JP2000147813A5 - - Google Patents

Description

[Document name] Statement
INDUSTRIAL APPLICABILITY: Electrophotographic photosensitive member, process cartridge and electrophotographic apparatus
[Claims]
[Claim 1] Conductive support and theOn a conductive supportBeen formedIn an electrophotographic photosensitive member having a photosensitive layer,
The photosensitive layerBut,Charge generating materialAsPhthalocyanine compoundContains,
The electrophotographic photosensitive memberSurface layerBut in the same molecule2Hole-transporting compound with one or more chain-growth functional groupsToCrosslinkGet itCuringStuffIncludingHave
An electrophotographic photosensitive member characterized by this.
2. The hole-transporting compound having a chain-growth functional group,The following general formula (1)Compounds indicated byThe electrophotographic photosensitive member according to claim 1.
[Chemical 1]

(Generalformula(1)Among them, A indicates a hole transporting group...P¹And P²Indicates a chain-growth functional group..P¹And P²May be the same or different..Z indicates an organic residue which may have a substituent.Su.Y indicates a hydrogen atom..a, b and d0 or moreIndicates the integer above..However, when a = 0, b + d is an integer of 3 or more, when b or d is 0, a is an integer of 2 or more, and in other cases, a + b + d is an integer of 3 or more...Also, when a is 2 or moreIsP¹May be the same or different, when d is 2 or moreIsP²May be the same or different, BWhen is 2 or moreIsZ may be the same or different..)
3. BeforeGeneral formula (1)InAInP¹And replace the binding site with Z with a hydrogen atomDerived fromHole transporting compounds,It is represented by the following general formula (2)Is a compoundThe electrophotographic photosensitive member according to claim 1 or 2.
[Chemical 2]

(Generalformula(2)Medium, R¹, R²And R³Indicates 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...However,R ¹ , R ² And R ³ Ofat least2Indicates an aryl group..Also, R¹, R²And R³May be the same or different..)
4. BeforeGeneral formula (1)InAInP¹And replace the binding site with Z with a hydrogen atomDerived fromThe compound is,It is represented by the following general formula (3)Is a compoundThe electrophotographic photosensitive member according to claim 1 or 2.
[Chemical 3]

(Generalformula(3)Medium, R⁴, R⁵, R⁸And R⁹Indicates 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.Su.R⁶And R⁷Indicates an alkylene group which may have a substituent or an arylene group which may have a substituent...R⁴, R⁵, R⁸And R⁹And R⁶And R⁷May be the same or different..Q indicates an organic residue which may have a substituent...)
5. BeforeGeneral formula (1)InAInP¹And the binding site with Z is placed on the hydrogen atomDerived in placeHole transporting compounds,It is represented by the following general formula (4)Is a compoundThe electrophotographic photosensitive member according to claim 1 or 2.
[Chemical 4]

(Generalformula(4)Medium, R¹⁰, R¹¹, R¹²And R¹³Indicates 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...Also, R¹⁰, R¹¹, R¹²And R¹³May be the same or different..Ar¹And Ar²Indicates an arylene group which may have a substituent, which may be the same or different...m indicates 0 or 1..)
6. BeforeGeneral formula (1)InAInP¹And replace the binding site with Z with a hydrogen atomDerived fromThe compound is,It is represented by the following general formula (5)Is a compoundThe electrophotographic photosensitive member according to claim 1 or 2.
[Chemical 5]

(Generalformula(5)Medium, Ar³And Ar⁴Indicates an aryl group that may have a substituentSu.Ar³And Ar⁴May be the same or different..R¹⁴Indicates 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...However, Ar³, Ar⁴And R¹⁴Ofofat least1One is the following general formula (6)Indicated bySubstituent1Have one or more..
[Chemical 6]

(Generalformula(6)Medium, R¹⁵And R¹⁶Indicates 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.Su.R¹⁵And R¹⁶May be the same or different..Ar⁵Indicates an aryl group that may have a substituent..n¹Is0 to 0Indicates an integer of 2..))
7. BeforeGeneral formula (1)InAInP¹And replace the binding site with Z with a hydrogen atomDerived fromThe compound is represented by a condensed ring hydrocarbon, a condensed complex ring or the following general formula (7).Is a compoundThe electrophotographic photosensitive member according to claim 1 or 2.
[Chemical 7]

(Generalformula(7)Medium, R¹⁷And R¹⁸Indicates 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.Su.R¹⁷And R¹⁸May be the same or different..Ar⁶Indicates an aryl group that may have a substituent..However,BeforeCondensation ring hydrocarbon,SaidCondensation complex ring andSaidGeneral formula (7)Compounds indicated byIs the following general formula (8)Indicated bySubstituent1Have one or more..
[Chemical 8]

(Generalformula(8)Medium, R¹⁹And R²⁰Indicates 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.Su.R¹⁹And R²⁰May be the same or different..Ar⁷Indicates an aryl group that may have a substituent..n²Is0 to 0Indicates an integer of 2..))
8. BeforeGeneral formula (1)During ~Z orSaidGeneral formula (3)During ~Q is an alkylene group which may have a substituent, an arylene group which may have a substituent, CR.²¹= CR²²(R²¹And R²²Indicates an alkyl group that may have a substituent, an aryl group that may have a substituent, or a hydrogen atom.Su.R²¹And R²²May be the same or different..), C = O, S = O, SO₂, Oxygen atomas well asSulfur atomOne organic residue selected from the group consisting of or theseCombinationDerivedOrganic residuesIsThe electrophotographic photosensitive member according to any one of claims 1 to 7.
9. BeforeGeneral formula (1)During ~Z orSaidGeneral formula (3)During ~Q is represented by the following general formula (9)Is the basisThe electrophotographic photosensitive member according to any one of claims 1 to 8.
[Chemical 9]

(Generalformula(9)Medium, X¹~ X³Is an alkylene group which may have a substituent, (CR²³= CR²⁴) M¹, C = O, S = O, SO₂, Indicates an oxygen atom or a sulfur atomSu.Ar⁸And Ar⁹Indicates an arylene group which may have a substituent...R²³And R²⁴Indicates an alkyl group that may have a substituent, an aryl group that may have a substituent, or a hydrogen atom.Su.R²³And R²⁴May be the same or different..m¹Is an integer from 1 to 5, p to t is0 to 0Indicates an integer of 10..However, pt cannot be 0 at the same time...)
10. BeforeGeneral formula (1)During ~Z orSaidGeneral formula (3)During ~Q is represented by the following general formula (10)Is the basisThe electrophotographic photosensitive member according to any one of claims 1 to 8.
[Chemical 10]

(Generalformula(10)Medium, Ar¹⁰Indicates an arylene group which may have a substituent...X⁴And X⁵Is (CH₂)_g, (CH = CR²⁵)_h, C = O or oxygen atom..R²⁵Indicates an alkyl group that may have a substituent, an aryl group that may have a substituent, or a hydrogen atom.Su.g is an integer of 1 to 10, h is an integer of 1 to 5, and u to w are0 to 0Indicates an integer of 10..However, u to w cannot be 0 at the same time...)
11. BeforeGeneral formula (2)During ~R¹, R²And R³Claims that is an aryl group which may have a substituent.3The electrophotographic photosensitive member according to.
12. BeforeGeneral formula (3)During ~R⁴ ,R⁵ ,R⁸And R⁹OfofAt least two are aryl groups, which may have substituents, and R⁶And R⁷Claims that is an arylene group which may have a substituent.4The electrophotographic photosensitive member according to.
13. BeforeGeneral formula (3)During ~R⁴ ,R⁵ ,R⁸And R⁹Is an aryl group that may have a substituent and R⁶And R⁷Claims that is an arylene group which may have a substituent.4The electrophotographic photosensitive member according to.
14. BeforeGeneral formula (4)During ~R¹⁰And R¹¹Claims that is an aryl group which may have a substituent.5The electrophotographic photosensitive member according to.
15. BeforeGeneral formula (4)During ~R¹⁰~ R¹³Claims that is an aryl group which may have a substituent.5The electrophotographic photosensitive member according to.
16. BeforeGeneral formula (5)During ~R¹⁴Claims that is an aryl group which may have a substituent.6The electrophotographic photosensitive member according to.
17. BeforeGeneral formula (6)During ~R¹⁶Claims that is an aryl group which may have a substituent.6The electrophotographic photosensitive member according to.
18. BeforeGeneral formula (7)During ~R¹⁷And R¹⁸Claims that is an aryl group which may have a substituent.7The electrophotographic photosensitive member according to.
19. BeforeGeneral formula (8)During ~R²⁰Claims that is an aryl group which may have a substituent.7The electrophotographic photosensitive member according to.
20. SaidChain polymerizableSensualGroup P¹ as well asP²One or both,The electrophotographic photosensitive member according to any one of claims 1 to 19, which is an unsaturated polymerizable functional group represented by the following general formula (11).
[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, an aralkyl group which may have a substituent or an aryl group which may have a substituent} or −CONR.²⁷R²⁸{R²⁷And R²⁸Indicates a hydrogen atom, a halogen atom, 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 may be the same as or different from each other. May}Su.W may have a substituentAllilenMay have groups and substituentsIaLucilene group, -COO-, -O-, -OO-, -S- or -CONR²⁹− {R²⁹Indicates a hydrogen atom, a halogen atom, 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}...f indicates 0 or 1..)
Claim21] SaidChain polymerizableSensualGroup P¹ as well asP²One or both,followingConstructionEquation (14)~ (20)In the group shownClaims 1 to19The electrophotographic photosensitive member according to any one of.
[Chemical12]

