Electrophotographic member, process cartridge, and electrophotographic apparatus
Provided is an electrophotographic member including an electro-conductive substrate and a surface layer on the substrate. The surface layer contains a urethane resin and a first polymer having a specific nitrogen-containing structure. The urethane resin has a structure derived from a second polymer containing a fluorine atom or a structure derived from a third polymer containing a fluorine atom and a silicon atom. The surface layer contains nitrogen atoms derived from the nitrogen-containing structure at a specific ratio in a region from the outer surface of the surface layer to a depth of 300 nm, and the atomic ratios of nitrogen atoms, fluorine atoms, and silicon atoms in a region from a depth of 100 nm from the outer surface of the surface layer to a depth of 300 nm and a region from the outer surface to a depth of 10 nm have specific relationships.
1. An electrophotographic member, comprising:
an electro-conductive substrate; and
an electro-conductive resin layer serving as a surface layer on the substrate,
wherein:
the surface layer contains
a urethane resin and
a first polymer having at least one structure selected from the group consisting of structures represented by the following structural formulae (1) to (6):
in the structural formulae (1) to (6),
R1, R5, R10, R13, R16, and R20 each independently represent a hydrogen atom or a methyl group,
R2 and R6 each independently represent a hydrocarbon chain having 2 to 4 carbon atoms,
R3 and R4 each independently represent a methyl group or an ethyl group,
R7, R8, and R9 each independently represent a hydrocarbon group having 1 to 18 carbon atoms,
R11, R14, R17, and R21 each independently represent a single bond or a hydrocarbon chain having 1 to 6 carbon atoms,
R12, R15, R18, and R22 each independently represent a hydrogen atom or a hydrocarbon group having 1 to 3 carbon atoms,
R19 and R23 each independently represent a hydrocarbon group having 1 to 13 carbon atoms, and
A − 's each independently represent a halogen ion or a p-toluenesulfonate ion;
the urethane resin has one of a structure derived from a second polymer containing a fluorine atom, and a structure derived from a third polymer containing a fluorine atom and a silicon atom;
wherein,
in a region from an outer surface of the surface layer to a depth of 300 nm,
a ratio of a total number of nitrogen atoms derived from the structures represented by the structural formulae (1) to (6) in the first polymer to a total number of atoms measured by X-ray photoelectron spectroscopy (ESCA), is 0.1 atomic % or more and 7.0 atomic % or less,
and wherein, when,
in a region from a depth of 100 nm from the outer surface of the surface layer to a depth of 300 nm,
a ratio of a total number of nitrogen atoms derived from the structures represented by the structural formulae (1) to (6) in the first polymer to a total number of atoms measured by the X-ray photoelectron spectroscopy (ESCA) is defined as Nna,
a ratio of a number of fluorine atoms derived from the urethane resin to the total number of the atoms measured by the X-ray photoelectron spectroscopy (ESCA) is defined as Fna, and
a ratio of a number of silicon atoms derived from the urethane resin to the total number of the atoms measured by the X-ray photoelectron spectroscopy (ESCA) is defined as Sina;
and
in a region from the outer surface of the surface layer to a depth of 10 nm,
a ratio of a total number of nitrogen atoms derived from the structures represented by the structural formulae (1) to (6) in the first polymer to a total number of atoms measured by the X-ray photoelectron spectroscopy (ESCA) is defined as Nnb,
a ratio of a number of fluorine atoms derived from the urethane resin to the total number of the atoms measured by the X-ray photoelectron spectroscopy (ESCA) is defined as Fnb, and
a ratio of a number of silicon atoms derived from the urethane resin to the total number of the atoms measured by the X-ray photoelectron spectroscopy (ESCA) is defined as Sinb,
the Nna, the Fna, the Sina, the Nnb, the Fnb, and the Sinb satisfy relationships represented by the following expression (1) and the following expression (2):
( Fna+Sina )<( Fnb+Sinb ) Expression (1)
Nna>Nnb. Expression (2)
2. An electrophotographic member according to claim 1 , wherein a sum (Fnb+Sinb) of the ratios of the numbers of the fluorine atoms and the silicon atoms derived from the urethane resin to the total number of the atoms measured by the X-ray photoelectron spectroscopy (ESCA) in the region from the outer surface of the surface layer to a depth of 10 nm is 10.0 atomic % or more.
