JP2005247988A - Semiconducting high-concentration polyimide precursor composition and semiconducting polyimide tubular product using the same - Google Patents
Semiconducting high-concentration polyimide precursor composition and semiconducting polyimide tubular product using the same Download PDFInfo
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- JP2005247988A JP2005247988A JP2004059593A JP2004059593A JP2005247988A JP 2005247988 A JP2005247988 A JP 2005247988A JP 2004059593 A JP2004059593 A JP 2004059593A JP 2004059593 A JP2004059593 A JP 2004059593A JP 2005247988 A JP2005247988 A JP 2005247988A
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- tetracarboxylic acid
- carbon black
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- aromatic tetracarboxylic
- semiconductive
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- 239000000203 mixture Substances 0.000 title claims abstract description 57
- 229920001721 polyimide Polymers 0.000 title claims abstract description 53
- 239000004642 Polyimide Substances 0.000 title claims abstract description 52
- 239000002243 precursor Substances 0.000 title claims abstract description 45
- -1 aromatic tetracarboxylic acid diester Chemical class 0.000 claims abstract description 64
- 239000006229 carbon black Substances 0.000 claims abstract description 51
- 239000006185 dispersion Substances 0.000 claims abstract description 32
- 238000004519 manufacturing process Methods 0.000 claims abstract description 26
- 238000010438 heat treatment Methods 0.000 claims abstract description 20
- 239000002798 polar solvent Substances 0.000 claims abstract description 18
- 150000004984 aromatic diamines Chemical class 0.000 claims abstract description 17
- 238000001175 rotational moulding Methods 0.000 claims abstract description 10
- 239000000463 material Substances 0.000 claims description 8
- 238000012546 transfer Methods 0.000 claims description 8
- 239000002245 particle Substances 0.000 description 24
- 239000000243 solution Substances 0.000 description 22
- 239000000843 powder Substances 0.000 description 19
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 16
- 125000003118 aryl group Chemical group 0.000 description 15
- 238000000034 method Methods 0.000 description 14
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 13
- 238000002156 mixing Methods 0.000 description 13
- 239000000178 monomer Substances 0.000 description 13
- 239000002904 solvent Substances 0.000 description 12
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 11
- 150000001875 compounds Chemical class 0.000 description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- 229910052799 carbon Inorganic materials 0.000 description 8
- 150000002148 esters Chemical class 0.000 description 8
- 239000002994 raw material Substances 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical class C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- 239000000523 sample Substances 0.000 description 6
- FYYYKXFEKMGYLZ-UHFFFAOYSA-N 4-(1,3-dioxo-2-benzofuran-5-yl)-2-benzofuran-1,3-dione Chemical compound C=1C=C2C(=O)OC(=O)C2=CC=1C1=CC=CC2=C1C(=O)OC2=O FYYYKXFEKMGYLZ-UHFFFAOYSA-N 0.000 description 5
- HLBLWEWZXPIGSM-UHFFFAOYSA-N 4-Aminophenyl ether Chemical compound C1=CC(N)=CC=C1OC1=CC=C(N)C=C1 HLBLWEWZXPIGSM-UHFFFAOYSA-N 0.000 description 5
- 239000002253 acid Substances 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 238000000465 moulding Methods 0.000 description 5
- 150000000000 tetracarboxylic acids Chemical class 0.000 description 5
- 239000004677 Nylon Substances 0.000 description 4
- 230000002378 acidificating effect Effects 0.000 description 4
- 125000005907 alkyl ester group Chemical group 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 125000002950 monocyclic group Chemical group 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 229920001778 nylon Polymers 0.000 description 4
- 229920005575 poly(amic acid) Polymers 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 230000002776 aggregation Effects 0.000 description 3
- 238000004220 aggregation Methods 0.000 description 3
- 125000003277 amino group Chemical group 0.000 description 3
- 150000001555 benzenes Chemical class 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 150000004985 diamines Chemical class 0.000 description 3
- 150000005690 diesters Chemical class 0.000 description 3
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical class C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 3
- 125000004185 ester group Chemical group 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- LLPKQRMDOFYSGZ-UHFFFAOYSA-N 2-methyl-4-methylimidazole Natural products CC1=CN=C(C)N1 LLPKQRMDOFYSGZ-UHFFFAOYSA-N 0.000 description 2
- XKGPQKUHMQMOBK-UHFFFAOYSA-N 4-(4-carboxy-3-methoxycarbonylphenyl)-2-methoxycarbonylbenzoic acid Chemical compound C1=C(C(O)=O)C(C(=O)OC)=CC(C=2C=C(C(C(O)=O)=CC=2)C(=O)OC)=C1 XKGPQKUHMQMOBK-UHFFFAOYSA-N 0.000 description 2
- HDJOFDHZESLURS-UHFFFAOYSA-N 4-[2,3-bis(methoxycarbonyl)phenyl]phthalic acid Chemical compound COC(=O)C1=CC=CC(C=2C=C(C(C(O)=O)=CC=2)C(O)=O)=C1C(=O)OC HDJOFDHZESLURS-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- 238000005411 Van der Waals force Methods 0.000 description 2
- GTDPSWPPOUPBNX-UHFFFAOYSA-N ac1mqpva Chemical compound CC12C(=O)OC(=O)C1(C)C1(C)C2(C)C(=O)OC1=O GTDPSWPPOUPBNX-UHFFFAOYSA-N 0.000 description 2
- 150000008065 acid anhydrides Chemical class 0.000 description 2
- 150000001454 anthracenes Chemical class 0.000 description 2
- GCAIEATUVJFSMC-UHFFFAOYSA-N benzene-1,2,3,4-tetracarboxylic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C(C(O)=O)=C1C(O)=O GCAIEATUVJFSMC-UHFFFAOYSA-N 0.000 description 2
- WKDNYTOXBCRNPV-UHFFFAOYSA-N bpda Chemical compound C1=C2C(=O)OC(=O)C2=CC(C=2C=C3C(=O)OC(C3=CC=2)=O)=C1 WKDNYTOXBCRNPV-UHFFFAOYSA-N 0.000 description 2
- 238000005266 casting Methods 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 125000004177 diethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 239000006232 furnace black Substances 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical group CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- 150000002790 naphthalenes Chemical class 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 238000006068 polycondensation reaction Methods 0.000 description 2
- 125000003367 polycyclic group Chemical group 0.000 description 2
- CYIDZMCFTVVTJO-UHFFFAOYSA-N pyromellitic acid Chemical compound OC(=O)C1=CC(C(O)=O)=C(C(O)=O)C=C1C(O)=O CYIDZMCFTVVTJO-UHFFFAOYSA-N 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- 125000006158 tetracarboxylic acid group Chemical group 0.000 description 2
- 239000003039 volatile agent Substances 0.000 description 2
- GIWQSPITLQVMSG-UHFFFAOYSA-N 1,2-dimethylimidazole Chemical compound CC1=NC=CN1C GIWQSPITLQVMSG-UHFFFAOYSA-N 0.000 description 1
- GEYOCULIXLDCMW-UHFFFAOYSA-N 1,2-phenylenediamine Chemical compound NC1=CC=CC=C1N GEYOCULIXLDCMW-UHFFFAOYSA-N 0.000 description 1
- CYSGHNMQYZDMIA-UHFFFAOYSA-N 1,3-Dimethyl-2-imidazolidinon Chemical compound CN1CCN(C)C1=O CYSGHNMQYZDMIA-UHFFFAOYSA-N 0.000 description 1
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 description 1
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 description 1
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 description 1
- ZCUJYXPAKHMBAZ-UHFFFAOYSA-N 2-phenyl-1h-imidazole Chemical compound C1=CNC(C=2C=CC=CC=2)=N1 ZCUJYXPAKHMBAZ-UHFFFAOYSA-N 0.000 description 1
- YBRVSVVVWCFQMG-UHFFFAOYSA-N 4,4'-diaminodiphenylmethane Chemical compound C1=CC(N)=CC=C1CC1=CC=C(N)C=C1 YBRVSVVVWCFQMG-UHFFFAOYSA-N 0.000 description 1
- KINKSULVWLKFFG-UHFFFAOYSA-N 4,5-bis(ethoxycarbonyl)phthalic acid Chemical compound CCOC(=O)C1=CC(C(O)=O)=C(C(O)=O)C=C1C(=O)OCC KINKSULVWLKFFG-UHFFFAOYSA-N 0.000 description 1
- YRNWTQDKUMSTIV-UHFFFAOYSA-N 4,5-bis(methoxycarbonyl)phthalic acid Chemical compound COC(=O)C1=CC(C(O)=O)=C(C(O)=O)C=C1C(=O)OC YRNWTQDKUMSTIV-UHFFFAOYSA-N 0.000 description 1
- UITKHKNFVCYWNG-UHFFFAOYSA-N 4-(3,4-dicarboxybenzoyl)phthalic acid Chemical compound C1=C(C(O)=O)C(C(=O)O)=CC=C1C(=O)C1=CC=C(C(O)=O)C(C(O)=O)=C1 UITKHKNFVCYWNG-UHFFFAOYSA-N 0.000 description 1
- DQIAUUVAPRATQY-UHFFFAOYSA-N 4-(4-carboxy-3-ethoxycarbonylphenyl)-2-ethoxycarbonylbenzoic acid Chemical compound C1=C(C(O)=O)C(C(=O)OCC)=CC(C=2C=C(C(C(O)=O)=CC=2)C(=O)OCC)=C1 DQIAUUVAPRATQY-UHFFFAOYSA-N 0.000 description 1
- VCAOEWHJDPTYRG-UHFFFAOYSA-N 4-[2,3-bis(ethoxycarbonyl)phenyl]phthalic acid Chemical compound CCOC(=O)C1=CC=CC(C=2C=C(C(C(O)=O)=CC=2)C(O)=O)=C1C(=O)OCC VCAOEWHJDPTYRG-UHFFFAOYSA-N 0.000 description 1
- JCRRFJIVUPSNTA-UHFFFAOYSA-N 4-[4-(4-aminophenoxy)phenoxy]aniline Chemical compound C1=CC(N)=CC=C1OC(C=C1)=CC=C1OC1=CC=C(N)C=C1 JCRRFJIVUPSNTA-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- 239000004594 Masterbatch (MB) Substances 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- SUAKHGWARZSWIH-UHFFFAOYSA-N N,N‐diethylformamide Chemical compound CCN(CC)C=O SUAKHGWARZSWIH-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 1
- 239000000010 aprotic solvent Substances 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- ZLSMCQSGRWNEGX-UHFFFAOYSA-N bis(4-aminophenyl)methanone Chemical group C1=CC(N)=CC=C1C(=O)C1=CC=C(N)C=C1 ZLSMCQSGRWNEGX-UHFFFAOYSA-N 0.000 description 1
- 239000006231 channel black Substances 0.000 description 1
- 239000011280 coal tar Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Natural products C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 1
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000006358 imidation reaction Methods 0.000 description 1
- 150000002460 imidazoles Chemical class 0.000 description 1
- 230000003116 impacting effect Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000003273 ketjen black Substances 0.000 description 1
- 229940018564 m-phenylenediamine Drugs 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- BBYQSYQIKWRMOE-UHFFFAOYSA-N naphthalene-1,2,6,7-tetracarboxylic acid Chemical compound C1=C(C(O)=O)C(C(O)=O)=CC2=C(C(O)=O)C(C(=O)O)=CC=C21 BBYQSYQIKWRMOE-UHFFFAOYSA-N 0.000 description 1
- DOBFTMLCEYUAQC-UHFFFAOYSA-N naphthalene-2,3,6,7-tetracarboxylic acid Chemical compound OC(=O)C1=C(C(O)=O)C=C2C=C(C(O)=O)C(C(=O)O)=CC2=C1 DOBFTMLCEYUAQC-UHFFFAOYSA-N 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 231100000989 no adverse effect Toxicity 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
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- 230000000379 polymerizing effect Effects 0.000 description 1
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- 239000007787 solid Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
- Electrostatic Charge, Transfer And Separation In Electrography (AREA)
- Moulding By Coating Moulds (AREA)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
Abstract
Description
本発明は、半導電性高濃度ポリイミド前駆体組成物及びそれを用いた半導電性のポリイミド管状物に関する。また、該製造方法により得られる半導電性ポリイミド管状物は、例えば電子写真方式等の中間転写ベルトとして使用される。 The present invention relates to a semiconductive high-concentration polyimide precursor composition and a semiconductive polyimide tubular material using the same. Moreover, the semiconductive polyimide tubular product obtained by the production method is used as an intermediate transfer belt for an electrophotographic system, for example.
