JP5845918B2 - Polyimide precursor and polyimide - Google Patents
Polyimide precursor and polyimide Download PDFInfo
- Publication number
- JP5845918B2 JP5845918B2 JP2012010527A JP2012010527A JP5845918B2 JP 5845918 B2 JP5845918 B2 JP 5845918B2 JP 2012010527 A JP2012010527 A JP 2012010527A JP 2012010527 A JP2012010527 A JP 2012010527A JP 5845918 B2 JP5845918 B2 JP 5845918B2
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- JP
- Japan
- Prior art keywords
- polyimide
- group
- acid
- polyimide precursor
- diamine
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- 229920001721 polyimide Polymers 0.000 title description 136
- 239000004642 Polyimide Substances 0.000 title description 102
- 239000002243 precursor Substances 0.000 title description 60
- 229910052757 nitrogen Inorganic materials 0.000 claims description 17
- OWXCYPJGJLJIFL-UHFFFAOYSA-N NC1=CC=C(C(=O)NC23CC4(CC(CC(C2)C4)C3)NC(C3=CC=C(C=C3)N)=O)C=C1 Chemical compound NC1=CC=C(C(=O)NC23CC4(CC(CC(C2)C4)C3)NC(C3=CC=C(C=C3)N)=O)C=C1 OWXCYPJGJLJIFL-UHFFFAOYSA-N 0.000 claims description 4
- 239000000126 substance Substances 0.000 description 43
- 150000004985 diamines Chemical class 0.000 description 35
- 239000002904 solvent Substances 0.000 description 35
- 239000000758 substrate Substances 0.000 description 35
- 125000004432 carbon atom Chemical group C* 0.000 description 28
- 125000002723 alicyclic group Chemical group 0.000 description 25
- 239000003960 organic solvent Substances 0.000 description 24
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 21
- 238000000034 method Methods 0.000 description 21
- 239000002253 acid Substances 0.000 description 18
- 150000000000 tetracarboxylic acids Chemical class 0.000 description 18
- GTDPSWPPOUPBNX-UHFFFAOYSA-N ac1mqpva Chemical compound CC12C(=O)OC(=O)C1(C)C1(C)C2(C)C(=O)OC1=O GTDPSWPPOUPBNX-UHFFFAOYSA-N 0.000 description 17
- -1 alicyclic tetracarboxylic acid Chemical class 0.000 description 17
- 125000003118 aryl group Chemical group 0.000 description 17
- 239000010408 film Substances 0.000 description 12
- 239000000203 mixture Substances 0.000 description 12
- 238000002834 transmittance Methods 0.000 description 12
- 239000003795 chemical substances by application Substances 0.000 description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 9
- 230000015572 biosynthetic process Effects 0.000 description 9
- 238000004519 manufacturing process Methods 0.000 description 9
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 8
- 125000004430 oxygen atom Chemical group O* 0.000 description 8
- 229920005575 poly(amic acid) Polymers 0.000 description 8
- 229910052717 sulfur Inorganic materials 0.000 description 8
- 125000004434 sulfur atom Chemical group 0.000 description 8
- 238000004817 gas chromatography Methods 0.000 description 7
- 238000003786 synthesis reaction Methods 0.000 description 7
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 6
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 6
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 6
- 230000003287 optical effect Effects 0.000 description 6
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 5
- 125000001931 aliphatic group Chemical group 0.000 description 5
- 238000004458 analytical method Methods 0.000 description 5
- 150000004984 aromatic diamines Chemical class 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 5
- 238000006722 reduction reaction Methods 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- DHKHKXVYLBGOIT-UHFFFAOYSA-N 1,1-Diethoxyethane Chemical compound CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 description 4
- CYSGHNMQYZDMIA-UHFFFAOYSA-N 1,3-Dimethyl-2-imidazolidinon Chemical compound CN1CCN(C)C1=O CYSGHNMQYZDMIA-UHFFFAOYSA-N 0.000 description 4
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 4
- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Chemical compound CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 4
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 4
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- FOLJMFFBEKONJP-UHFFFAOYSA-N adamantane-1,3-diamine Chemical compound C1C(C2)CC3CC1(N)CC2(N)C3 FOLJMFFBEKONJP-UHFFFAOYSA-N 0.000 description 4
- 150000001334 alicyclic compounds Chemical class 0.000 description 4
- 125000000217 alkyl group Chemical group 0.000 description 4
- 125000005103 alkyl silyl group Chemical group 0.000 description 4
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 4
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 4
- 150000001875 compounds Chemical class 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
- 125000006159 dianhydride group Chemical group 0.000 description 4
- 150000005690 diesters Chemical class 0.000 description 4
- JBFHTYHTHYHCDJ-UHFFFAOYSA-N gamma-caprolactone Chemical compound CCC1CCC(=O)O1 JBFHTYHTHYHCDJ-UHFFFAOYSA-N 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- FFUAGWLWBBFQJT-UHFFFAOYSA-N hexamethyldisilazane Chemical compound C[Si](C)(C)N[Si](C)(C)C FFUAGWLWBBFQJT-UHFFFAOYSA-N 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 239000004973 liquid crystal related substance Substances 0.000 description 4
- RLSSMJSEOOYNOY-UHFFFAOYSA-N m-cresol Chemical compound CC1=CC=CC(O)=C1 RLSSMJSEOOYNOY-UHFFFAOYSA-N 0.000 description 4
- 239000012046 mixed solvent Substances 0.000 description 4
- IWDCLRJOBJJRNH-UHFFFAOYSA-N p-cresol Chemical compound CC1=CC=C(O)C=C1 IWDCLRJOBJJRNH-UHFFFAOYSA-N 0.000 description 4
- 238000006116 polymerization reaction Methods 0.000 description 4
- 125000006158 tetracarboxylic acid group Chemical group 0.000 description 4
- 238000012546 transfer Methods 0.000 description 4
- NGNBDVOYPDDBFK-UHFFFAOYSA-N 2-[2,4-di(pentan-2-yl)phenoxy]acetyl chloride Chemical compound CCCC(C)C1=CC=C(OCC(Cl)=O)C(C(C)CCC)=C1 NGNBDVOYPDDBFK-UHFFFAOYSA-N 0.000 description 3
- SKDHHIUENRGTHK-UHFFFAOYSA-N 4-nitrobenzoyl chloride Chemical compound [O-][N+](=O)C1=CC=C(C(Cl)=O)C=C1 SKDHHIUENRGTHK-UHFFFAOYSA-N 0.000 description 3
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical group Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- 150000001408 amides Chemical class 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 230000021615 conjugation Effects 0.000 description 3
- VKIRRGRTJUUZHS-UHFFFAOYSA-N cyclohexane-1,4-diamine Chemical compound NC1CCC(N)CC1 VKIRRGRTJUUZHS-UHFFFAOYSA-N 0.000 description 3
- 125000000524 functional group Chemical group 0.000 description 3
- 238000006358 imidation reaction Methods 0.000 description 3
- 239000011261 inert gas Substances 0.000 description 3
- 150000002828 nitro derivatives Chemical class 0.000 description 3
- 238000000746 purification Methods 0.000 description 3
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- 238000007363 ring formation reaction Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 230000004580 weight loss Effects 0.000 description 3
- NAWXUBYGYWOOIX-SFHVURJKSA-N (2s)-2-[[4-[2-(2,4-diaminoquinazolin-6-yl)ethyl]benzoyl]amino]-4-methylidenepentanedioic acid Chemical compound C1=CC2=NC(N)=NC(N)=C2C=C1CCC1=CC=C(C(=O)N[C@@H](CC(=C)C(O)=O)C(O)=O)C=C1 NAWXUBYGYWOOIX-SFHVURJKSA-N 0.000 description 2
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical compound CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 description 2
- PTTPXKJBFFKCEK-UHFFFAOYSA-N 2-Methyl-4-heptanone Chemical compound CC(C)CC(=O)CC(C)C PTTPXKJBFFKCEK-UHFFFAOYSA-N 0.000 description 2
- NQBXSWAWVZHKBZ-UHFFFAOYSA-N 2-butoxyethyl acetate Chemical compound CCCCOCCOC(C)=O NQBXSWAWVZHKBZ-UHFFFAOYSA-N 0.000 description 2
- SVONRAPFKPVNKG-UHFFFAOYSA-N 2-ethoxyethyl acetate Chemical compound CCOCCOC(C)=O SVONRAPFKPVNKG-UHFFFAOYSA-N 0.000 description 2
- GTALYBOAEVNYOZ-UHFFFAOYSA-N 3-(2,3-dicarboxycyclohexyl)cyclohexane-1,2-dicarboxylic acid Chemical compound OC(=O)C1C(C(=O)O)CCCC1C1C(C(O)=O)C(C(O)=O)CCC1 GTALYBOAEVNYOZ-UHFFFAOYSA-N 0.000 description 2
- JUZVXGMLUGCXEQ-UHFFFAOYSA-N 3-(3,4-dicarboxycyclohexyl)cyclohexane-1,2-dicarboxylic acid Chemical compound C1C(C(O)=O)C(C(=O)O)CCC1C1C(C(O)=O)C(C(O)=O)CCC1 JUZVXGMLUGCXEQ-UHFFFAOYSA-N 0.000 description 2
- HORNXRXVQWOLPJ-UHFFFAOYSA-N 3-chlorophenol Chemical compound OC1=CC=CC(Cl)=C1 HORNXRXVQWOLPJ-UHFFFAOYSA-N 0.000 description 2
- BKQWDTFZUNGWNV-UHFFFAOYSA-N 4-(3,4-dicarboxycyclohexyl)cyclohexane-1,2-dicarboxylic acid Chemical compound C1C(C(O)=O)C(C(=O)O)CCC1C1CC(C(O)=O)C(C(O)=O)CC1 BKQWDTFZUNGWNV-UHFFFAOYSA-N 0.000 description 2
- BOFVBIYTBGDQGY-UHFFFAOYSA-N 4-(4-nitrophenyl)aniline Chemical group C1=CC(N)=CC=C1C1=CC=C([N+]([O-])=O)C=C1 BOFVBIYTBGDQGY-UHFFFAOYSA-N 0.000 description 2
- MKDLPGYIWJVADV-UHFFFAOYSA-N 4-(4-nitrophenyl)benzoyl chloride Chemical compound C1=CC([N+](=O)[O-])=CC=C1C1=CC=C(C(Cl)=O)C=C1 MKDLPGYIWJVADV-UHFFFAOYSA-N 0.000 description 2
- QIKYZXDTTPVVAC-UHFFFAOYSA-N 4-Aminobenzamide Chemical compound NC(=O)C1=CC=C(N)C=C1 QIKYZXDTTPVVAC-UHFFFAOYSA-N 0.000 description 2
- KCPNTFIHOJWYFK-UHFFFAOYSA-N 4-amino-N-[4-[(4-aminobenzoyl)amino]cyclohexyl]benzamide Chemical compound NC1=CC=C(C(=O)NC2CCC(CC2)NC(C2=CC=C(C=C2)N)=O)C=C1 KCPNTFIHOJWYFK-UHFFFAOYSA-N 0.000 description 2
- WXNZTHHGJRFXKQ-UHFFFAOYSA-N 4-chlorophenol Chemical compound OC1=CC=C(Cl)C=C1 WXNZTHHGJRFXKQ-UHFFFAOYSA-N 0.000 description 2
- TYMLOMAKGOJONV-UHFFFAOYSA-N 4-nitroaniline Chemical compound NC1=CC=C([N+]([O-])=O)C=C1 TYMLOMAKGOJONV-UHFFFAOYSA-N 0.000 description 2
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 2
- ZPAKUZKMGJJMAA-UHFFFAOYSA-N Cyclohexane-1,2,4,5-tetracarboxylic acid Chemical compound OC(=O)C1CC(C(O)=O)C(C(O)=O)CC1C(O)=O ZPAKUZKMGJJMAA-UHFFFAOYSA-N 0.000 description 2
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 2
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 2
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-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
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- NQRYJNQNLNOLGT-UHFFFAOYSA-N Piperidine Chemical compound C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- LKRUZYNPJUZODM-UHFFFAOYSA-N adamantane-1,3-dicarbonyl chloride Chemical compound C1C(C2)CC3CC1(C(=O)Cl)CC2(C(Cl)=O)C3 LKRUZYNPJUZODM-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 125000003277 amino group Chemical group 0.000 description 2
- 150000008064 anhydrides Chemical class 0.000 description 2
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- 230000004888 barrier function Effects 0.000 description 2
- CJYIPJMCGHGFNN-UHFFFAOYSA-N bicyclo[2.2.1]heptane-2,3,5,6-tetracarboxylic acid Chemical compound C1C2C(C(O)=O)C(C(=O)O)C1C(C(O)=O)C2C(O)=O CJYIPJMCGHGFNN-UHFFFAOYSA-N 0.000 description 2
- XQBSPQLKNWMPMG-UHFFFAOYSA-N bicyclo[2.2.2]octane-2,3,5,6-tetracarboxylic acid Chemical compound C1CC2C(C(O)=O)C(C(=O)O)C1C(C(O)=O)C2C(O)=O XQBSPQLKNWMPMG-UHFFFAOYSA-N 0.000 description 2
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- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 239000007822 coupling agent Substances 0.000 description 2
- HXTYZWJVMWWWDK-UHFFFAOYSA-N cyclohexane-1,4-dicarbonyl chloride Chemical compound ClC(=O)C1CCC(C(Cl)=O)CC1 HXTYZWJVMWWWDK-UHFFFAOYSA-N 0.000 description 2
- 230000018044 dehydration Effects 0.000 description 2
- 238000006297 dehydration reaction Methods 0.000 description 2
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- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 description 2
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- 239000007789 gas Substances 0.000 description 2
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 2
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- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
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- 239000012535 impurity Substances 0.000 description 2
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- AWJUIBRHMBBTKR-UHFFFAOYSA-N isoquinoline Chemical compound C1=NC=CC2=CC=CC=C21 AWJUIBRHMBBTKR-UHFFFAOYSA-N 0.000 description 2
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- 239000005340 laminated glass Substances 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- CZRKJHRIILZWRC-UHFFFAOYSA-N methyl acetate;propane-1,2-diol Chemical compound COC(C)=O.CC(O)CO CZRKJHRIILZWRC-UHFFFAOYSA-N 0.000 description 2
- 239000011707 mineral Substances 0.000 description 2
- 235000010755 mineral Nutrition 0.000 description 2
- 125000002950 monocyclic group Chemical group 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- CTSLXHKWHWQRSH-UHFFFAOYSA-N oxalyl chloride Chemical compound ClC(=O)C(Cl)=O CTSLXHKWHWQRSH-UHFFFAOYSA-N 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052763 palladium Inorganic materials 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 125000003367 polycyclic group Chemical group 0.000 description 2
- 230000008569 process Effects 0.000 description 2
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- CYIDZMCFTVVTJO-UHFFFAOYSA-N pyromellitic acid Chemical compound OC(=O)C1=CC(C(O)=O)=C(C(O)=O)C=C1C(O)=O CYIDZMCFTVVTJO-UHFFFAOYSA-N 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 125000003003 spiro group Chemical group 0.000 description 2
- 238000004544 sputter deposition Methods 0.000 description 2
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 2
- 238000001308 synthesis method Methods 0.000 description 2
- 150000003505 terpenes Chemical class 0.000 description 2
- 235000007586 terpenes Nutrition 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
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Description
本発明は、高耐熱性に優れた特性を有し、さらに極めて高い透明性を併せ有するポリイミド前駆体及びポリイミドに関する。 The present invention relates to a polyimide precursor and a polyimide that have excellent heat resistance and also have extremely high transparency.
