KR100988187B1 - Electrophotographic photoreceptor - Google Patents

Abstract

When the electron transfer material which consists of a compound represented by following General formula (1), the hole transfer material which has a compound represented by following General formula (25)-(27), and a charge generating material are used, Obtained.

Electrophotographic photosensitive member

Description

Electrophotographic photosensitive member {ELECTROPHOTOGRAPHIC PHOTORECEPTOR}

TECHNICAL FIELD This invention relates to the technical field of an electrophotographic photosensitive member. Specifically, It is related with the electrophotographic photosensitive member containing an electron transfer material, a hole transfer material, and a charge generating substance.

In the electrophotographic photosensitive member, a single-layer dispersed photosensitive member in which a charge generating material and a charge transfer agent are dispersed in one photosensitive layer, and one photosensitive layer has a function of both charge generation and charge transfer is used as the charge generation layer and the charge transfer layer. Compared with the laminated photosensitive member that is functionally separated, there is less layer structure, so that the production is easy and low cost.

However, since there is no electron transfer material with high electron mobility, it is still not put to practical use. Although diphenoquinone exhibits excellent electron mobility, sufficient sensitivity with the hole transfer material and the charge generating material cannot be obtained. Therefore, the present inventors have found that a compound in which a compound having an active methylene in quinone is condensed shows an excellent electron transport ability, thereby realizing a monolayer dispersed photosensitive member. However, in particular, since a high speed printing is required in a photosensitive member for a printer, a study for obtaining a more sensitive photosensitive member has been desired.

Disclosure of Invention

This invention is made | formed in order to solve such a subject of the prior art, and an object of this invention is to provide the highly sensitive single-layer dispersion type electrophotographic photosensitive member.

The present inventors have found that in the course of improving the properties of a single-layer dispersed photoconductor, the present invention exhibits high sensitivity by containing a hole-transfer material specific to the photosensitive layer and an electron-transfer material condensed with a compound having an active methylene in the quinone, and the present invention. Came to complete.

The present invention made on the basis of the above-mentioned knowledge is an electrophotographic photosensitive member having a support and a photosensitive layer formed on the support, wherein the photosensitive layer contains a charge generating material, an electron transfer material, and a hole transfer material. A transfer material is a compound represented by following General formula (1), The said hole transfer material is represented by the compound represented by following General formula (25), the compound represented by General formula (26), and General formula (27) It is an electrophotographic photosensitive member characterized by at least 1 sort (s) of compound chosen from the group which consists of compounds which become.

(Wherein in the formula (1), the substituent R ₁ ~R ₄ Is a hydrogen atom, cyano group, nitro group, halogen atom, hydroxy group, alkyl group, aryl group, heterocyclic group, ester group, alkoxy group, aralkyl group, allyl group, amide group, amino group, acyl group , Alkenyl group, alkynyl group, carboxyl group, carbonyl group and any one kind of substituent selected from the group consisting of carboxylic acid groups. The substituent X is any one kind of substituent selected from the group consisting of oxygen, sulfur and C (CN) ₂ . Substituent W is a ring having 4 or more rings and 8 or less rings, and when General Formula (1) is changed to the following General Formula (1 ′),

The substituent Y is an element of either oxygen or sulfur, and the structure Z is composed of two or more atoms constituting the ring.)

(In General Formula (25), R ₇ to R _9. Are each one of the substituents selected from the group consisting of a hydrogen atom, a halogen atom, an alkyl group, an allyl group, an alkoxy group, an aryl group, a dialkylamino group, and a diphenylamino group, wherein l, m and n in the formula Represents an integer of 0 or more and 2 or less.)

(In the general formula (26), R ₁₀ to R ₁₃ Represents a hydrogen atom, an alkyl group, an allyl group, an alkoxy group, an aryl group, a dialkylamino group, and any one kind of substituents selected from the group consisting of diphenylamino groups, respectively,

(In General Formula (27), R ₁₄ to R _17. Represents any one kind of substituent selected from the group consisting of a hydrogen atom, an alkyl group, an allyl group, and an aryl group.)

This invention is an electrophotographic photosensitive member, The said electrophoretic material is a compound represented by following General formula (2), It is the electrophotographic photosensitive member of Claim 1 characterized by the above-mentioned.

(Wherein in the formula (2), the substituents R ₁ ~R ₅ Is a hydrogen atom, cyano group, nitro group, halogen atom, hydroxy group, alkyl group, aryl group, heterocyclic group, ester group, alkoxy group, aralkyl group, allyl group, amide group, amino group, acyl group , Alkenyl group, alkynyl group, carboxyl group, carbonyl group and any one kind of substituent selected from the group consisting of carboxylic acid groups. The substituent X is any one kind of substituent selected from the group consisting of oxygen, sulfur and = C (CN) ₂ , and the substituent Y is composed of any one element of oxygen or sulfur.)

The present invention is an electrophotographic photosensitive member, wherein the electrophoretic material is a compound represented by the following general formula (3).

(Wherein in the formula (3), the substituent R ₁ ~R ₆ Silver, hydrogen atom, cyano group, nitro group, halogen atom, hydroxy group, alkyl group, aryl group, heterocyclic group, ester group, alkoxy group, aralkyl group, allyl group, amide group, amino group, acyl group , Alkenyl group, alkynyl group, carboxyl group, carbonyl group and any one kind of substituent selected from the group consisting of carboxylic acid groups. The substituent X is any one kind of substituent selected from the group consisting of oxygen, sulfur and = C (CN) ₂ , and the substituent Y is composed of any one element of oxygen or sulfur.)

