JPS62109819A - Organic semiconductor - Google Patents
Organic semiconductorInfo
- Publication number
- JPS62109819A JPS62109819A JP60248391A JP24839185A JPS62109819A JP S62109819 A JPS62109819 A JP S62109819A JP 60248391 A JP60248391 A JP 60248391A JP 24839185 A JP24839185 A JP 24839185A JP S62109819 A JPS62109819 A JP S62109819A
- Authority
- JP
- Japan
- Prior art keywords
- group
- groups
- formula
- general formula
- aryl
- 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.)
- Pending
Links
- 239000004065 semiconductor Substances 0.000 title claims description 12
- 229920000642 polymer Polymers 0.000 claims abstract description 34
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 15
- 125000003118 aryl group Chemical group 0.000 claims abstract description 15
- 125000005336 allyloxy group Chemical group 0.000 claims abstract description 10
- 239000000126 substance Substances 0.000 claims abstract description 8
- 230000000379 polymerizing effect Effects 0.000 claims abstract description 4
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 15
- 150000001875 compounds Chemical class 0.000 claims description 8
- 125000003545 alkoxy group Chemical group 0.000 claims description 7
- 125000005843 halogen group Chemical group 0.000 claims description 7
- 125000000101 thioether group Chemical group 0.000 claims description 6
- 125000003277 amino group Chemical group 0.000 claims description 3
- 125000003172 aldehyde group Chemical group 0.000 claims description 2
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 2
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 2
- -1 pyrrole compound Chemical class 0.000 abstract description 30
- KAESVJOAVNADME-UHFFFAOYSA-N 1H-pyrrole Natural products C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 abstract description 28
- 229920003227 poly(N-vinyl carbazole) Polymers 0.000 abstract description 14
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N N-phenyl amine Natural products NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 abstract description 11
- 238000006116 polymerization reaction Methods 0.000 abstract description 5
- 229910052736 halogen Inorganic materials 0.000 abstract description 2
- 150000002367 halogens Chemical class 0.000 abstract description 2
- 239000003960 organic solvent Substances 0.000 abstract description 2
- 239000000470 constituent Substances 0.000 abstract 2
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 18
- 238000006243 chemical reaction Methods 0.000 description 13
- 239000000243 solution Substances 0.000 description 8
- JLTDJTHDQAWBAV-UHFFFAOYSA-N N,N-dimethylaniline Chemical compound CN(C)C1=CC=CC=C1 JLTDJTHDQAWBAV-UHFFFAOYSA-N 0.000 description 7
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 7
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 6
- 229920001940 conductive polymer Polymers 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- 229920000128 polypyrrole Polymers 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 5
- 125000004054 acenaphthylenyl group Chemical group C1(=CC2=CC=CC3=CC=CC1=C23)* 0.000 description 5
- HXGDTGSAIMULJN-UHFFFAOYSA-N acetnaphthylene Natural products C1=CC(C=C2)=C3C2=CC=CC3=C1 HXGDTGSAIMULJN-UHFFFAOYSA-N 0.000 description 5
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 4
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 4
- 125000001624 naphthyl group Chemical group 0.000 description 4
- 125000003944 tolyl group Chemical group 0.000 description 4
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 230000015654 memory Effects 0.000 description 3
- 125000006606 n-butoxy group Chemical group 0.000 description 3
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 3
- 125000003506 n-propoxy group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])O* 0.000 description 3
- 230000003287 optical effect Effects 0.000 description 3
- 239000012071 phase Substances 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
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 3
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 2
- VOWZNBNDMFLQGM-UHFFFAOYSA-N 2,5-dimethylaniline Chemical compound CC1=CC=C(C)C(N)=C1 VOWZNBNDMFLQGM-UHFFFAOYSA-N 0.000 description 2
- JJYPMNFTHPTTDI-UHFFFAOYSA-N 3-methylaniline Chemical compound CC1=CC=CC(N)=C1 JJYPMNFTHPTTDI-UHFFFAOYSA-N 0.000 description 2
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical group [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- QMMFVYPAHWMCMS-UHFFFAOYSA-N Dimethyl sulfide Chemical group CSC QMMFVYPAHWMCMS-UHFFFAOYSA-N 0.000 description 2
- 241000209219 Hordeum Species 0.000 description 2
- 235000007340 Hordeum vulgare Nutrition 0.000 description 2
- 239000002216 antistatic agent Substances 0.000 description 2
- 125000001309 chloro group Chemical group Cl* 0.000 description 2
- LJSQFQKUNVCTIA-UHFFFAOYSA-N diethyl sulfide Chemical group CCSCC LJSQFQKUNVCTIA-UHFFFAOYSA-N 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 2
- 125000001153 fluoro group Chemical group F* 0.000 description 2
- 239000012456 homogeneous solution Substances 0.000 description 2
- 239000012212 insulator Substances 0.000 description 2
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 2
- 239000008267 milk Substances 0.000 description 2
- 210000004080 milk Anatomy 0.000 description 2
- 235000013336 milk Nutrition 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- KKFHAJHLJHVUDM-UHFFFAOYSA-N n-vinylcarbazole Chemical compound C1=CC=C2N(C=C)C3=CC=CC=C3C2=C1 KKFHAJHLJHVUDM-UHFFFAOYSA-N 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- AKEJUJNQAAGONA-UHFFFAOYSA-N sulfur trioxide Chemical compound O=S(=O)=O AKEJUJNQAAGONA-UHFFFAOYSA-N 0.000 description 2