一般にカーボンブラック分散ポリイミド前駆体組成物は、テトラカルボン酸とジアミンを重合してなるポリアミック酸溶液にカーボンブラックを添加して、分散・混合されて作製されている。 In general, a carbon black-dispersed polyimide precursor composition is prepared by adding carbon black to a polyamic acid solution obtained by polymerizing tetracarboxylic acid and diamine, and dispersing and mixing them.
しかし、この溶液にカーボンブラックを添加すると、粘度の増加率が高く、ボールミルなどの分散機中で行われるボール間の衝撃力によってもカーボンブラックの粉砕が困難である。カーボンブラックを添加してポリアミック酸溶液に均一に分散するには、分散機で行われるカーボンブラックの粉砕と、ほぐされていくカーボンブラックの溶媒液による「ぬれ」という界面現象が伴わなければならない。そのため、カーボンブラックと共に有機極性溶媒を多量に添加することで、カーボンブラックを均一分散する方法が取られている。その結果、カーボンブラックを高濃度に含むマスターバッチ溶液の不揮発分濃度は、16重量％以下と低濃度のものしか得ることができなかった。 However, when carbon black is added to this solution, the rate of increase in viscosity is high, and it is difficult to pulverize carbon black due to the impact force between balls performed in a dispersing machine such as a ball mill. In order to add carbon black and uniformly disperse it in the polyamic acid solution, there must be an interfacial phenomenon of pulverization of carbon black performed by a disperser and “wetting” by the solvent solution of carbon black being loosened. Therefore, a method of uniformly dispersing carbon black by adding a large amount of an organic polar solvent together with carbon black is used. As a result, only a low concentration of the nonvolatile content of the master batch solution containing carbon black at a high concentration of 16% by weight or less could be obtained.
この問題を解消するために、テトラカルボン酸ジエステルとジアミン成分からなる、いわゆるナイロン塩型モノマー溶液に、カーボンブラックを添加して分散・混合する方法が、特許文献１に記載されている。 In order to solve this problem, Patent Document 1 describes a method in which carbon black is added to a so-called nylon salt type monomer solution composed of a tetracarboxylic acid diester and a diamine component and dispersed and mixed.
しかし、このナイロン塩型モノマーにカーボンブラックを添加して分散機で均一分散しようとすると、分散機中で行われる衝撃力による発熱によってナイロン塩型モノマーが変化して、結果としてカーボンブラックの分散状態に好ましくない影響を与える。
本発明の目的は、上記の従来技術の問題点に鑑み、カーボンブラックの分散安定性に優れ溶媒を極力低減した高濃度の半導電性ポリイミド前駆体組成物を提供することにあり、さらに該半導電性高濃度ポリイミド前駆体組成物を用いて製造される、優れた電気的特性を有する高品位の半導電性ポリイミド管状物を提供することにある。 An object of the present invention is to provide a high-concentration semiconductive polyimide precursor composition having excellent carbon black dispersion stability and reducing the solvent as much as possible in view of the above-mentioned problems of the prior art. An object of the present invention is to provide a high-quality semiconductive polyimide tubular product having excellent electrical characteristics, which is produced using a conductive high concentration polyimide precursor composition.
本発明者は、上記の課題を解決するため鋭意検討を行った結果、有機極性溶媒にカーボンブラックを均一に分散させてなるカーボンブラック分散液に、芳香族テトラカルボン酸ジエステルと芳香族ジアミンとの略等モル量を溶解させることにより、カーボンブラックの分散性に優れた半導電性高濃度ポリイミド前駆体組成物を調製できることを見出した。また、半導電性高濃度ポリイミド前駆体組成物を用いて回転成形し続いてイミド化処理することにより、均質な電気抵抗率を有する半導電性ポリイミド管状物が得られることを見出した。さらにこれを発展させて本発明を完成するに至った。 As a result of intensive studies to solve the above-mentioned problems, the present inventors have found that a carbon black dispersion obtained by uniformly dispersing carbon black in an organic polar solvent contains an aromatic tetracarboxylic acid diester and an aromatic diamine. It was found that a semiconductive high concentration polyimide precursor composition excellent in carbon black dispersibility can be prepared by dissolving substantially equimolar amounts. Further, it has been found that a semiconductive polyimide tubular product having a uniform electrical resistivity can be obtained by rotational molding using a semiconductive high concentration polyimide precursor composition followed by imidization treatment. This has been further developed to complete the present invention.
すなわち、本発明は以下の半導電性高濃度ポリイミド前駆体組成物及びその製造方法、それを用いた半導電性ポリイミド管状物及びその製造方法を提供する。 That is, this invention provides the following semiconductive high concentration polyimide precursor composition and its manufacturing method, a semiconductive polyimide tubular product using the same, and its manufacturing method.
項１． 有機極性溶媒にカーボンブラックを均一に分散させてなるカーボンブラック分散液に、芳香族テトラカルボン酸ジエステルと芳香族ジアミンとを略等モル量を溶解することを特徴とする半導電性高濃度ポリイミド前駆体組成物の製造方法。 Item 1. Semiconducting high-concentration polyimide precursor characterized by dissolving approximately equimolar amounts of aromatic tetracarboxylic acid diester and aromatic diamine in a carbon black dispersion obtained by uniformly dispersing carbon black in an organic polar solvent A method for producing a body composition.
項２． 芳香族テトラカルボン酸ジエステルが、非対称性芳香族テトラカルボン酸ジエステル10〜50モル％と対称性芳香族テトラカルボン酸ジエステル90〜50モル％とからなる混合物である項１に記載の製造方法。 Item 2. Item 2. The production method according to Item 1, wherein the aromatic tetracarboxylic acid diester is a mixture of 10 to 50 mol% of the asymmetric aromatic tetracarboxylic acid diester and 90 to 50 mol% of the symmetric aromatic tetracarboxylic acid diester.
項３． 芳香族テトラカルボン酸ジエステルが、非対称性の2,3,3',4'-ビフェニルテトラカルボン酸ジエステル10〜50モル％と対称性の3,3',4,4'-ビフェニルテトラカルボン酸ジエステル90〜50モル％とからなる混合物である項２に記載の製造方法。 Item 3. Aromatic tetracarboxylic diester is asymmetric 2,3,3 ', 4'-biphenyltetracarboxylic diester 10-50 mol% and symmetrical 3,3', 4,4'-biphenyltetracarboxylic diester Item 3. The production method according to Item 2, which is a mixture comprising 90 to 50 mol%.
項４． 芳香族テトラカルボン酸ジエステルと芳香族ジアミンの合計量100重量部に対し、カーボンブラックが5〜35重量部程度である項１〜３のいずれかに記載の製造方法。 Item 4. Item 4. The production method according to any one of Items 1 to 3, wherein the carbon black is about 5 to 35 parts by weight with respect to 100 parts by weight of the total amount of the aromatic tetracarboxylic acid diester and the aromatic diamine.
項５． 項１〜４のいずれかに記載の製造方法により製造される半導電性高濃度ポリイミド前駆体組成物。 Item 5. The semiconductive high concentration polyimide precursor composition manufactured by the manufacturing method in any one of claim | item 1 -4.
項６． 項５に記載の半導電性高濃度ポリイミド前駆体組成物を回転成形法にて管状物に成形し、加熱処理してイミド化することを特徴とする半導電性ポリイミド管状物の製造方法。 Item 6. Item 6. A process for producing a semiconductive polyimide tubular product, comprising molding the semiconductive high-concentration polyimide precursor composition according to Item 5 into a tubular product by a rotational molding method and imidizing by heat treatment.
項７． 項６に記載の製造方法により製造される表面抵抗率107〜1014Ω／□である、電子写真方式の中間転写ベルトに用いられる半導電性ポリイミド管状物。 Item 7. A semiconductive polyimide tubular article used for an electrophotographic intermediate transfer belt having a surface resistivity of 10 7 to 10 14 Ω / □ produced by the production method according to Item 6.
以下、本発明を詳述する。 The present invention is described in detail below.
本発明の半導電性ポリイミド管状物（以下、「半導電性ＰＩ管状物」とも呼ぶ）は、半導電性高濃度ポリイミド前駆体組成物（以下、「半導電性高濃度ＰＩ前駆体組成物」とも呼ぶ）を用いて回転成形し加熱処理（イミド化）することにより製造される。
I．半導電性高濃度ポリイミド前駆体組成物
本発明の半導電性高濃度ポリイミド前駆体組成物は、有機極性溶媒にカーボンブラック（以下、「ＣＢ」とも呼ぶ）を均一に分散させてなるカーボンブラック分散液に、芳香族テトラカルボン酸ジエステルと芳香族ジアミンとの略等モル量を溶解させることにより製造される。すなわち、予め調製したＣＢの均一分散液に等モル量の成形原料であるモノマー（芳香族テトラカルボン酸ジエステルと芳香族ジアミンの等モル量）を加えるという手順により製造される点に特徴を有している。
（１）カーボンブラック分散液
本発明においては、ＰＩ前駆体組成物に半導電性を付与するために導電性ＣＢ粉体が用いられる。このＣＢ粉体が使用される理由は、（他の一般に知られている金属や金属酸化物の導電材と比較して）調製された半導電性高濃度ポリイミド前駆体組成物におけるＣＢの混合分散性と分散安定性（混合分散後の経時変化）に優れ、且つ重縮合反応への悪影響がないことによる。
The semiconductive polyimide tubular product of the present invention (hereinafter also referred to as “semiconductive PI tubular product”) is a semiconductive high concentration polyimide precursor composition (hereinafter referred to as “semiconductive high concentration PI precursor composition”). It is manufactured by rotational molding using heat treatment (imidization).
