JP3747633B2 - Electrophotographic equipment - Google Patents
Electrophotographic equipment Download PDFInfo
- Publication number
- JP3747633B2 JP3747633B2 JP16344398A JP16344398A JP3747633B2 JP 3747633 B2 JP3747633 B2 JP 3747633B2 JP 16344398 A JP16344398 A JP 16344398A JP 16344398 A JP16344398 A JP 16344398A JP 3747633 B2 JP3747633 B2 JP 3747633B2
- Authority
- JP
- Japan
- Prior art keywords
- pure water
- contact
- contact angle
- image
- degrees
- 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 - Lifetime
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 33
- 108091008695 photoreceptors Proteins 0.000 claims description 15
- 230000002209 hydrophobic effect Effects 0.000 claims description 7
- 239000010410 layer Substances 0.000 description 27
- 238000011109 contamination Methods 0.000 description 23
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- 238000012546 transfer Methods 0.000 description 12
- 239000000463 material Substances 0.000 description 11
- 238000011156 evaluation Methods 0.000 description 10
- 239000010954 inorganic particle Substances 0.000 description 10
- 239000011241 protective layer Substances 0.000 description 10
- 230000007547 defect Effects 0.000 description 9
- 239000000049 pigment Substances 0.000 description 9
- 239000000356 contaminant Substances 0.000 description 7
- 239000011230 binding agent Substances 0.000 description 6
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- 230000000052 comparative effect Effects 0.000 description 5
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
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- 150000002148 esters Chemical class 0.000 description 3
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 3
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- 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
- 229920000515 polycarbonate Polymers 0.000 description 3
- 239000004417 polycarbonate Substances 0.000 description 3
- 229920002554 vinyl polymer Polymers 0.000 description 3
- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical compound O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 description 2
- UJOBWOGCFQCDNV-UHFFFAOYSA-N 9H-carbazole Chemical compound C1=CC=C2C3=CC=CC=C3NC2=C1 UJOBWOGCFQCDNV-UHFFFAOYSA-N 0.000 description 2
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 2
- -1 Hydrazone compound Chemical class 0.000 description 2
- SIKJAQJRHWYJAI-UHFFFAOYSA-N Indole Chemical compound C1=CC=C2NC=CC2=C1 SIKJAQJRHWYJAI-UHFFFAOYSA-N 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
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- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
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- 239000002184 metal Substances 0.000 description 2
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- NRCMAYZCPIVABH-UHFFFAOYSA-N Quinacridone Chemical compound N1C2=CC=CC=C2C(=O)C2=C1C=C1C(=O)C3=CC=CC=C3NC1=C2 NRCMAYZCPIVABH-UHFFFAOYSA-N 0.000 description 1
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- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- NRTOMJZYCJJWKI-UHFFFAOYSA-N Titanium nitride Chemical compound [Ti]#N NRTOMJZYCJJWKI-UHFFFAOYSA-N 0.000 description 1
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
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- OTCHGXYCWNXDOA-UHFFFAOYSA-N [C].[Zr] Chemical compound [C].[Zr] OTCHGXYCWNXDOA-UHFFFAOYSA-N 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
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- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 1
- 125000002490 anilino group Chemical class [H]N(*)C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 1
