JP2001166509A5 - - Google Patents

Description

[Claims]
1. Conductive supportAnd conductive supportaboveProvidedIn an electrophotographic photosensitive member having a photosensitive layer,
The photosensitive layer,Polymers of hole-transporting compounds having two or more chain-growth functional groups in the same molecule, and,An electrophotographic photosensitive member containing a lubricant.
2. SaidThe photosensitive layer,Charge generation layerandIt has a structure in which charge transport layers are laminated in this order.TheCharge transport layerBut the abovePolymers of hole-transporting compounds having two or more chain-growth functional groups in the same molecule, and, SaidContains lubricantRequestDemand 1ToThe electrophotographic photosensitive member of the description.
3. The lubricant.But,Fluorine atom-containing resin, fluorine carbNAnd at least one selected from the group consisting of polyolefin resinsIsClaim 1Or 2The electrophotographic photosensitive member according to.
4. The above.Two or more in the same moleculeThe hole transporting compounds having a chain-growth functional group are as follows.GeneralEquation (1)Compounds indicated byThe electrophotographic photosensitive member according to any one of claims 1 to 3.
[Chemical 1]

(Generalformula(1)Medium, A indicates a hole-transporting groupSu.P¹And P²Indicates a chain-growth functional group, P¹And P²Can be the same or differentI.Z indicates an organic group which may have a substituent.Su.a, b and d indicate an integer of 0 or 1 or more, a + b × d indicates an integer of 2 or more, and P when a is 2 or more.¹May be the same or different, and if d is 2 or more, P²May be the same or different, B2 or more placesGo Z andAnd P²May be the same or different. )
5. BeforeGeneral formula (1)During ~A of,A and P¹ Binding site withandWith AA hole-transporting compound in which the binding site with Z is replaced with a hydrogen atom,The following general formula (2)soShownCompounds, compounds represented by the following general formula (3), compounds represented by the following general formula (4), compounds represented by the following general formula (5), compounds represented by the following general formula (7), condensed ring hydrocarbons. , And a fused heterocycle (however, the compound represented by the following general formula (7), the fused ring hydrocarbon, and the condensed heterocycle have a substituent represented by the following general formula (8)). At least one selected fromClaim 4ToThe electrophotographic photosensitive member of the description.
[Chemical 2]

(Generalformula(2)Medium, R¹, R²And R³Is an alkyl group which may have a substituent and an aralkyl group which may have a substituent.,Or,Indicates an aryl group that may have a substituent,R ¹ , R ² And R ³ ofAt leastAlso 2Indicates an aryl group, R ¹, R²And R³May be the same or different. )
[3]

(In general formula (3), R ⁴ , R ⁵ , R ⁸ And R ⁹ Indicates an alkyl group which may have a substituent, an aralkyl group which may have a substituent, or an aryl group which may have a substituent, and R ⁴ , R ⁵ , R ⁸ And R ⁹ May be the same or different, R ⁶ And R ⁷ Indicates an alkyl group which may have a substituent or an arylene group which may have a substituent, and R ⁶ And R ⁷ May be the same or different. Q indicates an organic group which may have a substituent. )
[4]

(In general formula (4), R ¹⁰ , R ¹¹ , R ¹² And R ¹³ Indicates an alkyl group which may have a substituent, an aralkyl group which may have a substituent, or an aryl group which may have a substituent, and R ¹⁰ , R ¹¹ , R ¹² And R ¹³ May be the same or different. Ar ¹ And Ar ² Indicates an arylene group which may have a substituent, which may be the same or different. m ¹ Indicates 0 or 1. )
[5]

(In general formula (5), Ar ³ And Ar ⁴ Indicates an aryl group that may have a substituent, Ar ³ And Ar ⁴ May be the same or different. R ¹⁴ Indicates an alkyl group which may have a substituent, an aralkyl group which may have a substituent, or an aryl group which may have a substituent. Ar ³ , Ar ⁴ And R ¹⁴ At least one of them has a substituent represented by the following general formula (6). )
[6]

