JP3509451B2 - Charge transport material and method for producing the same - Google Patents
Charge transport material and method for producing the sameInfo
- Publication number
- JP3509451B2 JP3509451B2 JP04824497A JP4824497A JP3509451B2 JP 3509451 B2 JP3509451 B2 JP 3509451B2 JP 04824497 A JP04824497 A JP 04824497A JP 4824497 A JP4824497 A JP 4824497A JP 3509451 B2 JP3509451 B2 JP 3509451B2
- Authority
- JP
- Japan
- Prior art keywords
- general formula
- carbon atoms
- represented
- compound
- formula
- 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.)
- Expired - Fee Related
Links
- 239000000463 material Substances 0.000 title claims description 34
- 238000004519 manufacturing process Methods 0.000 title claims description 10
- 150000001875 compounds Chemical class 0.000 claims description 47
- 125000004432 carbon atom Chemical group C* 0.000 claims description 35
- 125000000217 alkyl group Chemical group 0.000 claims description 19
- 229910052739 hydrogen Inorganic materials 0.000 claims description 16
- 239000001257 hydrogen Substances 0.000 claims description 16
- 230000015572 biosynthetic process Effects 0.000 claims description 15
- 239000000126 substance Substances 0.000 claims description 15
- 238000003786 synthesis reaction Methods 0.000 claims description 14
- 239000002253 acid Substances 0.000 claims description 13
- 125000003118 aryl group Chemical group 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 10
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 8
- 125000004665 trialkylsilyl group Chemical group 0.000 claims description 5
- 239000003960 organic solvent Substances 0.000 claims description 4
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims 6
- 229910052736 halogen Inorganic materials 0.000 claims 2
- 150000002367 halogens Chemical class 0.000 claims 2
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 66
- 239000010410 layer Substances 0.000 description 48
- 238000006243 chemical reaction Methods 0.000 description 37
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 36
- 239000002904 solvent Substances 0.000 description 33
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 24
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 24
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 18
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 18
- 239000013078 crystal Substances 0.000 description 16
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 15
- AOSZTAHDEDLTLQ-AZKQZHLXSA-N (1S,2S,4R,8S,9S,11S,12R,13S,19S)-6-[(3-chlorophenyl)methyl]-12,19-difluoro-11-hydroxy-8-(2-hydroxyacetyl)-9,13-dimethyl-6-azapentacyclo[10.8.0.02,9.04,8.013,18]icosa-14,17-dien-16-one Chemical compound C([C@@H]1C[C@H]2[C@H]3[C@]([C@]4(C=CC(=O)C=C4[C@@H](F)C3)C)(F)[C@@H](O)C[C@@]2([C@@]1(C1)C(=O)CO)C)N1CC1=CC=CC(Cl)=C1 AOSZTAHDEDLTLQ-AZKQZHLXSA-N 0.000 description 12
- 229940126657 Compound 17 Drugs 0.000 description 12
- 239000011248 coating agent Substances 0.000 description 11
- 238000000576 coating method Methods 0.000 description 11
- 150000004820 halides Chemical class 0.000 description 11
- 108091008695 photoreceptors Proteins 0.000 description 11
- -1 silicon wafer Chemical class 0.000 description 11
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 10
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 description 10
- 239000010408 film Substances 0.000 description 9
- 238000002329 infrared spectrum Methods 0.000 description 9
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 9
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 8
- NQRYJNQNLNOLGT-UHFFFAOYSA-N Piperidine Chemical compound C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 description 8
- 150000002431 hydrogen Chemical class 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 125000005370 alkoxysilyl group Chemical group 0.000 description 7
- CUONGYYJJVDODC-UHFFFAOYSA-N malononitrile Chemical compound N#CCC#N CUONGYYJJVDODC-UHFFFAOYSA-N 0.000 description 7
- 229920005989 resin Polymers 0.000 description 7
- 239000011347 resin Substances 0.000 description 7
- 239000000203 mixture Substances 0.000 description 6
- 238000001953 recrystallisation Methods 0.000 description 6
- GHYOCDFICYLMRF-UTIIJYGPSA-N (2S,3R)-N-[(2S)-3-(cyclopenten-1-yl)-1-[(2R)-2-methyloxiran-2-yl]-1-oxopropan-2-yl]-3-hydroxy-3-(4-methoxyphenyl)-2-[[(2S)-2-[(2-morpholin-4-ylacetyl)amino]propanoyl]amino]propanamide Chemical compound C1(=CCCC1)C[C@@H](C(=O)[C@@]1(OC1)C)NC([C@H]([C@@H](C1=CC=C(C=C1)OC)O)NC([C@H](C)NC(CN1CCOCC1)=O)=O)=O GHYOCDFICYLMRF-UTIIJYGPSA-N 0.000 description 5
- ONBQEOIKXPHGMB-VBSBHUPXSA-N 1-[2-[(2s,3r,4s,5r)-3,4-dihydroxy-5-(hydroxymethyl)oxolan-2-yl]oxy-4,6-dihydroxyphenyl]-3-(4-hydroxyphenyl)propan-1-one Chemical compound O[C@@H]1[C@H](O)[C@@H](CO)O[C@H]1OC1=CC(O)=CC(O)=C1C(=O)CCC1=CC=C(O)C=C1 ONBQEOIKXPHGMB-VBSBHUPXSA-N 0.000 description 5
- NPRYCHLHHVWLQZ-TURQNECASA-N 2-amino-9-[(2R,3S,4S,5R)-4-fluoro-3-hydroxy-5-(hydroxymethyl)oxolan-2-yl]-7-prop-2-ynylpurin-8-one Chemical compound NC1=NC=C2N(C(N(C2=N1)[C@@H]1O[C@@H]([C@H]([C@H]1O)F)CO)=O)CC#C NPRYCHLHHVWLQZ-TURQNECASA-N 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- 239000003153 chemical reaction reagent Substances 0.000 description 5
- 238000004440 column chromatography Methods 0.000 description 5
- 229940125797 compound 12 Drugs 0.000 description 5
- 229940126142 compound 16 Drugs 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N hydrochloric acid Substances Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 5
- 238000010992 reflux Methods 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 4
- 238000009835 boiling Methods 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000003618 dip coating Methods 0.000 description 4
- 239000012153 distilled water Substances 0.000 description 4
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 4
- 230000006870 function Effects 0.000 description 4
- 230000002140 halogenating effect Effects 0.000 description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 4
- 239000012299 nitrogen atmosphere Substances 0.000 description 4
- 239000012044 organic layer Substances 0.000 description 4
- 239000000049 pigment Substances 0.000 description 4
- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Chemical compound [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 0.000 description 4
- 229910052938 sodium sulfate Inorganic materials 0.000 description 4
- 235000011152 sodium sulphate Nutrition 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 125000006575 electron-withdrawing group Chemical group 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 238000007689 inspection Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- IEQIEDJGQAUEQZ-UHFFFAOYSA-N phthalocyanine Chemical compound N1C(N=C2C3=CC=CC=C3C(N=C3C4=CC=CC=C4C(=N4)N3)=N2)=C(C=CC=C2)C2=C1N=C1C2=CC=CC=C2C4=N1 IEQIEDJGQAUEQZ-UHFFFAOYSA-N 0.000 description 3
- 230000035945 sensitivity Effects 0.000 description 3
- OGFAWKRXZLGJSK-UHFFFAOYSA-N 1-(2,4-dihydroxyphenyl)-2-(4-nitrophenyl)ethanone Chemical compound OC1=CC(O)=CC=C1C(=O)CC1=CC=C([N+]([O-])=O)C=C1 OGFAWKRXZLGJSK-UHFFFAOYSA-N 0.000 description 2
- NIKGQZVVLDLFOL-UHFFFAOYSA-N 2,7-dinitro-9-oxofluorene-4-carbonyl chloride Chemical compound [O-][N+](=O)C1=CC(C(Cl)=O)=C2C3=CC=C([N+](=O)[O-])C=C3C(=O)C2=C1 NIKGQZVVLDLFOL-UHFFFAOYSA-N 0.000 description 2
- XKCGWCQMEUASJF-UHFFFAOYSA-N 9-oxofluorene-4-carbonyl chloride Chemical compound O=C1C2=CC=CC=C2C2=C1C=CC=C2C(=O)Cl XKCGWCQMEUASJF-UHFFFAOYSA-N 0.000 description 2
- USFZMSVCRYTOJT-UHFFFAOYSA-N Ammonium acetate Chemical compound N.CC(O)=O USFZMSVCRYTOJT-UHFFFAOYSA-N 0.000 description 2
- 239000005695 Ammonium acetate Substances 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- 206010034972 Photosensitivity reaction Diseases 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 235000019257 ammonium acetate Nutrition 0.000 description 2
- 229940043376 ammonium acetate Drugs 0.000 description 2
- 238000013459 approach Methods 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 239000002800 charge carrier Substances 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- GNOIPBMMFNIUFM-UHFFFAOYSA-N hexamethylphosphoric triamide Chemical compound CN(C)P(=O)(N(C)C)N(C)C GNOIPBMMFNIUFM-UHFFFAOYSA-N 0.000 description 2
- 239000012433 hydrogen halide Substances 0.000 description 2
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- 230000007062 hydrolysis Effects 0.000 description 2
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- 230000001678 irradiating effect Effects 0.000 description 2
- 239000012046 mixed solvent Substances 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- UHZYTMXLRWXGPK-UHFFFAOYSA-N phosphorus pentachloride Chemical compound ClP(Cl)(Cl)(Cl)Cl UHZYTMXLRWXGPK-UHFFFAOYSA-N 0.000 description 2
- FAIAAWCVCHQXDN-UHFFFAOYSA-N phosphorus trichloride Chemical compound ClP(Cl)Cl FAIAAWCVCHQXDN-UHFFFAOYSA-N 0.000 description 2
- 230000036211 photosensitivity Effects 0.000 description 2
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 description 2
- 235000011056 potassium acetate Nutrition 0.000 description 2
- 238000000634 powder X-ray diffraction Methods 0.000 description 2
- 239000011241 protective layer Substances 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 238000007634 remodeling Methods 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 239000001632 sodium acetate Substances 0.000 description 2
- 235000017281 sodium acetate Nutrition 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- 125000001424 substituent group Chemical group 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- HFRXJVQOXRXOPP-UHFFFAOYSA-N thionyl bromide Chemical compound BrS(Br)=O HFRXJVQOXRXOPP-UHFFFAOYSA-N 0.000 description 2
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 2
- LNAZSHAWQACDHT-XIYTZBAFSA-N (2r,3r,4s,5r,6s)-4,5-dimethoxy-2-(methoxymethyl)-3-[(2s,3r,4s,5r,6r)-3,4,5-trimethoxy-6-(methoxymethyl)oxan-2-yl]oxy-6-[(2r,3r,4s,5r,6r)-4,5,6-trimethoxy-2-(methoxymethyl)oxan-3-yl]oxyoxane Chemical compound CO[C@@H]1[C@@H](OC)[C@H](OC)[C@@H](COC)O[C@H]1O[C@H]1[C@H](OC)[C@@H](OC)[C@H](O[C@H]2[C@@H]([C@@H](OC)[C@H](OC)O[C@@H]2COC)OC)O[C@@H]1COC LNAZSHAWQACDHT-XIYTZBAFSA-N 0.000 description 1
- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCN SJECZPVISLOESU-UHFFFAOYSA-N 0.000 description 1
- QPAPQRFSPBUJAU-UHFFFAOYSA-N 5-methyl-4-[(3-methyl-5-oxo-1-phenyl-4h-pyrazol-4-yl)methylidene]-2-phenylpyrazol-3-one Chemical compound CC1=NN(C=2C=CC=CC=2)C(=O)C1C=C(C1=O)C(C)=NN1C1=CC=CC=C1 QPAPQRFSPBUJAU-UHFFFAOYSA-N 0.000 description 1
- XVMSFILGAMDHEY-UHFFFAOYSA-N 6-(4-aminophenyl)sulfonylpyridin-3-amine Chemical compound C1=CC(N)=CC=C1S(=O)(=O)C1=CC=C(N)C=N1 XVMSFILGAMDHEY-UHFFFAOYSA-N 0.000 description 1
- AFQYQSWTVCNJQT-UHFFFAOYSA-N 9-oxofluorene-4-carboxylic acid Chemical compound O=C1C2=CC=CC=C2C2=C1C=CC=C2C(=O)O AFQYQSWTVCNJQT-UHFFFAOYSA-N 0.000 description 1
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- 239000004952 Polyamide Substances 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- 235000010724 Wisteria floribunda Nutrition 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- FJWGYAHXMCUOOM-QHOUIDNNSA-N [(2s,3r,4s,5r,6r)-2-[(2r,3r,4s,5r,6s)-4,5-dinitrooxy-2-(nitrooxymethyl)-6-[(2r,3r,4s,5r,6s)-4,5,6-trinitrooxy-2-(nitrooxymethyl)oxan-3-yl]oxyoxan-3-yl]oxy-3,5-dinitrooxy-6-(nitrooxymethyl)oxan-4-yl] nitrate Chemical compound O([C@@H]1O[C@@H]([C@H]([C@H](O[N+]([O-])=O)[C@H]1O[N+]([O-])=O)O[C@H]1[C@@H]([C@@H](O[N+]([O-])=O)[C@H](O[N+]([O-])=O)[C@@H](CO[N+]([O-])=O)O1)O[N+]([O-])=O)CO[N+](=O)[O-])[C@@H]1[C@@H](CO[N+]([O-])=O)O[C@@H](O[N+]([O-])=O)[C@H](O[N+]([O-])=O)[C@H]1O[N+]([O-])=O FJWGYAHXMCUOOM-QHOUIDNNSA-N 0.000 description 1
- 238000007112 amidation reaction Methods 0.000 description 1
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- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
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- YUYCVXFAYWRXLS-UHFFFAOYSA-N trimethoxysilane Chemical compound CO[SiH](OC)OC YUYCVXFAYWRXLS-UHFFFAOYSA-N 0.000 description 1
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Description
【０００１】[0001]
【発明の属する技術分野】本発明は、有機電子デバイ
ス、特に電子写真感光体に有用な新規化合物と、その製
造方法に関する。TECHNICAL FIELD The present invention relates to a novel compound useful for an organic electronic device, particularly an electrophotographic photoreceptor, and a method for producing the same.