Claim22] SaidChain polymerizableSensualGroup P¹ as well asP²One or both,BeforeRecordConstructionEquation (14)Or(15)In the group indicated byA claim21The electrophotographic photosensitive member according to.
Claim23] SaidIn the same molecule2Hole-transporting compound with one or more chain-growth functional groupsAcidClaims 1 to which the conversion potential is 0.4 to 1.2 (V).22The electrophotographic photosensitive member according to any one of.
Claim24] SaidThe cured product is a cured product obtained by cross-linking a hole-transporting compound having two or more chain-growth functional groups in the same molecule with radiation.Claims 1 to23The electrophotographic photosensitive member according to any one of.
25. The electrophotographic photosensitive member according to claim 24, wherein the radiation is an electron beam.
Claim26】 BeforePower recordingThe acceleration voltage of the child line is 300kClaims that are V or less25The electrophotographic photosensitive member according to.
Claim27The claim that the irradiation dose of the electron beam is 1 to 100 mad.25 or 26The electrophotographic photosensitive member according to.
Claim281 to claim that the phthalocyanine compound is oxytitanium phthalocyanine.27The electrophotographic photosensitive member according to any one of.
Claim291 to claim that the phthalocyanine compound is chlorogallium phthalocyanine.27The electrophotographic photosensitive member according to any one of.
Claim301 to claim that the phthalocyanine compound is hydroxygallium phthalocyanine.27The electrophotographic photosensitive member according to any one of.
Claim311 to claim that the phthalocyanine compound is a metal-free phthalocyanine.27The electrophotographic photosensitive member according to any one of.
Claim32] Claims 1 to31The electrophotographic photosensitive member according to any one ofWhen, Charging the electrophotographic photosensitive memberSuCharging means,TheElectrophotographic photosensitive memberElectrostatic latent image formed on the surface ofDeveloped with tonerTo form a toner imageDevelopment means and, The electrographPhotoreceptorSurface transfer residueTonerRemovalSelected from a group of cleaning meansRuat least1With one meansToSupports integrally and attaches / detaches to / from the electrophotographic device bodyPossibleA process cartridge characterized by being.
Claim33] Claims 1 to31The electrophotographic photosensitive member according to any one of the above, the electrophotographic photosensitive member is charged.SuCharging means, chargedTheImage exposure is performed on the electrophotographic photosensitive member.On the surface of the electrophotographic photosensitive memberImage exposure means for forming an electrostatic latent image,TheElectrophotographic photosensitive memberElectrostatic latent image formed on the surface ofDeveloped with tonerTo form a toner imageDevelopment means and, Formed on the surface of the electrophotographic photosensitive memberToner imageTransfer to transfer materialAn electrophotographic apparatus comprising a transfer means for performing.
Description: TECHNICAL FIELD [Detailed description of the invention]
[0001]
[Technical field to which the invention belongs]
The present invention relates to an electrophotographic photosensitive member, a process cartridge having an electrophotographic photosensitive member, and an electrophotographic apparatus. Specifically, the present invention relates to an electrophotographic photosensitive member having a surface layer containing a specific resin, a process cartridge having an electrophotographic photosensitive member, and an electron. Regarding photographic equipment.
0002.
[Conventional technology]
Conventionally, inorganic materials such as selenium, cadmium sulfide, and zinc oxide have been known as photoconducting materials used for electrophotographic photosensitive members. On the other hand, organic materials such as polyvinylcarbazole, phthalocyanine, and azo pigments are attracting attention for their advantages such as high productivity and non-pollution properties, and tend to be inferior to inorganic materials in terms of photoconductivity and durability. , Has come to be widely used.
0003
These electrophotographic photosensitive members are often used as function-separated photoconductors in which a charge generating layer and a charge transporting layer are laminated in order to satisfy both electrical and mechanical properties. On the other hand, as a matter of course, the electrophotographic photosensitive member is required to have sensitivity, electrical characteristics, optical characteristics, and durability characteristics according to the electrophotographic process applied.
0004
In recent years, while digitization in copiers has rapidly developed, high speed / high definition / high durability has also progressed in the field of laser beam printers, and the development of electrophotographic photosensitive members commensurate with this is required. .. At present, when digitization has become mainstream, electrophotographic devices using a semiconductor laser as a light source are common, but the oscillation wavelength is 790 ± 20 nm, which is an infrared region, and sufficient sensitivity is provided in this wavelength region. Of charge generating material with1As a result, phthalocyanine compounds have been widely used conventionally.
0005
There are many types, and they are classified into non-metallic phthalocyanines and metallic phthalocyanines. Among the metallic phthalocyanines, copper phthalocyanines as shown in JP-A-50-38543, JP-A-61-21705, and JP-A61. Oxytitanium phthalocyanines shown in JP-A-239248, JP-A-64-17066, JP-A-3-128973, etc. are well known. Further, in recent years, chlorogallium phthalocyanine disclosed in JP-A 1-221459, JP-A-5-98181, JP-A-7-207171, etc., JP-A-5-236007, JP-A-7-53892 Phthalocyanine compounds having a novel central metal are provided, including hydroxygallium phthalocyanine and the like disclosed in Japanese Patent Publication No. In addition, the existence of various crystalline forms has been reported for each of the above phthalocyanine compounds.
0006
In order to exhibit sufficient sensitivity and electrophotographic properties when these phthalocyanine compounds are used as charge generating materials, the combination of charge transporting materials is very important. In general, the photoconductivity of an electrophotographic photosensitive member will be explained by taking, for example, a laminated function-separated photosensitive member, which is the current mainstream, as an example. First, light is absorbed by a charge generating material to generate photocarriers. It is believed that the photocarriers are expressed when they are injected and transported into the charge transport layer. Here, it has been reported that the charge transporting material is very involved not only in the charge transporting ability but also in the charge generation and injection in the charge generating material, and the phthalocyanine compound is no exception.
0007
Generally, the charge transport layer is formed by mixing a low molecular weight charge transport material with an inert linear polymer, but as described above, it sufficiently exhibits charge generation / injection efficiency and charge transport capacity. It is desirable that the concentration of the charge transport material is sufficiently high in order to allow the charge to be transported. However, on the other hand, increasing the content of such a low molecular weight material lowers the film forming property and causes precipitation, cracks and the like. Further, since the mechanical strength of the film itself is lowered, the film is scraped or scratched during repeated use in the electrophotographic process, and sufficient durability cannot be ensured.
0008
As a means for solving these problems, an attempt to use a curable resin as a resin for a charge transport layer is disclosed, for example, in Japanese Patent Application Laid-Open No. 2-127652, but even in this case, the low molecular weight component is still contained. However, since it acts as a plasticizer in the binder resin, it has not been a fundamental solution to the problems of precipitation and cracks as described above.
0009
Further, although it is a curable resin, it is difficult to obtain sufficient mechanical strength due to the large plastic effect due to the addition of a large amount of low molecular weight components responsible for exhibiting sufficient photosensitivity. Further, in JP-A-5-216249, JP-A-7-72640, etc., the charge transport layer contains a monomer having a carbon-carbon double bond and is a charge transport material.FeeAlthough an electrophotographic photosensitive member in which a charge transport layer cured film is formed by reacting with a carbon-carbon double bond of the above by heat or light energy is disclosed, the charge transport material is disclosed.FeeIs only fixed to the polymer main skeleton in a pendant shape, and its mechanical strength is not sufficient because the plastic action mentioned above cannot be sufficiently eliminated. In addition, a charge transport material is used to improve the charge transport capacity.FeeIf the concentration of is high, the crosslink density becomes low and sufficient mechanical strength cannot be ensured. Furthermore, there is concern about the influence on the electrophotographic properties of the initiators required for polymerization.
0010
Further, as another solution, for example, Japanese Patent Application Laid-Open No. 8-248649 discloses an electrophotographic photosensitive member in which a group having a charge transporting ability is introduced into a thermoplastic polymer main chain to form a charge transporting layer. However, compared to the conventional molecular dispersion type charge transport layer, it is effective against precipitation and improves mechanical strength, but it is a thermoplastic resin to the last, and its mechanical strength is limited. Therefore, it cannot be said that it is sufficient in terms of handling and productivity including the solubility of the resin. As described above, the conventional systems have not achieved both high mechanical intensity and excellent optical sensitivity, and improvement of them is strongly desired at present.
0011
[Problems to be Solved by the Invention]
An object of the present invention is to exhibit excellent photosensitivity and excellent wear resistance during repeated use, and there is very little change or deterioration of photoconductor characteristics such as an increase in residual potential during repeated use, and during repeated use. The purpose is to provide an electrophotographic photosensitive member capable of exhibiting stable performance.
0012
Another object of the present invention is to provide an electrophotographic photosensitive member having improved wear resistance and scratch resistance of the surface layer of the photoconductor, a long life and high image quality, a process cartridge having the electrophotographic photosensitive member, and an electrophotographic apparatus. There is.
0013
[Means for solving problems]
According to the present inventionConductive support and theOn a conductive supportBeen formedIn an electrophotographic photosensitive member having a photosensitive layer,
The photosensitive layerBut,Charge generating materialAsPhthalocyanine compoundContains,
The electrophotographic photosensitive memberSurface layerBut in the same molecule2Hole-transporting compound with one or more chain-growth functional groupsToCrosslinkGet itCuringStuffIncludingHave
An electrophotographic photosensitive member, which is characterized byAndA process cartridge and an electrophotographic apparatus having an electrophotographic photosensitive member are provided.
0014.
BEST MODE FOR CARRYING OUT THE INVENTION
Hereinafter, embodiments of the present invention will be described in detail.
0015.
First, the chain-growth functional group in the present invention will be described. The chain polymerization in the present invention indicates the former polymerization reaction form when the reaction for producing a polymer is roughly divided into chain polymerization and step-growth polymerization. For details, for example, "Chemistry of basic synthetic resin" by Tadahiro Miwa, Gihodo Publishing Co., Ltd. (New Edition) ”July 25, 1995 (1st edition, 8 prints) P.M. As described in 24, it refers to unsaturated polymerization, ring-opening polymerization, isomerization polymerization, etc., in which the reaction proceeds mainly via intermediates such as radicals or ions.
0016.
The chain-growth functional group P in the general formula (1) means a functional group capable of the above-mentioned reaction form, but here, unsaturated polymerization or ring-opening polymerizable functional group which occupies most of the functional groups and has a wide range of applications. A specific example of is shown.
[0017]
Unsaturated polymerization is a reaction in which unsaturated groups such as C = C, C≡C, C = O, C = N, C≡N, etc. are polymerized by radicals, ions, etc., but mainly C = C. In most cases. Specific examples of unsaturated polymerizable functional groups are shown in Table 1, but the present invention is not limited thereto.
0018
[Table 1]

0019
In the table, R has an alkyl group such as a methyl group, an ethyl group and a propyl group which may have a substituent, an aralkyl group such as a benzyl group and a phenethyl group which may have a substituent, and a substituent. It may indicate an aryl group such as a phenyl group, a naphthyl group or an anthryl group, or a hydrogen atom.
0020
In ring-opening polymerization, an unstable cyclic structure having strains such as a carbocycle, an oxo ring, and a nitrogen heterocycle is activated by the action of a catalyst, and at the same time the ring is opened, the polymerization is repeated to produce a chain polymer. Although it is a reaction, in this case, most of the ions basically act as active species. Specific examples of the ring-opening polymerizable functional group are shown in Table 2, but the present invention is not limited thereto.
0021.
[Table 2]

0022.
In the table, R has an alkyl group such as a methyl group, an ethyl group and a propyl group which may have a substituent, an aralkyl group such as a benzyl group and a phenethyl group which may have a substituent, and a substituent. It may indicate an aryl group such as a phenyl group, a naphthyl group or an anthryl group, or a hydrogen atom.
[0023]
Among the chain-growth functional groups according to the present invention as described above, the followingKiichiIt is represented by the general formulas (11) to (13).BasicIs preferable.
0024
[Chemical13]