近年、高度情報化社会の到来に伴い、光通信分野の光ファイバーや光導波路等、表示装置分野の液晶配向膜やカラーフィルター用保護膜等の光学材料の開発が進んでいる。特に表示装置分野で、ガラス基板代替として軽量でフレキシブル性に優れたプラスチック基板の検討や、曲げたり丸めたりすることが可能なディスプレイの開発が盛んに行われており、その様な用途に用いることができる、より高性能の光学材料が求められている。 In recent years, with the arrival of an advanced information society, development of optical materials such as a liquid crystal alignment film and a protective film for a color filter in the display device field, such as an optical fiber and an optical waveguide in the optical communication field, is progressing. Especially in the field of display devices, we are actively investigating plastic substrates that are lightweight and have excellent flexibility as glass substrate substitutes, and developing displays that can be bent and rolled, and are used for such applications. There is a need for higher performance optical materials that can be used.
芳香族ポリイミドは、分子内共役や電荷移動錯体の形成により、本質的に黄褐色に着色する。このため着色を抑制する手段として、例えば分子内へのフッ素原子の導入、主鎖への屈曲性の付与、側鎖として嵩高い基の導入などによって、分子内共役や電荷移動錯体の形成を阻害して、透明性を発現させる方法が提案されている。また、原理的に電荷移動錯体を形成しない半脂環式または全脂環式ポリイミドを用いることにより透明性を発現させる方法も提案されている。 Aromatic polyimide is essentially yellowish brown due to intramolecular conjugation and the formation of charge transfer complexes. For this reason, as a means to suppress coloration, for example, introduction of fluorine atoms into the molecule, imparting flexibility to the main chain, introduction of bulky groups as side chains, etc. inhibits intramolecular conjugation and charge transfer complex formation. Thus, a method for expressing transparency has been proposed. In addition, a method for expressing transparency by using a semi-alicyclic or fully alicyclic polyimide that does not form a charge transfer complex in principle has been proposed.
特許文献１には、液晶ディスプレイ用基板、有機エレクトロルミネッセンスディスプレイ用基板、電子ペーパー用基板、太陽電池用基板等に利用される高透明性、高膜靭性、高ガラス転移温度、溶液加工性を持つプラスチック基板を得るために、エステル結合含有テトラカルボン酸前駆体を有するポリイミドを用いることが開示されている。
特許文献２には、液晶配向剤としてアミド結合含有化合物を用いたポリアミック酸及び／またはポリイミドが開示されている。そのポリアミック酸及び/またはポリイミドは、用いられたジアミン成分にアミド結合を有しており、酸二無水物成分は脂肪族または脂環族または芳香族を有している。
Patent Document 1 has high transparency, high film toughness, high glass transition temperature, and solution processability used for liquid crystal display substrates, organic electroluminescence display substrates, electronic paper substrates, solar cell substrates, and the like. In order to obtain a plastic substrate, it is disclosed to use a polyimide having an ester bond-containing tetracarboxylic acid precursor.
Patent Document 2 discloses a polyamic acid and / or polyimide using an amide bond-containing compound as a liquid crystal aligning agent. The polyamic acid and / or polyimide has an amide bond in the diamine component used, and the acid dianhydride component has aliphatic, alicyclic or aromatic.
ただ、特許文献１や特許文献２のポリイミドにおいては、高耐熱性及び透過率の両方の要件を満たしていない場合があり、これらの要件をすべて満たしてほしいという要望もあった。 However, in the polyimides of Patent Document 1 and Patent Document 2, there are cases where both the requirements of high heat resistance and transmittance are not satisfied, and there is a demand for satisfying all of these requirements.
本発明は、以上のような状況に鑑みてなされたものであり、テトラカルボン酸成分として脂環式テトラカルボン酸二無水物、ジアミン成分としてアミド結合及び脂環を有する芳香族ジアミンを用いた半脂環式ポリイミドにおいて、耐熱性及び透過率を改良することを目的とする。 The present invention has been made in view of the above circumstances, and is a semi-finished product using an alicyclic tetracarboxylic dianhydride as a tetracarboxylic acid component and an aromatic diamine having an amide bond and an alicyclic ring as a diamine component. The purpose of the alicyclic polyimide is to improve heat resistance and transmittance.
すなわち、本発明は、高耐熱性などの優れた特性を有し、さらに極めて高い透明性を併せ有するポリイミド前駆体及びポリイミドを提供することを目的とする。 That is, an object of the present invention is to provide a polyimide precursor and a polyimide that have excellent characteristics such as high heat resistance and also have extremely high transparency.
本発明は、以下の各項に関する。
１． 下記化学式（１）で表される繰り返し単位を含んで構成されたことを特徴とするポリイミド前駆体。
The present invention relates to the following items.
1. The polyimide precursor characterized by including the repeating unit represented by following Chemical formula (1).
２． Ａが、下記化学式（２）〜（５）からなる群から選択される２価の基であることを特徴とする前記項１に記載のポリイミド前駆体。 2. 2. The polyimide precursor according to item 1, wherein A is a divalent group selected from the group consisting of the following chemical formulas (2) to (5).
３． Ｂが、下記化学式（６）〜（９）からなる群から選択される４価の基であることを特徴とする前記項１に記載のポリイミド前駆体。 3. 2. The polyimide precursor according to item 1, wherein B is a tetravalent group selected from the group consisting of the following chemical formulas (6) to (9).
４． 前記項１〜３のいずれかに記載のポリイミド前駆体が有機溶媒中に均一に溶解していることを特徴とするポリイミド前駆体溶液組成物。 4). 4. The polyimide precursor solution composition, wherein the polyimide precursor according to any one of items 1 to 3 is uniformly dissolved in an organic solvent.
５． 下記化学式（１０）で表される繰り返し単位を含んで構成されたことを特徴とするポリイミド。 5. The polyimide characterized by including the repeating unit represented by following Chemical formula (10).
６． Ａが、下記化学式（１１）〜（１４）からなる群から選択される２価の基であることを特徴とする前記項５に記載のポリイミド。 6). Item 6. The polyimide according to Item 5, wherein A is a divalent group selected from the group consisting of the following chemical formulas (11) to (14).
７． Ｂが、下記化学式（１５）〜（１８）からなる群から選択される４価の基であることを特徴とする前記項５に記載のポリイミド。 7). Item 6. The polyimide according to Item 5, wherein B is a tetravalent group selected from the group consisting of the following chemical formulas (15) to (18).
８． 前記項４に記載のポリイミド前駆体溶液組成物を用いて得られたポリイミド、又は前記項５〜７に記載のポリイミドによって形成されたことを特徴とするポリイミドフィルム。 8). Item 8. A polyimide film formed using the polyimide obtained by using the polyimide precursor solution composition according to item 4 or the polyimide according to item 5-7.
下記化学式（１９）で表される構成であることを特徴とするジアミン。 A diamine having the structure represented by the following chemical formula (19).
本発明は、高耐熱性の優れた特性を有し、さらに極めて高い透明性を併せ有するポリイミド前駆体及びポリイミドを提供することを目的とする。 An object of the present invention is to provide a polyimide precursor and a polyimide that have excellent characteristics of high heat resistance and also have extremely high transparency.
本発明のポリイミド前駆体は、前記化学式（１）で表される繰り返し単位を含んで構成されたポリイミド前駆体である。
換言すれば、本発明のポリイミド前駆体は、化学構造中に少なくとも一つの脂肪族６員環を有し芳香族環を有さない脂環式テトラカルボン酸成分と、化学構造中に二つ以上のアミド結合と一つ以上の脂環を有する芳香族ジアミン成分から得られる半脂環式ポリイミド前駆体である。
The polyimide precursor of this invention is a polyimide precursor comprised including the repeating unit represented by the said Chemical formula (1).
In other words, the polyimide precursor of the present invention includes at least one alicyclic tetracarboxylic acid component having at least one aliphatic 6-membered ring in the chemical structure and no aromatic ring, and two or more in the chemical structure. It is a semi-alicyclic polyimide precursor obtained from an aromatic diamine component having an amide bond and one or more alicyclic rings.
本発明において、ジアミン成分は、化学構造中に二つ以上のアミド結合と一つ以上の脂環を有する芳香族ジアミン成分である。
本発明のポリイミド前駆体は、ジアミン成分によってアミド結合がその化学構造中に導入される。アミド結合が導入されたポリイミド前駆体から得られるポリイミドは、アミド結合によって分子間相互作用が増大されるので、耐溶剤性などが改良されると考えられる。したがって、ジアミン成分は、化学構造中に二つ以上のアミド結合を有することが好適である。なお、ジアミン成分中のアミド結合が多過ぎると、ポリイミド前駆体の溶解性が低下することがある。また、脂環構造を有することで、分子内外での共役や電荷移動相互作用が妨げられ、透明性が高まる。
In the present invention, the diamine component is an aromatic diamine component having two or more amide bonds and one or more alicyclic rings in the chemical structure.
In the polyimide precursor of the present invention, an amide bond is introduced into the chemical structure by the diamine component. The polyimide obtained from the polyimide precursor having an amide bond introduced is considered to have improved solvent resistance and the like because the intermolecular interaction is increased by the amide bond. Therefore, the diamine component preferably has two or more amide bonds in the chemical structure. In addition, when there are too many amide bonds in a diamine component, the solubility of a polyimide precursor may fall. Further, by having an alicyclic structure, conjugation and charge transfer interaction inside and outside the molecule are hindered, and transparency is increased.
前記化学式（２）〜（５）、（１１）〜（１４）の化学構造を導入するジアミン成分は、例えば特定の反応性基を有するニトロ化合物と、特定の反応性基を有する化合物を反応した後、ニトロ基の還元によって得られる。 The diamine component that introduces the chemical structures of the chemical formulas (2) to (5) and (11) to (14) is obtained by reacting, for example, a nitro compound having a specific reactive group and a compound having a specific reactive group. Later it is obtained by reduction of the nitro group.
ｎ１〜８は１〜１０の整数を示し、好ましくは１〜５の整数である。化合物（２）、（３）、（１１）、（１２）の合成方法としては、例えばジ酸クロライド基を有する脂環化合物と、ニトロ基を有するアミン化合物を溶媒中、塩基性存在下で反応させた後、その反応生成物のニトロ基をアミノ基に還元させる方法が挙げられる。 n1-8 shows the integer of 1-10, Preferably it is an integer of 1-5. As a synthesis method of the compounds (2), (3), (11), and (12), for example, an alicyclic compound having a diacid chloride group and an amine compound having a nitro group are reacted in a solvent in the presence of basicity. And then reducing the nitro group of the reaction product to an amino group.