I. Semiconductive high concentration polyimide precursor composition The semiconductive high concentration polyimide precursor composition of the present invention is a carbon black dispersion obtained by uniformly dispersing carbon black (hereinafter also referred to as "CB") in an organic polar solvent. It is produced by dissolving approximately equimolar amounts of an aromatic tetracarboxylic acid diester and an aromatic diamine in the liquid. That is, it is characterized in that it is produced by a procedure of adding an equimolar amount of a monomer (molding equimolar amount of an aromatic tetracarboxylic acid diester and an aromatic diamine) to a uniform dispersion of CB prepared in advance. ing.
(1) Carbon black dispersion In the present invention, conductive CB powder is used to impart semiconductivity to the PI precursor composition. The reason why this CB powder is used is that the mixed dispersion of CB in the semiconductive high-concentration polyimide precursor composition prepared (compared to other generally known metal and metal oxide conductive materials). This is because of excellent properties and dispersion stability (change over time after mixing and dispersion) and no adverse effect on the polycondensation reaction.
このＣＢ粉体は、その製造原料（天然ガス、アセチレンガス、コ−ルタ−ル等）と製造条件（燃焼条件）とによって種々の物性（電気抵抗、揮発分、比表面積、粒径、ＰＨ値、ＤＢＰ吸油量等）を有したものがある。可能なかぎり少量の混合分散でもって、所望する電気抵抗がバラツクこともなく、安定して得られ易いものを選ぶのが良い。 This CB powder has various physical properties (electrical resistance, volatile content, specific surface area, particle size, pH value) depending on its production raw materials (natural gas, acetylene gas, coal tar, etc.) and production conditions (combustion conditions). , DBP oil absorption, etc.). It is preferable to select a material that can be obtained stably and stably with the smallest possible amount of mixing and dispersion without variation in the desired electrical resistance.
この導電性ＣＢ粉体は、通常平均粒子径が15〜65ｎｍ程度であり、特にトナー複写機、カラー複写機、電子写真方式等の中間転写ベルト用フイルム用途に用いる場合、平均粒子径20〜40ｎｍ程度のものが好適である。 This conductive CB powder usually has an average particle size of about 15 to 65 nm, and particularly when used for a film for an intermediate transfer belt such as a toner copying machine, a color copying machine, and an electrophotographic system, an average particle size of 20 to 40 nm. A thing of a grade is suitable.
ケッチェンブラックやアセチレンブラックなどの導電指標の高いものは、２次凝集（ストラクチャー）が発生し易く、導電性の連鎖が起こりやすく半導電領域でのコントロールが困難である。そこで、ストラクチャー形成しにくい酸性カーボンブラックを用いることが有効である。 Those having a high conductivity index, such as ketjen black and acetylene black, are liable to cause secondary aggregation (structure), easily form conductive chains, and are difficult to control in the semiconductive region. Therefore, it is effective to use acidic carbon black which is difficult to form a structure.
例えば、チャンネルブラック、酸化処理したファーネスブラック等が挙げられる。具体的には、デグサ社製のスペシャルブラック４（PH3、揮発分14％、粒子径25nm）やスペシャルブラック５（PH3、揮発分15％、粒子径20nm）などが例示される。 For example, channel black, oxidized furnace black, and the like can be given. Specific examples include Special Black 4 (PH3, volatile content 14%, particle size 25 nm) and Special Black 5 (PH3, volatile content 15%, particle size 20 nm) manufactured by Degussa.
カーボンブラック分散液に用いられる有機極性溶媒としては、非プロトン系溶媒が好ましく、例えばN-メチル−2−ピロリドン（以下、「ＮＭＰ」と呼ぶ。）、N，N−ジメチルホルムアミド、N，N−ジエチルホルムアミド、N，N−ジメチルアセトアミド、ジメチルスルホキシド、ヘキサメチルホスホアミド、1，3−ジメチル−2−イミダゾリジノン等が使用される。これらのうちの１種又は２種以上の混合溶媒であってもよい。特に、ＮＭＰが好ましい。 The organic polar solvent used in the carbon black dispersion is preferably an aprotic solvent such as N-methyl-2-pyrrolidone (hereinafter referred to as “NMP”), N, N-dimethylformamide, N, N—. Diethylformamide, N, N-dimethylacetamide, dimethyl sulfoxide, hexamethylphosphoamide, 1,3-dimethyl-2-imidazolidinone and the like are used. One or two or more of these solvents may be used. In particular, NMP is preferable.
カーボンブラック分散液は、上記の有機極性溶媒にＣＢ粉体を均一に分散させて製造される。ＣＢ粉体の混合方法は、ＣＢ粉体が有機極性溶媒中に均一に混合、分散される方法であれば特に制限はない。例えば、ボールミル、サンドミル、超音波ミル等が用いられる。 The carbon black dispersion is produced by uniformly dispersing CB powder in the above organic polar solvent. The method for mixing the CB powder is not particularly limited as long as the CB powder is uniformly mixed and dispersed in the organic polar solvent. For example, a ball mill, a sand mill, an ultrasonic mill or the like is used.
ＣＢ粉体の配合量は、有機極性溶媒100重量部に対し、3〜25重量部程度であり、好ましくは5〜15重量部程度である。この配合量は、有機極性溶媒の粘度増加させない、またはCBがファンデルワールス力によって２次凝集体を形成しない範囲にある量である。なお、有機極性溶媒100重量部に対し下限が３重量部以上であるのは、製造される半導電性高濃度ポリイミド前駆体組成物の不揮発分濃度を下げないために必要な量である。上限が25重量部以下であるのは、均一に分散したCB粒子とCB粒子の距離を十分にとり、ファンデルワールス力による２次凝集を防ぐためである。
（２）芳香族テトラカルボン酸ジエステル（ハーフエステル）
成形原料である２種以上の芳香族テトラカルボン酸ジエステルとしては、非対称性芳香族テトラカルボン酸ジエステルの少なくとも１種と対称性芳香族テトラカルボン酸ジエステルの少なくとも１種との混合物が用いられる。
The blending amount of the CB powder is about 3 to 25 parts by weight, preferably about 5 to 15 parts by weight with respect to 100 parts by weight of the organic polar solvent. This blending amount is an amount that does not increase the viscosity of the organic polar solvent or that CB does not form secondary aggregates by van der Waals force. The lower limit of 3 parts by weight or more with respect to 100 parts by weight of the organic polar solvent is an amount necessary for preventing the concentration of non-volatile components of the produced semiconductive high concentration polyimide precursor composition from being lowered. The upper limit is 25 parts by weight or less because the distance between the uniformly dispersed CB particles and the CB particles is sufficient to prevent secondary aggregation due to van der Waals force.
(2) Aromatic tetracarboxylic acid diester (half ester)
As the two or more kinds of aromatic tetracarboxylic acid diesters as the forming raw material, a mixture of at least one kind of asymmetric aromatic tetracarboxylic acid diester and at least one kind of symmetric aromatic tetracarboxylic acid diester is used.
本発明で用いられる非対称性芳香族テトラカルボン酸のジエステルについて、以下説明する。 The asymmetric aromatic tetracarboxylic acid diester used in the present invention will be described below.
ここで、非対称性芳香族テトラカルボン酸とは、単環若しくは多環の芳香環（ベンゼン核、ナフタレン核、ビフェニル核、アントラセン核等）に４個のカルボキシル基が点対象でない位置に結合した化合物、或いは２個の単環芳香環（ベンゼン核等）が−ＣＯ−、−ＣＨ2−、−ＳＯ2−等の基又は単結合で架橋された化合物に４個のカルボキシル基が点対象でない位置に結合した化合物が挙げられる。 Here, the asymmetric aromatic tetracarboxylic acid is a compound in which four carboxyl groups are bonded to positions that are not point targets on a monocyclic or polycyclic aromatic ring (benzene nucleus, naphthalene nucleus, biphenyl nucleus, anthracene nucleus, etc.). Or a position in which two monocyclic aromatic rings (benzene nucleus, etc.) are not point-targeted to a group in which —CO—, —CH 2 —, —SO 2 — or the like or a single bond is bridged The compound couple | bonded with is mentioned.
非対称性芳香族テトラカルボン酸の具体例としては、１，２，３，４−ベンゼンテトラカルボン酸、１，２，６，７−ナフタレンテトラカルボン酸、２，３，３’，４’−ビフェニルテトラカルボン酸、２，３，３’，４’−ベンゾフェノンテトラカルボン酸、２，３，３’，４’−ジフェニルエーテルテトラカルボン酸、２，３，３’，４’−ジフェニルメタンテトラカルボン酸、２，３，３’，４’−ジフェニルスルフォンテトラカルボン酸等が挙げられる。 Specific examples of the asymmetric aromatic tetracarboxylic acid include 1,2,3,4-benzenetetracarboxylic acid, 1,2,6,7-naphthalenetetracarboxylic acid, 2,3,3 ′, 4′-biphenyl. Tetracarboxylic acid, 2,3,3 ′, 4′-benzophenonetetracarboxylic acid, 2,3,3 ′, 4′-diphenyl ether tetracarboxylic acid, 2,3,3 ′, 4′-diphenylmethanetetracarboxylic acid, 2 , 3,3 ′, 4′-diphenylsulfone tetracarboxylic acid and the like.
本発明で用いられる非対称性芳香族テトラカルボン酸ジエステル（ハーフエステル）としては、上記の非対称性芳香族テトラカルボン酸のジエステルを挙げることができ、具体的には、上記非対称性芳香族テトラカルボン酸の４個のカルボキシル基のうち２個のカルボキシル基がエステル化されており、かつ芳香環上の隣接する２個のカルボキシル基の一方がエステル化された化合物が挙げられる。 Examples of the asymmetric aromatic tetracarboxylic acid diester (half ester) used in the present invention include the above-mentioned asymmetric aromatic tetracarboxylic acid diesters. Specifically, the asymmetric aromatic tetracarboxylic acid is an asymmetric aromatic tetracarboxylic acid. Among the four carboxyl groups, a compound in which two carboxyl groups are esterified and one of two adjacent carboxyl groups on the aromatic ring is esterified can be mentioned.
上記非対称性芳香族テトラカルボン酸ジエステルにおける２個のエステルとしては、ジ低級アルキルエステル、好ましくはジメチルエステル、ジエチルエステル、ジプロピルエステル等のＣ1-3アルキルエステル（特に、ジメチルエステル）が挙げられる。 Examples of the two esters in the asymmetric aromatic tetracarboxylic acid diester include di-lower alkyl esters, preferably C 1-3 alkyl esters (particularly dimethyl esters) such as dimethyl esters, diethyl esters, and dipropyl esters. .
上記非対称性芳香族テトラカルボン酸のジエステルのうち、2,3,3',4'−ビフェニルテトラカルボン酸ジメチルエステル、2,3,3',4'−ビフェニルテトラカルボン酸ジエチルエステル、が好ましく、特に、2,3,3',4'−ビフェニルテトラカルボン酸ジメチルエステルが好ましく使用される。 Of the above asymmetric aromatic tetracarboxylic acid diesters, 2,3,3 ′, 4′-biphenyltetracarboxylic acid dimethyl ester, 2,3,3 ′, 4′-biphenyltetracarboxylic acid diethyl ester are preferred, In particular, 2,3,3 ′, 4′-biphenyltetracarboxylic acid dimethyl ester is preferably used.