【０００２】[0002]
【従来の技術】有機電子デバイスにおいて、電子輸送
性、正孔輸送性の電荷輸送材料は必須の材料である。特
に、電子輸送性材料は有機化合物の本質的な問題によ
り、高い輸送性を有するものが得られにくい。特に近
年、電子写真感光体の分野において電子輸送性材料につ
いて精力的な研究がなされ、例えば、特開平８−２４８
６５６号、同８−２４０９２１号、同８−１５７４７６
号、同８−１５１５３４号、同８−１５１５３２号、同
−１５１５３３号、同８−２４５６０１号、同８−２４
５５１８号、同８−２３１５０２号、同８−１１３５６
５号、同８−２１１６３５号などに種々のアクセプター
性化合物が提案されている。これらは特に、電子吸引性
の構造を持つことに由来する電子輸送性材料の溶剤に対
する溶解性の低さ、あるいは、樹脂との相溶性の悪さ
を、骨格および置換基の変更により改良し、電子輸送
性、製膜性を改善しようとするアプローチである。この
アプローチは電子輸送性材料をバインダーポリマー中に
溶解し、電荷発生層上に積層した正帯電型の電子写真感
光体や、あるいは、安定性を増すために少量の電子輸送
性材料をドーピングしようとする場合には有効である。2. Description of the Related Art In an organic electronic device, an electron-transporting and hole-transporting charge-transporting material is an essential material. In particular, it is difficult to obtain an electron transporting material having a high transporting property due to the intrinsic problem of organic compounds. Particularly in recent years, active researches have been made on electron transporting materials in the field of electrophotographic photoreceptors, and for example, JP-A-8-248.
No. 656, No. 8-240921, No. 8-157476.
No. 8, No. 8-151534, No. 8-151532, No. 151533, No. 8-245601, No. 8-24.
No. 5518, No. 8-231502, No. 8-11356.
Various acceptor compounds have been proposed in No. 5, No. 8-211635 and the like. In particular, these compounds have a low solubility in an electron-transporting material due to having an electron-withdrawing structure in a solvent, or a poor compatibility with a resin by improving a skeleton and a substituent, This is an approach to improve transportability and film forming property. This approach involves dissolving the electron-transporting material in a binder polymer and attempting to dope a positively charged electrophotographic photoreceptor laminated on the charge generation layer or a small amount of the electron-transporting material to increase stability. It is effective when doing.
【０００３】一方、感光層と基体との接着性、感光層の
塗工性等の向上、基体表面の保護、基体上の欠陥の被
覆、感光層の電気的破壊から保護、感光層のキャリア注
入性向上等のために、感光体の層構成中に感光性を有し
ていない下引き層、あるいは中間層と呼ばれる層を介在
させることが一般的であり、それらの層を構成する材料
としては、ポリウレタン、ポリアミド、ポリビニルアル
コール、エポキシエチレン−アクリル酸共重合体、エチ
レン−酢酸ビニル共重合体、カゼイン、メチルセルロー
ス、ニトロセルロース、フェノール樹脂、有機金属化合
物等などが使用される。（例えば、特開昭４８−４７３
３２号、同５１−１１４１３２号、同５２−４２１２３
号、同５９−２３４３９号、同６２−２８４３６２号
等）
しかしながら、感光性を有していない層を介在させるこ
とは、電荷発生層の組成によっては、基体側に流入すべ
き電荷担体の移動が妨げられ、電荷発生層中で他極性の
電荷担体と再結合したり、下引き層と電荷発生層との境
界に蓄積して空間電荷による障壁を形成するため、繰り
返し使用による帯電電位の低下、残留電位の上昇等の現
象を有する場合があった。また、これらの下引き層は、
電荷の輸送を主にその下引き層中の水分が担っているた
めに、湿度によって感光体特性が大きく変化してしまう
欠点があった。これらの欠陥を防止する手段として、例
えば、特公昭６１−３５５５１号公報及び特開昭５９−
１６０１４７号公報等には中間層に電子受容性物質を含
有させることが、さらに特開昭５８−２０９７５１号公
報には、Ｎ型色素あるいは顔料を含有したプレコート層
を設けることが、特開昭６３−２１０８４８号公報に
は、電子移動性顔料を含有する下引き層を設けること
が、記載されている。On the other hand, the adhesion between the photosensitive layer and the substrate, the coating property of the photosensitive layer, etc. are improved, the surface of the substrate is protected, the defects on the substrate are covered, the photosensitive layer is protected from electrical damage, and the carrier is injected into the photosensitive layer. In order to improve the property, it is common to interpose a layer having no photosensitivity in the layer structure of the photoreceptor such as an undercoat layer, or a layer called an intermediate layer. , Polyurethane, polyamide, polyvinyl alcohol, epoxy ethylene-acrylic acid copolymer, ethylene-vinyl acetate copolymer, casein, methyl cellulose, nitrocellulose, phenol resin, organometallic compound and the like are used. (For example, JP-A-48-473
No. 32, No. 51-114132, No. 52-42123
However, interposing a layer having no photosensitivity may prevent the movement of the charge carriers that should flow into the substrate side depending on the composition of the charge generation layer. It is hindered and recombines with charge carriers of other polarity in the charge generation layer, or accumulates at the boundary between the undercoat layer and the charge generation layer to form a space charge barrier, so that the charge potential is lowered by repeated use, In some cases, there was a phenomenon such as an increase in residual potential. Also, these undercoat layers are
Since moisture in the undercoating layer is mainly responsible for transporting electric charges, there is a drawback that the characteristics of the photoconductor largely change depending on humidity. As means for preventing these defects, for example, JP-B-61-35551 and JP-A-59-
In JP-A-160147 and the like, an electron-accepting substance is contained in the intermediate layer, and in JP-A-58-209751, a precoat layer containing an N-type dye or pigment is provided. -210848 describes that an undercoat layer containing an electron transfer pigment is provided.
【０００４】ところが、中間層の製造性、均一を高める
ために電子輸送性材料の溶解性を増すと、特に浸漬塗布
を行う場合、電子輸送性材料が感光層塗布液や感光層に
溶出してしまい、所望の機能をはたさないという問題点
があった。また、Ｎ型色素あるいは顔料を含有させた場
合には、顔料自身は溶剤に難溶あるいは不溶であるため
感光層に溶出することはないが、樹脂に分散して塗布す
る方法で下引き層を形成しているため、樹脂によっては
樹脂が溶剤に可溶であり、上層の感光層塗布によって、
樹脂が溶解することにより塗膜欠陥を起こし、下引き層
として充分な機能を果たすことが出来なくなる欠点があ
った。However, when the solubility of the electron transporting material is increased in order to improve the manufacturability and uniformity of the intermediate layer, the electron transporting material elutes in the photosensitive layer coating liquid or the photosensitive layer particularly when dip coating is performed. However, there is a problem that it does not have a desired function. Further, when the N-type dye or pigment is contained, the pigment itself is hardly soluble or insoluble in the solvent and therefore does not elute in the photosensitive layer, but the undercoat layer is dispersed by coating the resin to form the undercoat layer. Since it is formed, the resin is soluble in the solvent depending on the resin, and by coating the upper photosensitive layer,
When the resin is dissolved, a coating film defect is caused, and there is a drawback that the undercoat layer cannot sufficiently function.
【０００５】さらに、例えば、特公平７−８６６９４号
には電子受容性原子又は電子吸引性基を有するアルコキ
シシランを用いてオーバーコート層を形成することが、
また、特許番号第２，５７５，５３６号公報には無機ガ
ラス質ネットワークを形成可能な光応答性材料を用いた
電子写真感光体が提案されているが、本発明の化合物に
ついては開示されていない。Further, for example, in Japanese Examined Patent Publication No. 7-86694, it is possible to form an overcoat layer using an alkoxysilane having an electron-accepting atom or an electron-withdrawing group.
Further, Japanese Patent No. 2,575,536 proposes an electrophotographic photoreceptor using a photoresponsive material capable of forming an inorganic glass network, but does not disclose the compound of the present invention. .
【０００６】さらに、一般に、有機電子デバイスに用い
る有機材料はその構造により特性が大きく異なるため、
化合物の類似性のみで、最終的なデバイスの特性を予想
するのは困難でルある。Further, in general, the characteristics of organic materials used in organic electronic devices differ greatly depending on their structures.
