Process cartridge and image forming method
20 claims: 4 independent, 16 dependent
- 1電子写真装置本体に着脱可能なプロセスカートリッジであって、 該プロセスカートリッジが、 電子写真感光体、 該電子写真感光体に当接し該電子写真感光体を帯電する帯電手段、および 該電子写真感光体上にトナーを供給しトナー画像を形成する現像手段を有し、 該電子写真感光体が、支持体、電荷発生層、および該電荷発生層と隣接し、該電子写真感光体の最表層である電荷輸送層をこの順に有し、 該電荷輸送層が、ポリアリレート樹脂およびポリカーボネート樹脂から選択される少なくとも1種の樹脂を含有し、該樹脂が、その構造中に式(1)で示されるポリシロキサン構造を含み、 該トナーが、トナー粒子および該トナー粒子の表面に存在する有機無機複合微粒子を有し、 該有機無機複合微粒子は、無機微粒子と樹脂粒子を含み、かつ、該無機微粒子が、該樹脂粒子の表面に、該無機微粒子の粒子形状に由来する凸部が形成されるように存在していることを特徴とするプロセスカートリッジ。 (式(1)中、R 11 ~R 14 は、それぞれ独立に、アルキル基、フルオロアルキル基またはフェニル基である。Zは、水素原子、ハロゲン原子、アルキル基またはアリール基である。nは、10以上200以下である。)
- 2前記ポリアリレート樹脂および前記ポリカーボネート樹脂に占める、前記式(1)で示されるポリシロキサン構造の割合が、0.5質量%以上50質量%以下である請求項1に記載のプロセスカートリッジ。
- 3式(2)で示されるポリシロキサン構造が、前記式(1)で示されるポリシロキサン構造として、前記ポリアリレート樹脂および前記ポリカーボネート樹脂の末端の少なくとも一部に導入されている請求項1または2に記載のプロセスカートリッジ。 (式(2)中、R 21 ~R 24 は、それぞれ独立に、アルキル基、フルオロアルキル基またはフェニル基である。Zは、炭素数1~4のアルキル基、または、フェニル基である。nは、10以上200以下である。mは、1以上3以下である。)
- 4前記ポリアリレート樹脂が、式(3)で示される構造単位、式(4)で示される構造単位および式(5)で示される構造単位から選択される少なくとも1種の構造単位を含む樹脂である請求項1~3のいずれか1項に記載のプロセスカートリッジ。 (式(3)中、R 31 ~R 34 の少なくとも1つの基は、式(3-A)で示されるポリシロキサン構造であり、それ以外の基は、それぞれ独立に、水素原子、アルキル基またはフルオロアルキル基である。X 3 は、m-フェニレン基、p-フェニレン基または2つのp-フェニレン基が酸素原子を介して結合した2価の基である。Y 3 は単結合、メチレン基、エチリデン基、プロピリデン基またはフェニルエチリデン基である。) (式(3-A)中、R 311 ~R 314 は、それぞれ独立に、アルキル基、フルオロアルキル基またはフェニル基である。Zは、炭素数1~4のアルキル基、または、フェニル基である。nは、10以上200以下である。mは、0以上5以下である。) (式(4)中、R 41 ~R 44 は、それぞれ独立に水素原子、アルキル基またはフルオロアルキル基である。R 45 は、水素原子、アルキル基、フルオロアルキル基またはフェニル基である。X 4 は、m-フェニレン基、p-フェニレン基または2つのp-フェニレン基が酸素原子を介して結合した2価の基である。Vは、式(4-A)で示されるポリシロキサン構造または式(4-B)で示されるポリシロキサン構造である。) (式(4-A)中、R 411 ~R 414 は、それぞれ独立に、アルキル基、フルオロアルキル基またはフェニル基である。Zは、炭素数1~4のアルキル基、または、フェニル基である。nは、10以上200以下である。mは、3以上20以下である。) (式(4-B)中、R 421 ~R 428 は、それぞれ独立に、アルキル基、フルオロアルキル基またはフェニル基である。Z 1 およびZ 2 は、それぞれ独立に、炭素数1~4のアルキル基、または、フェニル基である。n 1 およびn 2 は、それぞれ独立に、10以上200以下であり、n 1 とn 2 の合計値は、20以上250以下である。mは、3以上20以下である。) (式(5)中、X 5 は、m-フェニレン基、p-フェニレン基または2つのp-フェニレン基が酸素原子を介して結合した2価の基である。m 1 およびm 2 は、それぞれ独立に、1以上3以下である。Wは式(5-A)で示されるポリシロキサン構造である。) (式(5-A)中、R 511 ~R 520 は、それぞれ独立に、アルキル基、フルオロアルキル基またはフェニル基である。Zは、炭素数1~4のアルキル基、または、フェニル基である。nは、10以上200以下である。kおよびlは、それぞれ独立に、1以上10以下である。)
- 5前記ポリアリレート樹脂が、式(5)で示される構造単位を含む樹脂である請求項1~3のいずれか1項に記載のプロセスカートリッジ。 (式(5)中、X 5 は、m-フェニレン基、p-フェニレン基または2つのp-フェニレン基が酸素原子を介して結合した2価の基である。m 1 およびm 2 は、それぞれ独立に、1以上3以下である。Wは式(5-A)で示されるポリシロキサン構造である。) (式(5-A)中、R 511 ~R 520 は、それぞれ独立に、アルキル基、フルオロアルキル基またはフェニル基である。Zは、炭素数1~4のアルキル基、または、フェニル基である。nは、10以上200以下である。kおよびlは、それぞれ独立に、1以上10以下である。)
- 6前記ポリカーボネート樹脂が、式(6)で示される構造単位、式(7)で示される構造単位および式(8)で示される構造単位から選択される少なくとも1種の構造単位を含む樹脂である請求項1~3のいずれか1項に記載のプロセスカートリッジ。 (式(6)中、R 61 ~R 64 の少なくとも1つの基は、式(6-A)で示されるポリシロキサン構造であり、それ以外の基は、それぞれ独立に、水素原子、アルキル基、フルオロアルキル基またはフェニル基である。Y 6 は、単結合、メチレン基、エチリデン基、プロピリデン基、フェニルエチリデン基、シクロヘキシリデン基または酸素原子である。) (式(6-A)中、R 611 ~R 614 は、それぞれ独立に、アルキル基、フルオロアルキル基またはフェニル基である。Zは、炭素数1~4のアルキル基、または、フェニル基である。nは、10以上200以下である。mは、0以上5以下である。) (式(7)中、R 71 ~R 74 は、それぞれ独立に水素原子、アルキル基、フルオロアルキル基またはフェニル基である。R 75 は、水素原子、アルキル基、フルオロアルキル基またはフェニル基である。Vは、式(7-A)で示されるポリシロキサン構造または式(7-B)で示されるポリシロキサン構造である。) (式(7-A)中、R 711 ~R 714 は、それぞれ独立に、アルキル基、フルオロアルキル基またはフェニル基である。Zは、炭素数1~4のアルキル基、または、フェニル基を示す。nは、10以上200以下である。mは、3以上20以下である。) (式(7-B)中、R 721 ~R 728 は、それぞれ独立に、アルキル基、フルオロアルキル基またはフェニル基である。Z 1 およびZ 2 は、それぞれ独立に、炭素数1~4のアルキル基、または、フェニル基である。n 1 およびn 2 は、それぞれ独立に、10以上200以下であり、n 1 とn 2 の合計値は、20以上250以下である。mは、3以上20以下である。) (式(8)中、m 1 およびm 2 は、それぞれ独立に、1以上3以下である。Wは式(8-A)で示されるポリシロキサン構造である。) (式(8-A)中、R 811 ~R 820 は、それぞれ独立に、アルキル基、フルオロアルキル基、またはフェニル基である。Zは、炭素数1~4のアルキル基、または、フェニル基である。nは、10以上200以下である。kおよびlは、それぞれ独立に、1以上10以下である。)
- 7前記ポリカーボネート樹脂が、式(8)で示される構造単位を含む樹脂である請求項1~3のいずれか1項に記載のプロセスカートリッジ。 (式(8)中、m 1 およびm 2 は、それぞれ独立に、1以上3以下である。Wは式(8-A)で示されるポリシロキサン構造である。) (式(8-A)中、R 811 ~R 820 は、それぞれ独立に、アルキル基、フルオロアルキル基、またはフェニル基である。Zは、炭素数1~4のアルキル基、または、フェニル基である。nは、10以上200以下である。kおよびlは、それぞれ独立に、1以上10以下である。)
- 8X線光電子分光法で測定される前記電荷輸送層の最表面における水素原子を除く全原子に対するケイ素原子の存在割合が、0.6atoms%以上である請求項5または7に記載のプロセスカートリッジ。
- 9前記無機微粒子が、シリカまたは金属酸化物粒子である請求項1~8のいずれか1項に記載のプロセスカートリッジ。
- 10前記有機無機複合微粒子の含有量が、前記トナー粒子の含有量に対して、0.5質量%以上5.0質量%以下である請求項1~9のいずれか1項に記載のプロセスカートリッジ。
- 11電子写真感光体を帯電する帯電工程と、 帯電された電子写真感光体の表面に静電潜像を形成する静電潜像形成工程と、 前記電子写真感光体表面に、トナーを前記静電潜像に現像してトナー画像を形成する現像工程と、 電子写真感光体の表面の前記トナー画像を中間転写体を介して又は介さずに、転写材に転写する転写工程と、 前記電子写真感光体の表面から転写残トナーを除去するクリーニング工程とを有する画像形成方法であって、 該電子写真感光体が、支持体、電荷発生層、および該電荷発生層と隣接し、該電子写真感光体の最表層である電荷輸送層をこの順に有し、 該電荷輸送層が、ポリアリレート樹脂およびポリカーボネート樹脂から選択される少なくとも1種の樹脂を含有し、該樹脂が、その構造中に式(1)で示されるポリシロキサン構造を含み、 該トナーが、トナー粒子および該トナー粒子の表面に存在する有機無機複合微粒子を有し、 該有機無機複合微粒子は、無機微粒子と樹脂粒子を含み、かつ、該無機微粒子が、該樹脂粒子の表面に、該無機微粒子の粒子形状に由来する凸部が形成されるように存在していることを特徴とする画像形成方法。 (式(1)中、R 11 ~R 14 は、それぞれ独立に、アルキル基、フルオロアルキル基またはフェニル基である。Zは、水素原子、ハロゲン原子、アルキル基またはアリール基である。nは、10以上200以下である。)
- 12前記ポリアリレート樹脂および前記ポリカーボネート樹脂に占める、前記式(1)で示されるポリシロキサン構造の割合が、0.5質量%以上50質量%以下である請求項11に記載の画像形成方法。
- 13式(2)で示されるポリシロキサン構造が、前記式(1)で示されるポリシロキサン構造として、前記ポリアリレート樹脂および前記ポリカーボネート樹脂の末端の少なくとも一部に導入されている請求項11または12に記載の画像形成方法。 (式(2)中、R 21 ~R 24 は、それぞれ独立に、アルキル基、フルオロアルキル基またはフェニル基である。Zは、炭素数1~4のアルキル基、または、フェニル基である。nは、10以上200以下である。mは、1以上3以下である。)
- 14前記ポリアリレート樹脂が、式(3)で示される構造単位、式(4)で示される構造単位および式(5)で示される構造単位から選択される少なくとも1種の構造単位を含む樹脂である請求項11~13のいずれか1項に記載の画像形成方法。 (式(3)中、R 31 ~R 34 の少なくとも1つの基は、式(3-A)で示されるポリシロキサン構造であり、それ以外の基は、それぞれ独立に、水素原子、アルキル基またはフルオロアルキル基である。X 3 は、m-フェニレン基、p-フェニレン基または2つのp-フェニレン基が酸素原子を介して結合した2価の基である。Y 3 は単結合、メチレン基、エチリデン基、プロピリデン基またはフェニルエチリデン基である。) (式(3-A)中、R 311 ~R 314 は、それぞれ独立に、アルキル基、フルオロアルキル基またはフェニル基である。Zは、炭素数1~4のアルキル基、または、フェニル基である。nは、10以上200以下である。mは、0以上5以下である。) (式(4)中、R 41 ~R 44 は、それぞれ独立に水素原子、アルキル基またはフルオロアルキル基である。R 45 は、水素原子、アルキル基、フルオロアルキル基またはフェニル基である。X 4 は、m-フェニレン基、p-フェニレン基または2つのp-フェニレン基が酸素原子を介して結合した2価の基である。Vは、式(4-A)で示されるポリシロキサン構造または式(4-B)で示されるポリシロキサン構造である。) (式(4-A)中、R 411 ~R 414 は、それぞれ独立に、アルキル基、フルオロアルキル基またはフェニル基である。Zは、炭素数1~4のアルキル基、または、フェニル基である。nは、10以上200以下である。mは、3以上20以下である。) (式(4-B)中、R 421 ~R 428 は、それぞれ独立に、アルキル基、フルオロアルキル基またはフェニル基である。Z 1 およびZ 2 は、それぞれ独立に、炭素数1~4のアルキル基、または、フェニル基である。n 1 およびn 2 は、それぞれ独立に、10以上200以下であり、n 1 とn 2 の合計値は、20以上250以下である。mは、3以上20以下である。) (式(5)中、X 5 は、m-フェニレン基、p-フェニレン基または2つのp-フェニレン基が酸素原子を介して結合した2価の基である。m 1 およびm 2 は、それぞれ独立に、1以上3以下である。Wは式(5-A)で示されるポリシロキサン構造である。 (式(5-A)中、R 511 ~R 520 は、それぞれ独立に、アルキル基、フルオロアルキル基またはフェニル基である。Zは、炭素数1~4のアルキル基、または、フェニル基である。nは、10以上200以下である。kおよびlは、それぞれ独立に、1以上10以下である。)
- 15前記ポリアリレート樹脂が、式(5)で示される構造単位を含む樹脂である請求項11~13のいずれか1項に記載の画像形成方法。 (式(5)中、X 5 は、m-フェニレン基、p-フェニレン基または2つのp-フェニレン基が酸素原子を介して結合した2価の基である。m 1 およびm 2 は、それぞれ独立に、1以上3以下である。Wは式(5-A)で示されるポリシロキサン構造である。) (式(5-A)中、R 511 ~R 520 は、それぞれ独立に、アルキル基、フルオロアルキル基またはフェニル基である。Zは、炭素数1~4のアルキル基、または、フェニル基である。nは、10以上200以下である。kおよびlは、それぞれ独立に、1以上10以下である。)
- 16前記ポリカーボネート樹脂が、式(6)で示される構造単位、式(7)で示される構造単位および式(8)で示される構造単位から選択される少なくとも1種の構造単位を含む樹脂である請求項11~13のいずれか1項に記載の画像形成方法。 (式(6)中、R 61 ~R 64 の少なくとも1つの基は、式(6-A)で示されるポリシロキサン構造であり、それ以外の基は、それぞれ独立に、水素原子、アルキル基、フルオロアルキル基またはフェニル基である。Y 6 は、単結合、メチレン基、エチリデン基、プロピリデン基、フェニルエチリデン基、シクロヘキシリデン基または酸素原子である。) (式(6-A)中、R 611 ~R 614 は、それぞれ独立に、アルキル基、フルオロアルキル基またはフェニル基である。Zは、炭素数1~4のアルキル基、または、フェニル基である。nは、10以上200以下である。mは、0以上5以下である。) (式(7)中、R 71 ~R 74 は、それぞれ独立に水素原子、アルキル基、フルオロアルキル基またはフェニル基である。R 75 は、水素原子、アルキル基、フルオロアルキル基またはフェニル基である。Vは、式(7-A)で示されるポリシロキサン構造または式(7-B)で示されるポリシロキサン構造である。) (式(7-A)中、R 711 ~R 714 は、それぞれ独立に、アルキル基、フルオロアルキル基またはフェニル基である。Zは、炭素数1~4のアルキル基、または、フェニル基を示す。nは、10以上200以下である。mは、3以上20以下である。) (式(7-B)中、R 721 ~R 728 は、それぞれ独立に、アルキル基、フルオロアルキル基またはフェニル基である。Z 1 およびZ 2 は、それぞれ独立に、炭素数1~4のアルキル基、または、フェニル基である。n 1 およびn 2 は、それぞれ独立に、10以上200以下であり、n 1 とn 2 の合計値は、20以上250以下である。mは、3以上20以下である。) (式(8)中、m 1 およびm 2 は、それぞれ独立に、1以上3以下である。Wは式(8-A)で示されるポリシロキサン構造である。) (式(8-A)中、R 811 ~R 820 は、それぞれ独立に、アルキル基、フルオロアルキル基、またはフェニル基である。Zは、炭素数1~4のアルキル基、または、フェニル基である。nは、10以上200以下である。kおよびlは、それぞれ独立に、1以上10以下である。)
- 17前記ポリカーボネート樹脂が、式(8)で示される構造単位を含む樹脂である請求項11~13のいずれか1項に記載の画像形成方法。 (式(8)中、m 1 およびm 2 は、それぞれ独立に、1以上3以下である。Wは式(8-A)で示されるポリシロキサン構造である。) (式(8-A)中、R 811 ~R 820 は、それぞれ独立に、アルキル基、フルオロアルキル基、またはフェニル基である。Zは、炭素数1~4のアルキル基、または、フェニル基である。nは、10以上200以下である。kおよびlは、それぞれ独立に、1以上10以下である。)
- 18X線光電子分光法で測定される前記電荷輸送層の最表面における水素原子を除く全原子に対するケイ素原子の存在割合が、0.6atoms%以上である請求項15または17に記載の画像形成方法。
- 19前記無機微粒子が、シリカまたは金属酸化物粒子である請求項11~18のいずれか1項に記載の画像形成方法。
- 20前記有機無機複合微粒子の含有量が、前記トナー粒子の含有量に対して、0.5質量%以上5.0質量%以下である請求項11~19のいずれか1項に記載の画像形成方法。
Independent claims20
126 paragraphs, as filed
The present invention relates to a process cartridge and an image forming method.