- PGEHNUUBUQTUJB-UHFFFAOYSA-N anthanthrone Chemical compound C1=CC=C2C(=O)C3=CC=C4C=CC=C5C(=O)C6=CC=C1C2=C6C3=C54 PGEHNUUBUQTUJB-UHFFFAOYSA-N 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- INAHAJYZKVIDIZ-UHFFFAOYSA-N boron carbide Chemical compound B12B3B4C32B41 INAHAJYZKVIDIZ-UHFFFAOYSA-N 0.000 description 1
- 229910052980 cadmium sulfide Inorganic materials 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- 239000000292 calcium oxide Substances 0.000 description 1
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 1
- 239000000378 calcium silicate Substances 0.000 description 1
- 229910052918 calcium silicate Inorganic materials 0.000 description 1
- OYACROKNLOSFPA-UHFFFAOYSA-N calcium;dioxido(oxo)silane Chemical compound [Ca+2].[O-][Si]([O-])=O OYACROKNLOSFPA-UHFFFAOYSA-N 0.000 description 1
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- 229940097275 indigo Drugs 0.000 description 1
- COHYTHOBJLSHDF-UHFFFAOYSA-N indigo powder Natural products N1C2=CC=CC=C2C(=O)C1=C1C(=O)C2=CC=CC=C2N1 COHYTHOBJLSHDF-UHFFFAOYSA-N 0.000 description 1
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- HCWCAKKEBCNQJP-UHFFFAOYSA-N magnesium orthosilicate Chemical compound [Mg+2].[Mg+2].[O-][Si]([O-])([O-])[O-] HCWCAKKEBCNQJP-UHFFFAOYSA-N 0.000 description 1
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- SJHHDDDGXWOYOE-UHFFFAOYSA-N oxytitamium phthalocyanine Chemical compound [Ti+2]=O.C12=CC=CC=C2C(N=C2[N-]C(C3=CC=CC=C32)=N2)=NC1=NC([C]1C=CC=CC1=1)=NC=1N=C1[C]3C=CC=CC3=C2[N-]1 SJHHDDDGXWOYOE-UHFFFAOYSA-N 0.000 description 1
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- CSHWQDPOILHKBI-UHFFFAOYSA-N peryrene Natural products C1=CC(C2=CC=CC=3C2=C2C=CC=3)=C3C2=CC=CC3=C1 CSHWQDPOILHKBI-UHFFFAOYSA-N 0.000 description 1
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 description 1
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- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
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- DNXIASIHZYFFRO-UHFFFAOYSA-N pyrazoline Chemical compound C1CN=NC1 DNXIASIHZYFFRO-UHFFFAOYSA-N 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
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- 230000035945 sensitivity Effects 0.000 description 1
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- 229910052814 silicon oxide Inorganic materials 0.000 description 1
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- 229920002803 thermoplastic polyurethane Polymers 0.000 description 1
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- VLLMWSRANPNYQX-UHFFFAOYSA-N thiadiazole Chemical compound C1=CSN=N1.C1=CSN=N1 VLLMWSRANPNYQX-UHFFFAOYSA-N 0.000 description 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
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- 239000010936 titanium Substances 0.000 description 1
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- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- MTPVUVINMAGMJL-UHFFFAOYSA-N trimethyl(1,1,2,2,2-pentafluoroethyl)silane Chemical compound C[Si](C)(C)C(F)(F)C(F)(F)F MTPVUVINMAGMJL-UHFFFAOYSA-N 0.000 description 1
- UONOETXJSWQNOL-UHFFFAOYSA-N tungsten carbide Chemical compound [W+]#[C-] UONOETXJSWQNOL-UHFFFAOYSA-N 0.000 description 1
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Images
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- Compositions Of Macromolecular Compounds (AREA)
- Paints Or Removers (AREA)
- Conductive Materials (AREA)
- Electrostatic Charge, Transfer And Separation In Electrography (AREA)
Description
【0001】
【発明の属する技術分野】
本発明は接触帯電部材および電子写真装置に関するものである。更に詳しくは、汚れの付着がなく鮮明な画像を得ることのできる接触帯電部材および電子写真装置に関する。
【0002】
