JP2005283995A - Developing member for electrophotographic apparatus - Google Patents
Developing member for electrophotographic apparatus Download PDFInfo
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- JP2005283995A JP2005283995A JP2004098251A JP2004098251A JP2005283995A JP 2005283995 A JP2005283995 A JP 2005283995A JP 2004098251 A JP2004098251 A JP 2004098251A JP 2004098251 A JP2004098251 A JP 2004098251A JP 2005283995 A JP2005283995 A JP 2005283995A
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- 239000002344 surface layer Substances 0.000 claims abstract description 44
- 229920000178 Acrylic resin Polymers 0.000 claims abstract description 34
- 239000004925 Acrylic resin Substances 0.000 claims abstract description 34
- 229920002803 thermoplastic polyurethane Polymers 0.000 claims abstract description 27
- 229920001971 elastomer Polymers 0.000 claims abstract description 19
- 150000001875 compounds Chemical class 0.000 claims abstract description 16
- 239000000463 material Substances 0.000 claims abstract description 16
- 239000002904 solvent Substances 0.000 claims abstract description 14
- 229920001577 copolymer Polymers 0.000 claims abstract description 11
- 239000000203 mixture Substances 0.000 claims abstract description 9
- 125000000022 2-aminoethyl group Chemical group [H]C([*])([H])C([H])([H])N([H])[H] 0.000 claims abstract description 8
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims description 18
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 14
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 12
- 239000007787 solid Substances 0.000 claims description 12
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 8
- 229910052739 hydrogen Inorganic materials 0.000 claims description 8
- 239000001257 hydrogen Substances 0.000 claims description 8
- 150000001412 amines Chemical class 0.000 claims description 7
- 229920002635 polyurethane Polymers 0.000 claims description 7
- 239000004814 polyurethane Substances 0.000 claims description 7
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 6
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 claims description 5
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 claims description 5
- 229920000728 polyester Polymers 0.000 claims description 5
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 3
- 229920000570 polyether Polymers 0.000 claims description 3
- 239000011248 coating agent Substances 0.000 description 11
- 238000000576 coating method Methods 0.000 description 11
- 239000000243 solution Substances 0.000 description 11
- 229910052751 metal Inorganic materials 0.000 description 10
- 239000002184 metal Substances 0.000 description 10
- 238000011156 evaluation Methods 0.000 description 9
- 239000010419 fine particle Substances 0.000 description 9
- 239000011347 resin Substances 0.000 description 8
- 229920005989 resin Polymers 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- 230000003746 surface roughness Effects 0.000 description 6
- 238000012360 testing method Methods 0.000 description 5
- 239000006229 carbon black Substances 0.000 description 4
- 239000012046 mixed solvent Substances 0.000 description 4
- 108091008695 photoreceptors Proteins 0.000 description 4
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 3
- 239000010410 layer Substances 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 239000012086 standard solution Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- NOWKCMXCCJGMRR-UHFFFAOYSA-N Aziridine Chemical compound C1CN1 NOWKCMXCCJGMRR-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- FQYUMYWMJTYZTK-UHFFFAOYSA-N Phenyl glycidyl ether Chemical compound C1OC1COC1=CC=CC=C1 FQYUMYWMJTYZTK-UHFFFAOYSA-N 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 230000001476 alcoholic effect Effects 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 229920002050 silicone resin Polymers 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229920002943 EPDM rubber Polymers 0.000 description 1
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 229920000800 acrylic rubber Polymers 0.000 description 1
- 229920003054 adipate polyester Polymers 0.000 description 1
- WNLRTRBMVRJNCN-UHFFFAOYSA-L adipate(2-) Chemical compound [O-]C(=O)CCCCC([O-])=O WNLRTRBMVRJNCN-UHFFFAOYSA-L 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 229930003836 cresol Natural products 0.000 description 1
- OBRMNDMBJQTZHV-UHFFFAOYSA-N cresol red Chemical compound C1=C(O)C(C)=CC(C2(C3=CC=CC=C3S(=O)(=O)O2)C=2C=C(C)C(O)=CC=2)=C1 OBRMNDMBJQTZHV-UHFFFAOYSA-N 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 1
- 239000001095 magnesium carbonate Substances 0.000 description 1
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 125000005395 methacrylic acid group Chemical group 0.000 description 1
- IWVKTOUOPHGZRX-UHFFFAOYSA-N methyl 2-methylprop-2-enoate;2-methylprop-2-enoic acid Chemical compound CC(=C)C(O)=O.COC(=O)C(C)=C IWVKTOUOPHGZRX-UHFFFAOYSA-N 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920005906 polyester polyol Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 238000011002 quantification Methods 0.000 description 1
- 229920005604 random copolymer Polymers 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
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Abstract
Description
本発明は、電子写真装置用現像部材に関し、詳しくは、摩擦によりトナーを負帯電させる現像ローラ、現像ブレード等の電子写真装置用現像部材に関する。 The present invention relates to a developing member for an electrophotographic apparatus, and particularly relates to a developing member for an electrophotographic apparatus such as a developing roller and a developing blade that negatively charge toner by friction.