0025
The above generalformula(11)Among them, E is a hydrogen atom, a halogen atom such as fluorine, chlorine or bromine, an alkyl group such as a methyl group which may have a substituent, an ethyl group, a propyl group or a butyl group, or a benzyl which may have a substituent. Aralkyl group such as group, phenethyl group, naphthylmethyl group, flufuryl group and thienyl group, phenyl group which may have substituent, naphthyl group, anthryl group, pyrenyl group, aryl group such as thiophenyl group and furyl group, CN Alkoxy groups such as groups, nitro groups, methoxy groups, ethoxy groups, propoxy groups, -COOR²⁶Or -CONR²⁷R²⁸Is shown.
0026
W is an arylene group such as a divalent phenylene group, a naphthylene group or an anthracenylene group which may have a substituent, a methylene group which may have a substituent, an ethylene group, a butylene group and the like.ALucilene group, -COO-, -O-, -OO-, -S- or -CONR²⁹Indicated by-.
[0027]
Here R²⁶~ R²⁹Is a hydrogen atom, a halogen atom such as fluorine, chlorine or bromine, an alkyl group such as a methyl group which may have a substituent, an ethyl group or a propyl group, a benzyl group which may have a substituent, a phenethyl group or the like. Indicates an aryl group such as a phenyl group, a naphthyl group, an anthryl group, which may have an aralkyl group and a substituent.Su.R²⁸And R²⁹May be the same or different from each other. Further, f indicates 0 or 1.
[0028]
The substituents that may be contained in E and W include halogen atoms such as fluorine, chlorine, bromine and iodine, or nitro groups or cyano groups or hydroxyl groups or methyl groups, ethyl groups, propyl groups, butyl groups and other alkyl groups. Alternatively, an alkoxy group such as a methoxy group, an ethoxy group or a propoxy group, an aryloxy group such as a phenoxy group or a naphthoxy group, a benzyl group, a phenethyl group, a naphthylmethyl group, a furfuryl group, a thienyl group or the like, an aralkyl group or a phenyl group or a naphthyl group. , Anthryl group, aryl group such as pyrenyl group and the like.
[0029]
[Chemical14]

[0030]
The above generalformula(12)Medium, R³⁰And R³¹Has an alkyl group such as a hydrogen atom, a methyl group which may have a substituent, an ethyl group, a propyl group and a butyl group, and an aralkyl group or a substituent such as a benzyl group and a phenethyl group which may have a substituent. Indicates an aryl group such as a phenyl group or a naphthyl group which may be used.Su.n represents an integer of 1 to 10 or less.
0031
[Chemical15]

[0032]
The above generalformula(13)Medium, R³²And R³³Has an alkyl group such as a hydrogen atom, a methyl group which may have a substituent, an ethyl group, a propyl group and a butyl group, and an aralkyl group or a substituent such as a benzyl group and a phenethyl group which may have a substituent. Indicates an aryl group such as a phenyl group or a naphthyl group which may be used.Su.n is0 to 010Indicates an integer.
0033
The general formula (12) and the general formula (13)During ~R³⁰~ R³³Examples of the substituent that may be possessed by the above are halogen atoms such as fluorine, chlorine, bromine and iodine, or alkyl groups such as methyl group, ethyl group, propyl group and butyl group, or alkoxy groups such as methoxy group, ethoxy group and propoxy group. An aryloxy group such as a group or a phenoxy group or a naphthoxy group, a benzyl group, a phenethyl group, a naphthylmethyl group, a furfuryl group, an aralkyl group such as a thienyl group or an aryl group such as a phenyl group, a naphthyl group, an anthryl group or a pyrenyl group. Can be mentioned.
0034
Further, among the above general formulas (11) to (13), the following chain-growth functional groups are more particularly preferable.ConstructionRepresented by equations (14) to (20)BasicCan be mentioned.
0035.
[Chemical16]

0036
Furthermore, the aboveConstructionIn equations (14) to (20)The above structureEquation (14)Indicated byAcryloyloxy group orThe above structureEquation (15)Indicated byA methacryloyloxy group is particularly preferable from the viewpoint of polymerization characteristics and the like.
0037
In the present invention, the "hole-transporting compound having a chain-growth functional group" is the chain-growth property described above.SensualAs a functional group, the group is a hole-transporting compound described above.2Indicates a compound that is chemically bonded to one or more. In this case, the chain-growth functional groups may all be the same or different. Those chain-growth functional groups2As a hole transporting compound having one or more, the followingKiichiGeneral formula (1)Compounds indicated byIs preferable.
[0038]
[Chemical17]

[0039]
The above generalformula(1)Medium, P¹And P²Indicates a chain-growth functional groupSu.P¹And P²May be the same or different. Z indicates an organic residue which may have a substituent.Su.Y represents a hydrogen atom. a, b and d are0 or moreIndicates the above integer. However, when a = 0, b + d indicates an integer of 3 or more, when b or d is 0, a indicates an integer of 2 or more, and in other cases, a + b + d indicates an integer of 3 or more. Also, when a is 2 or moreIsP¹May be the same or different, when d is 2 or moreIsP²May be the same or different, BWhen is 2 or moreIsZ may be the same or different.
0040
Here, "when a is 2 or more"IsP¹May be the same or different. "¹¹, P¹², P¹³, P¹⁴, P¹⁵・ ・ ・ ・ P¹ⁿIn the case of, for example, when a = 3, the chain-growth functional group P that directly binds to the hole-transporting compound A¹Even if all three are the same2Same1One is different (for example, P¹¹And P¹¹And P¹²But all three are different (for example, P)¹²And P¹⁵And P¹⁷It means that it may be (such as) ("When d is 2 or more"IsP²May be the same or different "because" when b is 2 or moreIs"Z may be the same or different" means the same thing...).
[0041]
The above general formula (1)During ~A indicates a hole-transporting group, and any one may be used as long as it exhibits a hole-transporting property.¹If it is shown as a hydrogen addition compound (hole transport compound) in which the binding site with or Z is replaced with a hydrogen atom, for example, a triarylamine derivative such as an oxazole derivative, an oxadiazole derivative, an imidazole derivative, or a triphenylamine, 9- (P-diethylaminostyryl) anthracene, 1,1-bis- (4-dibenzylaminophenyl) propane, styrylanthracene, styrylpyrazoline, phenylhydrazones, thiazole derivatives, triazole derivatives, phenazine derivatives, aclysine derivatives, benzofuran derivatives, Condensed ring hydrocarbons such as benzimidazole derivatives, thiophene derivatives, N-phenylcarbazole derivatives, naphthalene, anthracene, phenanthrene, pyrene, fluorene, fluoransene, azulene, inden, perylene, chrysen, coronen, etc., which may have substituents, or Examples thereof include a fused complex ring of benzofuran, indol, carbazole, benzcarbazole, aclysine, phenothiazine, quinoline and the like which may have a substituent.
[0042]
Further, among the hole transport compounds, they are represented by the following general formulas (2), (3), (4), (5) and (7).CompoundIs preferable.
[0043]
[Chemical18]

[0044]
The above generalformula(2)Medium, R¹, R²And R³Is a C such as a methyl group, an ethyl group, a propyl group, a butyl group, etc., which may have a substituent.₁~ C₁₀Alkyl group, benzyl group which may have a substituent, phenethyl group, naphthylmethyl group, flufuryl group, thienyl group and the like may have an aralkyl group or a substituent which may have a phenyl group, a naphthyl group, an anthryl group, a phenanthryl group. Indicates an aryl group such as a group, a 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 and a dibenzothiophenyl group.
0045
However, R¹, R²And R³Ofofat least2Indicates an aryl groupSu.R¹, R²And R³May be the same or different. Furthermore, among them, R¹, R²And R³It is particularly preferable that all of the above are aryl groups. In addition, the above general formula (2)During ~R¹Or R²Or R³Any of2Each of them may be bonded directly or via a bonding group, and the bonding group includes an alkylene group such as a methylene group, an ethylene group and a propylene group, a hetero atom such as an oxygen and a sulfur atom, and a CH = CH group. Can be mentioned.
[0046]
[Chemical19]

[0047]
The above generalformula(3)Medium, R⁴, R⁵, R⁸And R⁹Is a C such as a methyl group, an ethyl group, a propyl group, a butyl group, etc., which may have a substituent.₁~ C₁₀Alkyl group, benzyl group which may have a substituent, phenethyl group, naphthylmethyl group, flufuryl group, thienyl group and the like may have an aralkyl group or a substituent which may have a phenyl group, a naphthyl group, an anthryl group, a phenanthryl group. Indicates an aryl group such as a group, a pyrenyl group, a thiophenyl group, a fryl 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 or a dibenzothiophenyl group.Su.R⁴, R⁵, R⁸And R⁹May be the same or different. R⁶And R⁷Is a C such as a methylene group, an ethylene group, a propylene group, etc., which may have a substituent.₁~ C₁₀An arylene group (benzene, naphthalene, anthracene, phenanthrene, pyrene, benzothiophene, pyridine, quinoline, benzoquinoline, carbazole, phenothiazine, benzofuran, benzothiophene, dibenzofuran, dibenzothiophene, etc. (Allylene group from which two hydrogens have been removed)Su.R⁶And R⁷May be the same or different. Q indicates an organic residue which may have a substituent.
0048
Furthermore, among them, R in the above general formula (3)⁴, R⁵, R⁸And R⁹Two or more of them are aryl groups which may have a substituent, and R⁶And R⁷Is preferably an arylene group which may have a substituent, and further R⁴, R⁵, R⁸And R⁹Is particularly preferably an aryl group in which all four may have a substituent. In addition, the above general formula (3)During ~R⁴Or R⁵Or R⁶Any of2Tsu or R⁷Or R⁸Or R⁹Any of2Each of them may be bonded directly or via a bonding group, and the bonding group includes an alkylene group such as a methylene group, an ethylene group and a propylene group, a hetero atom such as an oxygen and a sulfur atom, and a CH = CH group. Can be mentioned.
[0049]
[Chemical20]