It is difficult to predict the properties of the final device only by the similarity of the compounds.
【０００７】[0007]
【発明が解決しようとする課題】本発明は上記のような
事情に鑑みてなされたものであって、本発明の目的は、
化合物自体が硬化性を有しており溶剤に可溶であるが、
硬化した後は耐溶剤性に優れた層を形成しうる、電子写
真感光体にも好適な新規電荷輸送材料を提供することに
ある。本発明のさらなる目的は、その新規電荷輸送材料
を効率よく製造しうる製造方法を提供することにある。The present invention has been made in view of the above circumstances, and the object of the present invention is to:
The compound itself has curability and is soluble in solvents,
Another object of the present invention is to provide a novel charge transport material suitable for an electrophotographic photoreceptor, which can form a layer having excellent solvent resistance after curing. A further object of the present invention is to provide a production method capable of efficiently producing the novel charge transport material.
【０００８】[0008]
【課題を解決するための手段】本発明の電荷輸送材料
は、下記一般式（Ｉ）で示される。The charge transport material of the present invention is represented by the following general formula (I).
【０００９】[0009]
【化７】 [Chemical 7]
【００１０】式中、Ａは下記一般式（Ａ−１）または
（Ａ−２）を示し、Ｒ1 は水素、炭素数１〜１０のアル
キル基、炭素数１〜１０の置換あるいは未置換のアリー
ル基、Ｒ2 は水素、炭素数１〜４のアルキル基、炭素数
１〜４のトリアルキルシリル基、Ｒ3 〜Ｒ6 は水素、又
は、ニトロ基を示し、Ｙ1 、Ｙ2 はそれぞれ独立に＝
Ｏ、＝Ｃ（ＣＮ）2 、＝Ｃ（ＣＯ2 Ｒ7 ）2 を示す。Ｒ
7 は炭素数１〜１０のアルキル基、炭素数１〜１０の置
換あるいは未置換のアリール基示し、ｍは１〜１０の整
数、ｎは１〜３の整数、ｏ〜ｒはそれぞれ独立に０、１
あるいは２を示す。In the formula, A represents the following general formula (A-1) or (A-2), R 1 is hydrogen, an alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted C 1 to 10 carbon atom. aryl group, R 2 represents hydrogen, an alkyl group having 1 to 4 carbon atoms, a trialkylsilyl group having 1 to 4 carbon atoms, R 3 to R 6 are hydrogen, also
Represents a nitro group , and Y 1 and Y 2 are independently =
O, ═C (CN) 2 and ═C (CO 2 R 7 ) 2 are shown. R
7 represents an alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted aryl group having 1 to 10 carbon atoms, m is an integer of 1 to 10, n is an integer of 1 to 3, and o to r are each independently 0. 1
Or 2 is shown.
【００１１】[0011]
【化８】 [Chemical 8]
【００１２】即ち、本発明の電荷輸送材料化合物は、ア
ルコキシシリル基を導入することにより中間層の形成時
には溶剤に可溶で、中間層上に感光層を形成する際には
難溶／不溶な中間層を得ることができる新規な電子輸送
材料である。またさらに、電荷輸送層上に電荷発生層を
形成した電子写真感光体の場合、最上面となる電荷発生
層の強度が弱いため、表面保護層を施す場合が多いが、
この場合にも電子輸送性を有する高強度の表面保護層が
必要となる。本発明の材料はアルコキシシリル基を有す
るため、シリコンハードコートなどの無機成分の多いマ
トリックスにも相溶させることができ、強度の高い膜を
得ることができる。また、シリコウエハー、ＩＴＯガラ
ス、Ａｌ、Ｆｅなどの種々の金属上にディッピング、Ｌ
Ｂ法、スピンキャスト法などで電子輸送性の単分子層、
あるいは、薄膜を形成することが可能であり、これら表
面の改質が可能となる。That is, the charge transport material compound of the present invention is soluble in a solvent when an intermediate layer is formed by introducing an alkoxysilyl group, and is hardly soluble / insoluble when a photosensitive layer is formed on the intermediate layer. It is a novel electron-transporting material capable of obtaining an intermediate layer. Furthermore, in the case of an electrophotographic photosensitive member having a charge generation layer formed on a charge transport layer, since the strength of the charge generation layer which is the uppermost surface is weak, a surface protective layer is often applied,
Also in this case, a high-strength surface protective layer having an electron transporting property is required. Since the material of the present invention has an alkoxysilyl group, it can be made compatible with a matrix having many inorganic components such as a silicon hard coat, and a film having high strength can be obtained. In addition, dipping on various metals such as silicon wafer, ITO glass, Al, Fe, L
Electron transporting monolayer by B method, spin casting method, etc.,
Alternatively, a thin film can be formed, and these surfaces can be modified.
【００１３】また、本発明の電荷輸送材料の製造方法
は、まず、式中Ａで表される基本骨格を合成した後、そ
れをハロゲン化して下記一般式（ＩＶ）で示される化合
物とし、合成の最終段階でその一般式（ＩＶ）で示され
る化合物と下記一般式（Ｖ）で示される化合物とを、非
プロトン性の有機溶剤中で反応させる、ことを特徴とす
る。Further, in the method for producing a charge transport material of the present invention, first, a basic skeleton represented by A in the formula is synthesized, and then halogenated to obtain a compound represented by the following general formula (IV). In the final step of, the compound represented by the general formula (IV) and the compound represented by the following general formula (V) are reacted in an aprotic organic solvent.
【００１４】[0014]
【化９】 [Chemical 9]
【００１５】式中、Ａは下記一般式（Ａ−１）または
（Ａ−２）を示し、Ｒ1 は水素、炭素数１〜１０のアル
キル基、炭素数１〜１０の置換あるいは未置換のアリー
ル基、Ｒ2 は水素、炭素数１〜４のアルキル基、炭素数
１〜４のトリアルキルシリル基、Ｒ3 〜Ｒ6 は水素、又
は、ニトロ基を示し、Ｙ1 、Ｙ2 はそれぞれ独立に＝
Ｏ、＝Ｃ（ＣＮ）2 、＝Ｃ（ＣＯ2 Ｒ7 ）2 を示す。Ｒ
7 は炭素数１〜１０のアルキル基、炭素数１〜１０の置
換あるいは未置換のアリール基示し、ｍは１〜１０の整
数、ｎは１〜３の整数、ｏ〜ｒはそれぞれ独立に０、１
あるいは２を示す。In the formula, A represents the following general formula (A-1) or (A-2), R 1 is hydrogen, an alkyl group having 1 to 10 carbon atoms, or a substituted or unsubstituted carbon atom having 1 to 10 carbon atoms. aryl group, R 2 represents hydrogen, an alkyl group having 1 to 4 carbon atoms, a trialkylsilyl group having 1 to 4 carbon atoms, R 3 to R 6 are hydrogen, also
Represents a nitro group , and Y 1 and Y 2 are independently =
O, ═C (CN) 2 and ═C (CO 2 R 7 ) 2 are shown. R
7 represents an alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted aryl group having 1 to 10 carbon atoms, m is an integer of 1 to 10, n is an integer of 1 to 3, and o to r are each independently 0. 1
Or 2 is shown.
【００１６】[0016]
【化１０】 [Chemical 10]
【００１７】[0017]
【発明の実施の形態】以下に、本発明を詳細に説明す
る。BEST MODE FOR CARRYING OUT THE INVENTION The present invention is described in detail below.
【００１８】前記一般式（Ｉ）において、Ａは前記一般
式（Ａ−１）または（Ａ−２）を示す。これらの基は電
荷輸送性に関与するものである。一般式（Ａ−１）にお
いてＲ3 及びＲ4 はそれぞれ独立に水素、又は、ニトロ
基を示す。また、Ａが−Ｃ（＝Ｏ）ＮＨ（ＣＨ2 ）m −
ＳｉＲ1 (3-n) （ＯＲ2 ）n と結合する結合手の位置
は、分子全体のダイポールモーメントを低下する位置で
あることが溶解性の観点からは好ましく、特に４位が好
ましい。In the general formula (I), A represents the general formula (A-1) or (A-2). These groups are involved in charge transportability. In formula (A-1), R 3 and R 4 are each independently hydrogen or nitro.
Indicates a group . Also, A is -C (= O) NH (CH 2) m -
From the viewpoint of solubility, the position of the bond for bonding to SiR 1 (3-n) (OR 2 ) n is preferably a position that reduces the dipole moment of the entire molecule, and the 4-position is particularly preferable.
【００１９】Ｙ1 は＝Ｏ、＝Ｃ（ＣＮ）2 、＝Ｃ（ＣＯ
2 Ｒ7 ）2 を示し、好ましくは、＝Ｃ（ＣＮ）2 であ
る。Ｒ7 は炭素数１〜１０のアルキル基、炭素数１〜１
０の置換あるいは未置換のアリール基示し、好ましく
は、メチル基、エチル基、フェニル基等である。Y 1 is = O, = C (CN) 2 , = C (CO
2 R 7 ) 2 is shown, and preferably = C (CN) 2 . R 7 is an alkyl group having 1 to 10 carbon atoms, 1 to 1 carbon atoms
It represents a substituted or unsubstituted aryl group of 0, and is preferably a methyl group, an ethyl group, a phenyl group or the like.
【００２０】ｏ及びｐはそれぞれ独立に０、１あるいは
２を示す。これらの基がそれぞれバランスすることによ
り、本発明の電荷輸送材料として好ましい機能を発現す
る。例えば、Ｙ1 が＝ＯのときはＲ3 及びＲ4 はそれぞ
れ電子吸引性の基、即ち、ニトロ基等の、一般式（Ｉ
Ｉ）で表される如きものが特に好ましい。O and p each independently represent 0, 1 or 2. By balancing each of these groups, the charge transport material of the present invention exhibits a preferable function. For example, each time the Y 1 is = O R 3 and R 4 are electron-withdrawing group, i.e., of a nitro group, the general formula (I
Those represented by I) are particularly preferable.
【００２１】また、一般式（Ａ−２）においてＲ5 及び
Ｒ6 はそれぞれ独立に水素、又は、ニトロ基を示す。ま
た、Ａが−Ｃ（＝Ｏ）ＮＨ（ＣＨ2 ）m −ＳｉＲ1
(3-n) （ＯＲ2 ）n と結合する結合手の位置は、分子全
体のダイポールモーメントを低下する位置であることが
溶解性の観点からは好ましく、特に２位が好ましい。In the general formula (A-2), R 5 and R 6 each independently represent hydrogen or a nitro group . Also, A is -C (= O) NH (CH 2) m -SiR 1
From the viewpoint of solubility, the position of the bond that bonds to (3-n) (OR 2 ) n is preferably a position that reduces the dipole moment of the entire molecule, and the position 2 is particularly preferable.
【００２２】ｑ及びｒはそれぞれ独立に０、１あるいは
２を示す。Ｙ1 、Ｙ2 はそれぞれ独立に、＝Ｏ、＝Ｃ
（ＣＮ）2 、＝Ｃ（ＣＯ2 Ｒ7 ）2 を示し、好ましく
は、＝Ｃ（ＣＮ）2 である。ここで、Ｒ5 及びＲ6 はそ
れぞれ電子吸引性の基、即ち、ニトロ基等である、一般
式（ＩＩＩ）で表される如きものが特に好ましい。Q and r each independently represent 0, 1 or 2. Y 1 and Y 2 are independently ═O and ═C.