- 229960003986 tuaminoheptane Drugs 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 1
- CTWQGTOWGFCWNW-UHFFFAOYSA-N 1,3-dimethylpyrrole Chemical compound CC=1C=CN(C)C=1 CTWQGTOWGFCWNW-UHFFFAOYSA-N 0.000 description 1
- OCJBOOLMMGQPQU-UHFFFAOYSA-N 1,4-dichlorobenzene Chemical compound ClC1=CC=C(Cl)C=C1 OCJBOOLMMGQPQU-UHFFFAOYSA-N 0.000 description 1
- OXHNLMTVIGZXSG-UHFFFAOYSA-N 1-Methylpyrrole Chemical compound CN1C=CC=C1 OXHNLMTVIGZXSG-UHFFFAOYSA-N 0.000 description 1
- VPUAYOJTHRDUTK-UHFFFAOYSA-N 1-ethylpyrrole Chemical compound CCN1C=CC=C1 VPUAYOJTHRDUTK-UHFFFAOYSA-N 0.000 description 1
- RIAJNRHROUYNKE-UHFFFAOYSA-N 1-methyl-3-phenylpyrrole Chemical compound CN1C=CC(C=2C=CC=CC=2)=C1 RIAJNRHROUYNKE-UHFFFAOYSA-N 0.000 description 1
- MFGOZCIHXVFZBC-UHFFFAOYSA-N 1-propylpyrrole Chemical compound CCCN1C=CC=C1 MFGOZCIHXVFZBC-UHFFFAOYSA-N 0.000 description 1
- KZMAWJRXKGLWGS-UHFFFAOYSA-N 2-chloro-n-[4-(4-methoxyphenyl)-1,3-thiazol-2-yl]-n-(3-methoxypropyl)acetamide Chemical compound S1C(N(C(=O)CCl)CCCOC)=NC(C=2C=CC(OC)=CC=2)=C1 KZMAWJRXKGLWGS-UHFFFAOYSA-N 0.000 description 1
- REBMNRMQTSWMMI-UHFFFAOYSA-N 3,4-dibromo-1h-pyrrole Chemical compound BrC1=CNC=C1Br REBMNRMQTSWMMI-UHFFFAOYSA-N 0.000 description 1
- CQZZXMMDKIFFFS-UHFFFAOYSA-N 3,4-diethyl-1-methylpyrrole Chemical compound CCC1=CN(C)C=C1CC CQZZXMMDKIFFFS-UHFFFAOYSA-N 0.000 description 1
- OJFOWGWQOFZNNJ-UHFFFAOYSA-N 3,4-dimethyl-1h-pyrrole Chemical compound CC1=CNC=C1C OJFOWGWQOFZNNJ-UHFFFAOYSA-N 0.000 description 1
- WNRGWPVJGDABME-UHFFFAOYSA-N 3,5-Dimethoxyaniline Chemical compound COC1=CC(N)=CC(OC)=C1 WNRGWPVJGDABME-UHFFFAOYSA-N 0.000 description 1
- MKARNSWMMBGSHX-UHFFFAOYSA-N 3,5-dimethylaniline Chemical compound CC1=CC(C)=CC(N)=C1 MKARNSWMMBGSHX-UHFFFAOYSA-N 0.000 description 1
- PWRKEYBSOWAIMY-UHFFFAOYSA-N 3,5-diphenylaniline Chemical compound C=1C(N)=CC(C=2C=CC=CC=2)=CC=1C1=CC=CC=C1 PWRKEYBSOWAIMY-UHFFFAOYSA-N 0.000 description 1
- ZZHFDFIWLDELCX-UHFFFAOYSA-N 3-bromo-1h-pyrrole Chemical compound BrC=1C=CNC=1 ZZHFDFIWLDELCX-UHFFFAOYSA-N 0.000 description 1
- YVJFJDGNKPVJQF-UHFFFAOYSA-N 3-ethoxy-1-ethylpyrrole Chemical compound CCOC=1C=CN(CC)C=1 YVJFJDGNKPVJQF-UHFFFAOYSA-N 0.000 description 1
- KEAYXGHOGPUYPB-UHFFFAOYSA-N 3-ethoxy-1h-pyrrole Chemical compound CCOC=1C=CNC=1 KEAYXGHOGPUYPB-UHFFFAOYSA-N 0.000 description 1
- WEZAHYDFZNTGKE-UHFFFAOYSA-N 3-ethoxyaniline Chemical compound CCOC1=CC=CC(N)=C1 WEZAHYDFZNTGKE-UHFFFAOYSA-N 0.000 description 1
- RLLBWIDEGAIFPI-UHFFFAOYSA-N 3-ethyl-1h-pyrrole Chemical compound CCC=1C=CNC=1 RLLBWIDEGAIFPI-UHFFFAOYSA-N 0.000 description 1
- AMKPQMFZCBTTAT-UHFFFAOYSA-N 3-ethylaniline Chemical compound CCC1=CC=CC(N)=C1 AMKPQMFZCBTTAT-UHFFFAOYSA-N 0.000 description 1
- VWSSZZBNUPLYAT-UHFFFAOYSA-N 3-ethylsulfanyl-1h-pyrrole Chemical compound CCSC=1C=CNC=1 VWSSZZBNUPLYAT-UHFFFAOYSA-N 0.000 description 1
- OXEBDAHOARLIIG-UHFFFAOYSA-N 3-methoxy-1-methylpyrrole Chemical compound COC=1C=CN(C)C=1 OXEBDAHOARLIIG-UHFFFAOYSA-N 0.000 description 1
- FEKWWZCCJDUWLY-UHFFFAOYSA-N 3-methyl-1h-pyrrole Chemical compound CC=1C=CNC=1 FEKWWZCCJDUWLY-UHFFFAOYSA-N 0.000 description 1
- TWPMMLHBHPYSMT-UHFFFAOYSA-N 3-methyl-n-phenylaniline Chemical compound CC1=CC=CC(NC=2C=CC=CC=2)=C1 TWPMMLHBHPYSMT-UHFFFAOYSA-N 0.000 description 1
- WRAPYPVHEAQARO-UHFFFAOYSA-N 3-methylsulfanyl-1h-pyrrole Chemical compound CSC=1C=CNC=1 WRAPYPVHEAQARO-UHFFFAOYSA-N 0.000 description 1
- DWRKUVHPZAVWPT-UHFFFAOYSA-N 3-naphthalen-1-yloxy-1h-pyrrole Chemical compound C=1C=CC2=CC=CC=C2C=1OC=1C=CNC=1 DWRKUVHPZAVWPT-UHFFFAOYSA-N 0.000 description 1
- BNQPUGPPVNNKBK-UHFFFAOYSA-N 3-phenoxy-1h-pyrrole Chemical compound C=1C=CC=CC=1OC=1C=CNC=1 BNQPUGPPVNNKBK-UHFFFAOYSA-N 0.000 description 1
- UCSYVYFGMFODMY-UHFFFAOYSA-N 3-phenoxyaniline Chemical compound NC1=CC=CC(OC=2C=CC=CC=2)=C1 UCSYVYFGMFODMY-UHFFFAOYSA-N 0.000 description 1
- LJDRAKFYYGCAQC-UHFFFAOYSA-N 3-phenyl-1h-pyrrole Chemical compound N1C=CC(C=2C=CC=CC=2)=C1 LJDRAKFYYGCAQC-UHFFFAOYSA-N 0.000 description 1
- MUNOBADFTHUUFG-UHFFFAOYSA-N 3-phenylaniline Chemical compound NC1=CC=CC(C=2C=CC=CC=2)=C1 MUNOBADFTHUUFG-UHFFFAOYSA-N 0.000 description 1
- IPWGAPCYYMTTLT-UHFFFAOYSA-N 3-propylaniline Chemical compound CCCC1=CC=CC(N)=C1 IPWGAPCYYMTTLT-UHFFFAOYSA-N 0.000 description 1
- ZXVONLUNISGICL-UHFFFAOYSA-N 4,6-dinitro-o-cresol Chemical group CC1=CC([N+]([O-])=O)=CC([N+]([O-])=O)=C1O ZXVONLUNISGICL-UHFFFAOYSA-N 0.000 description 1
- 229910021630 Antimony pentafluoride Inorganic materials 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 229920006361 Polyflon Polymers 0.000 description 1
- 229920000265 Polyparaphenylene Polymers 0.000 description 1
- 239000004809 Teflon Substances 0.000 description 1
- 229920006362 Teflon® Polymers 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 1
- VBVBHWZYQGJZLR-UHFFFAOYSA-I antimony pentafluoride Chemical compound F[Sb](F)(F)(F)F VBVBHWZYQGJZLR-UHFFFAOYSA-I 0.000 description 1
- YBGKQGSCGDNZIB-UHFFFAOYSA-N arsenic pentafluoride Chemical compound F[As](F)(F)(F)F YBGKQGSCGDNZIB-UHFFFAOYSA-N 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 125000001246 bromo group Chemical group Br* 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 229940117389 dichlorobenzene Drugs 0.000 description 1
- 239000002019 doping agent Substances 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 239000008240 homogeneous mixture Substances 0.000 description 1
