Electrophotographic photosensitive member and method of producing the electrophotographic photosensitive member, and process cartridge and electrophotographic apparatus each including the electrophotographic photosensitive member

• US 9,405,206 B2
• Filed: 12/16/2014
• Issued: 08/02/2016
• Est. Priority Date: 12/26/2013
• Status: Active Grant

• Current Assignee: Canon Kabushiki Kaisha (Canon Inc.)
• Original Assignee: Canon Kabushiki Kaisha (Canon Inc.)
• Inventors: Tanaka, Daisuke, Kawaguchi, Daisuke, Murakami, Takeshi, Sugiyama, Kazumichi
• Primary Examiner(s): Le, Hoa V
• Application Number:
  US14/571,699
• Publication Number:
  US 20150185639A1
• Time in Patent Office: 595 Days
• US Class Current: 1/1
• CPC Class Codes: G03G 5/0763 comprising arylamine moiety
• CPC Class Codes: G03G 5/144 comprising inorganic material

Abstract

Provided is an electrophotographic photosensitive member capable of suppressing a voltage fluctuation and occurrence of a black spot under a high-temperature/high-humidity environment. The electrophotographic photosensitive member includes: a support; a first intermediate layer formed on the support; a second intermediate layer formed on the first intermediate layer; and a photosensitive layer formed on the second intermediate layer, in which the first intermediate layer contains metal oxide particles having a number-average primary particle diameter of from 30 to 450 nm; and the second intermediate layer contains a cured product of a composition containing an electron transport substance having a polymerizable functional group represented by the formula (1) or (2), and having a molecular weight of from 100 to 1,000, and a crosslinking agent having 3 to 6 groups reactive with the polymerizable functional group represented by the formula (1) or (2), and having a molecular weight of from 200 to 1,300.

Claims

1. An electrophotographic photosensitive member, comprising:

a support;

a first intermediate layer on the support;

a second intermediate layer on the first intermediate layer; and

a photosensitive layer on the second intermediate layer,

wherein;

the first intermediate layer comprises metal oxide particles having a number-average primary particle diameter of 30 nm or more and 450 nm or less; and

the second intermediate layer comprises a polymerized product of a composition comprising;

an electron transport substance having a polymerizable functional group represented by the following formula (1) or (2), and having a molecular weight of 100 or more and 1,000 or less, and

a crosslinking agent having 3 to 6 groups reactive with the polymerizable functional group represented by the following formula (1) or (2), and having a molecular weight of 200 or more and 1,300 or less;

-A 

 

(1)

B₁C-D 

 

(2)

in the formulae (1) and (2);

at least one of A, B, C, and D represents a group having a polymerizable functional group, the polymerizable functional group is at least one kind of group selected from the group consisting of a hydroxy group, a thiol group, an amino group, and a carboxyl group, and l represents 0 or 1;

A represents a carboxyl group, a substituted or unsubstituted alkyl group having 1 to 6 main-chain atoms, a group having 1 to 6 main-chain atoms derived by substituting one of carbon atoms in a main chain of the substituted or unsubstituted alkyl group with an oxygen atom, a group having 1 to 6 main-chain atoms derived by substituting one of the carbon atoms in the main chain of the substituted or unsubstituted alkyl group with a sulfur atom, or a group having 1 to 6 main-chain atoms derived by substituting one of the carbon atoms in the main chain of the substituted or unsubstituted alkyl group with NR¹, these groups each have the polymerizable functional group, R¹ represents a hydrogen atom or an alkyl group, and a substituent of the substituted alkyl group is an alkyl group having 1 to 6 carbon atoms, a benzyl group, or a phenyl group;

B represents a substituted or unsubstituted alkylene group having 1 to 6 main-chain atoms, a group having 1 to 6 main-chain atoms derived by substituting one of carbon atoms in a main chain of the substituted or unsubstituted alkylene group with an oxygen atom, a group having 1 to 6 main-chain atoms derived by substituting one of the carbon atoms in the main chain of the substituted or unsubstituted alkylene group with a sulfur atom, or a group having 1 to 6 main-chain atoms derived by substituting one of the carbon atoms in the main chain of the substituted or unsubstituted alkylene group with NR², these groups may each have the polymerizable functional group, R² represents a hydrogen atom or an alkyl group, and a substituent of the substituted alkylene group is an alkyl group having 1 to 6 carbon atoms, a benzyl group, an alkoxycarbonyl group, or a phenyl group;

C represents a phenylene group, a phenylene group substituted with an alkyl group having 1 to 6 carbon atoms, a nitro-substituted phenylene group, a halogen-substituted phenylene group, or an alkoxy group-substituted phenylene group, and these groups may each have the polymerizable functional group; and

D represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or an alkyl group having 1 to 6 main-chain atoms substituted with an alkyl group having 1 to 6 carbon atoms, and these groups may each have the polymerizable functional group.