In addition, the substituent represented by R <_7> -R <_8> in said Formula (25), the substituent represented by R <_10> -R <_13> in said Formula (26), and are represented by R <_14> -R ₁₇ in said Formula (27) Another substituent may couple | bond with the substituent each. In addition, when the integer represented by l, m, n in Formula (25) is 2, when the two substituents (R <_7> ) _2- (R <_8> ) ₂ couple | bonded with the same phenyl group mutually bond and form a ring. There is.

In addition, the substituent represented by R <_1> -R <_6> in the said General formula (1), (1 '), (2), (3) is an alkyl group, an aryl group, a heterocyclic group, ester group, alkoxy group, aralkyl group, allyl In the case of a group, an amide group, an amino group, an acyl group, an alkenyl group, an alkynyl group, a carboxyl group, a carbonyl group, or a carboxylic acid group, the present invention also includes a substituent bonded to these groups. Moreover, those substituents R ₁ to R ₆ Medium, R ₁ And R ₂ , R ₃ And R ₄ May combine with each other to form a ring.

The substituents R ₁ ~R ₆ is R ₁ ~R ₆ may be a different type of each of the substituents, and, those of the substituents Of these, two or more substituents may be the same kind of substituents. In the above general formulas (1) to (3), the present invention also includes a case where a substituent W and a cyclic compound, which is a cyclic compound having a 4-membered ring or more and 8-membered rings, are condensed to form a condensed ring. do. In addition, when structure Z contains one or more hetero atoms, the case where structure Z consists only of carbon, and the case where a substituent couple | bonds with structure Z are also included in this invention.

BRIEF DESCRIPTION OF THE DRAWINGS It is sectional drawing which shows an example of a monolayer dispersion type | mold photosensitive member. In FIG.

To practice the invention  Best form for

The monolayer dispersion type electrophotographic photosensitive member (monolayer dispersion type photosensitive member) of the present invention includes at least one hole transport material selected from the group consisting of General Formula (25), General Formula (26), and General Formula (27), By combining a charge generating material and a compound of the general formula (1) which is an electron transfer material, the photosensitive member sensitivity can be improved.

The single layer dispersed photoconductor of the present invention has a layer structure shown in FIG. 1 as an example. Reference numeral 10 in FIG. 1 denotes a single layer dispersed photoconductor, and the single layer dispersed photoconductor 10 has a conductive support 11 and a photosensitive layer 12 disposed on the conductive support 11. The photosensitive layer 12 is formed by dispersing a charge generating material, an electron transfer material, and a hole transfer material together in a binder resin.

In addition, as another example of the single-layer dispersion type photosensitive member of the present invention, a lower layer may be formed between the conductive support 11 and the photosensitive layer 12 and may be protected on the photosensitive layer 12. It may also form a layer. Moreover, you may form both the said servant layer and the said protective layer.

As the method for forming the photosensitive layer 12, various methods can be used. In general, the coating liquid is prepared by dispersing or dissolving the charge generating material, the electron transfer material, and the hole transfer material with a binder resin in a suitable solvent. The coating liquid can be applied onto the conductive support 11 to be dried.

Although the film thickness of the photosensitive layer 12 is not specifically limited, 5 micrometers or more and 50 micrometers or less are preferable, Especially preferably, they are 10 micrometers or more and 35 micrometers or less. When the thickness of the photosensitive layer 12 is thin, the sensitivity of the photoconductor is improved, but the durability against film reduction and the like is lowered. When the thickness is thick, the durability is improved but the sensitivity tends to be lowered.

The electron transfer material used in the present invention is represented by the general formula (1), and the electron transfer material has a high electron mobility and is suitable for a single layer dispersed photosensitive member.

(Wherein in the formula (1), the substituent R ₁ ~R ₄ Is a hydrogen atom, cyano group, nitro group, halogen atom, hydroxy group, alkyl group, aryl group, heterocyclic group, ester group, alkoxy group, aralkyl group, allyl group, amide group, amino group, acyl group , Alkenyl group, alkynyl group, carboxyl group, carbonyl group and any one kind of substituent selected from the group consisting of carboxylic acid groups. The substituent X is any one kind of substituent selected from the group consisting of oxygen, sulfur and = C (CN) ₂ . The substituent W is a ring having 4 or more rings and 8 or less rings, when the general formula (1) is changed to the following general formula (1 '),

The substituent Y is an element of either oxygen or sulfur, and the structure Z is composed of two or more atoms constituting the ring.)

In addition, in the said General formula (1), the electron transfer material represented by following General formula (2) and General formula (3) is more preferable because of high mobility.

(Wherein in the formula (2), the substituents R ₁ ~R ₅ Is a hydrogen atom, cyano group, nitro group, halogen atom, hydroxy group, alkyl group, aryl group, heterocyclic group, ester group, alkoxy group, aralkyl group, allyl group, amide group, amino group, acyl group , Alkenyl group, alkynyl group, carboxyl group, carbonyl group and any one kind of substituent selected from the group consisting of carboxylic acid groups. The substituent X is any one kind of substituent selected from the group consisting of oxygen, sulfur and = C (CN) ₂ , and the substituent Y is composed of any one element of oxygen or sulfur.)