電子写真装置に於いては、感光体上に形成された静電潜像上にトナーを付着させるべく、トナーを負帯電させる現像ローラや現像ブレード等の現像部材が用いられている。
斯かる現像部材に於いては、トナーとの摩擦によってトナーに負電荷を与える機能（トナー帯電性）が必要である。従って、従来、この種の現像部材としては、アクリル樹脂やシリコーン樹脂の溶液を塗布することにより、ローラやブレードの形態を成す基材上に、これらの樹脂からなる表面層を形成したものが用いられている。
しかしながら、アクリル樹脂からなる表面層を備えた現像部材は、硬く、基材の変形等に追従し難いことから、割れやすいという問題を有している。また、シリコーン樹脂からなる表面層を備えた現像部材は、感光体を汚染するという問題を有している。
In the electrophotographic apparatus, a developing member such as a developing roller or a developing blade for negatively charging the toner is used to adhere the toner onto the electrostatic latent image formed on the photosensitive member.
Such a developing member needs to have a function (toner chargeability) of giving a negative charge to the toner by friction with the toner. Therefore, heretofore, as this type of developing member, a member in which a surface layer made of these resins is formed on a base material in the form of a roller or blade by applying an acrylic resin or silicone resin solution is used. It has been.
However, a developing member having a surface layer made of an acrylic resin is hard and difficult to follow the deformation of the base material, and thus has a problem of being easily broken. In addition, a developing member having a surface layer made of silicone resin has a problem of contaminating the photoreceptor.
これに対して、アクリル樹脂よりも柔軟な樹脂（ウレタン樹脂）の溶液にアクリル樹脂の粒子を混入して表面層を形成する方法が提案されている。しかしながら、この方法では、表面層の表面粗度の調整が煩雑で、製造が煩雑となる。
また、アクリル樹脂とウレタン樹脂との双方を溶媒に混入して混合液とし、該混合液を塗布することによって表面層を形成する方法も提案されている。しかしながら、アクリル樹脂は、本来、ウレタン樹脂と混ざり難いもの（即ち混和性の低いもの）であることから、この方法によって表面層を形成した場合には、アクリル樹脂とウレタン樹脂とが分離した塗布ムラが発生する。従って、このような方法によって表面層の形成された現像部材は、塗布ムラが原因となって、印刷画像等のムラ（濃淡ムラ等）を引き起こすという問題を有している。
On the other hand, a method for forming a surface layer by mixing acrylic resin particles in a solution of a resin (urethane resin) more flexible than an acrylic resin has been proposed. However, in this method, the adjustment of the surface roughness of the surface layer is complicated and the production is complicated.
There has also been proposed a method of forming a surface layer by mixing both an acrylic resin and a urethane resin in a solvent to form a mixed solution and applying the mixed solution. However, since acrylic resin is inherently difficult to mix with urethane resin (ie, low miscibility), when the surface layer is formed by this method, coating unevenness in which acrylic resin and urethane resin are separated. Will occur. Therefore, the developing member having the surface layer formed by such a method has a problem that unevenness (darkness unevenness or the like) of a printed image or the like is caused due to unevenness of coating.
斯かる問題に対して、表面層を形成するアクリル樹脂として、テトラヒドロフラン等に可溶で、ウレタン樹脂と混ざりやすいものも提案されているが（下記特許文献１）、入手が困難で且つ高価である等、実用性に乏しいものである。従って、ウレタン樹脂と共に塗布されるアクリル樹脂として別種のアクリル樹脂を用いつつも、塗布ムラの少ない表面層を備えた現像部材が要望されている。
本発明は、上記要望に鑑み、ウレタン樹脂と共に塗布されるアクリル樹脂として従来のものとは別種のアクリル樹脂を用いつつも、塗布ムラの少ないものとなりうる現像部材を提供することを課題とする。 An object of the present invention is to provide a developing member capable of reducing coating unevenness while using an acrylic resin different from the conventional one as an acrylic resin to be applied together with a urethane resin.
上記課題を解決すべく、本発明は、ゴム基材と、該ゴム基材の表面側に設けられ、摩擦によりトナーを負帯電させる表面層とを備え、該表面層が、ウレタン樹脂とアクリル樹脂との混合物からなる電子写真装置用現像部材であって、
前記表面層は、前記混合物が溶媒に溶解された溶液を塗布することにより形成されてなり、
前記アクリル樹脂として、メタクリル酸−メタクリル酸メチル共重合体からなる主鎖にアミノエチル基がグラフトされてなるグラフト化合物が用いられてなることを特徴とする電子写真装置用現像部材を提供する。
In order to solve the above problems, the present invention comprises a rubber base material and a surface layer provided on the surface side of the rubber base material to negatively charge the toner by friction, the surface layer comprising a urethane resin and an acrylic resin. A developing member for an electrophotographic apparatus comprising a mixture of
The surface layer is formed by applying a solution in which the mixture is dissolved in a solvent,
Provided is a developing member for an electrophotographic apparatus, wherein a graft compound in which an aminoethyl group is grafted on a main chain made of a methacrylic acid-methyl methacrylate copolymer is used as the acrylic resin.
斯かる電子写真装置用現像部材に於いては、メタクリル酸−メタクリル酸メチル共重合体からなる主鎖にアミノエチル基がグラフトされてなるグラフト化合物が、ウレタン樹脂を溶解する溶媒に対して十分に可溶であり且つウレタン樹脂との混和性が良好であることから、該グラフト化合物とウレタン樹脂とを溶媒に十分に溶解させて溶液とし、該溶液を用いて表面層を形成することにより、トナー帯電性に優れ且つ塗布ムラの少ないものとなりうる。 In such a developing member for an electrophotographic apparatus, a graft compound in which an aminoethyl group is grafted to a main chain composed of a methacrylic acid-methyl methacrylate copolymer is sufficiently sufficient for a solvent that dissolves a urethane resin. Since it is soluble and has good miscibility with the urethane resin, the toner is prepared by sufficiently dissolving the graft compound and the urethane resin in a solvent to form a surface layer using the solution. It can be excellent in chargeability and less uneven coating.
