒドロフラン=THF
2,2’−ビス(トリフルオロメチル)ベンジジン=TFMB
N,N−ジメチルアセトアミド=DMAc
1,2,3,4−シクロブタンテトラカルボン酸二無水物=CBDA
N−メチル−2−ピロリドン=NMP
ジメチルスルホキシド=DMSO
4,4’−(ヘキサフルオロイソプロピリデン)ジフタル酸無水物=6FDA
γ−ブチロラクトン=GBL。
[Abbreviation]
3-Methyl-4-nitrobenzoic acid = 3M4NB
3M4NB chlorinated body = 3M4NBC
N, N-dimethylformamide = DMF
Tetrahydrofuran = THF
2,2'-bis (trifluoromethyl) benzidine = TFMB
N, N-dimethylacetamide = DMAc
1,2,3,4-Cyclobutanetetracarboxylic dianhydride = CBDA
N-methyl-2-pyrrolidone = NMP
Dimethyl sulfoxide = DMSO
4,4'-(Hexafluoroisopropylidene) diphthalic anhydride = 6FDA
γ-Butyrolactone = GBL.
〔実施例1〕
<ジアミンの合成>
上記式(2)で表される本発明の一実施形態に係るジアミン(以下、M−ABMBと称する)は、M−ABMBの前駆体であるジニトロ化合物(以下、M−NBMBと称する)を合成し、ニトロ基を還元することで合成した。具体的には以下のような手順で行った。
[Example 1]
<Synthesis of diamine>
The diamine (hereinafter referred to as M-ABMB) according to the embodiment of the present invention represented by the above formula (2) synthesizes a dinitro compound (hereinafter referred to as M-NBMB) which is a precursor of M-ABMB. Then, it was synthesized by reducing the nitro group. Specifically, the procedure was as follows.
まずM−NBMBを以下のようにして合成した。三つ口フラスコ中に3M4NB(東京化成製)10.86g(60mmol)および塩化チオニル50mLを入れた。上記フラスコへ更に触媒としてDMFを3滴加え、80℃で3時間還流した。この溶液にベンゼンを加え、過剰の塩化チオニルを減圧下で共沸留去し、更に室温で12時間真空乾燥して黄色の3M4NBCを得た(融点32℃)。 First, M-NBMB was synthesized as follows. 10.86 g (60 mmol) of 3M4NB (manufactured by Tokyo Kasei) and 50 mL of thionyl chloride were placed in a three-necked flask. Three drops of DMF as a catalyst were further added to the flask, and the mixture was refluxed at 80 ° C. for 3 hours. Benzene was added to this solution, excess thionyl chloride was azeotropically distilled off under reduced pressure, and the mixture was further vacuum dried at room temperature for 12 hours to obtain yellow 3M4NBC (melting point 32 ° C.).
次にナスフラスコ中、上記3M4NBC5.15g(27mmol)を脱水済みのTHFに溶かし、セプタムキャップでシールしてA液とした。次に別のナスフラスコ中、TFMB3.20g(10mmol)を脱水THF(15mL)に溶かし、更に脱塩化水素剤としてピリジン2.5mL(31mmol)を加え、セプタムキャップでシールしてB液とした。B液を氷浴で冷却しながら、B液にA液をシリンジにてゆっくり加えた。得られたA液とB液との混合液を更に室温で12時間攪拌した。その後、得られた反応溶液に大量の水を注いで黒味がかった黄色沈殿物を析出させた。これを濾別し、水で洗浄後、120℃で12時間真空乾燥して粗生成物を得た。黒色残渣を除くため、この粗生成物を酢酸エチルに溶かしてシリカゲルカラムに通し、溶出液を得た。この溶出液をエバポレーターで濃縮して沈殿を析出させた。この沈殿を濾別して酢酸エチルで洗浄し、120℃で12時間乾燥して薄黄色生成物を収率76%で得た(融点:236℃)。FT−IRおよび1H−NMRスペクトルより、得られた生成物は目的とするジニトロ化合物(M−NBMB)であることが確認された。 Next, in an eggplant flask, 5.15 g (27 mmol) of the above 3M4NBC was dissolved in dehydrated THF and sealed with a septum cap to prepare Liquid A. Next, in another eggplant flask, 3.20 g (10 mmol) of TFMB was dissolved in dehydrated THF (15 mL), 2.5 mL (31 mmol) of pyridine was further added as a dehydrochlorination agent, and the mixture was sealed with a septum cap to prepare solution B. While cooling the liquid B in an ice bath, the liquid A was slowly added to the liquid B with a syringe. The obtained mixture of solution A and solution B was further stirred at room temperature for 12 hours. Then, a large amount of water was poured into the obtained reaction solution to precipitate a blackish yellow precipitate. This was separated by