(Wherein in the formula (3), the substituent R ₁ ~R ₆ Silver, hydrogen atom, cyano group, nitro group, halogen atom, hydroxy group, alkyl group, aryl group, heterocyclic group, ester group, alkoxy group, aralkyl group, allyl group, amide group, amino group, acyl group , Alkenyl group, alkynyl group, carboxyl group, carbonyl group and any one kind of substituent selected from the group consisting of carboxylic acid groups. The substituent X is any one kind of substituent selected from the group consisting of oxygen, sulfur and = C (CN) ₂ , and the substituent Y is composed of any one element of oxygen or sulfur.)

In the general formulas (2) and (3), the substituents X and Y are oxygen, and R ₁ and R ₃ This t-Bu group, R ₂ And R ₄ The compound whose hydrogen is easy is manufacture, and its mobility is high, and it is more preferable.

The compound represented by General formula (1) can also be made into the general formula shown by Table A (1) -Table A (26) other than the said General formula (2) and General formula (3).

Although the specific example of a compound represented by General formula (1) is shown to following Table B (1) -Table B (4), it is not limited to this.

One type of compound represented by General formula (1) may be contained in the photosensitive layer 12, and may be contained two or more types.

The concentration of the compound represented by the general formula (1) in the photosensitive layer 12 is not particularly limited because it depends on the required photoconductor performance and charging polarity, but is preferably 0.1% by weight or more and 70% by weight or less. If the concentration is low, electron transfer may be insufficient to affect the photoconductor characteristics. If the concentration is high, the compatibility with the binder resin used in the photosensitive layer 12 is deteriorated, and the photosensitive layer 12 becomes a nonuniform film. Since binder resin concentration becomes low, there exists a possibility that the film strength of the photosensitive layer 12 may fall.

The hole transport material which can be used for the monolayer dispersed photoconductor of the present invention is a compound represented by the following general formulas (25), (26) and (27).

As a compound of General formula (25), the compound represented by following General formula (28), General formula (29), and General formula (30) is preferable.

(R ₇ , R ₈ , R ₁₈ , R _{19 in the} above formula (28). Is any one kind of substituent selected from the group consisting of a hydrogen atom, a halogen atom, an alkyl group, an allyl group, an alkoxy group, an aryl group, a dialkylamino group and a diphenylamino group, and each of these substituents Sometimes combined. A, b, m, n in the formula (28) are each an integer of 0 or more and 2 or less, and when the integer represented by a, b, m, n is 2, two substituents bonded to the same phenyl group (R ₇₎ ) ₂ , (R ₈ ) ₂ , (R ₁₈ ) ₂ , and (R ₁₉ ) ₂ may combine with each other to form a ring.

(R ₇ , R ₈ of the above formula (29) Is a hydrogen atom, a halogen atom, an alkyl group, an allyl group, an alkoxy group, an aryl group, a dialkylamino group, or any one type of substituents selected from the group consisting of diphenylamino groups, and each of these substituents has a different substituent Sometimes combined. In Formula (29), m and n are integers of 0 or more and 2 or less, and when m and n are 2, two substituents (R ₇ ) ₂ and (R ₈ ) ₂ bonded to the same phenyl group are bonded to each other to form a ring. May be formed. In addition, in Formula (29), R <_20> , R <_21> represents any 1 type of substituent chosen from the group which consists of a hydrogen atom, an alkyl group, an aryl group, and an allyl group, and when a separate substituent couple | bonds these substituents, respectively have.)

(In formula (30), R ₇ , R ₈ , R ₂₂ , and R ₂₃ represent a hydrogen atom, a halogen atom, an alkyl group, an allyl group, an alkoxy group, an aryl group, a dialkylamino group, and a diphenylamino group. It may be any one kind of substituent selected from the group which consists of, and another substituent may couple | bond each with these substituents c, d, m, n in Formula (30) is an integer of 0 or more and 2 or less, c, d When the integer represented by, m, n is 2, two substituents (R ₇ ) ₂ , (R ₈ ) ₂ , (R ₂₂ ) ₂ , and (R ₂₃ ) ₂ bonded to the same phenyl group are bonded to each other to form a ring. May be formed.)

Moreover, as for the compound represented by General formula (26), the compound represented by following General formula (31) and General formula (32) is preferable.

(In said general formula (31), R <_24> , R <_25> is either substituent of a hydrogen atom or an alkyl group, and R <_26> is either substituent of a hydrogen atom or a dialkylamino group.)

(R ₂₇ to R ₃₀ of the general formula (32) Is any one type of substituent chosen from the group which consists of a hydrogen atom, a halogen atom, a C1-C6 alkyl group, a C1-C6 alkoxy group, and an aryl group. R ₃₁ is a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an aryl group, an alkenyl group, an alkadienyl group, and the following general formula (33) It is any 1 type of substituent chosen from the group which consists of a substituent. In addition, R _27- R ₃₁ When it consists of this aryl group or alkenyl group, another substituent may couple | bond with these substituents. In formula (32), e represents the integer of 0 or 1.)

(R ₃₂ in the general formula (33), R ₃₃ Is any one type of substituent selected from the group consisting of a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group and an aryl group, and the substituents R ₃₂ , R ₃₃ In the case of this aryl group, those substituents R ₃₂ and R ₃₃ Another substituent may bond to. F in Formula (33) represents the integer of 0 or 1.)

One type of compound represented by General formula (25), General formula (26), and General formula (27) may be contained in the photosensitive layer, and may be two or more types.