以上のように、本発明によれば、従来のものと異なるアクリル樹脂を用いつつも、表面層が塗布ムラの少ないものとなりうる電子写真装置用現像部材を提供しうる。従って、技術の多様化、実用性の向上を図ることができる。 As described above, according to the present invention, it is possible to provide a developing member for an electrophotographic apparatus in which the surface layer can have a coating unevenness while using an acrylic resin different from the conventional one. Therefore, diversification of technologies and improvement of practicality can be achieved.
以下、本発明の電子写真装置用現像部材の好ましい形態として、現像ローラを例に取って説明する。
図１は、本実施形態の現像ローラを示す斜視図である。
図１に示すように、本実施形態の現像ローラは、トナー８を担持して感光体５に供給しうるように構成され、芯金２と、該芯金２の外周に周設されたゴム基材３と、トナー８等との摩擦によりトナー８を負帯電させ且つ負帯電したトナー８を担持すべく、該ゴム基材３の表面に直接（他の層を介さずに）周設された表面層４とを備えている。
Hereinafter, as a preferred embodiment of the developing member for an electrophotographic apparatus of the present invention, a developing roller will be described as an example.
FIG. 1 is a perspective view showing the developing roller of this embodiment.
As shown in FIG. 1, the developing roller of this embodiment is configured to carry toner 8 and supply it to the photoreceptor 5, and a
前記ゴム基材３は、カーボンブラック及び絶縁性無機微粒子の配合されたゴム組成物から形成されてなり、表面層４の摩擦帯電量を所定範囲に調整すべく、所定の導電性に調整されている。
前記絶縁性無機微粒子としては、炭酸カルシウム、タルク、シリカ等を挙げることができる。
前記ゴム基材３を構成するゴムとしては、ＮＢＲ、ＣＲ、ＥＰＤＭ、ＳＢＲ、ＩＲ、アクリルゴム、エピクロルヒドリン、エピクロルヒドリン−エチレンオキサイド共重合体、エピクロルヒドリン−エチレンオキサイド−アリルグリシジルエーテル共重合体から選ばれし１種又は２種以上からなるものや熱可塑性ウレタン等を挙げることができる。
前記芯金２は、導電性の棒状体、具体的には、断面円形で且つ中空又は中実の金属製棒状体である。この芯金２を構成する材料としては、例えば、銅、鉄、ステンレス鋼、アルミニウム、ニッケル等を挙げることができる。
The
Examples of the insulating inorganic fine particles include calcium carbonate, talc, and silica.
The rubber constituting the
The
前記表面層４は、トナー８との摩擦によってトナー８に負電荷を付与するように、アクリル樹脂とウレタン樹脂との混合物から構成されている。
尚、この表面層４は、アクリル樹脂とウレタン樹脂とが溶媒に溶解された溶液を塗布することにより形成されてなる。
尚、前記表面層４の厚さは、通常、３〜８０ｍｍに調整されている。
The surface layer 4 is composed of a mixture of an acrylic resin and a urethane resin so as to impart a negative charge to the toner 8 by friction with the toner 8.
The surface layer 4 is formed by applying a solution in which an acrylic resin and a urethane resin are dissolved in a solvent.
In addition, the thickness of the surface layer 4 is usually adjusted to 3 to 80 mm.
前記アクリル樹脂としては、メタクリル酸−メタクリル酸メチル共重合体からなる主鎖に、アミノエチル基（−ＣＨ2ＣＨ2ＮＨ2）がグラフトされてなる下記一般式（１）で示される重合単位を含むグラフト化合物が用いられる。
Ｃ11Ｈ19ＮＯ4 ・・・（１）
具体的には、例えば、下記一般式（２）で示されるように、メタクリル酸−メタクリル酸メチルのランダム共重合体を主鎖とし、メタクリル酸のカルボキシル基の活性水素がアミノエチル基に置換されたグラフト化合物が用いられる。
前記グラフト化合物は、通常、メタクリル酸−メタクリル酸メチル共重合体にエチレンイミンを反応させて得ることができる。
斯かるグラフト化合物としては、通常、平均分子量Ｍｗが１万〜５０万のものが好ましい。
尚、平均分子量Ｍｗは、ＧＰＣ法により下記条件にて測定される。
標準試薬：ＴＳＫ標準ポリスチレン（Ａ−５００、Ａ−２５００、Ｆ−１、Ｆ−４、 Ｆ−２０、Ｆ−１２８；東ソー社製）
溶媒 ：ＴＨＦ
カラム ：ＧＦ−１Ｇ７Ｂ＋ＧＦ−７ＭＨＱ（昭和電工社製）
The acrylic resin includes a polymer unit represented by the following general formula (1) in which an aminoethyl group (—CH 2 CH 2 NH 2 ) is grafted to a main chain composed of a methacrylic acid-methyl methacrylate copolymer. Including graft compounds are used.
C 11 H 19 NO 4 (1)
Specifically, for example, as shown by the following general formula (2), a random copolymer of methacrylic acid-methyl methacrylate is used as the main chain, and the active hydrogen of the carboxyl group of methacrylic acid is substituted with an aminoethyl group. Graft compounds are used.