なお、上記非対称性芳香族テトラカルボン酸ジエステルは、市販又は公知の方法により製造される。例えば、対応する非対称性芳香族テトラカルボン酸二無水物１に対し、対応するアルコール（低級アルコール、好ましくはＣ1-3アルコール等）２（モル比）を反応させて容易に製造することができる。これにより、原料の酸無水物がアルコールと反応して開環して、芳香環上の隣接する炭素上にそれぞれエステル基とカルボキシル基を有するジエステル（ハーフエステル）が製造される。 The asymmetric aromatic tetracarboxylic acid diester is commercially available or produced by a known method. For example, it can be easily produced by reacting the corresponding asymmetric aromatic tetracarboxylic dianhydride 1 with the corresponding alcohol (lower alcohol, preferably C 1-3 alcohol, etc.) 2 (molar ratio). . Thereby, the acid anhydride of a raw material reacts with alcohol, and a ring is opened, and the diester (half ester) which has an ester group and a carboxyl group, respectively on adjacent carbon on an aromatic ring is manufactured.
次に、本発明で用いられる対称性芳香族テトラカルボン酸のジエステルについて、以下説明する。 Next, the symmetric aromatic tetracarboxylic acid diester used in the present invention will be described below.
ここで、対称性芳香族テトラカルボン酸とは、単環若しくは多環の芳香環（ベンゼン核、ナフタレン核、ビフェニル核、アントラセン核等）に４個のカルボキシル基が点対称な位置に結合した化合物、或いは２個の単環芳香環（ベンゼン核等）が−ＣＯ−、−Ｏ−、−ＣＨ2−、−ＳＯ2−等の基又は単結合で架橋された化合物に４個のカルボキシル基が点対称な位置に結合した化合物が挙げられる。 Here, the symmetric aromatic tetracarboxylic acid is a compound in which four carboxyl groups are bonded to a point-symmetrical position on a monocyclic or polycyclic aromatic ring (benzene nucleus, naphthalene nucleus, biphenyl nucleus, anthracene nucleus, etc.). Or four carboxyl groups on a compound in which two monocyclic aromatic rings (such as a benzene nucleus) are bridged by a group such as —CO—, —O—, —CH 2 —, —SO 2 — or the like, or a single bond. A compound bonded at a point-symmetrical position can be mentioned.
対称性芳香族テトラカルボン酸の具体例としては、１，２，４，５−ベンゼンテトラカルボン酸、2,3,6,7−ナフタレンテトラカルボン酸、3,3',4,4'−ビフェニルテトラカルボン酸、3,3',4,4'−ベンゾフェノンテトラカルボン酸、3,3',4,4'−ジフェニルエーテルテトラカルボン酸、3,3',4,4'−ジフェニルメタンテトラカルボン酸、3,3'4,4'−ジフェニルスルフォンテトラカルボン酸等が挙げられる。 Specific examples of the symmetric aromatic tetracarboxylic acid include 1,2,4,5-benzenetetracarboxylic acid, 2,3,6,7-naphthalenetetracarboxylic acid, 3,3 ′, 4,4′-biphenyl. Tetracarboxylic acid, 3,3 ′, 4,4′-benzophenone tetracarboxylic acid, 3,3 ′, 4,4′-diphenyl ether tetracarboxylic acid, 3,3 ′, 4,4′-diphenylmethane tetracarboxylic acid, 3 3,3'4,4'-diphenylsulfone tetracarboxylic acid and the like.
本発明で用いられる対称性芳香族テトラカルボン酸ジエステル（ハーフエステル）としては、上記の対称性芳香族テトラカルボン酸のジエステル（ハーフエステル）を挙げることができ、具体的には、上記対称性芳香族テトラカルボン酸の４個のカルボキシル基のうち２個のカルボキシル基がエステル化されており、かつ芳香環上の隣接する２個のカルボキシル基の一方がエステル化された化合物が挙げられる。 Examples of the symmetric aromatic tetracarboxylic acid diester (half ester) used in the present invention include the above-mentioned symmetric aromatic tetracarboxylic acid diester (half ester). Examples include compounds in which two of the four carboxyl groups of the group tetracarboxylic acid are esterified and one of the two adjacent carboxyl groups on the aromatic ring is esterified.
上記対称性芳香族テトラカルボン酸ジエステルにおける２個のエステルとしては、ジ低級アルキルエステル、好ましくはジメチルエステル、ジエチルエステル、ジプロピルエステル等のＣ1-3アルキルエステル（特に、ジメチルエステル）が挙げられる。 Examples of the two esters in the symmetric aromatic tetracarboxylic acid diester include di-lower alkyl esters, preferably C 1-3 alkyl esters (particularly dimethyl esters) such as dimethyl esters, diethyl esters, and dipropyl esters. .
上記対称性芳香族テトラカルボン酸ジエステルのうち、3,3',4,4'−ビフェニルテトラカルボン酸ジメチルエステル、3,3',4,4'−ビフェニルテトラカルボン酸ジエチルエステル、1,2,4,5-ベンゼンテトラカルボン酸ジメチルエステル、1,2,4,5−ベンゼンテトラカルボン酸ジエチルエステルが好ましく、特に、3,3',4,4'-ビフェニルテトラカルボン酸ジメチルエステルが好ましく使用される。 Among the above symmetrical aromatic tetracarboxylic acid diesters, 3,3 ′, 4,4′-biphenyltetracarboxylic acid dimethyl ester, 3,3 ′, 4,4′-biphenyltetracarboxylic acid diethyl ester, 1,2, 4,5-Benzenetetracarboxylic acid dimethyl ester and 1,2,4,5-benzenetetracarboxylic acid diethyl ester are preferred, and 3,3 ′, 4,4′-biphenyltetracarboxylic acid dimethyl ester is particularly preferred. The
なお、上記対称性芳香族テトラカルボン酸ジエステルは、市販又は公知の方法により製造することができる。例えば、対応する対称性芳香族テトラカルボン酸二無水物１に対し、対応するアルコール（低級アルコール、好ましくはＣ1-3アルコール等）２（モル比）を反応させる等の公知の方法により容易に製造することができる。これにより、原料の酸無水物がアルコールと反応して開環して、芳香環上の隣接する炭素上にそれぞれエステル基とカルボキシル基を有するジエステル（ハーフエステル）が製造される。 In addition, the said symmetrical aromatic tetracarboxylic-acid diester can be manufactured commercially or by a well-known method. For example, the corresponding symmetrical aromatic tetracarboxylic dianhydride 1 is easily reacted with a corresponding alcohol (lower alcohol, preferably C 1-3 alcohol, etc.) 2 (molar ratio) by a known method. Can be manufactured. Thereby, the acid anhydride of a raw material reacts with alcohol, and a ring is opened, and the diester (half ester) which has an ester group and a carboxyl group, respectively on adjacent carbon on an aromatic ring is manufactured.
非対称性及び対称性の芳香族テトラカルボン酸ジエステルの混合比は、非対称性芳香族テトラカルボン酸ジエステルが10〜50モル％（好ましくは20〜40モル％）程度であり、対称性芳香族テトラカルボン酸ジエステルが90〜50モル％（好ましくは80〜60モル％）程度で特定される。特に、非対称性及テトラカルボン酸ジエステルを20〜30モル％程度、対称性芳香族テトラカルボン酸ジエステルを70〜80モル％程度用いるのが好適である。 The mixing ratio of the asymmetric and symmetric aromatic tetracarboxylic acid diester is about 10 to 50 mol% (preferably 20 to 40 mol%) of the asymmetric aromatic tetracarboxylic acid diester, and the symmetric aromatic tetracarboxylic acid diester The acid diester is specified at about 90 to 50 mol% (preferably 80 to 60 mol%). In particular, it is preferable to use about 20 to 30 mol% of asymmetric and tetracarboxylic acid diesters and about 70 to 80 mol% of symmetric aromatic tetracarboxylic acid diesters.
なお、前記の対称性及び非対称性芳香族テトラカルボン酸ジエステルを配合することを必須とするのは、次の理由による。対称性の芳香族テトラカルボン酸ジエステルのみでは、ポリイミドフイルムが結晶性を発現するため加熱処理中に被膜が粉化してしまいフイルム化することが出来ない。一方、非対称性の芳香族テトラカルボン酸誘導体のみでは、無端管状ＰＩフイルムとして成形はされるが、得られた該フイルムの降伏強度と弾性率が弱く、回転ベルトとして使用した場合、駆動での応答性が悪いだけでなく、初期の段階でベルト伸びが発生してしまうなどの問題がある。 In addition, it becomes essential to mix | blend the said symmetrical and asymmetrical aromatic tetracarboxylic-acid diester for the following reason. Only with the symmetric aromatic tetracarboxylic acid diester, the polyimide film exhibits crystallinity, so that the film is pulverized during the heat treatment and cannot be formed into a film. On the other hand, an asymmetric aromatic tetracarboxylic acid derivative alone is formed into an endless tubular PI film, but the yield strength and elastic modulus of the obtained film are weak, and when used as a rotating belt, the response in driving In addition to the poor properties, there are problems such as belt elongation occurring at an early stage.
これに対し、混合芳香族テトラカルボン酸ジエステルを使用すると、極めて高い製膜性（成形性）が可能であり、しかも高い降伏強度と弾性率を有する半導電性の無端管状ＰＩフイルムが得られる。 On the other hand, when a mixed aromatic tetracarboxylic acid diester is used, a semiconductive endless tubular PI film having an extremely high film forming property (moldability) and having a high yield strength and elastic modulus can be obtained.
また、非対称芳香族テトラカルボン酸ジエステルを添加することによりポリアミック酸分子が曲がって、フレキシブル性が生まれると考えられる。 Moreover, it is thought that by adding an asymmetric aromatic tetracarboxylic acid diester, the polyamic acid molecule is bent and flexibility is born.
そして、前記の対称性と非対称性の芳香族テトラカルボン酸誘導体の共存効果は、両者が前記に示した混合比の場合に最も有効に発揮される。
（３）芳香族ジアミン
芳香族ジアミンとしては、１つの芳香環上に２個のアミノ基を有する化合物、又は２つ以上の芳香環（ベンゼン核等）が−Ｏ−、−Ｓ−、−ＣＯ−、−ＣＨ2−、−ＳＯ−、−ＳＯ2−等の基若しくは単結合で架橋された２個のアミノ基を有する化合物が挙げられる。具体的には、例えば、ｐ−フェニレンジアミン、ｏ−フェニレンジアミン、ｍ−フェニレンジアミン、4，4’−ジアミノジフェニルエーテル、4，4’−ジアミノジフェニルチオエーテル、4，4’−ジアミノジフェニルカルボニル、4，4’−ジアミノジフェニルメタン、1，4−ビス（４−アミノフェノキシ）ベンゼン等が挙げられる。中でも、4，4’−ジアミノジフェニルエーテルが特に好ましい。これらの芳香族ジアミンを用いることにより、反応がより円滑に進行すると共に、より強靭かつ高い耐熱性のフイルムを製造することができるからである。
（４）半導電性高濃度ポリイミド前駆体組成物
次に、得られるカーボンブラック分散液に、芳香族テトラカルボン酸ジエステルと芳香族ジアミンの略等モル量を添加し溶解する。
And the coexistence effect of the said symmetrical and asymmetrical aromatic tetracarboxylic acid derivative is most effectively exhibited when both have the mixing ratio shown above.