【従来の技術】
複写機、プリンター、ファクシミリなどの電子写真装置においては、感光体を帯電装置で帯電させるプロセスを必要とする。
帯電装置としては、大別して接触帯電装置と非接触帯電装置がある。前者の接触帯電装置は非帯電体としての感光体表面に、接触帯電用部材を接触させ、この接触帯電用部材に電圧を印加することによって、感光体表面を所定の電位に帯電させるものである。
【0003】
この接触帯電装置は、後者の例えばコロナ放電を利用した非接触帯電装置に比して印加電圧を低く抑えることができ、また、帯電時のオゾンの発生を低減することが可能であるなどの利点がある。
しかし、接触帯電方式は、長期の使用に伴い、押しつぶされた残留トナーなどの汚染物が感光体に固着し、帯電不良、ひいては画像不良を引き起こすという問題があり、その対策として、最外層に疎水化表面処理された無機粒子を配合して感光体表面を疎水化し、トナーの残留を防止することが行われている。
しかしながら、かかる残留トナー防止策はある程度の効果をあげてはいるが画像不良は依然としてある程度の密度で観察され、特に、接触帯電装置を有する電子写真装置の場合に、問題となっている。
【0004】
【発明が解決しようとする課題】
本発明は、長期の使用においても汚れの付着がなく、鮮明な画像を得ることのできる接触帯電部材および電子写真装置を提供することにある。
【0005】
【課題を解決するための手段】
本発明者らは、上記課題を解決すべく鋭意検討した結果、接触帯電装置を含む電子写真装置においては、感光体とこれを帯電する接触帯電用部材が直接接触しているために、感光体表面のみならず、接触帯電部材側にもトナーが残留、固着し、かかる残留トナーが、感光体の帯電不良箇所を発生させ、あるいは、感光体表面に戻ることにより画像不良が起こっていることを見出した。また、接触帯電部材の表面を純水接触角が特定の値以上になるまで疎水化することにより、画像不良を劇的に減少し得ることを見出し、本発明に到達した。
【0006】
本発明は、残留トナーなどの汚染物の固着を防止し、長期にわたって安定した帯電特性を維持し、良好な画像形成を可能とした電子写真装置を提供するものである。
すなわち、本発明は、電子写真感光体と該感光体に接触する位置に配設された接触帯電部材を有する電子写真装置において、接触帯電部材が、疎水性弾性体を用いて電子写真感光体との接触面を形成し、その表面の純水接触角を105度以上とすると共に、電子写真感光体の表面の純水接触角を95度以上とし、電子写真感光体表面の純水接触角Roと接触帯電部材表面の純水接触角Rcとが、次式を満足することを特徴とする電子写真装置を提供するものである。
0度≦|Ro−Rc|≦5度
【0007】
【発明の実施の形態】
電子写真装置1は、図1に示すように、電子写真感光体、図においてはドラム状の電子写真感光体2を有し、該感光体2の周囲には、帯電機構3、露光機構4、トナーによって画像を生じさせる現像機構5およびクリーナー6を有し、目的に応じて、画像を一旦転写する中間転写ベルト7、転写用荷電器8を設けて、中間転写ベルト7に転写された画像を用紙9に転写されるように構成されている。
【0008】
本発明は、帯電機構3が、電子写真感光体との接触面が疎水性弾性体で形成され、その表面を純水の接触角が90度以上とされる。
接触帯電部材の構造は特に制限はなく、帯電ローラ、帯電ブレード、帯電ブラシ、帯電フィルムなどを用いることができるが、帯電ローラが最も好適に使用することができる。
【0009】
以下、本発明接触帯電部材を帯電ローラを例にとって説明する。
帯電ローラ11としては、図2に示すように、ローラ状の芯金12の外周に弾性体によって弾性体層13が形成される。
本発明において弾性体とはその成形体が可撓性を示し得るものを広く意味し、ゴム状弾性を有するエラストマーからある程度硬質の樹脂状のものを意味するが帯電ローラ1としては、ある程度ゴム的性質を有するものが好ましく、加硫ゴム、注型ゴム、熱可塑性エラストマーなどのベース樹脂が用いられる。
【0010】
接触帯電部材11の感光体との接触面を形成する弾性体は、導電性を有することが望ましく、導電性成分が添加される。
導電性成分としては、カーボンブラック、金属粉、金属酸化物粉などの導電性フィラーや四級アンモニウム塩などの吸湿型導電剤をはじめ、公知のものを用いることができる。
【0011】
導電性成分の配合量としては、体積固有抵抗率が、1×104 〜1×1010Ω・cmになるように調製することが好ましい。
弾性体層13は、必要に応じて導電性あるいは弾性の異なる2以上の弾性体を積層することもできる。
本発明の帯電ローラは必要に応じて保護層14を有するものを用いることができる。
【0012】
保護層14を形成する場合、弾性体が用いられ、熱可塑性樹脂、溶媒可溶性樹脂などをベース樹脂として用いることができる。従って、保護層14は弾性体層13の一部を形成するものである。
保護層14は、抵抗値にも特に制限はなく、必要に応じて誘電体をベース樹脂に選択したり、導電性成分を配合することにより、所望の物性を得ることができる。 本発明においては、接触帯電部材11の最外層表面を純水接触角90度以上の疎水性とされる。
【0013】
接触帯電部材11の最外層の純水接触角を90度以上に設定することにより、残留トナーなどの汚染物固着を防止することができる。
具体的には、95度以上が好ましく、105度以上であればさらに好ましい。
一般に接触帯電部材11に用いられる弾性体層13、保護層を用いるときは保護層14などの最外層は、ポリウレタンやポリアミドなど、純水接触角があまり高くないものが多く用いられるが、最外層のベースに用いる樹脂の純水接触角物性が低い樹脂であっても、無機粒子、好ましくは表面疎水化無機粒子を分散させることにより、純水接触角の高い最外層を得ることができる。
【0014】
無機粒子としては、例えば酸化セリウム、酸化クロム、酸化アルミニウム、酸化マグネシウム、酸化ケイ素、酸化錫、酸化ジルコニウム、酸化鉄、酸化チタンなどの酸化物二硫酸カルシウム、硫酸バリウム、硫酸アルミニウムなどの硫酸塩;珪酸カルシウム、珪酸マグネシウムなどの珪酸塩;チッ化ホウ素、チッ化チタンなどのチッ化物;炭化ケイ素、炭化チタン、炭化ホウ素、炭化タングステン、炭化ジルコニウムなどの炭化物;ホウ化ジルコニウム、ホウ化チタンなどのホウ化物などが挙げられ、これらのうち1種を、または、必要に応じて2種以上が用いられる。
【0015】
無機粒子の物性に特に制限はないが、粒径が大きすぎると、分散不良を生じることがあるので、1μm以下が好ましく、100nm以下であるとさらに好ましい。
また、無機粒子の表面を疎水化処理すると、撥水効果を付与し、トナーの固着をさらに防ぐことができるようになるので、特に好ましい。
【0016】
疎水化処理としては、アルキル処理、アルキルシラン処理、ハロゲン化アルキルシラン処理などの手法を好適に用いることができる。
これらの無機粒子および疎水化無機粒子は、日本アエロジル(株)などから、市販品を入手することができる。
配合量は、比率が高いほど残留トナー固着を防ぐ効果が増すので、最外層において1重量%以上が好ましく、10重量%以上であるとさらに好ましい。また、多くなりすぎると、ローラが固くなりすぎるなどの問題が生じることがあるので、50重量%以下が好ましく、30重量%以下であるとさらに好ましい。
【0017】
図3は、帯電ブレード14を示すもので、芯金12の表面に弾性体層13が形成されており、最外層表面の純水接触角が90度以上とされる。
また、本発明においては、電子写真用感光体2についてもその表面を疎水性化することが望ましい。
感光体の構成としては、積層型、単層型などを用いることができる。
また、必要に応じ、磨耗防止などを目的とし、オーバーコート層を用いることもできる。
【0018】
積層型感光体の場合その電荷発生層に使用される電荷発生材料としては、例えば、セレニウム、およびその合金、硫化カドミニウム、その他無機系光導電材料、フタロシアニン顔料、アゾ顔料、キナクリドン顔料、インジゴ顔料、ペリレン顔料、多環キノン顔料、アントアントロン顔料、ベンズイミダゾール顔料などの有機顔料等各種が使用できるが、中でもフタロシアニン顔料、特にチタニルフタロシアニンは、感度、帯電性、繰り返し安定性に優れているため良好な電子写真特性を示す。
【0019】