0050
The above generalformula(4)Medium, m indicates 0 or 1Su.R¹⁰~ R¹³Is a C such as a methyl group, an ethyl group, a propyl group, a butyl group, etc., which may have a substituent.₁~ C₁₀Alkyl group, benzyl group which may have a substituent, phenethyl group, naphthylmethyl group, flufuryl group, thienyl group and the like may have an aralkyl group or a substituent which may have a phenyl group, a naphthyl group, an anthryl group, a phenanthryl group. Indicates an aryl group such as a group, a pyrenyl group, a thiophenyl group, a fryl 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 or a dibenzothiophenyl group.Su.R¹⁰~ R¹³May be the same or different.
0051
Ar¹Is two from an arylene group (benzene, naphthalene, anthracene, phenanthrene, pyrene, benzothiophene, pyridine, quinoline, benzoquinoline, carbazole, phenothiazine, benzofuran, benzothiophene, dibenzofuran, dibenzothiophene, etc.) which may have a substituent. Shows an arylene group from which hydrogen has been removed)Su.Ar²When m = 0, may have a substituent, a phenyl group, a naphthyl group, an anthryl group, a phenanthryl group, a pyrenyl group, a thiophenyl group, a furyl group, a pyridyl group, a quinolyl group, a benzoquinolyl group, a carbazolyl group, a phenothiazineyl. Indicates an aryl group such as a group, a benzofuryl group, a benzothiophenyl group, a dibenzofuryl group, or a dibenzothiophenyl group.Su.When m = 1, the above Ar¹Shows an arylene group similar to. If m = 1, Ar¹And Ar²May be the same or different.
[0052]
Furthermore, among them, R in the above general formula (4)¹⁰And R¹¹Is preferably an aryl group which may have a substituent, and R¹⁰~ R¹³Is particularly preferably an aryl group in which all four may have a substituent. In addition, the above general formula (4)During ~R¹⁰And R¹¹Or R¹²And R¹³Or Ar¹And Ar²May be bonded directly or via a bonding group, and examples of the bonding group include an alkylene group such as a methylene group, an ethylene group and a propylene group, a hetero atom such as an oxygen and a sulfur atom, and a CH = CH group. Can be mentioned.
[0053]
[Chemical21]

0054
The above generalformula(5)Medium, Ar³, Ar⁴And R¹⁴Ofofat least1One is the following general formula (6)Indicated bySubstituent1Have one or more.
0055
[Chemical22]

0056
In the above general formulas (5) and (6), Ar³, Ar⁴And Ar⁵Is a phenyl group, a naphthyl group, an anthryl group, a phenanthryl group, a pyrenyl group, a thiophenyl group, a furyl group, a pyridyl group, a quinolyl group, a benzoquinolyl group, a carbazolyl group, a phenothiazine group, a benzofuryl group, which may have a substituent. Indicates an aryl group such as a benzothiophenyl group, a dibenzofuryl group, or a dibenzothiophenyl group.Su.R¹⁴, R¹⁵And R¹⁶Is a C such as a methyl group, an ethyl group, a propyl group, a butyl group, etc., which may have a substituent.₁~ C₁₀Alkyl group, benzyl group which may have a substituent, phenethyl group, naphthylmethyl group, flufuryl group, aralkyl group such as thienyl group, phenyl group which may have a substituent, naphthyl group, anthryl group, phenanthryl Aryl group or hydrogen atom such as group, pyrenyl group, thiophenyl group, frill group, pyridyl group, quinolyl group, benzoquinolyl group, carbazolyl group, phenothiazinyl group, benzofuryl group, benzothiophenyl group, dibenzofuryl group, dibenzothiophenyl group. (However, R¹⁴Except when is a hydrogen atom). In addition, Ar³And Ar⁴And R¹⁵And R¹⁶May be the same or different.
[0057]
Furthermore, among them, R¹⁴And R¹⁶Is particularly preferably an aryl group. Also, R¹⁴Or Ar³Or Ar⁴Any of2Or Ar⁵And R¹⁶May be bonded directly or via a bonding group, and examples of the bonding group include an alkylene group such as a methylene group, an ethylene group and a propylene group, a hetero atom such as an oxygen and sulfur atom, and a CH = CH group. Be done. n¹Is0 to 0Indicates an integer of 2.
0058.
[Chemical23]

[0059]
However, the above general formula (7), the condensed ring hydrocarbon and the condensed composite ring are described in the following general formula (8).Indicated bySubstituent1Have one or more.
[0060]
[Chemical24]

[0061]
In the above general formulas (7) and (8), Ar⁶And Ar⁷May have a substituent, a phenyl group, a naphthyl group, an anthryl group, a phenanthryl group, a pyrenyl group, a thiophenyl group, a fryl group, a pyridyl group, a quinolyl group, a benzoquinolyl group, a carbazolyl group, a phenothiazine group, a benzofuryl group, a benzo. Indicates an aryl group such as a thiophenyl group, a dibenzofuryl group, or a dibenzothiophenyl group.Su.R¹⁷, R¹⁸, R¹⁹And R²⁰Is a C such as a methyl group, an ethyl group, a propyl group, a butyl group, etc., which may have a substituent.₁~ C₁₀Alkyl group, benzyl group which may have a substituent, phenethyl group, naphthylmethyl group, flufuryl group, aralkyl group such as thienyl group, phenyl group which may have a substituent, naphthyl group, anthryl group, phenanthryl Aryl group or hydrogen atom such as group, pyrenyl group, thiophenyl group, frill group, pyridyl group, quinolyl group, benzoquinolyl group, carbazolyl group, phenothiazinyl group, benzofuryl group, benzothiophenyl group, dibenzofuryl group, dibenzothiophenyl group. (However, R¹⁷And R¹⁸Except when is a hydrogen atom). In addition, R¹⁷And R¹⁸And R¹⁹And R²⁰May be the same or different.
[0062]
Among them, R²⁰Is preferably an aryl group, and the hole transporting group is of the general formula (7) and R.¹⁷And R¹⁸Is particularly preferably an aryl group. Also, R¹⁷Or R¹⁸Or Ar⁶Any of2Or Ar⁷And R²⁰May be bonded directly or via a bonding group, and examples of the bonding group include an alkylene group such as a methylene group, an ethylene group and a propylene group, a hetero atom such as an oxygen and sulfur atom, and a CH = CH group. Be done. n²Is0 to 0Indicates an integer of 2.
[0063]
Further, Z in the general formula (1) or Q in the general formula (3) is an alkylene group which may have a substituent, an arylene group which may have a substituent, and CR.²¹= CR²²(R²¹And R²²Indicates an alkyl group, an aryl group or a hydrogen atomSu.R²¹And R²²May be the same or different..), C = O, S = O, SO₂, Oxygen atomas well asSulfur atomOne organic residue selected from the group consisting of or theseCombinationDerivedShows organic residues. Among them, it is represented by the following general formula (9).BasicIs preferable, and is represented by the following general formula (10).BasicIs particularly preferable.
[0064]
[Chemical25]

[0065]
[Chemical26]

[0066]
In the above general formula (9), X¹~ X³Is a C such as a methylene group, an ethylene group, a propylene group, etc., which may have a substituent.₁~ C₂₀Alkylene, (CR²³= CR²⁴) M¹, C = O, S = O, SO₂, Indicates an oxygen atom or a sulfur atomSu.Ar⁸And Ar⁹Has two arylene groups (benzene, naphthalene, anthracene, phenanthrene, pyrene, benzothiophene, pyridine, quinoline, benzoquinoline, carbazole, phenothiazine, benzofuran, benzothiophene, dibenzofuran, dibenzothiophene, etc.) which may have a substituent. The arylene group from which the hydrogen atom has been removed) is shown. R²³And R²⁴Indicates 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.Su.R²³And R²⁴May be the same or different. m¹Is an integer from 1 to 5, p to t is0 to 0Indicates an integer of 10 (however, p to t cannot be 0 at the same time...).
[0067]
In the above general formula (10), X⁴And X⁵Is (CH₂)_g, (CH = CR²⁵)_h, C = O, or oxygen atomSu.Ar¹⁰Has two arylene groups (benzene, naphthalene, anthracene, phenanthrene, pyrene, benzothiophene, pyridine, quinoline, benzoquinoline, carbazole, phenothiazine, benzofuran, benzothiophene, dibenzofuran, dibenzothiophene, etc.) which may have a substituent. The arylene group from which the hydrogen atom has been removed) is shown. R²⁵Indicates 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. g is an integer of 1 to 10, h is an integer of 1 to 5, and u to w is 0.~Indicates an integer of 10 (especially0 to 0An integer of 5 is preferred. However, u to w cannot be 0 at the same time...).
[0068]
In addition, the above-mentioned general formulas (1) to (10)During ~R¹~ R²⁵, Ar¹~ Ar¹⁰, X¹~ X⁵, Z and Q may each have a halogen atom such as fluorine, chlorine, bromine, iodine or an alkyl such as a nitro group or a cyano group or a hydroxyl group or a methyl group, an ethyl group, a propyl group or a butyl group. Alkyl group such as group or methoxy group, ethoxy group, propoxy group or phenoxy group, aryloxy group such as naphthoxy group or benzyl group, phenethyl group, naphthylmethyl group, furfuryl group, thienyl group or the like, aralkyl group or phenyl group, naphthyl An aryl group such as a group, anthryl group or pyrenyl group or a substituted amino group such as a dimethylamino group, a diethylamino group, a dibenzylamino group, a diphenylamino group or a di (p-tolyl) amino group, a styryl group, a naphthylvinyl group or the like. Examples thereof include an arylvinyl group.
[0069]
Also, within the same molecule in the present invention2The hole-transporting compound having one or more chain-growth functional groups preferably has an oxidation potential of 1.2 (V) or less. That is, the hole-transporting compound having a chain-growth functional group represented by the general formula (1) and the hydrogen adduct of the hole-transporting group A preferably have an oxidation potential of 1.2 (V) or less. , 0.4 to 1.2 (V), more preferably. When the oxidation potential exceeds 1.2 (V), it is difficult for charge (holes) to be injected from the charge generating material, and problems such as an increase in residual potential, deterioration of sensitivity, and large potential fluctuation during repeated use occur. In addition to problems such as a decrease in chargeability when the value is less than 0.4 (V), the compound itself is easily oxidized and easily deteriorates, resulting in sensitivity deterioration, image blurring, and potential fluctuation during repeated use. This is because problems such as an increase in the electric charge occur.
[0070]
The oxidation potential described here is measured by the following method.
[0071]
(Measurement method of oxidation potential)
A saturated calomel electrode is used as a reference electrode, and 0.1 N (n-Bu) is added to the electrolytic solution.₄N^＋ClO₄ ⁻Using an acetonitrile solution, the potential applied to the working electrode (platinum) was swept by a potential sweeper, and the potential when the obtained current-potential curve showed a peak was taken as the oxidation potential. Specifically, the sample is 0.1 N (n-Bu).₄N^＋ClO₄ ⁻Dissolve in an acetonitrile solution to a concentration of about 5 to 10 mmol%. Then, a voltage is applied to this sample solution by a working electrode, and the current change when the voltage is linearly changed from a low potential (0V) to a high potential (+ 1.5V) is measured to obtain a current-potential curve. The potential at the time when the current value showed a peak (the first peak when there were a plurality of peaks) in this current-potential curve was defined as the oxidation potential.
[0072]
Furthermore, the hole-transporting compound having a chain-growth functional group has a hole-transporting ability of 1 × 10.^-7(Cm²/ V. Those having a drift mobility of sec) or more are preferable (however, applied electric field: 5 × 10).⁴V / cm). 1x10^-7(Cm²/ V. If it is less than sec), holes may not sufficiently move as an electrophotographic photosensitive member before development after exposure, so that there may be a problem that the sensitivity is apparently reduced and the residual potential is also increased.
[0073]
The following are typical examples of the hole-transporting compound having a chain-growth functional group according to the present invention, but the present invention is not limited thereto.
[0074]
[Chemical27]