2. An electrophotographic photosensitive member according to claim 1, wherein a content of the electron transport substance in the composition of the second intermediate layer with respect to the metal oxide particles of the first intermediate layer is 0.2 mass % or more and 15 mass % or less.

3. An electrophotographic photosensitive member according to claim 1, wherein a total content of the electron transport substance and the crosslinking agent in the composition of the second intermediate layer with respect to the metal oxide particles of the first intermediate layer is 0.5 mass % or more and 20 mass % or less.

4. An electrophotographic photosensitive member according to claim 1, wherein the crosslinking agent is one of an isocyanate compound having one of an isocyanate group and a blocked isocyanate group, and an amine compound having one of an N-methylol group and an alkyl-etherified N-methylol group.

5. An electrophotographic photosensitive member according to claim 1, wherein the composition of the second intermediate layer further comprises a thermoplastic resin having a polymerizable functional group.

6. An electrophotographic photosensitive member according to claim 5, wherein the polymerizable functional group of the thermoplastic resin is one of a hydroxy group, a thiol group, an amino group, a carboxyl group, and a methoxy group.

7. An electrophotographic photosensitive member according to claim 1, wherein the metal oxide particles is one of titanium oxide particles and zinc oxide particles.

9. A process cartridge, comprising:

the electrophotographic photosensitive member according to claim 1; and

at least one unit selected from the group consisting of a charging unit, a developing unit, and a cleaning unit,

the process cartridge integrally supporting the electrophotographic photosensitive member and the at least one unit,

the process cartridge being removably mounted onto a main body of an electrophotographic apparatus.

10. An electrophotographic apparatus, comprising:

the electrophotographic photosensitive member according to claim 1;

a charging unit;

an exposing unit;

a developing unit; and

a transferring unit.

8. A method of producing an electrophotographic photosensitive member comprising:

a support;

a first intermediate layer on the support;

a second intermediate layer on the first intermediate layer; and

a photosensitive layer on the second intermediate layer,

the method comprising;

forming a coat of an application liquid for a first intermediate layer that comprises metal oxide particles having a number-average primary particle diameter of 30 nm or more and 450 nm or less;

heating the coat to form the first intermediate layer;

forming a coat of an application liquid for a second intermediate layer that comprises a composition comprising an electron transport substance having a polymerizable functional group represented by the following formula (1) or (2), and having a molecular weight of 100 or more and 1,000 or less, and a crosslinking agent having 3 to 6 groups reactive with the polymerizable functional group represented by the following formula (1) or (2), and having a molecular weight of 200 or more and 1,300 or less; and

heating and curing the coat to form the second intermediate layer;

-A 

 

(1)

B₁C-D 

 

(2)

in the formulae (1) and (2);

at least one of A, B, C, and D represents a group having a polymerizable functional group, the polymerizable functional group is at least one kind of group selected from the group consisting of a hydroxy group, a thiol group, an amino group, and a carboxyl group, and l represents 0 or 1;

A represents a carboxyl group, a substituted or unsubstituted alkyl group having 1 to 6 main-chain atoms, a group having 1 to 6 main-chain atoms derived by substituting one of carbon atoms in a main chain of the substituted or unsubstituted alkyl group with an oxygen atom, a group having 1 to 6 main-chain atoms derived by substituting one of the carbon atoms in the main chain of the substituted or unsubstituted alkyl group with a sulfur atom, or a group having 1 to 6 main-chain atoms derived by substituting one of the carbon atoms in the main chain of the substituted or unsubstituted alkyl group with NR¹, these groups each have the polymerizable functional group, R¹ represents a hydrogen atom or an alkyl group, and a substituent of the substituted alkyl group is an alkyl group having 1 to 6 carbon atoms, a benzyl group, or a phenyl group;

B represents a substituted or unsubstituted alkylene group having 1 to 6 main-chain atoms, a group having 1 to 6 main-chain atoms derived by substituting one of carbon atoms in a main chain of the substituted or unsubstituted alkylene group with an oxygen atom, a group having 1 to 6 main-chain atoms derived by substituting one of the carbon atoms in the main chain of the substituted or unsubstituted alkylene group with a sulfur atom, or a group having 1 to 6 main-chain atoms derived by substituting one of the carbon atoms in the main chain of the substituted or unsubstituted alkylene group with NR², these groups may each have the polymerizable functional group, R² represents a hydrogen atom or an alkyl group, and a substituent of the substituted alkylene group is an alkyl group having 1 to 6 carbon atoms, a benzyl group, an alkoxycarbonyl group, or a phenyl group;

C represents a phenylene group, a phenylene group substituted with an alkyl group having 1 to 6 carbon atoms, a nitro-substituted phenylene group, a halogen-substituted phenylene group, or an alkoxy group-substituted phenylene group, and these groups may each have the polymerizable functional group; and

D represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or an alkyl group having 1 to 6 main-chain atoms substituted with an alkyl group having 1 to 6 carbon atoms, and these groups may each have the polymerizable functional group.