filtration, washed with water, and vacuum dried at 120 ° C. for 12 hours to obtain a crude product. In order to remove the black residue, this crude product was dissolved in ethyl acetate and passed through a silica gel column to obtain an eluate. This eluate was concentrated with an evaporator to precipitate a precipitate. The precipitate was filtered off, washed with ethyl acetate and dried at 120 ° C. for 12 hours to give a pale yellow product in 76% yield (melting point: 236 ° C.). From the FT-IR and 1 H-NMR spectra, it was confirmed that the obtained product was the target dinitro compound (M-NBMB).
次にM−NBMBを以下のようにして還元した。三つ口フラスコ中、M−NBMB4.69g(7.25mmol)を1,4−ジオキサンに溶解し、触媒としてPd/C(0.475g)を添加し、水素雰囲気中、80℃で10時間還流した。還元反応の完結は薄層クロマトグラフィーにより確認した。反応終了後、反応混合物を熱濾過して触媒を除去し、濾液を大量のイオン交換水中に滴下して沈殿を析出させた。この沈殿を濾別して120℃12時間真空乾燥し、還元反応収率85%で白色生成物を得た。 Next, M-NBMB was reduced as follows. In a three-necked flask, 4.69 g (7.25 mmol) of M-NBMB was dissolved in 1,4-dioxane, Pd / C (0.475 g) was added as a catalyst, and reflux was performed at 80 ° C. for 10 hours in a hydrogen atmosphere. did. The completion of the reduction reaction was confirmed by thin layer chromatography. After completion of the reaction, the reaction mixture was hot-filtered to remove the catalyst, and the filtrate was added dropwise to a large amount of ion-exchanged water to precipitate a precipitate. The precipitate was separated by filtration and vacuum dried at 120 ° C. for 12 hours to obtain a white product with a reduction reaction yield of 85%.
この白色生成物の分析結果は以下の通りである。FT−IR(KBr、cm−1):3368/3226(アミン、N−H)、3111/3050(芳香族C−H)、2959(CH3、C−H)、1627/1525(アミド、C=O)、1500(1,4−フェニレン)、1320/1255(CF3、C−F)。1H−NMR(400MHz、DMSO−d6、δ、ppm):10.15(s、2H、NHCO)、8.52(dd、2H、J=8.4、2.0Hz、中央ビフェニル基の5,5’−プロトン)、8.33(sd、2H、J=2.1Hz、中央ビフェニル基の3,3’−プロトン)、7.68−7.64(m、4H、末端アニリノ基の3,3’−プロトン+5,5’−プロトン)、7.32(d、2H、J=8.5Hz、中央ビフェニル基の6,6’−プロトン)、6.68(d、2H、J=8.5Hz、末端アニリノ基の6,6’−プロトン)、5.62(s、4H、NH2)、2.14(s、6H、CH3)。元素分析(C30H24O2N4F6、分子量586.54):推定値C;61.43%、H;4.12%、N;9.55%、分析値C;61.35%、H;4.26%、N;9.53%。これらの分析結果より、この生成物は目的とする式(1)で表されるジアミン(M−ABMB)であることが確認された。 The analysis results of this white product are as follows. FT-IR (KBr, cm -1 ): 3368/3226 (amine, NH), 3111/3050 (aromatic CH), 2959 (CH 3 , CH), 1627/1525 (amide, C) = O), 1500 (1,4-phenylene), 1320/1255 (CF 3 , CF). 1 1 H-NMR (400 MHz, DMSO-d 6 , δ, ppm): 10.15 (s, 2H, NHCO), 8.52 (dd, 2H, J = 8.4, 2.0 Hz, central biphenyl group 5,5'-proton), 8.33 (sd, 2H, J = 2.1Hz, central biphenyl group 3,3'-proton), 7.68-7.64 (m, 4H, terminal anilino group) 3,3'-proton + 5,5'-proton), 7.32 (d, 2H, J = 8.5Hz, central biphenyl group 6,6'-proton), 6.68 (d, 2H, J = 8.5 Hz, 6,6'-proton of terminal anilino group), 5.62 (s, 4H, NH 2 ), 2.14 (s, 6H, CH 3 ). Elemental analysis (C 30 H 24 O 2 N 4 F 6 , molecular weight 586.54): Estimated value C; 61.43%, H; 4.12%, N; 9.55%, Analytical value C; 61.35 %, H; 4.26%, N; 9.53%. From these analysis results, it was confirmed that this product was the diamine (M-ABMB) represented by the target formula (1).