As a general electrophotographic process, which is an image forming method, an electrical latent image is formed on an electrophotographic photosensitive member (hereinafter, also simply referred to as "photoreceptor"), and toner is supplied to the latent image to visualize it. A method is known in which a toner image is transferred to a transfer material such as paper, and then the toner image is fixed on the transfer material by heat or pressure to obtain a copy.
After the transfer step, cleaning is performed to remove the toner (transfer residual toner) remaining on the electrophotographic photosensitive member. The most widely used cleaning method is blade cleaning. Blade cleaning is a method of scraping off toner by pressing an elastic blade-like member such as rubber against the surface of an electrophotographic photosensitive member.
In the blade cleaning, the toner removed from the surface of the photoconductor includes not only the toner particles but also an external additive transferred from the toner particles to the surface of the photoconductor. The external additive transferred to the surface of the photoconductor is often more difficult to clean than the toner particles. This is because the particle size of the external additive is smaller than the particle size of the toner particles, so it penetrates deeper into the contact nip between the blade and the photoconductor, and the probability of slipping through the blade is high. It is believed to be a factor.
If the external additive transferred to the surface of the photoconductor is not sufficiently cleaned (cleanability is low), the external additive easily adheres to the charged member and contaminates the charged member. In the region where the charging member is contaminated, the charging process of the photoconductor is not performed normally, and the image quality tends to deteriorate. For this reason, it is necessary to provide a mechanism for removing the external additive adhering to the charging member, which may complicate the mechanism, increase the size of the process cartridge, and increase the cost.
In particular, in the initial stage of use of a new process cartridge or electrophotographic apparatus, it may not be possible to sufficiently clean the external additive that has migrated to the surface of the photoconductor. This is because the amount of toner and other inclusions present in the contact nip between the blade and the photoconductor is small in the initial stage of use of a new process cartridge or electrophotographic device, and the stick-slip motion of the blade becomes unstable. It is thought that one of the causes is that it is in a state where it is easy to become.
Toner, carbon fluoride, silica on the edges of cleaning blades during the manufacture of process cartridges and electrophotographic equipment to stabilize the stick-slip motion of the blade from the early stages of use of new process cartridges and electrophotographic equipment. Attempts have been made to apply such particles as a lubricant. However, since the countermeasure by applying the lubricant to the blade leads to the complicated manufacturing process, there is a demand for a means for suppressing the occurrence of cleaning failure without applying the lubricant.
As a means for improving the cleanability of the external additive transferred to the surface of the photoconductor, for example, an attempt to prevent the external additive from slipping through by increasing the linear pressure of pressing the edge of the blade onto the surface of the photoconductor. Has been done. However, this countermeasure measure by simply increasing the linear pressure may cause problems such as promotion of chipping of the blade edge portion, generation of abnormal noise due to chatter vibration of the blade, and promotion of wear of the photoconductor.
Patent Document 1 proposes a method for improving cleanability by using non-spherical and irregularly shaped large particle size silica particles as an external additive. However, the use of a large particle size inorganic external additive may impair the low temperature fixability of the toner. This may increase the power consumption in the fixing process.
Patent Document 2 proposes a method for improving cleanability by forming a layer in which irregular shapes having a large particle size or abrasive particles are retained on a blade edge portion. However, the method proposed in Patent Document 2 can clean toner particles having a large particle size of irregular shapes or larger than abrasive particles, but can suppress the slip-through of a small particle size external additive. difficult. Further, in order to form a stable retention layer on the blade edge portion, it is necessary to operate the electrophotographic process to some extent to sufficiently supply a large-diameter amorphous or abrasive particles to the blade edge portion. Therefore, in the initial stage of using a new process cartridge or electrophotographic apparatus, it is considered that the effect of improving the cleaning property by forming the retention layer cannot be sufficiently obtained.
<p><patcit num="1"><text>Japanese Unexamined Patent Publication No. 2007-279702</text></patcit><patcit num="2"><text>JP-A-2002-318467</text></patcit></p>
<p> In order to obtain good image quality, it is necessary to sufficiently remove not only the toner particles but also the external additive that has migrated to the surface of the photoconductor in the cleaning process. In particular, in the initial stage of use of a new process cartridge or electrophotographic apparatus, there is a need for a means for improving the cleanability and suppressing the slip-through of the external additive that has migrated to the surface of the photoconductor without applying a lubricant to the blade. ing.</p><p> An object of the present invention is a process cartridge and image formation capable of obtaining good image quality with high cleaning property of the external additive transferred to the surface of the photoconductor even in the initial stage of use of a new process cartridge or electrophotographic apparatus. To provide a method.</p>
<p> The present invention is a process cartridge that can be attached to and detached from the main body of the electrophotographic apparatus. It has a developing means for supplying toner onto a photoconductor to form a toner image, and the electrophotographic photoconductor is adjacent to a support, a charge generation layer, and the charge generation layer, and is the outermost layer of the electrophotographic photoconductor. The charge transport layers are in this order, and the charge transport layer contains at least one resin selected from a polyarylate resin and a polycarbonate resin, and the resin is represented by the formula (1) in its structure. The toner contains toner particles and organic-inorganic composite fine particles existing on the surface of the toner particles, and the organic-inorganic composite fine particles contain inorganic fine particles and resin particles, and the inorganic fine particles are contained. However, it is characterized in that a convex portion derived from the particle shape of the inorganic fine particles is formed on the surface of the resin particles.<chemistry num="1"><img file="JP6603555B2_D0001.tif" /></chemistry>(In equation (1), R<sup>11</sup>~ R<sup>14</sup>Are independently alkyl, fluoroalkyl or phenyl groups, respectively. Z is a hydrogen atom, a halogen atom, an alkyl group, or an aryl group. n is 10 or more and 200 or less. )</p>
<p> According to the present invention, it is possible to provide a process cartridge and an image forming method which have good cleanability even in the initial stage of use of a new process cartridge or an electrophotographic apparatus and can suppress deterioration of image quality.</p>
<figref num="1">It is a figure which shows an example of the schematic structure of the electrophotographic apparatus provided with the process cartridge of this invention.</figref>
The process cartridge of the present invention is a process cartridge that can be attached to and detached from the main body of the electrophotographic apparatus, and has an electrophotographic photosensitive member, a charging means, and a developing means. The charging means comes into contact with the electrophotographic photosensitive member and charges the electrophotographic photosensitive member. The developing means supplies toner onto the electrophotographic photosensitive member to form a toner image. The electrophotographic photosensitive member and the toner have the following characteristics.
The electrophotographic photosensitive member has a support, a charge generating layer, and a charge transporting layer which is adjacent to the charge generating layer and is the outermost layer of the electrophotographic photosensitive member in this order, and the charge transporting layer is a polyarylate resin. And at least one resin selected from the polycarbonate resin, the resin contains a polysiloxane structure represented by the formula (1) in the structure, and the toner is applied to the toner particles and the surface of the toner particles. The organic-inorganic composite fine particles are present, and the organic-inorganic composite fine particles contain inorganic fine particles and resin particles, and the inorganic fine particles are formed on the surface of the resin particles with protrusions derived from the particle shape of the inorganic fine particles. Exists to form.<chemistry num="2"><img file="JP6603555B2_D0002.tif" /></chemistry>(In equation (1), R<sup>11</sup>~ R<sup>14</sup>Are independently alkyl, fluoroalkyl or phenyl groups, respectively. Z is a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aryl group. n is 10 or more and 200 or less. )
<Electrophotophotograph Photoreceptor> The electrophotographic photosensitive member used in the present invention will be described in more detail. The electrophotographic photosensitive member used in the present invention has a support, a charge generation layer, and a charge transport layer which is adjacent to the charge generation layer and is the outermost layer of the electrophotographic photosensitive member. As the electrophotographic photosensitive member, generally, a cylindrical electrophotographic photosensitive member in which a photosensitive layer (charge generation layer, charge transport layer) is formed on a cylindrical support is widely used, but a belt-shaped or sheet is widely used. It is also possible to make it into a shape such as a shape.
The support preferably has conductivity (conductive support), and a metal support such as aluminum, aluminum alloy, or stainless steel can be used. In the case of a support made of aluminum or an aluminum alloy, an ED tube, an EI tube, or a support obtained by cutting, electrolytic compound polishing, wet or dry honing treatment of these can also be used. Further, a metal support or a resin support on which an aluminum, an aluminum alloy or an indium oxide-tin oxide alloy is formed by vacuum vapor deposition can also be used. The surface of the support may be subjected to a cutting treatment, a roughening treatment, an alumite treatment, or the like. Further, a support obtained by impregnating a resin or the like with conductive particles such as carbon black, tin oxide particles, titanium oxide particles, and silver particles, or a plastic having a conductive resin can also be used.
A conductive layer may be provided between the support and the undercoat layer or the charge generation layer described later for the purpose of suppressing interference fringes due to scattering of laser light or the like and covering scratches on the support. This is a layer formed by using a coating liquid for a conductive layer in which conductive particles are dispersed in a resin. Conductive particles include, for example, carbon black, acetylene black, metal powders such as aluminum, nickel, iron, nichrome, copper, zinc, and silver, and metal oxide powders such as conductive tin oxide and ITO. Can be mentioned.
Examples of the resin used for the conductive layer include polyarylate resin, polycarbonate resin, polyvinyl butyral resin, acrylic resin, silicone resin, epoxy resin, melamine resin, urethane resin, phenol resin and alkyd resin.
Examples of the solvent of the coating liquid for the conductive layer include an ether solvent, an alcohol solvent, a ketone solvent and an aromatic hydrocarbon solvent. The film thickness of the conductive layer is preferably 0.2 μm or more and 40 μm or less, more preferably 1 μm or more and 35 μm or less, and further preferably 5 μm or more and 30 μm or less.
In the electrophotographic photosensitive member used in the present invention, an undercoat layer may be provided between the support or the conductive layer and the charge generation layer. The undercoat layer can be formed by applying a resin-containing undercoat layer coating liquid onto a support or a conductive layer, and drying or curing the undercoat layer. Examples of the resin used for the undercoat layer include polyacrylic acids, methyl cellulose, ethyl cellulose, polyamide resin, polyimide resin, polyamide-imide resin, polyamic acid resin, melamine resin, epoxy resin, polyurethane resin, and polyolefin resin. The film thickness of the undercoat layer is preferably 0.05 μm or more and 7 μm or less, and more preferably 0.1 μm or more and 2 μm or less. Further, the undercoat layer may contain semi-conductive particles, an electron transporting substance, or an electron accepting substance.
A charge generating layer is provided on the support, the conductive layer or the undercoat layer. Examples of the charge generating substance used in the charge generating layer include azo pigments, phthalocyanine pigments, indigo pigments and perylene pigments. Only one kind of these charge generating substances may be used, or two or more kinds may be used. Among these, metal phthalocyanines such as oxytitanium phthalocyanine, hydroxygallium phthalocyanine, and chlorogallium phthalocyanine are particularly preferable because of their high sensitivity.
Examples of the resin used for the charge generation layer include polycarbonate resin, polyarylate resin, butyral resin, polyvinyl acetal resin, acrylic resin, vinyl acetate resin and urea resin. Among these, butyral resin is particularly preferable. These can be used alone, mixed or as a copolymer of one or more.
The charge generation layer can be formed by applying a coating liquid for a charge generation layer obtained by dispersing a charge generation substance together with a resin and a solvent, and drying the obtained coating film. Examples of the dispersion method include a method using a homogenizer, ultrasonic waves, a ball mill, a sand mill, an attritor, and a roll mill. The ratio of the charge generating substance to the resin is preferably in the range of 1:10 to 10: 1 (mass ratio), and more preferably in the range of 1: 1 to 3: 1 (mass ratio). Examples of the solvent used in the coating liquid for the charge generation layer include alcohol-based solvents, sulfoxide-based solvents, ketone-based solvents, ether-based solvents, ester-based solvents, aromatic hydrocarbon solvents, and the like. The film thickness of the charge generation layer is preferably 0.01 μm or more and 5 μm or less, and more preferably 0.1 μm or more and 2 μm or less.
Further, various sensitizers, antioxidants, ultraviolet absorbers, plasticizers and the like can be added to the charge generation layer as needed. Further, in order to prevent the flow of electric charge from being blocked in the charge generation layer, the charge generation layer may contain an electron transporting substance or an electron accepting substance.
A charge transport layer is provided on the charge generation layer. In the present invention, the charge transport layer is a polyarylate resin (hereinafter, also referred to as "polyarylate resin A") containing the polysiloxane structure represented by the above formula (1) in its structure, and the above formula in its structure. It contains at least one resin selected from the polycarbonate resin containing the polysiloxane structure shown in (1) (hereinafter, also referred to as "polycarbonate resin B").
(i) When the polysiloxane structure is introduced into at least a part of the end of the resin In the present invention, the polyarylate resin A or the polycarbonate resin B is a poly represented by the above formula (1) in at least a part of the end. It is preferable that a siloxane structure is introduced. Furthermore, it is more preferable that the polysiloxane structure represented by the following formula (2) is introduced as the polysiloxane structure represented by the formula (1).<chemistry num="3"><img file="JP6603555B2_D0003.tif" /></chemistry> Formula (2) is a monovalent group and is introduced into at least a part of the end of the resin at the left end of the above formula. In equation (2), R<sup>21</sup>~ R<sup>24</sup>Are independently alkyl, fluoroalkyl or phenyl groups, respectively. Of these, an alkyl group or a phenyl group is preferable, and a methyl group or a phenyl group is more preferable. Z in the formula (2) is an alkyl group having 1 to 4 carbon atoms or a phenyl group. N in the equation (2) indicates the number of repetitions of the structure in parentheses, and is 10 or more and 200 or less from the viewpoint of achieving both good cleanability and electrical characteristics. M in Eq. (2) indicates the number of repetitions of the structure in parentheses, which is 1 or more and 3 or less.
Specific examples of the structure represented by the equation (2) are shown below, but the present invention is not limited to these.<chemistry num="4"><img file="JP6603555B2_D0004.tif" /></chemistry>
Among these, the structures represented by the formulas (2-1), (2-2), (2-5), (2-7), (2-11) or (2-13) are preferable. Further, the above structure may be used alone or in combination.
(i-1) Polyarylate resin A In a polyarylate resin having a polysiloxane structure represented by the formula (2) at least a part of the terminal, a main chain to which the polysiloxane structure represented by the formula (2) is bonded to the terminal Examples of the structural unit to be constructed include the structural unit represented by the formulas (9) and (10) described later. That is, in the present invention, the polyarylate resin containing the polysiloxane structure represented by the above formula (1) in its structure is selected from the structural unit represented by the formula (9) and the structural unit represented by the formula (10). It is preferable that the resin contains at least one structural unit and has a polysiloxane structure represented by the formula (2) introduced into at least a part of the terminal thereof.
(i-2) Polycarbonate resin B In a polycarbonate resin having a polysiloxane structure represented by the formula (2) at least a part of the terminal, the polysiloxane structure represented by the formula (2) constitutes a main chain bonded to the terminal. Examples of the structural unit include structural units represented by equations (11) and (12) described later. That is, in the present invention, the polycarbonate resin containing the polysiloxane structure represented by the above formula (1) in its structure is selected from the structural unit represented by the formula (11) and the structural unit represented by the formula (12). It is preferable that the resin contains at least one structural unit and has a polysiloxane structure represented by the formula (2) introduced into at least a part of the terminal thereof.