化合物（４）、（５）、（１３）、（１４）の合成方法としては、例えばジアミンを有する脂環化合物と、酸クロライドを有するニトロ化合物を溶媒中、塩基性存在下で反応させた後、反応生成物のニトロ基をアミノ基に還元させる方法が挙げられる。 As a synthesis method of the compounds (4), (5), (13), and (14), for example, an alicyclic compound having a diamine and a nitro compound having an acid chloride are reacted in a solvent in the presence of a basic compound. And a method of reducing the nitro group of the reaction product to an amino group.
還元には、パラジウム−炭素、白金−炭素、ラネーニッケル、ロジウム−アルミナ、鉄などを触媒とし、水素ガス、塩酸、ヒドラジンなどによって還元を行うことができる。 For the reduction, palladium-carbon, platinum-carbon, Raney nickel, rhodium-alumina, iron or the like can be used as a catalyst, and reduction can be performed with hydrogen gas, hydrochloric acid, hydrazine or the like.
還元反応に用いる溶媒としては、例えば、１，３−ジメチル−２−イミダゾリジノン、、Ｎ−メチル−ピロリドン、Ｎ，Ｎ−ジメチルホルムアミド等の原料に対する溶解性の高い溶媒が好ましいが、溶媒が原料または生成物と反応を起こさなければどんな種類の溶媒であっても問題なく使用ができるので、特にその構造には限定されない。 As a solvent used for the reduction reaction, for example, a solvent having high solubility in raw materials such as 1,3-dimethyl-2-imidazolidinone, N-methyl-pyrrolidone, N, N-dimethylformamide is preferable, Any type of solvent can be used without any problem as long as it does not react with the raw material or product, so that the structure is not particularly limited.
前記化学式（２）〜（５）、（１１）〜（１４）のＲ２、Ｒ５、Ｒ８、Ｒ１１、Ｒ１８、Ｒ２１、Ｒ２４、Ｒ２７が炭素数３−１８の脂環を有する２価の基である。脂環とは、単環、多環、スピロ環、架橋環のいずれかである。その一例として下記化学式（２０）〜（２５）からなる群から選択される２価の基が挙げられる。特に下記化学式（２０）が好ましい。 R 2 , R 5 , R 8 , R 11 , R 18 , R 21 , R 24 , and R 27 in the chemical formulas (2) to (5) and (11) to (14) are an alicyclic ring having 3 to 18 carbon atoms. Is a divalent group. An alicyclic ring is any of a monocyclic ring, a polycyclic ring, a spiro ring, and a bridged ring. One example thereof is a divalent group selected from the group consisting of the following chemical formulas (20) to (25). In particular, the following chemical formula (20) is preferable.
前記化学式（２）〜（５）、（１１）〜（１４）のＲ１、Ｒ３、Ｒ４、Ｒ６、Ｒ７、Ｒ９、Ｒ１０、Ｒ１２、Ｒ１７、Ｒ１９、Ｒ２０、Ｒ２２、Ｒ２３、Ｒ２５、Ｒ２６、Ｒ２８が、下記化学式（２６）〜（２９）からなる群から選択される２価の基のいずれかである。 R < 1 >, R < 3 >, R < 4 >, R < 6 >, R < 7 >, R < 9 >, R < 10 >, R < 12 >, R <17> , R <19> , R < 20 > in the chemical formulas (2) to (5) and (11) to (14). , R 22 , R 23 , R 25 , R 26 , R 28 are any of divalent groups selected from the group consisting of the following chemical formulas (26) to (29).
ジ酸クロライドを有する脂環式化合物としては、例えば１，２−シクロプロパンジカルボン酸ジクロライド、１，２−シクロブタンジカルボン酸ジクロライド、１，３−シクロブタンジカルボン酸ジクロライド、１，２−シクロペンタンジカルボン酸ジクロライド、１，３−シクロペンタンジカルボン酸ジクロライド、１，２−シクロヘキサンジカルボン酸ジクロライド、１，３−シクロヘキサンジカルボン酸ジクロライド、１，４−シクロヘキサンジカルボン酸ジクロライド、１，４−（２−ノルボルネン）ジカルボン酸ジクロライド、１，４−ビシクロ［２．２．２］オクタンジカルボン酸ジクロライド、４，４’−スピロビシクロヘキサンジカルボン酸ジクロライド、１，３−アダマンタンジカルボン酸ジクロライドなどの脂環式ジカルボン酸ジクロライドが挙げられる。これらのうち、１，４−シクロヘキサンジカルボン酸ジクロライド、１，３−アダマンタンジカルボン酸ジクロライドが好ましい。 Examples of the alicyclic compound having diacid chloride include 1,2-cyclopropanedicarboxylic acid dichloride, 1,2-cyclobutanedicarboxylic acid dichloride, 1,3-cyclobutanedicarboxylic acid dichloride, and 1,2-cyclopentanedicarboxylic acid dichloride. 1,3-cyclopentanedicarboxylic acid dichloride, 1,2-cyclohexanedicarboxylic acid dichloride, 1,3-cyclohexanedicarboxylic acid dichloride, 1,4-cyclohexanedicarboxylic acid dichloride, 1,4- (2-norbornene) dicarboxylic acid dichloride 1,4-bicyclo [2.2.2] octane dicarboxylic acid dichloride, 4,4′-spirobicyclohexane dicarboxylic acid dichloride, 1,3-adamantane dicarboxylic acid dichloride, etc. Bonn acid dichloride and the like. Of these, 1,4-cyclohexanedicarboxylic acid dichloride and 1,3-adamantanedicarboxylic acid dichloride are preferred.
ニトロ基を有するアミノ化合物としては、ｏ−ニトロアニリン、ｍ−ニトロアニリン、ｐ−ニトロアニリン、４−アミノ−４’−ニトロビフェニル、３−アミノ−４’−ニトロビフェニル、４−アミノ−３’−ニトロビフェニル、１−アミノ−４−ニトロナフタレン、１−アミノ−５−ニトロナフタレンなどが挙げられる。これらのうちｐ−ニトロアニリン、４−アミノ−４’−ニトロビフェニルが好ましい。 Examples of amino compounds having a nitro group include o-nitroaniline, m-nitroaniline, p-nitroaniline, 4-amino-4'-nitrobiphenyl, 3-amino-4'-nitrobiphenyl, 4-amino-3 '. -Nitrobiphenyl, 1-amino-4-nitronaphthalene, 1-amino-5-nitronaphthalene and the like. Of these, p-nitroaniline and 4-amino-4'-nitrobiphenyl are preferred.
ジアミンを有する脂環式化合物としては、例えば１，２−ジアミノシクロプロパン、１，２−ジアミノシクロブタン、１，３−ジアミノシクロブタン、１，２−ジアミノシクロペンタン、１，３−ジアミノシクロペンタン、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、１，４−ジアミノ（２−ノルボルネン）、１，４−ジアミノビシクロ［２．２．２］オクタン、４，４’−ジアミノスピロビシクロヘキサン、１，３−ジアミノアダマンタンなどの脂環式ジアミンが挙げられる。これらのうち、１，４−ジアミノシクロヘキサン、１，３−ジアミノアダマンタンが好ましい。 Examples of the alicyclic compound having a diamine include 1,2-diaminocyclopropane, 1,2-diaminocyclobutane, 1,3-diaminocyclobutane, 1,2-diaminocyclopentane, 1,3-diaminocyclopentane, 1 , 2-diaminocyclohexane, 1,3-diaminocyclohexane, 1,4-diaminocyclohexane, 1,4-diamino (2-norbornene), 1,4-diaminobicyclo [2.2.2] octane, 4,4 ′ -Cycloaliphatic diamines such as diaminospirobicyclohexane and 1,3-diaminoadamantane. Of these, 1,4-diaminocyclohexane and 1,3-diaminoadamantane are preferred.
酸クロライドを有するニトロ化合物としては、２−ニトロベンゾイルクロライド、３−ニトロベンゾイルクロライド、４−ニトロベンゾイルクロライド、４’−ニトロ−１，１’−ビフェニル−４−カルボン酸クロライド、３’−ニトロ−１，１’−ビフェニル−４−カルボン酸クロライド、４’−ニトロ−１，１’−ビフェニル−３−カルボン酸クロライド、４−ニトロ−１−ナフタレンカルボン酸クロライド、５−ニトロ−１−ナフタレンカルボン酸クロライド、などが挙げられる。これらのうち４−ニトロベンゾイルクロライド、４’−ニトロ−１，１’−ビフェニル−４−カルボン酸クロライドが好ましい。 Nitro compounds having acid chloride include 2-nitrobenzoyl chloride, 3-nitrobenzoyl chloride, 4-nitrobenzoyl chloride, 4′-nitro-1,1′-biphenyl-4-carboxylic acid chloride, 3′-nitro- 1,1′-biphenyl-4-carboxylic acid chloride, 4′-nitro-1,1′-biphenyl-3-carboxylic acid chloride, 4-nitro-1-naphthalenecarboxylic acid chloride, 5-nitro-1-naphthalenecarboxylic acid And acid chloride. Of these, 4-nitrobenzoyl chloride and 4'-nitro-1,1'-biphenyl-4-carboxylic acid chloride are preferred.
本発明のジアミン成分は、前記化学式（２０）〜（２５）の脂環と前記化学式（２６）〜（２９）の芳香族における組合わせによるものである。このため、ジアミン成分としては、例えば、Ｎ，Ｎ’−（１，４−ビシクロ［２．２．２］オクタンジイル）ビス（４−アミノベンズアミド）、Ｎ，Ｎ’−（１，４−ビシクロ［２．２．１］ヘプタンジイル）ビス（４−アミノベンズアミド）、Ｎ，Ｎ’−（１，３−アダマンタンジイル）ビス（４−アミノベンズアミド）、Ｎ，Ｎ’−（１，４−シクロヘキサンジイル）ビス（４−アミノベンズアミド）、Ｎ，Ｎ’−ビス（４−アミノフェニル）−１，４−シクロヘキサンジカルボアミド、Ｎ，Ｎ’−ビス（４−アミノフェニル）−１，４−ビシクロ［２．２．２］オクタンジカルボアミド、Ｎ，Ｎ’−ビス（４−アミノフェニル）−１，４−ビシクロ［２．２．１］ヘプタンジカルボアミド、Ｎ，Ｎ’−ビス（４−アミノフェニル）−１，３−アダマンタンジカルボアミドなどが挙げられる。これらのうちＮ，Ｎ’−（１，３−アダマンタンジイル）ビス（４−アミノベンズアミド）、Ｎ，Ｎ’−（１，４−シクロヘキサンジイル）ビス（４−アミノベンズアミド）が好ましい。 The diamine component of the present invention is based on a combination of the alicycles of the chemical formulas (20) to (25) and the aromatics of the chemical formulas (26) to (29). For this reason, examples of the diamine component include N, N ′-(1,4-bicyclo [2.2.2] octanediyl) bis (4-aminobenzamide), N, N ′-(1,4-bicyclo). [2.2.1] Heptanediyl) bis (4-aminobenzamide), N, N ′-(1,3-adamantanediyl) bis (4-aminobenzamide), N, N ′-(1,4-cyclohexanediyl) ) Bis (4-aminobenzamide), N, N′-bis (4-aminophenyl) -1,4-cyclohexanedicarboxamide, N, N′-bis (4-aminophenyl) -1,4-bicyclo [ 2.2.2] Octanedicarboxamide, N, N′-bis (4-aminophenyl) -1,4-bicyclo [2.2.1] heptanedicarboxamide, N, N′-bis (4- Aminophenyl) -1 Such as 3-adamantane dicarboxamide amides. Of these, N, N ′-(1,3-adamantanediyl) bis (4-aminobenzamide) and N, N ′-(1,4-cyclohexanediyl) bis (4-aminobenzamide) are preferable.
本発明のジアミン成分は、複数組み合わせて使用することもでき、また一般的にポリイミドで使用される他のジアミン成分を本発明のポリイミドの特性が発現できる範囲で少量（好ましくは３０モル％未満、より好ましくは１０モル％未満）併用することもできる。 A plurality of the diamine components of the present invention can be used in combination, and other diamine components generally used in polyimide are in a small amount (preferably less than 30 mol%, within a range where the characteristics of the polyimide of the present invention can be expressed). More preferably, it can be used in combination.