The concentration of the hole transporting material in the photosensitive layer 12 is not particularly limited because it depends on the required photoconductor performance and charging polarity, but is preferably 0.1% by weight or more and 70% by weight or less. If the concentration is low, hole transport may be insufficient to affect the photoconductor properties. If the concentration is high, the compatibility with the binder resin used in the photosensitive layer 12 may be deteriorated, and the photosensitive layer 12 may be a nonuniform film. Since the binder resin concentration becomes low, there is a possibility that the film strength of the photosensitive layer 12 decreases.

As the charge generating material used in the present invention, oxytitanium phthalocyanine having a peak characteristic at 7.6 ° and 28.6 ° at an X-ray diffraction angle (2θ ± 0.2 °) with respect to a Cu-Kα ray, having a peak characteristic at 27.3 ° Oxytitanium phthalocyanine, oxytitanium phthalocyanine, dichlorotin phthalocyanine and metal-free phthalocyanine, disazo compound, tris azo pigment, perylene compound which did not show characteristic peaks can be used, but it is not limited to these.

Oxytitanium phthalocyanine having a characteristic peak at 7.6 ° and 28.6 ° at the X-ray diffraction angle (2θ ± 0.2 °) with respect to the Cu-Kα ray is generally the maximum peak at 7.6 °, but may be the maximum peak at 28.6 °. . In addition to these peaks, clear peaks are also shown at 12.5 °, 13.3 °, 22.5 °, and 25.4 °, but may be broad, split, or shifted depending on the crystal state, measurement conditions, and the like.

Oxytitanium phthalocyanine having a characteristic peak at 27.3 ° at an X-ray diffraction angle (2θ ± 0.2 °) with respect to a Cu-Kα ray shows peaks at 9.5, 14.2, and 24.1 °, except 27.3 °. There may be cases where it is broadened, split or shifted by measurement conditions or the like.

Oxytitanium phthalocyanine which does not exhibit characteristic peaks is an amorphous oxytitanium phthalocyanine, which does not show a clear peak, but may show a broad peak.

Tin dichloro phthalocyanine is to place the SnCl ₂ in the center of the phthalocyanine. As a crystalline form of dichlorotin phthalocyanine, it has a maximum peak at 10.5 ° at the X-ray diffraction angle (2θ ± 0.2 °) described in JP-A-11-286618, and has a peak intensity in the range of 5 ° to 9 °. 8.7 °, 9.9 °, 10.9 °, 13.1 °, 15.2 °, at an X-ray diffraction angle (2θ ± 0.2 °) described in JP-A-5-140472, which is 10% or less of the peak intensity of 10.5 °. Strong diffraction peaks at 16.3 °, 17.4 °, 21.9 °, 25.5 ° or 9.2 °, 12.2 °, 13.4 °, 14.6 °, 17.0 °, 25.3 °, or described in JP-A-6-228453 X-ray diffraction angle (2θ ± 0.2 °), 8.4 °, 10.6 °, 12.2 °, 13.8 °, 16.0 °, 16.5 °, 17.4 °, 19.1 °, 22.4 °, 28.2 °, 30.0 °, or 8.4 ° , 11.2 °, 14.6 °, 15.6 °, 16.9 °, 18.6 °, 19.6 °, 25.7 °, 27.2 °, and 28.5 ° may be used that exhibit strong diffraction peaks. Especially, it is especially preferable that it has a maximum peak at 10.5 degrees at X-ray-diffraction angle (2 (theta) ± 0.2 degrees), and the peak intensity of the range of 5 degrees-9 degrees is 10% or less of the peak intensity of 10.5 degrees.

Metal-free phthalocyanines are phthalocyanines that do not have a central metal disposed. Many crystalline forms have been reported as the metal-free phthalocyanine, but may be in any form. In particular, strong diffraction peaks at 7.5 °, 9.1 °, 15.1 °, 16.6 °, 17.3 °, 18.5 °, 22.2 °, 23.8 °, 25.9 °, 27.29 °, and 28.6 ° at the X-ray diffraction angle (2θ ± 0.2 °) It is preferable to indicate.

These charge generating materials may be used singly or in combination of two or more kinds in order to obtain appropriate light sensitivity wavelengths and sensitization effects. As for the density | concentration of the charge generation material in the photosensitive layer 12, 0.005 weight% or more and 70 weight% or less are generally used, Preferably they are 1 weight% or more and 10 weight% or less. When the concentration of the charge generating material is low, the photosensitive member sensitivity tends to be lowered, and when the concentration is high, the potential holding ratio and film strength tend to be lowered. Examples of the conductive support 11 in the photoconductor 10 of the present invention include metals such as aluminum, crude oil, stainless steel, nickel, chromium, titanium, gold, silver, copper, tin, platinum, molybdenum and indium. A single body or a workpiece of the alloy can be used.

A thin film of a conductive material may be further formed on the surface of the metal, alloy or the like by vapor deposition, plating or the like. The conductive support 11 itself may be made of a conductive material, but a thin film such as metal or carbon may be formed on the surface of the non-conductive plastic plate and the film by a method such as vapor deposition or plating to provide conductivity.

In addition, when resin is used as a constituent material of the conductive support 11, a conductive agent such as metal powder or conductive carbon may be contained in the resin, or a conductive resin may be used as the resin for gas formation. In addition, when glass is used for the conductive support 11, the surface may be coated with tin oxide, indium oxide, and aluminum iodide to give conductivity. The kind and shape are not specifically limited, The conductive support 11 can be comprised using the various material which has electroconductivity.