(ii) When the resin contains a structural unit containing a polysiloxane structure In the present invention, the polyarylate resin A or the polycarbonate resin B is a resin containing a structural unit containing a polysiloxane structure represented by the above formula (1). Is preferable. Further, the polyarylate resin A or the polycarbonate resin B containing a structural unit containing the polysiloxane structure represented by the above formula (1) has a poly represented by the above formula (1) or the above formula (2) at least a part of the terminal. A siloxane structure may be introduced.
(ii-1) Polyarylate Resin A In the present invention, the polyarylate resin A is selected from the structural unit represented by the formula (3), the structural unit represented by the formula (4), and the structural unit represented by the formula (5). It is preferable that the resin contains at least one structural unit. Above all, a resin containing the structural unit represented by the formula (5) is more preferable.
Further, in a polyarylate resin containing at least one structural unit selected from the structural units represented by the formulas (3), (4) and (5), the formula described later is used as the structural unit constituting the main chain. It may further have the structural units represented by (9) and (10).
Structural unit represented by equation (3)<chemistry num="5"><img file="JP6603555B2_D0005.tif" /></chemistry> In equation (3), R<sup>31</sup>~ R<sup>34</sup>At least one group of is a polysiloxane structure represented by the formula (3-A), and the other groups are independently hydrogen atoms, alkyl groups or fluoroalkyl groups. X<sup>3</sup>Is a divalent group in which an m-phenylene group, a p-phenylene group or two p-phenylene groups are bonded via an oxygen atom. Y<sup>3</sup>Is a single bond, methylene group, ethylidene group, propylidene group or phenylethylidene group.
<chemistry num="6"><img file="JP6603555B2_D0006.tif" /></chemistry> In equation (3-A), R<sup>311</sup>~ R<sup>314</sup>Are independently alkyl, fluoroalkyl or phenyl groups, respectively. Of these, an alkyl group or a phenyl group is preferable, and a methyl group is more preferable. Z is an alkyl group having 1 to 4 carbon atoms or a phenyl group. n indicates the number of repetitions of the structure in parentheses, and is 10 or more and 200 or less from the viewpoint of achieving both good cleanability and electrical characteristics. m indicates the number of repetitions of the structure in parentheses, which is 0 or more and 5 or less.
Specific examples of the groups represented by the formula (3-A) are shown below, but the present invention is not limited thereto.<chemistry num="7"><img file="JP6603555B2_D0007.tif" /></chemistry>
Among these, the structural unit represented by the formula (3-A-1), (3-A-2), (3-A-4) or (3-A-7) is preferable. Further, the above structural units may be used alone or in combination.
Specific examples of the structural unit represented by the equation (3) are shown below, but the present invention is not limited to these. In equations (3-1) to (3-14), A represents equation (3-A).<chemistry num="8"><img file="JP6603555B2_D0008.tif" /></chemistry>
Among these, equations (3-1), (3-2), (3-3), (3-4), (3-5), (3-6), (3-7) or (3- The structural unit shown in 11) is preferable. Further, the above structural units may be used alone or in combination.
Structural unit represented by equation (4)<chemistry num="9"><img file="JP6603555B2_D0009.tif" /></chemistry> In equation (4), R<sup>41</sup>~ R<sup>44</sup>Are independently hydrogen atoms, alkyl groups or fluoroalkyl groups. Of these, a hydrogen atom or a methyl group is preferable. R<sup>45</sup>Is a hydrogen atom, an alkyl group, a fluoroalkyl group or a phenyl group. Of these, a hydrogen atom, a methyl group or a phenyl group is preferable. X<sup>4</sup>Is a divalent group in which an m-phenylene group, a p-phenylene group or two p-phenylene groups are bonded via an oxygen atom. V is a polysiloxane structure represented by the formula (4-A) or a polysiloxane structure represented by the formula (4-B).
<chemistry num="10"><img file="JP6603555B2_D0010.tif" /></chemistry> In equation (4-A), R<sup>411</sup>~ R<sup>414</sup>Are independently alkyl, fluoroalkyl or phenyl groups, respectively. Of these, a methyl group is preferable. Z is an alkyl group having 1 to 4 carbon atoms or a phenyl group. n indicates the number of repetitions of the structure in parentheses, and is 10 or more and 200 or less from the viewpoint of achieving both good cleanability and electrical characteristics. m indicates the number of repetitions of the structure in parentheses, and is 3 or more and 20 or less from the viewpoint of obtaining good cleanability. Furthermore, the difference between the maximum value and the minimum value of m is preferably 0 or more and 3 or less.
<chemistry num="11"><img file="JP6603555B2_D0011.tif" /></chemistry> In equation (4-B), R<sup>421</sup>~ R<sup>428</sup>Are independently alkyl, fluoroalkyl or phenyl groups, respectively. Of these, a methyl group is preferable. Z<sup>1</sup>And Z<sup>2</sup>Are independently alkyl groups or phenyl groups having 1 to 4 carbon atoms. n<sup>1</sup>And n<sup>2</sup>Indicates the number of repetitions of the structure in parentheses, and is independently 10 or more and 200 or less, preferably 10 or more and 100 or less, from the viewpoint of achieving both good cleanability and electrical characteristics. In addition, n<sup>1</sup>And n<sup>2</sup>The total value of is 20 or more and 250 or less. m is 3 or more and 20 or less. Furthermore, the difference between the maximum value and the minimum value of m is preferably 0 or more and 3 or less.
Specific examples of the structural unit represented by the equation (4) are shown below, but the present invention is not limited to these. In equations (4-1) to (4-12), V represents equation (4-A) or (4-B).<chemistry num="12"><img file="JP6603555B2_D0012.tif" /></chemistry>
Among these, the structural units represented by the formulas (4-1), (4-2), (4-3), (4-4), (4-5) or (4-6) are preferable. Further, the above structural units may be used alone or in combination.
Structural unit represented by equation (5)<chemistry num="13"><img file="JP6603555B2_D0013.tif" /></chemistry> In equation (5), X<sup>5</sup>Is a divalent group in which an m-phenylene group, a p-phenylene group or two p-phenylene groups are bonded via an oxygen atom. m<sup>1</sup>And m<sup>2</sup>Are 1 or more and 3 or less independently of each other. W is a polysiloxane structure represented by the formula (5-A).
<chemistry num="14"><img file="JP6603555B2_D0014.tif" /></chemistry> In equation (5-A), R<sup>511</sup>~ R<sup>520</sup>Are independently alkyl, fluoroalkyl or phenyl groups, respectively. Of these, a methyl group is preferable. Z is an alkyl group having 1 to 4 carbon atoms or a phenyl group. n indicates the number of repetitions of the structure in parentheses, and is 10 or more and 200 or less, preferably 10 or more and 150 or less, from the viewpoint of achieving both good cleanability and electrical characteristics. k and l are independently greater than or equal to 1 and less than or equal to 10. Furthermore, the difference between the maximum value and the minimum value of k is preferably 0 or more and 3 or less. The difference between the maximum value and the minimum value of l is preferably 0 or more and 3 or less.
Specific examples of the structural unit represented by the equation (5) are shown below, but the present invention is not limited to these. In equations (5-1) to (5-6), W represents equation (5-A).<chemistry num="15"><img file="JP6603555B2_D0015.tif" /></chemistry>
Among these, the structural unit represented by the formula (5-1), (5-2) or (5-3) is preferable. Further, the above structural units may be used alone or in combination.
(ii-2) Polycarbonate resin B Polycarbonate resin B is at least one selected from the structural unit represented by the formula (6), the structural unit represented by the formula (7), and the structural unit represented by the formula (8). A resin containing a structural unit is preferable. Above all, a resin containing the structural unit represented by the formula (8) is more preferable.
Further, in a polycarbonate resin containing at least one structural unit selected from the structural units represented by the formulas (6), (7) and (8), the structural unit constituting the main chain will be described later. It may further have the structural units shown in 11) and (12).
Structural unit represented by equation (6)<chemistry num="16"><img file="JP6603555B2_D0016.tif" /></chemistry> In equation (6), R<sup>61</sup>~ R<sup>64</sup>At least one group of is a polysiloxane structure represented by the formula (6-A), and the other groups are independently hydrogen atoms, alkyl groups, fluoroalkyl groups or phenyl groups. Y<sup>6</sup>Is a single bond, a methylene group, an ethylidene group, a propylidene group, a phenylethylidene group, a cyclohexylidene group or an oxygen atom.
<chemistry num="17"><img file="JP6603555B2_D0017.tif" /></chemistry> In equation (6-A), R<sup>611</sup>~ R<sup>614</sup>Are independently alkyl, fluoroalkyl or phenyl groups, respectively. Of these, an alkyl group or a phenyl group is preferable, and a methyl group is more preferable. Z is an alkyl group having 1 to 4 carbon atoms or a phenyl group. n indicates the number of repetitions of the structure in parentheses, and is 10 or more and 200 or less from the viewpoint of achieving both good cleanability and electrical characteristics. m indicates the number of repetitions of the structure in parentheses, which is 0 or more and 5 or less.
Specific examples of the groups represented by the formula (6-A) are the same as those of the above formulas (3-A-1) to (3-A-9). However, it is not limited to these. Further, the above structure may be used alone or in combination.
Specific examples of the structural unit represented by the equation (6) are shown below, but the present invention is not limited to these. In equations (6-1) to (6-9), A represents equation (6-A).<chemistry num="18"><img file="JP6603555B2_D0018.tif" /></chemistry>
Among these, the structural units represented by the formulas (6-1), (6-3), (6-5), (6-6) or (6-8) are preferable. Further, the above structural units may be used alone or in combination.
Structural unit represented by equation (7)<chemistry num="19"><img file="JP6603555B2_D0019.tif" /></chemistry> In equation (7), R<sup>71</sup>~ R<sup>74</sup>Are independently hydrogen atoms, alkyl groups, fluoroalkyl groups or phenyl groups. Of these, a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or a phenyl group is preferable. R<sup>75</sup>Is a hydrogen atom, an alkyl group, a fluoroalkyl group or a phenyl group. Of these, a hydrogen atom or a methyl group is preferable. V is a polysiloxane structure represented by the formula (7-A) or a polysiloxane structure represented by the formula (7-B).
<chemistry num="20"><img file="JP6603555B2_D0020.tif" /></chemistry> In equation (7-A), R<sup>711</sup>~ R<sup>714</sup>Are independently alkyl, fluoroalkyl or phenyl groups, respectively. Of these, a methyl group is preferable. Z represents an alkyl group having 1 to 4 carbon atoms or a phenyl group. n indicates the number of repetitions of the structure in parentheses, and is 10 or more and 200 or less from the viewpoint of achieving both good cleanability and electrical characteristics. m indicates the number of repetitions of the structure in parentheses, which is 3 or more and 20 or less. Furthermore, the difference between the maximum value and the minimum value of m is preferably 0 or more and 3 or less.
<chemistry num="21"><img file="JP6603555B2_D0021.tif" /></chemistry> In equation (7-B), R<sup>721</sup>~ R<sup>728</sup>Are independently alkyl, fluoroalkyl or phenyl groups, respectively. Of these, a methyl group is preferable. Z<sup>1</sup>And Z<sup>2</sup>Are independently alkyl groups or phenyl groups having 1 to 4 carbon atoms. n<sup>1</sup>And n<sup>2</sup>Indicates the number of repetitions of the structure in parentheses, and from the viewpoint of achieving both good cleanability and electrical characteristics, each is independently 10 or more and 200 or less, and preferably 10 or more and 100 or less. Also n<sup>1</sup>And n<sup>2</sup>The total value of is 20 or more and 250 or less. m indicates the number of repetitions of the structure in parentheses, which is 3 or more and 20 or less. Furthermore, the difference between the maximum value and the minimum value of m is preferably 0 or more and 3 or less.
Specific examples of the structural unit represented by the equation (7) are shown below, but the present invention is not limited to these. In equations (7-1) to (7-4), V represents equation (7-A) or (7-B).<chemistry num="22"><img file="JP6603555B2_D0022.tif" /></chemistry>
Among these, the structural unit represented by the formula (7-1) or (7-2) is preferable. Further, the above structural units may be used alone or in combination.
Structural unit represented by equation (8)<chemistry num="23"><img file="JP6603555B2_D0023.tif" /></chemistry> In equation (8), m<sup>1</sup>And m<sup>2</sup>Indicates the number of repetitions of the structure in parentheses, each independently being 1 or more and 3 or less. W is a polysiloxane structure represented by the formula (8-A).
<chemistry num="24"><img file="JP6603555B2_D0024.tif" /></chemistry> In equation (8-A), R<sup>811</sup>~ R<sup>820</sup>Are independently alkyl, fluoroalkyl, or phenyl groups. Of these, a methyl group is preferable. Z is an alkyl group having 1 to 4 carbon atoms or a phenyl group. n indicates the number of repetitions of the structure in parentheses, and is 10 or more and 200 or less, preferably 10 or more and 150 or less, from the viewpoint of achieving both good cleanability and electrical characteristics. k and l are independently greater than or equal to 1 and less than or equal to 10. Furthermore, the difference between the maximum value and the minimum value of k is preferably 0 or more and 3 or less. The difference between the maximum value and the minimum value of l is preferably 0 or more and 3 or less.
Specific examples of the structural unit represented by the equation (8) are shown below, but the present invention is not limited to these. In equations (8-1) to (8-2), W represents equation (8-A).<chemistry num="25"><img file="JP6603555B2_D0025.tif" /></chemistry>
Among these, the structural unit represented by the formula (8-1) is preferable. Further, the above structural units may be used alone or in combination.
(iii) Structures other than polysiloxane structure (iii-1) Polyarylate resin In the present invention, polyarylate resin A uses structural units represented by the formulas (9) and (10) as structural units constituting the main chain. You may also have more. These may be used alone or in combination.<chemistry num="26"><img file="JP6603555B2_D0026.tif" /></chemistry> In equation (9), R<sup>91</sup>~ R<sup>98</sup>Independently indicate a hydrogen atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aryl group. Of these, a hydrogen atom or a methyl group is preferable. X<sup>9</sup>Indicates a divalent group in which an m-phenylene group, a p-phenylene group, or two p-phenylene groups are bonded via an oxygen atom. Y<sup>9</sup>Indicates a single bond, an oxygen atom, a sulfur atom, or a divalent organic group. Of these, a single bond or a divalent organic group having 1 to 3 carbon atoms is preferable.
<chemistry num="27"><img file="JP6603555B2_D0027.tif" /></chemistry> In equation (10), R<sup>101</sup>~ R<sup>104</sup>Independently indicate a methyl group, an ethyl group, or a phenyl group. X<sup>10</sup>Indicates a divalent group in which an m-phenylene group, a p-phenylene group, or two p-phenylene groups are bonded via an oxygen atom. n indicates the number of repetitions in parentheses, and is preferably 10 or more and 150 or less.
Specific examples of the structural units represented by the equations (9) and (10) are shown below, but the present invention is not limited thereto.<chemistry num="28"><img file="JP6603555B2_D0028.tif" /></chemistry>
<chemistry num="29"><img file="JP6603555B2_D0029.tif" /></chemistry>
(iii-2) Polycarbonate Resin In the present invention, the polycarbonate resin B may further have structural units represented by the formulas (11) and (12) as structural units constituting the main chain. These may be used alone or in combination.
<chemistry num="30"><img file="JP6603555B2_D0030.tif" /></chemistry> In equation (11), R<sup>111</sup>~ R<sup>118</sup>Independently indicate a hydrogen atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aryl group. Of these, a hydrogen atom or a methyl group is preferable. Y<sup>11</sup>Indicates a single bond, an oxygen atom, a sulfur atom, or a divalent organic group. Of these, a single bond, a divalent organic group having 1 to 3 carbon atoms, a phenylethylidene group, a cyclohexylidene group, or an oxygen atom is preferable.
<chemistry num="31"><img file="JP6603555B2_D0031.tif" /></chemistry> In equation (12), R<sup>121</sup>~ R<sup>124</sup>Independently indicate a methyl group, an ethyl group, or a phenyl group. n indicates the number of repetitions in parentheses, and is preferably 10 or more and 150 or less.
Specific examples of the structural units represented by the equations (11) and (12) are shown below, but the present invention is not limited thereto.<chemistry num="32"><img file="JP6603555B2_D0032.tif" /></chemistry>
<chemistry num="33"><img file="JP6603555B2_D0033.tif" /></chemistry>
From the viewpoint of the effect of the present invention, the proportion of the polysiloxane structure represented by the formula (1) in the polyarylate resin and the polycarbonate resin is preferably 0.5% by mass or more and 50% by mass or less. That is, the content of the structure represented by the formula (1) in the polyarylate resin A is preferably 0.5% by mass or more and 50% by mass or less with respect to the content of the entire polyarylate resin A. Further, the content of the structure represented by the formula (1) in the polycarbonate resin B is preferably 0.5% by mass or more and 50% by mass or less with respect to the content of the entire polycarbonate resin B. When it is 0.5% by mass or more, it is preferable in that better cleaning property can be obtained, and when it is 50% by mass or less, it is preferable in that good electrical characteristics of the photoconductor can be obtained.