The graft compound can be usually obtained by reacting a methacrylic acid-methyl methacrylate copolymer with ethyleneimine.
As such a graft compound, those having an average molecular weight Mw of 10,000 to 500,000 are usually preferred.
The average molecular weight Mw is measured by the GPC method under the following conditions.
Standard reagent: TSK standard polystyrene (A-500, A-2500, F-1, F-4, F-20, F-128; manufactured by Tosoh Corporation)
Solvent: THF
Column: GF-1G7B + GF-7MHQ (manufactured by Showa Denko)
前記グラフト化合物は、アミン水素当量が、１０００〜１５００（ｇ・ｓｏｌｉｄ／ｅｑ）であるものが好ましい。
斯かる範囲のものであれば、ウレタン樹脂との混和性により優れ、塗布ムラのより少ない表面層となりうる。
尚、アミン水素当量は、反応させるエチレンイミンの量を調整することにより調整され、下記測定により求められる。
〈アミン水素当量の測定〉
グラフト化合物１ｇにフェニルグリシジルエーテル溶液（フェニルグリシジルエーテル５重量％、プロピレングリコールモノメチルエーテル９５重量％）１５ｍｌを加えて溶解させ、更に、純水０．４ｇ、プロピレングリコールモノメチルエーテル４ｇを加えて混合し、１２０℃で１時間還流加熱する。冷却後、塩化水素剤（試薬特級塩酸３．５ｍｌ、ピリジン２５．０ｍｌ、プロピレングリコールモノメチルエーテル７５．０ｍｌを混合したもの）１５ｍｌを加え、１１０℃で４０分間還流加熱し、次いで、冷却後、クレゾールレッド（クレゾールレッド０．１ｇ、エタノール２０ｍｌ、水１００ｍｌの割合で混合したもの）を指示薬として、０．１ｍｏｌ／Ｌ−ＫＯＨアルコール性標準溶液で滴定し、同時に空試験も行い、下記式でアミン水素当量を求める。
アミン水素当量［ｇ・ｓｏｌｉｄ／ｅｑ］
＝〔（Ｗ×Ｖ×０．０１）÷｛０．１×Ｆ×（Ａ−Ｂ）｝〕×１０００
Ｗ：グラフト化合物量（ｇ）
Ｖ：固形分（ｗｔ％）
Ｆ：０．１ｍｏｌ／Ｌ−ＫＯＨアルコール性標準溶液の力価
Ａ：グラフト化合物液の標準液滴定量（ｍｌ）
Ｂ：空試験の標準溶液滴定量（ｍｌ）
The graft compound preferably has an amine hydrogen equivalent weight of 1000 to 1500 (g · solid / eq).
If it is in such a range, it is excellent in miscibility with a urethane resin, and can be a surface layer with less coating unevenness.
The amine hydrogen equivalent is adjusted by adjusting the amount of ethyleneimine to be reacted, and is determined by the following measurement.
<Measurement of amine hydrogen equivalent>
15 g of a phenyl glycidyl ether solution (phenyl glycidyl ether 5 wt%, propylene glycol monomethyl ether 95 wt%) is added to 1 g of the graft compound and dissolved, and 0.4 g of pure water and 4 g of propylene glycol monomethyl ether are added and mixed. Heat to reflux at 120 ° C. for 1 hour. After cooling, 15 ml of a hydrogen chloride agent (mixed with 3.5 ml of reagent grade hydrochloric acid, 25.0 ml of pyridine and 75.0 ml of propylene glycol monomethyl ether) was added and heated to reflux at 110 ° C. for 40 minutes, and after cooling, cresol Titrate red (0.1 g of cresol red, 20 ml of ethanol and 100 ml of water) as an indicator, and titrate with 0.1 mol / L-KOH alcoholic standard solution. Find the equivalent.
Amine hydrogen equivalent [g · solid / eq]
= [(W × V × 0.01) ÷ {0.1 × F × (A−B)}] × 1000
W: Graft compound amount (g)
V: Solid content (wt%)
F: Potency of 0.1 mol / L-KOH alcoholic standard solution
A: Standard droplet quantification of the graft compound solution (ml)
B: Standard solution titration of blank test (ml)
前記ウレタン樹脂としては、溶媒に可溶である限り特に限定されるものではないが、ポリエステルポリウレタン（ポリエステルポリオールとイソシアネートとの重合物）又はポリエーテルポリウレタンが好ましく、特に、ポリエステルウレタンが好ましい。
ポリエステルポリウレタンとしては、アジペート系ポリエステルポリウレタンが好ましい。
The urethane resin is not particularly limited as long as it is soluble in a solvent, but polyester polyurethane (polymer of polyester polyol and isocyanate) or polyether polyurethane is preferable, and polyester urethane is particularly preferable.
As the polyester polyurethane, an adipate polyester polyurethane is preferable.