Generally, as an electroconductive support body 11, the thing which carried out the Almite treatment of the cylindrical aluminum tube single-piece | unit, the surface thereof, or provided the lower layer on the aluminum tube is used frequently. This servant layer has an adhesion improving function, a barrier function for preventing the inflow current from the conductive support 11, a defect coating function on the surface of the conductive support 11, and the like. In this servant layer, polyethylene resin, acrylic resin, epoxy resin, polycarbonate resin, polyurethane resin, vinyl chloride resin, vinyl acetate resin, polyvinyl butyral resin, polyamide resin, polyimide resin, nylon resin, alkyd resin, Various resins, such as a melamine resin, can be used.

These servant layers may be comprised by independent resin, and may be comprised by mixing two or more types of resin. Moreover, a metal compound, carbon, silica, resin powder, etc. can also be disperse | distributed in a layer. In addition, various pigments, electron-accepting substances, electron-supply substances and the like may be included for improving the properties.

In the photosensitive layer 12, other phthalocyanine pigment, an azo pigment, etc. can also be mixed in order to acquire an appropriate light sensitivity wavelength and a sensitization effect. These are preferable at the point that the image of a sensitivity is good. In addition, for example, monoazo pigments, bis azo pigments, tris azo pigments, polyazo pigments, indigo pigments, sren pigments, toluidine pigments, pyrazoline pigments, perylene pigments, quinacridone pigments, pyryllium salts and the like can be used. have.

Examples of the binder resin for forming the photosensitive layer 12 include polycarbonate resin, styrene resin, acrylic resin, styrene-acrylic resin, ethylene-vinyl acetate resin, polypropylene resin, vinyl chloride resin, chlorinated polyether resin, and vinyl chloride- Vinyl acetate resin, polyester resin, furan resin, nitrile resin, alkyd resin, polyacetal resin, polymethylpentene resin, polyamide resin, polyurethane resin, epoxy resin, polyallylate resin, diallylate resin, polysulfone resin , Polyether sulfone resin, polyallyl sulfone resin, silicone resin, ketone resin, polyvinyl butyral resin, polyether resin, phenol resin, EVA (ethylene vinyl acetate) resin, ACS (acrylonitrile chlorinated polyethylene styrene) Resins such as resins, ABS (acrylonitrile butadiene styrene) resins and epoxy allylates. Although these may be used individually, it is also possible to mix and use 2 or more types. When mixing and using resins with different molecular weights, the hardness and the wear resistance can be improved, which is preferable.

Examples of the solvent used for the coating liquid include alcohols such as methanol, ethanol, n-propanol, i-propanol and butanol, saturated aliphatic hydrocarbons such as pentane, hexane, heptane, octane, cyclohexane and cycloheptane, toluene and xylene Chlorinated hydrocarbons such as aromatic hydrocarbons, dichloromethane, dichloroethane, chloroform and chlorobenzene, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone, ethyl formate, propyl formate, methyl acetate, ethyl acetate and acetic acid Ether solvents such as propyl, butyl acetate, esters such as methyl propionate, dimethyl ether, diethyl ether, dimethoxyethane, tetrahydrofuran, dioxolane (THF), methoxyethanol, dioxane, or anisole; N, N-dimethylformamide, dimethyl sulfoxide, and the like.

In particular, a ketone solvent, an ester solvent, an ether solvent, or a halogenated hydrocarbon solvent is preferable, and these can be used alone or as two or more kinds of mixed solvents.

Another charge transfer material may be added to the photoconductor of the present invention. In that case, since a sensitivity can be improved or a residual electric potential can be reduced, the characteristic of the electrophotographic photosensitive member of this invention can be improved.

Examples of charge transfer materials that can be added for such characteristics improvement include polyvinylcarbazole, halogenated polyvinylcarbazole, polyvinylpyrene, polyvinylinroquinoxaline, polyvinylbenzothiophene, polyvinylanthracene and polyvinyl. Acridine, polyvinylpyrazoline, polyacetylene, polythiophene, polypyrrole, polyphenylene, polyphenylenevinylene, polyisothianaphthene, polyaniline, polydiacetylene, polyheptaene, polypyridinediyl, polyquinoline Conductive polymer compounds such as polyphenylene sulfide, polyferrocenylene, polyperinaphthylene, and polyphthalocyanine can be used. Moreover, as a low molecular weight compound, polycyclic aromatic compounds, such as anthracene, pyrene, and phenanthrene, such as trinitrofluorenone, tetracyanoethylene, tetracyanoquinomethane, quinone, diphenoquinone, naphthoquinone, anthraquinone, and these derivatives, etc. Nitrogen-containing heterocyclic compounds such as indole, carbazole and imidazole, fluorenone, fluorene, oxadiazole, oxazole, pyrazoline, hydrazone, triphenylmethane, triphenylamine, enamine, stilbene, butadiene Compounds and the like can be used.

Moreover, the polymer solid electrolyte etc. which doped metal ion, such as Li (lithium) ion, in high molecular compounds, such as polyethylene oxide, a polypropylene oxide, polyacrylonitrile, and polymethacrylic acid, can also be used.

In addition, an electron donating compound typified by tetrathiaflubarene-tetracyanoquinomimethane and an organic charge transfer complex formed of an electron-accepting compound may be used, and even if only one of them is added, two or more compounds may be mixed and added. Also desired photoreceptor characteristics can be obtained.