The ratio of the polysiloxane structure represented by the above formula (1) is the ratio of the resin, which is a general method.<sup>1</sup>It can be confirmed by a conversion method based on the peak area ratio of hydrogen atoms by 1 H-NMR measurement.
Further, in the present invention, the viscosity average molecular weight (Mv) of the polyarylate resin A and the polycarbonate resin B is preferably 1,000 or more and 200,000 or less. Further, it is preferably 5,000 or more and 100,000 or less from the viewpoint of synthesis and film forming property.
In the present invention, the charge transport layer, which is the surface layer (outermost layer) of the electrophotographic photosensitive member, contains at least one resin selected from the group consisting of polyarylate resin A and polycarbonate resin B. Other resins may be used in combination as long as the effect is not impaired. In that case, the total content of the polyarylate resin A and the polycarbonate resin B in the charge transport layer may be 0.1% by mass or more and 50% by mass or less with respect to the total mass of the total solid content contained in the charge transport layer. preferable. Further, when the polyarylate resin A and the polycarbonate resin B have a polysiloxane structure represented by the formula (2) at least a part of the terminals, the range is as follows from the viewpoint that good electrical characteristics of the photoconductor can be obtained. Is preferable. That is, the total content of the polyarylate resin A and the polycarbonate resin B in the charge transport layer is 0.1% by mass or more and 20% by mass or less with respect to the total mass of the total solid content contained in the charge transport layer. preferable.
Examples of resins that can be used together include acrylic resin, acrylonitrile resin, allyl resin, alkyd resin, epoxy resin, silicone resin, phenol resin, phenoxy resin, butyral resin, polyacrylamide resin, polyacetal resin, polyamideimide resin, and polyamide resin. Polyallyl ether resin, polyallylate resin, polyimide resin, polyurethane resin, polyester resin, polyethylene resin, polycarbonate resin, polystyrene resin, polysulfone resin, polyvinyl butyral resin, polyphenylene oxide resin, polybutadiene resin, polypropylene resin, methacrylic resin, urea resin, Examples thereof include vinyl chloride resin and vinyl acetate resin. In particular, polyester resin, polyarylate resin, and polycarbonate resin are preferable. Further, a polyarylate resin having a structural unit represented by the formula (9) or a polycarbonate resin having a structural unit represented by the formula (11) is more preferable. Specific examples of the structural unit represented by the formula (9) and the structural unit represented by the formula (11) are as described above. The resin that can be used in combination with the polyarylate resin A or the polycarbonate resin B can be used alone, as a mixture, or as a copolymer of one or more.
The charge transport layer contains a charge transport material. Examples of the charge transporting substance include a triarylamine compound, a hydrazone compound, a styryl compound, a pyrazoline compound, an oxazole compound, a thiazole compound, a stilben compound, a butadiene compound, and an enamine compound. Only one kind of these charge transporting substances may be used, or two or more kinds may be used.
Specific examples of charge transporting substances are shown below, but the present invention is not limited to these.<chemistry num="34"><img file="JP6603555B2_D0034.tif" /></chemistry>
The charge transport layer is formed by at least one resin selected from the group consisting of polyarylate resin A and polycarbonate resin B, and a coating film of a coating liquid for a charge transport layer obtained by dissolving a charge transport substance in a solvent. be able to. Further, as described above, a resin other than the polyarylate resin A and the polycarbonate resin B may be used in combination. Further, the charge transport layer may have a laminated structure, and in that case, at least the charge transport layer on the outermost surface side is provided with at least one resin selected from the group consisting of the polyarylate resin A and the polycarbonate resin B. The ratio of the charge-transporting substance to the total resin in the charge-transporting layer is preferably in the range of 3:10 to 20:10 (mass ratio), and more preferably in the range of 5:10 to 12:10 (mass ratio). Examples of the solvent used in the coating liquid for the charge transport layer include a ketone solvent, an ester solvent, an ether solvent, and an aromatic hydrocarbon solvent. These solvents may be used alone or in combination of two or more. Among these solvents, it is preferable to use an ether solvent or an aromatic hydrocarbon solvent from the viewpoint of resin solubility. The film thickness of the charge transport layer is preferably 5 μm or more and 50 μm or less, and more preferably 10 μm or more and 35 μm or less.
Various additives can be added to each layer of the electrophotographic photosensitive member. Examples of the additive include deterioration inhibitors such as antioxidants, ultraviolet absorbers and light-resistant stabilizers, and particles such as organic particles and inorganic particles. Examples of the deterioration inhibitor include a hindered phenol-based antioxidant, a hindered amine-based light-resistant stabilizer, a sulfur atom-containing antioxidant, and a phosphorus atom-containing antioxidant. Examples of the organic particles include polymer resin particles such as fluorine atom-containing resin particles, polystyrene resin particles, and polyethylene resin particles. Examples of the inorganic particles include metal oxide particles such as silica and alumina . When applying the coating liquid for each of the above layers, a coating method such as a dip coating method (immersion coating method), a spray coating method, a spinner coating method, a roller coating method, a Meyer bar coating method, or a blade coating method can be used. ..
By measuring the abundance ratio of silicon atoms to all atoms excluding hydrogen atoms on the outermost surface of the electrophotographic photosensitive member, the degree of abundance of silicon-containing compounds on the outermost surface of the surface layer can be known. In the present invention, when the polyarylate resin A has the structural unit represented by the formula (5), or the polycarbonate resin B has the structural unit represented by the formula (8), the abundance ratio of silicon atoms is as follows. Is preferable. That is, the abundance ratio of silicon atoms to all atoms excluding hydrogen atoms on the outermost surface of the surface layer (charge transport layer) of the electrophotographic photosensitive member measured by X-ray photoelectron spectroscopy (ESCA) is 0.6 atoms% or more. Is preferable. When it is 0.6atoms% or more, better cleaning property can be obtained. Furthermore, it is preferable that the content is 20 atoms% or less because good cleaning properties can be obtained more stably. ESCA has no measurement sensitivity to hydrogen atoms.
In the present invention, the measurement of the abundance ratio of silicon atoms to all atoms excluding hydrogen atoms on the outermost surface of the surface layer of the electrophotographic photosensitive member by X-ray photoelectron spectroscopy (ESCA) was performed as follows. Equipment used: Quantum 2000 Scanning ESCA Microprobe manufactured by PHI (Physical Electronics Industries, INC.) Measurement conditions: X-ray source: Al Ka1486.6eV (25W15kV) Measurement area: φ100 μm Spectroscopic region: 1500 × 300 μm, angle 45 ° Pass Energy: From the peak intensity of each element measured under the conditions of 117.40 eV or higher, the surface atomic concentration (atoms%) is calculated using the relative sensitivity factor provided by PHI. The measurement peak top range of each element constituting the surface layer is as follows. C1s: 278 ~ 298eVF1s: 680 ~ 700eVSi2p: 90 ~ 110eVO1s: 525 ~ 545eVN1s: 390 ~ 410eV
<Toner> Next, the toner used in the present invention will be described. The toner has toner particles and organic-inorganic composite fine particles existing on the surface of the toner particles. Further, the organic-inorganic composite fine particles include inorganic fine particles and resin particles, and the inorganic fine particles exist so that convex portions derived from the particle shape of the inorganic fine particles are formed on the surface of the resin particles. ing. That is, the inorganic fine particles are exposed on the surface of the resin particles so that convex portions derived from the particle shape of the inorganic fine particles are formed on the surface. In order to improve the cleanability, it is important that the material added to the surface of the toner particles is an organic-inorganic composite fine particle having a convex portion. The organic-inorganic composite fine particles have a structure in which the inorganic fine particles are exposed on the surface of the resin particles, for example, a structure in which the inorganic fine particles are embedded in the surface of the resin particles, and the surface of the organic-inorganic composite fine particles is convex derived from the inorganic fine particles. There is a part. It is considered that these convex portions act as anchors for the surface of the toner particles, making it difficult for the organic-inorganic composite fine particles to migrate from the toner particles to the photoconductor.
Further, when the surface layer of the photoconductor contains at least one resin selected from the group consisting of the polyarylate resin A and the polycarbonate resin B described above, the phenomenon of organic-inorganic composite fine particles being transferred from the toner particles to the photoconductor occurs. More suppressed. Although the details of the mechanism are not clear, it is considered that the convex portion derived from the inorganic fine particles formed on the surface of the organic-inorganic composite fine particles and the polyarylate resin A and the polycarbonate resin B have a small adhesive force when they come into contact with each other. In this way, in the present invention, the generation of organic-inorganic composite fine particles as an external additive that migrates to the surface of the photoconductor, which is one of the causes of poor cleaning, is suppressed. As a result, it has good cleanability even in the initial stage of use of a new process cartridge or electrophotographic apparatus, and it is possible to suppress deterioration of image quality due to contamination of the charging member.
From the viewpoint of further obtaining the effects of the present invention, it is more preferable that the surface abundance of the inorganic fine particles constituting the organic-inorganic composite fine particles is 20% or more and 70% or less. The organic-inorganic composite fine particles preferably have a number average particle size of 70 nm or more and 500 nm or less. When the number average particle size is 70 nm or more and 500 nm or less, the organic-inorganic composite fine particles are likely to be stably present on the surface of the toner particles. Furthermore, it is more preferable that the number average particle size is 70 nm or more and 200 nm or less. The number average particle size of the organic-inorganic composite fine particles can be adjusted by changing the particle size of the inorganic fine particles used for the organic-inorganic composite fine particles and the amount ratio of the inorganic fine particles to the resin. The inorganic fine particles of the organic-inorganic composite fine particles are preferably silica or metal oxide fine particles. When the inorganic fine particles of the organic-inorganic composite fine particles are silica or metal oxide fine particles, good developability can be obtained because of excellent chargeability. The organic-inorganic composite fine particles can be produced, for example, according to the description of Examples of WO2013 / 063291. The content of the organic-inorganic composite fine particles is preferably 0.5% by mass or more and 5.0% by mass or less with respect to the content of the toner particles.
The binder resin in the toner particles in the present invention will be described. Examples of the binding resin include polyester resin, vinyl resin, epoxy resin, and polyurethane resin. In particular, from the viewpoint of uniformly dispersing the charge control agent having polarity, it is generally preferable to contain a polyester resin having high polarity from the viewpoint of developability.
The polyester resin can be obtained, for example, by reacting a divalent alcohol component with a divalent acid component. The divalent alcohol component includes chain aliphatic diols such as ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, dipropylene glycol, and 1,4-butanediol. , 1,4-butadiene glycol, trimethylene glycol, tetramethylene glycol, pentamethylene glycol, hexamethylene glycol, octamethylene glycol, nonamethylene glycol, decamethylene glycol, neopentyl glycol and the like.
Examples of the aromatic diol include bisphenol represented by the following formula (e-1) and its derivative, and diols represented by the following formula (e-2).<chemistry num="35"><img file="JP6603555B2_D0035.tif" /></chemistry>(In formula (e-1), R represents an ethylene group or a propylene group, x and y are integers of 1 or more, and the average value of x + y is 2 or more and 10 or less.)
<chemistry num="36"><img file="JP6603555B2_D0036.tif" /></chemistry>(In equation (e-2), R'is-CH<sub>2</sub>CH<sub>2</sub>, CH<sub>2</sub>CH (CH)<sub>3</sub>)-, CH<sub>2</sub>C (CH<sub>3</sub>)<sub>2</sub>-Indicates. )
Divalent acid components include benzenedicarboxylic acids such as phthalic acid, terephthalic acid, isophthalic acid, and phthalic anhydride or their anhydrides, lower alkyl esters; alkyldicarboxylic acids such as succinic acid, adipic acid, sebacic acid, and azelaic acid. Or its anhydride, lower alkyl ester; alkenyl succinic acid or alkyl succinic acid such as n-dodecenyl succinic acid, n-dodecyl succinic acid, or its anhydride, lower alkyl ester; fumaric acid, maleic acid, citraconic acid, itaconic acid, etc. Dicarboxylic acids such as unsaturated dicarboxylic acids or anhydrides thereof, lower alkyl esters; and derivatives thereof can be mentioned.
In the present invention, the polyester is obtained by condensing a carboxylic acid component containing 90 mol% or more of an aromatic carboxylic acid compound and an alcohol component, and 80 mol% or more of the aromatic carboxylic acid compound is terephthalic acid and / or isophthalic acid. It is preferably an acid.
In addition, by using or using a trivalent or higher alcohol component or a trivalent or higher acid component that acts as a cross-linking component alone or in combination, more uniform dispersibility of an internal additive such as magnetic iron oxide or wax is achieved. It is preferable to do so.
Polyhydric alcohol components of trihydric or higher include sorbitol, 1,2,3,6-hexanetetrol, 1,4-sorbitan, pentaerythritol, dipentaerythritol, tripentaerythritol, 1,2,4-butanetriol. , 1,2,5-pentanetriol, glycerol, 2-methylpropanetriol, 2-methyl-1,2,4-butanetriol, trimethylolethane, trimethylolpropane, 1,3,5-trihydroxybenzene Be done.
Trivalent or higher polyvalent carboxylic acid components include trimellitic acid, pyromellitic acid, 1,2,4-benzenetricarboxylic acid, 1,2,5-benzenetricarboxylic acid, 2,5,7-naphthalene tricarboxylic acid, 1,2,4-naphthalentricarboxylic acid, 1,2,4-butanetricarboxylic acid, 1,2,5-hexanetricarboxylic acid, 1,3-dicarboxy-2-methyl-2-methylenecarboxypropane, tetra (methylene) Examples include carboxyl) methane, 1,2,7,8-octanetetracarboxylic acid, empole trimeric acid, and anhydrides thereof.
The content of the alcohol component is 40 mol% or more and 60 mol% or less, preferably 45 mol% or more and 55 mol% or less, and the content of the acid component is 40 mol% or more and 60 mol% or less, preferably 45 mol% or more. It is preferably 55 mol% or less. The polyester resin is usually obtained by a generally known polycondensation.
On the other hand, examples of the vinyl-based monomer for producing the vinyl-based resin include the following. Styrene; o-methylstyrene, m-methylstyrene, p-methylstyrene, p-methoxystyrene, p-phenylstyrene, p-chlorostyrene, 3,4-dichlorostyrene, p-ethylstyrene, 2,4-dimethyl Derivatives of styrene such as styrene, pn-butylstyrene, p-tert-butylstyrene, pn-hexylstyrene, pn-octylstyrene, pn-nonylstyrene, pn-decylstyrene, pn-dodecylstyrene; ethylene, propylene, butylene, Unsaturated monoolefins such as isobutylene; unsaturated polyenes such as butadiene and isoprene; vinyl halides such as vinyl chloride, vinylidene chloride, vinyl bromide, vinyl boiled; vinyl acetate, vinyl propionate, vinyl benzoate Vinyl esters such as: methyl methacrylate, ethyl methacrylate, propyl methacrylate, n butyl methacrylate, isobutyl methacrylate, n octyl methacrylate, dodecyl methacrylate, diethylhexyl methacrylate, stearyl methacrylate, phenyl methacrylate, methacrylic acid Α-Methylene aliphatic monocarboxylic acid esters such as dimethylaminoethyl and diethylaminoethyl methacrylate; methyl acrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate, propyl acrylate, n-octyl acrylate, acrylic Acrylic acid esters such as dodecyl acid, 2-ethylhexyl acrylate, stearyl acrylate, 2-chloroethyl acrylate, phenyl acrylate; vinyl ethers such as vinyl methyl ether, vinyl ethyl ether, vinyl isobutyl ether; vinyl methyl ketone, vinyl Vinyl ketones such as hexyl ketone, methyl isopropenyl ketone; N-vinyl compounds such as N-vinylpyrrole, N-vinylcarbazole, N-vinylindole, N-vinylpyrrolidone; vinylnaphthalins; Such as acrylic acid or methacrylic acid derivative can be mentioned.