(In general formula (6), R ¹⁵ And R ¹⁶ Indicates an alkyl group which may have a substituent, an aralkyl group which may have a substituent, an aryl group which may have a substituent, or a hydrogen atom. ¹⁵ And R ¹⁶ May be the same or different. Ar ⁵ Indicates an aryl group that may have a substituent. n ¹ Indicates 0, 1 or 2. )
[7]

(In general formula (7), R ¹⁷ And R ¹⁸ Indicates an alkyl group which may have a substituent, an aralkyl group which may have a substituent, or an aryl group which may have a substituent, and R ¹⁷ And R ¹⁸ May be the same or different. Ar ⁶ Indicates an aryl group that may have a substituent. )
[8]

(In general formula (8), R ¹⁹ And R ²⁰ Indicates an alkyl group which may have a substituent, an aralkyl group which may have a substituent, an aryl group which may have a substituent, or a hydrogen atom. ¹⁹ And R ²⁰ May be the same or different. Ar ⁷ Indicates an aryl group that may have a substituent, n ² Indicates 0, 1 or 2. )
Claim6] BeforeGeneral formula (1)During ~ZOr the aboveGeneral formula (3)During ~Q is,Alkylene which may have a substituent, arylene which may have a substituent, CR²¹= CR²²(R²¹And R²²Indicates an alkyl group which may have a substituent, an aryl group which may have a substituent or a hydrogen atom, and R²¹And R²²May be the same or different. ), C = O, S = O, SO₂, Oxygen atomandSelected from a group of sulfur atoms1One orTwo or moreCombinedBecomeOrganic groupIsClaim5The electrophotographic photosensitive member according to.
Claim7] BeforeGeneral formula (1)During ~ZOr the aboveGeneral formula (3)During ~Q is,The following general formula (9)soShownIs the basisClaim5 or 6The electrophotographic photosensitive member according to.
[Chemical 9]

(Generalformula(9)Medium, X¹~ X³Is an alkylene group which may have a substituent, (CR²³= CR²⁴)_m2, C = O, S = O, SO₂, Oxygen atom,Or,Shows sulfur atomSu.Ar⁸And Ar⁹Indicates an arylene group which may have a substituent.Su.R²³And R²⁴Is an alkyl group which may have a substituent and an aryl group which may have a substituent.,Or,Indicates a hydrogen atom, R²³And R²⁴Can be the same or differentI.m2Indicates an integer from 1 to 5, where p, q, r, s and t are0 to 0It shows an integer of 10, but cannot be 0 at the same time. )
Claim8] BeforeGeneral formula (1)During ~ZOr the aboveGeneral formula (3)During ~Q is,The following general formula (10)soShownIs the basisClaim5 or 6The electrophotographic photosensitive member according to.
[Chemical 10]

(Generalformula(10)Medium, Ar¹⁰Indicates a divalent arylene group which may have a substituent.Su.X⁴And X⁵Is (CH₂)_m3, (CH = CR²⁵)_m4, C = O, or,Shows oxygen atomSu.R²⁵Is an alkyl group which may have a substituent and an aryl group which may have a substituent.,Or,Shows a hydrogen atomSu.m3Indicates an integer from 1 to 10, m4Indicates an integer from 1 to 5Su.u, v and w0 to 0It shows an integer of 10, but cannot be 0 at the same time. )
Claim9] BeforeGeneral formula (2)During ~R¹, R²And R³5 is an aryl group which may have a substituent.~ 8The electrophotographic photosensitive member according to any one of.
Claim10] BeforeGeneral formula (3)During ~R⁴, R⁵, R⁸ AndAnd R⁹At least two of them are aryl groups which may have a substituent and are R.⁶ AndAnd R⁷Claims that is an arylene group which may have a substituent.5-8The electrophotographic photosensitive member according to any one of.
Claim11] BeforeGeneral formula (3)During ~R⁴, R⁵, R⁸ AndAnd R⁹ButBothClaim that it is an aryl group which may have a substituent.10The electrophotographic photosensitive member according to.
Claim12] BeforeGeneral formula (4)During ~R¹⁰And R¹¹Claims that is an aryl group which may have a substituent.5-8The electrophotographic photosensitive member according to any one of.
Claim13] BeforeGeneral formula (4)During ~M¹Is 1 and R¹⁰, R¹¹, R¹²And R¹³ButBothClaim that it is an aryl group which may have a substituent.12The electrophotographic photosensitive member according to.
Claim14] BeforeGeneral formula (5)During ~R¹⁴Claims that is an aryl group which may have a substituent.5-8The electrophotographic photosensitive member according to any one of.
Claim15] BeforeGeneral formula (6)During ~R¹⁶Claims that is an aryl group which may have a substituent.14The electrophotographic photosensitive member according to.
Claim16] BeforeGeneral formula (8)During ~R²⁰Claims that is an aryl group which may have a substituent.5-8The electrophotographic photosensitive member according to any one of.
Claim17] BeforeGeneral formula (7)During ~R¹⁷And R¹⁸Claims that is an aryl group which may have a substituent.16The electrophotographic photosensitive member according to.
Claim18] SaidChain polymerizableSensualGroup P¹ andP²OneAlsoBoth,followingGeneralEquation (11)soClaim 4 to the unsaturated polymerizable functional group shown.17The electrophotographic photosensitive member according to any one of.
[Chemical 11]