(3) Aromatic diamine As the aromatic diamine, a compound having two amino groups on one aromatic ring, or two or more aromatic rings (such as a benzene nucleus) are —O—, —S—, —CO. Examples thereof include a compound such as —, —CH 2 —, —SO—, —SO 2 — or the like, or a compound having two amino groups bridged by a single bond. Specifically, for example, p-phenylenediamine, o-phenylenediamine, m-phenylenediamine, 4,4′-diaminodiphenyl ether, 4,4′-diaminodiphenylthioether, 4,4′-diaminodiphenylcarbonyl, 4, 4'-diaminodiphenylmethane, 1,4-bis (4-aminophenoxy) benzene and the like can be mentioned. Among these, 4,4′-diaminodiphenyl ether is particularly preferable. This is because by using these aromatic diamines, the reaction proceeds more smoothly and a tougher and higher heat-resistant film can be produced.
(4) Semiconductive high-concentration polyimide precursor composition Next, approximately equimolar amounts of aromatic tetracarboxylic acid diester and aromatic diamine are added and dissolved in the resulting carbon black dispersion.
上記の芳香族テトラカルボン酸成分と有機ジアミン成分の略等モル量を、カーボンブラック分散液中に加えて撹拌し均一に溶解することにより、半導電性高濃度ポリイミド前駆体組成物が製造される。両成分をカーボンブラック分散液に均一に溶解させる場合に、必要に応じ加熱（例えば、40〜70℃程度）してもよい。両性分は、撹拌等の公知の混合方法を用いて有機極性溶媒に溶解させればよい。 A semiconducting high-concentration polyimide precursor composition is produced by adding approximately equimolar amounts of the above-mentioned aromatic tetracarboxylic acid component and organic diamine component to the carbon black dispersion and stirring to dissolve uniformly. . When both components are uniformly dissolved in the carbon black dispersion, heating may be performed as necessary (for example, about 40 to 70 ° C.). The amphoteric component may be dissolved in an organic polar solvent using a known mixing method such as stirring.
芳香族テトラカルボン酸ジエステル及び芳香族ジアミンの配合量は、芳香族テトラカルボン酸ジエステルと芳香族ジアミンの合計量100重量部に対し、カーボンブラック分散液中のカーボンブラックが5〜35重量部程度（好ましくは8〜30重量部程度）になるように調製すればよい。配合量を上記の範囲とするのは、フイルムに半導電領域にある体積抵抗率（ＶＲ）及び表面抵抗率（ＳＲ）を付与するためである。 The amount of aromatic tetracarboxylic acid diester and aromatic diamine is about 5 to 35 parts by weight of carbon black in the carbon black dispersion with respect to 100 parts by weight of the total amount of aromatic tetracarboxylic acid diester and aromatic diamine ( It may be prepared so that it is preferably about 8 to 30 parts by weight. The reason why the blending amount is in the above range is to give the film volume resistivity (VR) and surface resistivity (SR) in the semiconductive region.
上記の半導電性高濃度ポリイミド前駆体組成物は、例えば、有機極性溶媒中で芳香族テトラカルボン酸ジエステルのカルボン酸イオンと芳香族ジアミンのアンモニウムイオンのイオン対が実質的モノマー状態をとっていると考えられる。（例えば下記式を参照）。 In the above semiconductive high concentration polyimide precursor composition, for example, an ion pair of an aromatic tetracarboxylic acid diester carboxylate ion and an aromatic diamine ammonium ion is in a substantially monomer state in an organic polar solvent. it is conceivable that. (For example, see the formula below).
また、実質的モノマー状態であるため上記の有機極性溶媒に溶解しやすく、使用する溶媒の量を極力低減できるというメリットがある。なお、該組成物中の不揮発分濃度は、例えば、35〜60重量％程度、好ましくは40〜60重量％程度の高濃度に設定することができる。該不揮発性分中におけるＣＢ濃度は、例えば、4〜30重量％程度、好ましくは10〜25重量％程度に設定することができる。なお、本明細書で用いる「不揮発分濃度」とは、実施例１に記載の方法により測定された濃度を意味する。
Moreover, since it is in a substantially monomer state, it is easily dissolved in the above-mentioned organic polar solvent, and there is an advantage that the amount of the solvent used can be reduced as much as possible. In addition, the non-volatile content density | concentration in this composition can be set to the high density | concentration of about 35 to 60 weight%, for example, Preferably about 40 to 60 weight%. The CB concentration in the non-volatile component can be set to, for example, about 4 to 30% by weight, preferably about 10 to 25% by weight. The “nonvolatile content concentration” used in the present specification means a concentration measured by the method described in Example 1.
なお、本発明の効果に悪影響を与えない範囲で、上記組成物中に、イミダゾール系化合物（2-メチルイミダゾール、1,2−ジメチルイミダゾール、2-メチル-4-メチルイミダゾール、2-エチル-4-エチルイミダゾール、2-フェニルイミダゾール）、界面活性剤（フッ素系界面活性剤等）等の添加剤を加えてもよい。 It should be noted that the imidazole compounds (2-methylimidazole, 1,2-dimethylimidazole, 2-methyl-4-methylimidazole, 2-ethyl-4 are included in the composition as long as the effects of the present invention are not adversely affected. Additives such as -ethylimidazole, 2-phenylimidazole) and surfactants (fluorine surfactants, etc.) may be added.
かくしてＣＢ粉体が均一に分散し、かつ不揮発分が高濃度に溶解又は分散した半導電性ＰＩ前駆体組成物が製造される。 Thus, a semiconductive PI precursor composition in which the CB powder is uniformly dispersed and the non-volatile content is dissolved or dispersed at a high concentration is produced.
本発明の半導電性高濃度ＰＩ前駆体組成物では、ＣＢ粉体を均一に分散させてなるカーボンブラック分散液を調製し、これに芳香族テトラカルボン酸ジエステルと芳香族ジアミン成分とを溶解させることにより、ＣＢ粉体が均一に分散し、かつ、ＣＢ粉体が均一分散した状態の貯蔵安定性が格段に向上する。しかも、これを用いた半導電性ＰＩ前駆体組成物を回転成形して得られる導電性ポリイミド管状物は、その厚み方向に極めて安定かつ均質な電気抵抗率を有する導電性が付与される。 In the semiconductive high concentration PI precursor composition of the present invention, a carbon black dispersion liquid in which CB powder is uniformly dispersed is prepared, and an aromatic tetracarboxylic acid diester and an aromatic diamine component are dissolved therein. As a result, the storage stability of the CB powder uniformly dispersed and the CB powder uniformly dispersed is significantly improved. Moreover, the conductive polyimide tubular product obtained by rotational molding of the semiconductive PI precursor composition using the same is imparted with conductivity having extremely stable and uniform electrical resistivity in the thickness direction.
また、本発明の半導電性高濃度ＰＩ前駆体組成物は、カーボンブラック分散液に成形原料であるモノマーを溶解させるため、不揮発分濃度を35〜60重量％程度と格段に高めることができる。そのため、本発明の半導電性高濃度ＰＩ前駆体組成物では、容易に膜厚のあるフイルムを製造することができ、使用する溶媒の量が少ないためコストが抑えられ溶媒の蒸発除去が簡便になる。 Moreover, since the semiconductive high concentration PI precursor composition of this invention dissolves the monomer which is a shaping | molding raw material in a carbon black dispersion liquid, the non volatile matter density | concentration can be raised significantly to about 35 to 60 weight%. Therefore, the semiconductive high concentration PI precursor composition of the present invention can easily produce a film having a film thickness, and the amount of solvent to be used is small, so that the cost can be suppressed and the solvent can be easily removed by evaporation. Become.
さらに、本発明の半導電性高濃度ＰＩ前駆体組成物は、その粘度も１０〜６０ポイズ程度に高くすることができるため、ＰＩフイルムにおける回転成形の遠心力の影響を受けにくい。
II．半導電性ポリイミド管状物
次に、前記調製された半導電性ＰＩ前駆体組成物を使った半導電性ＰＩ管状物の成形手段について説明する。
Furthermore, since the viscosity of the semiconductive high concentration PI precursor composition of the present invention can be increased to about 10 to 60 poise, it is not easily affected by the centrifugal force of rotational molding in the PI film.
II. Semiconductive polyimide tubular material Next, a means for forming a semiconductive PI tubular material using the prepared semiconductive PI precursor composition will be described.
この成形手段は、回転ドラムを使う回転成形方法が採用される。まず半導電性ＰＩ前駆体組成物を回転ドラムの内面に注入し、内面全体に均一に流延する。 As this molding means, a rotational molding method using a rotary drum is adopted. First, the semiconductive PI precursor composition is injected into the inner surface of the rotating drum and cast uniformly over the entire inner surface.
注入・流延の方法は、例えば停止している回転ドラムに、最終フイルム厚さを得るに相当する量の半導電性ＰＩ前駆体組成物を注入した後、遠心力が働く速度にまで徐々に回転速度を上げる。遠心力でもって内面全体に均一に流延する。或いは注入・流延は遠心力を使わなくてもできる。例えば、横長のスリット状のノズルを回転ドラム内面に配置し、該ドラムをゆっくりと回転しつつ、（その回転速度よりも速い速度で）該ノズルも回転する。そして成形用の半導電性ＰＩ前駆体組成物を該ノズルから該ドラム内面に向って全体に均一に噴射する方法である。 The injection / casting method is performed by, for example, injecting a semiconductive PI precursor composition in an amount equivalent to obtaining a final film thickness into a rotating drum that is stopped, and then gradually increasing the speed until centrifugal force works. Increase the rotation speed. Cast uniformly over the entire inner surface with centrifugal force. Alternatively, injection and casting can be performed without using centrifugal force. For example, a horizontally long slit-like nozzle is arranged on the inner surface of the rotating drum, and the nozzle is rotated (at a speed higher than the rotating speed) while the drum is slowly rotated. In this method, the semiconductive PI precursor composition for molding is uniformly sprayed from the nozzle toward the inner surface of the drum.
尚、いずれの方法も回転ドラムは、内面が鏡面仕上げされ、両端縁には、液モレ防止のためのバリヤーが周設される。該ドラムは、回転ローラ上に載置し、該ローラの回転により間接的に回転が行われる。 In both methods, the inner surface of the rotating drum is mirror-finished, and barriers for preventing liquid leakage are provided around both ends. The drum is placed on a rotating roller and indirectly rotated by the rotation of the roller.
また加熱は、該ドラムの周囲に例えば遠赤外線ヒータ等の熱源が配置され外側からの間接加熱が行われる。また該ドラムの大きさは、所望する半導電管状ＰＩフイルムの大きさにより決まる。 For heating, a heat source such as a far infrared heater is disposed around the drum, and indirect heating from the outside is performed. The size of the drum is determined by the size of the desired semiconductive tubular PI film.