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- NCBZRJODKRCREW-UHFFFAOYSA-N m-anisidine Chemical compound COC1=CC=CC(N)=C1 NCBZRJODKRCREW-UHFFFAOYSA-N 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- VFNOZYFHJTZTLD-UHFFFAOYSA-N n,n-diethyl-3,5-dimethylaniline Chemical compound CCN(CC)C1=CC(C)=CC(C)=C1 VFNOZYFHJTZTLD-UHFFFAOYSA-N 0.000 description 1
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 229920001197 polyacetylene Polymers 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 238000003756 stirring Methods 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
- VSRBKQFNFZQRBM-UHFFFAOYSA-N tuaminoheptane Chemical compound CCCCCC(C)N VSRBKQFNFZQRBM-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/10—Organic polymers or oligomers
- H10K85/111—Organic polymers or oligomers comprising aromatic, heteroaromatic, or aryl chains, e.g. polyaniline, polyphenylene or polyphenylene vinylene
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/10—Organic polymers or oligomers
- H10K85/141—Organic polymers or oligomers comprising aliphatic or olefinic chains, e.g. poly N-vinylcarbazol, PVC or PTFE
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/10—Organic polymers or oligomers
- H10K85/141—Organic polymers or oligomers comprising aliphatic or olefinic chains, e.g. poly N-vinylcarbazol, PVC or PTFE
- H10K85/146—Organic polymers or oligomers comprising aliphatic or olefinic chains, e.g. poly N-vinylcarbazol, PVC or PTFE poly N-vinylcarbazol; Derivatives thereof
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/549—Organic PV cells
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Photovoltaic Devices (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Polymers With Sulfur, Phosphorus Or Metals In The Main Chain (AREA)
- Polyoxymethylene Polymers And Polymers With Carbon-To-Carbon Bonds (AREA)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
Abstract
Description
【発明の詳細な説明】
〈産業上の利用分野〉
本発明は、特定の構成単位を有する高分子の存在下に特
定の含窒素化合物を重合させることによって得られる新
規な有機半導体に関づるものである。[Detailed Description of the Invention] <Industrial Application Field> The present invention relates to a novel organic semiconductor obtained by polymerizing a specific nitrogen-containing compound in the presence of a polymer having a specific structural unit. It is.
〈従来の技術〉
1977年、ポリアセチレンがハロゲン原子と接触させ
ることにより電気伝導度が著しく向上し、良好な導電性
高分子を与えることが報告された。<Prior Art> In 1977, it was reported that when polyacetylene is brought into contact with halogen atoms, its electrical conductivity is significantly improved, providing a highly conductive polymer.
その後、高分子の主鎖に共役二重結合を有する各種の高
分子、ポリパラフェニレン、ポリチェニレン、ポリピロ
ール、ポリパラフェニレンビニレンなどが倹約され、五
フッ化砒素、五フッ化アンチモン、沃素、臭素、三酸化
イオウ、窒素酸化物、n−プチルリヂウム、ナフタレシ
ナ1〜リウムのような種々なP型必るいはへ型のドーピ
ング剤で処理すると電気伝導性が著しく向上し、絶縁体
から半導体、ざらに導電体になることが報告されている
。Subsequently, various polymers with conjugated double bonds in the main chain of the polymer, such as polyparaphenylene, polythenylene, polypyrrole, polyparaphenylenevinylene, etc., were saved, and arsenic pentafluoride, antimony pentafluoride, iodine, bromine, When treated with various P-type or H-type doping agents such as sulfur trioxide, nitrogen oxide, n-butyllidium, and naphthalesina di- or helium, the electrical conductivity is significantly improved, changing from an insulator to a semiconductor to a rough conductor. It has been reported that the body
これらの導電性高分子は、粉状2粒状、塊状、フィルム
状で得られ、目的に応じてそのまま又は加工成形して使
用され、帯電防止材料、電磁波遮i月料、電子−光機能
素子、光メモリ−(ホログラフィックメモリ)ヤ各種セ
ンサー。These conductive polymers are obtained in the form of powder, particles, blocks, or films, and are used as they are or after processing and molding depending on the purpose, and are used as antistatic materials, electromagnetic shielding materials, electro-optical functional devices, Optical memory (holographic memory) and various sensors.
表示素子(エレクトロクロシズム)、スイッチ。Display elements (electrocrocism), switches.
各種ハイブリット材料(透明導電性フィルム等)、各種
端末機器、並びに二次電池用電極月料などの広い分野に
応用されている。It is applied to a wide range of fields such as various hybrid materials (transparent conductive films, etc.), various terminal devices, and electrode materials for secondary batteries.
〈発明が解決しようとする問題点〉
しかしながら、これらの導電性高分子は、空気中での安
定性がなく、容易に酸化されて高分子の劣化が進行した
り、また、成形性が不十分でおったり、更には製造方法
が煩雑で再現性に乏しい等といった種々の問題点をかか
えていた。<Problems to be solved by the invention> However, these conductive polymers are not stable in air, are easily oxidized and deteriorate, and have insufficient moldability. They have had various problems such as dryness, complicated manufacturing methods, and poor reproducibility.
く問題点を解決するための手段〉
本発明者は上記した従来の導電性高分子のような問題点
のない、iIi現な導電性高分子について研究した所、
少なくともビニルカルバゾール系重合体又はアセナフチ
レン系重合体のいずれか一方の高分子の存在下に、少な
くともピロール系化合物上ツマ−又はアニリン系化合物
モノマーのいずれか一方を重合させることにより、空気
中で安定で成形性が良好のみならず製造容易な有機半導
体を提供できることを見出して本発明を完成した。Means for Solving the Problems> The present inventor conducted research on modern conductive polymers that do not have the problems of the conventional conductive polymers mentioned above, and found that
By polymerizing at least one of a pyrrole-based compound monomer or an aniline-based compound monomer in the presence of at least one of a vinylcarbazole-based polymer or an acenaphthylene-based polymer, it becomes stable in air. The present invention was completed by discovering that it is possible to provide an organic semiconductor that not only has good moldability but also is easy to manufacture.
ずなわら、本発明の要旨は、 少なくとも一般式 %式% 又は一般式 (式中R1〜R4は水素原子、アルキル基。However, the gist of the present invention is at least a general formula %formula% or general formula (In the formula, R1 to R4 are hydrogen atoms and alkyl groups.