3. An electrophotographic member according to claim 1 , wherein the first polymer further has a structure represented by the following structural formula (7):
in the structural formula (7), R24 represents a hydrogen atom or a methyl group, and R25 represents a hydrocarbon group having 1 to 18 carbon atoms.
4. An electrophotographic member according to claim 1 , wherein the first polymer has at least one of the structures represented by the structural formulae (1) and (2).
5. An electrophotographic member according to claim 1 , wherein the second polymer comprises a polymer of a polymer polyol containing a fluorine atom and a polyisocyanate.
6. An electrophotographic member according to claim 5 , wherein the polymer polyol containing a fluorine atom comprises a polymer of one of a fluoroethylene and a (meth)acrylate having a fluoroalkyl group, and a monomer having a hydroxy group.
7. An electrophotographic member according to claim 1 , wherein the third polymer comprises a polymer of a polymer polyol containing a fluorine atom and a silicon atom, and a polyisocyanate.
8. An electrophotographic member according to claim 7 , wherein the polymer polyol containing a fluorine atom and a silicon atom comprises a polymer of one of a fluoroethylene and a (meth)acrylate having a fluoroalkyl group, a (meth)acrylate having a silicone group, and a monomer having a hydroxy group.
9. An electrophotographic member according to claim 1 , wherein the surface layer comprises a cured product of a layer of a paint for forming a surface layer containing the following (a1) to (a4):
(a1) the first polymer;
(a2) at least one of the second polymer or the third polymer;
(a3) a polymer polyol free of a fluorine atom and a silicon atom; and
(a4) a polyisocyanate.
10. A process cartridge, comprising an electrophotographic member, the process cartridge being removably mounted onto a main body of an electrophotographic apparatus, wherein:
the electrophotographic member includes
an electro-conductive substrate and
an electro-conductive resin layer serving as a surface layer on the substrate;
the surface layer contains
a urethane resin and
a first polymer having at least one structure selected from the group consisting of structures represented by the following structural formulae (1) to (6):
in the structural formulae (1) to (6),
R1, R5, R10, R13, R16, and R20 each independently represent a hydrogen atom or a methyl group,
R2 and R6 each independently represent a hydrocarbon chain having 2 to 4 carbon atoms,
R3 and R4 each independently represent a methyl group or an ethyl group,
R7, R8, and R9 each independently represent a hydrocarbon group having 1 to 18 carbon atoms,
R11, R14, R17, and R21 each independently represent a single bond or a hydrocarbon chain having 1 to 6 carbon atoms,
R12, R15, R18, and R22 each independently represent a hydrogen atom or a hydrocarbon group having 1 to 3 carbon atoms,
R19 and R23 each independently represent a hydrocarbon group having 1 to 13 carbon atoms, and
A − 's each independently represent a halogen ion or a p-toluenesulfonate ion;
the urethane resin has one of a structure derived from a second polymer containing a fluorine atom, and a structure derived from a third polymer containing a fluorine atom and a silicon atom;
wherein,
in a region from an outer surface of the surface layer to a depth of 300 nm,
a ratio of a total number of nitrogen atoms derived from the structures represented by the structural formulae (1) to (6) in the first polymer to a total number of atoms measured by X-ray photoelectron spectroscopy (ESCA), is 0.1 atomic % or more and 7.0 atomic % or less,
and wherein, when,
in a region from a depth of 100 nm from the outer surface of the surface layer to a depth of 300 nm,
a ratio of a total number of nitrogen atoms derived from the structures represented by the structural formulae (1) to (6) in the first polymer to a total number of atoms measured by the X-ray photoelectron spectroscopy (ESCA) is defined as Nna,
a ratio of a number of fluorine atoms derived from the urethane resin to the total number of the atoms measured by the X-ray photoelectron spectroscopy (ESCA) is defined as Fna, and
a ratio of a number of silicon atoms derived from the urethane resin to the total number of the atoms measured by the X-ray photoelectron spectroscopy (ESCA) is defined as Sina;