本発明において、テトラカルボン酸成分は、化学構造中に少なくとも一つの脂肪族６員環を有し芳香族環を有さない脂環式テトラカルボン酸成分であり、従って６員環は複数であってよく、複数の６員環が二つ以上の共通の炭素原子によって構成されていても構わない。また、６員環は環を構成する（６員環の内部の）炭素原子同士が化学結合によって更に環を形成した架橋環型であっても構わない。
テトラカルボン酸成分は、非対称性ではなく、対称性が高い６員環構造を有するものが、高分子鎖の密なパッキングが可能となり、ポリイミドの耐溶剤性、耐熱性、機械強度に優れるため好ましい。さらに、テトラカルボン酸成分は、複数の６員環が二つ以上の共通の炭素原子によって構成された多脂環型、及び６員環が環を構成する炭素原子同士が化学結合によって更に環を形成した架橋環型であることが、ポリイミドの良好な耐熱性、耐溶剤性、低線膨張性を達成し易いのでより好ましい。
In the present invention, the tetracarboxylic acid component is an alicyclic tetracarboxylic acid component having at least one aliphatic 6-membered ring and no aromatic ring in the chemical structure, and therefore there are a plurality of 6-membered rings. A plurality of 6-membered rings may be composed of two or more common carbon atoms. Further, the 6-membered ring may be a bridged ring type in which carbon atoms constituting the ring (inside the 6-membered ring) further form a ring by a chemical bond.
A tetracarboxylic acid component having a six-membered ring structure that is not asymmetrical and highly symmetric is preferable because it enables high-density packing of polymer chains and is excellent in solvent resistance, heat resistance, and mechanical strength of polyimide. . Furthermore, the tetracarboxylic acid component is a polyalicyclic type in which a plurality of 6-membered rings are constituted by two or more common carbon atoms, and the carbon atoms in which the 6-membered rings form a ring further form a ring by a chemical bond. The formed crosslinked ring type is more preferable because good heat resistance, solvent resistance, and low linear expansion property of polyimide can be easily achieved.
前記化学式（６）、（７）、（１５）、（１６）の化学構造を導入するテトラカルボン酸成分としては、例えばシクロヘキサン−１，２，４，５−テトラカルボン酸、[１，１’−ビ（シクロヘキサン）]−３，３’，４，４’−テトラカルボン酸、[１，１’−ビ（シクロヘキサン）]−２，３，３’，４’−テトラカルボン酸、[１，１’−ビ（シクロヘキサン）]−２，２’，３，３’−テトラカルボン酸、４，４’−メチレンビス（シクロヘキサン−１，２−ジカルボン酸）、４，４’−（プロパン−２，２−ジイル）ビス（シクロヘキサン−１，２−ジカルボン酸）、４，４’−オキシビス（シクロヘキサン−１，２−ジカルボン酸）、４，４’−チオビス（シクロヘキサン−１，２−ジカルボン酸）、４，４’−スルホニルビス（シクロヘキサン−１，２−ジカルボン酸）、４，４’−（ジメチルシランジイル）ビス（シクロヘキサン−１，２−ジカルボン酸）、４，４’−（テトラフルオロプロパン−２，２−ジイル）ビス（シクロヘキサン−１，２−ジカルボン酸）等の誘導体やこれらの酸二無水物が挙げられる。これらのうちでは、シクロヘキサン−１，２，４，５−テトラカルボン酸、[１，１’−ビ（シクロヘキサン）]−３，３’，４，４’−テトラカルボン酸、[１，１’−ビ（シクロヘキサン）]−２，３，３’，４’−テトラカルボン酸、[１，１’−ビ（シクロヘキサン）]−２，２’，３，３’−テトラカルボン酸の誘導体やこれらの酸二無水物が好ましい。
これらのテトラカルボン酸成分は、特に限定されないが、分離精製等をおこない特定の立体異性体の比率を８０％以上、より好ましくは９０％以上、特に好ましくは９５％以上にすることで、ポリイミドの耐熱性や耐溶剤性が優れる。また、そのテトラカルボン酸成分の特定の立体異性体としては、１Ｒ，２Ｓ，４Ｓ，５Ｒ−シクロヘキサンテトラカルボン酸（以下ＰＭＴＡ−ＨＳと略すことがあり、更にその酸二無水物をＰＭＤＡ−ＨＳと略すことがある。）、１Ｓ，２Ｓ，４Ｒ，５Ｒ−シクロヘキサンテトラカルボン酸（以下ＰＭＴＡ−ＨＨと略すことがあり、更にその酸二無水物をＰＭＤＡ−ＨＨと略すことがある。）、（1Ｒ，１’Ｓ，３Ｒ，３’Ｓ，４Ｒ，４’Ｓ）ジシクロヘキシル−３，３’，４，４’−テトラカルボン酸（以下ｔｒａｎｓ−ＤＣＴＡと略すことがあり、更にその酸二無水物をｔｒａｎｓ−ＤＣＤＡと略すことがある。）、（1Ｒ，１’Ｓ，３Ｒ，３’Ｓ，４Ｓ，４’Ｒ）ジシクロヘキシル−３，３’，４，４’−テトラカルボン酸（以下ｃｉｓ−ＤＣＴＡと略すことがあり、更にその酸二無水物をｃｉｓ−ＤＣＤＡと略すことがある。）が好ましく、ＰＭＴＡ−ＨＳ、ｔｒａｎｓ−ＤＣＴＡ、ｃｉｓ−ＤＣＴＡは、酸二無水物とした場合の反応性に優れるため、より好ましい。
Examples of the tetracarboxylic acid component into which the chemical structures of the chemical formulas (6), (7), (15), and (16) are introduced include cyclohexane-1,2,4,5-tetracarboxylic acid, [1,1 ′ -Bi (cyclohexane)]-3,3 ', 4,4'-tetracarboxylic acid, [1,1'-bi (cyclohexane)]-2,3,3', 4'-tetracarboxylic acid, [1, 1′-bi (cyclohexane)]-2,2 ′, 3,3′-tetracarboxylic acid, 4,4′-methylenebis (cyclohexane-1,2-dicarboxylic acid), 4,4 ′-(propane-2, 2-diyl) bis (cyclohexane-1,2-dicarboxylic acid), 4,4′-oxybis (cyclohexane-1,2-dicarboxylic acid), 4,4′-thiobis (cyclohexane-1,2-dicarboxylic acid), 4,4′-sulfonylbis (cyclohexane-1,2- Carboxylic acid), 4,4 ′-(dimethylsilanediyl) bis (cyclohexane-1,2-dicarboxylic acid), 4,4 ′-(tetrafluoropropane-2,2-diyl) bis (cyclohexane-1,2- And derivatives thereof such as dicarboxylic acids) and acid dianhydrides thereof. Among these, cyclohexane-1,2,4,5-tetracarboxylic acid, [1,1′-bi (cyclohexane)]-3,3 ′, 4,4′-tetracarboxylic acid, [1,1 ′ -Bi (cyclohexane)]-2,3,3 ', 4'-tetracarboxylic acid, [1,1'-bi (cyclohexane)]-2,2', 3,3'-tetracarboxylic acid derivatives and these The acid dianhydride is preferred.
Although these tetracarboxylic acid components are not particularly limited, the ratio of specific stereoisomers is 80% or more, more preferably 90% or more, and particularly preferably 95% or more by performing separation and purification. Excellent heat resistance and solvent resistance. The specific stereoisomer of the tetracarboxylic acid component is 1R, 2S, 4S, 5R-cyclohexanetetracarboxylic acid (hereinafter abbreviated as PMTA-HS, and the acid dianhydride is further referred to as PMDA-HS. 1S, 2S, 4R, 5R-cyclohexanetetracarboxylic acid (hereinafter may be abbreviated as PMTA-HH, and the acid dianhydride may be abbreviated as PMDA-HH), (1R , 1 ′S, 3R, 3 ′S, 4R, 4 ′S) dicyclohexyl-3,3 ′, 4,4′-tetracarboxylic acid (hereinafter sometimes abbreviated as trans-DCTA). trans-DCDA may be abbreviated.), (1R, 1 ′S, 3R, 3 ′S, 4S, 4′R) dicyclohexyl-3,3 ′, 4,4′-tetracarboxylic acid (hereinafter cis-DCTA) And abbreviation In some cases, the acid dianhydride may be abbreviated as cis-DCDA.) PMTA-HS, trans-DCTA, and cis-DCTA are excellent in reactivity when acid dianhydride is used. More preferable.
前記化学式（８）、（９）、（１７）、（１８）の化学構造を導入する多脂環型や架橋環型のテトラカルボン酸成分としては、例えばオクタヒドロペンタレン−１，３，４，６−テトラカルボン酸、ビシクロ[２．２．１]ヘプタン−２，３，５，６−テトラカルボン酸、６−（カルボキシメチル）ビシクロ[２．２．１]ヘプタン−２，３，５−トリカルボン酸、ビシクロ[２．２．２]オクタン−２，３，５，６−テトラカルボン酸、ビシクロ[２．２．２]オクタ−５−エン−２，３，７，８−テトラカルボン酸、トリシクロ[４．２．２．０２，５]デカン−３，４，７，８−テトラカルボン酸、トリシクロ[４．２．２．０２，５]デカ−７−エン−３，４，９，１０−テトラカルボン酸、９−オキサトリシクロ[４．２．１．０２，５]ノナン−３，４，７，８−テトラカルボン酸、デカヒドロ−１，４：５，８−ジメタノナフタレン−２，３，６，７−テトラカルボン酸等の誘導体やこれらの酸二無水物が挙げられる。これらのうちでは、ビシクロ[２．２．１]ヘプタン−２，３，５，６−テトラカルボン酸、ビシクロ[２．２．２]オクタン−２，３，５，６−テトラカルボン酸、デカヒドロ−１，４：５，８−ジメタノナフタレン−２，３，６，７−テトラカルボン酸等の誘導体やこれらの酸二無水物が、製造方法が容易であり、得られるポリイミドの耐熱性に優れることから、より好ましい。
これらのテトラカルボン酸成分は、特に限定されないが、分離精製等をおこない特定の立体異性体の比率を８０％以上、より好ましくは９０％以上、特に好ましくは９５％以上にすることで、ポリイミドの耐熱性や耐溶剤性が優れる。また、そのテトラカルボン酸成分の特定の立体異性体としては、
１ｒＣ７−ビシクロ［２．２．２］オクタン−２ｔ，３ｔ，５ｃ，６ｃ−テトラカルボン酸−２，３：５，６−二無水物（以下ｃｉｓ／ｔｒａｎｓ−ＢＴＴＡ−Ｈと略すことがあり、更にその酸二無水物をｃｉｓ／ｔｒａｎｓ−ＢＴＡ−Ｈと略すことがある。）
１ｒＣ７−ビシクロ［２．２．２］オクタン−２ｃ，３ｃ，５ｃ，６ｃ−テトラカルボン酸−２，３：５，６−二無水物（以下ｃｉｓ／ｃｉｓ−ＢＴＴＡ−Ｈと略すことがあり、更にその酸二無水物をｃｉｓ／ｃｉｓ−ＢＴＡ−Ｈと略すことがある。）
（４ａｒＨ，８ａｃＨ）−デカヒドロ−１ｔ，４ｔ：５ｃ，８ｃ−ジメタノナフタレン−２ｔ，３ｔ，６ｃ，７ｃ−テトラカルボン酸（以下ＤＮＴＡｘｘと略すことがあり、更にその酸二無水物をＤＮＤＡｘｘと略すことがある。）
（４ａｒＨ，８ａｃＨ）−デカヒドロ−１ｔ，４ｔ：５ｃ，８ｃ−ジメタノナフタレン−２ｃ，３ｃ，６ｃ，７ｃ−テトラカルボン酸（以下ＤＮＴＡｄｘと略すことがあり、更にその酸二無水物をＤＮＤＡｄｘと略すことがある。）
が好ましく、ＤＮＤＡｘｘ、ＤＮＤＡｄｘは、ジアミンとの反応性に優れるため、より好ましい。
Examples of the polyalicyclic or cross-linked tetracarboxylic acid component that introduces the chemical structures of the chemical formulas (8), (9), (17), and (18) include, for example, octahydropentalene-1,3,4. , 6-tetracarboxylic acid, bicyclo [2.2.1] heptane-2,3,5,6-tetracarboxylic acid, 6- (carboxymethyl) bicyclo [2.2.1] heptane-2,3,5 -Tricarboxylic acid, bicyclo [2.2.2] octane-2,3,5,6-tetracarboxylic acid, bicyclo [2.2.2] oct-5-ene-2,3,7,8-tetracarboxylic Acid, tricyclo [4.2.2.02,5] decane-3,4,7,8-tetracarboxylic acid, tricyclo [4.2.2.02,5] dec-7-ene-3,4 9,10-tetracarboxylic acid, 9-oxatricyclo [4.2.1.02,5] nonane-3 4,7,8- tetracarboxylic acid, decahydro-1,4: 5,8-dimethanol naphthalene 2,3,6,7 derivatives and their acid dianhydrides such as tetracarboxylic acid. Among these, bicyclo [2.2.1] heptane-2,3,5,6-tetracarboxylic acid, bicyclo [2.2.2] octane-2,3,5,6-tetracarboxylic acid, decahydro -1,4: 5,8-dimethanonaphthalene-2,3,6,7-tetracarboxylic acid and the like and their acid dianhydrides are easy to produce and the heat resistance of the resulting polyimide It is more preferable because it is excellent.