The coating liquid for producing the photoconductor of the present invention may be added with an antioxidant, a ultraviolet absorber, a radical scavenger, a softener, a curing agent, a crosslinking agent and the like in a range that does not impair the characteristics of the electrophotographic photoconductor. Durability and mechanical properties can be improved. In addition, addition of a dispersion stabilizer, a sedimentation inhibitor, a color separation inhibitor, a leveling agent, a defoamer, a thickener, a gloss remover, and the like can improve the finish appearance of the photoconductor and the life of the coating solution.

Furthermore, on the photosensitive layer 12, it is formed with organic thin films, such as an epoxy resin, a melamine resin, polyvinyl formal resin, a polycarbonate resin, a fluororesin, a polyurethane resin, and a silicone resin, or the hydrolyzate of a silane coupling agent. A protective layer may be formed by forming a thin film made of a siloxane structure. In that case, since the durability of a photosensitive member improves, it is preferable. You may form this protective layer in order to improve other functions other than improvement of durability.

EXAMPLE

EMBODIMENT OF THE INVENTION Hereinafter, the Example of the electrophotographic photosensitive member which concerns on this invention is described in detail.

 <Specific example of single layer dispersed negative charging photosensitive member>

<Examples 1 to 21>

1 part by weight of oxytitanium phthalocyanine as a charge generating material and 10 parts by weight of polycarbonate as a binder resin are kneaded and dispersed with 80 parts by weight of THF as a solvent, 9 parts by weight of a compound represented by the formula (4) as an electron transfer material, and hole transport As a material, 2 weight part of triphenylamine compounds represented by following General formula (34) were melt | dissolved, and the coating liquid was prepared.

Subsequently, the coating solution was immersed and coated on an aluminum drum as the conductive support 11, and dried at 80 ° C. for 1 hour to form a photosensitive layer 12 having both a charge of 20 μm and a charge transfer. And the negatively charged electrophotographic photosensitive member of Example 1 (single layer dispersion negatively charged photosensitive member; 10).

In addition, 20 types of coating liquids were adjusted on the same conditions as Example 1 except having changed the electron transfer material used in the said Example 1 into the compound represented by Formula (5)-(24), respectively, These coating liquids The single-layer dispersion type negative charging photosensitive member 10 of Examples 2 to 21 was produced under the same conditions as in Example 1.

<Examples 22 to 42>

In Examples 1 to 21, the monolayer dispersion was carried out in the same manner as in Examples 1 to 21, except that the hole transport material was changed to a mixture of the compound represented by the following formula (35a) and the compound represented by the following formula (35b): The type negative charging photosensitive member 10 was produced. Each was set to Examples 22 to 42.

<Examples 43 to 63>

In Examples 1-21, the monolayer dispersed negative charging photosensitive member 10 was produced like Example 1-21 except having changed the hole transport material into the compound represented by following General formula (36). Each of Examples 43 to 63 was used.

<Examples 64 to 84>

In Examples 1-21, the monolayer dispersed negative charging photosensitive member 10 was produced like Example 1-21 except having changed the hole transport material into the compound represented by following General formula (37). Each of Examples 64 to 84 was used.

<Examples 85 to 105>

In Examples 1-21, the monolayer dispersed negative charging photosensitive member 10 was produced like Example 1-21 except having changed the hole transport material into the compound represented by following formula (38). Each of Examples 85 to 105 was used.

<Examples 106 to 126>

In Examples 1-21, the monolayer dispersed negative charging photosensitive member 10 was produced like Example 1-21 except having changed the hole transport material into the compound represented by following General formula (39). Each of Examples 106 to 126 was used.

<Examples 127 to 147>

In Examples 1-21, the monolayer dispersed negative charging photosensitive member 10 was produced like Example 1-21 except having changed the hole transport material into the compound represented by following General formula (40). Each of Examples 127 to 147 was used.

<Examples 148 to 168>

In Examples 1-21, the monolayer dispersed negative charging photosensitive member 10 was produced like Example 1-21 except having changed the hole transport material into the compound represented by following General formula (41). It set as Examples 148-168, respectively.

<Comparative Examples 1 to 21>

In Examples 1-21, the monolayer dispersed negative charging photosensitive member was produced like Example 1-21 except having changed the hole transport material into the compound represented by following General formula (42). It was set as the comparative examples 1-21, respectively.

<Comparative Examples 22-29>

In Example 1, monolayer dispersion | distribution was carried out similarly to Example 1 except having changed the electron transfer material into the compound represented by following General formula (43), and changing the hole transfer material to Formula (34)-Formula (41). A negative charging photosensitive member was produced. It was set as the comparative examples 22-29, respectively.

<Specific example of single layer dispersion type static charging photosensitive member>

<Examples 169-189>

1 part by weight of oxytitanium phthalocyanine as a charge generating material, 10 parts by weight of polycarbonate as a binder resin, and kneaded and dispersed in 80 parts by weight of THF as a solvent, 2 parts by weight of a compound represented by formula (4) as an electron transfer material, and a hole 8 weight part of triphenylamine compounds represented by General formula (34) which are transfer materials were melt | dissolved, and the coating liquid of the compounding ratio different from Example 1 was prepared.

Subsequently, the coating solution was used to immerse on an aluminum drum, which is the conductive support 11, and dried at 80 ° C. for 1 hour to form a photosensitive layer 12 which combined charge generation and charge transfer with a film thickness of 20 μm. And the electrostatic photosensitive member (single layer dispersion type electrostatic photosensitive member; 10) of Example 169 was produced.

