Electrophotographic member with surface layer having fluorine resin powder and fluorine graft polymer

• US 4,792,507 A
• Filed: 03/16/1987
• Issued: 12/20/1988
• Est. Priority Date: 03/18/1986
• Status: Expired due to Term

• Current Assignee: Canon Kabushiki Kaisha (Canon Inc.)
• Original Assignee: Canon Kabushiki Kaisha (Canon Inc.)
• Inventors: Kimura, Tomohiro, Yoshihara, Toshiyuki, Hiro, Masaaki
• Primary Examiner(s): Martin, Roland E.
• Application Number:
  US07/026,176
• Time in Patent Office: 645 Days
• Field of Search: 430/58, 430/59, 430/66, 430/67
• US Class Current: 430/59.6
• CPC Class Codes: G03G 5/14786 Macromolecular compounds characterised by specific side-chain substituents or end groups
• CPC Class Codes: G03G 5/14791 Macromolecular compounds characterised by their structure, e.g. block polymers, reticulated polymers, or by their chemical properties, e.g. by molecular weight or acidity

Abstract

An electrophotographic photosensitive member having a photosensitive layer on an electroconductive substrate comprises a surface layer containing a fluorine type resin powder and a fluorine type graft polymer.

Claims

1. An electrophotographic photosensitive member having a photosensitive layer on an electroconductive substrate, which includes a surface layer containing a binder, a fluorine type resin powder and a fluorine type graft polymer.

2. An electrophotographic photosensitive member according to claim 1, wherein said fluorine type resin powder is selected from the group consisting of tetrafluoroethylene resins, trifluorochloroethylene resins, tetrafluoroethylenehexafluoropropylene resins, vinyl fluoride resins, vinylidene fluoride resins, difluorodichloroethylene resins and copolymers thereof.

3. An electrophotographic photosensitive member according to claim 2, wherein said fluorine type resin powder is selected from the group consisting of tetrafluoroethylene resins and vinylidene fluoride resins.

4. An electrophotographic photosensitive member according to claim 2, wherein said fluorine type resin powder is tetrafluoroethylene resin.

5. An electrophotograhic photosensitive member according to claim 1, wherein the content of said fluorine type resin powder is 1 to 50% by weight of the components constituting the surface layer.

6. An electrophotograhic photosensitive member according to claim 1, wherein the amount of said fluorine type graft polymer added is 0.1 to 30% by weight based on the fluorine type resin powder.

7. An electrophotographic photosensitive member according to claim 1, wherein a binder resin in said surface layer is selected from the group consisting of polymethyl methacrylate and polycarbonate.

8. An electrophotographic photosensitive member according to claim 1, wherein said photosensitive layer has a laminated structure of a charge generation layer and a charge transport layer, and the charge transport layer is laminated on the charge generation layer.

9. An electrophotographic photosensitive member according to claim 1, wherein said photosensitive layer has a laminated structure of a charge generation layer and a charge transport layer, and the charge generation layer is laminated on the charge transport layer.

10. An electrophotographic photosensitive member according to claim 1, wherein said photosensitive layer comprises a single layer containing a charge generation substance and a charge transport substance.

11. An electrophotographic photosensitive member according to claim 1, wherein said photosensitive layer has a protective layer as the surface layer.

12. An electrophotographic photosensitive member according to claim 1, wherein said fluorine type graft polymer is a copolymer of a non-fluorine type oligomer having a polymerizable functional group at one terminal end and repeating units and a fluorine type polymerizable monomer.

13. An electrophotographic photosensitive member according to claim 1, wherein said fluorine type graft polymer is a copolymer of a fluorine type oligomer having a polymerizable functional group at one terminal end and repeating units and a non-fluorine type polymerizable monomer.

14. An electrophotographic photosensitive member according to claim 12, wherein said non-fluorine type oligomer has a molecular weight of 1,000 to 10,000 and said fluorine type graft polymer has molecular weight of 10,000 to 100,000.

15. An electrophotographic photosensitive member according to claim 13, wherein said fluorine type oligomer has a molecular weight of 1,000 to 10,000 and said fluorine type graft polymer has a molecular weight of 10,000 to 100,000.