(CN) 2 and ═C (CO 2 R 7 ) 2 are shown, and preferably ═C (CN) 2 . Here, it is particularly preferable that R 5 and R 6 are each an electron-withdrawing group, that is, a nitro group or the like, as represented by the general formula (III).
【００２３】全体としてＡは、還元電位が対ＳＣＥで−
０．８Ｖ以上のものが好ましい。また、Ｒ1 は水素、炭
素数１〜１０のアルキル基、炭素数１〜１０の置換ある
いは未置換のアリール基を表すが、なかでも炭素数１〜
１０のアルキル基、置換フェニル基が好ましく、具体的
には、メチル基、エチル基等である。ここでアリール基
に結合する置換基としては、メチル基、エチル基等が挙
げられる。As a whole, A has a reduction potential with respect to SCE-
It is preferably 0.8 V or more. R 1 represents hydrogen, an alkyl group having 1 to 10 carbon atoms, or a substituted or unsubstituted aryl group having 1 to 10 carbon atoms.
The alkyl group and the substituted phenyl group of 10 are preferable, and specifically, a methyl group, an ethyl group and the like. Here, examples of the substituent bonded to the aryl group include a methyl group and an ethyl group.
【００２４】Ｒ2 は水素、炭素数１〜４のアルキル基、
炭素数１〜４のトリアルキルシリル基であり、これらの
アルキル基として具体的には、メチル基、エチル基等が
挙げられる。R 2 is hydrogen, an alkyl group having 1 to 4 carbon atoms,
A trialkylsilyl group having 1 to 4 carbon atoms, and specific examples of these alkyl groups include a methyl group and an ethyl group.
【００２５】ｍは１〜１０の整数、ｎは１〜３の整数で
ある。本発明の電荷輸送材料においては、Ａが電荷輸送
性に、−Ｃ（＝Ｏ）ＮＨ（ＣＨ2 ）m −ＳｉＲ1 (3-n)
（ＯＲ2 ）n が製膜性と、形成された膜の強度、耐溶剤
性に寄与している。M is an integer of 1 to 10 and n is an integer of 1 to 3. In the charge-transporting material of the present invention, A in the charge transport, -C (= O) NH ( CH 2) m -SiR 1 (3-n)
(OR 2 ) n contributes to the film forming property, strength of the formed film, and solvent resistance.
【００２６】次に、本発明の化合物の合成方法について
説明する。例えば下記式（Ｃ）で示すような化合物［一
般式（Ｉ）においてＡが一般式（Ａ−１）、Ｙ1 が＝Ｏ
である化合物］は下記合成ルート １の方法で、化合物
（Ｄ）で示すような化合物［一般式（Ｉ）においてＡが
一般式（Ａ−１）、Ｙ1 がＣ（ＣＮ）2 である化合物］
は合成ルート １、２のどちらの方法でも合成できる。Next, a method for synthesizing the compound of the present invention will be described. For example, a compound represented by the following formula (C) [in the general formula (I), A is the general formula (A-1) and Y 1 is ═O
Is a compound represented by compound (D) [a compound of the general formula (I) in which A is the general formula (A-1) and Y 1 is C (CN) 2 by the method of the following synthetic route 1] ]
Can be synthesized by either of the synthetic routes 1 and 2.
【００２７】[0027]
【化１１】 [Chemical 11]
【００２８】まず、合成ルート １について説明する。
まず、一般式（Ａ−１）あるいは一般式（Ａ−２）で示
される構造を有するカルボン酸誘導体から、第４版実検
化学講座、２２巻ｐ．１１５〜１２７に記載されたよう
な常法により酸ハロゲン化物を合成する。ハロゲン化試
薬としては塩化チオニル、三塩化リン、五塩化リン、臭
化チオニル、五臭化リンなどが使用でき、カルボン酸誘
導体に対して通常は１〜３当量、好ましくは１〜２当量
使用される。First, the synthesis route 1 will be described.
First, from the carboxylic acid derivative having a structure represented by the general formula (A-1) or the general formula (A-2), 4th edition, practical inspection chemistry course, 22 volumes p. The acid halide is synthesized by a conventional method as described in 115-127. As the halogenating reagent, thionyl chloride, phosphorus trichloride, phosphorus pentachloride, thionyl bromide, phosphorus pentabromide and the like can be used, and it is usually used in 1 to 3 equivalents, preferably 1 to 2 equivalents relative to the carboxylic acid derivative. It
【００２９】反応にはベンゼン、トルエン、ジクロロメ
タン、クロロホルムなどの溶剤を使用することもでき
る。使用する溶剤の量はカルボン酸誘導体１重量部に対
し１〜５０重量部、好ましくは、１．５〜３０重量部で
用いられる。さらに反応を促進するために、ＤＭＦ、ピ
リジン、ＨＭＰＡなどを加えてもよい。これらの量は任
意であるが、カルボン酸誘導体１重量部に対し０．００
１〜５重量部、好ましくは、０．００５〜３重量部で用
いられる。反応は０°Ｃ〜溶剤の沸点の間で任意に設定
できる。さらに、反応終了後、過剰のハロゲン化試薬を
減圧蒸留や再結晶により除去することが好ましい。A solvent such as benzene, toluene, dichloromethane or chloroform may be used in the reaction. The amount of the solvent used is 1 to 50 parts by weight, preferably 1.5 to 30 parts by weight, based on 1 part by weight of the carboxylic acid derivative. To further accelerate the reaction, DMF, pyridine, HMPA or the like may be added. Although these amounts are arbitrary, 0.001 part by weight of the carboxylic acid derivative is used.
It is used in an amount of 1 to 5 parts by weight, preferably 0.005 to 3 parts by weight. The reaction can be arbitrarily set between 0 ° C and the boiling point of the solvent. Further, it is preferable to remove excess halogenating reagent by distillation under reduced pressure or recrystallization after completion of the reaction.
【００３０】得られた酸ハロゲン化物を用い、第４版実
検化学講座、２２巻ｐ．１４４〜１４６に記載されたよ
うな方法で化合物（Ｃ）を得ることができる。反応は、
まず、酸ハロゲン化物をベンゼン、トルエン、ジクロロ
メタン、クロロホルムなどの溶剤中に加え、これに酸ハ
ロゲン化物に対し１当量以上の前記一般式（Ｖ）で示さ
れるアミン化合物を、所望によってはベンゼン、トルエ
ン、ジクロロメタン、クロロホルムなどの溶剤に溶解し
た溶液とし、ゆっくりと滴下する。この際、反応が激し
く起こる場合には必要により冷却する。反応の際に生じ
るハロゲン化水素を中和するために、ピリジンや炭酸ナ
トリウムなどの塩基を加えるか、あるいは、（Ｖ）で示
されるアミン化合物をカルボン酸誘導体に対して２当量
以上加えてアミン化合物自身で中和させてもよい。Using the obtained acid halide, 4th edition, actual inspection chemistry course, 22 volumes p. Compound (C) can be obtained by the method as described in 144-146. The reaction is
First, an acid halide is added to a solvent such as benzene, toluene, dichloromethane, and chloroform, and 1 equivalent or more of the amine compound represented by the general formula (V) is added to the solvent, if desired. , A solution dissolved in a solvent such as dichloromethane or chloroform, and slowly add dropwise. At this time, if the reaction occurs violently, it is cooled if necessary. In order to neutralize hydrogen halide generated during the reaction, a base such as pyridine or sodium carbonate is added, or an amine compound represented by (V) is added in an amount of 2 equivalent or more with respect to the carboxylic acid derivative. You may neutralize it yourself.
【００３１】得られた化合物（Ｃ）を所望によってはカ
ラムクロマトグラフィー、再結晶などにより精製し、次
の反応に用いる。化合物（Ｄ）は化合物（Ｃ）とマロノ
ニトリルを、たとえば、Ｅｎｃｙｃｌｏｐｅｄｉａ ｏ
ｆ Ｒｅａｇｅｎｔｓ ｆｏｒ Ｏｒｇａｎｉｃ Ｓｙ
ｎｔｈｅｓｉｓ， ｖｏｌ．５， ｐ．３２１４〜３２
１７（Ｊｏｈｎ Ｗｉｌｅｙ ＆ Ｓｏｎｓ， １９９
５）に記載された様な方法で縮合させ合成することがで
きる。化合物（Ｃ）１重量部を１〜５０重量部、好まし
くは、１．５〜３０重量部のベンゼン、トルエン、ジク
ロロメタン、クロロホルム、メタノール、エタノール、
ＤＭＦなどの溶剤に溶解させ、これに化合物（Ｃ）に対
し１〜５当量、好ましくは１〜３当量のマロノニトリル
を加え、触媒として酢酸アンモニウム、酢酸カリウム、
酢酸ナトリウム、ピリジン、ピペリジン、四塩化チタン
などが任意の量で使用できる。The obtained compound (C) is, if desired, purified by column chromatography, recrystallization or the like and used in the next reaction. The compound (D) is obtained by combining the compound (C) with malononitrile, for example, Encyclopedia o
f Reagents for Organic Sy
nthesis, vol. 5, p. 3214-32
17 (John Wiley & Sons, 199)
It can be synthesized by condensation by the method described in 5). 1 to 50 parts by weight of compound (C), preferably 1.5 to 30 parts by weight of benzene, toluene, dichloromethane, chloroform, methanol, ethanol,
It is dissolved in a solvent such as DMF, 1-5 equivalents, preferably 1-3 equivalents of malononitrile is added to the compound (C), and ammonium acetate, potassium acetate as a catalyst,
Sodium acetate, pyridine, piperidine, titanium tetrachloride and the like can be used in any amount.
【００３２】反応は、室温〜溶剤の沸点の間で任意に設
定できる。特に、アルコキシシリル基の加水分解を防ぐ
ため、Ｒ2 と同じ骨格を有するアルコールＲ2 ＯＨを溶
剤として使用することが好ましい。得られた化合物
（Ｄ）は、カラムクロマトグラフィー、再結晶などによ
り精製することが好ましい。The reaction can be arbitrarily set between room temperature and the boiling point of the solvent. In particular, to prevent hydrolysis of the alkoxysilyl group, it is preferable to use the alcohol R 2 OH having the same skeleton as R 2 as the solvent. The obtained compound (D) is preferably purified by column chromatography, recrystallization or the like.
【００３３】ついで合成ルート ２について説明する。Next, the synthesis route 2 will be described.
【００３４】[0034]
【化１２】 [Chemical 12]
【００３５】一般式（Ａ−１）あるいは（Ａ−２）で示
される構造を有するカルボン酸誘導体とマロノニトリル
を、たとえば、Ｅｎｃｙｃｌｏｐｅｄｉａ ｏｆ Ｒｅ
ａｇｅｎｔｓ ｆｏｒ Ｏｒｇａｎｉｃ Ｓｙｎｔｈｅ
ｓｉｓ， ｖｏｌ．５， ｐ．３２１４〜３２１７（Ｊ
ｏｈｎ Ｗｉｌｅｙ ＆ Ｓｏｎｓ，１９９５）に記載
された様な方法で縮合させ合成することができる。A carboxylic acid derivative having a structure represented by the general formula (A-1) or (A-2) and malononitrile are prepared, for example, from Encyclopedia of Re.
agents for Organic Synthes
sis, vol. 5, p. 3214-3217 (J
ohn Wiley & Sons, 1995).