In addition, unsaturated dibasic acids such as maleic acid, citraconic acid, itaconic acid, alkenyl succinic acid, fumaric acid, mesaconic acid; such as maleic acid anhydride, citraconic acid anhydride, itaconic acid anhydride, alkenyl succinic acid anhydride. Unsaturated dibasic acid anhydride; maleic acid methyl half ester, maleic acid ethyl half ester, maleic acid butyl half ester, citraconic acid methyl half ester, citraconic acid ethyl half ester, citraconic acid butyl half ester, itaconic acid methyl half ester, Half ester of unsaturated dibasic acid such as alkenyl succinic acid methyl half ester, fumaric acid methyl half ester, mesaconic acid methyl half ester; unsaturated dibasic acid ester such as dimethyl maleic acid, dimethyl fumaric acid; acrylic acid, methacrylic acid Α, β-unsaturated acids such as crotonic acid and silicic acid; α, β-unsaturated acid anhydrides such as crotonic acid anhydrides and silicic acid anhydrides, the α, β-unsaturated acids and lower fatty acids. Anhydrous; examples thereof include alkenyl malonic acid, alkenyl glutaric acid, alkenyl adipic acid, these acid anhydrides and monomers having a carboxyl group such as their monoesters.
In addition, acrylic acids or methacrylate esters such as 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate; 4- (1-hydroxy-1-methylbutyl) styrene, 4- (1-hydroxy-1). -Methylhexyl) Examples thereof include monomers having a hydroxy group such as styrene.
In the toner used in the present invention, the vinyl-based resin of the binder resin may have a crosslinked structure crosslinked with a crosslinking agent having two or more vinyl groups. Examples of the cross-linking agent used in this case include divinylbenzene and divinylnaphthalene as aromatic divinyl compounds; and, for example, ethylene glycol diacrylate and 1,3-butylene glycol di as diacrylate compounds linked by an alkyl chain. Acrylate, 1,4-butanediol diacrylate, 1,5-pentanediol diacrylate, 1,6-hexanediol diacrylate, neopentyl glycol diacrylate, and acrylates of the above compounds replaced with methacrylate. Examples of diacrylate compounds linked by an alkyl chain containing an ether bond include diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, polyethylene glycol # 400 diacrylate, and polyethylene glycol # 600 diacrylle. Ito, dipropylene glycol diacrylate, and the above compounds in which the acrylate is replaced with methacrylate; as diacrylate compounds enclosed in chains containing aromatic groups and ether bonds, for example, poly. Oxyethylene (2) -2,2-bis (4-hydroxyphenyl) propan diacrylate, polyoxyethylene (4) -2,2-bis (4-hydroxyphenyl) propandiacrylate, and the above compounds. Examples thereof include those in which the acrylate of the above is replaced with a metal acrylate; examples of the polyester type diacrylate compounds include the trade name MANDA (Nippon Kayaku). Examples of the polyfunctional cross-linking agent include pentaerythritol triacrylate, trimethylolethane triacrylate, trimethylolpropane triacrylate, tetramethylolmethanetetraacrylate, oligoester acrylate, and acrylates of the above compounds replaced with methacrylate. Triallyl cyanurate, triallyl trimellitate; can be mentioned. These cross-linking agents are preferably 0.
Among these cross-linking agents, those preferably used include aromatic divinyl compounds (particularly divinylbenzene) and diacrylate compounds linked by chains containing aromatic groups and ether bonds.
Examples of the polymerization initiator used in producing a vinyl-based copolymer include 2,2'-azobisisobutyronitrile and 2,2'-azobis (4-methoxy-2,4-dimethyl). Valeronitrile), 2,2'-azobis (2,4-dimethylvaleronitrile), 2,2'-azobis (2-methylbutyronitrile), dimethyl-2,2'-azobisisobutyrate, 1, 1'-azobis (1-cyclohexanecarbonitrile), 2- (carbamoylazo) -isobutyronitrile, 2,2'-azobis (2,4,4-trimethylpentane), 2-phenylazo-2,4-dimethyl- Ketone peroxides such as 4-methoxyvaleronitrile, 2,2-azobis (2-methylpropane), methylethylketone peroxide, acetylacetone peroxide, cyclohexanone peroxide, 2,2-bis (t-butylperoxy) butane , T-butyl hydroperoxide, cumene hydroperoxide, 1,1,3,3-tetramethylbutyl hydroperoxide, di-t-butyl peroxide, t-butyl cumyl peroxide, dicumyl peroxide, α, α'-bis (t-butylperoxyisopropyl) benzene, isobutyl peroxide, octanoyl peroxide, decanoyl peroxide, lauroyl peroxide, 3,5,5-trimethylhexanoyl peroxide, benzoyl peroxide, m-toluyl peroxide, diisopropylperoxydicarbonate, di-2-ethylhexylperoxydicarbonate, di-n-propylperoxydicarbonate, di-2- Toxiethyl peroxycarbonate, dimethoxyisopropylperoxydicarbonate, di (3-methyl-3-methoxybutyl) peroxycarbonate, acetylcyclohexylsulfonyl peroxide, t-butylperoxyacetate, t-butylperoxyisobutyrate , T-Butylperoxyneodecanoate, t-Butylperoxy-2-ethylhexanoate, t-Butylperoxylaurate, t-Butylperoxybenzoate, t-Butylperoxyisopropylcarbonate, Di- t-Butylperoxyisophthalate, t-butylperoxyallyl carbonate, t-amylperoxy-2-ethylhexanoate, di-t-butylperoxyhexahydroterephthalate, di-t-butylperoxyazelate Can be mentioned.
From the viewpoint of storage stability and low-temperature fixability, the binder resin preferably has a glass transition point (Tg) of 45 ° C or more and 70 ° C or less, preferably 50 ° C or more and 70 ° C or less. The softening point Tm is preferably 90 ° C or higher and 130 ° C or lower from the viewpoint of suppressing the high temperature offset at the end while maintaining the low temperature fixability.
In the present invention, the weight average particle size of the toner is preferably 2.5 μm or more and 10.0 μm or less, more preferably 5.0 μm or more and 9.0 μm or less, and particularly preferably 6.0 μm or more and 8.0 μm or less.
The toner used in the present invention may further contain magnetic iron oxide particles and may be used as a magnetic toner. In this case, the magnetic iron oxide particles can also serve as a colorant. The magnetic iron oxide particles contained in the magnetic toner include iron oxide particles such as magnetite, hematite, and ferrite, metals such as iron, cobalt, and nickel, or these metals and aluminum, cobalt, copper, lead, magnesium, tin, and the like. Examples include alloys of metals such as zinc, antimony, bismuth, calcium, manganese, titanium, tungsten, vanadium and mixtures thereof. These magnetic iron oxide particles preferably have an average particle size of 2 μm or less, preferably 0.05 μm or more and 0.5 μm or less. The amount contained in the toner is 20 parts by mass or more and 200 parts by mass or less with respect to 100 parts by mass of the binder resin, and particularly preferably 40 parts by mass or more and 150 parts by mass or less with respect to 100 parts by mass of the binder resin.
As the colorant used in the present invention, carbon black, grafted carbon, or a yellow / magenta / cyan colorant shown below is used as the black colorant and the colorant is adjusted to black. Examples of the yellow colorant include compounds typified by condensed azo compounds, isoindolinone compounds, anthraquinone compounds, azo metal complexes, methine compounds, and allylamide compounds. Examples of the magenta colorant include condensed azo compounds, diketopyrrolopyrrole compounds, anthraquinones, quinacridone compounds, basic dye lake compounds, naphthol compounds, benzimidazolone compounds, thioindigo compounds, perylene compounds and the like. Examples of the cyan colorant include a copper phthalocyanine compound and its derivative, an anthraquinone compound, and a basic dye lake compound. These colorants can be used alone or in the form of a solid solution. The colorant is selected in terms of hue angle, saturation, lightness, weather resistance, OHP transparency, and dispersibility in toner. The amount of the colorant added is 1 part by mass or more and 20 parts by mass or less with respect to 100 parts by mass of the binder resin.
The toner used in the present invention may contain wax. Wax includes the following. Aliphatic hydrocarbon waxes such as low molecular weight polyethylene, low molecular weight polypropylene, polyolefin copolymers, polyolefin waxes, microcrystalline waxes, paraffin waxes, Fishertropch waxes; oxides of aliphatic hydrocarbon waxes such as polyethylene oxide wax Or their block copolymers; plant waxes such as candelilla wax, carnauba wax, wood wax, jojoba wax; animal waxes such as mitsuro, lanolin, whale wax; minerals such as ozokelite, ceresin, petrolactam Waxes; waxes containing mainly aliphatic esters such as montanic acid ester wax and Custer wax; and partially or completely deoxidized aliphatic esters such as deoxidized carnauba wax. In addition, saturated linear fatty acids such as palmitic acid, stearic acid, montanic acid, or even longer chain alkylcarboxylic acids with long alkyl groups; unsaturated fatty acids such as brazic acid, eleostearic acid, parinaphosphate; stearyl alcohols. , Eikosyl alcohols, behenyl alcohols, kaunavir alcohols, ceryl alcohols, melisyl alcohols, or saturated alcohols such as alkyl alcohols with longer chain alkyl groups; polyhydric alcohols such as sorbitol; linoleic acid amides, oleic acid amides, laurin Aliphatic amides such as acid amides; saturated aliphatic bisamides such as methylene bisstearic acid amides, ethylene biscapric acid amides, ethylene bislauric acid amides, hexamethylene bisstearic acid amides; ethylene bisoleic acid amides, hexamethylene bisoleic acid. Unsaturated fatty acid amides such as amides, N, N'-diorail adipic acid amides, N, N'-diorail sebacic acid amides; m-xylenebis stearate amides, N, N'-distearyl isophthalic acid amides Aromatic bisamides such as; Aliphatic metal salts such as calcium stearate, calcium laurate, zinc stearate, magnesium stearate (generally referred to as metal soap); grafted on aliphatic hydrocarbon waxes using vinyl monomers such as styrene and acrylic acid. Chemicalized waxes; partial esters of fatty acids and polyhydric alcohols such as behenic acid monoglycerides; methyl ester compounds with hydroxyl groups obtained by hydrogenating vegetable fats and oils. In addition, these waxes have a sharp molecular weight distribution using a press sweating method, a solvent method, a recrystallization method, a vacuum distillation method, a supercritical gas extraction method, or a fusion liquid crystallography method, low molecular weight solid fatty acids, and low molecular weight. Solid alcohols, low molecular weight solid compounds, and those from which other impurities have been removed are also preferably used.
Specific examples of waxes that can be used as mold release agents include Viscol® 330-P, 550-P, 660-P, TS-200 (Sanyo Kasei Kogyo Co., Ltd.), High Wax 400P, 200P, 100P, 410P, 420P, 320P, 220P, 210P, 110P (Mitsui Chemicals), Sazole H1, H2, C80, C105, C77 (Schumann Sazol), HNP-1, HNP-3, HNP-9, HNP-10, HNP-11, HNP-12 (Nippon Seiwa Co., Ltd.), Unilin (registered trademark) 350, 425, 550, 700, Unisid (registered trademark), Unisid (registered trademark) 350, 425, 550, 700 (Toyo Petrolite) , Wood wax, beeswax, rice wax, candelilla wax, carnauba wax (available at Ceralica NODA Co., Ltd.).
It is preferable to use a charge control agent for the toner used in the present invention in order to stabilize its chargeability. As such a charge control agent, an organometallic complex or a chelate compound in which an acid group or a hydroxyl group existing at the terminal of the binder resin and a central metal easily interact with each other is effective. Examples thereof include monoazo metal complexes; acetylacetone metal complexes; metal complexes or metal salts of aromatic hydroxycarboxylic acids or aromatic dicarboxylic acids. Specific examples that can be used are Spilon Black TRH, T-77, T-95 (Hodogaya Chemical Co., Ltd.), BONTRON (registered trademark) S-34, S-44, S-54, E-84, E- 88, E-89 (Orient Chemical Co., Ltd.) can be mentioned. Further, the charge control resin can also be used in combination with the above-mentioned charge control agent.
It is preferable to add a fluidity improver to the toner used in the present invention in order to improve the fluidity and chargeability of the toner. Examples of the fluidity improver include fluororesin powders such as vinylidene fluoride fine powder and polytetrafluoroethylene fine powder; fine powder silica such as wet manufacturing silica and dry manufacturing silica, fine powder titanium oxide, and fine powder alumina. Treated silica surface-treated with silane compounds, titanium coupling agents, and silicone oil; oxides such as zinc oxide and tin oxide; strontium titanate, barium titanate, calcium titanate, strontium zirconate, and calcium zirconate. Compound oxides such as: Calcium titanate and carbonate compounds such as magnesium carbonate. A preferable fluidity improver is a fine powder produced by vapor phase oxidation of a silicon halogen compound, which is so-called dry silica or fumed silica. For example, it utilizes the pyrolysis oxidation reaction of silicon tetrachloride gas in oxyhydrogen flame, and the basic reaction formula is as follows. SiCl<sub>4</sub>+ 2H<sub>2</sub>+ O<sub>2</sub> SiO<sub>2</sub>+ 4HCl In this manufacturing process, it is also possible to obtain composite fine powders of silica and other metal oxides by using other metal halogen compounds such as aluminum chloride or titanium chloride together with silicon halogen compounds. Also includes. It is preferable that the average primary particle size in the particle size distribution based on the number of fluidity improvers is 5 nm or more and 30 nm or less because high chargeability and fluidity can be obtained.
Furthermore, as the fluidity improver used in the present invention, treated silica fine powder obtained by hydrophobizing the silica fine powder produced by the vapor phase oxidation of the silicon halogen compound is more preferable. The fluidity improver has a specific surface area of 30 m due to nitrogen adsorption measured by the BET method.<sup>2</sup>/ g or more 300m<sup>2</sup>It is preferably less than / g. It is preferable to use a total amount of 0.01 part by mass or more and 3 parts by mass or less of the fluidity improver with respect to 100 parts by mass of the toner.
The toner used in the present invention can be mixed with the fluidity improver and, if necessary, further mixed with another external additive (for example, a charge control agent) and used as a one-component developer. It can also be used as a two-component developer in combination with a carrier. As the carrier when used in the two-component developing method, all conventionally known carriers can be used. Specifically, metals such as surface-oxidized or unoxidized iron, nickel, cobalt, manganese, chromium, and rare earths, and alloys or oxides thereof are preferably used.
Further, those in which substances such as styrene resin, acrylic resin, silicone resin, fluorine resin and polyester resin are adhered or coated on the surface of these carrier particles are preferably used.
The method for producing the toner used in the present invention is not particularly limited, but a pulverization method is preferable. To prepare toner by the pulverization method, the binder resin, colorant, wax, charge control agent, etc. that make up the toner particles are sufficiently mixed with a mixer such as a Henschel mixer or ball mill, and then a twin-screw kneading extruder is used. Wax, magnetic iron oxide particles and metal-containing compounds are dispersed or dissolved in melt-kneading using a heat kneader such as a heating roll, a kneader, or an extruder to dissolve the resins with each other. The toner particles according to the present invention can be obtained by classifying.
Then, the toner particles according to the present invention can be obtained by sufficiently mixing the organic-inorganic composite fine particles and, if necessary, a desired external agent other than the organic-inorganic composite fine particles with a mixer such as a Henschel mixer. Examples of the mixer include the following. Henschel Mixer (manufactured by Nippon Coke); Super Mixer (manufactured by Kawata); Ribocorn (manufactured by Okawara Seisakusho); Nowter Mixer, Turbulizer, Cyclomix (manufactured by Hosokawa Micron); Spiral Pin Mixer (manufactured by Pacific Kiko) Ladyge mixer (manufactured by Matsubo). Examples of the kneading machine include the following. KRC Kneader (Kurimoto Iron Works); Bus Co Kneader (Buss); TEM Extruder (Toshiba Machine Co., Ltd.); TEX Biaxial Kneader (Japan Steel Works); PCM Kneader (Ikegai) Iron Works); Three roll mill, mixing roll mill, kneader (Inoue Mfg. Co., Ltd.); Kneedex (Mitsui Mine Co., Ltd.); MS type pressurized kneader, Nider Ruder (Moriyama Mfg. Co., Ltd.); Made by Tokorosha). Examples of the crusher include the following. Counter jet mill, micron jet, innomizer (manufactured by Hosokawa Micron); IDS type mill, PJM jet crusher (manufactured by Nippon Pneumatic Industries); cross jet mill (manufactured by Kurimoto Iron Works); Ulmax (manufactured by Nippon Soda Engineering Co., Ltd.) ); SK Jet O Mill (manufactured by Seishin Enterprise); Cryptron (manufactured by Kawasaki Heavy Industries); Turbo Mill (manufactured by Turboe Co., Ltd.); Super Rotor (manufactured by Nisshin Engineering Co., Ltd.). Examples of the classifier include the following. Classile, Micron Classifier, Spedic Classifier (Seishin Enterprise); Turbo Classifier (Nisshin Engineering); Micron Separator, Turboplex (ATP), TSP Separator (Hosokawa Micron); Elbow Jet (Japan) Iron Mining Co., Ltd.), Dispersion Separator (Nittetsu Mining Co., Ltd.); YM Microcut (Yasukawa Shoji Co., Ltd.). Examples of the sieving device used for sieving coarse particles include the following. Ultra Sonic (Koei Sangyo Co., Ltd.); Resona Sheave, Gyro Shifter (Tokuju Kosakusho Co., Ltd.); Vibra Sonic System (Dalton Co., Ltd.); Soni Clean (Shinto Kogyo Co., Ltd.); Turbo Screener (Turbo E Industry Co., Ltd.); Micro shifter (manufactured by Makino Sangyo Co., Ltd.); Circular vibrating sieve. As another method, toner can be produced by a so-called polymerization method such as an emulsion polymerization method, a suspension polymerization method, or a dissolution suspension method. The method for measuring the physical properties of the toner used in the present invention is as follows. Production examples and examples described below are also based on this method.