(Generalformula(11)Among them, E is an alkyl group which may have a hydrogen atom, a halogen atom and a substituent.,Aryl group, cyano group, nitro group, alkoxy group, -COOR, which may have a substituent.²⁶(R²⁶Is a hydrogen atom, a halogen atom, an alkyl group which may have a substituent, and an aralkyl group which may have a substituent., OrIndicates an aryl group that may have a substituent. ),Or-CONR²⁷R²⁸(R²⁷ andR²⁸Is a hydrogen atom, a halogen atom, an alkyl group which may have a substituent, and an aralkyl group which may have a substituent., OrThey indicate aryl groups that may have substituents and may be the same or different from each other. ) IndicatesSu.W is a divalent aryl group which may have a substituent.,Divalent alkylene group, which may have a substituent, -COO-, -CH₂-, -O-, -OO-, -S-,Or-CONR²⁹-(R²⁹Is a hydrogen atom, a halogen atom, an alkyl group which may have a substituent, and an aralkyl group which may have a substituent.,Or,Indicates an aryl group that may have a substituent. ) IndicatesSu.f indicates 0 or 1. )
Claim19] SaidChain polymerizableSensualGroup P¹ andP²OneAlsoBoth,followingGeneralEquation (12)so4. The cyclic ether group shown.To any of 17The electrophotographic photosensitive member of the description.
[Chemical 12]

(Generalformula(12)Medium, R³⁰And R³¹Is a hydrogen atom, an alkyl group which may have a substituent, an aralkyl group which may have a substituent, or,Indicates an aryl group that may have a substituentSu.n represents an integer of 1 to 10. )
Claim20] SaidChain polymerizableSensualGroup P¹ andP²OneAlsoBoth,followingGeneralEquation (13)soClaim 4 to the alicyclic epoxy group shown.17The electrophotographic photosensitive member according to any one of.
[Chemical 13]

(Generalformula(13)Medium, R³²And R³³Is a hydrogen atom, an alkyl group which may have a substituent, an aralkyl group which may have a substituent, or,Indicates an aryl group that may have a substituentSu.n is0 to 0Indicates an integer of 10. )
Claim21] SaidChain polymerizableSensualGroup P¹ andP²OneAlsoBoth,followingConstructionEquation (14) ~(20)ofIn eitherIn the group shownClaims 1 to17The electrophotographic photosensitive member according to any one of.
[Chemical 14]