前記溶媒としては、通常、メチルイソブチルケトン、メチルエチルケトン、テトラヒドロフラン、トルエンの群から選ばれし１種以上を含むものが用いられる。前記溶媒として、好ましくは、メチルイソブチルケトン、メチルエチルケトン、テトラヒドロフラン・メチルエチルケトン混合溶媒、テトラヒドロフラン・メチルイソブチルケトン混合溶媒、トルエン・メチルエチルケトン混合溶媒、トルエン・メチルイソブチルケトン混合溶媒が用いられる。
特に、前記ウレタン樹脂がアジペート系ポリウレタンの場合には、溶媒としてはメチルエチルケトン、テトラヒドロフランが好ましい。
As the solvent, those containing at least one selected from the group of methyl isobutyl ketone, methyl ethyl ketone, tetrahydrofuran and toluene are usually used. As the solvent, preferably used are methyl isobutyl ketone, methyl ethyl ketone, tetrahydrofuran / methyl ethyl ketone mixed solvent, tetrahydrofuran / methyl isobutyl ketone mixed solvent, toluene / methyl ethyl ketone mixed solvent, and toluene / methyl isobutyl ketone mixed solvent.
In particular, when the urethane resin is an adipate-based polyurethane, methyl ethyl ketone and tetrahydrofuran are preferable as the solvent.
前記アクリル樹脂及びウレタン樹脂の配合割合は、全樹脂成分中、アクリル樹脂２０〜８０重量％、ウレタン樹脂８０〜２０重量％が好ましい。
アクリル樹脂を２０重量％以上とすることにより、ＯＰＣカブリの発生を著しく低減できる。
前記溶液中に於けるこれらの総樹脂濃度は、通常１〜３０重量％、好ましくは３〜２０重量％である。
The blending ratio of the acrylic resin and the urethane resin is preferably 20 to 80% by weight of acrylic resin and 80 to 20% by weight of urethane resin in all resin components.
By setting the acrylic resin to 20% by weight or more, generation of OPC fog can be remarkably reduced.
The total resin concentration in the solution is usually 1 to 30% by weight, preferably 3 to 20% by weight.
前記溶液には、表面層４が所望の半導電性となるように、通常、カーボンブラックや無機微粒子が配合される。
カーボンブラックの配合量は、通常、樹脂成分１００重量部に対して０．１〜１０重量部、絶縁性無機微粒子の配合量は、通常、樹脂成分１００重量部に対して１〜３０重量部である。
Usually, carbon black or inorganic fine particles are blended in the solution so that the surface layer 4 has a desired semiconductivity.
The amount of carbon black is usually 0.1 to 10 parts by weight with respect to 100 parts by weight of the resin component, and the amount of insulating inorganic fine particles is usually 1 to 30 parts by weight with respect to 100 parts by weight of the resin component. is there.
本実施形態の電子写真装置用現像ローラは、例えば、芯金２に未加硫ゴム組成物を周設した後、加硫すること等によって、芯金２にゴム基材３が周設された成形体を調製し、次いで、該成形体のゴム基材３表面に前記溶液を塗布し、溶媒を揮発させることと等によって製造される。
In the developing roller for an electrophotographic apparatus according to the present embodiment, for example, the
本実施形態の現像ローラは、上記の如く構成されてなるが、次に、該現像ローラの好ましい使用態様について説明する。
図２は、本実施形態の現像ローラを用いた電子写真装置の要部一例を示す概略模式図である。
図２に示すように、前記現像ローラは、ドラム状の感光体５とトナー供給ローラ７との間に介装され且つこれらに当接するように配置されて使用される。このように使用されることで、該現像ローラは、トナー供給ローラ７から供給されたトナー８を摩擦によって負帯電させると共に、負帯電したトナー８を表面層４で担持し、感光体５に供給しうるものとなる。
尚、現像ローラに担持されるトナー８の層の厚さは、現像ローラ近傍に配された現像ブレード６によって薄層化される。
The developing roller of the present embodiment is configured as described above. Next, a preferred usage mode of the developing roller will be described.
FIG. 2 is a schematic diagram showing an example of a main part of an electrophotographic apparatus using the developing roller of this embodiment.
As shown in FIG. 2, the developing roller is interposed between a drum-shaped photosensitive member 5 and a toner supply roller 7 and is used so as to be in contact therewith. By using the developing roller in this way, the toner 8 supplied from the toner supply roller 7 is negatively charged by friction, and the negatively charged toner 8 is carried on the surface layer 4 and supplied to the photoreceptor 5. It will be possible.
Note that the thickness of the toner 8 layer carried on the developing roller is reduced by the developing blade 6 disposed in the vicinity of the developing roller.
本実施形態の現像部材は、上記の如く構成され上記の如く使用されたが、本発明の現像部材は、上記構成に限定されるものではない。
例えば、本実施形態に於いては、ゴム基材３に表面層４が直接周設されたが、他の層を介して周設されているものであっても本発明の意図する範囲内である。
また、本発明の現像部材は、現像ローラに限定されるものではなく、摩擦によりトナー８を負帯電させる上述と同様の表面層４を備えた現像ブレード（図２、符号６参照）であっても本発明の意図する範囲内である。
The developing member of this embodiment is configured as described above and used as described above, but the developing member of the present invention is not limited to the above configuration.
For example, in the present embodiment, the surface layer 4 is directly provided around the
The developing member of the present invention is not limited to the developing roller, but is a developing blade (see reference numeral 6 in FIG. 2) having the same surface layer 4 as described above for negatively charging the toner 8 by friction. Are also within the intended scope of the present invention.