〔実施例2〕
<ポリイミド前駆体の重合、化学イミド化、製膜および膜物性>
反応容器中、実施例1に記載のジアミン(M−ABMB)1.1731g(2mmol)を脱水済みのDMAcに溶解した。得られた溶液にCBDA粉末0.3922g(2mmol)を少しずつ加え、密閉した。反応初期の固形分濃度は30重量%であった。室温で攪拌を続けたところ、重合反応が進み、溶液粘度が増加して十分に攪拌しにくくなった。そのため、反応容器へ徐々にDMAcを添加していき、72時間攪拌後は固形分濃度が18重量%になるまで溶液を希釈した。72時間攪拌後、粘性のある均一なポリイミド前駆体溶液を得た。得られたポリイミド前駆体の固有粘度は1.75dL/gであった。
[Example 2]
<Polyimide precursor polymerization, chemical imidization, film formation and film physical characteristics>
In the reaction vessel, 1.1731 g (2 mmol) of the diamine (M-ABMB) described in Example 1 was dissolved in dehydrated DMAc. 0.3922 g (2 mmol) of CBDA powder was added little by little to the obtained solution, and the mixture was sealed. The solid content concentration at the beginning of the reaction was 30% by weight. When stirring was continued at room temperature, the polymerization reaction proceeded, the viscosity of the solution increased, and it became difficult to sufficiently stir. Therefore, DMAc was gradually added to the reaction vessel, and after stirring for 72 hours, the solution was diluted until the solid content concentration reached 18% by weight. After stirring for 72 hours, a viscous and uniform polyimide precursor solution was obtained. The intrinsic viscosity of the obtained polyimide precursor was 1.75 dL / g.
ポリイミド前駆体溶液をDMAcで適度に希釈(この場合は6.0重量%に希釈)した。この希釈したポリイミド前駆体溶液を攪拌しながら、化学イミド化剤として無水酢酸(20mmol)とピリジンとの混合溶液(無水酢酸とピリジンとの体積比:7/3)を室温でゆっくりと滴下し、滴下完了後更に24時間密閉容器中で攪拌した。この反応溶液をDMAcで適度に希釈後、大量の水に滴下して白色沈殿を析出させた。この白色沈殿を濾別して水およびメタノールで十分洗浄し、100℃で12時間真空乾燥した。得られた粉末を重水素化DMSOに溶かして1H−NMRスペクトルを測定した。その結果、ポリイミド前駆体に由来するNHCOプロトンおよびCOOHプロトンシグナルが共に完全に消失していたことから、化学イミド化の完結が確認された。 The polyimide precursor solution was appropriately diluted with DMAc (in this case, diluted to 6.0% by weight). While stirring this diluted polyimide precursor solution, a mixed solution of acetic anhydride (20 mmol) and pyridine (volume ratio of acetic anhydride to pyridine: 7/3) was slowly added dropwise at room temperature as a chemical imidizing agent. After the dropping was completed, the mixture was further stirred in a closed container for 24 hours. This reaction solution was appropriately diluted with DMAc and then added dropwise to a large amount of water to precipitate a white precipitate. The white precipitate was filtered off, washed thoroughly with water and methanol, and vacuum dried at 100 ° C. for 12 hours. The obtained powder was dissolved in deuterated DMSO and 1 H-NMR spectrum was measured. As a result, both the NHCO proton and COOH proton signals derived from the polyimide precursor were completely eliminated, confirming the completion of chemical imidization.