これらの微粒子を例えば、ポリエステル樹脂、ポリビニルアセテート、ポリアクリル酸エステル、ポリエステル、ポリカーボネート、ポリビニルアセトアセタール、ポリビニルプロピオナール、ポリビニルブチラール、フェノキシ樹脂、エポキシ樹脂、ウレタン樹脂、セルロースエステルなどの各種バインダー樹脂で結着した形で使用される。
【0020】
この場合の使用比率はバインダー樹脂100重量部に対して30から50重量部の範囲より使用され、その膜厚は通常0.1μmから1μm、好ましくは、0.15μmから0.6μmが好適である。
電荷移動層の電荷移動材料としては、例えば、2,4,7−トリニトロフルオレノン、テトラシアノキノジメタンなどの電子吸引性物質、カルバゾール、インドール、イミダゾール、オキサゾール、ピラゾール、オキサジアゾール、ピラゾリン、チアジアゾールなどの複素環化合物、アニリン誘導体、或いはこれらの化合物からなる基を主鎖もしくは側鎖に有する重合体などの電子供与性物質が挙げられる。
【0021】
これらの電荷移動材料とともに必要に応じてバインダー樹脂が配合される。好ましいバインダー樹脂としては、例えばポリメチルメタクリレート、ポリスチレン、ポリ塩化ビニル等のビニル重合体、およびその共重合体、ポリカーボネート、ポリエステル、ポリエステルカーボネート、ポリスルホン、ポリイミド、フェノキシ、エポキシ、シリコーン樹脂等があげられ、またこれらの部分的架橋硬化物も使用できる。また電荷移動層には、必要に応じて酸化防止剤、増感剤等の各種添加剤を含んでいても良い。電荷移動層の膜厚は、10〜40μm、好ましくは、13〜35μmの厚みで使用されるのがよい。
【0022】
単層分散型の場合前述の電荷発生材料および電荷移動材料を例えば、ポリエステル樹脂、ポリビニルアセテート、ポリアクリル酸エステル、ポリメタクリル酸エステル、ポリエステル、ポリカーボネート等のバインダー樹脂で結着した形で使用される。この場合バインダー樹脂100重量部に対して電荷発生材料は1から50重量部、電荷移動材料は30から150重量部の範囲より使用されるのが好ましい。また膜厚は通常5から50μm、好ましくは10から35μmが好適である。また必要に応じて酸化防止剤、増感剤等の各種添加剤を含んでいても良い。
【0023】
感光体最外層の純水接触角も接触帯電部材同様、90度以上と高く設定することにより、残留トナーなどの汚染物の固着を防止する事ができるので、好ましい。
具体的には、95度以上が好ましく、105度以上であればさらに好ましい。
最外層のベースに用いる樹脂が純水接触角の低いものであっても、接触帯電部材の最外層同様、無機粒子、好ましくは表面疎水化無機粒子を分散させることにより、純水接触角の高い最外層を得ることができる。
【0024】
感光体2としては、円筒状の感光ドラムや、フィルム状の感光ベルトなどが好適に用いられる。
該感光体2に接触帯電用部材11が、設定された接触圧力をもって接触して配置され、接触帯電用部材からのびる電極が電源に接続され、接触帯電用部材に導電性ローラを用いた場合は、芯金が電極としての役割を果たす。
【0025】
電極に印加されたバイアスは、接触帯電用部材11を介して感光体に印加され、感光体表面を帯電する仕組みになっている。
また、接触帯電部材あるいは感光体として純水接触角の高いものを用いることにより、感光体の汚染を低減することができる。105度以上が好ましく、120度以上であれば汚染を極度に抑えることができるので特に好ましい。
【0026】
しかしながら、接触帯電用部材11と感光体2の純水接触角の差異が大きすぎると、各々の値がたとえ100度を越えていても長期にわたる使用により、接触角の低い方に選択的に汚染物が累積してしまう問題が生じる。この問題は、接触帯電部材11と感光体2の純水接触角の差異が小さい組み合わせを用いると、汚染物が片側に累積する前に、それぞれのクリーニングブレードなどでの清掃機構により除去される確率が高くなるので、総合的効果として抑制することができる。具体的には、接触帯電用部材と感光体の純水接触角の差異が10度以下が好ましく、5度以下であれば選択的な汚染が低減されるので特に好ましい。
上記のように、接触帯電方式は、感光体に接触帯電用部材が設定された接触圧力をもって接触して配置されるため、接触部に残留トナーなどの汚染物が入り込むと、接触圧力により押しつぶされて、一部は固着してしまう問題が生じるが、本発明はかかる障害が一掃される。
【0027】
【実施例】
本発明について、実施例により、更に具体的に説明するが、本発明の要旨を越えない限り、以下の実施例に限定されるものではない。
尚、以下の評価雰囲気は全て25℃、50%RHであり、本実施例に使用した原料、手法、評価方法は以下の通りである。
【0028】
○導電性ローラ
・ベース層原料
スチレン系熱可塑性エラストマー
(三菱化学(株)製 ラバロンT320C JIS−A硬度 15)
カーボンブラック
(三菱化学(株)製 3030B)
【0029】
・ベース層用樹脂混練方法
各原料を表1の配合比にて、二軸混練押出機「PCM45」(池貝機販(株)製)を用いて混練、造粒して熱可塑性エラストマー組成物のペレットを得た。
・ベース層成形方法
上記ペレットを、下記条件で、クロスヘッドダイを有する直径40mm押出機を用いて導電性ローラを製造した。
成形温度 ;190℃
使用芯金形状 ;直径8mm、全長340mm(SUS)
ローラ形状 ;芯金上に3.5mm厚で形成(全体の直径15mm)
【0030】
・保護層原料
アルコール可溶性ナイロン
(デュポン(株)製 エルバミド)
表面疎水化SiO2
(日本アエルジル(株)製 アエロジルR812)
・保護層形成
各原料を表1に記載の配合比、濃度に調整後、ディップコート手法により、保護層を形成した。
【0031】
○感光体
・CGL塗布液
オキシチタニウムフタロシアニン10重量部に、ポリビニルブチラール(電気化学工業(株)製:デンカブチラール#6000−C)5重量部に1,2−ジメトキシエタン500重量部を加え、サンドグラインドミルで粉砕、分散処理を行ってCGL塗布液を調液した。
・CTL塗布液
次に示すヒドラゾン化合物A、
【0032】
【化1】
次に示すヒドラゾン化合物B、
【0033】
【化2】
下記シアノ化合物、
【0034】
【化3】
および下記に示すポリカーボネート樹脂
【0035】
【化4】
【0036】
を1,4−ジオキサンに溶解させた液に、表面疎水化SiO2 (日本アエルジル(株)製 アエロジルR812)を添加混合した。各原料の配合比は表1に示す通りである。
表面を鏡面仕上げした肉厚1mm、外径30mm、長さ254mmのアルミシリンダーにCGL塗布液を浸漬塗布し、乾燥後の着量が0.3g/m2 になるよう電荷発生層を設けた。
【0037】
更にこのシリンダーをCTL塗布液に浸漬塗布し、乾燥後の膜厚が17μmとなるように電荷移動層を設けた。
○接触帯電装置および画像形成装置
上述の接触帯電部材としての導電性ローラと感光体を画像形成装置の接触帯電装置として所定の位置に設置。
【0038】
○評価
・純水接触角
ゴニオメーター式接触角測定器によって測定。
測定液は、精密蒸留水を用いた。
【0039】
・画像評価
室温25℃、湿度50%RH環境下で、画像出力を5万枚実施し、出力画像を目視にて評価した。
◎ ;画像良好
○ ;軽微な画像不良発生
× ;帯電不良画像発生
××;帯電不良画像発生
【0040】
・帯電ローラの汚染度評価
画像出力のすんだ画像形成装置から帯電ローラを取り出し、残留トナーの固着などの汚染度を目視で評価した。
◎ ;汚染微
○ ;軽微な汚染
× ;汚染大
××;汚染激
【0041】
・感光体の汚染度評価
画像出力のすんだ画像形成装置から感光体を取り出し、残留トナーの固着などの汚染度を目視で評価した。
◎ ;汚染微
○ ;軽微な汚染
× ;汚染大
××;汚染激
【0042】
○結果
結果一覧を別表に示す。
○参考例1
表1に示す通り、汚染起因による画像不良の少ない画像を得た。
○参考例2
参考例1よりも、純水接触角の高い帯電ローラを用いることにより、画像出力後の帯電ローラの汚染は減少した。
画像評価結果は、参考例1とほぼ同レベルであった。
【0043】
○参考例3
参考例1よりも、純水接触角の高い感光体を用いることにより、画像出力後の感光体の汚染は減少した。
画像評価結果は、参考例1とほぼ同レベルであった。
○実施例4
参考例1よりも、純水接触角の高い帯電ローラおよび純水接触角の高い感光体を用いることにより、画像出力後の帯電ローラおよび感光体の汚染は減少した。