Claim22] SaidIn the same molecule2Hole-transporting compound with one or more chain-growth functional groupsAcidThe potential for conversion,Claims 4 to 1.2 (V)21The electrophotographic photosensitive member according to any one of.
Claim23] SaidThe polymer is a hole-transporting compound having two or more chain-growth functional groups in the same molecule.By electron beamWhatpolymerizationIt is a polymer obtained by lettingClaim1~22The electrophotographic photosensitive member according to any one of.
Claim24] SaidThe acceleration voltage of the electron beam,Claims of 250 kV or less23The electrophotographic photosensitive member according to.
Claim25] The dose of the electron beam,Claims of 1-100 Mrad23Or24The electrophotographic photosensitive member according to.
Claim26] Claims 1 to25The electrophotographic photosensitive member according to any one of, Primary charging means, image exposure means, developing means and transfer meansToYesRuCharacterized byElectrophotographic equipment.
Claim27] Claims 1 to25The electrophotographic photosensitive member according to any one ofIt is characterized in that it integrally supports at least one of a primary charging means, a developing means, and a cleaning means, and is configured to be detachably attached to the main body of the electrophotographic apparatus.Process cartridge.

0014.
[Means for solving problems]
The present inventors have results of extensive research, an electrophotographic photosensitive member having a photosensitive layer provided on the conductive support and a conductive support member,
The above-mentioned problem is that the photosensitive layer contains a polymer of a hole-transporting compound having two or more chain-growth functional groups in the same molecule and a lubricant. I found that it is a solution.

Among the chain-growth functional groups according to the present invention as described above, those represented by the following general formulas (11 ) to (13 ) are preferable.

In the general formula (11) , E has a hydrogen atom, a halogen atom such as fluorine, chlorine and bromine, an alkyl group such as a methyl group, an ethyl group, a propyl group and a butyl group which may have a substituent, and a substituent. Aralkyl groups such as benzyl group, phenethyl group, naphthylmethyl group, flufuryl group and thienyl group, which may have a substituent, phenyl group which may have a substituent, naphthyl group, anthryl group, pyrenyl group, thiophenyl group, frill group and the like. Shows an alkoxy group such as an aryl group, a CN group, a nitro group, a methoxy group, an ethoxy group or a propoxy group, −COOR ²⁶ , or −CONR ²⁷ R ²⁸ .

In the general formula (12) , R ³⁰ and R ³¹ are a hydrogen atom, an alkyl group such as a methyl group which may have a substituent, an ethyl group, a propyl group and a butyl group, and a benzyl group which may have a substituent. , aralkyl or phenyl group which may have a substituent, such as a phenethyl group, shows the aryl group such as phenyl or naphthyl. n represents an integer of 1 to 10.

In the general formula (12) , R ³² and R ³³ are a hydrogen atom, an alkyl group such as a methyl group which may have a substituent, an ethyl group, a propyl group and a butyl group, and a benzyl group which may have a substituent. , aralkyl or phenyl group which may have a substituent, such as a phenethyl group, shows the aryl group such as phenyl or naphthyl. n represents an integer from 0 to 10.

In addition, among the above general formulas (11) to (13), as a further particularly preferred chain-polymerizable functional group include groups represented by the structural formula (14) to (20).

Further , among the structural formulas (14) to (20), the acryloyloxy group of the structural formula (14) and the methylenedioxy group of the structural formula (15) are particularly preferable from the viewpoint of polymerization characteristics and the like.

The hole-transporting compound having at least two of these chain-growth functional groups is represented by the following general formula (1 ) .

In the general formula (1), P ¹ and P ² represent chain-growth functional groups, and P ¹ and P ² may be the same or different. Z is shows the organic group which may have a substituent. a, b and d indicate an integer of 0 or 1 or more, and a + b × d indicates an integer of 2 or more. Also, a well even if P ¹ of 2 or more have the same or different and when d is 2 or more P ² may be different even in the same, b is 2 or more if Z And P ² may be the same or different.

Further, among the above hole transport compounds, the compound represented by the following general formula (2 ), the compound represented by the following general formula (3 ), the compound represented by the following general formula (4 ), and the compound represented by the following general formula (5 ). compounds represented by the compound Contact and the following general formula (7), condensed hydrocarbons, and, fused heterocyclic (provided that the compound represented by the following general formula (7), condensed hydrocarbons, and a condensed heterocycle , It has a substituent represented by the following general formula (8)) . Among them, the compounds represented by the general formulas (2), (3) and (4) are particularly preferable.