得られた繊維状のポリイミド粉末をDMAcに固形分濃度10重量%で再溶解して、均一な溶液を得た。これをガラス基板上に流延し、60℃で2時間、熱風乾燥器中で乾燥した。更に真空中200℃で1時間、次いで300℃で1時間乾燥した。その後得られたフィルムを基板から剥がし、真空中330℃で1時間熱処理して可撓性で白濁したポリイミドフィルムを得た。このフィルムについて物性評価を実施したところ、極めて低いCTE値(3.6ppm/K)および高い耐熱性(Tg=325℃)を示した。その他の物性値は表1に示す。化学イミド化したポリイミド粉末はNMPおよびDMAcに室温で優れた溶解性を示した。なお、実施例2は、テトラカルボン酸二無水物として、CBDAを100mol%使用した実施例に相当する。 The obtained fibrous polyimide powder was redissolved in DMAc at a solid content concentration of 10% by weight to obtain a uniform solution. This was cast on a glass substrate and dried at 60 ° C. for 2 hours in a hot air dryer. Further, it was dried in vacuum at 200 ° C. for 1 hour and then at 300 ° C. for 1 hour. After that, the obtained film was peeled off from the substrate and heat-treated in vacuum at 330 ° C. for 1 hour to obtain a flexible and cloudy polyimide film. When the physical properties of this film were evaluated, it showed an extremely low CTE value (3.6 ppm / K) and high heat resistance (T g = 325 ° C.). Other physical property values are shown in Table 1. The chemically imidized polyimide powder showed excellent solubility in NMP and DMAc at room temperature. Example 2 corresponds to an example in which 100 mol% of CBDA was used as the tetracarboxylic dianhydride.
〔実施例3〕
テトラカルボン酸二無水物として、CBDAを95mol%、6FDAを5mol%用いた以外は実施例2に記載した方法と同様にしてポリイミド前駆体を重合し、化学イミド化およびキャスト製膜を行ってポリイミドフィルムを得た。図1に別途作製したポリイミド薄膜の赤外線吸収スペクトルを示す。当該赤外線吸収スペクトルは、フーリエ変換赤外分光光度計FT/IR−4100 type A(日本分光株式会社製)を用いて測定した。また表1に物性値を示す。このフィルム(膜厚約20μm)は、実施例2のフィルムより高いT400値、より低いYI値およびより低いヘイズ値を示すことから、透明性が改善されていることがわかる。これは6FDAを5mol%共重合することで、溶媒溶解性が改善され、製膜時の溶媒蒸発過程において主鎖の凝集が妨げられた結果であると考えられる。また、低いCTE値(16.9ppm/K)に加えて高い耐熱性(Tg=348℃)を示した。化学イミド化したポリイミド粉末はDMAc、DMAc/GBLの混合溶媒(体積比1/1)およびDMAc/CPNの混合溶媒(体積比1/1)に対して優れた溶解性を示し、固形分濃度約10重量%のワニスを得ることが可能であった。
[Example 3]
The polyimide precursor was polymerized in the same manner as in Example 2 except that 95 mol% of CBDA and 5 mol% of 6FDA were used as the tetracarboxylic dianhydride, and the polyimide was chemically imidized and cast film-formed. I got a film. FIG. 1 shows an infrared absorption spectrum of a polyimide thin film prepared separately. The infrared absorption spectrum was measured using a Fourier transform infrared spectrophotometer FT / IR-4100 type A (manufactured by JASCO Corporation). Table 1 shows the physical property values. This film (thickness of about 20 μm) shows a higher T 400 value, a lower YI value, and a lower haze value than the film of Example 2, indicating that the transparency is improved. It is considered that this is a result of improving the solvent solubility by copolymerizing 6 FDA by 5 mol% and preventing the aggregation of the main chain in the solvent evaporation process during film formation. Moreover, in addition to a low CTE value (16.9 ppm / K), it showed high heat resistance (T g = 348 ° C.). The chemically imidized polyimide powder shows excellent solubility in a mixed solvent of DMAc, DMAc / GBL (
〔実施例4〕