16. An electrophotographic photosensitive member according to claim 12, wherein said non-fluorine type oligomer is a compound of formula (I) as follows:

##STR43## R₁ is hydrogen atom, alkyl group, halogen atom, halogen-substituted alkyl group, or aryl group;

A₁ is alkylene chain or halogen-substituted alkylene chain;

A₂ is ##STR44## R₂ -R₁₁ are each hydrogen atom, alkyl group or halogen-substituted alkyl group;

A₃ is an alkylene chain or halogen-substituted alkylene chain;

A₄ is a repeating unit of a polymer of at least one polymerizable monomer selected from the group consisting of low molecular weight straight chain unsaturated hydrocarbons, vinyl halides, vinyl esters of organic acids, vinylaromatic compounds, acrylic acid and methacrylic acid esters, N-vinyl compounds, vinylsilicon compounds, maleic anhydride, esters of maleic acid and fumaric acid;

a is a positive integer; and

said fluorine-type polymerizable monomer is a Compound (II) selected from the group consisting of fluorine-substituted low molecular weight straight chain unsaturated hydrocarbons, fluorine-substituted vinyl halides, fluorine-substituted organic acid vinyl esters, fluorine-substituted alkyl vinyl ethers, fluorine-substituted alkyl esters and amides of acrylic acid and methacrylic acid, fluorine-substituted aromatic containing esters and amides of acrylic acid and methacrylic acid, fluorinated maleic anhydride, fluorine-substituted alkyl esters of maleic acid and fumaric acid, α

-fluorinated styrene and α

, β

, β

-fluorinated styrene.

17. An electrophotographic photosensitive member according to claim 13, wherein said fluorine type oligomer is represented by the formula (III) compounds as follows:

##STR45## A₅ is a repeating unit of a polymer of at least one polymerizable monomer selected from the group consisting of fluorine-substituted low molecular weight straight chain unsaturated hydrocarbons, fluorine-substituted vinyl halides, fluorine-substituted organic acid vinyl esters, fluorine-substituted alkyl vinyl ethers, fluorine-substituted alkyl esters and amides of acrylic acid and methacrylic acid, fluorine-substituted aromatic containing esters and amides of acrylic acid and methacrylic acid, fluorinated maleic anhydride, fluorine-substituted alkyl esters of maleic acid and fumaric acid, α

-fluorinated styrene and α

, β

, β

-fluorinated styrene;

a is a positive integer;

R₁ is hydrogen atom, alkyl group, halogen atom, halogen-substituted alkyl group, or aryl group;

A₁ is an alkylene chain or halogen-substitute alkylene chain;

A₂ is ##STR46## R₂ -R₁₁ are each hydrogen atom, alkyl group or halogen-substituted alkyl group;

A₃ is an alkylene chain or halogen-substituted alkylene chain; and

said non-fluorine type polymerizable monomer is selected from the group consisting of low molecular weight straight chain unsaturated hydrocarbons, vinyl halides, vinyl esters or organic acids, vinylaromatic compounds, acrylic acid and methacrylic acid esters, N-vinyl compounds, vinylsilicon compounds, maleic anhydride, esters of maleic acid and fumaric acid.

18. An electrophotographic photosensitive member according to claim 12, wherein said non-fluorine type oligomer is a compound represented by the formula (V) as follows:

##STR47## R₁₂ is hydrogen atom, alkyl group, halogen atom or halogen-substituted alkyl group;

A₆ is an alkylene chain;

X is ##STR48## R₁₃ is hydrogen atom or alkyl group;

b is 0 or a positive integer;

A₇ is ##STR49## R₁₄ is hydrogen atom or alkyl group;

A₈, A₉, A₁₀ are each alkylene chain, cycloalkylene chain, substituted or unsubstituted arylene chain. ##STR50## R₁₅, R₁₆, R₁₇, R₁₈ are each hydrogen atom, alkyl group, or R₁₅ and R₁₆ or R₁₇ and R₁₈ may form a ring through an alkylene chain;

A₃ is an alkylene chain or halogen-substituted alkylene chain;