In the above general formula (2), R ¹ , R ² and R ³ are alkyl groups and substituents having 1 to 10 carbon atoms such as a methyl group, an ethyl group, a propyl group and a butyl group which may have a substituent. An aralkyl group such as a benzyl group, a phenethyl group, a naphthylmethyl group, a flufuryl group or a thienyl group, or a phenyl group, a naphthyl group, an thrill group, a phenanthryl group, a pyrenyl group, which may have a substituent, Indicates an aryl group such as a thiophenyl group, a fryl group, a pyridyl group, a quinolyl group, a benzoquinolyl group, a carbazolyl group, a phenothiazine group, a benzofuryl group and a benzothiophenyl group.

In the above general formula (3), R ⁴ , R ⁵ , R ⁸ and R ⁹ are alkyl groups having 1 to 10 carbon atoms such as a methyl group, an ethyl group, a propyl group and a butyl group which may have a substituent. , An aralkyl group such as a benzyl group, a phenethyl group, a naphthylmethyl group, a flufuryl group, a thienyl group, which may have a substituent, or a phenyl group, a naphthyl group, an anthryl group, a phenanthryl group, which may have a substituent, pyrenyl group, a thiophenyl group, a furyl group, a pyridyl group, a quinolyl group, a benzoquinolyl group, a carbazolyl group, a phenothiazinyl group, a benzofuryl group, a benzothiophenyl group, a dibenzofuryl group, an aryl group such as a dibenzothiophenyl group, R ⁴ , R ⁵ , R ⁸ and R ⁹ may be the same or different, respectively. R ⁶ and R ⁷ are an alkylene group having 10 or less carbon atoms such as a methylene group, an ethylene group, and a propylene group which may have a substituent, or an arylene group (benzene, naphthalene, anthracene) which may have a substituent. , phenanthrene, pyrene, thiophene, furan, pyridine, quinoline, benzoquinoline, carbazole, phenothiazine, benzofuran, benzothiophene, dibenzofuran, shows the groups) that removal of two hydrogen atoms from dibenzothiophene etc., R ⁶ and R ⁷ It may be the same or different. Q indicates an organic group which may have a substituent.

In the general formula (4), ^{m 1} represents 0 or ^1, have preferred be a ^m 1 = 1. R ^{10 to} R ¹³ are an alkyl group having 1 to 10 carbon atoms such as a methyl group, an ethyl group, a propyl group and a butyl group which may have a substituent, a benzyl group which may have a substituent, and a phenethyl group. , Naftylmethyl group, flufuryl group, aralkyl group such as thienyl group, or phenyl group, naphthyl group, anthryl group, phenanthryl group, pyrenyl group, thiophenyl group, furyl group, pyridyl group, quinolyl group which may have a substituent. , Benzoquinolyl group, carbazolyl group, phenothiazinyl group, benzofuryl group, benzothiophenyl group, dibenzofuryl group, dibenzothiophenyl group and other aryl groups, and R ^{10 to} R ¹³ may be the same or different. Good.

However, in the general formula ^(5), at least one of Ar 3, Ar ⁴ and ^{Ar 14} may be have a substituent represented by the following general formula (6).

In the above general formulas (5) and (6), Ar ³ , Ar ⁴ and Ar ⁵ may have a substituent, a phenyl group, a naphthyl group, an anthryl group, a phenanthryl group, a pyrenyl group, a thiophenyl group, a frill group, a pyridyl group, a quinolyl group, a benzoquinolyl group, a carbazolyl group, a phenothiazinyl group, a benzofuryl group, a benzothiophenyl group, a dibenzofuryl group, shows the aryl group such as a dibenzothiophenyl group. R ¹⁴ , R ¹⁵ and R ¹⁶ may have an alkyl group having 1 to 10 carbon atoms such as a methyl group, an ethyl group, a propyl group and a butyl group, which may have a substituent, and a benzyl group which may have a substituent. , Fenetyl group, naphthylmethyl group, furfuryl group, aralkyl group such as thienyl group, phenyl group which may have a substituent, naphthyl group, anthryl group, phenanthryl group, pyrenyl group, thiophenyl group, frill group, pyridyl group, It represents an aryl group such as a quinolyl group, a benzoquinolyl group, a carbazolyl group, a phenothiazinyl group, a benzofuryl group, a benzothiophenyl group, a dibenzofuryl group, a dibenzothiophenyl group, or a hydrogen atom. However, this does not apply when ^{R 14 is a hydrogen atom.} It should be noted that Ar ³ and Ar ⁴ and R ¹⁵ and R ¹⁶ may be the same or different, respectively.