汚染起因による画像不良は参考例1よりも少ない良好な画像を得た。
【0044】
○比較例1
帯電ローラ、感光体ともに純水接触角の低いものを用いたため、画像出力後の汚染は帯電ローラ、感光体ともに大きかった。
画像評価では帯電ローラ、感光体ともに汚染が大きかったことに起因した画像不良が発生した。
【0045】
○比較例2
比較例1よりも純水接触角の高い感光体を用いることにより、画像出力後の感光体の汚染は減少した。
しかし、帯電ローラの汚染は、比較例1よりも大きかった。
画像評価結果は、比較例1よりも悪かった。
汚染物が選択的に帯電ローラに固着したためと考えられる。
【0046】
【発明の効果】
本発明によれば、汚染起因の画像不良が少なく、総合的性能のバランスした電子写真装置を得ることができる。
【0047】
【表1】
【0048】
【表2】
【図面の簡単な説明】
【図1】電子写真装置の構造を示す側面図
【図2】接触帯電ローラの斜視図
【図3】接触帯電ブレードの縦断面図
【符号の説明】
1 電子写真装置
2 電子写真感光体
3 帯電機構
4 露光機構
5 現像機構
6 クリーナー
7 中間転写ベルト
9 用紙
11 接触帯電部材
12 芯金
13 弾性体層
14 保護層[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a contact charging member and an electrophotographic apparatus. More specifically, the present invention relates to a contact charging member and an electrophotographic apparatus capable of obtaining a clear image without adhesion of dirt.
[0002]
[Prior art]
In an electrophotographic apparatus such as a copying machine, a printer, or a facsimile, a process for charging a photosensitive member with a charging device is required.
The charging device is roughly classified into a contact charging device and a non-contact charging device. In the former contact charging device, a contact charging member is brought into contact with the surface of a photoreceptor as an uncharged body, and a voltage is applied to the contact charging member to charge the surface of the photoreceptor to a predetermined potential. .
[0003]
This contact charging device has the advantage that the applied voltage can be kept lower than the latter non-contact charging device using corona discharge, for example, and the generation of ozone during charging can be reduced. There is.
However, the contact charging method has a problem that, with long-term use, contaminants such as crushed residual toner adhere to the photoconductor, causing charging failure and eventually image failure. It has been practiced to blend the inorganic particles that have been surface treated to make the surface of the photoreceptor hydrophobic, thereby preventing toner from remaining.
However, although such residual toner prevention measures are effective to some extent, image defects are still observed at a certain density, which is a problem particularly in the case of an electrophotographic apparatus having a contact charging device.
[0004]
[Problems to be solved by the invention]
SUMMARY OF THE INVENTION An object of the present invention is to provide a contact charging member and an electrophotographic apparatus capable of obtaining a clear image without being attached with dirt even in long-term use.
[0005]
[Means for Solving the Problems]
As a result of intensive studies to solve the above problems, the present inventors have found that in an electrophotographic apparatus including a contact charging device, the photosensitive member and the contact charging member for charging the photosensitive member are in direct contact with each other. The toner remains and adheres not only to the surface but also to the contact charging member side, and the residual toner generates a defective charging portion of the photoconductor or returns to the surface of the photoconductor to cause an image defect. I found it. Further, the present inventors have found that image defects can be drastically reduced by hydrophobizing the surface of the contact charging member until the pure water contact angle exceeds a specific value.
[0006]
The present invention provides an electrophotographic apparatus that prevents adhesion of contaminants such as residual toner, maintains stable charging characteristics over a long period of time, and enables good image formation.