Although these tetracarboxylic acid components are not particularly limited, the ratio of specific stereoisomers is 80% or more, more preferably 90% or more, and particularly preferably 95% or more by performing separation and purification. Excellent heat resistance and solvent resistance. Moreover, as a specific stereoisomer of the tetracarboxylic acid component,
1rC7-bicyclo [2.2.2] octane-2t, 3t, 5c, 6c-tetracarboxylic acid-2,3: 5,6-dianhydride (hereinafter sometimes abbreviated as cis / trans-BTTA-H, Further, the acid dianhydride may be abbreviated as cis / trans-BTA-H.)
1rC7-bicyclo [2.2.2] octane-2c, 3c, 5c, 6c-tetracarboxylic acid-2,3: 5,6-dianhydride (hereinafter sometimes abbreviated as cis / cis-BTTA-H, Further, the acid dianhydride may be abbreviated as cis / cis-BTA-H.)
(4arH, 8acH) -decahydro-1t, 4t: 5c, 8c-dimethanonaphthalene-2t, 3t, 6c, 7c-tetracarboxylic acid (hereinafter sometimes abbreviated as DNTAxx, and the acid dianhydride is further abbreviated as DNDAxx. Sometimes.)
(4arH, 8acH) -decahydro-1t, 4t: 5c, 8c-dimethanonaphthalene-2c, 3c, 6c, 7c-tetracarboxylic acid (hereinafter sometimes abbreviated as DNTAdx, and the acid dianhydride is further abbreviated as DNDAdx) Sometimes.)
Are preferred, and DNDAxx and DNDAdx are more preferred because of their excellent reactivity with diamines.
テトラカルボン酸成分は、前記のようなテトラカルボン酸成分を、単独でもよく、また複数種を組み合わせて使用することもできる。また、一般的にポリイミドで使用される他の芳香族または脂肪族テトラカルボン酸成分を本発明のポリイミドの特性が発現できる範囲内で少量（好ましくは３０モル％未満、より好ましくは１０モル％未満）併用することもできる。例えば、本発明で使用することができる他の芳香族または脂肪族テトラカルボン酸成分としては、２，２−ビス（３，４−ジカルボキシフェニル）ヘキサフルオロプロパン、４−（２，５−ジオキソテトラヒドロフラン−３−イル）−１，２，３，４−テトラヒドロナフタレン−１，２−ジカルボン酸、ピロメリット酸、ベンゾフェノンテトラカルボン酸、ビフェニルテトラカルボン酸、オキシジフタル酸、ビスカルボキシフェニルジメチルシラン、ビスジカルボキシフェノキシジフェニルスルフィド、スルホニルジフタル酸、シクロブタンテトラカルボン酸、イソプロピリデンジフェノキシビスフタル酸とこれらの酸二無水物が挙げられる。 The tetracarboxylic acid component may be a single tetracarboxylic acid component as described above, or may be used in combination of two or more. In addition, other aromatic or aliphatic tetracarboxylic acid components generally used in polyimide are in a small amount (preferably less than 30 mol%, more preferably less than 10 mol%) within the range in which the characteristics of the polyimide of the present invention can be expressed. ) Can be used together. For example, other aromatic or aliphatic tetracarboxylic acid components that can be used in the present invention include 2,2-bis (3,4-dicarboxyphenyl) hexafluoropropane, 4- (2,5-dioxy). Oxotetrahydrofuran-3-yl) -1,2,3,4-tetrahydronaphthalene-1,2-dicarboxylic acid, pyromellitic acid, benzophenonetetracarboxylic acid, biphenyltetracarboxylic acid, oxydiphthalic acid, biscarboxyphenyldimethylsilane, bis Examples include dicarboxyphenoxydiphenyl sulfide, sulfonyldiphthalic acid, cyclobutanetetracarboxylic acid, isopropylidenediphenoxybisphthalic acid, and acid dianhydrides thereof.
本発明のポリイミド前駆体は、前記化学式（１）のＸ１、Ｘ２はそれぞれ独立に水素、炭素数１〜３のアルキル基、炭素数３〜９のアルキルシリル基のいずれかである。Ｘ１、Ｘ２は、後述する製造方法によって、その官能基の種類及び、官能基の導入率を変化させることができる。製造方法が容易であることから、Ｘ１、Ｘ２は水素であることが好ましい。また、ポリイミド前駆体の保存安定性に優れることから、Ｘ１、Ｘ２は炭素数１〜３のアルキル基が好ましく、メチル基もしくはエチル基であることがより好ましい。更にポリイミドの熱線膨張係数が小さくなることから、Ｘ１、Ｘ２は炭素数３〜９のアルキルシリル基が好ましく、トリメチルシリル基もしくはｔ−ブチルジメチルシリル基であることがより好ましい。官能基の導入率は、特に限定されないが、アルキル基もしくはアルキルシリル基を導入する場合、Ｘ１、Ｘ２はそれぞれ、２５％以上、好ましくは５０％以上、より好ましくは７５％以上である。 In the polyimide precursor of the present invention, X 1 and X 2 in the chemical formula (1) are each independently hydrogen, an alkyl group having 1 to 3 carbon atoms, or an alkylsilyl group having 3 to 9 carbon atoms. X 1 and X 2 can change the type of the functional group and the introduction rate of the functional group by a production method described later. X 1 and X 2 are preferably hydrogen because the production method is easy. Further, because of excellent storage stability of the polyimide precursor, X 1, X 2 is preferably an alkyl group having 1 to 3 carbon atoms, and more preferably a methyl group or an ethyl group. Furthermore, since the linear thermal expansion coefficient of polyimide becomes small, X 1 and X 2 are preferably an alkylsilyl group having 3 to 9 carbon atoms, and more preferably a trimethylsilyl group or a t-butyldimethylsilyl group. The introduction rate of the functional group is not particularly limited, but when an alkyl group or an alkylsilyl group is introduced, X 1 and X 2 are each 25% or more, preferably 50% or more, more preferably 75% or more.
本発明のポリイミド前駆体は、Ｘ１及びＸ２が取る化学構造に従って、１）ポリアミド酸、２）ポリアミド酸エステル、３）ポリアミド酸シリルエステルに化学構造として分類することができる。そして前記分類ごとに、以下の製造方法により容易に製造することができる。ただし、本発明のポリイミド前駆体の製造方法は、以下の製造方法に限定されるわけではない。 The polyimide precursor of the present invention can be classified as a chemical structure into 1) polyamic acid, 2) polyamic acid ester, and 3) polyamic acid silyl ester according to the chemical structure taken by X 1 and X 2 . And it can manufacture easily with the following manufacturing methods for every said classification. However, the manufacturing method of the polyimide precursor of this invention is not necessarily limited to the following manufacturing methods.
１）ポリアミド酸
有機溶剤にジアミンを溶解し、この溶液に攪拌しながら、テトラカルボン酸二無水物を徐々に添加し、０〜１２０℃好ましくは５〜８０℃の範囲で１〜７２時間攪拌することで、ポリイミド前駆体が得られる。８０℃以上で反応させる場合、分子量が重合時の温度履歴に依存して変動し、また熱によりイミド化が進行することから、ポリイミド前駆体を安定して製造できなくなる可能性がある。
また、テトラカルボン酸成分とジアミン成分のモル比がジアミン成分過剰である場合、必要に応じて、ジアミン成分の過剰モル数に略相当する量のカルボン酸誘導体を添加し、テトラカルボン酸成分とジアミン成分のモル比を略当量に近づけることができる。ここでのカルボン酸誘導体としては、実質的にポリイミド前駆体溶液の粘度を増加させない、つまり実質的に分子鎖延長に関与しないテトラカルボン酸、もしくは末端停止剤として機能するトリカルボン酸とその無水物、ジカルボン酸とその無水物などが好適である。
1) Polyamic acid A diamine is dissolved in an organic solvent, and tetracarboxylic dianhydride is gradually added to this solution while stirring, followed by stirring at 0 to 120 ° C, preferably 5 to 80 ° C for 1 to 72 hours. Thereby, a polyimide precursor is obtained. When the reaction is carried out at 80 ° C. or higher, the molecular weight varies depending on the temperature history at the time of polymerization, and imidization proceeds due to heat, so there is a possibility that the polyimide precursor cannot be produced stably.
Moreover, when the molar ratio of the tetracarboxylic acid component and the diamine component is an excess of the diamine component, if necessary, an amount of a carboxylic acid derivative substantially corresponding to the excess mole number of the diamine component is added, and the tetracarboxylic acid component and the diamine are added. The molar ratio of the components can be approximated to the equivalent. As the carboxylic acid derivative herein, a tetracarboxylic acid that does not substantially increase the viscosity of the polyimide precursor solution, that is, substantially does not participate in molecular chain extension, or a tricarboxylic acid that functions as a terminal terminator and its anhydride, Dicarboxylic acid and its anhydride are preferred.
２）ポリアミド酸エステル
テトラカルボン酸二無水物を任意のアルコールで反応させ、ジエステルジカルボン酸を得た後、塩素化試薬（チオニルクロライド、オキサリルクロライドなど）と反応させ、ジエステルジカルボン酸クロライドを得る。このジエステルジカルボン酸クロライドとジアミンを−２０〜１２０℃好ましくは−５〜８０℃の範囲で１〜７２時間攪拌することで、ポリイミド前駆体が得られる。８０℃以上で反応させる場合、分子量が重合時の温度履歴に依存して変動し、また熱によりイミド化が進行することから、ポリイミド前駆体を安定して製造できなくなる可能性がある。また、ジエステルジカルボン酸とジアミンを、リン系縮合剤や、カルボジイミド縮合剤などを用いて脱水縮合することでも、簡便にポリイミド前駆体が得られる。この方法で得られるポリイミド前駆体は、安定なため、水やアルコールなどの溶剤を加え再沈殿などの精製をおこなうこともできる。
2) Polyamic acid ester After reacting tetracarboxylic dianhydride with an arbitrary alcohol to obtain a diester dicarboxylic acid, it is reacted with a chlorinating reagent (thionyl chloride, oxalyl chloride, etc.) to obtain a diester dicarboxylic acid chloride. A polyimide precursor is obtained by stirring the diester dicarboxylic acid chloride and the diamine at -20 to 120 ° C, preferably -5 to 80 ° C for 1 to 72 hours. When the reaction is carried out at 80 ° C. or higher, the molecular weight varies depending on the temperature history at the time of polymerization, and imidization proceeds due to heat, so there is a possibility that the polyimide precursor cannot be produced stably. Alternatively, a polyimide precursor can be easily obtained by dehydrating and condensing diester dicarboxylic acid and diamine using a phosphorus condensing agent or a carbodiimide condensing agent. Since the polyimide precursor obtained by this method is stable, it can also be purified by reprecipitation by adding a solvent such as water or alcohol.
３）ポリアミド酸シリルエステル
あらかじめ、ジアミンとシリル化剤を反応させ、シリル化されたジアミンを得（必要に応じて、蒸留等によりシリル化されたジアミンの精製をおこなう。）、脱水された溶剤中にシリル化されたジアミンを溶解させておき、攪拌しながら、テトラカルボン酸二無水物を徐々に添加し、０〜１２０℃好ましくは５〜８０℃の範囲で１〜７２時間攪拌することで、ポリイミド前駆体が得られる。８０℃以上で反応させる場合、分子量が重合時の温度履歴に依存して変動し、また熱によりイミド化が進行することから、ポリイミド前駆体を安定して製造できなくなる可能性がある。ここで用いるシリル化剤として、塩素を含有しないシリル化剤を用いることは、シリル化されたジアミンを精製する必要がないため、好適である。塩素原子を含まないシリル化剤としては、Ｎ,Ｏ-ビス（トリメチルシリル）トリフルオロアセトアミド、Ｎ,Ｏ-ビス（トリメチルシリル）アセトアミド、ヘキサメチルジシラザンが挙げられる。フッ素原子を含まず低コストであることから、Ｎ,Ｏ-ビス（トリメチルシリル）アセトアミド、ヘキサメチルジシラザンが好ましい。また、ジアミンのシリル化反応には、反応を促進するために、ピリジン、ピペリジン、トリエチルアミンなどのアミン系触媒を用いることができる。この触媒はポリイミド前駆体の重合触媒として、そのまま使用することができる。
3) Polyamic acid silyl ester A diamine and a silylating agent are reacted in advance to obtain a silylated diamine (if necessary, purification of the silylated diamine by distillation or the like), and in a dehydrated solvent In the solution, the silylated diamine is dissolved, and while stirring, tetracarboxylic dianhydride is gradually added, and the mixture is stirred at 0 to 120 ° C., preferably 5 to 80 ° C. for 1 to 72 hours, A polyimide precursor is obtained. When the reaction is carried out at 80 ° C. or higher, the molecular weight varies depending on the temperature history at the time of polymerization, and imidization proceeds due to heat, so there is a possibility that the polyimide precursor cannot be produced stably. As the silylating agent used here, it is preferable to use a silylating agent not containing chlorine because it is not necessary to purify the silylated diamine. Examples of the silylating agent not containing a chlorine atom include N, O-bis (trimethylsilyl) trifluoroacetamide, N, O-bis (trimethylsilyl) acetamide, and hexamethyldisilazane. N, O-bis (trimethylsilyl) acetamide and hexamethyldisilazane are preferred because they do not contain fluorine atoms and are low in cost. In addition, amine-based catalysts such as pyridine, piperidine and triethylamine can be used in the silylation reaction of diamine in order to accelerate the reaction. This catalyst can be used as it is as a polymerization catalyst for the polyimide precursor.