Further, any two of ^{R 14} or Ar ³ or Ar ^{4 , or Ar 5} and R ¹⁶ may be bonded directly or via a bonding group, respectively, and the bonding groups include methylene, ethylene, propylene and the like. Examples thereof include alkylene groups, heteroatoms such as oxygen and sulfur atoms, and CH = CH groups. n ¹ represents an integer of 0 , 1 or 2.

However, the general formula (7) will have a substituent represented by the following general formula (8).

In the above general formulas (7) and (8), a phenyl group, a naphthyl group, an anthryl group, a phenanthryl group, a pyrenyl group, a thiophenyl group, a furyl group, a pyridyl group, and a quinolyl group which may have ^{an Ar 6 or} Ar ^{7 substituent may be used.} group, benzoquinolyl group, a carbazolyl group, a phenothiazinyl group, a benzofuryl group, a benzothiophenyl group, a dibenzofuryl group, shows the aryl group such as a dibenzothiophenyl group. R ¹⁷ , R ¹⁸ , R ¹⁹ and R ²⁰ may have a substituent. They may have an alkyl group having 1 to 10 carbon atoms such as a methyl group, an ethyl group, a propyl group and a butyl group, and a substituent. Good benzyl group, phenethyl group, naphthylmethyl group, fulfuryl group, aralkyl group such as thienyl group, phenyl group which may have a substituent, naphthyl group, anthryl group, phenanthryl group, pyrenyl group, thiophenyl group, frill group, It represents an aryl group or a hydrogen atom such as a pyridyl group, a quinolyl group, a benzoquinolyl group, a carbazolyl group, a phenothiazinyl group, a benzofuryl group, a benzothiophenyl group, a dibenzofuryl group and a dibenzothiophenyl group. However, this does not apply when ^{R 17} and R ^{18 are hydrogen atoms.} R ¹⁷ and R ¹⁸ and R ¹⁹ and R ²⁰ may be the same or different, respectively.

Further, any two of ^{R 17} , R ¹⁸ and Ar ^{6 or Ar 7} and R ²⁰ may be bonded directly or via a bonding group, respectively, and the bonding groups include methylene, ethylene, propylene and the like. Examples thereof include alkylene groups, heteroatoms such as oxygen and sulfur atoms, and CH = CH groups. n ² represents an integer of 0 , 1 or 2.

Further, Z in the general formula (1) or Q in the general formula (3) is an alkylene having a substituent or an arylene having a substituent, CR ²¹ = CR ²² (R). ²¹ and R ²² represent an alkyl group, an aryl group or a hydrogen atom, and R ²¹ and R ²² may be the same or different), C = O, S = O, SO ₂ , a group consisting of an oxygen atom and a sulfur atom. exhibits one or two or more combined organic group selected from. Preferably a group represented by the following general formula (9) Among them, particularly preferably a group represented by the following general formula (10).

In the above general formula (9), X ^{1 to} X ³ are alkylenes having 1 to 20 carbon atoms such as a methylene group, an ethylene group, and a propylene group which may have a substituent, (CR ²³ = CR ²⁴ ) _m2 , C = O, S = O, SO 2, oxygen atom or a sulfur atom to indicate. Ar ⁸ and Ar ⁹ are divalent arylenes (benzene, naphthalene, anthracene, phenanthrene, pyrene, thiophene, pyridine, furan, quinoline, benzoquinoline, carbazole, phenothiazine, benzofuran, benzothiophene, dibenzofuran) which may have substituents. , Dibenzothiophene, etc. with two hydrogen atoms removed). R ²³ and R ²⁴ are an alkyl group such as a methyl group, an ethyl group or a propyl group which may have a substituent, an aryl group such as a phenyl group, a naphthyl group or a thiophenyl group which may have a substituent or a hydrogen atom. , And R ²³ and R ²⁴ may be the same or different. m 2 represents an integer from 1 to 5, and p, q, r, s and t represent integers from 0 to 10 but cannot be 0 at the same time).