加熱は、ドラム内面を徐々に昇温し、まず100〜190℃程度、好ましくは110℃〜130℃程度に到達せしめる（第１加熱段階）。昇温速度は、例えば、1〜2℃／min程度であればよい。上記の温度で１〜３時間維持し、およそ半分以上の溶剤を揮発させて自己支持性のある管状フイルムを成形する。イミド化を行うためには280℃以上の温度まで達する必要があるが、最初からこのような高温で加熱するとポリイミドが高い結晶化を発現し、ＣＢの分散状態に影響を与えるだけでなく、強靭な被膜が形成されないなどの問題がある。そのため、第１加熱段階として、せいぜい上限温度を190℃程度に押え、この温度で重縮合反応を終了させて強靭な管状ＰＩフイルムを得る。 In the heating, the inner surface of the drum is gradually heated to first reach about 100 to 190 ° C., preferably about 110 to 130 ° C. (first heating stage). The temperature raising rate may be about 1 to 2 ° C./min, for example. It is maintained at the above temperature for 1 to 3 hours, and approximately half or more of the solvent is volatilized to form a self-supporting tubular film. In order to perform imidization, it is necessary to reach a temperature of 280 ° C. or higher. However, when heated at such a high temperature from the beginning, the polyimide exhibits high crystallization, which not only affects the dispersion state of CB, but also is tough. There is a problem that a thick film is not formed. Therefore, as the first heating stage, the upper limit temperature is suppressed to about 190 ° C. at most, and the polycondensation reaction is terminated at this temperature to obtain a tough tubular PI film.
この段階が終了したら次に第２段階加熱としてイミド化を完結するため加熱を行うが、その温度は280〜400℃程度（好ましくは300〜380℃程度）である。この場合も、第１段階加熱温度から一挙にこの温度に到達するのではなく、徐々に昇温して、その温度に達するようにするのが良い。 When this stage is completed, the second stage heating is followed by heating to complete imidation, and the temperature is about 280 to 400 ° C. (preferably about 300 to 380 ° C.). Also in this case, it is preferable not to reach this temperature from the first stage heating temperature all at once, but to gradually increase the temperature to reach that temperature.
なお、第２段階加熱は、無端管状フイルムを回転ドラムの内面に付着したまま行っても良いし、第１加熱段階を終わったら、回転ドラムから無端管状フイルムを剥離し、取出して別途イミド化のための加熱手段に供して、280〜400℃に加熱してもよい。このイミド化の所用時間は、通常約2〜3時間程度である。従って、第１及び第２加熱段階の全工程の所要時間は、通常4〜7時間程度となる。 The second stage heating may be performed while the endless tubular film is adhered to the inner surface of the rotating drum. When the first heating stage is finished, the endless tubular film is peeled off from the rotating drum, taken out, and separately imidized. For heating to 280 to 400 ° C. The time required for this imidization is usually about 2 to 3 hours. Therefore, the time required for all the steps of the first and second heating stages is usually about 4 to 7 hours.
かくして本発明の半導電性ＰＩ管状物（フイルム）が製造される。このフイルムの厚みは特に限定はないが、通常30〜200μｍ程度、好ましくは60〜120μｍ程度である。特に、電子写真方式の中間転写ベルトとして用いる場合は、75〜100μｍ程度が好ましい。 Thus, the semiconductive PI tubular product (film) of the present invention is produced. The thickness of the film is not particularly limited, but is usually about 30 to 200 μm, preferably about 60 to 120 μm. In particular, when used as an electrophotographic intermediate transfer belt, about 75 to 100 μm is preferable.
このフイルムの半導電性は、体積抵抗率（Ω・ｃｍ）（以下、「ＶＲ」と呼ぶ。）と表面抵抗率（Ω/□）（以下、「ＳＲ」と呼ぶ。）との両立によって決まる電気抵抗特性であり、この特性は、ＣＢ粉体の混合分散により付与される。そしてこの抵抗率の範囲は、基本的には該ＣＢ粉体の混合量によって自由に変えられる。本発明のフイルムにおける抵抗率の範囲としては、ＶＲ：１０2〜１０14、ＳＲ：１０3〜１０15であり、好ましい範囲としては、ＶＲ：１０6〜１０13、ＳＲ：１０7〜１０14が例示できる。これらの抵抗率の範囲は、上述のＣＢ粉体の配合量を採用することにより容易に達成することができる。なお、本発明のフイルム中におけるＣＢの含有量は、通常5〜25重量％程度、好ましくは8〜20重量％程度となる。 The semiconductivity of this film is determined by coexistence of volume resistivity (Ω · cm) (hereinafter referred to as “VR”) and surface resistivity (Ω / □) (hereinafter referred to as “SR”). It is an electric resistance characteristic, and this characteristic is imparted by mixing and dispersing CB powder. The resistivity range can be freely changed basically depending on the mixing amount of the CB powder. The resistivity ranges of the film of the present invention are VR: 10 2 to 10 14 and SR: 10 3 to 10 15. Preferred ranges are VR: 10 6 to 10 13 , SR: 10 7 to 10 14. Can be illustrated. These resistivity ranges can be easily achieved by adopting the blending amount of the above-mentioned CB powder. In addition, the content of CB in the film of the present invention is usually about 5 to 25% by weight, preferably about 8 to 20% by weight.
本発明の半導電性ＰＩフイルムは、極めて均質な電気抵抗率を有している。すなわち、本発明の半導電性ＰＩフイルムは、表面抵抗率ＳＲ及び体積抵抗率ＶＲの対数換算値のバラツキが小さいという特徴を有し、それぞれフイルム内全測定点の対数換算値の標準偏差が0.2以内、好ましくは、0.15以下である。また、フイルム表面と裏面の表面抵抗率（対数換算値）の差が小さいという特徴を有し、その差は0.4以内、好ましくは0.2以内である。さらに、表面抵抗率の対数換算値LogSRから体積抵抗率の対数換算値LogVRを引いた値が、1.0〜3.0、好ましくは1.5〜3.0と高い値に維持できるという特徴を備えている。 The semiconductive PI film of the present invention has a very homogeneous electrical resistivity. That is, the semiconductive PI film of the present invention is characterized by small variations in logarithmically converted values of the surface resistivity SR and volume resistivity VR, and the standard deviation of logarithmically converted values of all measurement points in the film is 0.2. Or less, preferably 0.15 or less. In addition, there is a feature that the difference in surface resistivity (logarithmic conversion value) between the film surface and the back surface is small, and the difference is within 0.4, preferably within 0.2. Furthermore, the value obtained by subtracting the logarithmic conversion value LogVR of the volume resistivity from the logarithmic conversion value LogSR of the surface resistivity can be maintained at a high value of 1.0 to 3.0, preferably 1.5 to 3.0.
本発明のＰＩフイルムが上記の優れた電気的特性を有するのは、該フイルムの製造工程で、「芳香族アミド酸オリゴマー」とＣＢ粉体とが混合された半導電性芳香族アミド酸組成物を採用しているためであると考えられる。すなわち、該組成物ではＣＢ粉体が芳香族アミド酸オリゴマー中に均一に分散しているが、フイルム製造工程においてその均一分散性を保持したま高分子量化することができるため、本発明のＰＩフイルムには優れた特性が付与されたと考えられる。 The PI film of the present invention has the above-mentioned excellent electrical characteristics because it is a semiconductive aromatic amic acid composition in which "aromatic amic acid oligomer" and CB powder are mixed in the production process of the film. This is thought to be due to the adoption of That is, in the composition, the CB powder is uniformly dispersed in the aromatic amic acid oligomer, but it can be increased in molecular weight while maintaining the uniform dispersibility in the film production process. It is thought that excellent properties were imparted to the film.
本発明のＰＩフイルムはその優れた電気抵抗特性等の機能によって、その用途は多岐にわたる。例えば、帯電特性を必要とする重要な用途として、カラー複写機、カラープリンター等の電子写真方式の中間転写ベルト等が挙げられる。該ベルトとして必要な半導電性（抵抗率）は、例えばＶＲ１０9〜１０12、ＳＲ１０10〜１０13であり、本発明の半導電性無端管状ＰＩフイルムを好適に用いることができる。 The PI film of the present invention has a wide variety of uses depending on functions such as excellent electrical resistance characteristics. For example, an important application requiring charging characteristics is an electrophotographic intermediate transfer belt such as a color copying machine or a color printer. The semiconductivity (resistivity) necessary for the belt is, for example, VR10 9 to 10 12 or SR10 10 to 10 13 , and the semiconductive endless tubular PI film of the present invention can be suitably used.
本発明の半導電性高濃度ＰＩ前駆体組成物では、ＣＢ粉体が均一に分散し、かつ、ＣＢ粉体が均一分散した状態の貯蔵安定性が格段に向上する。しかも、これを用いた半導電性ＰＩ前駆体組成物を回転成形して得られる導電性ポリイミド管状物は、その厚み方向に極めて安定かつ均質な電気抵抗率を有する導電性が付与される。すなわち、例えば転写ベルト等として使用した場合、電荷の徐電、帯電を適切に行うことができ、優れた画像処理が可能となる。 In the semiconductive high concentration PI precursor composition of the present invention, the CB powder is uniformly dispersed, and the storage stability in a state where the CB powder is uniformly dispersed is remarkably improved. Moreover, the conductive polyimide tubular product obtained by rotational molding of the semiconductive PI precursor composition using the same is imparted with conductivity having extremely stable and uniform electrical resistivity in the thickness direction. That is, for example, when used as a transfer belt or the like, it is possible to appropriately charge and charge the charge, and to perform excellent image processing.
また、本発明の半導電性高濃度ＰＩ前駆体組成物は、カーボンブラック分散液に成形原料であるモノマーを溶解させるため、不揮発性分濃度を35〜60重量％程度と格段に高めることができる。そのため、本発明の半導電性高濃度ＰＩ前駆体組成物では、容易に膜厚のあるフイルムを製造することができ、使用する溶媒の量が少ないためコストが抑えられ溶媒の蒸発除去が簡便になる。 In addition, since the semiconductive high concentration PI precursor composition of the present invention dissolves the monomer as the forming raw material in the carbon black dispersion, the nonvolatile content concentration can be remarkably increased to about 35 to 60% by weight. . Therefore, the semiconductive high concentration PI precursor composition of the present invention can easily produce a film having a film thickness, and the amount of solvent to be used is small, so that the cost can be suppressed and the solvent can be easily removed by evaporation. Become.
本発明の半導電性ポリイミド管状物は、均質な電気的特性を有していることから、カラー複写機用等の電子写真方式の中間転写ベルトとしてより好適に用いられる。 Since the semiconductive polyimide tubular article of the present invention has uniform electrical characteristics, it is more suitably used as an electrophotographic intermediate transfer belt for a color copying machine or the like.
次に本発明を、比較例と共に実施例によって更に詳述する。なお、以下、2、3、3’、4’−ビフェニルテトラカルボン酸二無水物を「a-BPDA」と、3、3’、4、4’−ビフェニルテトラカルボン酸二無水物を「s-BPDA」と表記する。 Next, the present invention will be described in more detail by way of examples together with comparative examples. Hereinafter, 2,3,3 ′, 4′-biphenyltetracarboxylic dianhydride is referred to as “a-BPDA”, and 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride is referred to as “s-BPDA”. It is written as “BPDA”.