A₄ is a repeating unit of a polymer of at least one polymerizable monomer selected from the group consisting of low molecular weight straight chain unsaturated hydrocarbons, vinyl halides, vinyl esters of organic acids, vinylaromatic compounds, acrylic acid and methacrylic acid esters, N-vinyl compounds, vinylsilicon compounds, maleic anhydride, esters of maleic acid and fumaric acid;

a is a positive integer; and

said fluorine type polymerizable monomer is a Compound II selected from the group consisting of fluorine-substituted low molecular weight straight chain unsaturated hydrocarbons, fluorine-substituted vinyl halides, fluorine-substituted organic acid vinyl esters, fluorine-substituted alkyl vinyl ethers, fluorine-substituted alkyl esters and amides of acrylic acid and methacrylic acid, fluorine-substituted aromatic containing esters and amides of acrylic acid and methacrylic acid, fluorinated maleic anhydride, fluorine-substituted alkyl esters of maleic acid and fumaric acid, α

-fluorinated styrene and α

, β

, β

-fluorinated styrene.

19. An electrophotographic photosensitive member according to claim 13, wherein said fluorine type oligomer is a compound represented by the formula (VI) as follows:

##STR51## R₁₂ is hydrogen atom, alkyl group, halogen atom or halogen-substituted alkyl group;

A₆ is an alkylene chain;

X is ##STR52## R₁₃ is hydrogen atom or alkyl group;

b is 0 or a positive integer;

A₇ is ##STR53## R₁₄ is hydrogen atom or alkyl group;

A₈, A₉, A₁₀ are each alkylene chain, cycloalkylene chain, substituted or unsubstituted arylene chain, ##STR54## R₁₅, R₁₆, R₁₇, R₁₈ are each hydrogen atom, alkyl group, or R₁₅ and R₁₆ or R₁₇ and R₁₈ may form a ring through an alkylene chain;

A₃ is alkylene chain or halogen-substituted alkylene chain;

A₅ is a repeating unit of a polymer of at least one polymerizable monomer selected from the group consisting of fluorine-substituted low molecular weight straight chain unsaturated hydrocarbons, fluorine-substituted vinyl halides, fluorine-substituted organic acid vinyl esters, fluorine-substituted alkyl vinyl ethers, fluorine-substituted alkyl esters and amides of acrylic acid and methacrylic acid, fluorine-substituted aromatic containing esters and amides of acrylic acid and methacrylic acid, fluorinated maleic anhydride, fluorine-substituted alkyl esters of maleic acid and fumaric acid, α

-fluorinated styrene and α

, β

, β

-fluorinated styrene.

20. An electrophotographic photosensitive member according to claim 12, wherein said non-fluorine type oligomer is formed by the reaction of an active polymer intermediate having a polymerizable functional group at one terminal end and repeating units of the formula (VII) with a compound represented by the formula (VIII), the units of formula VII being:

space="preserve" listing-type="equation">(R.sub.19 [A.sub.11 ].sub.n [R.sub.20 -O].sub.m) ⊖

+M⊕

(VII)

R₁₉ is a hydrogen atom, alkyl group or aryl group;

A₁₁ is a repeating unit comprising a polymer of at least one selected from the group consisting of styrene, α

-alkylstyrene, α

-olefin, (meth)acrylic acid ester and α

-cyano(meth)acrylic acid ester;

n is a positive integer;

R₂₀ is an alkylene chain;

m is 0 or a positive integer;

M is an alkali metal;

wherein the formula VIII compounds are;

##STR55## R₂₁ is a hydrogen atom, alkyl group or aryl group;

A₁₂ is ##STR56## c is 0 or 1;

A₁₃ is a substituted or unsubstituted alkylene chain;

d is 0 or 1;

Y is a halogen atom; and

said fluorine type polymerizable monomer is selected from the group consisting of fluorine-substituted low molecular weight straight chain unsaturated hydrocarbons, fluorine-substituted vinyl halides, fluorine-substituted organic acid vinyl esters, fluorine-substituted alkyl vinyl ethers, fluorine-substituted alkyl esters and amides of acrylic acid and methacrylic acid, fluorine-substituted aromatic containing esters and amides of acrylic acid and methacrylic acid, fluorinated maleic anhydride, fluorine-substituted alkyl esters of maleic acid and fumaric acid, α

-fluorinated styrene and α

, β

, β

-fluorinated styrene.