[0075]
[Chemical28]

[0076]
[Chemical29]

[0077]
[Chemical30]

[0078]
[Chemical31]

[0079]
[Chemical32]

[0080]
[Chemical33]

[0081]
[Chemical34]


[882]
[Chemical35]

[0083].
[Chemical36]

[0084]
[Chemical37]

[0085]
[Chemical38]

0083.
[Chemical39]

[0087]
[Chemical40]

[0088]
[Chemical40]

[089]
[Chemical42]

[0090]
[Chemical43]

[0091]
[Chemical44]

[0092]
[Chemical45]

[093]
[Chemical46]

[0094]
[Chemical47]

[0995]
[Chemical48]

[0906]
[Chemical49]

[097]
[Chemical50]

[0998]
[Chemical51]

[00099]
[Chemical52]

[0100]
[Chemical53]

[0101]
[Chemical54]

[0102]
[Chemical55]

[0103]
[Chemical56]

[0104]
[Chemical57]

[0105]
[Chemical58]

[0106]
[Chemical59]

[0107]
[Chemical60]

[0108]
[Chemical61]

[0109]
[Chemical62]

[0110]
[Chemical63]

[0111]
[Chemical64]

[0112]
[Chemical65]

[0113]
[Chemical66]

[0114]
[Chemical67]

[0115]
[Chemical68]

[0116]
[Chemical69]

[0117]
[Chemical70]

[0118]
[Chemical71]

[0119]
[Chemical72]

[0120]
[Chemical73]

[0121]
[Chemical74]

[0122]
[Chemical75]

[0123]
[Chemical76]

[0124]
[Chemical77]

[0125]
[Chemical78]

[0126]
[Chemical79]

[0127]
[Chemical80]


[0128]
[Chemical81]

[0129]
[Chemical82]

[0130]
[Chemical83]

[0131]
[Chemical84]

[0132]
[Chemical85]

[0133]
[Chemical86]

[0134]
[Chemical87]

[0135]
[Chemical88]

[0136].
[Chemical89]

[0137]
[Chemical90]

[0138]
[Chemical91]

[0139]
[Chemical92]

[0140]
[Chemical93]

[0141]
[Chemical94]

[0142]
[Chemical95]

[0143]
[Chemical96]

[0144]
[Chemical97]

[0145]
[Chemical98]

[0146]
[Chemical99]

[0147]
[Chemical100]

[0148]
[Chemical101]

[0149]
[Chemical102]

[0150]
[Chemical103]

[0151]
[Chemical104]

[0152]
[Chemical105]

[0153]
[Chemical106]

[0154]
[Chemical107]

[0155]
[Chemical108]

[0156]
[Chemical109]

[0157]
[Chemical110]

[0158]
[Chemical111]

[0159]
[Chemical112]

[0160]
[Chemical113]

[0161]
[Chemical114]

[0162]
[115]

[0163]
In the present invention, a typical method for synthesizing a hole-transporting compound having a chain-growth functional group is shown below.
[0164]
(Synthesis Example 1: Synthesis of Compound No. 6)
It was synthesized according to the following route.
[0165]
[Chemical116]

[0166]
1 (50 g: 0.47 mol), 2 (406 g: 1.4 mol), anhydrous potassium carbonate (193 g) and copper powder (445 g) were heated and stirred at 180 to 190 ° C. with 1.2 kg 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 132 g of 3.
[0167]
3 (120 g: 0.28 mol) was added to 1.5 kg of methyl cell solution, and sodium methylate (150 g) was slowly added while stirring at room temperature. After completion of the addition, the mixture was stirred as it was at room temperature for 1 hour, and then heated and stirred at 70 to 80 ° C. for 10 hours. The reaction mixture was poured into water, neutralized with dilute hydrochloric acid, extracted with ethyl acetate, the organic layer was 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 78 g of 4.
[0168]
4 (70 g: 0.2 mol) and triethylamine (40 g: 0.4 mol) were added to 400 ml of dry tetrahydrofuran THF, cooled to 0 to 5 ° C., and then acryloyl chloride (55 g: 0.6 mol) was slowly added dropwise. After completion of the dropping, the mixture was slowly returned to room temperature, and the mixture was stirred at room temperature for 4 hours. The reaction mixture was poured into water for neutralization, extracted with ethyl acetate, the organic layer was dried over anhydrous sodium sulfate, and the solvent was removed. The residue was column-purified using a silica gel column to obtain 42 g of 5 (Compound No. 6) (oxidation potential: 0.83 V).
[0169]
(Synthesis Example 2: Synthesis of Compound No. 71)
4 (10 g: 29 mmol) obtained in Synthesis Example 1 was added to 50 ml of dry THF, cooled to 0 to 5 ° C., and then 3.5 g of oily sodium hydride (about 60%) was slowly added. After completion of the addition, the temperature was returned to room temperature, the mixture was stirred for 1 hour, cooled to 0 to 5 ° C. again, and allyl bromide (17.5 g: 145 mmol) was slowly added dropwise. After completion of the dropping, the mixture was stirred as it was for 1 hour, returned to room temperature, and further stirred for 5 hours. The reaction mixture was poured into water for neutralization, extracted with toluene, the organic layer was dried over anhydrous sodium sulfate, and the solvent was removed. The residue was purified by column using a silica gel column to obtain 5.6 g of the target compound (Compound No. 71) (oxidation potential: 0.81 V).
[0170]
(Synthesis Example 3: Synthesis of Compound No. 55)
Compound No. obtained in Synthesis Example 2 above. 71 3.0 g is dissolved in 20 ml of dichloromethane, cooled to 0 to 5 ° C., 5.2 g of m-chloroperbenzoic acid (~ 70%) is slowly added, and the mixture is stirred for 1 hour, then returned to room temperature and stirred for 12 hours. It was. The reaction mixture was poured into water and extracted with dichloromethane. The organic layer was dried over anhydrous sodium sulfate, the solvent was removed, and the residue was column-purified using a silica gel column to obtain 2.1 g of the target compound (Compound No. 55) (oxidation potential: 0.81 V).
[0171]
(Synthesis Example 4: Synthesis of Compound No. 152)
It was synthesized according to the following route.
[0172]
[Chemical117]

[0173]
1 (70 g: 0.35 mol), 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. for 10 hours together with 600 g of 1,2-dichlorobenzene. It was. 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 3.
[0174]
3 (80 g: 0.26 mol) was added to 300 g of N, N-dimethylformamide (DMF), and ethanethiol sodium salt (about 90%: 62 g) was slowly added with stirring at room temperature. After the addition is completed, the mixture is stirred at room temperature for 1 hour and then refluxed.With 3Heating and stirring were performed for hours. After cooling, the reaction mixture was poured into water, weakly acidic with dilute hydrochloric acid, extracted with ethyl acetate, the organic layer was further extracted with a 1.2N aqueous sodium hydroxide solution, the aqueous layer was 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 4.
[0175]
4 (60 g: 0.21 mol) was added to 300 g of N, N-dimethylformamide, and caustic soda (8.3 g) was slowly added while 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 and 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 5.
[0176]
After cooling 182 g of DMF to 0 to 5 ° C., 63.6 g of phosphorus oxychloride was slowly added dropwise so as not to exceed 10 ° C. After the completion of the dropping, the mixture was stirred as it was for 15 minutes, and then a 5 (42.2 g: 0.07 mol) / DMF 102 g solution was slowly added dropwise. After completion of the dropping, the mixture was stirred as it was for 30 minutes, returned to room temperature, stirred for 2 hours, further heated to 80 to 85 ° C., and stirred for 15 hours. The reaction mixture was poured into 1.5 kg of an approximately 15% aqueous sodium acetate solution and stirred for 12 hours. After neutralizing it, it was extracted with toluene, the organic layer was dried over anhydrous sodium sulfate, the solvent was removed, and the residue was purified by column using a silica gel column to obtain 23 g of 6.
[0177]
0.89 g of lithium aluminum hydride was added to 100 ml of dry THF, and a solution of 6 (15 g: 0.023 mol) / 100 ml of dry THF was slowly added dropwise to the place where the mixture was stirred at room temperature. After completion of the dropping, the mixture was stirred at room temperature for 4 hours, and then 200 ml of a 5% aqueous hydrochloric acid solution was slowly added dropwise. After completion of the dropping, the mixture was extracted with toluene, the organic layer was dried over anhydrous sodium sulfate, the solvent was removed, and the residue was purified by column using a silica gel column to obtain 13.6 g of 7.
[0178]
7 (10 g: 0.015 mol) and triethylamine (6.1 g: 0.06 mol) were added to 120 ml of dry THF and cooled to 0 to 5 ° C., and then acryloyl chloride (4.1 g: 0.045 mol) was slowly added dropwise. After completion of the dropping, the mixture was slowly returned to room temperature, and the mixture was stirred at room temperature for 6 hours. The reaction mixture was poured into water for neutralization, extracted with ethyl acetate, the organic layer was dried over anhydrous sodium sulfate, and the solvent was removed. The residue was column-purified using a silica gel column to obtain 6.4 g of 8 (Compound No. 152) (oxidation potential: 0.78 V).
[0179]
(Synthesis Example 5: Synthesis of Compound No. 263)
It was synthesized according to the following route.
[0180]
[Chemical118]