実施例１
有機極性溶媒 N-メチル-2-ピロリドン153gに、酸性カーボン（pH3.0, 揮発分14.5％）を27g添加して、予備分散後、ボールミルにて主分散を行った。カーボンブラックの平均粒径は0.29μm、最大粒径は0.55μmであった。次に、この溶液120gにa-BPDAを14gとs-BPDAを56g、メタノール22.8g、を投入し、バス温度60℃にて窒素流通下反応させた。
Example 1
27 g of acidic carbon (pH 3.0, volatile content 14.5%) was added to 153 g of organic polar solvent N-methyl-2-pyrrolidone. After pre-dispersion, main dispersion was performed with a ball mill. Carbon black had an average particle size of 0.29 μm and a maximum particle size of 0.55 μm. Next, 14 g of a-BPDA, 56 g of s-BPDA, and 22.8 g of methanol were added to 120 g of this solution, and reacted at a bath temperature of 60 ° C. under a nitrogen flow.
次に、バス温度50℃まで冷却後、4,4'-ジアミノジフェニルエーテル（ODA）を47.6g投入し、ゆっくり撹拌してモノマーからなるカーボンブラック分散高濃度ポリイミド前駆体組成物260gを得た。この溶液は粘度32ポイズ、不揮発分濃度48.9重量％、該不揮発分中のCB濃度14.2重量％であり、カーボンブラックの平均粒径は0.29μm、最大粒径は0.58μmであった。また、10日後のカーボンブラックの平均粒径は0.31μm、最大粒径は0.67μmであり、ほとんど変化しなかった。 Next, after cooling to a bath temperature of 50 ° C., 47.6 g of 4,4′-diaminodiphenyl ether (ODA) was added and the mixture was slowly stirred to obtain 260 g of a carbon black-dispersed high-concentration polyimide precursor composition composed of monomers. This solution had a viscosity of 32 poise, a non-volatile content of 48.9% by weight, a CB concentration of 14.2% by weight in the non-volatile content, the average particle size of carbon black was 0.29 μm, and the maximum particle size was 0.58 μm. Further, the average particle diameter of carbon black after 10 days was 0.31 μm and the maximum particle diameter was 0.67 μm.
なお、本明細書における「不揮発分濃度」とは次のように算出された値である。試料（カーボンブラック分散高濃度ポリイミド前駆体組成物等）を金属カップ等の耐熱性容器で精秤しこの時の試料の重量をAｇとする。試料を入れた耐熱性容器を電気オーブンに入れて、120℃×12分、180℃×12分、260℃×30分、及び300℃×30分で順次昇温しながら加熱、乾燥し、得られる固形分の重量（不揮発分重量）をBｇとする。同一試料について５個のサンプルのA及びBの値を測定し（n=5）、次式（Ｉ）にあてはめて不揮発分濃度を求めた。その5個のサンプルの平均値を、本発明における不揮発分濃度として採用した。 The “nonvolatile content concentration” in this specification is a value calculated as follows. A sample (carbon black dispersed high concentration polyimide precursor composition or the like) is precisely weighed in a heat resistant container such as a metal cup, and the weight of the sample at this time is defined as Ag. Put the heat-resistant container containing the sample in an electric oven, heat and dry while heating up in order of 120 ℃ × 12min, 180 ℃ × 12min, 260 ℃ × 30min, and 300 ℃ × 30min. The weight of the solid content (non-volatile content weight) is Bg. The values of A and B of five samples of the same sample were measured (n = 5), and applied to the following formula (I) to determine the nonvolatile content concentration. The average value of the five samples was adopted as the nonvolatile content concentration in the present invention.
不揮発分濃度＝B/A×100（％） （Ｉ）
実施例２
有機極性溶媒 N-メチル-2-ピロリドン 120gに、ファーネスブラック（pH9.0, 揮発分1.5％）を10g添加して、予備分散後、ボールミルにて主分散を行った。カーボンブラックの平均粒径は0.67μm、最大粒径は3.92μmであった。次に、この溶液125gにa-BPDAを35gとs-BPDAを35g、メタノール22.8g、を投入し、バス温度70℃にて窒素流通下反応させた。次に、バス温度50℃まで冷却後、4,4'-ジアミノジフェニルエーテル（ODA）を47.6g投入し、ゆっくり撹拌してモノマーからなるカーボンブラック分散高濃度ポリイミド前駆体組成物265gを得た。この溶液は粘度12ポイズ、不揮発分濃度44.7重量％、不揮発分中のCB濃度8.2重量％であり、カーボンブラックの平均粒径は0.77μm、最大粒径は3.92μmであった。さらに、10日後のカーボンブラックの平均流径は0.77μm、最大粒径は4.47μmであり、ほとんど変化しなかった。
Nonvolatile content concentration = B / A x 100 (%) (I)
Example 2
10 g of furnace black (pH 9.0, volatile matter 1.5%) was added to 120 g of organic polar solvent N-methyl-2-pyrrolidone, and after preliminary dispersion, main dispersion was performed with a ball mill. Carbon black had an average particle size of 0.67 μm and a maximum particle size of 3.92 μm. Next, 35 g of a-BPDA, 35 g of s-BPDA, and 22.8 g of methanol were added to 125 g of this solution, and reacted at a bath temperature of 70 ° C. under nitrogen flow. Next, after cooling to a bath temperature of 50 ° C., 47.6 g of 4,4′-diaminodiphenyl ether (ODA) was added, and the mixture was slowly stirred to obtain 265 g of a carbon black-dispersed high-concentration polyimide precursor composition composed of monomers. This solution had a viscosity of 12 poise, a non-volatile content of 44.7% by weight, a CB concentration of non-volatile content of 8.2% by weight, the average particle size of carbon black was 0.77 μm, and the maximum particle size was 3.92 μm. Furthermore, the average flow diameter of carbon black after 10 days was 0.77 μm, and the maximum particle diameter was 4.47 μm, showing almost no change.
比較例1
s-BPDAとODAから合成された高分子量のポリアミック酸溶液（粘度50ポイズ、不揮発分濃度18.0重量％）600gに、酸性カーボン（pH3.0, 揮発分14.5％）を20g添加して、ボールミルにて主分散を行ったが、溶液の増粘率が高くゲル状になってしまい。そこで、この溶液に有機溶媒（NMP）を300g加えて、再分散を行った。この溶液は粘度8ポイズ、不揮発分濃度13.9重量％、不揮発分中のCB濃度15.6重量％であり、カーボンブラックの平均粒径は0.32μm、最大粒径は0.77μmであった。さらに、10日後のカーボンブラックの平均流径は0.32μm、最大粒径は0.77μmであり、ほとんど変化しなかった。
Comparative Example 1
Add 20g of acidic carbon (pH3.0, volatile matter 14.5%) to 600g of high molecular weight polyamic acid solution (viscosity 50 poise, nonvolatile concentration 18.0% by weight) synthesized from s-BPDA and ODA, and add to ball mill The main dispersion was performed, but the solution had a high viscosity increase rate and became a gel. Therefore, 300 g of an organic solvent (NMP) was added to this solution for redispersion. This solution had a viscosity of 8 poises, a non-volatile content of 13.9% by weight, a CB concentration of 15.6% by weight in non-volatiles, the average particle size of carbon black was 0.32 μm, and the maximum particle size was 0.77 μm. Furthermore, the average flow diameter of carbon black after 10 days was 0.32 μm, and the maximum particle diameter was 0.77 μm, which was almost unchanged.
比較例2
a-BPDAを35gとs-BPDAを35g（50モル％：50モル％）に、メタノール22.8g、N-メチル-2-ピロリドン160gを投入し、バス温度70℃にて窒素流通下反応させた。次に、バス温度60℃まで冷却後、4,4'-ジアミノジフェニルエーテル（ODA）を47.6g投入し、ゆっくり撹拌してナイロン塩型モノマー溶液300.4gを得た。この溶液は粘度；1.8ポイズ、不揮発分濃度36.3重量％であった。この溶液に、酸性カーボン（pH3.0, 揮発分14.5％）16.5gと有機溶媒（NMP）140gを添加して、ボールミルにて主分散を行った。この溶液は粘度5ポイズ、不揮発分濃度27.5重量％、不揮発分中のCB濃度12.3重量％であり、カーボンブラックの平均粒径は0.47μm、最大粒径は1.73μmであった。さらに、10日後のカーボンブラックの平均流径は0.78μm、最大粒径は5.12μmであり、カーボンブラックの凝集が確認できた。
Comparative Example 2
35 g of a-BPDA and 35 g of s-BPDA (50 mol%: 50 mol%) were charged with 22.8 g of methanol and 160 g of N-methyl-2-pyrrolidone, and reacted under nitrogen flow at a bath temperature of 70 ° C. . Next, after cooling to a bath temperature of 60 ° C., 47.6 g of 4,4′-diaminodiphenyl ether (ODA) was added and stirred slowly to obtain 300.4 g of a nylon salt monomer solution. This solution had a viscosity of 1.8 poise and a nonvolatile content concentration of 36.3% by weight. To this solution, 16.5 g of acidic carbon (pH 3.0, volatile content 14.5%) and 140 g of an organic solvent (NMP) were added, and main dispersion was performed with a ball mill. This solution had a viscosity of 5 poises, a non-volatile content of 27.5% by weight, a CB concentration in the non-volatiles of 12.3% by weight, the average particle size of carbon black was 0.47 μm, and the maximum particle size was 1.73 μm. Further, after 10 days, the average flow diameter of carbon black was 0.78 μm and the maximum particle diameter was 5.12 μm, and aggregation of carbon black was confirmed.
実施例３（回転成形法によるポリイミド管状体の作製）
外径300mm、内径270mm、長さ500mmの円筒状金型を、回転速度100rpm（10.5rad/s）で回転させながら、その円筒状金型の内面に実施例１、２叉は比較例１、２の溶液を均一に幅480mmで塗布した。塗布厚さは不揮発分濃度から算出し、ポリイミドベルト厚さが100μmになるよう決定した。溶剤の揮発は60分間で100℃に昇温し、その後100℃で溶剤の揮発を目視で観察し、溶媒揮発が終了させるのに必要な時間を測定した。
Example 3 (Production of polyimide tubular body by rotational molding method)
While rotating a cylindrical mold having an outer diameter of 300 mm, an inner diameter of 270 mm, and a length of 500 mm at a rotational speed of 100 rpm (10.5 rad / s), Example 1, 2 or Comparative Example 1, The solution of 2 was uniformly applied with a width of 480 mm. The coating thickness was calculated from the nonvolatile content concentration, and was determined so that the polyimide belt thickness was 100 μm. The volatilization of the solvent was raised to 100 ° C. in 60 minutes, and then the volatilization of the solvent was visually observed at 100 ° C., and the time required for the completion of the solvent volatilization was measured.
次に、この管状物を円筒状金型の内面に付着したまま高温加熱炉に投入し、120分間で320℃に昇温し、320℃で60分間高温加熱することでポリイミド転化した。その後、常温まで冷却して金型よりポリイミド管状物を取り出した。以上の結果を表１に示す。なお、管状物中のCB含有量及び該管状物の厚さもあわせて表１に示す。 Next, this tubular product was put into a high-temperature heating furnace while adhering to the inner surface of the cylindrical mold, heated to 320 ° C. in 120 minutes, and heated at 320 ° C. for 60 minutes to perform polyimide conversion. Then, it cooled to normal temperature and took out the polyimide tubular material from the metal mold | die. The results are shown in Table 1. The CB content in the tubular product and the thickness of the tubular product are also shown in Table 1.