また、前記製造方法は、いずれも有機溶媒中で好適に行なうことができるので、その結果として、本発明のポリイミド前駆体溶液組成物を容易に得ることができる。 Moreover, since all the said manufacturing methods can be performed suitably in an organic solvent, as a result, the polyimide precursor solution composition of this invention can be obtained easily.
ポリイミド前駆体を調製する際に使用する溶媒は、例えばＮ，Ｎ−ジメチルホルムアミド、Ｎ，Ｎ−ジメチルアセトアミド、Ｎ−メチル−２−ピロリドン、ジメチルスルホオキシド等の非プロトン性溶媒が好ましいが、原料モノマー成分と生成するポリイミド前駆体が溶解すれば、どんな種類の溶媒であっても問題なく使用できるので、特にその構造には限定されない。Ｎ，Ｎ−ジメチルホルムアミド、Ｎ，Ｎ−ジメチルアセトアミド、Ｎ−メチルピロリドン等のアミド溶媒、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、α−メチル−γ−ブチロラクトン等の環状エステル溶媒、エチレンカーボネート、プロピレンカーボネート等のカーボネート溶媒、トリエチレングリコール等のグリコール系溶媒、ｍ−クレゾール、ｐ−クレゾール、３−クロロフェノール、４−クロロフェノール等のフェノール系溶媒、アセトフェノン、１，３−ジメチル−２−イミダゾリジノン、スルホラン、ジメチルスルホキシドなどが好ましく採用される。さらに、その他の一般的な有機溶剤、即ちフェノール、０−クレゾール、酢酸ブチル、酢酸エチル、酢酸イソブチル、プロピレングリコールメチルアセテート、エチルセロソルブ、プチルセロソルブ、２−メチルセロソルブアセテート、エチルセロソルブアセテート、ブチルセロソルブアセテート、テトラヒドロフラン、ジメトキシエタン、ジエトキシエタン、ジブチルエーテル、ジエチレングリコールジメチルエーテル、メチルイソブチルケトン、ジイソブチルケトン、シクロペンタノン、シクロへキサノン、メチルエチルケトン、アセトン、ブタノール、エタノール、キシレン、トルエン、クロルベンゼン、ターペン、ミネラルスピリット、石油ナフサ系溶媒なども使用できる。 The solvent used in preparing the polyimide precursor is preferably an aprotic solvent such as N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, dimethyl sulfoxide, etc. If the monomer component and the polyimide precursor to be produced are dissolved, any type of solvent can be used without any problem, and the structure is not particularly limited. Amide solvents such as N, N-dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone, γ-butyrolactone, γ-valerolactone, δ-valerolactone, γ-caprolactone, ε-caprolactone, α-methyl-γ -Cyclic ester solvents such as butyrolactone, carbonate solvents such as ethylene carbonate and propylene carbonate, glycol solvents such as triethylene glycol, phenol solvents such as m-cresol, p-cresol, 3-chlorophenol, 4-chlorophenol, Acetophenone, 1,3-dimethyl-2-imidazolidinone, sulfolane, dimethyl sulfoxide and the like are preferably employed. In addition, other common organic solvents such as phenol, 0-cresol, butyl acetate, ethyl acetate, isobutyl acetate, propylene glycol methyl acetate, ethyl cellosolve, ptyl cellosolve, 2-methyl cellosolve acetate, ethyl cellosolve acetate, butyl cellosolve acetate, Tetrahydrofuran, dimethoxyethane, diethoxyethane, dibutyl ether, diethylene glycol dimethyl ether, methyl isobutyl ketone, diisobutyl ketone, cyclopentanone, cyclohexanone, methyl ethyl ketone, acetone, butanol, ethanol, xylene, toluene, chlorobenzene, terpene, mineral spirit, Petroleum naphtha solvents can also be used.
ポリイミド前駆体を調製する際に使用する溶媒及び、後記のポリイミド前駆体溶液組成物に用いる溶媒（以降、これらを併せて使用される有機溶剤と記すことがある。）は、下記の純度に関わる特性、即ち、（ａ）光透過率、（ｂ）加熱還流処理後の光透過率、（ｃ）ガスクロマトグラフィー分析による純度、（ｄ）ガスクロマトグラフィー分析による不純物ピークの割合、（ｅ）不揮発成分の量、および（ｆ）金属成分の含有率からなる特性の少なくとも１つに関して、下に規定される条件を満たすことが好ましく、通常、より多くの条件を満たすことがより好ましい。 The solvent used in preparing the polyimide precursor and the solvent used in the polyimide precursor solution composition described below (hereinafter, sometimes referred to as an organic solvent used in combination) are related to the following purity. Characteristics, ie, (a) light transmittance, (b) light transmittance after heat reflux treatment, (c) purity by gas chromatography analysis, (d) impurity peak ratio by gas chromatography analysis, (e) non-volatile It is preferable to satisfy the conditions defined below with respect to at least one of the component amount and (f) the metal component content, and it is usually more preferable to satisfy more conditions.
（ａ）使用される有機溶剤として、光路長１ｃｍ、４００ｎｍにおける光透過率が８９％以上、より好ましくは９０％以上、特に好ましくは９１％以上である有機溶剤
（ｂ）使用される有機溶剤として、窒素中で３時間加熱還流した後の光路長１ｃｍ、４００ｎｍにおける光透過率が２０％以上、より好ましくは４０％以上、特に好ましくは８０％以上である有機溶剤
（ｃ）使用される有機溶剤として、ガスクロマトグラフィー分析より求められた純度が９９．８％以上、より好ましくは９９．９％以上、さらに好ましくは９９．９９％以上である有機溶剤
（ｄ）使用される有機溶剤として、ガスクロマトグラフィー分析で求められる主成分ピークの保持時間に対し、長時間側に現れる不純物ピークの総量が、０．２％未満、より好ましくは０．１％以下であり、特に好ましくは０．０５％以下である有機溶剤
（ｅ）使用される有機溶剤の２５０℃での不揮発成分が０．１％以下、より好ましくは０．０５％以下がより好ましく、特に好ましくは０．０１％以下であること
（ｆ）使用される有機溶剤の金属成分（例えば、Ｌｉ，Ｎａ，Ｍｇ，Ｃａ，Ａｌ，Ｋ，Ｃａ，Ｔｉ，Ｃｒ，Ｍｎ，Ｆｅ，Ｃｏ，Ｎｉ，Ｃｕ，Ｚｎ，Ｍｏ，Ｃｄ）の含有率が、１０ｐｐｍ以下が好ましく、１ｐｐｍ以下がより好ましく、特に５００ｐｐｂ以下、より特に好ましくは３００ｐｐｂ以下であること
(A) As an organic solvent to be used, an organic solvent having a light transmittance of 89% or more, more preferably 90% or more, particularly preferably 91% or more at an optical path length of 1 cm and 400 nm. (B) As an organic solvent to be used An organic solvent having an optical path length of 1 cm after refluxing in nitrogen for 3 hours and a light transmittance at 400 nm of 20% or more, more preferably 40% or more, and particularly preferably 80% or more. (C) Organic solvent used An organic solvent having a purity determined by gas chromatography analysis of 99.8% or more, more preferably 99.9% or more, and even more preferably 99.99% or more (d) The total amount of impurity peaks appearing on the long side with respect to the retention time of the main component peak obtained by chromatography analysis is less than 0.2%, more preferably Organic solvent that is 0.1% or less, and particularly preferably 0.05% or less (e) The non-volatile component at 250 ° C. of the organic solvent used is 0.1% or less, more preferably 0.05% or less (F) Metal component of the organic solvent used (for example, Li, Na, Mg, Ca, Al, K, Ca, Ti, Cr, Mn, Fe) , Co, Ni, Cu, Zn, Mo, Cd) is preferably 10 ppm or less, more preferably 1 ppm or less, particularly 500 ppb or less, and particularly preferably 300 ppb or less.
また、これらの特性における条件は、使用される有機溶剤の総和に基づくものである。即ち、使用される有機溶剤は、１種類に限らず、２種類以上であってもよい。使用される有機溶剤が２種類以上とは、特定の工程において混合溶剤が使用される場合と、例えば重合溶媒と添加剤の希釈溶剤が異なる場合のように工程により異なる溶剤を使用する場合のどちらも意味する。使用される有機溶剤が２種類以上のときは（以下、混合溶剤という）、混合溶剤全体に対して純度に関わる各特性の条件が適用され、複数の工程で有機溶剤が使用される場合には、最終的にワニス中に含まれることになる全ての有機溶剤を混合した混合溶剤に対して、純度に関わる各特性の条件が適用される。実際に有機溶剤を混合して、各特性を測定してもよいし、個別の有機溶剤について特性を求め、計算により混合物全体の特性を求めてもよい。例えば、純度１００％の溶剤Ａを７０部、純度９０％の溶剤Ｂを３０部使用したとき、使用される有機溶剤の純度は、９７％と計算される。 Moreover, the conditions in these characteristics are based on the sum total of the organic solvent used. That is, the organic solvent used is not limited to one type and may be two or more types. Two or more types of organic solvents are used when a mixed solvent is used in a specific process or when a different solvent is used depending on the process, for example, when a polymerization solvent and a diluent solvent for an additive are different. Also means. When two or more types of organic solvents are used (hereinafter referred to as mixed solvents), the conditions of each characteristic relating to purity are applied to the entire mixed solvent, and when organic solvents are used in multiple steps The condition of each characteristic relating to purity is applied to a mixed solvent in which all organic solvents to be finally contained in the varnish are mixed. Each characteristic may be measured by actually mixing an organic solvent, or the characteristics of each organic solvent may be obtained, and the characteristics of the entire mixture may be obtained by calculation. For example, when 70 parts of solvent A having a purity of 100% and 30 parts of solvent B having a purity of 90% are used, the purity of the organic solvent used is calculated to be 97%.
本発明のポリイミド前駆体溶液組成物に用いる溶媒としては、ポリイミド前駆体が溶解すれば問題はなく、特にその構造は限定されない。Ｎ，Ｎ−ジメチルホルムアミド、Ｎ，Ｎ−ジメチルアセトアミド、Ｎ−メチルピロリドン等のアミド溶媒、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、α−メチル−γ−ブチロラクトン等の環状エステル溶媒、エチレンカーボネート、プロピレンカーボネート等のカーボネート溶媒、トリエチレングリコール等のグリコール系溶媒、ｍ−クレゾール、ｐ−クレゾール、３−クロロフェノール、４−クロロフェノール等のフェノール系溶媒、アセトフェノン、１，３−ジメチル−２−イミダゾリジノン、スルホラン、ジメチルスルホキシドなどが好ましく採用される。さらに、その他の一般的な有機溶剤、即ちフェノール、０−クレゾール、酢酸ブチル、酢酸エチル、酢酸イソブチル、プロピレングリコールメチルアセテート、エチルセロソルブ、プチルセロソルブ、２−メチルセロソルブアセテート、エチルセロソルブアセテート、ブチルセロソルブアセテート、テトラヒドロフラン、ジメトキシエタン、ジエトキシエタン、ジブチルエーテル、ジエチレングリコールジメチルエーテル、メチルイソブチルケトン、ジイソブチルケトン、シクロペンタノン、シクロへキサノン、メチルエチルケトン、アセトン、ブタノール、エタノール、キシレン、トルエン、クロルベンゼン、ターペン、ミネラルスピリット、石油ナフサ系溶媒なども使用できる。また、これらを複数組み合わせて使用できる。 The solvent used in the polyimide precursor solution composition of the present invention is not a problem as long as the polyimide precursor is dissolved, and the structure is not particularly limited. Amide solvents such as N, N-dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone, γ-butyrolactone, γ-valerolactone, δ-valerolactone, γ-caprolactone, ε-caprolactone, α-methyl-γ -Cyclic ester solvents such as butyrolactone, carbonate solvents such as ethylene carbonate and propylene carbonate, glycol solvents such as triethylene glycol, phenol solvents such as m-cresol, p-cresol, 3-chlorophenol, 4-chlorophenol, Acetophenone, 1,3-dimethyl-2-imidazolidinone, sulfolane, dimethyl sulfoxide and the like are preferably employed. In addition, other common organic solvents such as phenol, 0-cresol, butyl acetate, ethyl acetate, isobutyl acetate, propylene glycol methyl acetate, ethyl cellosolve, ptyl cellosolve, 2-methyl cellosolve acetate, ethyl cellosolve acetate, butyl cellosolve acetate, Tetrahydrofuran, dimethoxyethane, diethoxyethane, dibutyl ether, diethylene glycol dimethyl ether, methyl isobutyl ketone, diisobutyl ketone, cyclopentanone, cyclohexanone, methyl ethyl ketone, acetone, butanol, ethanol, xylene, toluene, chlorobenzene, terpene, mineral spirit, Petroleum naphtha solvents can also be used. A combination of these can be used.