以下、本発明の実施例について説明する。
実施例１〜５、比較例１〜５
まず、芯金に、ＪＩＳ Ａ硬度４０°、表面粗度Ｒｚ６μｍ、５０Ｖに於ける電気抵抗値１×１０4Ωに設定されたポリエステル系ウレタン樹脂製のゴム基材が周設された成形体をそれぞれ準備した。
各成形体のゴム基材表面に、下記表１の割合でそれぞれ配合された溶液を塗布し乾燥させることにより、表面層が表１にそれぞれ示す厚さに調整された実施例１〜５、比較例１〜５の現像ローラを得た。
Examples of the present invention will be described below.
Examples 1-5, Comparative Examples 1-5
First, a molded body in which a rubber base material made of a polyester-based urethane resin having a JIS A hardness of 40 °, a surface roughness Rz of 6 μm, and an electric resistance value of 1 × 10 4 Ω at 50 V is provided around a core metal. Prepared each.
Examples 1 to 5, in which the surface layers were adjusted to the thicknesses shown in Table 1, respectively, by applying and drying solutions blended in the proportions of Table 1 below on the rubber substrate surface of each molded body, and comparison The developing rollers of Examples 1 to 5 were obtained.
尚、アクリル樹脂Ａとして、メタクリル酸−メタクリル酸メチル共重合体からなる主鎖にアミノエチル基がグラフトされてなる上記化学式（２）で示される市販のグラフト化合物（Ｔｇ＝１００℃、Ｍｗ＝１０万、アミン水素当量＝１１００（ｇ・ｓｏｌｉｄ／ｅｑ））を用いた。また、アクリル樹脂Ｂとして、メタクリル酸−メタクリル酸メチル共重合体からなる主鎖にアミノエチル基がグラフトされてなる上記化学式（２）で示される市販のグラフト化合物（Ｔｇ＝４０、Ｍｗ＝１０万、アミン水素当量＝１４００（ｇ・ｓｏｌｉｄ／ｅｑ））を、アクリル樹脂Ｃとして、メタクリル酸−メタクリル酸メチル共重合体（Ｍｗ＝１０万）を、ウレタン樹脂として、熱可塑性ポリエーテル系ウレタン樹脂を、カーボンブラックとして、ケッチェンブラックＥＣを、無機微粒子として、炭酸マグネシウム（商品名「ＰＳ」、神島化学製）を、有機微粒子として、アクリル微粒子（商品名「テクポリマーＭＢ３０Ｘ−５」、積水化成品工業製）をそれぞれ用いた。 As the acrylic resin A, a commercially available graft compound (Tg = 100 ° C., Mw = 10) represented by the above chemical formula (2) in which an aminoethyl group is grafted to a main chain composed of a methacrylic acid-methyl methacrylate copolymer. Ten thousand, amine hydrogen equivalent = 1100 (g · solid / eq)) was used. Further, as the acrylic resin B, a commercially available graft compound represented by the above chemical formula (2) obtained by grafting an aminoethyl group onto a main chain composed of a methacrylic acid-methyl methacrylate copolymer (Tg = 40, Mw = 100,000) , Amine hydrogen equivalent = 1400 (g · solid / eq)) as acrylic resin C, methacrylic acid-methyl methacrylate copolymer (Mw = 100,000) as urethane resin, thermoplastic polyether urethane resin Ketjen black EC as carbon black, magnesium carbonate (trade name “PS”, manufactured by Kamishima Chemical) as inorganic fine particles, acrylic fine particles (trade name “Techpolymer MB30X-5”, Sekisui Plastics as organic fine particles) Kogyo) were used.
試験例
各実施例及び比較例の現像ローラを用いて下記試験に供した。
Test Example The following test was performed using the developing roller of each Example and Comparative Example.
＜表面層の表面状態＞
目視により、塗布ムラが認められないものを良好、認められるものを不良と評価した。
＜表面粗度＞
表面層の表面粗度Ｒｚを、ＪＩＳ Ｂ０６０１に準拠して測定した。
尚、測定装置としては、サーフテスト（「ＳＪ−３０１」、（株）ミツトヨ社製）を用いた。
＜ローラ抵抗＞
各現像ローラーを導電平板上に静置し、芯金両端部に５００ｇ下方荷重をかけた後、芯金と導電平板との間に１００Ｖの電圧を印加し、印加開始３０秒後の抵抗値を測定した。 尚、抵抗測定器は、アドバンテスト製エレクトロメーターＲ８３４０Ａを使用した。
<Surface condition of surface layer>
Visually, the thing by which application | coating nonuniformity was not recognized was evaluated as favorable, and the thing recognized is evaluated as bad.
<Surface roughness>
The surface roughness Rz of the surface layer was measured according to JIS B0601.
A surf test (“SJ-301”, manufactured by Mitutoyo Corporation) was used as a measuring device.
<Roller resistance>
Each developing roller is allowed to stand on a conductive flat plate, a 500 g downward load is applied to both ends of the metal core, a voltage of 100 V is applied between the metal core and the conductive flat plate, and the resistance value 30 seconds after the start of application is determined. It was measured. Note that an electrometer R8340A manufactured by Advantest was used as the resistance measuring instrument.