【００３６】化合物（Ｃ）１重量部を１〜５０重量部、
好ましくは、１．５〜３０重量部のベンゼン、トルエ
ン、ジクロロメタン、クロロホルム、メタノール、エタ
ノール、ＤＭＦなどの溶剤に溶解させ、これに化合物
（Ｃ）に対し１〜５当量、好ましくは１〜３当量のマロ
ノニトリルを加え、触媒として酢酸アンモニウム、酢酸
カリウム、酢酸ナトリウム、ピリジン、ピペリジン、四
塩化チタンなどが任意の量で使用できる。反応は、室温
〜溶剤の沸点の間で任意に設定できる。所望によっては
カラムクロマトグラフィー、再結晶などにより精製し、
次の反応に用いる。1 to 50 parts by weight of the compound (C),
Preferably, it is dissolved in a solvent such as 1.5 to 30 parts by weight of benzene, toluene, dichloromethane, chloroform, methanol, ethanol and DMF, and 1 to 5 equivalents, preferably 1 to 3 equivalents relative to the compound (C). Malononitrile of is added, and ammonium acetate, potassium acetate, sodium acetate, pyridine, piperidine, titanium tetrachloride and the like can be used in any amount as a catalyst. The reaction can be arbitrarily set between room temperature and the boiling point of the solvent. Purify by column chromatography, recrystallization, etc. if desired,
Used for the next reaction.
【００３７】次いで、第４版実検化学講座、２２巻ｐ．
１１５〜１２７に記載されたような常法により酸ハロゲ
ン化物を合成する。ハロゲン化試薬としては塩化チオニ
ル、三塩化リン、五塩化リン、臭化チオニル、五臭化リ
ンなどが使用でき、カルボン酸誘導体に対して通常は１
〜３当量、好ましくは１〜２当量使用される。反応はベ
ンゼン、トルエン、ジクロロメタン、クロロホルムなど
の溶剤を使用することもできる。使用する溶剤の量はカ
ルボン酸誘導体１重量部に対し１〜５０重量部、好まし
くは、１．５〜３０重量部で用いられる。さらに反応を
促進するために、ＤＭＦ、ピリジン、ＨＭＰＡなどを加
えてもよい。これらの量は任意であるが、カルボン酸誘
導体１重量部に対し０．００１〜５重量部、好ましく
は、０．００５〜３重量部で用いられる。反応は０°Ｃ
〜溶剤の沸点の間で任意に設定できる。さらに、反応終
了後、過剰のハロゲン化試薬を減圧蒸留や再結晶により
除去することが好ましい。Then, the fourth edition, actual inspection chemistry course, vol. 22, p.
The acid halide is synthesized by a conventional method as described in 115-127. As the halogenating reagent, thionyl chloride, phosphorus trichloride, phosphorus pentachloride, thionyl bromide, phosphorus pentabromide and the like can be used, and it is usually 1 for the carboxylic acid derivative.
~ 3 equivalents, preferably 1-2 equivalents are used. For the reaction, a solvent such as benzene, toluene, dichloromethane or chloroform can be used. The amount of the solvent used is 1 to 50 parts by weight, preferably 1.5 to 30 parts by weight, based on 1 part by weight of the carboxylic acid derivative. To further accelerate the reaction, DMF, pyridine, HMPA or the like may be added. Although these amounts are arbitrary, they are used in an amount of 0.001 to 5 parts by weight, preferably 0.005 to 3 parts by weight, based on 1 part by weight of the carboxylic acid derivative. Reaction is 0 ° C
~ It can be arbitrarily set between the boiling points of the solvent. Further, it is preferable to remove excess halogenating reagent by distillation under reduced pressure or recrystallization after completion of the reaction.
【００３８】得られた酸ハロゲン化物を用い、第４版実
検化学講座、２２巻ｐ．１４４〜１４６に記載されたよ
うな方法で化合物（Ｄ）を得ることができる。反応は、
まず酸ハロゲン化物をベンゼン、トルエン、ジクロロメ
タン、クロロホルムなどの溶剤中に加え、これに酸ハロ
ゲン化物に対し１当量以上の一般式（Ｖ）で示されるア
ミン化合物を所望によってはベンゼン、トルエン、ジク
ロロメタン、クロロホルムなどの溶剤に溶解した溶液と
し、ゆっくりと滴下する。この際、反応が激しく起こる
場合には必要により冷却する。反応の際に生じるハロゲ
ン化水素を中和するために、ピリジンや炭酸ナトリウム
などの塩基を加えるか、あるいは、一般式（Ｖ）で示さ
れるアミン化合物をカルボン酸誘導体に対して２当量以
上加えてアミン化合物自身で中和させてもよい。得られ
た化合物（Ｄ）は、カラムクロマトグラフィー、再結晶
などにより精製することが好ましい。Using the obtained acid halide, 4th edition Practical Chemistry Lecture, Vol. 22, p. Compound (D) can be obtained by the method as described in 144-146. The reaction is
First, an acid halide is added to a solvent such as benzene, toluene, dichloromethane or chloroform, and 1 equivalent or more of the amine compound represented by the general formula (V) based on the acid halide is added thereto, if desired, benzene, toluene, dichloromethane, Make a solution dissolved in a solvent such as chloroform and add slowly. At this time, if the reaction occurs violently, it is cooled if necessary. In order to neutralize the hydrogen halide generated during the reaction, a base such as pyridine or sodium carbonate is added, or an amine compound represented by the general formula (V) is added in an amount of 2 equivalents or more with respect to the carboxylic acid derivative. You may neutralize with an amine compound itself. The obtained compound (D) is preferably purified by column chromatography, recrystallization or the like.
【００３９】ここで一般式（Ｄ）に示した如き、Ｙ1 が
Ｃ（ＣＮ）2 である化合物を合成する場合、先に示すよ
うに合成ルート １、２のいずれの過程を経ても合成は
可能である。しかしながら、本発明の化合物において、
硬化性という重要な機能に寄与するアルコキシシリル基
は加水分解を受けやすいため、合成ルート ２を用いる
ことが特に好ましい。When synthesizing a compound in which Y 1 is C (CN) 2 as shown in the general formula (D), the synthesis is performed through either of the synthetic routes 1 and 2 as described above. It is possible. However, in the compounds of the present invention,
It is particularly preferable to use Synthesis Route 2 because the alkoxysilyl group that contributes to the important function of curability is susceptible to hydrolysis.
【００４０】即ち、合成ルート １では最終ステップで
Ｃ（ＣＮ）2 基を導入する目的で過剰のマロノニトリル
を使用するため、その除去のためにカラムクロマトグラ
フィーなどの精製が必要であり、精製中にアルコキシシ
リル基の分解が起こり、収率の低下が生じる。これに対
し、合成ルート ２では、まず、Ｃ（ＣＮ）2 基を導入
し、その後、アルコキシシリル基よりも安定な酸ハロゲ
ン化物の段階で十分に精製しておけば、最後のステップ
で一般式（Ｖ）で示されるアミン化合物を反応させるア
ミド化反応が定量的に進行することにより高い収率が達
成され、さらに、最終段階で用いられる一般式（Ｖ）で
示されるアミン化合物に水溶性のものを使用すること
で、不純物である過剰なアミン化合物は水洗のみにより
除去され、純度の高い化合物（Ｄ）を得ることができ
る。That is, in Synthesis Route 1, since excess malononitrile is used for the purpose of introducing a C (CN) 2 group in the final step, purification such as column chromatography is required for its removal, and during purification, Decomposition of the alkoxysilyl group occurs, resulting in a decrease in yield. On the other hand, in the synthetic route 2, first, a C (CN) 2 group is introduced, and then, if it is sufficiently purified at the stage of an acid halide that is more stable than an alkoxysilyl group, the general formula is used in the final step. A high yield is achieved by quantitatively advancing the amidation reaction of reacting the amine compound represented by (V), and further, the amine compound represented by the general formula (V) used in the final stage is water-soluble. By using the compound, the excess amine compound as an impurity is removed only by washing with water, and the compound (D) having high purity can be obtained.
【００４１】このように、本発明の電荷輸送材料化合物
を製造するにあたっては、まず、目的とする化合物のう
ち、Ａで示される構造に所望の官能基を導入した後、そ
れを酸ハロゲン化物（即ち、一般式（ＩＶ）で示される
中間体）とし、合成の最終段階においてその酸ハロゲン
化物と一般式（Ｖ）で示されるアルコキシシリル基を有
するアミン化合物とを反応させることが収率の観点から
好ましい。このとき、一般式（ＩＶ）で示される化合物
と一般式（Ｖ）示される化合物との反応は非プロトン性
の有機溶媒中で行われることが好ましい。プロトン系の
溶媒を用いると溶媒自体は酸ハロゲン化物と反応して、
主たる反応が効率よく行われず、所望の化合物の収率が
著しく低下するため好ましくない。非プロトン性の有機
溶媒は、公知のものから選択しうるが、具体的には、ベ
ンゼン、トルエン、ジクロロメタン、クロロホルム、ク
ロロベンゼン等が好ましい。As described above, in producing the charge transport material compound of the present invention, first, of the target compounds, a desired functional group is introduced into the structure represented by A, and then the compound is converted into an acid halide ( That is, the intermediate represented by the general formula (IV) is used, and the acid halide thereof is reacted with the amine compound having the alkoxysilyl group represented by the general formula (V) in the final stage of the synthesis from the viewpoint of yield. Is preferred. At this time, the reaction between the compound represented by the general formula (IV) and the compound represented by the general formula (V) is preferably carried out in an aprotic organic solvent. When using a proton-based solvent, the solvent itself reacts with the acid halide,
It is not preferable because the main reaction is not efficiently carried out and the yield of the desired compound is significantly reduced. The aprotic organic solvent can be selected from known ones, but specifically, benzene, toluene, dichloromethane, chloroform, chlorobenzene and the like are preferable.
【００４２】本発明の化合物の具体的な構造を下記表１
〜表４に示す。Specific structures of the compounds of the present invention are shown in Table 1 below.
~ Shown in Table 4.
【００４３】[0043]
【表１】 [Table 1]
【００４４】[0044]
【表２】 [Table 2]
【００４５】[0045]
【表３】 [Table 3]
【００４６】[0046]
【表４】 [Table 4]
【００４７】[0047]
【実施例】以下、実施例によって本発明を説明するが、
本発明はこれらに限定されるものではない。
（実施例１）
（化合物３２の合成）
１００ｍｌの三口フラスコ中にアントラキノン−２−カ
ルボニルクロライド（東京化成製） １．０ｇ、トルエ
ン ２０ｍｌを入れ、窒素雰囲気下、室温で撹拌しなが
ら３−アミノプロピルトリメトキシシラン １．３３ｇ
を２０ｍｌのトルエンに溶解した溶液をゆっくりと滴下
した。滴下終了後、反応溶液を６０°Ｃで１時間加熱
し、反応を完結させたのち、室温まで冷却した。反応溶
液を十分に蒸留水で洗浄し、有機層を硫酸ナトリウムで
乾燥したのち、溶剤を減圧留去して、化合物３２の淡黄
色の結晶 １．３ｇ（収率８５％）を得た。EXAMPLES The present invention will be described below with reference to examples.