In the above general formula (10), X ⁴ and X ⁵ represent (CH ₂ ) _m3 , (CH = CR ²⁵ ) _m4 , C = O, or an oxygen atom, and Ar ¹⁰ may have a substituent 2 Valuable arylene (benzene, naphthalene, anthracene, phenanthrene, pyrene, thiophene, furan, pyridine, quinoline, benzoquinoline, carbazole, phenothiazine, benzofuran, benzothiophene, dibenzofuran, dibenzothiophene, etc. with two hydrogen atoms removed) Is shown. R ²⁵ represents an alkyl group such as a methyl group, an ethyl group or a propyl group which may have a substituent, an aryl group such as a phenyl group, a naphthyl group or a thiophenyl group which may have a substituent or a hydrogen atom. Although m 3 represents an integer of 1 to 10, m 4 represents an integer of 1 to 5, and u, v and w represent an integer of 0 to 10 (preferably an integer of 0 to 5). It cannot be 0 at the same time).

Copper powder (445 g) was heated and stirred at 180 to 190 ° C. for 15 hours together with 1.2 kg of 1,2-dichlorobenzene. After filtering the reaction solution, the solvent was removed under reduced pressure, and the residue was purified by column using a silica gel column to obtain 132 g of Compound 3.

Compound 1 (70 g: 0.35 mol), compound 2 (98 g: 0.42 mol), anhydrous potassium carbonate (73 g) and copper powder (111 g) were heated and stirred at 180 to 190 ° C. with 600 g of 1,2-dichlorobenzene. I went for hours. After filtering the reaction solution, the solvent was removed under reduced pressure, and the residue was purified by column using a silica gel column to obtain 86.2 g of Compound 3.

Compound 3: addition (80 g 0.26 mol) in N, N- dimethyl e formamide 300 g, while stirring ethanethiol sodium salt (about 90%: 62 g) at room temperature was added slowly. After completion of the addition, the mixture was stirred as it was at room temperature for 1 hour, and then heated and stirred under reflux for 3 hours. After cooling, the reaction solution is poured into water, weakly acidic with dilute hydrochloric acid, extracted with ethyl acetate, the organic layer is further extracted with a 1.2 M aqueous sodium hydroxide solution, the aqueous layer is acidified with dilute hydrochloric acid and extracted with ethyl acetate. After drying with anhydrous sodium sulfate, the solvent was removed under reduced pressure. The residue was purified by column using a silica gel column to obtain 64 g of Compound 4.

Compound 4 (60g: 0.21mol) in N, was added to N- dimethyl e formamide 300 g, it was slowly added sodium hydroxide (8.3 g) with stirring at room temperature. After completion of the addition, the mixture was stirred as it was at room temperature for 30 minutes, and then 1,2-diiodoethane (31.7 g: 0.1 mol) was slowly added dropwise. After completion of the dropping, the mixture was stirred for 30 minutes, and then heated and stirred at 70 ° C. for 5 hours. The reaction mixture was poured into water, extracted with toluene, the organic layer was further washed with water, dried over anhydrous sodium sulfate, and the solvent was removed under reduced pressure. The residue was purified by column using a silica gel column to obtain 49.1 g of compound 5.

Compound 1 (50 g: 0.123 mol), Compound 2 (62.4 g: 0.369 mol), anhydrous potassium carbonate (25.5 g) and copper powder (32 g) together with 200 g of 1,2-dichlorobenzene at 180-190 ° C. Heating and stirring were performed for 18 hours. After filtering the reaction solution, the solvent was removed under reduced pressure, and the residue was recrystallized twice with a mixed toluene / methanol solvent to obtain 60.2 g of Compound 3.