＜初期トナー帯電量Ｑ／Ｍ＞
各現像ローラを、それぞれ市販の電子写真プリンターに組み込み、非印字パターン（ホワイトパターン）を１枚印字後、該現像ローラを取り出し、表面層上のトナーをファラデーゲージに吸引して、エレクトロメーターにて電荷量を測定した。得られた測定値を、ファラデーゲージに吸引したトナー重量で除してＱ／Ｍ（μｃ／ｇ）を求めた。
＜初期トナー搬送量Ｍ／Ａ＞
ファラデーゲージに吸引したトナー重量を測定し、得られた測定値を吸引した面積で除してＭ／Ａ（ｇ／ｃｍ2）を求めた。
<Initial toner charge amount Q / M>
Each developing roller is incorporated into a commercially available electrophotographic printer, and after printing one sheet of non-printing pattern (white pattern), the developing roller is taken out, and the toner on the surface layer is sucked into a Faraday gauge and then electrometered. The amount of charge was measured. Q / M (μc / g) was determined by dividing the obtained measured value by the toner weight sucked into the Faraday gauge.
<Initial toner transport amount M / A>
The weight of the toner sucked into the Faraday gauge was measured, and the measured value obtained was divided by the sucked area to obtain M / A (g / cm 2 ).
＜初期画像印刷後の評価＞
各現像ローラを、それぞれ市販の電子写真プリンターに組み込み、黒ベタ部分、ハーフトーン部分（６００ｄｐｉ解像度パターンに於ける２ｄｏｔ／インチパターンで印刷）、白色部分を含む同一の画像を２枚印刷し、下記評価（１）〜（３）を行った。
（１）表面層のはがれ、クラック
現像ローラを取り外し、表面層の表面を１００倍に拡大して、表面層のはがれ、クラックの有無を目視にて判断した。
（２）画像濃度、地かぶり、ハーフトーンの画像あれ（ハーフトーンの濃淡ムラ）、黒ベタ部の抜け
画像濃度は、黒ベタ部分を対象とし、地かぶりは、白色部分に現れた地かぶり部分を対象とし、マクベス反射型濃度計を用いて濃度を測定した。
ハーフトーン濃度ムラ、黒ベタ部の濃淡ムラは、目視によりその有無を判断した。
（３）ＯＰＣかぶり
ホワイトパターンで印字する際の静電潜像現像後の感光体表面（本来トナーが現像されていては行けない状態の感光体表面）に、メンディングテープを貼付して剥離することにより、感光体表面のトナーはがし取り、そのテープを白色の紙に貼付した後、そのテープ貼付部分の濃度をマクベス濃度計により測定した。
<Evaluation after initial image printing>
Each developing roller is incorporated into a commercially available electrophotographic printer, and two identical images including a black solid portion, a halftone portion (printed with a 2 dot / inch pattern in a 600 dpi resolution pattern), and a white portion are printed. Evaluation (1)-(3) was performed.
(1) Surface layer peeling and cracks The developing roller was removed, the surface layer surface was magnified 100 times, and the presence or absence of cracking of the surface layer was visually determined.
(2) Image density, ground cover, halftone image irregularity (half-tone shading unevenness), missing black solid part Image density is for the black solid part, and the ground cover is the part of the ground cover that appears in the white part The density was measured using a Macbeth reflection densitometer.
The presence / absence of the halftone density unevenness and the density unevenness of the black solid portion was visually determined.
(3) OPC fog A mending tape is affixed to the surface of the photoconductor after development of the electrostatic latent image when printing with a white pattern (the surface of the photoconductor that cannot be developed when toner is originally developed) and peeled off. As a result, the toner on the surface of the photoreceptor was peeled off, and the tape was affixed to white paper, and then the density of the tape affixed portion was measured with a Macbeth densitometer.
＜５０００枚印刷後の評価＞
５０００枚印刷後、初期画像印刷後の評価と同様に、上記（１）〜（３）の評価を行った。
<Evaluation after printing 5000 sheets>
After the printing of 5000 sheets, the evaluations (1) to (3) were performed in the same manner as the evaluation after the initial image printing.
各評価結果を下記表２に示した。また、＜初期画像印刷後の評価＞に於ける（３）ＯＰＣかぶりの結果に基づき、表面層の樹脂成分中に於けるアクリル樹脂比率（ｗｔ％）とＯＰＣかぶりとの関係を表３に示した。 The evaluation results are shown in Table 2 below. Table 3 shows the relationship between the acrylic resin ratio (wt%) in the resin component of the surface layer and the OPC fogging based on the results of (3) OPC fogging in <Evaluation after initial image printing>. It was.
表２に示すように、各実施例の現像ローラは、表面層に塗布ムラが無く、各試験に於いて良好な結果を示した。
また、アクリル樹脂Ａ、Ｂを用いていない比較例１に於いては、塗布ムラが発生した。更に、この現像ローラを用いた印刷画像に於いては、塗布ムラに起因したムラ模様（黒ベタ部濃度ムラ）が現れた。
アクリル樹脂を用いていない比較例２、３は、トナー帯電性の低いものであった。
アクリル微粒子を用いた比較例４は、表面粗度が高いものであった。この結果から明らかなように、アクリル微粒子を用いると、表面粗度の調整が煩雑になると認められる。
ウレタン樹脂を用いていない比較例５は、初期画像印刷後の評価と５０００枚印刷後の評価とを対比すると明らかなように、表面層が脆く、経時劣化することが認められた。
また、表２及び表３から明らかなように、表面層に於けるアクリル樹脂Ａの割合が２０重量％（前記樹脂成分中）以上のものは、トナー帯電性に優れ、ＯＰＣかぶりが著しく低減されたものであった。
As shown in Table 2, the developing roller of each example had no coating unevenness on the surface layer and showed good results in each test.
In Comparative Example 1 in which acrylic resins A and B were not used, coating unevenness occurred. Furthermore, in the printed image using this developing roller, a uneven pattern (black solid portion density unevenness) due to coating unevenness appeared.