[0181]
1 (50 g: 0.123 mol), 2 (62.4 g: 0.369 mol), anhydrous potassium carbonate (25.5 g) and copper powder (32 g) are heated and stirred together with 200 g of 1,2-dichlorobenzene at 180 to 190 ° C. Was carried out for 18 hours. After filtering the reaction solution, the solvent was removed under reduced pressure, and the residue was recrystallized twice with a mixed solvent of toluene / methanol to obtain 60.2 g of 3.
[0182]
After cooling 242 g of DMF to 0 to 5 ° C., phosphorus oxychloride (84.8 g: 553.2 mmol) was slowly added dropwise so as not to exceed 10 ° C. After stirring as it was for 15 minutes after the completion of the dropping, a solution of 3 (45.0 g: 92.2 mmol) / DMF135 g was slowly added dropwise. After completion of the dropping, the mixture was stirred as it was for 30 minutes, returned to room temperature, stirred for 2 hours, further heated to 80 to 85 ° C., and stirred for 8 hours. The reaction mixture was poured into 2.5 kg of an approximately 15% aqueous sodium acetate solution and stirred for 12 hours. After neutralizing it, it was extracted with toluene, the organic layer was dried over anhydrous sodium sulfate, the solvent was removed, and the residue was purified by column using a silica gel column to obtain 40.5 g of 4.
[0183]
0.89 g of lithium aluminum hydride was added to 100 ml of dry THF, and a solution of 4 (37 g: 68 mmol) / 600 ml of dry THF was slowly added dropwise to the place where the mixture was stirred at room temperature. After completion of the dropping, the mixture was stirred at room temperature for 4 hours, and then 500 ml of a 5% aqueous hydrochloric acid solution was slowly added dropwise. After completion of the dropping, the mixture was extracted with toluene, the organic layer was dried over anhydrous sodium sulfate, the solvent was removed, and the residue was purified by column using a silica gel column to obtain 26.3 g of 5.
[0184]
5 (20 g: 36 mmol) and triethylamine (12.8 g: 126 mol) were added to 130 ml of dry THF and cooled to 0 to 5 ° C., and then acryloyl chloride (9.8 g: 108 mmol) was slowly added dropwise. After completion of the dropping, the mixture was slowly returned to room temperature, and the mixture was stirred at room temperature for 6 hours. The reaction mixture was poured into water for neutralization, extracted with ethyl acetate, and the organic layer was dried over anhydrous sodium sulfate, and the solvent was removed. The residue was column-purified using a silica gel column to obtain 11.2 g of 6 (Compound No. 263) (oxidation potential: 0.80 V).
[0185]
(Synthesis Example 6: Synthesis of Compound No. 320)
It was synthesized according to the following route.
[0186]
[Chemical119]

[0187].
1 (50 g: 0.173 mol), 2 (8.0 g: 86 mmol), anhydrous potassium carbonate (47.8 g) and copper powder (55 g) were heated and stirred at 180 to 190 ° C. with 200 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 recrystallized twice with an acetone / methanol mixed solvent to obtain 51 g of 3.
[0188]
After cooling 35 g of DMF to 0 to 5 ° C., phosphorus oxychloride (18.4 g: 0.12 mol) was slowly added dropwise so as not to exceed 10 ° C. After stirring as it was for 15 minutes after the completion of the dropping, a 3 (50.0 g: 0.12 mol) / DMF 50 g solution was slowly added dropwise. After completion of the dropping, the mixture was stirred as it was for 30 minutes, returned to room temperature, stirred for 1 hour, further heated to 80 to 85 ° C., and stirred for 5 hours. The reaction mixture was poured into 800 g of an approximately 15% aqueous sodium acetate solution and stirred for 12 hours. After neutralizing it, it was extracted with toluene, the organic layer was dried over anhydrous sodium sulfate, the solvent was removed, and the residue was purified by column using a silica gel column to obtain 37.8 g of 4.
[0189]
4 (30 g: 67 mmol) and 1,1-diphenylmethyldiethyl phosphate (20.5 g: 67 mmol) were dissolved in 200 ml of dry THF, and oily sodium hydride (about 60%: 2.97 g: about 74 mmol) was dissolved therein at room temperature. Was added slowly. After completion of the addition, the mixture was stirred at room temperature for 30 minutes and then heated and stirred for 3 hours. The reaction mixture was cooled, poured into water, extracted with toluene, the organic layer was dried over anhydrous sodium sulfate, and the solvent was removed. The residue was purified by column using a silica gel column to obtain 21.1 g of 5.
[0190]
5 (20 g: 33.6 mmol) was added to 200 g of methyl cell solution, and sodium methylate (7.0 g) was slowly added while stirring at room temperature. After completion of the addition, the mixture was stirred as it was at room temperature for 1 hour, and then heated and stirred at 70 to 80 ° C. for 12 hours. The reaction mixture was poured into water, neutralized with dilute hydrochloric acid, extracted with ethyl acetate, the organic layer was 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 15.1 g of 6.
[0191]
6 (15 g: 29.3 mmol) and triethylamine (8.88 g: 87.9 mmol) were added to 100 ml of dry THF and cooled to 0 to 5 ° C., and then acryloyl chloride (8.0 g: 88.4 mmol) was slowly added dropwise. After completion of the dropping, the mixture was slowly returned to room temperature, and the mixture was stirred at room temperature for 6 hours. The reaction mixture was poured into water for neutralization, extracted with ethyl acetate, the organic layer was dried over anhydrous sodium sulfate, and the solvent was removed. The residue was column-purified using a silica gel column to obtain 9.8 g of 7 (Compound No. 320) (oxidation potential: 0.76 V).
[0192]
(Synthesis Example 7: Synthesis of Compound No. 410)
It was synthesized according to the following route.
[0193]
[Chemical120]