なお、表面抵抗率（SR）の測定は、得られたポリイミド管状物を長さ４００ｍｍにカットしたものをサンプルとして、三菱化学株式会社製の抵抗測定器“ハイレスタＩＰ・ＵＲプロ−ブ”を使って、幅方向に等ピッチで３カ所と縦（周）方向に４カ所の合計１２ヶ所について各々測定し、全体の平均値で示した。表面抵抗率（SR）は電圧５００Ｖ印加の下１０秒経過後に測定した。 In addition, the surface resistivity (SR) is measured using a resistance measuring instrument “HIRESTA IP / UR probe” manufactured by Mitsubishi Chemical Corporation using a sample obtained by cutting the obtained polyimide tubular material to a length of 400 mm. In addition, a total of 12 points were measured at 3 points at equal pitches in the width direction and 4 points in the longitudinal (circumferential) direction, and indicated as the average value of the whole. The surface resistivity (SR) was measured after 10 seconds had elapsed under application of a voltage of 500V.
従来法（比較例）では、成形原料の不揮発分濃度が低くなり、大量の有機極性溶媒を揮発するのに多大な時間が必要となり生産効率が非常に悪い。また、モノマー溶液などにCBを添加して分散する方法では、分散時の発熱によってモノマー溶液の反応が進行し溶液の状態が不安定になる。
In the conventional method (comparative example), the concentration of non-volatile components in the forming raw material is low, and a large amount of time is required to volatilize a large amount of the organic polar solvent, resulting in very poor production efficiency. Further, in the method in which CB is added and dispersed in a monomer solution or the like, the reaction of the monomer solution proceeds due to heat generated during dispersion, and the state of the solution becomes unstable.
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| JP2004059593A JP4993845B2 (en) | 2004-03-03 | 2004-03-03 | Semiconductive high concentration polyimide precursor composition and semiconductive polyimide tubular product using the same |
| CN2009101590363A CN101638480B (en) | 2004-03-03 | 2004-10-08 | Aromatic amic acid composition and a preparing method thereof, and a seamless tubular polyimide film and a preparing method thereof |
| KR1020067020029A KR20060134129A (en) | 2004-03-03 | 2004-10-08 | Endless tubular polyimide film |
| KR1020137009810A KR101544112B1 (en) | 2004-03-03 | 2004-10-08 | Endless tubular polyimide film |
| US10/591,326 US8097693B2 (en) | 2004-03-03 | 2004-10-08 | Endless tubular polyimide film |
| CNB2004800429327A CN100545194C (en) | 2004-03-03 | 2004-10-08 | Endless tubular polyimide film |
| KR1020117021427A KR101443830B1 (en) | 2004-03-03 | 2004-10-08 | Endless tubular polyimide film |
| PCT/JP2004/015309 WO2005085324A1 (en) | 2004-03-03 | 2004-10-08 | Endless tubular polyimide film |
| EP04773760.6A EP1721924B1 (en) | 2004-03-03 | 2004-10-08 | Endless tubular polyimide film |
| HK07110940.3A HK1105650A1 (en) | 2004-03-03 | 2007-10-10 | Endless tubular polyimide film |
| HK10104420.0A HK1138302A1 (en) | 2004-03-03 | 2010-05-05 | Aromatic amic acid composition and method of preparing the same, and endless tubular polyimide film and method of preparing the same |
| US13/280,713 US8314204B2 (en) | 2004-03-03 | 2011-10-25 | Endless tubular polyimide film |
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| JP2004059593A JP4993845B2 (en) | 2004-03-03 | 2004-03-03 | Semiconductive high concentration polyimide precursor composition and semiconductive polyimide tubular product using the same |
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Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5638324A (en) * | 1979-09-06 | 1981-04-13 | Ube Ind Ltd | Preparation of polyimide solution |
| JPH10182820A (en) * | 1996-10-29 | 1998-07-07 | Ube Ind Ltd | Polyimide precursor composition and polyimide film |
| JP2001047451A (en) * | 1999-08-12 | 2001-02-20 | Gunze Ltd | Endless tubular semiconductive aromatic polyimide film and its manufacture |
| JP2001241313A (en) * | 2000-02-29 | 2001-09-07 | Yanmar Diesel Engine Co Ltd | Lubricating oil supplying device of internal combustion engine |
| JP2001277264A (en) * | 2000-03-30 | 2001-10-09 | Unitika Ltd | Polyimide seamless tube and method for preparing it |
| JP2002292656A (en) * | 2001-03-29 | 2002-10-09 | Nitto Denko Corp | Method for manufacturing semiconductive polyimide belt |
| JP2003213014A (en) * | 2002-01-17 | 2003-07-30 | Gunze Ltd | Tubular film of semiconductive wholly aromatic polyimide and method for producing the same |
| JP2003261768A (en) * | 2002-03-12 | 2003-09-19 | Hitachi Chem Co Ltd | Semiconductive tubular polyamide-imide film and method for producing the same |
| JP2003277502A (en) * | 2002-03-27 | 2003-10-02 | Nitto Denko Corp | Process for preparing polyamic acid solution having carbon black dispersed therein and electrically semiconductor polyimide belt using it |
| JP2004323834A (en) * | 2003-04-10 | 2004-11-18 | Gunze Ltd | Method for manufacturing seamless tubular polyimide film |
| JP2005025052A (en) * | 2003-07-04 | 2005-01-27 | Fuji Xerox Co Ltd | Semiconductive belt, its manufacturing method, and intermediate transfer belt and image forming apparatus using the same |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE69115076T2 (en) * | 1990-02-20 | 1996-05-09 | Nat Starch Chem Invest | Diarylacetylene end-capped polyimides. |
| JP3530065B2 (en) * | 1999-03-31 | 2004-05-24 | グンゼ株式会社 | Semiconductive polyamic acid composition liquid and semiconductive endless tubular polyimide film using the same |
| JP4263825B2 (en) * | 1999-11-15 | 2009-05-13 | 日東電工株式会社 | Semi-conductive belt for intermediate transfer and method for producing the same |
-
2004
- 2004-03-03 JP JP2004059593A patent/JP4993845B2/en not_active Expired - Fee Related
- 2004-10-08 CN CNB2004800429327A patent/CN100545194C/en not_active Expired - Fee Related
- 2004-10-08 CN CN2009101590363A patent/CN101638480B/en not_active Expired - Fee Related
Patent Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5638324A (en) * | 1979-09-06 | 1981-04-13 | Ube Ind Ltd | Preparation of polyimide solution |
| JPH10182820A (en) * | 1996-10-29 | 1998-07-07 | Ube Ind Ltd | Polyimide precursor composition and polyimide film |
| JP2001047451A (en) * | 1999-08-12 | 2001-02-20 | Gunze Ltd | Endless tubular semiconductive aromatic polyimide film and its manufacture |
| JP2001241313A (en) * | 2000-02-29 | 2001-09-07 | Yanmar Diesel Engine Co Ltd | Lubricating oil supplying device of internal combustion engine |
| JP2001277264A (en) * | 2000-03-30 | 2001-10-09 | Unitika Ltd | Polyimide seamless tube and method for preparing it |
| JP2002292656A (en) * | 2001-03-29 | 2002-10-09 | Nitto Denko Corp | Method for manufacturing semiconductive polyimide belt |
| JP2003213014A (en) * | 2002-01-17 | 2003-07-30 | Gunze Ltd | Tubular film of semiconductive wholly aromatic polyimide and method for producing the same |
| JP2003261768A (en) * | 2002-03-12 | 2003-09-19 | Hitachi Chem Co Ltd | Semiconductive tubular polyamide-imide film and method for producing the same |
| JP2003277502A (en) * | 2002-03-27 | 2003-10-02 | Nitto Denko Corp | Process for preparing polyamic acid solution having carbon black dispersed therein and electrically semiconductor polyimide belt using it |
| JP2004323834A (en) * | 2003-04-10 | 2004-11-18 | Gunze Ltd | Method for manufacturing seamless tubular polyimide film |
| JP2005025052A (en) * | 2003-07-04 | 2005-01-27 | Fuji Xerox Co Ltd | Semiconductive belt, its manufacturing method, and intermediate transfer belt and image forming apparatus using the same |
Cited By (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007333904A (en) * | 2006-06-13 | 2007-12-27 | Fuji Xerox Co Ltd | Polyamic acid composition, method for preparing the same, polyimide endless belt and image forming apparatus equipped with polyimide endless belt |
| JP2008009248A (en) * | 2006-06-30 | 2008-01-17 | Ricoh Co Ltd | Method for manufacturing coating liquid for electrophotographic seamless belt, and intermediate transfer belt |
| JP2008074900A (en) * | 2006-09-19 | 2008-04-03 | Gunze Ltd | Semiconductive polyimide resin belt and method for producing the same |
| JP2008076518A (en) * | 2006-09-19 | 2008-04-03 | Gunze Ltd | Semiconductive polyimide resin belt and method for manufacturing the same |
| JP2009138103A (en) * | 2007-12-06 | 2009-06-25 | Gunze Ltd | Semiconductive copolymerized polyimide belt, its production method and intermediate transfer belt |
| JP2010105258A (en) * | 2008-10-30 | 2010-05-13 | Unimatec Co Ltd | Method of manufacturing tubular polyimide belt |
| US9902824B2 (en) | 2009-10-09 | 2018-02-27 | Ube Industries, Ltd. | Colored polyimide molded article, and process for production thereof |
| EP2487196A4 (en) * | 2009-10-09 | 2014-04-09 | Ube Industries | Colored polyimide molded article, and process for production thereof |
| US9346927B2 (en) | 2009-10-09 | 2016-05-24 | Ube Industries, Ltd. | Colored polyimide molded article, and process for production thereof |
| US8886106B2 (en) | 2011-03-02 | 2014-11-11 | Konica Minolta Business Technologies, Inc. | Intermediate transfer belt and method for producing the same |
| US9193828B2 (en) | 2012-03-02 | 2015-11-24 | Fuji Xerox Co., Ltd. | Polyimide precursor composition, polyimide-molded product, and image forming apparatus |
| JP2013181136A (en) * | 2012-03-02 | 2013-09-12 | Fuji Xerox Co Ltd | Polyimide precursor composition, production method of endless belt, and image forming device |
| JP2016164279A (en) * | 2016-05-31 | 2016-09-08 | 富士ゼロックス株式会社 | Polyimide precursor composition, polyimide molded product, and image formation device |
| JP2018146634A (en) * | 2017-03-01 | 2018-09-20 | 富士ゼロックス株式会社 | Transfer belt for electrophotographic device, image forming apparatus, and transfer belt unit |
| JP6996090B2 (en) | 2017-03-01 | 2022-01-17 | 富士フイルムビジネスイノベーション株式会社 | Transfer belt for electrophotographic equipment, image forming equipment and transfer belt unit |
| CN113528155A (en) * | 2021-07-05 | 2021-10-22 | 合肥中聚合臣电子材料有限公司 | Orientation agent for improving liquid crystal display afterimage performance |
Also Published As
| Publication number | Publication date |
|---|---|
| CN100545194C (en) | 2009-09-30 |
| CN101638480B (en) | 2011-06-08 |
| CN101638480A (en) | 2010-02-03 |
| JP4993845B2 (en) | 2012-08-08 |
| CN1946767A (en) | 2007-04-11 |
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