テトラカルボン酸二無水物として、CBDAを70mol%、6FDAを30mol%用いた以外は実施例2に記載した方法と同様にしてポリイミド前駆体を重合し、化学イミド化およびキャスト製膜を行ってポリイミドフィルムを得た。表1に物性値を示す。このフィルムは高いT400値、低いYI値および低いヘイズ値で示されるように、優れた透明性を有していた。また、低いCTE値(17.9ppm/K)に加えて高い耐熱性(Tg=334℃)を示した。化学イミド化したポリイミド粉末はNMP、DMAcおよびDMFに室温で優れた溶解性を示した。
[Example 4]
The polyimide precursor was polymerized in the same manner as in Example 2 except that 70 mol% of CBDA and 30 mol% of 6FDA were used as the tetracarboxylic dianhydride, and the polyimide was chemically imidized and cast film-formed. I got a film. Table 1 shows the physical property values. This film had excellent transparency, as shown by the high T 400 value, low YI value and low haze value. Moreover, in addition to a low CTE value (17.9 ppm / K), it showed high heat resistance (T g = 334 ° C.). The chemically imidized polyimide powder showed excellent solubility in NMP, DMAc and DMF at room temperature.
〔実施例5〕
テトラカルボン酸二無水物として、CBDAを50mol%、6FDAを50mol%用いた以外は実施例2に記載した方法と同様にしてポリイミド前駆体を重合し、化学イミド化およびキャスト製膜を行ってポリイミドフィルムを得た。表1に物性値を示す。このフィルムは高いT400値、低いYI値、低いヘイズ値より、優れた透明性を有していた。また、比較的低いCTE値(23.6ppm/K)に加えて高い耐熱性(Tg=349℃)を示した。化学イミド化したポリイミド粉末はNMP、DMAc、DMFおよびDMSOに室温で優れた溶解性を示した。
[Example 5]
The polyimide precursor was polymerized in the same manner as in Example 2 except that 50 mol% of CBDA and 50 mol% of 6FDA were used as the tetracarboxylic dianhydride, and the polyimide was chemically imidized and cast film-formed. I got a film. Table 1 shows the physical property values. This film had better transparency than a high T 400 value, a low YI value and a low haze value. Moreover, in addition to a relatively low CTE value (23.6 ppm / K), it showed high heat resistance (T g = 349 ° C.). The chemically imidized polyimide powder showed excellent solubility in NMP, DMAc, DMF and DMSO at room temperature.
〔実施例6〕
テトラカルボン酸二無水物として、CBDAの代わりに6FDAを用いた以外は実施例2に記載した方法と同様にしてポリイミド前駆体を重合し、化学イミド化およびキャスト製膜を行ってポリイミドフィルムを得た。表1に物性値を示す。このフィルムは高いT400値、低いYI値、低いヘイズ値より、優れた透明性を有していた。また、化学イミド化したポリイミド粉末はNMP、DMAc、DMF、DMSO、GBL、トリグライム、シクロペンタノン、アセトンおよびTHFに室温で優れた溶解性を示した。GBLを溶媒として固形分濃度15重量%の濃度で安定なワニスが得られた。THFを溶出溶媒としてゲル浸透クロマトグラフィーにより分子量を測定したところ、数平均分子量(Mn)=2.3×104、重量平均分子量(Mw)=5.7×104であった。
[Example 6]
A polyimide precursor was polymerized in the same manner as in Example 2 except that 6FDA was used as the tetracarboxylic dianhydride, and chemical imidization and cast film formation were performed to obtain a polyimide film. rice field. Table 1 shows the physical property values. This film had better transparency than a high T 400 value, a low YI value and a low haze value. In addition, the chemically imidized polyimide powder showed excellent solubility in NMP, DMAc, DMF, DMSO, GBL, triglime, cyclopentanone, acetone and THF at room temperature. A stable varnish was obtained at a solid content concentration of 15% by weight using GBL as a solvent. When the molecular weight was measured by gel permeation chromatography using THF as an elution solvent, it was found that the number average molecular weight (M n ) = 2.3 × 10 4 and the weight average molecular weight (M w ) = 5.7 × 10 4 .