The present invention is not limited to these. (Example 1) (Compound 32 Synthesis of) anthraquinone-2-carbonyl chloride in a three-necked flask 100 ml (manufactured by Tokyo Kasei) 1.0 g, was placed toluene 20 ml, under nitrogen, with stirring at room temperature for 3 Aminopu b Pyrtrimethoxysilane 1.33 g
Was dissolved in 20 ml of toluene and the solution was slowly added dropwise. After completion of the dropping, the reaction solution was heated at 60 ° C. for 1 hour to complete the reaction, and then cooled to room temperature. The reaction solution was thoroughly washed with distilled water, the organic layer was dried over sodium sulfate, and then the solvent was distilled off under reduced pressure to obtain 1.3 g (yield 85%) of pale yellow crystals of Compound 32.
【００４８】得られた化合物３２のＩＲスペクトルを図
１に示す。
（実施例２）
（化合物１２の合成）５００ｍｌの三口フラスコ中に９
−フルオレノン−４−カルボン酸 ３０ｇ、トルエン
１００ｍｌ、ピリジン ０．３ｍｌを入れ、氷浴で冷却
しながらチオニルクロライド １２ｍｌをゆっくりと滴
下した。滴下終了後２時間加熱還流し、反応を完結させ
たのち、室温まで冷却した。これにジクロロメタン ３
００ｍｌを加え、不溶物を除去し、さらにヘキサン ２
５０ｍｌを加えて結晶を析出させた。得られた結晶をさ
らにジクロロメタン １３０ｍｌ、ヘキサン ８０ｍｌ
から再結晶して９−フルオレノン−４−カルボニルクロ
ライド ２５ｇ（収率７７％）を得た。The IR spectrum of the compound 32 thus obtained is shown in FIG. Example 2 (Synthesis of Compound 12) 9 in a 500 ml three-necked flask.
-Fluorenone-4-carboxylic acid 30 g, toluene
100 ml and pyridine 0.3 ml were put, and thionyl chloride 12 ml was slowly added dropwise while cooling with an ice bath. After completion of dropping, the mixture was heated under reflux for 2 hours to complete the reaction, and then cooled to room temperature. Dichloromethane 3
00 ml was added to remove insoluble matter, and hexane 2
50 ml was added to precipitate crystals. The crystals obtained were further added with 130 ml of dichloromethane and 80 ml of hexane.
The crystals were recrystallized from 9 to give 25 g (yield 77%) of 9-fluorenone-4-carbonyl chloride.
【００４９】得られた９−フルオレノン−４−カルボニ
ルクロライド １ｇを１００ｍｌの三口フラスコに入
れ、トルエン １０ｍｌを加え、窒素雰囲気下、室温で
撹拌しながら３−アミノプロピルトリメトキシシラン
１．４８ｇを１０ｍｌのトルエンに溶解した溶液をゆっ
くりと滴下した。滴下終了後、反応溶液を室温で１時間
撹拌し、反応を完結させたのち、反応溶液を十分に蒸留
水で洗浄し、有機層を硫酸ナトリウムで乾燥し、溶剤を
減圧留去して、化合物１２を淡黄色の油状物として
１．４ｇ（収率８８％）を得た。[0049] The resulting 9-fluorenone-4-carbonyl chloride 1g necked flask 100 ml, of toluene 10ml was added, under nitrogen atmosphere, with stirring at room temperature for 3 Aminopu b pills trimethoxysilane
A solution of 1.48 g dissolved in 10 ml of toluene was slowly added dropwise. After completion of the dropwise addition, the reaction solution was stirred at room temperature for 1 hour to complete the reaction, and then the reaction solution was thoroughly washed with distilled water, the organic layer was dried over sodium sulfate, and the solvent was distilled off under reduced pressure. 12 as a pale yellow oil
1.4 g (88% yield) was obtained.
【００５０】得られた化合物１２のＩＲスペクトルを図
２に示す。
（実施例３）
（化合物１７の合成ルート １による合成）実施例２で
合成した１ｇの化合物１２を５０ｍｌのフラスコに入
れ、マロノニトリル ０．５４ｇ、メタノール １０ｍ
ｌ、ピペリジン １滴を加え、窒素雰囲気下で１．５時
間加熱還流した。反応終了後、室温まで冷却し、溶剤を
減圧留去したのち、ジクロロメタンを用いてシリカゲル
カラムクロマトグラフィーにより精製した。これをトル
エンとヘキサンの混合溶剤で再結晶して、化合物１７を
０．２９ｇ（収率２６％）得た。The IR spectrum of the resulting compound 12 is shown in FIG. (Example 3) (Synthesis route 1 of compound 17) 1 g of the compound 12 synthesized in Example 2 was placed in a 50 ml flask, and malononitrile (0.54 g) and methanol (10 m) were added.
1, 1 drop of piperidine were added, and the mixture was heated under reflux for 1.5 hours in a nitrogen atmosphere. After completion of the reaction, the mixture was cooled to room temperature, the solvent was distilled off under reduced pressure, and the residue was purified by silica gel column chromatography using dichloromethane. This was recrystallized with a mixed solvent of toluene and hexane to obtain 0.29 g of Compound 17 (yield 26%).
【００５１】得られた化合物１７のＩＲスペクトルを図
３に示す。
（実施例４）
（化合物１７の合成ルート ２による合成）２００ｍｌ
の三口フラスコ中に９−フルオレノン−４−カルボン酸
１０ｇ、マロノニトリル ５．９ｇ、メタノール １
５０ｍｌ、ピペリジン ２ｍｌを入れ、窒素雰囲気下で
３時間加熱還流し、反応を完結させたのち、室温まで冷
却した。これに１Ｎ−塩酸 １５ｍｌを加えて９−ジシ
アノメチレニルフルオレン−４−カルボン酸を橙色結晶
として １０．３ｇ（収率８４％）得た。得られた結晶
５ｇを１００ｍｌのフラスコに入れ、、トルエン ５
０ｍｌ、ピリジン ０．５ｍｌを入れ、氷浴で冷却しな
がら撹拌している中にチオニルクロライド ３．３ｇを
トルエン ２０ｍｌに溶かした溶液をゆっくりと滴下し
た。滴下終了後、２時間加熱還流し、反応を完結させた
のち、室温まで冷却した。デカンテーションで不溶物を
除去したのち、ヘキサン ４０ｍｌを加えて結晶を析出
させた。得られた結晶をヘキサンで十分に洗浄し、乾燥
して９−ジシアノメチレニルフルオレン−４−カルボニ
ルクロライドを橙色結晶として ４．７ｇ（収率８８
％）得た。９−ジシアノメチレニルフルオレン−４−カ
ルボニルクロライド １ｇを１００ｍｌの三口フラスコ
に入れ、トルエン ２０ｍｌを加え、素雰囲気化、室温
で撹拌しながら３−アミノプトピルトリメトキシシラン
１．２３ｇを１０ｍｌのトルエンに溶解した溶液をゆ
っくりと滴下した。滴下終了後、反応溶液を室温で１時
間撹拌し、反応を完結させたのち、反応溶液を十分に蒸
留水で洗浄し、有機層を硫酸ナトリウムで乾燥した。溶
剤を減圧留去した後、トルエンとヘキサンの混合溶剤で
再結晶して、化合物１７を１．１５ｇ（収率７７％）得
た。得られた化合物のＩＲスペクトルを測定したとこ
ろ、実施例３において示した図３と同様であった。
（実施例５）
（化合物１６の合成）５００ｍｌの三口フラスコ中に
２，７−ジニトロ−９−フルオレノン−４−カルボン酸
３０ｇ、トルエン ２００ｍｌ、ピリジン １．０ｍ
ｌを入れ、氷浴で冷却しながらチオニルクロライド １
３．６ｇをゆっくりと滴下した。滴下終了後２時間加熱
還流し、反応を完結させたのち、室温まで冷却した。不
溶物を除去し、ヘキサン ２００ｍｌを加えて結晶を析
出させた。得られた結晶をさらにヘキサンで洗浄して、
２，７−ジニトロ−９−フルオレノン−４−カルボニル
クロライド ２７．３ｇ（収率８６％）を得た。The IR spectrum of the obtained compound 17 is shown in FIG. (Example 4) (Synthesis route 2 of compound 17) 200 ml
9-fluorenone-4-carboxylic acid 10 g, malononitrile 5.9 g, methanol 1 in a 3-necked flask.
After adding 50 ml and 2 ml of piperidine and heating and refluxing for 3 hours under nitrogen atmosphere, the reaction was completed and then cooled to room temperature. To this was added 15 ml of 1N-hydrochloric acid to obtain 10.3 g (yield 84%) of 9-dicyanomethylenylfluorene-4-carboxylic acid as orange crystals. 5 g of the obtained crystal was placed in a 100 ml flask, and toluene 5
A solution of 3.3 g of thionyl chloride in 20 ml of toluene was slowly added dropwise to 0 ml of pyridine and 0.5 ml of pyridine while stirring with cooling in an ice bath. After completion of dropping, the mixture was heated under reflux for 2 hours to complete the reaction, and then cooled to room temperature. After removing the insoluble matter by decantation, 40 ml of hexane was added to precipitate crystals. The obtained crystals were thoroughly washed with hexane and dried to give 9-dicyanomethylenylfluorene-4-carbonyl chloride as orange crystals (4.7 g, yield 88).
%)Obtained. 1-g of 9-dicyanomethylenylfluorene-4-carbonyl chloride was put into a 100-ml three-necked flask, 20 ml of toluene was added, and 1.23 g of 3-aminotopyrtrimethoxysilane was added to 10 ml of toluene while stirring at room temperature and at room temperature. The dissolved solution was slowly added dropwise. After completion of dropping, the reaction solution was stirred at room temperature for 1 hour to complete the reaction, and then the reaction solution was thoroughly washed with distilled water, and the organic layer was dried over sodium sulfate. After the solvent was distilled off under reduced pressure, it was recrystallized with a mixed solvent of toluene and hexane to obtain 1.15 g of Compound 17 (yield 77%). When the IR spectrum of the obtained compound was measured, it was similar to that shown in FIG. (Example 5) (Synthesis of Compound 16) 30 g of 2,7-dinitro-9-fluorenone-4-carboxylic acid, 200 ml of toluene, 1.0 m of pyridine in a 500 ml three-necked flask.
Add 1 L and cool with an ice bath while thionyl chloride 1
3.6 g was slowly added dropwise. After completion of dropping, the mixture was heated under reflux for 2 hours to complete the reaction, and then cooled to room temperature. The insoluble matter was removed, and 200 ml of hexane was added to precipitate crystals. The obtained crystals are further washed with hexane,
27.3 g (yield 86%) of 2,7-dinitro-9-fluorenone-4-carbonyl chloride was obtained.