That is, the present invention relates to an electrophotographic apparatus having an electrophotographic photosensitive member and a contact charging member disposed at a position in contact with the photosensitive member, wherein the contact charging member uses a hydrophobic elastic body and the electrophotographic photosensitive member. of forming a contact surface, the pure water contact angle of the surface with a 105 ° or more, the pure water contact angle of the surface of the electrophotographic photosensitive member and at least 95 degrees, the pure water contact angle Ro of the electrophotographic photosensitive member surface And the pure water contact angle Rc on the surface of the contact charging member satisfies the following formula .
0 degrees ≦ | Ro−Rc | ≦ 5 degrees
DETAILED DESCRIPTION OF THE INVENTION
As shown in FIG. 1, the electrophotographic apparatus 1 includes an electrophotographic photosensitive member, which is a drum-shaped electrophotographic photosensitive member 2 in the figure, and around the photosensitive member 2, a
[0008]
In the present invention, the
The structure of the contact charging member is not particularly limited, and a charging roller, a charging blade, a charging brush, a charging film, and the like can be used. However, the charging roller can be most preferably used.
[0009]
Hereinafter, the contact charging member of the present invention will be described taking a charging roller as an example.
As the charging roller 11, as shown in FIG. 2, an
In the present invention, the elastic body broadly means that the molded body can exhibit flexibility, and means an elastomer having rubber-like elasticity to a somewhat hard resinous form. Those having properties are preferred, and base resins such as vulcanized rubber, cast rubber, and thermoplastic elastomer are used.
[0010]
The elastic body forming the contact surface of the contact charging member 11 with the photoreceptor is desirably conductive, and a conductive component is added.
As the conductive component, known materials such as conductive fillers such as carbon black, metal powder and metal oxide powder, and hygroscopic conductive agents such as quaternary ammonium salts can be used.
[0011]
The amount of the conductive components, the specific volume resistivity, it is preferable to prepare to be 1 × 10 4 ~1 × 10 10 Ω · cm.
The
As the charging roller of the present invention, a roller having a
[0012]
When forming the
The resistance value of the
[0013]
By setting the pure water contact angle of the outermost layer of the contact charging member 11 to 90 degrees or more, it is possible to prevent adhesion of contaminants such as residual toner.
Specifically, it is preferably 95 degrees or more, and more preferably 105 degrees or more.
In general, when the
[0014]
Examples of the inorganic particles include cerium oxide, chromium oxide, aluminum oxide, magnesium oxide, silicon oxide, tin oxide, zirconium oxide, calcium oxide such as iron oxide and titanium oxide, sulfate such as barium sulfate and aluminum sulfate; Silicates such as calcium silicate and magnesium silicate; nitrides such as boron nitride and titanium nitride; carbides such as silicon carbide, titanium carbide, boron carbide, tungsten carbide and zirconium carbide; boron such as zirconium boride and titanium boride Among them, one kind or two or more kinds are used as necessary.
[0015]
Although there is no restriction | limiting in particular in the physical property of an inorganic particle, Since a dispersion | distribution defect may arise when a particle size is too large, 1 micrometer or less is preferable and it is more preferable that it is 100 nm or less.
Further, it is particularly preferable that the surface of the inorganic particles is subjected to a hydrophobization treatment because a water repellency effect is imparted and toner sticking can be further prevented.
[0016]
As the hydrophobization treatment, techniques such as alkyl treatment, alkylsilane treatment, halogenated alkylsilane treatment, and the like can be suitably used.
These inorganic particles and hydrophobic inorganic particles are commercially available from Nippon Aerosil Co., Ltd.
The higher the ratio, the greater the effect of preventing residual toner sticking, and therefore the outermost layer is preferably 1% by weight or more, and more preferably 10% by weight or more. On the other hand, if the amount is too large, problems such as the roller becoming too hard may occur. Therefore, the amount is preferably 50% by weight or less, and more preferably 30% by weight or less.
[0017]
FIG. 3 shows the
In the present invention, it is also desirable to make the surface of the electrophotographic photoreceptor 2 hydrophobic.
As the configuration of the photoreceptor, a laminated type, a single layer type, or the like can be used.
If necessary, an overcoat layer can be used for the purpose of preventing wear.
[0018]
In the case of a multilayer photoreceptor, charge generation materials used for the charge generation layer include, for example, selenium and its alloys, cadmium sulfide, other inorganic photoconductive materials, phthalocyanine pigments, azo pigments, quinacridone pigments, indigo pigments, Various organic pigments such as perylene pigments, polycyclic quinone pigments, anthanthrone pigments, and benzimidazole pigments can be used. Among them, phthalocyanine pigments, particularly titanyl phthalocyanine, are excellent because of their excellent sensitivity, chargeability, and repetitive stability. The electrophotographic characteristics are shown.
[0019]
These fine particles are bonded with various binder resins such as polyester resin, polyvinyl acetate, polyacrylate ester, polyester, polycarbonate, polyvinyl acetoacetal, polyvinyl propional, polyvinyl butyral, phenoxy resin, epoxy resin, urethane resin, and cellulose ester. Used in a worn form.
[0020]
The use ratio in this case is used in the range of 30 to 50 parts by weight with respect to 100 parts by weight of the binder resin, and the film thickness is usually 0.1 μm to 1 μm, preferably 0.15 μm to 0.6 μm. .
Examples of the charge transfer material for the charge transfer layer include electron withdrawing substances such as 2,4,7-trinitrofluorenone and tetracyanoquinodimethane, carbazole, indole, imidazole, oxazole, pyrazole, oxadiazole, pyrazoline, Examples thereof include electron donating substances such as heterocyclic compounds such as thiadiazole, aniline derivatives, and polymers having groups composed of these compounds in the main chain or side chain.