〔比較例1〕
本発明の一実施形態に係るジアミンにおけるメチル置換基の効果を調査するために、メチル置換基のないジアミン(ABMB)を用い、実施例2に記載した方法によりCBDAと重付加反応させてポリイミド前駆体を得た。なお、ABMBは下記式(9)で表される。
[Comparative Example 1]
In order to investigate the effect of the methyl substituent on the diamine according to the embodiment of the present invention, a diamine without a methyl substituent (ABMB) was used and subjected to a double addition reaction with CBDA by the method described in Example 2 to carry out a polyimide precursor. I got a body. ABMB is represented by the following formula (9).
上記ポリイミド前駆体の溶液に実施例2に記載した方法と同様にして化学イミド化剤を滴下したところ、反応溶液がゲル化したため、化学イミド化を実施することは困難であった。これはCBDAとABMBとから得られるポリイミドの溶媒溶解性が不十分であるためである。この結果は、本発明の一実施形態に係るジアミンを使用した結果(実施例2)とは対照的であり、本発明の一実施形態に係るジアミンにおけるメチル置換基の存在がポリイミドの溶解性に大きく寄与していることを示唆している。 When the chemical imidizing agent was added dropwise to the solution of the polyimide precursor in the same manner as in Example 2, it was difficult to carry out chemical imidization because the reaction solution gelled. This is because the solvent solubility of the polyimide obtained from CBDA and ABMB is insufficient. This result is in contrast to the result of using the diamine according to the embodiment of the present invention (Example 2), and the presence of the methyl substituent in the diamine according to the embodiment of the present invention determines the solubility of the polyimide. It suggests that it contributes significantly.
〔比較例2〕
ジアミンとしてM−ABMBの代わりにTFMBを用いた以外は、実施例2に記載した方法と同様にしてポリイミド前駆体を重合した。その溶液に実施例2に記載した方法と同様にして化学イミド化剤を滴下したところ、反応溶液がゲル化したため、化学イミド化を実施することは困難であった。これはCBDAとTFMBとから得られるポリイミドの溶媒溶解性が不十分であるためである。
[Comparative Example 2]
The polyimide precursor was polymerized in the same manner as in Example 2 except that TFMB was used instead of M-ABMB as the diamine. When a chemical imidizing agent was added dropwise to the solution in the same manner as in Example 2, it was difficult to carry out chemical imidization because the reaction solution gelled. This is because the solvent solubility of the polyimide obtained from CBDA and TFMB is insufficient.
本発明の一実施形態に係るポリイミドは、例えば、フィルムとして、基板、カラーフィルター、印刷物、光学材料、電子デバイス、画像表示装置などに好適に使用される。よって、これらの産業分野に広く利用することが可能である。 The polyimide according to one embodiment of the present invention is suitably used as a film, for example, in a substrate, a color filter, a printed matter, an optical material, an electronic device, an image display device, or the like. Therefore, it can be widely used in these industrial fields.
Claims (9)
(式(1)中、置換基Rは独立して、炭素数1〜4のアルキル基またはアルコキシ基を表し、nは置換基Rの数を表し、1〜4の整数である)。 The following formula (1):
(式(3)中、置換基Rは独立して、炭素数1〜4のアルキル基またはアルコキシ基を表し、nは置換基Rの数を表し、1〜4の整数であり、X1は4価の脂肪族基および芳香族基の少なくともいずれか一方を表す)。 The following formula (3):
(式(4)中、X1は4価の脂肪族基および芳香族基の少なくともいずれか一方を表す)。 The following formula (4):
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