【００５２】得られた２，７−ジニトロ−９−フルオレ
ノン−４−カルボニルクロライド１０ｇを５００ｍｌの
三口フラスコに入れ、トルエン ２００ｍｌを加え、窒
素雰囲気下、室温で撹拌しながら３−アミノプトピルト
リメトキシシラン １０．８ｇを１００ｍｌのトルエン
に溶解した溶液をゆっくりと滴下した。滴下終了後、反
応溶液を室温で１時間撹拌し、反応を完結させたのち、
反応溶液を十分に蒸留水で洗浄し、有機層を硫酸ナトリ
ウムで乾燥し、溶剤を減圧留去して、化合物１６を１
０．８ｇ（収率７５％）得た。10 g of the obtained 2,7-dinitro-9-fluorenone-4-carbonyl chloride was placed in a 500 ml three-necked flask, 200 ml of toluene was added, and 3-aminoputopyrtrimethoxy was added while stirring at room temperature under a nitrogen atmosphere. A solution prepared by dissolving 10.8 g of silane in 100 ml of toluene was slowly added dropwise. After completion of the dropping, the reaction solution was stirred at room temperature for 1 hour to complete the reaction,
The reaction solution was thoroughly washed with distilled water, the organic layer was dried over sodium sulfate, and the solvent was distilled off under reduced pressure to give compound 16 (1).
0.8 g (yield 75%) was obtained.
【００５３】得られた化合物１６のＩＲスペクトルを図
４に示す。
（応用例１）実施例４で合成した化合物１７を１重量
部、ポリビニルブチラール樹脂（商品名：エスレックＢ
Ｍ−Ｓ、積水化学社製）１重量部、メタノール１０重量
部、ブタノール１０重量部を混合し、溶解した。これ
に、１Ｎ−塩酸を５０μｌ加えて塗布液を調製した。得
られた塗布液をホーニング処理を施したアルミニウムパ
イプを支持体として、その上に浸漬コーティング法で塗
布し、１７０°Ｃにおいて１０分加熱乾燥して膜厚１．
０μｍの下引き層を形成した。The IR spectrum of the resulting compound 16 is shown in FIG. (Application Example 1) 1 part by weight of the compound 17 synthesized in Example 4, polyvinyl butyral resin (trade name: S-REC B
(MS, manufactured by Sekisui Chemical Co., Ltd.) 1 part by weight, methanol 10 parts by weight, butanol 10 parts by weight were mixed and dissolved. To this, 50 μl of 1N-hydrochloric acid was added to prepare a coating solution. The obtained coating liquid was applied onto the aluminum pipe which had been subjected to a honing treatment as a support by the dip coating method, and was dried by heating at 170 ° C. for 10 minutes to give a film thickness of 1.
An undercoat layer of 0 μm was formed.
【００５４】次いで、図５に示したような粉末Ｘ線回折
パターンを示すヒドロキシガリウムフタロシアニン結晶
０．１部をポリビニルブチラール樹脂（商品名：エスレ
ックＢＭ−Ｓ、積水化学社製）０．１部および酢酸ｎ−
ブチル １０部と混合し、ガラスビーズとともにペイン
トシェーカーで１時間処理して分散した後、得られた塗
布液を上記下引層上に浸漬コーティング法で塗布し、１
００°Ｃにおいて１０分間加熱乾燥し、膜厚約０．１５
μｍの電荷発生層を形成した。また分散後の前記ヒドロ
キシガリウムフタロシアニン結晶の結晶形はＸ線回折に
よって分散前の結晶形と比較して変化していないことを
確認した。Next, 0.1 part of hydroxygallium phthalocyanine crystal showing a powder X-ray diffraction pattern as shown in FIG. 5 was added with 0.1 part of polyvinyl butyral resin (trade name: S-REC BM-S, manufactured by Sekisui Chemical Co., Ltd.) and Acetic acid n-
After mixing with 10 parts of butyl and treating with glass beads for 1 hour with a paint shaker to disperse, the obtained coating liquid is applied onto the above subbing layer by a dip coating method, and 1
Heat dried at 00 ° C for 10 minutes, film thickness about 0.15
A charge generation layer of μm was formed. It was also confirmed by X-ray diffraction that the crystal form of the hydroxygallium phthalocyanine crystal after dispersion was not changed as compared with the crystal form before dispersion.
【００５５】次に下記構造式（ＶＩ）で示される電荷輸
送材料２部と構造式（ＶＩＩ）で示されるポリカーボネ
ート樹脂３部とをモノクロロベンゼン ２０部に溶解
し、得られた塗布液を電荷発生層が形成されたアルミニ
ウム支持体上に浸漬コーティング法で塗布し、１２０°
Ｃにおいて１時間加熱乾燥、膜厚２０μｍの電荷輸送層
を形成した。Next, 2 parts of the charge transporting material represented by the following structural formula (VI) and 3 parts of the polycarbonate resin represented by the structural formula (VII) are dissolved in 20 parts of monochlorobenzene, and the resulting coating solution is subjected to charge generation. It is applied by a dip coating method on an aluminum support on which a layer has been formed, and 120 °
By heating and drying in C for 1 hour, a charge transport layer having a film thickness of 20 μm was formed.
【００５６】[0056]
【化１３】 [Chemical 13]
【００５７】このようにして得られた電子写真用感光体
の電子写真特性を、レーザープリンター改造スキャナー
（ＸＰ−１５改造機、富士ゼロックス社製）を用いて、
（１）常温常湿（２０°Ｃ、４０％ＲＨ）環境下、グリ
ッド印加電圧−７００Ｖのスコロトロン帯電器で帯電し
（Ａ）、７８０ｎｍの半導体レーザーを用いて、１秒後
に１０．０ｅｒｇ／ｃｍ2 の光を照射して放電を行い
（Ｂ）、１秒後に５０．０ｅｒｇ／ｃｍ2 の赤色ＬＥＤ
光を照射して除電を行う（Ｃ）というプロセスによっ
て、各部の電位を測定した。（Ａ）の電位ＶＨが高いほ
ど、感光体の受容電位が高いので、コントラストを高く
とることができ、（Ｂ）の電位ＶＬは低いほど高感度で
あり、（Ｃ）のＶＲＰの電位は低いほど、残留電位が少
なく、画像メモリーやカブリが少ない感光体と評価され
る。また、１万回繰り返し帯電、露光後の各部の電位の
測定も行った。The electrophotographic characteristics of the electrophotographic photosensitive member thus obtained were measured with a laser printer remodeling scanner (XP-15 remodeling machine, manufactured by Fuji Xerox Co., Ltd.).
(1) Under normal temperature and normal humidity (20 ° C., 40% RH) environment, charged with a scorotron charger with a grid applied voltage of -700 V (A), and using a semiconductor laser of 780 nm, 1 second later, 10.0 erg / cm. Discharges by irradiating with 2 light (B), 1 second later, 50.0 erg / cm 2 red LED
The potential of each part was measured by a process of (C) of irradiating light to remove electricity. The higher the potential VH in (A), the higher the receptive potential of the photoconductor, and thus the higher the contrast, the lower the potential VL in (B), the higher the sensitivity, and the lower the potential in VRP in (C). The smaller the residual potential, the more evaluated as a photoconductor with less image memory and fogging. Also, the potential of each part after charging and exposure was repeated 10,000 times was measured.
【００５８】さらにこの測定を（２）低温低湿（１０°
Ｃ、１５％ＲＨ）、（３）高温高湿（２８°Ｃ、８５％
ＲＨ）の各環境下でも行い、（１）〜（３）環境間での
各部の電位の変動量（ΔＶＨ、ΔＶＬ、ΔＶＲＰ）を測
定し、環境安定性の評価を行った。その結果を表５に示
す。
（比較応用例 １）応用例１で使用した化合物１７の代
わりに下記構造式（ＶＩＩＩ）で表される３−アミノプ
ロピルトリメトキシシランを用い、さらに塗布液に１Ｎ
−塩酸を加えなかった以外は応用例１と同様に電子写真
用感光体を作製し、応用例１と同様に評価した。結果を
表５に示す。Further, this measurement is carried out by (2) low temperature and low humidity (10 °
C, 15% RH), (3) High temperature and high humidity (28 ° C, 85%
RH) under each environment, the amount of variation (ΔVH, ΔVL, ΔVRP) of the potential of each part between (1) to (3) environments was measured to evaluate the environmental stability. The results are shown in Table 5. (Comparative Application Example 1) 3-aminopropyltrimethoxysilane represented by the following structural formula (VIII) was used in place of the compound 17 used in Application Example 1, and 1N was further added to the coating solution.
An electrophotographic photosensitive member was prepared in the same manner as in Application Example 1 except that hydrochloric acid was not added, and was evaluated in the same manner as in Application Example 1. The results are shown in Table 5.
【００５９】[0059]
【化１４】
Ｈ2 Ｎ−（ＣＨ2 ）3 −Ｓｉ（ＯＣＨ3 ）3 （ＶＩＩＩ）
（比較応用例 ２）応用例１で使用した化合物１７の代
わりに下記構造式（ＩＸ）で示される化合物を用い、さ
らに塗布液に１Ｎ−塩酸を加えなかった以外は応用例１
と同様に電子写真用感光体を作製したが、電荷輸送層を
形成する際に下引き層が溶解したため、良好な層形成を
行うことができず、感光体としては評価不能であった。Embedded image H 2 N— (CH 2 ) 3 —Si (OCH 3 ) 3 (VIII) (Comparative Application Example 2) Instead of the compound 17 used in Application Example 1, a compound represented by the following structural formula (IX) Application Example 1 except that 1N-hydrochloric acid was not added to the coating solution
An electrophotographic photosensitive member was produced in the same manner as in 1. but the undercoat layer was dissolved during the formation of the charge transport layer, so that satisfactory layer formation could not be performed and evaluation as a photosensitive member was impossible.
【００６０】[0060]
【化１５】 [Chemical 15]
【００６１】（応用例 ２）応用例１で使用した化合物
１７の代わりに実施例１で得られた化合物３２を用いた
以外は応用例１と同様に電子写真用感光体を作製し、応
用例１と同様に評価した。結果を表５に示す。
（応用例 ３）応用例１で使用した化合物１７の代わり
に実施例２で得られた化合物１２を用いた以外は応用例
１と同様に電子写真用感光体を作製し、応用例１と同様
に評価した。結果を表５に示す。
（応用例 ４）応用例１で使用した化合物１７の代わり
に実施例５で得られた化合物１６を用いた以外は応用例
１と同様に電子写真用感光体を作製し、応用例１と同様
に評価した。結果を表５に示す。(Application Example 2) An electrophotographic photoreceptor was prepared in the same manner as in Application Example 1, except that the compound 32 obtained in Example 1 was used instead of the compound 17 used in Application Example 1. It evaluated similarly to 1. The results are shown in Table 5. (Application Example 3) An electrophotographic photoreceptor was prepared in the same manner as in Application Example 1 except that the compound 12 obtained in Example 2 was used in place of the compound 17 used in Application Example 1, and the same as in Application Example 1. Evaluated to. The results are shown in Table 5. (Application Example 4) An electrophotographic photoreceptor was prepared in the same manner as in Application Example 1 except that the compound 16 obtained in Example 5 was used in place of the compound 17 used in Application Example 1, and the same as in Application Example 1. Evaluated to. The results are shown in Table 5.