本発明のポリイミド前駆体溶液組成物は、必要に応じて、化学イミド化剤（無水酢酸などの酸無水物や、ピリジン、イソキノリンなどのアミン化合物）、酸化防止剤、フィラー、染料、顔料、シランカップリング剤などのカップリング剤、プライマー、難燃材、消泡剤、レベリング剤、レオロジーコントロール剤（流動補助剤）、剥離剤などを添加することができる。 The polyimide precursor solution composition of the present invention may contain chemical imidizing agents (acid anhydrides such as acetic anhydride, amine compounds such as pyridine and isoquinoline), antioxidants, fillers, dyes, pigments, silanes as necessary. Coupling agents such as coupling agents, primers, flame retardants, antifoaming agents, leveling agents, rheology control agents (flow aids), release agents and the like can be added.
本発明のポリイミドは、前記化学式（１０）で表される繰り返し単位を含んで構成されたことを特徴とするが、本発明のポリイミド前駆体を脱水閉環反応（イミド化反応）することで好適に製造することができる。イミド化の方法は特に限定されず、公知の熱イミド化、化学イミド化の方法を好適に適用することができる。得られるポリイミドの形態は、フィルム、ポリイミドフィルムと他の基材との積層体、コーティング膜、粉末、ビーズ、成型体、発泡体およびワニスなどを好適に挙げることができる。 The polyimide of the present invention is characterized by including a repeating unit represented by the chemical formula (10), and is suitably obtained by subjecting the polyimide precursor of the present invention to a dehydration ring-closing reaction (imidation reaction). Can be manufactured. The imidization method is not particularly limited, and known thermal imidization and chemical imidization methods can be suitably applied. As for the form of the polyimide to be obtained, a film, a laminate of the polyimide film and another substrate, a coating film, powder, beads, a molded body, a foam, a varnish, and the like can be preferably exemplified.
本発明のポリイミドは、膜厚１０μｍのフィルムにしたとき、４００ｎｍにおける光透過率が６５％以上、好ましくは７０％以上、より好ましくは７５％以上であり、特に好ましくは８０％以上であり、優れた透明性を有する。 When the polyimide of the present invention is a film having a thickness of 10 μm, the light transmittance at 400 nm is 65% or more, preferably 70% or more, more preferably 75% or more, and particularly preferably 80% or more. It has high transparency.
さらに、本発明のポリイミドは、フィルムにしたときの５％重量減少の温度が４２０℃以上、好ましくは４５０℃以上、より好ましくは４７７℃以上であり、優れた耐熱性を有する。 Further, the polyimide of the present invention has a 5% weight loss temperature of 420 ° C. or higher, preferably 450 ° C. or higher, more preferably 477 ° C. or higher when formed into a film, and has excellent heat resistance.
なお、本発明のポリイミドからなるフィルムは、用途にもよるが、フィルムの厚みとしては、好ましくは１μｍ〜２５０μｍ程度、さらに好ましくは１μｍ〜１５０μｍ程度である。 In addition, although the film which consists of a polyimide of this invention is based also on a use, Preferably it is about 1 micrometer-250 micrometers as a film thickness, More preferably, it is about 1 micrometer-150 micrometers.
本発明のポリイミドは、高耐熱性の優れた特性を有し、さらに極めて高い透明性を併せ有することから、ディスプレイ用透明基板、タッチパネル用透明基板、或いは太陽電池用基板の用途において、好適に用いることができる。 The polyimide of the present invention has excellent properties such as high heat resistance, and also has extremely high transparency. Therefore, the polyimide of the present invention is suitably used in applications for transparent substrates for displays, transparent substrates for touch panels, or substrates for solar cells. be able to.
以下では、本発明のポリイミド前駆体を用いた、ポリイミドフィルム／基材積層体、もしくはポリイミドフィルムの製造方法の一例について述べる。ただし、以下の方法に限定されるものではない。
例えばセラミック（ガラス、シリコン、アルミナ）、金属（銅、アルミニウム、ステンレス）、耐熱プラスチックフィルム（ポリイミド）などの基材に、本発明のポリイミド前駆体溶液組成物を流延し、真空中、窒素等の不活性ガス中、或いは空気中で、熱風もしくは赤外線を用いて、２０〜１８０℃、好ましくは２０〜１５０℃の温度範囲で乾燥する。次いで得られたポリイミド前駆体フィルムを基材上で、もしくはポリイミド前駆体フィルムを基材上から剥離し、そのフィルムの端部を固定した状態で、真空中、窒素等の不活性ガス中、或いは空気中で、熱風もしくは赤外線を用い、２００〜５００℃、より好ましくは２５０〜４５０℃程度の温度で加熱イミド化することでポリイミドフィルム／基材積層体、もしくはポリイミドフィルムを製造することができる。なお、得られるポリイミドフィルムが酸化劣化するのを防ぐため、加熱イミド化は、真空中、或いは不活性ガス中で行うことが望ましい。加熱イミド化の温度が高すぎなければ空気中で行なっても差し支えない。ここでのポリイミドフィルム（ポリイミドフィルム／基材積層体の場合は、ポリイミドフィルム層）の厚さは、以後の工程の搬送性のため、好ましくは１〜２５０μｍ、より好ましくは１〜１５０μｍである。
Below, an example of the manufacturing method of a polyimide film / base material laminated body or a polyimide film using the polyimide precursor of this invention is described. However, it is not limited to the following method.
For example, the polyimide precursor solution composition of the present invention is cast on a base material such as ceramic (glass, silicon, alumina), metal (copper, aluminum, stainless steel), heat-resistant plastic film (polyimide), nitrogen, etc. In an inert gas or in the air, using hot air or infrared rays, and drying in a temperature range of 20 to 180 ° C, preferably 20 to 150 ° C. Next, the obtained polyimide precursor film is peeled off from the substrate, or the polyimide precursor film is peeled off from the substrate, and the end of the film is fixed, in vacuum, in an inert gas such as nitrogen, or A polyimide film / substrate laminate or a polyimide film can be produced by hot imidization in air using hot air or infrared rays at a temperature of about 200 to 500 ° C., more preferably about 250 to 450 ° C. In order to prevent the resulting polyimide film from being oxidized and deteriorated, it is desirable to carry out the heating imidization in a vacuum or in an inert gas. If the temperature of the heating imidization is not too high, it may be performed in air. The thickness of the polyimide film here (in the case of a polyimide film / substrate laminate) is preferably 1 to 250 μm, more preferably 1 to 150 μm, for transportability in the subsequent steps.
またポリイミド前駆体のイミド化反応は、前記のような加熱処理による加熱イミド化に代えて、ポリイミド前駆体をピリジンやトリエチルアミン等の３級アミン存在下、無水酢酸等の脱水環化試薬を含有する溶液に浸漬するなどの化学的処理によって行うことも可能である。また、これらの脱水環化試薬をあらかじめ、ポリイミド前駆体溶液組成物中に投入・攪拌し、それを基材上に流延・乾燥することで、部分的にイミド化したポリイミド前駆体を作製することもでき、これを更に前記のような加熱処理することで、ポリイミドフィルム／基材積層体、もしくはポリイミドフィルムを得ることができる。 Further, the imidation reaction of the polyimide precursor contains a dehydration cyclization reagent such as acetic anhydride in the presence of a tertiary amine such as pyridine or triethylamine instead of the heating imidation by the heat treatment as described above. It is also possible to carry out by chemical treatment such as immersion in a solution. Also, a partially imidized polyimide precursor is prepared by previously charging and stirring these dehydrating cyclization reagents in a polyimide precursor solution composition, and casting and drying them on a substrate. In addition, a polyimide film / substrate laminate or a polyimide film can be obtained by further heat-treating this as described above.
この様にして得られたポリイミドフィルム／基材積層体、もしくはポリイミドフィルムは、その片面もしくは両面に導電性層を形成することによって、フレキシブルな導電性基板を得ることができる。 The polyimide film / base laminate or the polyimide film thus obtained can be used to form a flexible conductive substrate by forming a conductive layer on one side or both sides thereof.
フレキシブルな導電性基板は、例えば次の方法によって得ることができる。すなわち、第一の方法としては、ポリイミドフィルム／基材積層体を基材からポリイミドフィルムを剥離せずに、そのポリイミドフィルム表面に、スパッタ蒸着、印刷などによって、導電性物質（金属もしくは金属酸化物、導電性有機物、導電性炭素など）の導電層を形成させ、導電性層／ポリイミドフィルム／基材の導電性積層体を製造する。その後必要に応じて、基材より電気導電層／ポリイミドフィルム積層体を剥離することによって、導電性層／ポリイミドフィルム積層体からなる透明でフレキシブルな導電性基板を得ることができる。
第二の方法としては、ポリイミドフィルム／基材積層体の基材からポリイミドフィルムを剥離して、ポリイミドフィルムを得、そのポリイミドフィルム表面に、導電性物質（金属もしくは金属酸化物、導電性有機物、導電性炭素など）の導電層を、第一の方法と同様にして形成させ、導電性層／ポリイミドフィルム積層体からなる透明でフレキシブルな導電性基板を得ることができる。
なお、第一、第二の方法において、必要に応じて、ポリイミドフィルムの表面に導電層を形成する前に、スパッタ蒸着やゲル−ゾル法などによって、水蒸気、酸素などのガスバリヤ層、光調整層などの無機層を形成しても構わない。
また、導電層は、フォトリソグラフィ法や各種印刷法、インクジェット法などの方法によって、回路が好適に形成される。
A flexible conductive substrate can be obtained, for example, by the following method. That is, as a first method, a conductive material (metal or metal oxide) is formed on the polyimide film surface by sputtering deposition, printing or the like without peeling the polyimide film / substrate laminate from the substrate. , Conductive organic material, conductive carbon, etc.) are formed to produce a conductive layer / polyimide film / substrate laminate. Thereafter, if necessary, a transparent and flexible conductive substrate composed of the conductive layer / polyimide film laminate can be obtained by peeling the electric conductive layer / polyimide film laminate from the base material.
As a second method, the polyimide film is peeled off from the substrate of the polyimide film / substrate laminate to obtain a polyimide film, and a conductive substance (metal or metal oxide, conductive organic substance, A conductive layer of conductive carbon or the like can be formed in the same manner as in the first method, and a transparent and flexible conductive substrate comprising a conductive layer / polyimide film laminate can be obtained.
In the first and second methods, if necessary, before forming a conductive layer on the surface of the polyimide film, a gas barrier layer such as water vapor or oxygen, a light adjusting layer, etc. by sputtering deposition or gel-sol method. An inorganic layer such as may be formed.
The conductive layer is preferably formed with a circuit by a photolithography method, various printing methods, an inkjet method, or the like.
本発明の基板は、本発明のポリイミドによって構成されたポリイミドフィルムの表面に、必要に応じてガスバリヤ層や無機層を介し、導電層の回路を有するものである。この基板は、フレキシブルであり、透明性、折り曲げ性、耐熱性が優れ、さらに極めて低い熱線膨張係数や耐溶剤性を併せ有するので微細な回路の形成が容易である。したがって、この基板は、ディスプレイ用、タッチパネル用、または太陽電池用の基板として好適に用いることができる。
すなわち、この基板に、蒸着、各種印刷法、或いはインクジェット法などによって、さらにトランジスタ（無機トランジスタ、有機トランジスタ）が形成されてフレキシブル薄膜トランジスタが製造され、そして、表示デバイス用の液晶素子、ＥＬ素子、光電素子として好適に用いられる。
The board | substrate of this invention has a circuit of a conductive layer on the surface of the polyimide film comprised by the polyimide of this invention through a gas barrier layer and an inorganic layer as needed. This substrate is flexible, excellent in transparency, bendability, and heat resistance, and has an extremely low coefficient of thermal expansion and solvent resistance, so that a fine circuit can be easily formed. Therefore, this board | substrate can be used suitably as a board | substrate for displays, a touch panel, or a solar cell.
That is, a transistor (inorganic transistor, organic transistor) is further formed on this substrate by vapor deposition, various printing methods, an ink jet method or the like to manufacture a flexible thin film transistor, and a liquid crystal element, an EL element, a photoelectric transistor for a display device are manufactured. It is suitably used as an element.
以下、実施例及び比較例によって本発明を更に説明する。尚、本発明は以下の実施例に限定されるものではない。 Hereinafter, the present invention will be further described with reference to Examples and Comparative Examples. In addition, this invention is not limited to a following example.
以下の各例において評価は次の方法で行った。 In each of the following examples, the evaluation was performed by the following method.