Instead of using the compounds represented by the formulas (5) to (24), respectively, in place of the electron transfer material used in Example 169, 20 kinds of coating solutions were prepared at the same compounding ratio as in Example 169, and these coatings were prepared. Using the liquid, the single-layer dispersion type positive electrostatic photosensitive member 10 of Examples 170 to 189 was produced under the same conditions as in Example 169.

<Examples 190 to 210>

In Examples 169 to 189, the monolayer dispersion was carried out in the same manner as in Examples 169 to 189 except that the hole transport material was changed to a mixture of the compound represented by the formula (35a) and the compound represented by the formula (35b). A type charged photosensitive member 10 was produced. Each of Examples 190 to 210 was used.

<Examples 211 to 231>

In Examples 169-189, the monolayer dispersion | distribution type positive charging photosensitive member 10 was produced like Example 169-189 except having changed the hole-transporting material into the compound represented by the said General formula (36). It was set as Examples 211-231, respectively.

<Examples 232 to 252>

In Examples 1-21, the monolayer dispersion | distribution type positive charging photosensitive member 10 was produced like Example 169-189 except having changed the hole transport material into the compound represented by the said General formula (37). Each of Examples 232 to 252 was used.

<Examples 253 to 273>

In Examples 169 to 189, a single-layer dispersion type positive charging photosensitive member 10 was produced in the same manner as in Examples 169 to 189 except that the hole transport material was changed to the compound represented by the formula (38). Each was set to Examples 253 to 273.

<Examples 274 to 294>

In Examples 169-189, the monolayer dispersion | distribution type positive charging photosensitive member 10 was produced like Example 169-189 except having changed the hole transport material into the compound represented by the said General formula (39). Each of Examples 274 to 294 was used.

<Examples 295-315>

In Examples 169-189, the monolayer dispersion | distribution type positive charging photosensitive member 10 was produced like Example 169-189 except having changed the hole-transporting material into the compound represented by the said General formula (40). It was set as Examples 295-315, respectively.

<Examples 316 to 336>

In Examples 169-189, the monolayer dispersion | distribution type positive charging photosensitive member 10 was produced like Example 169-189 except having changed the hole-transporting material into the compound represented by the said General formula (41). Each of Examples 316 to 336 was used.

<Comparative Example 30-50>

In Examples 169-189, the monolayer dispersion | distribution type positive charging photosensitive member was produced like Example 169-189 except having changed the hole-transporting material into the compound represented by the said General formula (42). It was set as the comparative examples 28-48, respectively.

<Comparative Examples 51-58>

In Example 169, it replaces the electron transport material with the compound represented by the said General formula (43), and is the same as Example 169 except having changed the hole transport material into the compound represented by the said General formula (34)-(41). A monolayer distributed type positive electrode photosensitive member was produced. It was set as the comparative examples 51-58, respectively.

<Single-layer distributed negative charging photosensitive member measuring condition>

By setting the corona discharger so that the corona discharge current is 17 mA, the single-layer dispersed photosensitive member 10 prepared in Examples 1 to 168 and Comparative Examples 1 to 27 was negatively charged by corona discharge in a dark place, and thus initially charged. The potential was measured. Surface potential at this time is made into charging property (V).

Thereafter, the discharge current was adjusted so that the surface potential of the photoconductor 10 was -700V, the exposure was performed with light of 780 nm, and the exposure amount for reducing the surface potential of each photoconductor 10 from -700V to -350 was measured. . The exposure amount at this time is made into half exposure exposure amount (microJ / cm <2>). This half exposure exposure value is a value which shows the sensitivity of the photosensitive member 10, and shows that a sensitivity is so high that a value is small.

Moreover, the surface potential at the time of irradiating 780 nm light (exposure energy 10 microJ / cm <2>) at the surface potential of -700V of each photosensitive member 10 was measured. Let surface potential at this time be residual potential (V).

Thereafter, the surface potential of the photoconductor 10 is again charged to be -700V, and the surface potential V10 when it is left in a dark place for 10 seconds is measured to find the potential holding ratio (%) = V10 / -700 × 100. This potential holding ratio becomes an index indicating the insulation of the photoconductor 10.

The measurement is carried out under three environments of LL environment (temperature 15 ° C., humidity 15%), NN environment (temperature 25 ° C., humidity 40%), and HH environment (temperature 35 ° C., humidity 80%). The average of the half-sensitive exposure amounts in three environments of each photoconductor 10 is calculated, and the value obtained by multiplying the difference with the half-sensitive exposure amounts under each environment in each photoconductor 10 is obtained as a sensitivity environmental stability index. The sensitivity environmental stability index is represented by the following equation (1).

Equation (1): sensitivity environmental stability index = (average of half-exposure exposure amount under LL environment -3 environment) ² + (half-life exposure amount under NN environment-average of half-life exposure amount under NN environment) ² + (half-life of HH environment Exposure dose-average of half exposure dose under environment) ²

This value represents the magnitude of variation in the sensitivity of the photoconductor to the environment, and the smaller the value, the less the change in the photoconductor sensitivity even if the environment changes.

<Measurement Conditions of Single Layer Dispersion Type Static Electrostatic Photosensitive Body>

The corona discharger was set so that the corona discharge current was 17 mA, and the single-layer dispersed photoconductor prepared in Examples 169 to 336 and Comparative Examples 28 to 54 was charged in the dark by corona discharge to measure the initial charging potential. It was. Surface potential at this time is made into charging property (V).