<Measuring method of number average particle size of organic-inorganic composite fine particles> Measurement of the number average particle size of organic-inorganic composite fine particles is performed using a scanning electron microscope "S-4800" (trade name; manufactured by Hitachi, Ltd.). By observing the toner externally attached with the organic-inorganic composite fine particles, the major axis (the length of the longest part) of the primary particles of 100 organic-inorganic composite fine particles is randomly measured in a field magnified up to 200,000 times. To find the number average particle size. The observation magnification is adjusted as appropriate.
<Method of measuring the surface abundance of inorganic fine particles constituting organic-inorganic composite fine particles> The surface abundance of inorganic fine particles constituting organic-inorganic composite fine particles is measured by ESCA (X-ray photoelectron spectroscopic analysis). It is calculated from the amount of atoms derived from inorganic fine particles present on the surface. ESCA is an analytical method that detects atoms in the region of several nm or less in the depth direction of the sample surface. Therefore, it is possible to detect atoms on the surface of the organic-inorganic composite fine particles. When measuring the surface abundance of the inorganic fine particles constituting the organic-inorganic composite fine particles externally attached to the toner, for example, the organic-inorganic composite fine particles are isolated from the toner as follows. First, the toner is "Contaminone N" (10% by mass aqueous solution of neutral detergent for cleaning pH 7 precision measuring instruments consisting of nonionic surfactant, anionic surfactant, and organic builder, manufactured by Wako Pure Chemical Industries, Ltd.). Disperse in the added ion-exchanged water by ultrasonic waves and let stand for 24 hours. By collecting the supernatant and drying it, the organic-inorganic composite fine particles can be isolated. When a plurality of external additives are added to the toner, the supernatant can be separated by a centrifugal separation method to isolate organic-inorganic composite fine particles. The ESCA equipment and measurement conditions are as follows. Equipment used: ULVAC-PHI Quantum 2000 Analytical method: Narrow analysis Measurement condition: X-ray source: Al-Kα X-ray condition: 100 μm 25W15kV Photoelectron uptake angle: 45 ° PassEnergy: 58.70eV Measurement range: φ100 μm or more Do. Here, an example in which silica particles are used as the inorganic fine particles of the organic-inorganic composite fine particles will be described. First, the organic-inorganic composite fine particles are measured, and the number of Si atoms derived from silica with respect to the total atomic weight of the organic-inorganic composite fine particles excluding hydrogen atoms is determined. Next, the inorganic fine particles (silica particles) constituting the organic-inorganic composite fine particles are measured, and the number of Si atoms derived from silica with respect to the total atomic weight of the inorganic fine particles (silica particles) excluding hydrogen atoms is determined. The ratio of the number of Si atoms when measuring the organic-inorganic composite fine particles to the number of Si atoms when measuring the silica particles is defined as the surface abundance ratio (%) of the inorganic fine particles constituting the organic-inorganic composite fine particles. For example, as the silica particles, the colloidal silica particles (number average particle size 101 nm) described in the production example are used for the calculation. When particles other than silica are used as the inorganic fine particles, the abundance rate is similarly calculated by the above method by measuring the atomic quantity of the inorganic element contained in the inorganic fine particles instead of the Si atomic quantity. be able to.
<Method for quantifying organic-inorganic composite fine particles in toner> For toner in which multiple external additives are added to the toner particles, when measuring the content of the organic-inorganic composite fine particles, remove the external additives from the toner. Furthermore, it is necessary to isolate and recover multiple types of external preparations. Specific examples include the following methods. (1) Put 5 g of toner in a sample bottle and add 200 ml of methanol. (2) Disperse the sample with an ultrasonic cleaner for 5 minutes to separate the external additive. (3) Separate the toner particles and the external additive by suction filtration (10 μm membrane filter). Alternatively, a neodymium magnet may be applied to the bottom of the sample bottle to fix the toner particles and separate only the supernatant liquid. (4) Repeat steps (2) and (3) above three times in total. By the above operation, the external additive is isolated from the toner. The recovered aqueous solution is centrifuged to separate and recover the organic-inorganic composite fine particles and other external additives. When the external additive is only organic-inorganic composite fine particles, the operation by this centrifuge does not have to be performed. Then, the solvent is removed, the mixture is sufficiently dried in a vacuum dryer, and the weight is measured to obtain the content of the organic-inorganic composite fine particles.
<Image forming method> The image forming method of the present invention includes a charging step of charging an electrophotographic photosensitive member, an electrostatic latent image forming step of forming an electrostatic latent image on the surface of the charged electrophotographic photosensitive member, and an electron. A development step of developing a toner into an electrostatic latent image on the surface of a photographic photosensitive member to form a toner image, and transferring a toner image on the surface of an electrophotographic photosensitive member to a transfer material with or without an intermediate transfer body. An image forming method including a transfer step of performing and a cleaning step of removing transfer residual toner from the surface of the electrophotographic photosensitive member, wherein the above-mentioned <electrophotographic photosensitive member> is used as the electrophotographic photosensitive member and the above-mentioned toner is used. <Toner> is used. The image forming method of the present invention will be further described by using an electrophotographic apparatus as an example of an image forming apparatus to which the image forming method of the present invention can be applied.
FIG. 1 shows an example of a schematic configuration of an electrophotographic apparatus including a process cartridge having an electrophotographic photosensitive member and toner. In FIG. 1, reference numeral 1 denotes a cylindrical electrophotographic photosensitive member, which is rotationally driven at a predetermined peripheral speed in the direction of an arrow about an axis 2. The surface of the rotationally driven electrophotographic photosensitive member 1 is uniformly charged to a predetermined positive or negative potential by the charging means (primary charging means: charging roller or the like) 3 in the rotation process (charging step). Next, it receives exposure light (image exposure light) 4 output from an exposure means (not shown) such as slit exposure or laser beam scanning exposure. In this way, electrostatic latent images corresponding to the target image are sequentially formed on the surface of the electrophotographic photosensitive member 1 (electrostatic latent image forming step). The electrostatic latent image formed on the surface of the electrophotographic photosensitive member 1 is developed by reverse development with the toner T contained in the developing means 5 to obtain a toner image (development process). Next, the toner image formed and supported on the surface of the electrophotographic photosensitive member 1 is sequentially transferred to the transfer material (paper, etc.) P by the transfer bias from the transfer means (transfer roller, etc.) 6 (transfer step). .. In the transfer step, the transfer of the toner image on the surface of the electrophotographic photosensitive member may or may not be via an intermediate transfer body. The transfer material P is taken out from the transfer material supply means (not shown) between the electrophotographic photosensitive member 1 and the transfer means 6 (contact portion) in synchronization with the rotation of the electrophotographic photosensitive member 1 and fed. Will be done. The transfer material P to which the toner image has been transferred is separated from the surface of the electrophotographic photosensitive member 1 and introduced into the fixing means 8 to receive image fixing, so that the transfer material P is printed out as an image forming product (print, copy) to the outside of the device. Will be done. The surface of the electrophotographic photosensitive member 1 after the toner image transfer is cleaned by the cleaning means (cleaning blade or the like) 7 after removing the developer (toner) remaining on the transfer (cleaning step). In the present invention, since the specific electrophotographic photosensitive member and the specific toner are used, the occurrence of cleaning defects of the external additive that has migrated to the surface of the electrophotographic photosensitive member in the cleaning step is suppressed, and good image quality is obtained. Can be obtained. Then, after being statically eliminated by the pre-exposure light (not shown) from the pre-exposure means (not shown), it is repeatedly used for image formation. As shown in FIG. 1, when the charging means 3 is a contact charging means using a charging roller or the like, pre-exposure is not always necessary. As described above, the components such as the electrophotographic photosensitive member 1, the charging means 3, the developing means 5, the transferring means 6, and the cleaning means 7 as needed are housed in a container and integrally bonded. The process cartridge of the present invention. This process cartridge is configured to be removable from the main body of an electrophotographic apparatus such as a copier or a laser beam printer. In FIG. 1, the electrophotographic photosensitive member 1 and the charging means 3, the developing means 5, and the cleaning means 7 are integrally supported to form a cartridge, and the electrophotographic apparatus is formed by using a guiding means 10 such as a rail of the electrophotographic apparatus main body. The process cartridge 9 is removable from the main body.
<p> Hereinafter, the present invention will be described in more detail with reference to specific examples. However, the present invention is not limited thereto.</p><p> [Synthesis of resin]</p><p> The polyarylate resin A and the polycarbonate resin B used in the present invention can be appropriately selected and synthesized from known methods such as a transesterification method, an interfacial polymerization method, and a direct polymerization method. An example of synthesis of polyarylate resin A and polycarbonate resin B is shown below.</p><p> [Synthesis Example A1] 3.3 g of isophthalic acid chloride and 3.3 g of terephthalic acid chloride were dissolved in dichloromethane to prepare an acid halide solution. In addition to the acid halide solution, 4.2 g of the siloxane derivative represented by the following formula (a-1), 6.8 g of the diol represented by the following formula (a-2), and 3.6 g of the diol represented by the following formula (a-3). g was dissolved in a 10% aqueous sodium hydroxide solution. Further, tributylbenzylammonium chloride was added as a polymerization catalyst and stirred to prepare a diol compound solution. Next, the acid halide solution was added to the diol compound solution with stirring to initiate polymerization. The polymerization reaction was carried out for 3 hours with stirring while keeping the reaction temperature at 25 ° C. or lower. Then, the polymerization reaction was terminated by adding acetic acid, and washing with water was repeated until the aqueous phase became neutral. Subsequently, this liquid phase was added dropwise to methanol, and the precipitate was filtered and dried to obtain a white polymer (resin A1). The viscosity average molecular weight of the obtained resin A1 was 21,000. The viscosity average molecular weight was calculated as follows. Dissolve 0.5 g of the sample in 100 ml of dichloromethane and measure the specific viscosity at 25 ° C using a Ubelode viscometer. Obtain the ultimate viscosity from this specific viscosity, and set K and a of the Mark-Houwink viscosity formula to 1.23 x 10 respectively.<sup>-4</sup>And 0.83, the viscosity average molecular weight was calculated. Further, when the content of the portion corresponding to the structure represented by the formula (1) contained in the resin A1 was analyzed by the above method, it was found to be 20% by mass.<chemistry num="37"><img file="JP6603555B2_D0037.tif" /></chemistry><chemistry num="38"><img file="JP6603555B2_D0038.tif" /></chemistry><chemistry num="39"><img file="JP6603555B2_D0039.tif" /></chemistry></p><p> [Synthesis Examples A2 to A8] Resins A2 to A8 were synthesized using the synthesis method described in Synthesis Example A1 and the raw materials corresponding to the structures shown in Table 1. The viscosity average molecular weight of the resins A2 to A8 was controlled by adjusting the time from the start of polymerization to the end of polymerization.</p><p> Table 1 shows the composition and viscosity average molecular weight of the resins A1 to A8.</p><p><tables num="1"><img file="JP6603555B2_D0040.tif" /></tables></p><p> "Equation (2)" in Table 1 shows the structure represented by Eq. (2). The "content of the formula (1)" in Table 1 means the content (mass%) of the structure represented by the formula (1) contained in the resin. "Equation (9)" in Table 1 indicates the structural unit represented by Eq. (9). When the structural units represented by the formula (9) are mixed and used, the types of structural units and the mixing ratio (mass standard) are shown. "Equation (10)" in Table 1 indicates the structural unit represented by Eq. (10). When the structural units represented by the formula (10) are mixed and used, the types of structural units and the mixing ratio (mass standard) are shown. "N in equation (10)" in Table 1 means the number of repetitions n of the structure in parentheses in the structural unit represented by equation (10).</p><p> [Synthesis Example B1] 12.0 g of the diol represented by the following formula (b-1) was dissolved in a 10% aqueous sodium hydroxide solution. Dichloromethane was added to this solution and stirred, and 15 g of phosgene was blown over 1 hour while keeping the solution temperature at 10 ° C. or higher and 15 ° C. or lower. When about 70% of phosgene was blown in, 4.2 g of the siloxane derivative represented by the formula (a-1) and 4.0 g of the diol represented by the formula (a-3) were added to the solution. After the introduction of phosgene was completed, the reaction solution was emulsified with vigorous stirring, triethylamine was added, and the mixture was stirred for 1 hour. Then, the dichloromethane phase was neutralized with phosphoric acid, and washing with water was repeated until the pH became about 7. Subsequently, this liquid phase was added dropwise to isopropanol, and the precipitate was filtered and dried to obtain a white polymer (resin B1). The viscosity average molecular weight of the obtained resin B1 was 18,000. The content of the portion of the resin B1 corresponding to the structure represented by the formula (1) was 10% by mass.<chemistry num="40"><img file="JP6603555B2_D0041.tif" /></chemistry></p><p> [Synthesis Examples B2 to B9] Resins B2 to B9 were synthesized using the synthesis method described in Synthesis Example B1 and the raw materials corresponding to the structures shown in Table 2. The viscosity average molecular weight of the resins B2 to B9 was controlled by adjusting the time from the start of polymerization to the end of polymerization.</p><p> Table 2 shows the composition and viscosity average molecular weight of the resins B1 to B9.</p><p><tables num="2"><img file="JP6603555B2_D0042.tif" /></tables></p><p> "Equation (2)" in Table 2 shows the structure represented by Eq. (2). The "content of the formula (1)" in Table 2 means the content (mass%) of the structure represented by the formula (1) contained in the resin. "Equation (11)" in Table 2 indicates the structural unit represented by Eq. (11). When the structural units represented by the formula (11) are mixed and used, the types of structural units and the mixing ratio (mass standard) are shown. "Equation (12)" in Table 2 indicates the structural unit represented by Eq. (12). "N in equation (12)" in Table 2 means the number of repetitions n of the structure in parentheses in the structural unit represented by equation (12).</p><p> [Synthesis Example A9] Using the siloxane derivative represented by the following formula (a-4) and the diol represented by the formula (a-2), resin A9 having the structure shown in Table 3 was synthesized according to the method of Synthesis Example A1. did. The viscosity average molecular weight of the obtained resin A9 was 22,000. The content of the portion of the resin A9 corresponding to the structure represented by the formula (1) was 20% by mass.<chemistry num="41"><img file="JP6603555B2_D0043.tif" /></chemistry> The siloxane derivative represented by the formula (a-4) is, for example, a compound that can be obtained by a hydrosilylation reaction between a bisphenol having a carbon-carbon double bond in the side chain and a polysiloxane having a one-terminal Si-H structure. ..</p><p> [Synthesis Examples A10 to A14] Resins A10 to A14 were synthesized using the synthesis method described in Synthesis Example A1 and the raw materials corresponding to the structures shown in Table 3. The viscosity average molecular weight of the resins A10 to A14 was controlled by adjusting the time from the start of polymerization to the end of polymerization.</p><p> Table 3 shows the composition and viscosity average molecular weight of the resins A9 to A14.</p><p><tables num="3"><img file="JP6603555B2_D0044.tif" /></tables></p><p> "Equation (3)" in Table 3 indicates the structural unit represented by Eq. (3). When the structural units represented by the formula (3) are mixed and used, the types of structural units and the mixing ratio (mass standard) are shown. "Formula (3-A)" in Table 3 indicates the group represented by the formula (3-A). The "content of the formula (1)" in Table 3 means the content (mass%) of the structure represented by the formula (1) contained in the resin. "Equation (9)" in Table 3 indicates the structural unit represented by Eq. (9). When the structural units represented by the formula (9) are mixed and used, the types of structural units and the mixing ratio (mass standard) are shown. "Equation (10)" in Table 3 indicates the structural unit represented by Eq. (10). When the structural units represented by the formula (10) are mixed and used, the types of structural units and the mixing ratio (mass standard) are shown. "N in equation (10)" in Table 3 means the number of repetitions n of the structure in parentheses in the structural unit represented by equation (10).