[0194]
1 (50 g: 0.173 mol), 2 (7.5 g: 81 mmol), anhydrous potassium carbonate (47.8 g) and copper powder (55 g) were heated and stirred at 180 to 190 ° C. with 200 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 using a silica gel column to obtain 58 g of 3.
[0195]
After cooling 35 g of DMF to 0 to 5 ° C., phosphorus oxychloride (18.4 g: 0.12 mol) was slowly added dropwise so as not to exceed 10 ° C. After stirring as it was for 15 minutes after the completion of the dropping, a 3 (50.0 g: 0.12 mol) / DMF 50 g solution was slowly added dropwise. After completion of the dropping, the mixture was stirred as it was for 30 minutes, returned to room temperature, stirred for 1 hour, further heated to 80 to 85 ° C., and stirred for 5 hours. The reaction mixture was poured into 800 g of an approximately 15% aqueous sodium acetate solution and stirred for 12 hours. After neutralizing it, it was extracted with toluene, the organic layer was dried over anhydrous sodium sulfate, the solvent was removed, and the residue was purified by column using a silica gel column to obtain 37.8 g of 4.
[0196]
4 (25 g: 56 mmol) was added to 200 ml of ethanol, and 1,1-diphenylhydrazine hydrochloride (35 g: 159 mmol) was added thereto. After completion of the addition, the mixture was stirred as it was at room temperature for 1 hour, and then heated and stirred at 50 ° C. for another 2 hours. The reaction mixture was cooled, poured into water, extracted with toluene, the organic layer was dried over anhydrous sodium sulfate, and the solvent was removed. The residue was purified by column using a silica gel column to obtain 24.5 g of 5.
[0197]
5 (20 g: 33 mmol) was added to 200 g of methyl cell solution, and sodium methylate (12.0 g) was slowly added while stirring at room temperature. After completion of the addition, the mixture was stirred as it was at room temperature for 1 hour, and then heated and stirred at 40 to 50 ° C. for 8 hours. The reaction mixture was poured into water, neutralized with dilute hydrochloric acid, extracted with ethyl acetate, the organic layer was 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 7.1 g of 6.
[0198]
6 (7.0 g: 11 mmol) and triethylamine (3.5 g: 35 mmol) were added to 100 ml of dry THF and cooled to 0 to 5 ° C., and then acryloyl chloride (2.5 g: 28 mmol) was slowly added dropwise. After completion of the dropping, the mixture was slowly returned to room temperature and stirred at room temperature for 4 hours. The reaction mixture was poured into water for neutralization, extracted with ethyl acetate, the organic layer was dried over anhydrous sodium sulfate, and the solvent was removed. The residue was column-purified using a silica gel column to obtain 2.8 g of 7 (Compound No. 410) (oxidation potential: 0.69 V).
[0199]
In the present invention, in the same molecule2By polymerizing and cross-linking a hole-transporting compound having one or more chain-growth functional groups, the compound having hole-transporting ability in the photosensitive layer can be obtained.2With one or more cross-linking points, it is incorporated into the three-dimensional cross-linking structure via a covalent bond. The hole-transporting compound may polymerize and crosslink only itself, or may have other chain-growth properties.SensualAny of them can be mixed with a compound having a group, and the types / ratios thereof are all arbitrary. Other chain polymerizable properties hereSensualA compound having a group is a chain-growth property.SensualBoth monomers and oligomers / polymers with groups are included.
[0200]
When the functional group of the hole transporting compound and the functional group of the other chain-growth polymerizable compound are the same group or a group that can be polymerized with each other, both shall have a copolymerized three-dimensional crosslinked structure via a covalent bond. Is possible. When both functional groups are functional groups that do not polymerize with each other, the photosensitive layer is2It is composed of a mixture of two or more three-dimensional cured products or a three-dimensional cured product of the main component containing another chain-growth compound monomer or a cured product thereof. With good control, it is also possible to form an IPN (Inter Penetrating Network), that is, a mutual approach network structure.
[0201]
In addition, it is chain-polymerizable with the hole-transporting compound.SensualThe photosensitive layer may be formed from a monomer or oligomer / polymer having no group, a monomer or oligomer / polymer having a polymerizable group other than chain polymerizable, and the like.
[0202]
Further, in some cases, it is possible to contain a hole transporting compound which is not chemically bonded to the three-dimensional crosslinked structure, that is, which does not have a chain-growth functional group. Further, various other additives, a lubricant such as fluorine atom-containing resin fine particles, and the like may be contained.
[0203]
The structure of the photoconductor of the present invention includes a structure in which a charge generating layer containing a charge generating material and a charge transporting layer containing a charge transporting material are laminated in this order as a photosensitive layer on a conductive support, or vice versa. Further, it is possible to take any configuration consisting of a single layer in which the charge generating material and the charge transporting material are dispersed in the same layer. In the former laminated type, two or more charge transport layers may be formed, and in the latter single layer type, a charge transport layer may be further formed on a photosensitive layer containing the same charge generating material and charge transport material. Furthermore, a protective layer can be formed on the charge generation layer or the charge transport layer.
[0204]
In any of these cases, the chain-growth property mentioned aboveSensualThe photosensitive layer may contain one or both of a hole-transporting compound having a group and a pre-hole-transporting compound polymerized or crosslinked and cured. However, from the viewpoint of characteristics as an electrophotographic photosensitive member, particularly electrical characteristics such as residual potential and durability, a function-separated photoconductor configuration in which charge generating layers / charge transport layers are laminated in this order is preferable, and the present invention has a preferred structure. The advantage is that the surface layer can be made highly durable without reducing the charge generation / injection efficiency and the charge transport capacity.
[0205]
Next, the method for producing the electrophotographic photosensitive member according to the present invention will be specifically shown.
[0206]
The support of the electrophotographic photosensitive member may be any as long as it has conductivity. For example, a metal or alloy such as aluminum, copper, chromium, nickel, zinc and stainless steel formed into a drum or a sheet, aluminum and the like. A metal foil such as copper laminated on a plastic film, aluminum, indium oxide, tin oxide, etc. deposited on a plastic film, a metal provided with a conductive layer by applying a conductive material alone or together with a binder resin, or plastic. Examples include film and paper.
[0207]
In the present invention, an undercoat layer having a barrier function and an adhesive function can be provided on the conductive support. The undercoat layer is used to improve the adhesiveness of the photosensitive layer, improve the coatability, protect the support, cover defects on the support, improve the charge injection property from the support, and protect the photosensitive layer from electrical destruction. Is formed in.
[0208]
Materials for the undercoat layer include polyvinyl alcohol, poly-N-vinylimidazole, polyethylene oxide, ethyl cellulose, ethylene-acrylic acid copolymer, casein, polyamide, N-methoxymethylated 6 nylon, copolymerized nylon, sardines and gelatin. Etc. are known. These are dissolved in a solvent suitable for each and applied onto the support. The film thickness at that time is preferably 0.1 to 2 μm.
[0209]
When the photoconductor of the present invention is a function-separated photoconductor, a charge generation layer and a charge transport layer are laminated. The charge generation layer contains a metal-free or metallic phthalocyanine compound, and is composed of those charge generation materials and a suitable binder resin, if necessary. Here, the central metal can take any form of a simple metal element or a metal compound such as an oxide, a halide such as chlorine and fluorine, and a hydroxide. Further, it may have a dimer or more multimer structure and a substituent.
[0210]
Among these, among the metal-free phthalocyanines and the metal phthalocyanines, oxytitanium phthalocyanines, chlorogallium phthalocyanines, and hydroxygallium phthalocyanines are particularly preferable because they exhibit particularly good photoconductor properties. Further, these phthalocyanines have crystalline types such as α, β, γ, ε and X type, and the selection thereof is arbitrary. It is also possible to use a mixture of two or more various phthalosinine compounds. Furthermore, as other charge generating materials, inorganic materials such as selenium and silicon, anthanthron pigments, dibenzpyrene quinone pigments, pyranthron pigments, trisazo pigments, disazo pigments, monoazo pigments, indigo pigments, quinacridone pigments, and asymmetric quinocyanine pigments , Organic materials such as quinocyanine can also be mixed.
[0211]
In the case of a function-separated photoconductor, the charge generation layer is a method of homogenizing the charge generation material together with a binder resin and a solvent in an amount of 0.3 to 4 times, ultrasonic dispersion, a ball mill, a vibration ball mill, a sand mill, an attritor, a roll mill, or the like. It is well dispersed in the above, coated with a dispersion liquid, and dried to be formed, or is formed as a film having a single composition such as a vapor-deposited film of the charge generating material. The film thickness is preferably 5 μm or less, and particularly preferably in the range of 0.1 to 2 μm.
[0212]
When a binder resin is used, for example, polymers and copolymers of vinyl compounds such as styrene, vinyl acetate, vinyl chloride, acrylic acid ester, methacrylic acid ester, vinylidene fluoride, trifluoroethylene, polyvinyl alcohol, polyvinyl acetal, polycarbonate. , Polysulfone, polysulfone, polyphenylene oxide, polyurethane, cellulose resin, phenol resin, melamine resin, silicon resin, epoxy resin and the like.
[0213]
The hole-transporting compound having a chain-growth functional group in the present invention forms a charge-transporting layer made of a charge-transporting material and a binder resin on the above-mentioned charge-generating layer as a charge-transporting layer or on the charge-generating layer. Later, it can be used as a surface protective layer having a hole transporting ability. In either case, the method for forming the surface layer is generally to apply the solution containing the hole-transporting compound and then carry out a polymerization / cross-linking reaction. However, in any case, a solution containing the hole-transporting compound is used in advance. After the reaction is carried out to obtain a cured product, it is also possible to form a surface layer by using a compound or the like which is dispersed or dissolved in a solvent again.
[0214]
As a method for applying these solutions, for example, a dip coating method, a spray coating method, a curtain coating method, a spin coating method and the like are known, but the dip coating method is preferable from the viewpoint of efficiency and productivity. In addition, vapor deposition, plasma, and other known film forming methods can be appropriately selected.
[0215]
In the present invention, chain polymerizableSensualThe hole-transporting compound having a group is preferably polymerized and crosslinked by radiation. The greatest advantage of radiation polymerization is that it does not require a polymerization initiator, which allows the production of very high purity 3D photosensitive layer matrices and ensures good electrophotographic properties. .. In addition, because it is a short-time and efficient polymerization reaction, it is highly productive, and because of its good radiation permeability, it inhibits curing when the film is thick or when a shielding material such as an additive is present in the film. The influence of is very small. However, chain polymerizableSensualDepending on the type of group and the type of central skeleton, the polymerization reaction may not proceed easily, and in that case, it is possible to add the polymerization initiator within a range that does not affect it. The radiation used at this time is an electron beam and a γ ray.
[0216]
As the accelerator for electron beam irradiation, any type such as scanning type, electrocurtain type, broad beam type, pulse type and laminar type can be used. When irradiating an electron beam, the irradiation conditions are very important for exhibiting electrical characteristics and durability in the photoconductor of the present invention. In the present invention, the acceleration voltage is 300.kV or less is preferable, and the optimum is 150.kIt is V or less. The irradiation dose is preferably 1.~Range of 100Mrad, more preferably 3~It is in the range of 50Mrad. When the acceleration voltage exceeds the above, the damage of electron beam irradiation to the photoconductor characteristics tends to increase. Further, it should be noted that when the irradiation dose is less than the above range, cross-linking tends to be insufficient, and when the dose is large, the properties of the photoconductor tend to deteriorate.
[0217]
The chain polymerizableSensualWhen the hole-transporting compound having a group is used as the charge-transporting layer, the amount of the hole-transporting compound varies depending on the type, crystal type, film thickness and other conditions of the phthalocyanine which is the charge generating material. Generally, the hydrogen adduct of the hole transporting group A having a chain polymerizable functional group represented by the general formula (1) is 20% or more in terms of molecular weight with respect to the total weight of the charge transporting layer film after polymerization curing. It is preferably contained in an amount of 40% or more. If it is less than that, the charge generation / injection efficiency and the charge transporting ability are lowered, and problems such as a decrease in sensitivity and an increase in residual potential occur. In this case, the film thickness of the charge transport layer is preferably 1 to 50 μm, and particularly preferably 3 to 30 μm.
[0218]
When the hole transporting compound is used as a surface protection layer on the charge generation layer / charge transport layer, the charge transport layer corresponding to the lower layer is an appropriate charge transport material such as poly-N-vinylcarbazole, polystyrylanthracene or the like. High molecular weight compounds having heterocycles and condensed polycyclic aromatic compounds, heterocyclic compounds such as pyrazoline, imidazole, oxazole, triazole and carbazole, triarylalkane derivatives such as triphenylmethane, and triarylamine derivatives such as triphenylamine. A low molecular weight compound such as a phenylenediamine derivative, an N-phenylcarbazole derivative, a stilben derivative, or a hydrazone derivative can be selected from an appropriate binder resin (the above-mentioned resin for a charge generation layer)...) And a solution dispersed / dissolved in a solvent can be applied and dried by the above-mentioned known method.
[0219]
In this case, the ratio of the charge transport material to the binder resin is preferably 30 to 100, preferably 50 to 100, and is appropriately selected when the total weight of both is 100. If the amount of the charge transporting material is less than that, the charge generation / injection efficiency and the charge transporting ability are lowered, and problems such as a decrease in sensitivity and an increase in residual potential occur. The film thickness of the charge transport layer is determined so that the total film thickness including the surface protective layer of the upper layer is 1 to 50 μm, and is preferably adjusted in the range of 5 to 30 μm.
[0220]
In the present invention, in any of the above cases, the chain polymerizable propertySensualThe charge transport material can be contained in a photosensitive layer containing a cured product of a hole transporting compound having a group. In the case of a single-layer photosensitive layer, a charge generating material is simultaneously contained in the solution containing the hole-transporting compound, and an appropriate undercoat layer or intermediate layer may be provided on this solution. The hole-transporting compound may be formed by coating on a support and then polymerized and crosslinked, or on a single-layer photosensitive layer composed of a charge-generating material and a charge-transporting material provided on the conductive support. After applying the solution containing the above, it is possible to carry out any case of polymerization and cross-linking.
[0221]
Various additives can be added to the photosensitive layer in the present invention. Additives are deterioration inhibitors such as antioxidants and ultraviolet absorbers, and lubricants such as fluorine atom-containing resin fine particles.
[0222]
FIG. 1 shows a schematic configuration of an electrophotographic apparatus having a process cartridge having the electrophotographic photosensitive member of the present invention.
[0223]
In the figure, reference numeral 1 denotes a drum-shaped electrophotographic photosensitive member of the present invention, which is rotationally driven at a predetermined peripheral speed in the direction of an arrow about a shaft 2. In the rotation process, the photoconductor 1 is uniformly charged with a predetermined positive or negative potential on its peripheral surface by the primary charging means 3, and then an image from an image exposure means (not shown) such as slit exposure or laser beam scanning exposure. Receives exposure light 4. In this way, electrostatic latent images are sequentially formed on the peripheral surface of the photoconductor 1.
[0224]
The formed electrostatic latent image is then subjected to toner development by the developing means 5.thisdevelopingFormed byTona-StatueIs sequentially transferred by the transfer means 6 to the transfer material 7 which is taken out from the paper feed unit (not shown) between the photoconductor 1 and the transfer means 6 in synchronization with the rotation of the photoconductor 1 and is fed. ..
[0225]
The transfer material 7 that has undergone image transfer is separated from the surface of the photoconductor, introduced into the image fixing means 8, receives image fixing, and is printed out as a copy to the outside of the apparatus.
[0226]
The surface of the photoconductor 1 after image transfer is cleaned by removing the transfer residual toner by the cleaning means 9, and further subjected to static elimination treatment by the pre-exposure light 10 from the pre-exposure means (not shown), and then repeated. Used for image formation. When the primary charging means 3 is a contact charging means using a charging roller or the like, pre-exposure is not always necessary.
[0227]
In the present invention, among the above-mentioned components such as the electrophotographic photosensitive member 1, the primary charging means 3, the developing means 5, and the cleaning means 9, a plurality of the components are integrally coupled as a process cartridge, and the process cartridge is formed. May be detachably configured to be detachable from the main body of an electrophotographic apparatus such as a copying machine or a laser beam printer. For example, at least of the primary charging means 3, the developing means 5 and the cleaning means 9.1This can be integrally supported together with the photoconductor 1 to form a cartridge, and the process cartridge 11 can be attached to and detached from the apparatus main body by using a guide means such as a rail 12 of the apparatus main body.
[0228]
Further, when the electrophotographic apparatus is a copying machine or a printer, the image exposure light 4 reads the document with reflected light or transmitted light from the document or a sensor, converts the document into a signal, and scans the laser beam performed according to this signal. , The light emitted by driving the LED array, driving the liquid crystal shutter array, and the like.
[0229]
The electrophotographic photosensitive member of the present invention can be widely used not only in electrophotographic copying machines but also in electrophotographic application fields such as laser beam printers, CRT printers, LED printers, liquid crystal printers and laser plate making.
[0230]
【Example】
Hereinafter, the present invention will be described in more detail with reference to examples. In addition, "part" indicates a weight part.
[0231]
(Example 1)
First, a paint for the conductive layer was prepared by the following procedure. 50 parts of conductive titanium oxide powder coated with tin oxide containing 10% antimony oxide, 25 parts of phenol formaldehyde, 20 parts of methyl cellosolve, 5 parts of methanol and silicone oil (polydimethylsiloxane polyoxyalkylene copolymer, average) A molecular weight of 3000) 0.002 part was dispersed in a sand mill device using 1 mmφ glass beads for 2 hours to prepare. This paint was applied onto an aluminum cylinder having a diameter of 30 mm by a dip coating method and dried at 140 ° C. for 30 minutes to form a conductive layer having a film thickness of 20 μm.
[0232]
Next, 5 parts of N-methoxymethylated nylon was dissolved in 95 parts of methanol to prepare a coating material for an intermediate layer. This coating material was applied onto the conductive layer by a dip coating method and dried at 100 ° C. for 20 minutes to form an intermediate layer having a film thickness of 0.6 μm.
[0233]
Next, three parts of oxytitanium phthalocyanine having strong peaks at 9.0 °, 14.2 °, 23.9 ° and 27.1 ° of the Bragg angle (2θ ± 0.2 °) of CuKα characteristic X-ray diffraction. , 2 parts of polyvinyl butyral resin and 35 parts of cyclohexanone were dispersed for 2 hours in a sand mill device using 1 mmφ glass beads, and then 60 parts of ethyl acetate was added to prepare a paint for a charge generation layer. This paint was applied onto the intermediate layer by a dip coating method and dried at 90 ° C. for 10 minutes to form a charge generation layer having a film thickness of 0.2 μm.
[0234]
Next, Compound Example No. 60 parts of the hole transporting compound of No. 6 was dissolved in a mixed solvent of 30 parts of monochlorobenzene / 30 parts of dichloromethane to prepare a coating material for a charge transport layer. This paint is coated on the charge generation layer, and the acceleration voltage is 150.kAn electron beam was irradiated under the conditions of V and an irradiation dose of 20 Mrad to cure the resin, and a charge transport layer having a film thickness of 15 μm was formed to obtain an electrophotographic photosensitive member.
[0235]
The produced electrophotographic photosensitive member was attached to LBP-SX manufactured by Canon Inc., and the electrophotographic characteristics and durability were evaluated. Initial photoconductor characteristics [dark area potential Vd, light attenuation sensitivity (light intensity required to attenuate light to -150 V at dark area potential -700 V setting) and residual potential Vsl (light intensity three times the light intensity of light attenuation sensitivity) The potential of time)] was measured, and a durability test of 10,000 sheets was further performed, visually observing the presence or absence of image defects, the amount of scraping of the photoconductor, and the photoconductor characteristics after durability were measured, and each of them was measured. The change values ΔVd, ΔVl (the amount of change in Vl when the same amount of light as the amount of light at which Vl initially became −150 V was irradiated after endurance) and ΔVsl were determined.
[0236]
The results are shown in Table 3. It is said that the photoconductor of the present invention has very good initial photoconductor characteristics, a small amount of scraping during durability, and almost no change in photoconductor characteristics even during durability. As such, it shows very stable and good characteristics.
[0237]
(Example 2)
In Example 1, oxytitanium phthalocyanine was used in Bragg angles (2θ ± 0.2 °) of CuKα characteristic X-ray diffraction described in JP-A-5-98181 at 7.4 °, 16.6 °, 25.5 °, An electrophotographic photosensitive member was prepared and evaluated in the same manner as in Example 1 except that it was replaced with a crystalline chlorogallium phthalocyanine having a strong peak at 28.3 °. The results are shown in Table 3.
[0238]
(Example 3)
In Example 1, oxytitanium phthalocyanine was used in Bragg angles (2θ ± 0.2 °) of CuKα characteristic X-ray diffraction described in JP-A-5-263007 at 7.4 °, 9.9 °, 25.0 °, An electrophotographic photosensitive member was prepared and evaluated in the same manner as in Example 1 except that it was replaced with a crystalline hydroxygallium phthalocyanine having strong peaks at 26.2 ° and 28.2 °. The results are shown in Table 3.
[0239]
(Example 4)
An electrophotographic photosensitive member was prepared and evaluated in the same manner as in Example 1 except that the oxytitanium phthalocyanine was replaced with the τ-type metal-free phthalocyanine described in JP-A-58-182639. The results are shown in Table 3.
[0240]
(Examples 5 to 15)
In Example 1, the hole transporting compound No. An electrophotographic photosensitive member was prepared and evaluated in the same manner as in Example 1 except that 6 was replaced as shown in Table 4. The results are shown in Table 3.
[0241]
(Example 16)
In Example 3, the hole transporting compound No. No. 6 instead of 6. An electrophotographic photosensitive member was prepared and evaluated in the same manner as in Example 1 except that 263 was used. The results are shown in Table 3.
[0242]
(Example 17)
In Example 11, the hole transporting compound No. The amount of 263 is 48 parts, and the following structural formula (21)Indicated byAn electrophotographic photosensitive member was prepared and evaluated in the same manner as in Example 1 except that 12 parts of the acrylic monomer was added. The results are shown in Table 3.
[0243]
[Chemical121]