In Comparative Examples 2 and 3 in which no acrylic resin was used, the toner chargeability was low.
Comparative Example 4 using acrylic fine particles had a high surface roughness. As is clear from this result, it is recognized that the adjustment of the surface roughness becomes complicated when acrylic fine particles are used.
In Comparative Example 5 in which no urethane resin was used, it was recognized that the surface layer was brittle and deteriorated with time, as is apparent when the evaluation after printing the initial image was compared with the evaluation after printing 5000 sheets.
Further, as is apparent from Tables 2 and 3, when the ratio of the acrylic resin A in the surface layer is 20% by weight (in the resin component) or more, the toner chargeability is excellent and the OPC fog is remarkably reduced. It was.
３・・・ゴム基材、 ４・・・表面層、 ８・・・トナー 3 ... Rubber base material 4 ... Surface layer 8 ... Toner
Claims (4)
前記表面層は、前記混合物が溶媒に溶解された溶液を塗布することにより形成されてなり、
前記アクリル樹脂として、メタクリル酸−メタクリル酸メチル共重合体からなる主鎖にアミノエチル基がグラフトされてなるグラフト化合物が用いられてなることを特徴とする電子写真装置用現像部材。 An electrophotographic apparatus developing member comprising a rubber base material and a surface layer provided on the surface side of the rubber base material to negatively charge the toner by friction, wherein the surface layer is made of a mixture of urethane resin and acrylic resin Because
The surface layer is formed by applying a solution in which the mixture is dissolved in a solvent,
A developing member for an electrophotographic apparatus, wherein a graft compound in which an aminoethyl group is grafted to a main chain made of a methacrylic acid-methyl methacrylate copolymer is used as the acrylic resin.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2004098251A JP4190449B2 (en) | 2004-03-30 | 2004-03-30 | Developing member for electrophotographic apparatus |
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| Application Number | Priority Date | Filing Date | Title |
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| JP2004098251A JP4190449B2 (en) | 2004-03-30 | 2004-03-30 | Developing member for electrophotographic apparatus |
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| JP2005283995A true JP2005283995A (en) | 2005-10-13 |
| JP4190449B2 JP4190449B2 (en) | 2008-12-03 |
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| JP2004098251A Expired - Fee Related JP4190449B2 (en) | 2004-03-30 | 2004-03-30 | Developing member for electrophotographic apparatus |
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Cited By (10)
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| JP2007316200A (en) * | 2006-05-24 | 2007-12-06 | Bando Chem Ind Ltd | Conductive roller |
| JP2009175372A (en) * | 2008-01-23 | 2009-08-06 | Oki Data Corp | Developing device and image forming apparatus |
| JP2010210795A (en) * | 2009-03-09 | 2010-09-24 | Canon Inc | Developer carrier and developing device |
| JP2010210794A (en) * | 2009-03-09 | 2010-09-24 | Canon Inc | Developing roller, electrophotographic process cartridge, and electrophotographic image forming apparatus |
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| JP2013088672A (en) * | 2011-10-19 | 2013-05-13 | Oki Data Corp | Image forming unit and image forming apparatus |
| US10331054B2 (en) | 2016-05-11 | 2019-06-25 | Canon Kabushiki Kaisha | Electrophotographic member, process cartridge and electrophotographic image forming apparatus |
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|---|---|---|---|---|
| JP2007316200A (en) * | 2006-05-24 | 2007-12-06 | Bando Chem Ind Ltd | Conductive roller |
| JP2009175372A (en) * | 2008-01-23 | 2009-08-06 | Oki Data Corp | Developing device and image forming apparatus |
| JP4599414B2 (en) * | 2008-01-23 | 2010-12-15 | 株式会社沖データ | Developing device and image forming apparatus |
| US7945196B2 (en) | 2008-01-23 | 2011-05-17 | Oki Data Corporation | Developing device with supply member and image forming apparatus |
| JP2010210795A (en) * | 2009-03-09 | 2010-09-24 | Canon Inc | Developer carrier and developing device |
| JP2010210794A (en) * | 2009-03-09 | 2010-09-24 | Canon Inc | Developing roller, electrophotographic process cartridge, and electrophotographic image forming apparatus |
| JP2012127981A (en) * | 2010-12-10 | 2012-07-05 | Canon Inc | Developer carrier, process cartridge and electrophotographic apparatus |
| JP2013033238A (en) * | 2011-06-29 | 2013-02-14 | Canon Inc | Developer carrier, electrophotographic process cartridge, electrophotographic image forming apparatus |
| JP2013088672A (en) * | 2011-10-19 | 2013-05-13 | Oki Data Corp | Image forming unit and image forming apparatus |
| US10331054B2 (en) | 2016-05-11 | 2019-06-25 | Canon Kabushiki Kaisha | Electrophotographic member, process cartridge and electrophotographic image forming apparatus |
| JP2019168614A (en) * | 2018-03-23 | 2019-10-03 | 信越ポリマー株式会社 | Developing roller, developing device, and image forming apparatus |
| JP7010537B2 (en) | 2018-03-23 | 2022-01-26 | 信越ポリマー株式会社 | Developing rollers, developing equipment and image forming equipment |
| JP2020197665A (en) * | 2019-06-04 | 2020-12-10 | 信越ポリマー株式会社 | Developing roller, developing device, and image forming device |
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