アルコキシ基、アリール基、アリロキシ基。Alkoxy group, aryl group, allyloxy group.
チオエーテル基、アミン基、ハロゲン原子。Thioether group, amine group, halogen atom.
シアノ阜、二1・口塞を表わす)
で示される構成単位を有する高分子のいずれか一方の存
在下に
少なくとも一般式
(式中R5,R6は水素原子、アルキル基。In the presence of at least one of the polymers having the structural unit represented by the general formula (wherein R5 and R6 are a hydrogen atom or an alkyl group).
アルコギシ塁、アリール基、アリロキシ基。Arcogysyl group, aryl group, allyloxy group.
チオエーテル基、ハロゲン原子を表わし、R7は水素原
子、アルギル基、アリール基を表わす)
で示されるピロール系化合物
又は一般式
(式中R8,R9は水素原子、アルキル基。a thioether group, a halogen atom, and R7 represents a hydrogen atom, an argyl group, or an aryl group) or a pyrrole compound represented by the general formula (wherein R8 and R9 are a hydrogen atom or an alkyl group).
アルフキ9塁、アリール基、アリロキシ基を表わし、R
10,R11は水素原子、アルキル基、アリール基を表
わす)
で示されるアニリン系化合物のいずれか一方の化合物を
重合させることによって得られる有機半導体に存する。Represents Alfuki 9th base, aryl group, allyloxy group, R
10 and R11 represent a hydrogen atom, an alkyl group, or an aryl group).
前記一般式(1)で示されるビニルカルバゾール系重合
体及び一般式(2)で示されるアセナフチレン系重合体
にa3いて、式中、R1−R4は水素原子、メチル基、
エチル基、n−プロピル基、1so−プロピル基、n−
エチル基、 1so−ブチル基、5ec−ブチル基、t
ert−ブチル基などのアルキル基、メトキシ基、エト
キシ基、n−プロポキシ基、 1so−プロポキシ基、
n−ブトキシ基などのアルコキシ基、フェニル基、トル
イル基、ナフチル基などのアリール基、フェノキシ基、
メチルフェノキシ基、ナフトキシ基などのアリロキシ基
、メチルチオエーテル基、エチルチオエーテル基などの
チオエーテル基、アミノ基、フッ素原子、塩素原子、臭
素原子、沃素原子等のハロゲン原子、アルデヒド基、シ
アノ基、ニトロ基を表わす。In the vinylcarbazole polymer represented by the general formula (1) and the acenaphthylene polymer represented by the general formula (2), in the formula, R1-R4 are hydrogen atoms, methyl groups,
Ethyl group, n-propyl group, 1so-propyl group, n-
Ethyl group, 1so-butyl group, 5ec-butyl group, t
Alkyl groups such as ert-butyl groups, methoxy groups, ethoxy groups, n-propoxy groups, 1so-propoxy groups,
Alkoxy groups such as n-butoxy groups, aryl groups such as phenyl groups, tolyl groups, naphthyl groups, phenoxy groups,
Allyloxy groups such as methylphenoxy groups and naphthoxy groups, thioether groups such as methylthioether groups and ethylthioether groups, amino groups, halogen atoms such as fluorine atoms, chlorine atoms, bromine atoms, and iodine atoms, aldehyde groups, cyano groups, and nitro groups. represents.
具体的には、ビニルカルバゾール系重合体では、ポリビ
ニルカルバゾール
ビニルカルバゾール、4,7−シメチルボリビニルカル
バゾール
ゾール、4−メトキシポリビニルカルバゾール、4−エ
トキシボ1ノビニルカルバゾールェニルポリビニルカル
バゾール、4,7−ジフェニルポリビニルカルバゾール
、4・−ナフヂルポリビニル力ルバゾール、4−フエノ
キシボリビ二ルカルバゾール、4−メチルチオポリビニ
ルカルバゾール
ル
ポリビニルカルバゾール−
4−シアノポリビニルカルバゾール
アノポリビニルカルバゾール等が挙げられる。Specifically, vinylcarbazole-based polymers include polyvinylcarbazolevinylcarbazole, 4,7-dimethylborivinylcarbazole, 4-methoxypolyvinylcarbazole, 4-ethoxybo-1novinylcarbazolenylpolyvinylcarbazole, and 4,7-diphenyl. Examples include polyvinylcarbazole, 4-naphdylpolyvinylcarbazole, 4-phenoxyborivinylcarbazole, 4-methylthiopolyvinylcarbazole, polyvinylcarbazole, 4-cyanopolyvinylcarbazole, and anopolyvinylcarbazole.
また、アセプフレン系重合体としては、ボリアレプフチ
レン、5−メヂルボ1ノアセナフヂレン、5−エチルポ
リアセナフチレン、5−メトキシポリアセナフヂレン、
5−エトキシポリアセナフチレン、5,6−ジメ1〜キ
シポリアセナフヂレン、5−フェニルポリアセナフチレ
ン、5−1〜ルイルボリアセナフチレン、5−ナフチル
ポリアセナフチレン、5−フエノキシボリアセナフヂレ
ン、5−メヂルチオボリアセナフチレン、5−アミノポ
リアセナフチレン、5−ブロムポリアセナフチレン、5
,6−ジブロムポリアセナフチレン、ボリアセナフヂレ
ン5ーアルデヒド、5−シアノポリアセナフチレン、5
,6ジニトロポリアセナフチレン、等が挙げられる。In addition, examples of the acepphrene-based polymers include borialepphthylene, 5-medylbo-1 noacenaphthylene, 5-ethylpolyacenaphthylene, 5-methoxypolyacenaphthylene,
5-ethoxypolyacenaphthylene, 5,6-dime-1-xypolyacenaphthylene, 5-phenylpolyacenaphthylene, 5-1-ruylboreacenaphthylene, 5-naphthylpolyacenaphthylene, 5-phenylpolyacenaphthylene Enoxyboriacenaphthylene, 5-methylthioboriacenaphthylene, 5-aminopolyacenaphthylene, 5-bromopolyacenaphthylene, 5
, 6-dibromopolyacenaphthylene, boriacenaphthylene 5-aldehyde, 5-cyanopolyacenaphthylene, 5
, 6 dinitro polyacenaphthylene, and the like.
使用するビニルカルバゾール系重合体及びアセナフチレ
ン系重合体の分子1は5000〜800000であり、
好ましくは10000〜500000で必る。The molecule 1 of the vinyl carbazole polymer and acenaphthylene polymer used is 5000 to 800000,
Preferably it is 10,000 to 500,000.