[0244]
(Example 18)
After forming the charge generation layer in Example 11, the following structural formula (22)Indicated by20 parts of styryl compound and the following structural formula (23)Indicated byA charge transport layer was formed on the charge generation layer using a paint for a charge transport layer prepared by dissolving 10 parts of a polycarbonate resin having a repeating unit in a mixed solvent of 50 parts of monochlorobenzene / 20 parts of dichloromethane. The film thickness of the charge transport layer at this time was 10 μm.
[0245]
[Chemical122]

[0246]
[Chemical123]

[0247]
Next, the hole transporting compound No. 263 60 parts were dissolved in a mixed solvent of 50 parts of monochlorobenzene / 30 parts of dichloromethane to prepare a coating material for a surface protective layer. This paint is applied onto the previous charge transport layer by the spray coating method, and the acceleration voltage is 150.kThe resin was cured by irradiating an electron beam under the conditions of V and an irradiation dose of 20 Mrad to form a surface protective layer having a film thickness of 5 μm, and an electrophotographic photosensitive member was obtained. This photoconductor was evaluated in the same manner as in Example 1. The results are shown in Table 3.
[0248]
(Examples 19 to 22)
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 5 in Example 11. As a result, the amount of scraping and durability were good, but by increasing the irradiation dose, a slight decrease in sensitivity and an increase in residual potential were observed in the initial electrophotographic characteristics. The results are shown in Table 3.
[0249]
[Table 3]

[0250]
[Table 4]

[0251]
[Table 5]

[0252]
(Comparative Example 1)
After forming the charge generation layer in Example 1, the structural formula (22)Indicated by15 parts of styryl compound and the following structural formula (24)Indicated byA charge transport layer was formed on the charge generation layer using a paint for a charge transport layer prepared by dissolving 15 parts of a polymethylmethacrylate resin having a repeating unit in a mixed solvent of 50 parts of monochlorobenzene / 20 parts of dichloromethane. .. 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. There is. 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. The results are shown in Table 6.
[0253]
[Chemical124]

[0254]
(Comparative Example 2)
An electrophotographic photosensitive member was prepared and evaluated in the same manner as in Comparative Example 1 except that the polycarbonate resin represented by the structural formula (23) was used instead of the polymethylmethacrylate resin represented by the structural formula (24) in Comparative Example 1. As a result, although the durability was slightly improved as compared with the case of the polymethyl methacrylate resin, it was not sufficient, and image defects after the durability also occurred. The results are shown in Table 6.
[0255]
(Comparative Example 3)
An electrophotographic photosensitive member was prepared and evaluated in the same manner as in Comparative Example 2 except that 10 parts of the styryl compound represented by the structural formula (22) and 15 parts of the polycarbonate resin represented by the structural formula (23) were used in Comparative Example 2. As a result, although the durability was improved as compared with Comparative Example 2, the charge transporting ability was lowered due to the increase in the distance between the charge transporting materials, and the sensitivity was lowered and the residual potential was increased. As a result, ghosting was observed in the image. The results are shown in Table 6.
[0256]
(Comparative Example 4)
An electrophotographic photosensitive member was prepared and evaluated in the same manner as in Comparative Example 2, except that 15 parts of the styryl compound represented by the structural formula (22) and 10 parts of the polycarbonate resin represented by the structural formula (23) were used in Comparative Example 2. As a result, the sensitivity increased and the residual potential decreased as compared with Comparative Example 2, and good photoconductor characteristics were obtained, but the film strength was significantly reduced due to the plastic effect of the charge transport material, and the durability was significantly reduced. did. The results are shown in Table 6.
[0257]
(Comparative Example 5)
The hole transporting compound No. 1 in Example 1. Instead of 6, the following structural formula (25) disclosed in Japanese Patent Application Laid-Open No. 5-216249Indicated byAn electrophotographic photosensitive member was prepared and evaluated in the same manner as in Example 1 except that the compound was used. Results Initial electrophotographic properties were good, but durability was significantly reduced compared to Example 1. The results are shown in Table 6.
[0258]
[Chemical125]

[0259]
(Comparative Example 6)
After forming the charge generation layer in Example 1, P of JP-A-8-248649.¹⁰The following structural formula (26) synthesized according to the production method described in ~ 11.Indicated byA charge transport layer was formed on the charge generation layer using a paint for a charge transport layer prepared by dissolving 20 parts of a polycarbonate resin in 80 parts of tetrahydrofuran. 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, although the mechanical strength was improved as compared with Comparative Example 1 and Comparative Example 2, sufficient durability could not be ensured. The results are shown in Table 6.
[0260]
[Chemical126]

[0261]
[Table 6]

[0262]
【Effect of the invention】
The electrophotographic photosensitive member of the present invention has an excellent effect of abrasion resistance and scratch resistance. Further, the electrophotographic characteristics such as sensitivity and residual potential are very good, and stable performance can be exhibited even after repeated use. Further, the effect of the electrophotographic photosensitive member is naturally exhibited in the process cartridge and the electrophotographic apparatus having the electrophotographic photosensitive member, and the high image quality is maintained for a long period of time.
[Simple explanation of drawings]
FIG. 1
It is a figure which shows the example of the schematic structure of the electrophotographic apparatus which has the process cartridge which has the electrophotographic photosensitive member of this invention.