Then, the discharge current was adjusted so that the surface potential of the photosensitive member might be set to 700V, it was exposed by 780 nm light, and the exposure amount which cuts the surface potential of each photosensitive member from 700V to 350 was measured. The exposure amount at this time is made into half exposure exposure amount (microJ / cm <2>). This half exposure exposure value is a value which shows the sensitivity of a photosensitive member, and it shows that a sensitivity is so high that a value is small.

Moreover, the surface potential at the time of irradiating 780 nm light (exposure energy 10 microJ / cm <2>) at the surface potential 700V of each photosensitive member was measured. The surface potential at this time is referred to as the residual potential (V).

Thereafter, the surface potential of the photoconductor is charged again to 700 V, the surface potential V10 when left for 10 seconds in a dark place is measured, and the potential holding ratio (%) = V10 / 700 x 100 is obtained. This potential holding ratio is an index indicating the insulation of the photosensitive member.

The measurement is carried out under three environments of LL environment (temperature 15 ° C., humidity 15%), NN environment (temperature 25 ° C., humidity 40%), and HH environment (temperature 35 ° C., humidity 80%). The average of the half-sensitive exposure amounts in three environments of each photosensitive member is calculated | required, and the value which multiplied the difference with the half-sensitive exposure amount in each environment in each photosensitive body is calculated | required as a sensitivity environmental stability index.

<Measurement result>

The measurement result of Examples 1-168 and Comparative Examples 1-27 is the same as Table C (1) -Table C (9).

The measurement result of Examples 169-336 and Comparative Examples 28-54 is the same as Table D (1) -Table D (9).

Comparing the said Example with a comparative example, it turns out that an Example has obtained the photosensitive member which has a small half-sensitivity exposure amount, and is highly sensitive. Examples 1 to 63 and Examples 169 to 231 using the hole transporting material represented by the general formula (25) and the electron transporting material represented by the general formula (1) in the monolayer dispersed photosensitive member of the present invention are charged and displaceable. It can be seen that the retention rate is higher than the value of the photoconductor using another hole transfer material and exhibits stable characteristics.

It can be seen that Examples 64 to 105 and Examples 232 to 273 using hole transfer materials represented by the general formula (26) are superior to photoconductors using other hole transfer materials with different environmental stability indices. In addition, it turns out that Examples 106-168 and Examples 274-336 using the hole transport material represented by General formula (27) are high in chargeability.

As described above, the single-layer dispersed photoconductor of the present invention is highly sensitive.

Claims (3)

 A positively charged electrophotographic photosensitive member having a support and a photosensitive layer formed on the support, wherein the photosensitive layer contains a charge generating material, a charge generating material, an electron transfer material, and a hole transfer material dispersed therein, The electron transfer material is a compound represented by the following general formula (3), The hole transport material is at least one compound selected from the group consisting of a compound represented by the following general formula (29), a compound represented by the general formula (31), and a compound represented by the general formula (32). Electrophotographic photosensitive member.

(In the general formula (3), the substituents R ₁ to R ₆ are a hydrogen atom, a cyano group, a nitro group, a halogen atom, a hydroxy group, an alkyl group, an aryl group, a heterocyclic group, an ester group, and an alkoxy group. , An aralkyl group, an allyl group, an amide group, an amino group, an acyl group, an alkenyl group, an alkynyl group, a carboxyl group, a carbonyl group, or any one kind of substituent selected from the group consisting of a carboxylic acid group. Oxygen, sulfur, and any one kind of substituent selected from the group consisting of = C (CN) ₂ , and substituent Y is composed of any one element of oxygen or sulfur.)

(In formula (29), R ₇ and R ₈ are any one selected from the group consisting of a hydrogen atom, a halogen atom, an alkyl group, an allyl group, an alkoxy group, an aryl group, a dialkylamino group and a diphenylamino group. It is one type of substituent, and the other substituent may couple | bond with these substituents, respectively.m and n are the integers of 0 or more and 2 or less in Formula (29), and when m and n are 2, they are bonded to the same phenyl group. In some cases, two substituents (R ₇ ) ₂ and (R ₈ ) ₂ may be bonded to each other to form a ring, and in Formula (29), R ₂₀ and R ₂₁ may each represent a hydrogen atom, an alkyl group, an aryl group, Any one type of substituent selected from the group which consists of an allyl group is shown, and another substituent may couple | bond each with these substituents.)

(In said general formula (31), R <_24> , R <_25> is either substituent of a hydrogen atom or an alkyl group, and R <_26> is either substituent of a hydrogen atom or a dialkylamino group.)

(R <_27> -R <_30> of the said General formula (32) is any 1 selected from the group which consists of a hydrogen atom, a halogen atom, a C1-C6 alkyl group, a C1-C6 alkoxy group, and an aryl group. R ₃₁ is a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an aryl group, an alkenyl group, an alkadienyl group, and the following general formula ( It is any one kind of substituent selected from the group which consists of a substituent shown by 33. In addition, when R <_27> -R <_31> consists of an aryl group or an alkenyl group, another substituent may couple | bond with these substituents. E in 32) represents an integer of 0 or 1.)

(R <_32> , R <_33> in the said General formula (33) is any one type of substituent chosen from the group which consists of a hydrogen atom, a halogen atom, a C1-C6 alkyl group, an alkoxy group, and an aryl group, and a substituent. When R <_32> , R <_33> is an aryl group, another substituent may couple | bond with these substituents R <_32> , R _33. f in Formula (33) represents the integer of 0 or 1.) delete delete

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