また前記一般式(3)で示されるピロール系化合物とし
て、R5.r:<6は水素原子、メチル基、エチル基、
n−プロピル基、 iso−プロピル基、n−ブチル基
、iso−ブチル基、sec−ブチル基などのアルキル
基、メトキシ基、エトキシ基、n−プロポキシ基、is
o−プロポキシ基、n−ブトキシ基などのアルコキシ基
、フェニル基、1ヘルイル基、ナフチル基などの7リー
ル塞、フェノキシ基、メチルフェノキシ基、ナフトキシ
基などのアリロキシ基、メチルチオエーテル基、エチル
チオエーテル塁などのチオエーテル基、フッ素原子、塩
素原子、臭素原子、沃素原子などのハロゲン原子であり
、R7は水素原子、メチル基、エチル基、n−プロピル
基、iSO−プロピル基などのアルキルλ(、フェニル
基、トルイル基、ナフキル基な.どのアリール基を表わ
す。Further, as the pyrrole compound represented by the general formula (3), R5. r:<6 is a hydrogen atom, methyl group, ethyl group,
Alkyl groups such as n-propyl group, iso-propyl group, n-butyl group, iso-butyl group, sec-butyl group, methoxy group, ethoxy group, n-propoxy group, is
Alkoxy groups such as o-propoxy group and n-butoxy group, 7-aryl group such as phenyl group, 1-helyl group, and naphthyl group, allyloxy group such as phenoxy group, methylphenoxy group, and naphthoxy group, methylthioether group, and ethylthioether group. R7 is a halogen atom such as a thioether group, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, etc., and R7 is a hydrogen atom, an alkyl λ(, phenyl represents an aryl group such as a tolyl group, a tolyl group, or a naphkyl group.
具体的には、ピロール、N−メチルピロール、N−エチ
ルピロール、N−n−プロピルピロール、3−メチルピ
ロール、3−エチルピロール、3−メチル−N−メチル
ピロール、3−エヂルーN−メヂルピロール、3−メ1
〜ギシピロール、3−エトキシピロール、3−メトキシ
−N−メチルピロール、3−エトキシ−N−エチルピロ
ール、3−フェニルピロール、3−フェニル−N−メチ
ルピロール、3−フェノキシピロール、3−ナフトキシ
ピロール、3−メチルチオピロール、3−エチルチオピ
ロール、3−ブロムピロール、3.4−ジブロムピロー
ル、3,4−ジメチルピロール、3,4−ジエチル−N
−メチルピロール等が挙げられる。Specifically, pyrrole, N-methylpyrrole, N-ethylpyrrole, N-n-propylpyrrole, 3-methylpyrrole, 3-ethylpyrrole, 3-methyl-N-methylpyrrole, 3-edy-N-methylpyrrole, 3-me 1
~Gicipyrrole, 3-ethoxypyrrole, 3-methoxy-N-methylpyrrole, 3-ethoxy-N-ethylpyrrole, 3-phenylpyrrole, 3-phenyl-N-methylpyrrole, 3-phenoxypyrrole, 3-naphthoxypyrrole , 3-methylthiopyrrole, 3-ethylthiopyrrole, 3-bromopyrrole, 3,4-dibromopyrrole, 3,4-dimethylpyrrole, 3,4-diethyl-N
-Methylpyrrole and the like.
また、前記一般式(4)で示されるアニリン系化合物と
して、R8,R9は水素原子、メチル基、エチル塁、n
−プロピル基、 1so−プロピル基、n−ブチル基、
1so−ブチル基、5ec−ブチル基、tert−ブチ
ル基などのアルキル基、メトキシリ、工1ヘキシ基、n
−プロポキシ基、 1so−プロポキシ基、n−ブトキ
シ基などのアルコキシ基、フェニル基、1〜ルイル塁、
ナフチル基などのアリール基、フェノキシ基、メチルフ
ェノルキシ基、ブフトキシ基などのアリロキシ基を表わ
し、R10,R11は水素原子、メチル基、エチル基、
n−プロピル基、1so−プロピル基、n−ブチル基な
どのアルキル基、フェニル基、トルイル基、ナフチル基
などのアリール基を表わず。Further, as the aniline compound represented by the general formula (4), R8 and R9 are hydrogen atoms, methyl groups, ethyl groups, n
-propyl group, 1so-propyl group, n-butyl group,
Alkyl groups such as 1so-butyl group, 5ec-butyl group, tert-butyl group, methoxyly, 1hexyl group, n
-propoxy group, 1so-propoxy group, alkoxy group such as n-butoxy group, phenyl group, 1-ruyl group,
It represents an aryl group such as a naphthyl group, an allyloxy group such as a phenoxy group, a methylphenoloxy group, a bufthoxy group, and R10 and R11 are a hydrogen atom, a methyl group, an ethyl group,
It does not represent alkyl groups such as n-propyl group, 1so-propyl group, n-butyl group, or aryl groups such as phenyl group, tolyl group, naphthyl group.
具体的には、アニリン、3−メチルアニリン、3.5−
ジメチルアニリン、3−エチルアニリン、3−n−プロ
ピルアニリン、3−メトキシアニリン、3,5−ジメト
キシアニリン、3−エトキシアニリン、3,5−ジェト
キシアニリン、3−フェニルアニリン、3,5−ジフェ
ニルアニリン、3−ナフチルアニワン、3−トルイルア
ニリン、2.5−ジメチルアニリン、3−フェノキシア
ニリン、3−プフトキシアニ1ノン、N、N−ジメチル
アニリン、N、N−ジメチルアニリン、3−メチルN。Specifically, aniline, 3-methylaniline, 3.5-
Dimethylaniline, 3-ethylaniline, 3-n-propylaniline, 3-methoxyaniline, 3,5-dimethoxyaniline, 3-ethoxyaniline, 3,5-jethoxyaniline, 3-phenylaniline, 3,5-diphenyl Aniline, 3-naphthylanione, 3-tolylaniline, 2,5-dimethylaniline, 3-phenoxyaniline, 3-pufthoxyanilon, N,N-dimethylaniline, N,N-dimethylaniline, 3-methylN.
N−ジメチルアニリン、3,5−ジメチルN、N−ジエ
チルアニリン、3−エチルN。N−ジメチルアニリン、
3−メ1ヘキシN。N-dimethylaniline, 3,5-dimethylN, N-diethylaniline, 3-ethylN. N-dimethylaniline,
3-Me1hexyN.
N−ジメチル)アニリン、3,5−ジメトキシN。N-dimethyl)aniline, 3,5-dimethoxyN.
N−ジメチルアニリン、3−フェノキシN、 N=ニジ
メチルアニリン等が)(げられる。N-dimethylaniline, 3-phenoxyN, N=nidimethylaniline, etc.).
ビニルカルバゾール系重合体又はアセナフチレン系重合
体に対するピロール系化合物又はアニリン系化合物の使
用伍は0.01〜100倍モルであり、好ましくは0.
05−・50倍モルである。The amount of the pyrrole compound or aniline compound to be used is 0.01 to 100 times the mole of the vinylcarbazole polymer or acenaphthylene polymer, preferably 0.01 to 100 times the molar amount.
05-.50 times the mole.