Next, 5 parts of the bisazo pigment, 2 parts of the polyvinyl butyral resin and 60 parts of cyclohexanone shown in (21 ) below were dispersed for 24 hours in a sand mill device using φ1 mm glass beads, and 60 parts of tetrahydrofuran was further added for the charge generation layer. It was made into paint. This paint was applied onto the intermediate layer by a dip coating method and dried at 100 ° C. for 15 minutes to form a charge generation layer having a film thickness of 0.2 μm.

Then, 6 parts of tetrafluoroethylene resin particles (Lubron L-2, manufactured by Daikin Industries, Ltd.) and 50 parts of monochlorobenzene were dispersed by a sand mill device using glass beads. In this tetrafluoroethylene resin particle dispersion liquid, the compound example No. of Table 9 was added. 60 parts of the hole transporting compound of 29 was added and dissolved, and then 30 parts of dichloromethane was added to prepare a coating material for a charge transport layer.

(Example 20)
In Example 11, the hole transporting compound No. An electrophotographic photosensitive member was prepared and evaluated in the same manner as in Example 11 except that the amount of 263 was 48 parts and 12 parts of an acrylic monomer having a structure represented by the following formula (17) was added.

(Examples 21 to 25)
An electrophotographic photosensitive member was prepared and evaluated in the same manner as in Example 1 except that the electron beam irradiation conditions were changed as shown in Table 95 in Example 1. As a result, the amount of scraping and the durable image were good, but by increasing the dose, a slight decrease in sensitivity and an increase in residual potential were observed in the initial electrophotographic characteristics.

(Example 26)
After forming the charge generation layer in Example 1, 20 parts of the styryl compound represented by the following structural formula (18)

The charge generation layer is prepared by dissolving 10 parts of a polycarbonate resin having a repeating unit represented by the following structural formula (19 ) in a mixed solvent of 50 parts of monochlorobenzene and 20 parts of dichloromethane. A charge transport layer was formed on top. The film thickness of the charge transport layer at this time was 10 μm.
Next, the hole transporting compound No. was added to 56 parts of the tetrafluoroethylene resin dispersion prepared in Example 1. 660 parts were added and dissolved, and then 30 parts of dichloromethane was further added to prepare a coating material for a surface protective layer. This paint is applied onto the previous charge transport layer by a spray coating method, dried at 50 ° C. for 10 minutes, and then irradiated with an electron beam under the conditions of an acceleration voltage of 150 kV and a dose of 30 Mrad to cure the resin to a thickness of 5 μm. A surface protective layer was formed to obtain an electrophotographic photosensitive member. This photoconductor was evaluated in the same manner as in Example 1.

(Comparative Example 1)
After forming the charge generation layer in Example 1, 15 parts of the styryl compound of the structural formula (18) in Example 26 and 15 parts of the polymethylmethacrylate resin having the repeating unit represented by the following structural formula (20).

A charge transport layer was formed on the charge generation layer using a paint for a charge transport layer prepared by dissolving 50 parts of monochlorobenzene and 20 parts of dichloromethane in a mixed solvent. The film thickness of the charge transport layer at this time was 15 μm. As a result of evaluating this electrophotographic photosensitive member in the same manner as in Example 1, the initial electrophotographic characteristics were good, but the amount of scraping of the surface layer during durability was large, and image defects such as fog and scratches occurred. It was. Further, after 8000 sheets, the film thickness of the charge transport layer became thin due to scraping, and charging defects occurred, making it impossible to form an image.

(Comparative Example 3)
10 parts of tetrafluoroethylene resin particles (Lubron L-2, manufactured by Daikin Industries, Ltd.) and 50 parts of monochlorobenzene were dispersed in a sand mill containing glass beads. To this tetrafluoroethylene resin particle dispersion, 15 parts of the styryl compound of the structural formula (18) and 15 parts of the polycarbonate resin represented by the structural formula (21) are added and dissolved, and then 30 parts of dichloromethane is added to prepare a coating material for a charge transport layer. Prepared.

As a result of producing and evaluating an electrophotographic photosensitive member in the same manner as in Comparative Example 1 using this paint, durability was improved as compared with Comparative Examples 1 and 2, but image defects after durability occurred. ..