[0021]
A binder resin is blended with these charge transfer materials as required. Preferred binder resins include, for example, vinyl polymers such as polymethyl methacrylate, polystyrene, and polyvinyl chloride, and copolymers thereof, polycarbonate, polyester, polyester carbonate, polysulfone, polyimide, phenoxy, epoxy, silicone resin, and the like. These partially crosslinked cured products can also be used. The charge transfer layer may contain various additives such as an antioxidant and a sensitizer as necessary. The charge transfer layer has a thickness of 10 to 40 μm, preferably 13 to 35 μm.
[0022]
In the case of a single layer dispersion type, the charge generation material and the charge transfer material described above are used in a form bound with a binder resin such as polyester resin, polyvinyl acetate, polyacrylic acid ester, polymethacrylic acid ester, polyester, polycarbonate, etc. . In this case, the charge generating material is preferably used in an amount of 1 to 50 parts by weight and the charge transfer material in an amount of 30 to 150 parts by weight with respect to 100 parts by weight of the binder resin. The film thickness is usually 5 to 50 μm, preferably 10 to 35 μm. Moreover, various additives, such as antioxidant and a sensitizer, may be included as needed.
[0023]
It is preferable that the pure water contact angle of the outermost layer of the photoreceptor is set to a high value of 90 degrees or more as in the case of the contact charging member because it is possible to prevent adhesion of contaminants such as residual toner.
Specifically, it is preferably 95 degrees or more, and more preferably 105 degrees or more.
Even if the resin used for the base of the outermost layer has a low pure water contact angle, like the outermost layer of the contact charging member, by dispersing inorganic particles, preferably surface-hydrophobized inorganic particles, the pure water contact angle is high. The outermost layer can be obtained.
[0024]
As the photosensitive member 2, a cylindrical photosensitive drum, a film-shaped photosensitive belt, or the like is preferably used.
When the contact charging member 11 is placed in contact with the photosensitive member 2 with a set contact pressure, the electrode extending from the contact charging member is connected to a power source, and a conductive roller is used as the contact charging member. The cored bar serves as an electrode.
[0025]
The bias applied to the electrode is applied to the photoconductor via the contact charging member 11 to charge the surface of the photoconductor.
Further, by using a contact charging member or a photoreceptor having a high pure water contact angle, contamination of the photoreceptor can be reduced. 105 degrees or more is preferable, and 120 degrees or more is particularly preferable because contamination can be extremely suppressed.
[0026]
However, if the difference in pure water contact angle between the contact charging member 11 and the photosensitive member 2 is too large, even if each value exceeds 100 degrees, it will be selectively contaminated to the lower contact angle due to long-term use. There is a problem that things accumulate. The problem is that if a combination in which the difference in pure water contact angle between the contact charging member 11 and the photosensitive member 2 is small is used, the probability that contaminants are removed by a cleaning mechanism such as each cleaning blade before accumulating on one side. Can be suppressed as a comprehensive effect. Specifically, the difference in pure water contact angle between the contact charging member and the photosensitive member is preferably 10 degrees or less, and 5 degrees or less is particularly preferable because selective contamination is reduced.
As described above, in the contact charging method, the contact charging member is placed in contact with the photosensitive member with the set contact pressure, and therefore, when contaminants such as residual toner enter the contact portion, the contact pressure is crushed by the contact pressure. As a result, there is a problem that a part is fixed, but the present invention eliminates such an obstacle.
[0027]
【Example】
The present invention will be described more specifically with reference to examples. However, the present invention is not limited to the following examples as long as the gist of the present invention is not exceeded.
The following evaluation atmospheres are all 25 ° C. and 50% RH, and the raw materials, methods, and evaluation methods used in this example are as follows.
[0028]
○ Conductive roller / Base layer raw material Styrenic thermoplastic elastomer (Mitsubishi Chemical Co., Ltd. Lavalon T320C JIS-A hardness 15)
Carbon black (Mitsubishi Chemical Corporation 3030B)
[0029]
・ Base layer resin kneading method Each raw material is kneaded and granulated using a biaxial kneading extruder “PCM45” (manufactured by Ikekai Kikai Co., Ltd.) at the mixing ratio shown in Table 1. Pellets were obtained.
Base layer forming method A conductive roller was produced from the above pellets using a 40 mm diameter extruder having a crosshead die under the following conditions.
Molding temperature: 190 ° C
Core shape used: diameter 8mm, total length 340mm (SUS)
Roller shape: 3.5mm thick on the core (15mm overall diameter)
[0030]
・ Protective layer material alcohol-soluble nylon (Elbamide, manufactured by DuPont)
Surface hydrophobized SiO 2
(Nippon Aerosil Co., Ltd. Aerosil R812)
-Protective layer formation After adjusting each raw material to the mixture ratio and density | concentration of Table 1, the protective layer was formed with the dip coating method.
[0031]
○ Photosensitive material / CGL coating solution 10 parts by weight of oxytitanium phthalocyanine, 500 parts by weight of 1,2-dimethoxyethane are added to 5 parts by weight of polyvinyl butyral (manufactured by Denki Kagaku Kogyo Co., Ltd .: Denka Butyral # 6000-C), and sand The CGL coating solution was prepared by pulverizing and dispersing with a grind mill.
CTL coating solution Hydrazone compound A shown below,
[0032]
[Chemical 1]
Hydrazone compound B shown below,
[0033]
[Chemical formula 2]
The following cyano compound,
[0034]
[Chemical 3]
And the polycarbonate resin shown below:
[Formula 4]
[0036]
Surface hydrophobized SiO 2 (Aerosil R812, manufactured by Nippon Aerosil Co., Ltd.) was added to and mixed with the solution obtained by dissolving the compound in 1,4-dioxane. The mixing ratio of each raw material is as shown in Table 1.