一般式(1)又は(2)で示される重合体の存在下で行
なう一般式(3)又は(4)で示される七ツマー化合物
の重合反応は、同相、液相、気相の任意の相で実施する
ことができるか、一般式(1)又は(2)で示される重
合体が均一に溶解する有機溶媒の存在下で一般式(3)
又は(/1)で示される七ツマー化合物の重合反応を行
なうのが好ましい。殊に、一般式(1)又は(2)で示
される重合体を含む均一溶液に一般式(3)又は(4)
で示される七ツマー化合物が均一に溶解する完全均一溶
液系で反応を行なうことにより、(1)又は(2)で示
される重合体と(3)又は(4)で示される=しツマ−
化合物の重合体が均質に分散する。The polymerization reaction of the heptamer compound represented by the general formula (3) or (4) in the presence of the polymer represented by the general formula (1) or (2) can be carried out in any phase of the same phase, liquid phase, or gas phase. or the polymer represented by the general formula (3) in the presence of an organic solvent in which the polymer represented by the general formula (1) or (2) is uniformly dissolved.
It is preferable to carry out a polymerization reaction of a heptamer compound represented by (/1). In particular, in a homogeneous solution containing a polymer represented by general formula (1) or (2), general formula (3) or (4) is added.
By carrying out the reaction in a completely homogeneous solution system in which the heptamine compound represented by is uniformly dissolved, the polymer represented by (1) or (2) and the heptamine represented by (3) or (4) can be reacted.
The polymer of the compound is homogeneously dispersed.
一1lu式(3)又は(4)で示される七ツマー化合物
の重合反応は、通常、強酸残基やハロゲン、シアンを有
する金属塩、過酸化物や窒素酸化物類が使用される。具
体的にはFe(C104)3、Fe (BF4 )3
、Fe2 (s i F6 )3、Cu (CCC4
)2 、Cu (BF4 )2、CuS i F6 、
FeCn3 、CuC,g2、K (Fe(CN)6
)、RuCf!、3、Mocz5、WCβ 、(NH4
)28208、に2320B 、N 82820B 、
\a B O3,1−1202、N0BF4、No28
F4、N0CJ20/l 、N0RsF6 、N0PF
6などである。In the polymerization reaction of the heptamer compound represented by formula (3) or (4), metal salts, peroxides, and nitrogen oxides having strong acid residues, halogen, and cyan are usually used. Specifically, Fe(C104)3, Fe(BF4)3
, Fe2 (s i F6 )3, Cu (CCC4
)2, Cu (BF4)2, CuS i F6,
FeCn3, CuC,g2, K (Fe(CN)6
), RuCf! ,3,Mocz5,WCβ,(NH4
) 28208, 2320B, N 82820B,
\a B O3, 1-1202, N0BF4, No28
F4, N0CJ20/l, N0RsF6, N0PF
6 etc.
使用mlは七ツマー化合物に対して0.01〜100倍
モルであり、好ましくは0,05〜50倍モルで必る。The amount of ml used is 0.01 to 100 times, preferably 0.05 to 50 times, the mole of the heptamer compound.
また、使用する打機溶媒としては一般式(1)又は(2
)で示される重合体を均一に溶解づる溶媒なら任意に使
用することかできるか、テトラヒドロフラン、ジオキサ
ン、クロロホルム、ジクロルエタン、ジクロルメタン、
ジクロルベンゼンなどが良好な溶媒として使用すること
ができる。In addition, as the battering machine solvent to be used, the general formula (1) or (2
) Any solvent can be used as long as it can uniformly dissolve the polymer shown in the formula, such as tetrahydrofuran, dioxane, chloroform, dichloroethane, dichloromethane,
Dichlorobenzene and the like can be used as good solvents.
溶媒に対する一般式(1)又は(2)で示される重合体
の使用量は0.1〜60重d%で、好ましくは1〜50
徂量%である。反応温度は−20〜ioo°C1好まし
くはO〜80’Cであり、反応時間は反応温度と関連す
るが、通常0.5〜100時間、好ましくは1〜50時
間でおる。The amount of the polymer represented by general formula (1) or (2) relative to the solvent used is 0.1 to 60% by weight, preferably 1 to 50% by weight.
The amount is %. The reaction temperature is -20 to 100°C, preferably 0 to 80'C, and the reaction time is related to the reaction temperature, but is usually 0.5 to 100 hours, preferably 1 to 50 hours.
反応生成物は暗褐色〜黒色の固体状物質で必り、溶媒存
在下の反応では反応終了後、溶媒を通常の方法で除去す
るか、水又はアルコール中に移し、生成物を瀘取、洗浄
することにより容易に分離、精製することができる。The reaction product is necessarily a dark brown to black solid substance; in the case of a reaction in the presence of a solvent, after the reaction is complete, the solvent is removed in the usual way, or it is transferred to water or alcohol, and the product is filtered and washed. It can be easily separated and purified by
く作 用〉
以上の手段を用いることにより、空気中で安定で酸化さ
れることがなく、また成形性が良好且つ製造容易な導電
性高分子(有機半導体)を得ることができる。Effect> By using the above-described means, it is possible to obtain a conductive polymer (organic semiconductor) that is stable in the air, is not oxidized, has good moldability, and is easy to manufacture.
〈実施例〉 以下に実施例を挙げて本発明を具体的に説明する。<Example> The present invention will be specifically explained below with reference to Examples.
実施例1
300 mu丸底フラスコにポリビニルカルバゾール(
分子量21万) 6.0gをとり、テトラヒドロフラ
ン70mβを添加して溶解し均一な粘稠液を調製した。Example 1 Polyvinyl carbazole (
6.0 g (molecular weight: 210,000) was taken, and 70 mβ of tetrahydrofuran was added and dissolved to prepare a uniform viscous liquid.
この粘稠液にピロール2.0gを加えてポリビニルカル
バゾールとピロールとの均一混合液を調製し、この混合
液を室温窒素気流下で攪拌しながら、FeCβ34.8
7gを溶解したテトラヒドロフラン30m、llを10
分間かけて滴下した。この時、反応液ははじめ無色であ
ったが時間の経過とともに黒色化し、3時間俊には黒色
の粘稠な液が得られた。この液を一夜放置後大量のメタ
ノール中にあけ、枦残を200 mgのメタノールで3
回洗浄し、その後60°C減圧下で乾燥すると均一な黒
色粉末7.18gが1qられた。Add 2.0 g of pyrrole to this viscous liquid to prepare a homogeneous mixture of polyvinylcarbazole and pyrrole, and while stirring this mixture at room temperature under a nitrogen stream, FeCβ34.8
7g dissolved in 30ml of tetrahydrofuran, 10ml
It was added dropwise over a period of minutes. At this time, the reaction solution was initially colorless, but turned black over time, and a black viscous solution was obtained after 3 hours. After leaving this solution overnight, pour it into a large amount of methanol, and dissolve the residue in 200 mg of methanol.
After washing twice and drying at 60° C. under reduced pressure, 7.18 g of a uniform black powder was obtained.
尚、ピロールを使用せずその他は全く同一の方法で処理
するとポリビニルカルバゾールが定量的に回収された。In addition, polyvinylcarbazole was quantitatively recovered when the treatment was performed in exactly the same manner except that pyrrole was not used.