</p><p> [Synthesis Example B10] Using the siloxane derivative represented by the formula (a-4) and the diol represented by the formula (b-1), a resin B10 having the structure shown in Table 4 was synthesized according to the method of Synthesis Example B1. .. The viscosity average molecular weight of the obtained resin B10 was 19,000. The content of the portion of the resin B10 corresponding to the structure represented by the formula (1) was 20% by mass.</p><p> [Synthesis Examples B11 to B16] Resins B11 to B16 were synthesized by using the synthesis method described in Synthesis Example B1 and using the raw materials corresponding to the structures shown in Table 4. The viscosity average molecular weight of the resins B11 to B16 was controlled by adjusting the time from the start of polymerization to the end of polymerization.</p><p> Table 4 shows the composition and viscosity average molecular weight of the resins B10 to B16.</p><p><tables num="4"><img file="JP6603555B2_D0045.tif" /></tables></p><p> "Equation (6)" in Table 4 indicates the structural unit represented by Eq. (6). "Formula (6-A)" in Table 4 indicates the group represented by the formula (6-A). The "content of the formula (1)" in Table 4 means the content (mass%) of the structure represented by the formula (1) contained in the resin. "Equation (11)" in Table 4 indicates the structural unit represented by Eq. (11). When the structural units represented by the formula (11) are mixed and used, the types of structural units and the mixing ratio (mass standard) are shown. "Equation (12)" in Table 4 indicates the structural unit represented by Eq. (12). "N in equation (12)" in Table 4 means the number of repetitions n of the structure in parentheses in the structural unit represented by equation (12).</p><p> [Synthesis Example A15] Using the siloxane derivative represented by the following formula (a-5) and the diol represented by the formula (a-2), resin A15 having the structure shown in Table 5 was synthesized according to the method of Synthesis Example A1. did. The viscosity average molecular weight of the obtained resin A15 was 23,000. The content of the portion of the resin A15 corresponding to the structure represented by the formula (1) was 20% by mass.<chemistry num="42"><img file="JP6603555B2_D0046.tif" /></chemistry> The siloxane derivative represented by the formula (a-5) is, for example, a compound that can be obtained by a hydrosilylation reaction between a bisphenol having a carbon-carbon double bond at a substituent of the central skeleton and a polysiloxane having a one-terminal Si-H structure. Is.</p><p> [Synthesis Examples A16 to A21] Resins A16 to A21 were synthesized by using the synthesis method described in Synthesis Example A1 and using the raw materials corresponding to the structures shown in Tables 5 and 6. The viscosity average molecular weight of the resins A16 to A21 was controlled by adjusting the time from the start of polymerization to the end of polymerization.</p><p> The composition and viscosity average molecular weight of the resins A15 to A21 are shown in Tables 5 and 6.</p><p><tables num="5"><img file="JP6603555B2_D0047.tif" /></tables></p><p><tables num="6"><img file="JP6603555B2_D0048.tif" /></tables></p><p> "Equation (4)" in Tables 5 and 6 indicates the structural unit represented by Eq. (4). When the structural units represented by the formula (4) are mixed and used, the types of structural units and the mixing ratio (mass standard) are shown. "Formula (4-A)" in Table 5 indicates the group represented by the formula (4-A). "Formula (4-B)" in Table 6 indicates a group represented by the formula (4-B). The "content of the formula (1)" in Tables 5 and 6 means the content (mass%) of the structure represented by the formula (1) contained in the resin. "Equation (9)" in Tables 5 and 6 indicates the structural unit represented by Eq. (9). When the structural units represented by the formula (9) are mixed and used, the types of structural units and the mixing ratio (mass standard) are shown. "Equation (10)" in Table 5 indicates the structural unit represented by Eq. (10). When the structural units represented by the formula (10) are mixed and used, the types of structural units and the mixing ratio (mass standard) are shown. "N in equation (10)" in Table 5 means the number of repetitions n of the structure in parentheses in the structural unit represented by equation (10).</p><p> [Synthesis Example B17] Using the siloxane derivative represented by the formula (a-5) and the diol represented by the formula (b-1), a resin B17 having the structure shown in Table 7 was synthesized according to the method of Synthesis Example B1. .. The viscosity average molecular weight of the obtained resin B17 was 18,000. The content of the portion of the resin B17 corresponding to the structure represented by the formula (1) was 20% by mass.</p><p> [Synthesis Examples B18 to B22] Resins B18 to B22 were synthesized by using the synthesis method described in Synthesis Example B1 and using the raw materials corresponding to the structures shown in Tables 7 and 8. The viscosity average molecular weight of the resins B18 to B22 was controlled by adjusting the time from the start of polymerization to the end of polymerization.</p><p> The composition and viscosity average molecular weight of the resins B17 to B22 are shown in Tables 7 and 8.</p><p><tables num="7"><img file="JP6603555B2_D0049.tif" /></tables></p><p><tables num="8"><img file="JP6603555B2_D0050.tif" /></tables></p><p> "Equation (7)" in Tables 7 and 8 indicates the structural unit represented by Eq. (7). "Formula (7-A)" in Table 7 indicates the group represented by the formula (7-A). "Formula (7-B)" in Table 8 indicates the group represented by the formula (7-B). The "content of the formula (1)" in Tables 7 and 8 means the content (mass%) of the structure represented by the formula (1) contained in the resin. "Equation (11)" in Tables 7 and 8 indicates the structural unit represented by Eq. (11). When the structural units represented by the formula (11) are mixed and used, the types of structural units and the mixing ratio (mass standard) are shown. "Equation (12)" in Table 7 indicates the structural unit represented by Eq. (12). "N in equation (12)" in Table 7 means the number of repetitions n of the structure in parentheses in the structural unit represented by equation (12).</p><p> [Synthesis Example A22] Using the siloxane derivative represented by the following formula (a-6) and the diol represented by the formula (a-2), resin A22 having the structure shown in Table 9 was synthesized according to the method of Synthesis Example A1. did. The viscosity average molecular weight of the obtained resin A22 was 40,000. The content of the portion of the resin A22 corresponding to the structure represented by the formula (1) was 20% by mass.<chemistry num="43"><img file="JP6603555B2_D0051.tif" /></chemistry></p><p> [Synthesis Examples A23 to A26] Resins A23 to A26 were synthesized by using the synthesis method described in Synthesis Example A1 and using the raw materials corresponding to the structures shown in Table 9. The viscosity average molecular weight of the resins A23 to A26 was controlled by adjusting the time from the start of polymerization to the end of polymerization.</p><p> Table 9 shows the composition and viscosity average molecular weight of the resins A22 to A26.</p><p><tables num="9"><img file="JP6603555B2_D0052.tif" /></tables></p><p> "Equation (5)" in Table 9 indicates the structural unit represented by Eq. (5). When the structural units represented by the formula (5) are mixed and used, the types of structural units and the mixing ratio (mass standard) are shown. "Formula (5-A)" in Table 9 indicates a group represented by the formula (5-A). The "content of the formula (1)" in Table 9 means the content (mass%) of the structure represented by the formula (1) contained in the resin. "Equation (9)" in Table 9 indicates the structural unit represented by Eq. (9). When the structural units represented by the formula (9) are mixed and used, the types of structural units and the mixing ratio (mass standard) are shown. "Equation (10)" in Table 9 indicates the structural unit represented by Eq. (10). When the structural units represented by the formula (10) are mixed and used, the types of structural units and the mixing ratio (mass standard) are shown. "N in equation (10)" in Table 9 means the number of repetitions n of the structure in parentheses in the structural unit represented by equation (10).</p><p> [Synthesis Example A27] Using the siloxane derivative represented by the formula (a-1), the siloxane derivative represented by the formula (a-6), and the diol represented by the formula (a-2), according to the method of Synthesis Example A1. Resin A27 having the structure shown in Table 10 was synthesized. The viscosity average molecular weight of the obtained resin A27 was 30,000. The content of the structure represented by the formula (1) contained in the resin A27 was 10% by mass.</p><p><tables num="10"><img file="JP6603555B2_D0053.tif" /></tables></p><p> "Equation (2)" in Table 10 shows the structure represented by Eq. (2). "Equation (5)" indicates the structural unit represented by the equation (5). When the structural units represented by the formula (5) are mixed and used, the types of structural units and the mixing ratio (mass standard) are shown. "Formula (5-A)" indicates a group represented by the formula (5-A). The "content of the formula (1)" means the content (mass%) of the structure represented by the formula (1) contained in the resin. "Equation (9)" indicates a structural unit represented by Eq. (9). When the structural units represented by the formula (9) are mixed and used, the types of structural units and the mixing ratio (mass standard) are shown.</p><p> [Synthesis Example B23] Using the siloxane derivative represented by the formula (a-6) and the diol represented by the formula (b-1), a resin B23 having the structure shown in Table 11 was synthesized according to the method of Synthesis Example B1. .. The viscosity average molecular weight of the obtained resin B23 was 31,000. The content of the portion of the resin B23 corresponding to the structure represented by the formula (1) was 20% by mass.</p><p> [Synthesis Examples B24 to B31] Resins B24 to B31 were synthesized by using the synthesis method described in Synthesis Example B1 and using the raw materials corresponding to the structures shown in Table 11. The viscosity average molecular weight of the resins B24 to B31 was controlled by adjusting the time from the start of polymerization to the end of polymerization.</p><p> Table 11 shows the composition and viscosity average molecular weight of the resins B23 to B31.</p><p><tables num="11"><img file="JP6603555B2_D0054.tif" /></tables></p><p> "Equation (8)" in Table 11 indicates the structural unit represented by Eq. (8). "Formula (8-A)" in Table 11 indicates the group represented by the formula (8-A). The "content of the formula (1)" in Table 11 means the content (mass%) of the structure represented by the formula (1) contained in the resin. "Equation (11)" in Table 11 indicates the structural unit represented by Eq. (11). When the structural units represented by the formula (11) are mixed and used, the types of structural units and the mixing ratio (mass standard) are shown. "Equation (12)" in Table 11 indicates the structural unit represented by Eq. (12). "N in equation (12)" in Table 11 means the number of repetitions n of the structure in parentheses in the structural unit represented by equation (12).</p><p> [Synthesis Example B32] Using the siloxane derivative represented by the formula (a-1), the siloxane derivative represented by the formula (a-6), and the diol represented by the formula (b-1), according to the method of Synthesis Example B1. Resin B32 having the structure shown in Table 12 was synthesized. The viscosity average molecular weight of the obtained resin B32 was 25,000. The content of the structure represented by the formula (1) contained in the resin B32 was 5% by mass.</p><p><tables num="12"><img file="JP6603555B2_D0055.tif" /></tables></p><p> "Equation (2)" in Table 12 shows the structure represented by Eq. (2). "Equation (8)" indicates the structural unit represented by the equation (8). "Formula (8-A)" indicates the group represented by the formula (8-A). The "content of the formula (1)" means the content (mass%) of the structure represented by the formula (1) contained in the resin. "Equation (11)" indicates the structural unit represented by the equation (11).</p><p> [Preparation of electrophotographic photosensitive member]</p><p> An example of manufacturing the electrophotographic photosensitive member used in the present invention is shown below. Unless otherwise specified, the number of copies described in the production example of the photoconductor is based on mass.</p><p> [Manufacturing example of photoconductor 1] An aluminum cylinder having a diameter of 30 mm and a length of 261 mm was used as a support (conductive support). Next, as metal oxide particles, oxygen-deficient tin oxide (SnO)<sub>2</sub>) Is coated with titanium oxide (TiO)<sub>2</sub>) 214 parts of particles, phenol resin (monomer / oligomer of phenol resin) as binding material (trade name: Pryofen J-325, manufactured by Dainippon Ink and Chemicals Co., Ltd., resin solid content: 60% by mass) 132 parts, Then, 98 parts of 1-methoxy-2-propanol as a solvent was placed in a sand mill using 450 parts of glass beads with a diameter of 0.8 mm, and the rotation speed was 2000 rpm, the dispersion treatment time was 4.5 hours, and the set temperature of the cooling water was 18 °. The dispersion treatment was carried out under the condition of C to obtain a dispersion liquid. Glass beads were removed from this dispersion with a mesh. Silicone resin particles as a surface roughening agent (trade name: Tospearl 120,) so that the total mass of the metal oxide particles and the binder material in the dispersion after removing the glass beads is 10% by mass. Momentive Performance Materials Co., Ltd., average particle size (2 μm) was added to the dispersion. In addition, silicone oil (trade name: SH28PA, manufactured by Toray Dow Corning Co., Ltd.) as a leveling agent is used so that it is 0.01% by mass with respect to the total mass of the metal oxide particles and the binder material in the dispersion liquid. A coating liquid for a conductive layer was prepared by adding to the dispersion liquid and stirring the mixture. This coating liquid for a conductive layer was immersed and coated on a support, and the obtained coating film was dried and thermoset at 150 ° C. for 30 minutes to form a conductive layer having a film thickness of 30 μm.</p><p> Next, a coating solution for the undercoat layer was prepared by dissolving 3 parts of N-methoxymethylated nylon and 3 parts of copolymerized nylon in a mixed solvent of 65 parts of methanol / 30 parts of n-butanol. The undercoat layer coating liquid was immersed and coated on the conductive layer and dried at 100 ° C. for 10 minutes to form an undercoat layer having a film thickness of 0.7 μm.</p><p> Next, 10 parts of crystalline hydroxygallium phthalocyanine (charge generator) having peaks at 7.5 °, 9.9 °, 16.3 °, 18.6 °, 25.1 ° and 28.3 ° at Bragg angles 2θ ± 0.2 ° in CuKα characteristic X-ray diffraction. I prepared. In addition, 250 parts of cyclohexanone and 5 parts of polyvinyl butyral resin (trade name: Eslek BX-1, manufactured by Sekisui Chemical Co., Ltd.) are mixed, and a sand mill device using glass beads with a diameter of 1 mm is used under an atmosphere of 23 ± 3 ° C. Dispersed for 1 hour. After dispersion, 250 parts of ethyl acetate was added to prepare a coating liquid for a charge generation layer. The coating liquid for the charge generating layer was immersed and coated on the undercoat layer, and the obtained coating film was dried at 100 ° C. for 10 minutes to form a charge generating layer having a film thickness of 0.26 μm.</p><p> Next, as a charge transporting substance, 8 parts of the compound represented by the formula (13-1) and 2 parts of the compound represented by the formula (13-8), and as a resin, 0.7 part of the resin A1 synthesized in Synthesis Example A1 and 0.7 parts. 40 parts of dimethoxymethane and 9.3 parts of polyallylate resin (viscosity average molecular weight: 40,000) containing the structural unit represented by the formula (9-1) and the structural unit represented by the formula (9-2) in a ratio of 5: 5. , O-Xylene and 5 parts of methyl benzoate were dissolved in a mixed solvent to prepare a coating liquid for a charge transport layer. The coating liquid for the charge transport layer was immersed and coated on the charge generation layer, and the obtained coating film was dried at 120 ° C. for 1 hour to form a charge transport layer having a film thickness of 16 μm.</p><p> In this way, the photoconductor 1 having the charge transport layer as the surface layer was produced. Table 13 shows the composition of the charge-transporting substance and the resin contained in the charge-transporting layer.</p><p> [Production Examples of Photoreceptors 2 to 83] In Photoreceptor 1, the same as Photoreceptor 1 except that the charge-transporting substance and resin in the charge-transporting layer were changed as shown in Tables 13 and 14. 2 to 83 were prepared. Tables 13 and 14 show the configurations of the charge-transporting substances and resins contained in the charge-transporting layers of the photoconductors 2 to 83. Table 15 shows the abundance ratio of silicon atoms to all atoms excluding hydrogen atoms on the outermost surface of the charge transport layer of the photoconductors 63 to 83 measured by X-ray photoelectron spectroscopy.</p><p><tables num="13"><img file="JP6603555B2_D0056.tif" /></tables></p><p><tables num="14"><img file="JP6603555B2_D0057.tif" /></tables></p><p> "Charge transport material" in Tables 13 and 14 indicates the type and number of copies of the charge transport material. "Resin A and resin B" in Tables 13 and 14 indicate the resins shown in Tables 1 to 12. "Other resins" in Tables 13 and 14 indicate structural units of resins other than resin A or resin B contained in the charge transport layer. When structural units are mixed and used, the type of structural unit and mixing ratio (mass standard) are shown. The "ratio of resin A and resin B" in Tables 13 and 14 means the content (mass%) of resin A or resin B with respect to the total solid content in the charge transport layer.</p><p><tables num="15"><img file="JP6603555B2_D0058.tif" /></tables></p><p> "Silicon atom ratio" in Table 15 means the abundance ratio (atoms%) of silicon atoms to all atoms excluding hydrogen atoms on the outermost surface of the charge transport layer, as measured using ESCA.