and
in a region from the outer surface of the surface layer to a depth of 10 nm,
a ratio of a total number of nitrogen atoms derived from the structures represented by the structural formulae (1) to (6) in the first polymer to a total number of atoms measured by the X-ray photoelectron spectroscopy (ESCA) is defined as Nnb,
a ratio of a number of fluorine atoms derived from the urethane resin to the total number of the atoms measured by the X-ray photoelectron spectroscopy (ESCA) is defined as Fnb, and
a ratio of a number of silicon atoms derived from the urethane resin to the total number of the atoms measured by the X-ray photoelectron spectroscopy (ESCA) is defined as Sinb,
the Nna, the Fna, the Sina, the Nnb, the Fnb, and the Sinb satisfy relationships represented by the following expression (1) and the following expression (2):
( Fna+Sina )<( Fnb+Sinb ) Expression (1)
Nna>Nnb. Expression (2)
11. An electrophotographic apparatus, comprising an electrophotographic member, wherein:
the electrophotographic member includes
an electro-conductive substrate and
an electro-conductive resin layer serving as a surface layer on the substrate;
the surface layer contains
a urethane resin and
a first polymer having at least one structure selected from the group consisting of structures represented by the following structural formulae (1) to (6):
in the structural formulae (1) to (6),
R1, R5, R10, R13, R16, and R20 each independently represent a hydrogen atom or a methyl group,
R2 and R6 each independently represent a hydrocarbon chain having 2 to 4 carbon atoms,
R3 and R4 each independently represent a methyl group or an ethyl group,
R7, R8, and R9 each independently represent a hydrocarbon group having 1 to 18 carbon atoms,
R11, R14, R17, and R21 each independently represent a single bond or a hydrocarbon chain having 1 to 6 carbon atoms,
R12, R15, R18, and R22 each independently represent a hydrogen atom or a hydrocarbon group having 1 to 3 carbon atoms,
R19 and R23 each independently represent a hydrocarbon group having 1 to 13 carbon atoms, and
A − 's each independently represent a halogen ion or a p-toluenesulfonate ion;
the urethane resin has one of a structure derived from a second polymer containing a fluorine atom, and a structure derived from a third polymer containing a fluorine atom and a silicon atom;
wherein,
in a region from an outer surface of the surface layer to a depth of 300 nm,
a ratio of a total number of nitrogen atoms derived from the structures represented by the structural formulae (1) to (6) in the first polymer to a total number of atoms measured by X-ray photoelectron spectroscopy (ESCA), is 0.1 atomic % or more and 7.0 atomic % or less,
and wherein, when,
in a region from a depth of 100 nm from the outer surface of the surface layer to a depth of 300 nm,
a ratio of a total number of nitrogen atoms derived from the structures represented by the structural formulae (1) to (6) in the first polymer to a total number of atoms measured by the X-ray photoelectron spectroscopy (ESCA) is defined as Nna,
a ratio of a number of fluorine atoms derived from the urethane resin to the total number of the atoms measured by the X-ray photoelectron spectroscopy (ESCA) is defined as Fna, and
a ratio of a number of silicon atoms derived from the urethane resin to the total number of the atoms measured by the X-ray photoelectron spectroscopy (ESCA) is defined as Sina;
and
in a region from the outer surface of the surface layer to a depth of 10 nm,
a ratio of a total number of nitrogen atoms derived from the structures represented by the structural formulae (1) to (6) in the first polymer to a total number of atoms measured by the X-ray photoelectron spectroscopy (ESCA) is defined as Nnb,
a ratio of a number of fluorine atoms derived from the urethane resin to the total number of the atoms measured by the X-ray photoelectron spectroscopy (ESCA) is defined as Fnb, and
a ratio of a number of silicon atoms derived from the urethane resin to the total number of the atoms measured by the X-ray photoelectron spectroscopy (ESCA) is defined as Sinb,
the Nna, the Fna, the Sina, the Nnb, the Fnb, and the Sinb satisfy relationships represented by the following expression (1) and the following expression (2):
( Fna+Sina )<( Fnb+Sinb ) Expression (1)
Nna>Nnb. Expression (2)