以上の結果から、上記の処理によってピロールが干合し
且つポリビニルカルバゾール中に均一に分散したポリピ
ロールからなるポリマーが生成したことを示している。The above results indicate that the above treatment produced a polymer consisting of polypyrrole in which pyrrole was combined and uniformly dispersed in polyvinylcarbazole.
また、ff1l増加から、1昇られたポリマーはポリビ
ニルカルバゾール6.0(l中にポリピロール1.18
(]を含むポリマーでおることを示している。In addition, from the increase in ff1l, the polymer increased by 1 is polyvinylcarbazole 6.0 (polypyrrole 1.18 in 1).
It shows that it is made of polymer containing ( ).
このポリマーについて2端子法による電気伝導度の測定
を行なった結果3.3x 10”63cm−’で必り、
半導体領域の導電性をもった有機半導体て必ることがわ
かった。そして、ポリビニルカルバゾールのみでは10
−10−158Cの絶縁体であることが知られている。The electrical conductivity of this polymer was measured using the two-terminal method, and the result was 3.3 x 10"63 cm-', which was
It has been found that organic semiconductors with conductivity in the semiconductor region are necessary. And polyvinylcarbazole alone has 10
It is known to be a -10-158C insulator.
従って上記で得られたポリマーは電気伝導度が大幅に向
上している。Therefore, the electrical conductivity of the polymer obtained above is significantly improved.
尚、上記電気伝導度の測定は次のように行なった。まず
、上記処理により賀た黒色粉末を乳汁で十分細かく扮砕
した後、直径1Qmmのディスク状に加圧成形(5トン
/C1!!2)シた。次いでこのディスクサンプルに同
一大のステンレス製ディスクを両側から夫々挟み、テフ
ロン製のボルト、ナツトの間におき、締付けることによ
ってこれらのディスクを十分に圧着固定した後、ドライ
ボックス中に保存し、エレクトロメータ(タケダ理仙T
R−8651>を使用してディスクサンプルの電気伝導
度を測定した。The electrical conductivity was measured as follows. First, the black powder obtained by the above treatment was ground sufficiently finely with milk, and then pressure-molded (5 tons/C1!!2) into a disk shape with a diameter of 1 Qmm. Next, stainless steel disks of the same size were sandwiched between both sides of this disk sample, placed between Teflon bolts and nuts, and the disks were sufficiently crimped and fixed by tightening, then stored in a dry box and electrolyzed. Meter (Takeda Risen T)
The electrical conductivity of the disk samples was measured using R-8651>.
また、上記で得られたポリマー0.95gとポリテ1〜
ラフルオロエチレン粉末(ダイキン製ポリフロンファイ
ンパウダーF 103) 0.05(Jを乳汁に秤取
し、フレーク状になるまで予備混練した後、ロールで混
練、シート化すると黒色の均一な可1尭性シート(厚み
200μ)を1qることかできた。この可撓性シートを
目視!Lli!察した所、全体がやや博い黒色で不均一
な部分は全く認められず、ポリビニルカルバゾール(単
体では白色)とポリピロール(単体では黒色)の分散性
は極めて良好であることがわかった。In addition, 0.95 g of the polymer obtained above and Polyte 1~
Lafluoroethylene powder (Polyflon Fine Powder F 103 manufactured by Daikin) 0.05 (J) was weighed into milk, pre-kneaded until it became flaky, then kneaded with a roll and formed into a sheet, resulting in a black uniform powder. I was able to remove 1 q of flexible sheet (thickness: 200 μm). Visually inspecting this flexible sheet, I found that the entire sheet was a slightly wide black color with no uneven parts observed. It was found that the dispersibility of polypyrrole (white) and polypyrrole (black when used alone) was extremely good.
比較例
300 mM丸底フラスコにジオキ」ノンioo mΩ
、ポリカーボネー1〜(分子ff120万) 6.O
i;lをとり均一に溶解して粘稠液を調製した(麦、ピ
ロール2.51gを加え撹拌して均一に混合した。次い
で、この混合液を室温窒素気流下、で贋拌しながら、混
合液中にFe(439,73(lを溶解したジオキサン
100mfJを少しずつ添加した。この時、反応液は黒
色化し黒色の粒子状固体が分離しているのが認められた
。2時間撹拌した債、室温で1夜放置すると、反応液の
下層部に沈澱している黒色物が認められた。この反応液
並びに黒色沈殿物全量を大量のメタノール中におけ、瀘
残を200 mNのメタノールで4回洗浄し、60℃減
圧下で屹燥すると、フワフワした灰色と黒色の不均一な
色調の固体7.21gが1qられた。得られたこの固体
を直径10mmのディスク状に加圧成形(51〜ン/c
m2)すると、表面は黒色と灰白色の部分が明瞭に分離
してあり両ポリマーの均一分散性が極めて悪いことが示
された。Comparative Example 300 mΩ in a round bottom flask
, polycarbonate 1~(molecule ff 1.2 million) 6. O
A viscous liquid was prepared by uniformly dissolving 2.51 g of barley and pyrrole (2.51 g of barley and pyrrole were added and stirred to mix uniformly. Next, this mixed liquid was stirred at room temperature under a nitrogen stream, 100 mfJ of dioxane in which Fe (439,73 (l) was dissolved was added little by little to the mixed solution. At this time, the reaction solution turned black and separation of black particulate solids was observed. Stirred for 2 hours. However, when left overnight at room temperature, a black substance precipitated in the lower layer of the reaction solution was observed.The reaction solution and the entire amount of black precipitate were placed in a large amount of methanol, and the filtrate was dissolved in 200 mN methanol. After washing four times and drying under reduced pressure at 60°C, 7.21 g of a fluffy gray and black non-uniform solid was obtained. 51~n/c
m2), the surface was clearly separated into black and gray areas, indicating that the uniform dispersibility of both polymers was extremely poor.
実施例2
ポリビニルカルバゾールの代りにポリアセナフチレン6
.0g(分子呈15万)、並びにFeC,C39,74
gを使用したほかは実施例1と同様にして、均一溶解し
たポリアセナフチレンの存在下にピロールの手合反応を
行なった。この時、反応液の色は、FeCJ?、3−テ
トラヒドロフランを添加すると、反応初期は赤味を帯び
ているが、時間の経過とともに黒色化が進行し、2時間
接反応液全体が粘稠な黒色液になった。Example 2 Polyacenaphthylene 6 instead of polyvinylcarbazole
.. 0g (molecular weight: 150,000), and FeC, C39,74
A reaction of pyrrole was carried out in the same manner as in Example 1, except that G was used in the presence of homogeneously dissolved polyacenaphthylene. At this time, the color of the reaction solution is FeCJ? When 3-tetrahydrofuran was added, the reaction was reddish at the initial stage, but the blackening progressed over time, and the entire reaction solution after 2 hours of contact became a viscous black liquid.