【００６２】[0062]
【表５】 [Table 5]
【００６３】表５にも明らかなように、本発明の電荷輸
送材料を用いた応用例１〜４の電子写真用感光体は、受
容電位が高く、高感度であり、残留電位も少ない優れた
特性を示し、しかも、いずれの環境下においても安定し
た特性を示した。一方、公知のアミノ化合物を用いた比
較応用例１は繰り返し使用後に感度及び残留電位の特性
が低下し、高温高湿、低温低湿等の環境安定性も応用例
に比較して劣っていた。また、耐溶剤性に寄与する基を
有さない公知の化合物を用いた比較応用例２は電荷輸送
層を形成する際に下引き層が溶解し、良好な層形成が不
可能であった。As is clear from Table 5, the electrophotographic photoreceptors of Application Examples 1 to 4 using the charge transport material of the present invention have a high receptive potential, high sensitivity, and excellent residual potential. The characteristics are shown, and the characteristics are stable under any environment. On the other hand, in Comparative Application Example 1 using a known amino compound, the sensitivity and residual potential characteristics were reduced after repeated use, and environmental stability such as high temperature and high humidity and low temperature and low humidity was also inferior to the application example. Further, in Comparative Application Example 2 in which a known compound having no group contributing to solvent resistance was used, the undercoat layer was dissolved when the charge transport layer was formed, and it was impossible to form a good layer.
【００６４】[0064]
【発明の効果】本発明の電荷輸送材料は溶剤に可溶であ
り、硬化性を有し、且つ、硬化により形成された膜は溶
剤に対して耐性があるため、たとえば、電子写真感光体
などに好適に応用できる。また、本発明の製造方法によ
れば、その新規電荷輸送材料を効率よく製造しうるとい
う効果を奏する。The charge transport material of the present invention is soluble in a solvent and has curability, and the film formed by curing is resistant to the solvent. Therefore, for example, an electrophotographic photoreceptor or the like. Can be suitably applied to. Further, according to the manufacturing method of the present invention, there is an effect that the novel charge transport material can be efficiently manufactured.
【図１】実施例１で得られた化合物１７のＩＲスペクト
ルを示す。FIG. 1 shows an IR spectrum of compound 17 obtained in Example 1.
【図２】実施例２で得られた化合物３２のＩＲスペクト
ルを示す。FIG. 2 shows an IR spectrum of compound 32 obtained in Example 2.
【図３】実施例３、４で得られた化合物１２のＩＲスペ
クトルを示す。FIG. 3 shows an IR spectrum of compound 12 obtained in Examples 3 and 4.
【図４】実施例５で得られた化合物１６のＩＲスペクト
ルを示す。FIG. 4 shows an IR spectrum of compound 16 obtained in Example 5.
【図５】応用例１で用いたヒドロキシガリウムフタロシ
アニン結晶の粉末Ｘ線回折パターンを示す。FIG. 5 shows a powder X-ray diffraction pattern of the hydroxygallium phthalocyanine crystal used in Application Example 1.
───────────────────────────────────────────────────── フロントページの続き (56)参考文献 特開 昭61−143764（ＪＰ，Ａ) 特開 昭47−28338（ＪＰ，Ａ) 特開 平９−15880（ＪＰ，Ａ) 特開 平８−286403（ＪＰ，Ａ) 特開 平８−179527（ＪＰ，Ａ) 特開 平８−134019（ＪＰ，Ａ) 特開 平７−199487（ＪＰ，Ａ) 特開 平２−203352（ＪＰ，Ａ) 特開 平２−135362（ＪＰ，Ａ) (58)調査した分野(Int.Cl.7，ＤＢ名) G03G 5/00 ＣＡ（ＳＴＮ) ＲＥＧＩＳＴＲＹ（ＳＴＮ)─────────────────────────────────────────────────── ─── Continuation of front page (56) Reference JP-A-61-143764 (JP, A) JP-A-47-28338 (JP, A) JP-A-9-15880 (JP, A) JP-A-8- 286403 (JP, A) JP-A-8-179527 (JP, A) JP-A-8-134019 (JP, A) JP-A-7-199487 (JP, A) JP-A-2-203352 (JP, A) JP-A-2-135362 (JP, A) (58) Fields investigated (Int.Cl. 7 , DB name) G03G 5/00 CA (STN) REGISTRY (STN)
Claims (7)
料。 【化１】 式中、Ａは下記一般式（Ａ−１）または（Ａ−２）を示
し、Ｒ1 は水素、炭素数１〜１０のアルキル基、炭素数
１〜１０の置換あるいは未置換のアリール基、Ｒ2 は水
素、炭素数１〜４のアルキル基、炭素数１〜４のトリア
ルキルシリル基、Ｒ3 〜Ｒ6 は水素、又は、ニトロ基を
示し、Ｙ1 、Ｙ2 はそれぞれ独立に＝Ｏ、＝Ｃ（ＣＮ）
2 、＝Ｃ（ＣＯ2 Ｒ7 ）2 を示す。Ｒ7 は炭素数１〜１
０のアルキル基、炭素数１〜１０の置換あるいは未置換
のアリール基示し、ｍは１〜１０の整数、ｎは１〜３の
整数、ｏ〜ｒはそれぞれ独立に０、１あるいは２を示
す。 【化２】 1. A charge transport material represented by the following general formula (I). [Chemical 1] In the formula, A represents the following general formula (A-1) or (A-2), R 1 represents hydrogen, an alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted aryl group having 1 to 10 carbon atoms, R 2 is hydrogen, an alkyl group having 1 to 4 carbon atoms, a trialkylsilyl group having 1 to 4 carbon atoms, R 3 to R 6 are hydrogen , or a nitro group , and Y 1 and Y 2 are each independently = O, = C (CN)
2 , ═C (CO 2 R 7 ) 2 is shown. R 7 has 1 to 1 carbon atoms
0 represents an alkyl group, a substituted or unsubstituted aryl group having 1 to 10 carbon atoms, m represents an integer of 1 to 10, n represents an integer of 1 to 3, and o to r each independently represent 0, 1 or 2. . [Chemical 2]
（ＩＩ）で示されることを特徴とする請求項１記載の電
荷輸送材料。 【化３】 式中、Ｙ1 は＝Ｏ、＝Ｃ（ＣＮ）2 、＝Ｃ（ＣＯ
2 Ｒ7 ）2 を示し、Ｒ7 は炭素数１〜１０のアルキル
基、炭素数１〜１０の置換あるいは未置換のアリール基
を示し、ｏ、ｐはそれぞれ独立に０、１あるいは２を示
す。2. The charge transport material according to claim 1, wherein A in the general formula (I) is represented by the following general formula (II). [Chemical 3] In the formula, Y 1 is ═O, ═C (CN) 2 , ═C (CO
2 R 7 ) 2 , R 7 represents an alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted aryl group having 1 to 10 carbon atoms, and o and p each independently represent 0, 1 or 2. .
（ＩＩＩ）で示されることを特徴とする請求項１記載の
電荷輸送材料。 Ｙ1 、Ｙ2 はそれぞれ独立に＝Ｏ、＝Ｃ（ＣＮ）2 、＝
Ｃ（ＣＯ2 Ｒ7 ）2 を示し、Ｒ7 は炭素数１〜１０のア
ルキル基、炭素数１〜１０の置換あるいは未置換のアリ
ール基を示し、ｑ、ｒはそれぞれ独立に０、１あるいは
２を示す。 【化４】 3. The charge transport material according to claim 1, wherein A in the general formula (I) is represented by the following structural formula (III). Y 1 and Y 2 are independently = O, = C (CN) 2 , =
C (CO 2 R 7) shows a 2, R 7 is an alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted aryl group having 1 to 10 carbon atoms, q, r independently is 0, 1 or 2 is shown. [Chemical 4]
料の製造において、 まず、式中Ａで表される基本骨格
を合成した後、それを下記一般式（ＩＶ）で示される酸
ハロゲン化物とし、 合成の最終段階でその一般式（ＩＶ）で示される化合物
と下記一般式（Ｖ）で示される化合物とを、非プロトン
性の有機溶剤中で反応させる、 ことを特徴とする前記一般式（Ｉ）で示される電荷輸送
材料の製造方法。 【化５】 式中、Ａは下記一般式（Ａ−１）または（Ａ−２）を示
し、Ｒ1 は水素、炭素数１〜１０のアルキル基、炭素数
１〜１０の置換あるいは未置換のアリール基、Ｒ2 は水
素、炭素数１〜４のアルキル基、炭素数１〜４のトリア
ルキルシリル基、Ｒ3 〜Ｒ6 は水素、又は、ニトロ基を
示し、Ｙ1 、Ｙ2 はそれぞれ独立に＝Ｏ、＝Ｃ（ＣＮ）
2 、＝Ｃ（ＣＯ2 Ｒ7 ）2 を示す。Ｒ7 は炭素数１〜１
０のアルキル基、炭素数１〜１０の置換あるいは未置換
のアリール基示し、ｍは１〜１０の整数、ｎは１〜３の
整数、ｏ〜ｒはそれぞれ独立に０、１あるいは２を示
す。 【化６】 4. In the production of the charge transport material represented by the general formula (I), first, a basic skeleton represented by A in the formula is synthesized, and then the acid halogen represented by the following general formula (IV) is prepared. The compound represented by the general formula (IV) and the compound represented by the following general formula (V) are reacted in an aprotic organic solvent at the final stage of the synthesis. A method for producing a charge transport material represented by formula (I). [Chemical 5] In the formula, A represents the following general formula (A-1) or (A-2), R 1 represents hydrogen, an alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted aryl group having 1 to 10 carbon atoms, R 2 is hydrogen, an alkyl group having 1 to 4 carbon atoms, a trialkylsilyl group having 1 to 4 carbon atoms, R 3 to R 6 are hydrogen, or a nitro group , and Y 1 and Y 2 are each independently = O, = C (CN)
2 , ═C (CO 2 R 7 ) 2 is shown. R 7 has 1 to 1 carbon atoms
0 represents an alkyl group, a substituted or unsubstituted aryl group having 1 to 10 carbon atoms, m represents an integer of 1 to 10, n represents an integer of 1 to 3, and o to r each independently represent 0, 1 or 2. . [Chemical 6]
料の製造において、 まず、式中Ａで表される基本骨格
を合成した後、それを前記一般式（ＩＶ）で示される酸
ハロゲン化物とし、 合成の最終段階でその一般式（ＩＶ）で示される化合物
と、一般式（ＩＶ）で示される化合物に対し２当量以上
の前記一般式（Ｖ）で示される化合物とを、非プロトン
性の有機溶剤中で反応させることを特徴とし、 かつ、前記一般式（Ｖ）で示される化合物が水溶性であ
ること、 を特徴とする前記一般式（Ｉ）で示される電荷輸送材料
の製造方法。5. In the production of the charge transport material represented by the general formula (I), first, a basic skeleton represented by A in the formula is synthesized, and then the acid halogen represented by the general formula (IV) is prepared. A compound represented by the general formula (IV) at the final stage of the synthesis, and 2 equivalents or more of the compound represented by the general formula (V) with respect to the compound represented by the general formula (IV) are aprotic. Of a charge transporting material represented by the general formula (I), characterized in that the compound represented by the general formula (V) is water-soluble. Method.
（ＩＩ）で示されることを特徴とする請求項４又は５記
載の前記一般式（Ｉ）で示される電荷輸送材料の製造方
法。6. The production of the charge transport material represented by the general formula (I) according to claim 4 or 5, wherein A in the general formula (I) is represented by the general formula (II). Method.
（ＩＩＩ）で示されることを特徴とする請求項４又は５
記載の前記一般式（Ｉ）で示される電荷輸送材料の製造
方法。7. The compound represented by the formula (I), wherein A is represented by the formula (III).
The method for producing the charge transport material represented by the general formula (I) described above.
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