A CGL coating solution was dip-coated on an aluminum cylinder having a mirror finished surface with a thickness of 1 mm, an outer diameter of 30 mm, and a length of 254 mm, and a charge generation layer was provided so that the amount deposited after drying was 0.3 g / m 2 .
[0037]
Further, this cylinder was dip-coated in a CTL coating solution, and a charge transfer layer was provided so that the film thickness after drying was 17 μm.
○ Contact charging device and image forming apparatus The conductive roller and the photoconductor as the contact charging member described above are installed at predetermined positions as the contact charging device of the image forming apparatus.
[0038]
○ Evaluation ・ Measured with pure water contact angle goniometer type contact angle measuring instrument.
Precision distilled water was used as the measurement liquid.
[0039]
Image evaluation 50,000 images were output under an environment of room temperature 25 ° C. and humidity 50% RH, and the output image was visually evaluated.
◎; Image good ○; Minor image defect occurrence ×; Poorly charged image occurrence × ×; Poorly charged image generation [0040]
-Evaluation of contamination level of charging roller The charging roller was taken out from the image forming apparatus with a high image output, and the contamination level of residual toner and the like was visually evaluated.
◎ : Small contamination ○ : Minor contamination × : Large contamination XX;
-Evaluation of contamination level of photosensitive member The photosensitive member was taken out from an image forming apparatus which has output an image, and the contamination level such as fixing of residual toner was visually evaluated.
◎ : Small contamination ○ : Minor contamination × : Large contamination XX;
○ Results The results list is shown in the attached table.
○ Reference Example 1
As shown in Table 1, an image with few image defects due to contamination was obtained.
○ Reference example 2
By using a charging roller having a higher pure water contact angle than in Reference Example 1, contamination of the charging roller after image output was reduced.
The image evaluation result was almost the same level as in Reference Example 1.
[0043]
○ Reference Example 3
By using a photoconductor having a higher pure water contact angle than in Reference Example 1, contamination of the photoconductor after image output was reduced.
The image evaluation result was almost the same level as in Reference Example 1.
Example 4
By using a charging roller having a higher pure water contact angle and a photoconductor having a higher pure water contact angle than in Reference Example 1, contamination of the charging roller and the photoconductor after image output was reduced.
The image defect due to contamination was less than that of Reference Example 1, and a good image was obtained.
[0044]
○ Comparative Example 1
Since both the charging roller and the photoconductor have low pure water contact angles, the contamination after image output was large for both the charging roller and the photoconductor.
In the image evaluation, an image defect occurred due to the large contamination of both the charging roller and the photoreceptor.
[0045]
○ Comparative Example 2
By using a photoconductor having a higher pure water contact angle than Comparative Example 1, the contamination of the photoconductor after image output was reduced.
However, the contamination of the charging roller was greater than that of Comparative Example 1.
The image evaluation result was worse than Comparative Example 1.
This is probably because the contaminants are selectively adhered to the charging roller.
[0046]
【The invention's effect】
According to the present invention, it is possible to obtain an electrophotographic apparatus with few image defects due to contamination and balanced overall performance.
[0047]
[Table 1]
[0048]
[Table 2]
[Brief description of the drawings]
FIG. 1 is a side view showing the structure of an electrophotographic apparatus. FIG. 2 is a perspective view of a contact charging roller. FIG. 3 is a longitudinal sectional view of a contact charging blade.
DESCRIPTION OF SYMBOLS 1 Electrophotographic apparatus 2
Claims (2)
0度≦|Ro−Rc|≦5度 In an electrophotographic apparatus having an electrophotographic photoreceptor and a contact charging member disposed at a position in contact with the photoreceptor, the contact charging member forms a contact surface with the electrophotographic photoreceptor using a hydrophobic elastic body. The pure water contact angle of the surface is set to 105 degrees or more, the pure water contact angle of the surface of the electrophotographic photosensitive member is set to 95 degrees or more, and the pure water contact angle Ro of the surface of the electrophotographic photosensitive member and the surface of the contact charging member are An electrophotographic apparatus characterized in that the pure water contact angle Rc satisfies the following formula .
0 degrees ≦ | Ro−Rc | ≦ 5 degrees
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP16344398A JP3747633B2 (en) | 1998-06-11 | 1998-06-11 | Electrophotographic equipment |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP16344398A JP3747633B2 (en) | 1998-06-11 | 1998-06-11 | Electrophotographic equipment |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH11352752A JPH11352752A (en) | 1999-12-24 |
| JP3747633B2 true JP3747633B2 (en) | 2006-02-22 |
Family
ID=15773996
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP16344398A Expired - Lifetime JP3747633B2 (en) | 1998-06-11 | 1998-06-11 | Electrophotographic equipment |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3747633B2 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7725054B2 (en) | 2006-12-22 | 2010-05-25 | Ricoh Company, Ltd. | Electrifying apparatus, a processing unit, and an image formation apparatus |
| EP4425262A1 (en) | 2023-03-03 | 2024-09-04 | FUJIFILM Business Innovation Corp. | Process cartridge and image forming apparatus |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP5196089B2 (en) * | 2001-03-15 | 2013-05-15 | 株式会社ブリヂストン | Charging member and charging device |
| JP5039460B2 (en) * | 2006-12-22 | 2012-10-03 | 株式会社リコー | Image forming apparatus |
-
1998
- 1998-06-11 JP JP16344398A patent/JP3747633B2/en not_active Expired - Lifetime
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7725054B2 (en) | 2006-12-22 | 2010-05-25 | Ricoh Company, Ltd. | Electrifying apparatus, a processing unit, and an image formation apparatus |
| EP4425262A1 (en) | 2023-03-03 | 2024-09-04 | FUJIFILM Business Innovation Corp. | Process cartridge and image forming apparatus |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH11352752A (en) | 1999-12-24 |
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