この黒色液を一夜放@後大母のメタノール中に移し、枦
残を200 mfJのメタノールで4回洗浄し、60℃
減圧下で屹燥すると、均一な黒色固体6.68Clが1
qられた。After leaving this black liquid overnight, it was transferred to methanol in a large pot, and the residue was washed four times with 200 mfJ of methanol, and then heated at 60°C.
When dried under reduced pressure, 6.68 Cl of a homogeneous black solid becomes 1
I was pissed.
尚、ピロールを使用ヒずにその他は全く同一の方法でf
f1Llするとポリアセナフチレンが定量的に回収され
た。In addition, f was prepared in exactly the same way except without using pyrrole.
When f1Ll was carried out, polyacenaphthylene was quantitatively recovered.
以上の結果から、上記の処理によってピロールが重合し
且つポリアセナフチレン中に均一に分散したポリピロー
ルからなるポリマーが生成したことを示している。また
、重d増加から、得られたポリマーはポリアセナフチレ
ン6.0g中にポリごロール0.68gを含むポリマー
であることを示している。尚、このポリマーの電気伝導
度は4.2x 10 ’5cm−1テS V)、半導体
領域の導電性をもった有機半導体でおることがわかった
。The above results indicate that pyrrole was polymerized by the above treatment and a polymer consisting of polypyrrole uniformly dispersed in polyacenaphthylene was produced. Furthermore, the increase in weight d indicates that the obtained polymer contains 0.68 g of polygorol in 6.0 g of polyacenaphthylene. The electrical conductivity of this polymer was 4.2 x 10'5 cm-1 TeSV), indicating that it was an organic semiconductor with conductivity in the semiconductor region.
実施例3〜・11
各種のビニルカルバゾール系重合体又はアセナフチレン
系重合体の存在下に、ピロール系化合物おるいはアニリ
ン系化合物の重合を実施例1と同様にして行ない、jq
られた黒色固体の結果を第1表に示す。Examples 3 to 11 Polymerization of a pyrrole compound or aniline compound was carried out in the same manner as in Example 1 in the presence of various vinyl carbazole polymers or acenaphthylene polymers, and jq
The results for the black solids obtained are shown in Table 1.
〈発明の効果〉
以上のように構成される本発明の有機半導体は、空気中
で安定で酸化されることもなく、また成形性が良好且つ
製造容易であり、実用的価値が極めて大である。かくし
て本発明の有機半導体は、帯電防止材料、N磁波遮断材
料、電子・光機能素子、光メモリ−、各種センサー、表
示素子、スイッチ、各種端末機器、並びに蓄電池など広
い分野への適用が可能でおる。<Effects of the Invention> The organic semiconductor of the present invention configured as described above is stable in air and does not oxidize, has good moldability and is easy to manufacture, and has extremely great practical value. . Thus, the organic semiconductor of the present invention can be applied to a wide range of fields such as antistatic materials, N magnetic wave blocking materials, electronic/optical functional devices, optical memories, various sensors, display devices, switches, various terminal devices, and storage batteries. .
Claims (1)
キシ基、アリール基、アリロキシ基、チオエーテル基、
アミノ基、ハロゲン原子、アルデヒド基、シアノ基、ニ
トロ基を表わ す) で示される構成単位を有する高分子のいずれか一方の存
在下に 少なくとも一般式 ▲数式、化学式、表等があります▼・・・(3) (式中R^5、R^6は水素原子、アルキル基、アルコ
キシ基、アリール基、アリロキシ基、チオエーテル基、
ハロゲン原子を表わし、 R^7は水素原子、アルキル基、アリール基を表わす) で示されるピロール系化合物 又は一般式 ▲数式、化学式、表等があります▼・・・(4) (式中R^8、R^9は水素原子、アルキル基、アルコ
キシ基、アリール基、アリロキシ基 を表わし、R^1^0、R^1^1は水素原子、アルキ
ル基、アリール基を表わす) で示されるアニリン系化合物のいずれか一方の化合物を
重合させることによつて得られる有機半導体。[Claims] 1. At least a general formula▲There are mathematical formulas, chemical formulas, tables, etc.▼...(1) Or a general formula▲There are mathematical formulas, chemical formulas, tables, etc.▼...(2) (R in the formula ^1 to R^4 are hydrogen atoms, alkyl groups, alkoxy groups, aryl groups, allyloxy groups, thioether groups,
At least a general formula ▲ mathematical formula, chemical formula, table, etc. exists in the presence of one of the polymers having a constitutional unit represented by amino group, halogen atom, aldehyde group, cyano group, nitro group ▼... (3) (In the formula, R^5 and R^6 are hydrogen atoms, alkyl groups, alkoxy groups, aryl groups, allyloxy groups, thioether groups,
(represents a halogen atom, and R^7 represents a hydrogen atom, an alkyl group, or an aryl group) or general formula ▲ Numerical formulas, chemical formulas, tables, etc. are available ▼...(4) (In the formula R^ 8, R^9 represents a hydrogen atom, an alkyl group, an alkoxy group, an aryl group, or an allyloxy group, and R^1^0 and R^1^1 represent a hydrogen atom, an alkyl group, or an aryl group) An organic semiconductor obtained by polymerizing either one of the system compounds.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP60248391A JPS62109819A (en) | 1985-11-06 | 1985-11-06 | Organic semiconductor |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP60248391A JPS62109819A (en) | 1985-11-06 | 1985-11-06 | Organic semiconductor |
Publications (1)
Publication Number | Publication Date |
---|---|
JPS62109819A true JPS62109819A (en) | 1987-05-21 |
Family
ID=17177407
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP60248391A Pending JPS62109819A (en) | 1985-11-06 | 1985-11-06 | Organic semiconductor |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPS62109819A (en) |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS63135418A (en) * | 1986-11-26 | 1988-06-07 | Mitsui Toatsu Chem Inc | Composite membrane of aromatic compound polymer and its production |
JPH01154572A (en) * | 1987-12-11 | 1989-06-16 | Ricoh Co Ltd | Photoelectric converter |
JPH01254588A (en) * | 1988-04-01 | 1989-10-11 | Ibiden Co Ltd | Tray case of semiconductor mounting board |
JPH0269525A (en) * | 1988-09-05 | 1990-03-08 | Nitto Denko Corp | Thin film composite material of electroconductive organic polymer |
-
1985
- 1985-11-06 JP JP60248391A patent/JPS62109819A/en active Pending
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS63135418A (en) * | 1986-11-26 | 1988-06-07 | Mitsui Toatsu Chem Inc | Composite membrane of aromatic compound polymer and its production |
JPH01154572A (en) * | 1987-12-11 | 1989-06-16 | Ricoh Co Ltd | Photoelectric converter |
JPH01254588A (en) * | 1988-04-01 | 1989-10-11 | Ibiden Co Ltd | Tray case of semiconductor mounting board |
JPH0269525A (en) * | 1988-09-05 | 1990-03-08 | Nitto Denko Corp | Thin film composite material of electroconductive organic polymer |
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