ポリイミドフィルムの評価
[光透過率]
大塚電子製ＭＣＰＤ−３００を用いて、膜厚１０μｍのポリイミド膜の４００ｎｍにおける光透過率を測定した。
[５％重量減少温度]
膜厚１０μｍのポリイミドフィルムを試験片とし、エスアイアイ・ナノテクノロジー製 熱量計測定装置（Ｑ−５０００）を用い、窒素気流中、昇温速度１０℃／ｍｉｎで２５℃から６００℃まで昇温した。得られた重量曲線から、５％重量減少温度を求めた。
Evaluation of polyimide film
[Light transmittance]
The light transmittance at 400 nm of a 10 μm-thick polyimide film was measured using MCPD-300 manufactured by Otsuka Electronics.
[5% weight loss temperature]
A polyimide film having a thickness of 10 μm was used as a test piece, and the temperature was increased from 25 ° C. to 600 ° C. at a temperature increase rate of 10 ° C./min in a nitrogen stream using a calorimeter measuring device (Q-5000) manufactured by SII Nanotechnology. . From the obtained weight curve, a 5% weight loss temperature was determined.
以下の各例で使用した原材料の略称、純度は、次のとおりである。
ＮＡＡＢＡ: Ｎ，Ｎ’−（１，３−アダマンタンジイル）ビス（４−アミノベンズアミド）純度 ９９．３％（ＬＣ分析）
ＮＣＨＡＢＡ: Ｎ，Ｎ’−（１，４−シクロヘキサンジイル）ビス（４−アミノベンズアミド）純度 ９９．２％（ＬＣ分析）
４−ＡＰＴＰ: Ｎ，Ｎ’−ビス（４−アミノフェニル）テレフタルアミド 純度 ９９．９５％（ＧＣ分析）
ＰＭＤＡ−ＨＳ： １Ｒ，２Ｓ，４Ｓ，５Ｒ−シクロヘキサンテトラカルボン酸二無水物 純度 ９２．７％（ＧＣ分析），水素化ピロメリット酸二無水物としての純度９９．９％（ＧＣ分析）
ＢＴＡ−Ｈ： 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 純度 ９９．９％（ＧＣ分析）
ＤＮＤＡｘｘ：（４ａｒＨ，８ａｃＨ）−デカヒドロ-１ｔ,４ｔ：５ｃ，８ｃ−ジメタノナフタレン−２ｔ，３ｔ，６ｃ，７ｃ−テトラカルボン酸二無水物 純度 ９９．２％（ＮＭＲ分析）
The abbreviations and purity of the raw materials used in the following examples are as follows.
NAABA: N, N ′-(1,3-adamantanediyl) bis (4-aminobenzamide) purity 99.3% (LC analysis)
NCHABA: N, N ′-(1,4-cyclohexanediyl) bis (4-aminobenzamide) purity 99.2% (LC analysis)
4-APTP: N, N′-bis (4-aminophenyl) terephthalamide Purity 99.95% (GC analysis)
PMDA-HS: 1R, 2S, 4S, 5R-cyclohexanetetracarboxylic dianhydride purity 92.7% (GC analysis), purity 99.9% as hydrogenated pyromellitic dianhydride (GC analysis)
BTA-H: Bicyclo [2.2.2] octane-2,3: 5,6-tetracarboxylic dianhydride purity 99.9% (GC analysis)
DNDAxx: (4arH, 8acH) -decahydro-1t, 4t: 5c, 8c-dimethananaphthalene-2t, 3t, 6c, 7c-tetracarboxylic dianhydride purity 99.2% (NMR analysis)
〔合成例１〕
ｐ−ニトロ安息香酸クロリド１６．１ｇとピリジン１０．３ｇをジメチルホルムアミド８０ｇに溶解させた後、１，３−ジアミノアダマンタン７．２ｇとＮ，Ｎ−ジメチルホルムアミド２０ｇを徐々に滴下し、２５℃で５時間反応させた。続いて、反応液を炭酸水素ナトリウム溶液で３回洗浄した後、溶媒を除去した。その後、クロロホルムとＮ，Ｎ−ジメチルホルムアミドより再結晶を行い、淡黄色結晶のジニトロ化合物を得た。
[Synthesis Example 1]
After dissolving 16.1 g of p-nitrobenzoic acid chloride and 10.3 g of pyridine in 80 g of dimethylformamide, 7.2 g of 1,3-diaminoadamantane and 20 g of N, N-dimethylformamide are gradually added dropwise at 25 ° C. The reaction was allowed for 5 hours. Subsequently, the reaction solution was washed three times with a sodium hydrogen carbonate solution, and then the solvent was removed. Thereafter, recrystallization was performed from chloroform and N, N-dimethylformamide to obtain dinitro compounds as pale yellow crystals.
〔合成例２〕
合成例１で得られたジニトロ化合物４ｇと１０％Ｐｄ／Ｃ４００ｍｇを１，３−ジメチル−２−イミダゾリジノン２５ｇに溶解させた後、水素を吹き込み３ＭＰａの圧をかけた。次いで、７０℃で７時間反応を行い、室温まで冷却した後、圧抜きを行った。その後、セライトろ過により１０％Ｐｄ／Ｃを除去した後、超純水もしくは貧溶媒を加え、ＮＡＡＢＡを得た。（収率８２％、純度９９．３％）
[Synthesis Example 2]
After dissolving 4 g of the dinitro compound obtained in Synthesis Example 1 and 400 mg of 10% Pd / C in 25 g of 1,3-dimethyl-2-imidazolidinone, hydrogen was blown in and a pressure of 3 MPa was applied. Next, the reaction was performed at 70 ° C. for 7 hours, and after cooling to room temperature, depressurization was performed. Thereafter, 10% Pd / C was removed by Celite filtration, and then ultrapure water or a poor solvent was added to obtain NAABA. (Yield 82%, purity 99.3%)
〔合成例３〕
合成例１において、１，３−ジアミノアダマンタンの代わりに１，４−ジアミノシクロヘキサンを用いた以外は、合成例１と同様にしてジニトロ体を得、合成例２と同様の還元反応を行い、ＮＣＨＡＢＡを得た。
[Synthesis Example 3]
A dinitro compound was obtained in the same manner as in Synthesis Example 1 except that 1,4-diaminocyclohexane was used in place of 1,3-diaminoadamantane in Synthesis Example 1, and a reduction reaction similar to Synthesis Example 2 was performed. Got.
表１に実施例、比較例で使用したテトラカルボン酸成分、ジアミン成分の構造式を記す。 Table 1 shows the structural formulas of the tetracarboxylic acid component and the diamine component used in Examples and Comparative Examples.
〔実施例１〕
窒素ガスで置換した反応容器中にＮＡＡＢＡ０．６０ｇ（１．５ミリモル）を入れ、モレキュラーシーブを用いて脱水したＮ，Ｎ−ジメチルアセトアミドを、仕込みモノマー総質量（ジアミン成分とカルボン酸成分の総和）が２０質量％となる量を加え、２５℃で２時間攪拌した。
この溶液にＢＴＡ−Ｈ ０．３７ｇ（１．５ミリモル）を徐々に加えた。８０℃で６時間撹拌し、均一で粘稠なポリイミド前駆体溶液を得た。
[Example 1]
In a reaction vessel substituted with nitrogen gas, 0.60 g (1.5 mmol) of NAABA was put, and N, N-dimethylacetamide dehydrated using molecular sieve was charged, and the total mass of monomers (total of diamine component and carboxylic acid component) Was added in an amount of 20% by mass and stirred at 25 ° C. for 2 hours.
To this solution, 0.37 g (1.5 mmol) of BTA-H was gradually added. The mixture was stirred at 80 ° C. for 6 hours to obtain a uniform and viscous polyimide precursor solution.
ＰＴＦＥ製メンブレンフィルターでろ過したポリイミド前駆体溶液をガラス基板に塗布し、窒素雰囲気下（酸素濃度２００ｐｐｍ以下）そのままガラス基板上で１２０℃で１時間、１５０℃で３０分間、２００℃で３０分間、３５０℃まで昇温して５分間、加熱して熱的にイミド化を行い、無色透明なポリイミドフィルム／ガラス積層体を得た。次いで、得られたポリイミドフィルム／ガラス積層体を水に浸漬した後剥離し、膜厚が１０μｍのポリイミドフィルムを得た。
このポリイミドフィルムの特性を測定した結果を表２に示す。
A polyimide precursor solution filtered through a PTFE membrane filter was applied to a glass substrate, and the nitrogen atmosphere (oxygen concentration of 200 ppm or less) was maintained as it was on a glass substrate at 120 ° C. for 1 hour, 150 ° C. for 30 minutes, 200 ° C. for 30 minutes, The temperature was raised to 350 ° C. and heated for 5 minutes to thermally imidize to obtain a colorless and transparent polyimide film / glass laminate. Next, the obtained polyimide film / glass laminate was immersed in water and then peeled to obtain a polyimide film having a thickness of 10 μm.
The results of measuring the properties of this polyimide film are shown in Table 2.
〔実施例２〜４、比較例１、２〕
ジアミン成分、カルボン酸成分を表２に記載した化学組成とし、実施例１と同様にして、ポリイミド前駆体溶液、ポリイミドフィルムを得た。
このポリイミドフィルムの特性を測定した結果を表２に示す。
[Examples 2 to 4, Comparative Examples 1 and 2]
The diamine component and the carboxylic acid component were set to the chemical compositions described in Table 2, and a polyimide precursor solution and a polyimide film were obtained in the same manner as in Example 1.
The results of measuring the properties of this polyimide film are shown in Table 2.
表２に示した結果から、本発明のアミド結合及び脂環を有するジアミンを用いたポリイミド前駆体から得られたポリイミドは、芳香環のジアミンを用いたポリイミド前駆体から得られたポリイミドより高い透過率を示すことが分かる。また、芳香環は脂環より耐熱性が高いことが知られているが、本発明の脂環を有するジアミンを用いたポリイミド前駆体から得られたポリイミドにおいては、芳香環のジアミンを用いたポリイミド前駆体から得られたポリイミドと同等の耐熱性を示すことが分かる。
さらに、実施例２、４のジアミン成分の比較から、アダマンタン骨格のジアミンを用いたポリイミド前駆体から得られたポリイミドは、シクロヘキサン骨格のジアミンを用いたポリイミド前駆体から得られたポリイミドよりも高耐熱性、高透過率を示すことが分かる。
前記のとおり、本発明のポリイミド前駆体から得られたポリイミドは、優れた光透過性を有すると伴に、高耐熱性を有しており、本発明のポリイミドフィルムは、ディスプレイ用途などの無色透明で微細な回路形成可能な透明基板として好適に用いることができる。
From the results shown in Table 2, the polyimide obtained from the polyimide precursor using the diamine having an amide bond and an alicyclic ring of the present invention has a higher transmission than the polyimide obtained from the polyimide precursor using the aromatic diamine. It can be seen that the rate is shown. In addition, the aromatic ring is known to have higher heat resistance than the alicyclic ring, but in the polyimide obtained from the polyimide precursor using the diamine having the alicyclic ring of the present invention, the polyimide using the aromatic diamine is used. It turns out that the heat resistance equivalent to the polyimide obtained from the precursor is shown.
Furthermore, from the comparison of the diamine components in Examples 2 and 4, the polyimide obtained from the polyimide precursor using the adamantane skeleton diamine has higher heat resistance than the polyimide obtained from the polyimide precursor using the cyclohexane skeleton diamine. It can be seen that it exhibits high transmittance and high transmittance.
As described above, the polyimide obtained from the polyimide precursor of the present invention has excellent light transmittance and high heat resistance, and the polyimide film of the present invention is colorless and transparent for display applications and the like. And can be suitably used as a transparent substrate capable of forming a fine circuit.
本発明は、高耐熱性の優れた特性を有し、さらに極めて高い透明性を併せ有するポリイミド前駆体及びポリイミドを提供することができる。このポリイミド前駆体及びポリイミドは、透明性が高く且つ微細な回路の形成が容易な低線膨張係数であることから、ディスプレイ用途などの基板を形成するために好適に用いることができる。 The present invention can provide a polyimide precursor and a polyimide having excellent heat resistance and extremely high transparency. This polyimide precursor and polyimide have high transparency and a low linear expansion coefficient that facilitates the formation of fine circuits, and therefore can be suitably used for forming substrates for display applications and the like.
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| JP6768234B2 (en) * | 2016-05-09 | 2020-10-14 | 三菱瓦斯化学株式会社 | Polyimide and polyimide film |
| TWI791277B (en) * | 2016-05-31 | 2023-02-01 | 日商Ｕｂｅ股份有限公司 | Polyimide precursor, polyimide, polyimide film and substrate, and tetracarboxylic dianhydride used in manufacture of polyimide |
| KR20180009651A (en) * | 2016-07-19 | 2018-01-29 | 코오롱인더스트리 주식회사 | Polyamic acid, Polyimide Resin, Polyimide Film and Display Device Comprising Thereof |
| WO2019009259A1 (en) | 2017-07-03 | 2019-01-10 | 日産化学株式会社 | Composition for forming flexible device substrate |
| KR20230084144A (en) * | 2020-10-09 | 2023-06-12 | 호도가야 가가쿠 고교 가부시키가이샤 | Adamantane compounds and organic electroluminescent elements, electronic devices |
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