</p><p> [Production example of photoconductor 84] In photoconductor 2, the method for producing the undercoat layer was changed as follows, and the ratio of the resin in the charge transport layer was changed as shown in Table 16. The photoconductor 84 was prepared in the same manner as in the above. That is, the undercoat layer consists of 8.5 parts of an electron transporting substance represented by the following formula (d-1), 15 parts of a blocked isocyanate compound (trade name: SBN-70D, manufactured by Asahi Kasei Chemicals Co., Ltd.), and polyvinyl alcohol as a resin. Acetal resin (trade name: KS-5Z, manufactured by Sekisui Chemical Co., Ltd.) 0.97 parts, zinc hydrochloride (II) as a catalyst (trade name: zinc hexanoate (II), manufactured by Mitsuwa Chemical Co., Ltd.) 0.15 The parts were dissolved in a mixed solvent of 88 parts of 1-methoxy-2-propanol and 88 parts of tetrahydrofuran to prepare a coating liquid for an undercoat layer. This undercoat layer coating liquid is immersed and coated on the conductive layer, and the obtained coating film is heated at 170 ° C for 20 minutes and cured (polymerized) to form an undercoat layer with a film thickness of 0.6 μm. did. Table 16 shows the composition of the charge-transporting substance and the resin contained in the charge-transporting layer of the photoconductor 84.<chemistry num="44"><img file="JP6603555B2_D0059.tif" /></chemistry></p><p> [Production Examples of Photoreceptors 85 and 86] In the photoconductor 84, the photoconductors 85 and 86 were used in the same manner as the photoconductor 84, except that the charge transporting substance and the resin in the charge transport layer were changed as shown in Table 16. Made. Table 16 shows the composition of the charge-transporting substance and the resin contained in the charge-transporting layers of the photoconductors 85 and 86.</p><p><tables num="16"><img file="JP6603555B2_D0060.tif" /></tables></p><p> "Charge transport material" in Table 16 indicates the type and number of copies of the charge transport material. "Resin A, resin B" in Table 16 indicates the resin shown in any of Tables 1 to 10. "Other resins" in Table 16 indicate structural units of resins other than the above "resins A and B" contained in the charge transport layer. When structural units are mixed and used, the types and mixing ratios of the structural units are shown. The "ratio of resin A and resin B" in Table 16 means the content (mass%) of the above "resin A and resin B" in the total solid content contained in the charge transport layer.</p><p> [Production Examples of Photoreceptors 87 and 88] In the photoconductor 1, the photoconductors 87 and 88 were the same as those of the photoconductor 1 except that the charge transporting substance and the resin in the charge transporting layer were changed as shown in Table 17. Was produced. Table 17 shows the composition of the charge-transporting substance and the resin contained in the charge-transporting layers of the photoconductors 87 and 88.</p><p><tables num="17"><img file="JP6603555B2_D0061.tif" /></tables></p><p> "Charge transport material" in Table 17 indicates the type and number of copies of the charge transport material. "Resin A, resin B" indicates the resin shown in any of Tables 1 to 12. "Other resin" indicates a structural unit of a resin other than the above-mentioned "resin A and resin B" contained in the charge transport layer. When structural units are mixed and used, the types and mixing ratios of the structural units are shown. The "ratio of resin A and resin B" means the content (mass%) of the above "resin A and resin B" in the total solid content contained in the charge transport layer.</p><p> [Production Example of Comparative Photoreceptor 1] The comparative photoconductor 1 was produced in the same manner as the photoconductor 1 except that the resin A1 in the charge transport layer was not used in the photoconductor 1. Table 18 shows the composition of the charge-transporting substance and the resin contained in the charge-transporting layer of the comparative photoconductor 1.</p><p> [Production example of comparative photoconductor 2] In the photoconductor 1, the same as the photoconductor 1 except that the resin A1 in the charge transport layer was changed to a silicone graft acrylic resin (GS-101, manufactured by Toagosei Co., Ltd.). A comparative photoconductor 2 was prepared. Table 18 shows the composition of the charge-transporting substance and the resin contained in the charge-transporting layer of the comparative photoconductor 2.</p><p> [Production Example of Comparative Photoreceptor 3] In the photoconductor 1, the resin A1 in the charge transport layer has a structure represented by the following formula (C-1) and does not have a polysiloxane structure at the end. A comparative photoconductor 3 was prepared in the same manner as the photoconductor 1 except that it was changed to C. Table 18 shows the composition of the charge-transporting substance and the resin contained in the charge-transporting layer of the comparative photoconductor 3.<chemistry num="45"><img file="JP6603555B2_D0062.tif" /></chemistry></p><p><tables num="18"><img file="JP6603555B2_D0063.tif" /></tables></p><p> "Charge transport material" in Table 18 indicates the type and number of copies of the charge transport material. "Siloxane-containing resin" in Table 18 indicates the type of resin having a polysiloxane structure in the resin contained in the charge transport layer. "Other resins" in Table 18 indicate structural units of resins other than the above-mentioned "siloxane-containing resin" contained in the charge transport layer. When structural units are mixed and used, the types and mixing ratios of the structural units are shown. The "ratio of the siloxane-containing resin" in Table 18 means the content (mass%) of the above-mentioned "siloxane-containing resin" in the total solid content contained in the charge transport layer.</p><p> [Making toner]</p><p> An example of manufacturing the toner used in the present invention is shown below. Unless otherwise specified, the number of copies described in the toner production example is all based on mass.</p><p> [Production Examples of Organic-Inorganic Composite Fine Particles 1 to 6] The organic-inorganic composite fine particles can be produced according to the description of Examples of WO2013 / 063291. The organic-inorganic composite fine particles 1 to 6 were prepared according to Example 1 of WO2013 / 063291 using the silica shown in Table 19. Table 19 shows the physical characteristics of the organic-inorganic composite fine particles 1 to 6. In addition, each of the organic-inorganic composite fine particles 1 to 6 has a structure in which the inorganic fine particles are embedded in the surface of the resin particles, and the inorganic fine particles are exposed on the surface of the resin particles, and the surface of the organic-inorganic composite fine particles is inorganic. It had a plurality of protrusions derived from fine particles.</p><p> [Production Example of Organic-Inorganic Composite Fine Particles 7] The organic-inorganic composite fine particles 7 can be produced according to the description of Examples of JP-A-2005-202131. Table 19 shows the physical characteristics of the organic-inorganic composite fine particles 7. The organic-inorganic composite fine particles 7 have a structure in which the inorganic fine particles are embedded in the surface of the resin particles, and the inorganic fine particles are exposed on the surface of the resin particles, and the surface of the organic-inorganic composite fine particles is derived from the inorganic fine particles. It had multiple protrusions.</p><p><tables num="19"><img file="JP6603555B2_D0064.tif" /></tables></p><p> [Production example of toner 1] As a polyester monomer, 400 g of an adduct of 2 mol of bisphenol A propylene oxide, 280 g of an adduct of 3 mol of bisphenol A propylene oxide, 120 g of terephthalic acid and 120 g of isophthalic acid are mixed, and 2 g of tetrabutyl titanate as a condensation catalyst is mixed. Then, the reaction was carried out while distilling off the water generated under a 220 ° C nitrogen stream. Then, the mixture was cooled to 180 ° C., and 250 g of trimellitic anhydride was added to carry out the reaction. After completion of the reaction, the mixture was taken out from the container, cooled and pulverized to obtain a polyester resin. Polyester resin: 100 parts, magnetic iron oxide particles: 75 parts, polyethylene wax (PW2000: manufactured by Toyo Petrolite, melting point 120 ° C): 4 parts, charge control agent (T-77: manufactured by Hodogaya Chemical Co., Ltd.): 2 parts Was premixed with a Henshell mixer, melt-kneaded with a twin-screw extruder heated to 110 ° C, and the cooled kneaded product was coarsely pulverized with a hammer mill to obtain a coarsely pulverized toner. The obtained coarse crushed product is coated with a mechanical crusher Turbo Mill (manufactured by Turbo Industries; Ltd .; the surfaces of the rotor and stator are coated with a chromium alloy containing chromium carbide (plating thickness 150 μm, surface hardness HV1050)). It was mechanically crushed and finely crushed. The obtained finely pulverized product was simultaneously classified and removed from fine powder and coarse powder by a multi-division classification device (elvo jet classifier manufactured by Nittetsu Mining Co., Ltd.) using the Coanda effect. After classification, the surface of the magnetic toner particles was treated using a surface modifier Faculty F-600 (manufactured by Hosokawa Micron) to modify the surface and remove fine powder. Toner particles were obtained through the above steps. The weight average particle size (D4) of the obtained toner particles is measured by the precision particle size distribution measuring device "Coulter Counter Multisizer" by the pore electrical resistance method. When measured using "3" (registered trademark, manufactured by Beckman Coulter), it was 6.9 μm. For 100 parts of toner particles, 1.1 parts of organic-inorganic composite fine particles 1 and 0.2 parts of fumed silica (number average particle size 15 nm) are externally mixed with a Henshell mixer, sieved with a mesh with an opening of 100 μm, and toner 1 is added. Obtained. The configuration of toner 1 is shown in Table 20.</p><p> [Production Examples of Toners 2 to 7] In Toner 1, the same as Toner 1 except that the type and mass part of the organic-inorganic composite fine particles and the mass part of fumed silica were changed as shown in Table 20. 2 to 7 were manufactured. Table 20 shows the configurations of toners 2 to 7.</p><p> [Production example of comparative toner 1] In toner 1, it is the same as toner 1 except that the organic-inorganic composite fine particles 1 are changed to organic fine particles 1 and the mass parts of the organic fine particles 1 and fumed silica are as shown in Table 20. The comparative toner 1 was produced. For the organic fine particles 1, the Eposter series (number average particle size 150 nm) manufactured by Nippon Shokubai Co., Ltd. was used. Table 20 shows the configuration of the comparative toner 1.</p><p> [Production example of comparative toner 2] In toner 1, the organic-inorganic composite fine particles 1 are changed to inorganic fine particles 1 (coloidal silica, number average particle size 101 nm), and the mass parts of the inorganic fine particles 1 and fumed silica are shown in Table 20. Comparative toner 2 was produced in the same manner as toner 1 except that the same was true. Table 20 shows the configuration of the comparative toner 2.</p><p> [Production Example of Comparative Toner 3] Comparative toner 3 is produced in the same manner as toner 1 except that the organic-inorganic composite fine particles 1 are not used and the mass part of fumed silica is as shown in Table 20. did. Table 20 shows the configuration of the comparative toner 3.</p><p><tables num="20"><img file="JP6603555B2_D0065.tif" /></tables></p><p> In Table 20, "parts by mass" of "organic-inorganic composite fine particles / organic fine particles / inorganic fine particles" means the mixing amount with respect to 100 parts by mass of toner particles in the external addition step of the above production example. In Table 20, "content of organic-inorganic composite fine particles (parts by mass)" is obtained when the toner is evaluated by the above <method for quantifying organic-inorganic composite fine particles in toner>, and is organic with respect to 100 parts by mass of toner particles. It means the content of inorganic composite fine particles. In Table 20, the "number average particle size (nm)" and "inorganic fine particle surface abundance (%)" of the "organic-inorganic composite fine particles" are the measurement of the number average particle size of the <organic-inorganic composite fine particles, respectively. It means the value obtained when evaluated by the method> and <Method for measuring the surface abundance of the inorganic fine particles constituting the organic-inorganic composite fine particles>.</p><p> [Example 1] <Preparation of process cartridge> HP (Hewlett-Packard Co., Ltd.) monochrome laser toner printer cartridge CE390X was used. The cleaning blade was thoroughly wiped with an ethanol-impregnated cloth and allowed to dry for a day to eliminate concerns that deposits on the cleaning blade would affect the evaluation. Photoreceptor 1 was used as the photoconductor, and the developing container was filled with toner 1. In this way, a process cartridge having the photoconductor 1 and the toner 1 was obtained.</p><p> <Evaluation> The evaluation device used the HP LaserJet Enterprise600 M603dn with the process speed modified to 400 mm / s in consideration of further speeding up of the printer in the future. In addition, the evaluation was performed in a low-temperature and low-humidity environment (temperature 10 ° C / humidity 14% RH) where cleaning becomes more severe. It is considered that the reason why cleaning becomes strict under low temperature and low humidity is that the hardness of the cleaning blade increases and the followability to the photoconductor decreases. -Image evaluation Under a low temperature and low humidity environment (temperature 10 ° C / humidity 14% RH), 20 charts with solid black images formed on the entire surface of the printing paper were output continuously and evaluated according to the following criteria. The evaluation results are shown in Table 21. A: No white streaky vertical lines can be seen in any of the 20 images. B: Among the 20 images, there is an image in which one or two white streaky vertical lines are thinly seen. C: Among the 20 images, there are images in which clear white streaky vertical lines are seen, or three or more thin vertical lines are seen. . Contamination of charged members After performing the above image evaluation, the charged member in the cartridge was collected, and it was visually confirmed whether or not stains due to the adhesion of the external additive were observed, and the evaluation was made according to the following criteria. The evaluation results are shown in Table 21. A: No white stains can be seen. B: Some white stains can be seen. C: White stains are noticeable.</p><p> [Examples 2 to 86, 89, 90] In Example 1, a process cartridge was prepared in the same manner as in Example 1 except that the photoconductor 1 and the toner 1 were changed to the photoconductor and the toner shown in Table 21. , Image evaluation and evaluation of charging member contamination were performed. The results are shown in Table 21.</p><p> [Examples 87 and 88] In Examples 11 and 77, a process cartridge was prepared in the same manner as in Examples 11 and 77 except that the process speed of the evaluation device was changed to 250 mm / s, and image evaluation and contamination of charged members were performed. Was evaluated. The results are shown in Table 21.</p><p><tables num="21"><img file="JP6603555B2_D0066.tif" /></tables></p><p> [Comparative Examples 1 to 6] In Example 1, a process cartridge was prepared in the same manner as in Example 1 except that the photoconductor 1 and the toner 1 were changed to the photoconductor and the toner shown in Table 22, and image evaluation was performed. The contamination of charged members was evaluated. The results are shown in Table 22.</p><p><tables num="22"><img file="JP6603555B2_D0067.tif" /></tables></p><p> From the comparison between the examples and the comparative examples, in the comparative examples, the effect of suppressing the contamination of the charged members is not sufficiently obtained, and the image quality is deteriorated due to the contamination of the charged members. From this, the present invention has an advantage in that it has good cleaning property even in the initial stage of use of a new process cartridge or an electrophotographic apparatus, and can suppress deterioration of image quality due to contamination of charged members. Shown.</p>
1 Electrophotographic Photoreceptor 2 Axis 3 Charging Means 4 Exposure Light 5 Developing Means 6 Transfer Means 7 Cleaning Means 8 Fixing Means 9 Process Cartridge 10 Guidance Means P Transfer Material T Toner
108 sheets
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| 2014234934 | Japan | A | |
| 2014234934 | Japan | – | |
| JP20140234934 | – | – | – |
Members4
| Document | Office | Kind | |
|---|---|---|---|
| US2016139556A1 | United States of America | A1 | |
| JP2016105165A | Japan | A | |
| US9684277B2 | United States of America | B2 | |
| JP6603555B2This record | Japan | B2 |
8 legal events, as the office reported them to INPADOC
Over the term
Point at a mark for the eventEvents
| Event | Code | |
|---|---|---|
| Written notification of patent or utility model registrationJAPANESE INTERMEDIATE CODE: R151R151 | R151 | |
| First payment of annual fees (during grant procedure)JAPANESE INTERMEDIATE CODE: A61A61 | A61 | |
| Written decision to grant a patent or to grant a registration (utility model)JAPANESE INTERMEDIATE CODE: A01A01 | A01 | |
| Decision of grant or rejection writtenTRDD | TRDD | |
| Report on retrievalJAPANESE INTERMEDIATE CODE: A971007A977 | A977 | |
| Written request for application examinationJAPANESE INTERMEDIATE CODE: A621A621 | A621 | |
| Notification of resignation of power of attorneyJAPANESE INTERMEDIATE CODE: A7424RD04 | RD04 | |
| Notification of revocation of power of attorneyJAPANESE INTERMEDIATE CODE: A7425RD05 | RD05 |
Numbers
- Publication
- 6603555
- Publication, DOCDB
- 6603555
- Publication, EPODOC
- JP6603555B
- Application
- 224174
- Application, DOCDB
- 2015224174
- Application, EPODOC
- JP20150224174
Titles2
- Japanese
- プロセスカートリッジおよび画像形成方法
- English
- Process cartridge and image formation method
Classification
- CPC, 13
- G03G21/1814
- G03G5/14752
- G03G5/14756
- G03G5/14773
- G03G9/09716
- G03G9/09725
- G03G15/75
- G03G2215/00957
- G03G5/0546
- G03G5/0564
- G03G5/0589
- G03G5/078
- G03G9/097
- IPC, 2
- G03G5 05
- G03G9 097
