JP2003255576A - Electrophotographic photoreceptor, process cartridge and electrophotographic apparatus - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a new electrophotographic photoreceptor using in a photosensitive layer a high molecular weight compound derived from DNA and having a structure derived from a photosensitizing dye in a part thereof and to further provide an electrophotographic photoreceptor having enhanced sensitivity and extended selectivity of exposure wavelength, a process cartridge with the electrophotographic photoreceptor and an electrophotographic apparatus. <P>SOLUTION: In an electrophotographic photoreceptor having on an electrically conductive support a photosensitive layer comprising a high molecular weight compound derived from organic solvent-soluble DNA, the high molecular weight compound has a structure derived from a photosensitizing dye in a part thereof. <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to an electrophotographic photoreceptor,
More specifically, the present invention relates to a novel electrophotographic photoreceptor using a high molecular weight compound derived from DNA (deoxyribonucleic acid) in a photosensitive layer, a process cartridge having the electrophotographic photoreceptor, and an electrophotographic apparatus.

[0002]

2. Description of the Related Art Conventionally, various organic photoconductive substances have been proposed and used as photoconductive materials used in electrophotographic photoreceptors. When used in combination with a binder polymer, they are superior to inorganic photoconductive materials in film formability, light weight, productivity, etc., and have the advantage that an inexpensive electrophotographic photoreceptor can be provided. . Further, it has the advantage that the photosensitive wavelength can be freely selected by selecting the dyes and pigments to be used, and has been extensively studied so far.

Particularly, recently, a laminated electrophotographic photosensitive member has been proposed and used in which a photosensitive layer is functionally separated into a charge generating layer and a charge transporting layer. The electrophotographic photoreceptor having the laminated electrophotographic photoreceptor as a photosensitive layer has sensitivity to visible light, charge retention, surface hardness, compared to conventional single-layer electrophotographic photoreceptors.
It has become possible to improve durability and other aspects.

As the binder polymer used in these photosensitive layers, synthetic resin materials such as polycarbonate and polyester are mainly used in consideration of abrasion resistance and compatibility with organic compounds.

In recent years, the problem of disposal of plastic materials has become an important issue, especially the disposal of waste materials that have been thrown away until now. Similar problems will be pointed out for electrophotographic photoreceptor materials in the future. there is a possibility. Also, leakage of organic compounds generated from plastic raw materials and additives into the environment may pose a problem in the future.

[0006] As is well known, DNA that controls genetic information is an ultra-high molecular weight body of several hundred to several billion in vivo, and is a biological substance having a unique structure which is also known to have a double helix structure. . In order to use such DNA as a material so that it can be used, it is necessary to extract it from the living body to remove impurities, and to make the molecular weight easy to use. At present, DNA is extracted from salmon testes by such an operation and used as an additive for health foods, cosmetics and the like. However, since they are water-soluble, it was difficult to use them as industrial materials as they were. Okabata et al. Reported that water-insoluble DNA while maintaining a double helix structure was obtained by ion-exchanging a water-soluble substance such as DNA-sodium salt or potassium salt extracted as described above with a quaternary ammonium salt or the like. −
It was found that a lipid complex film can be produced (J.
Chem. Soc. Chem. Commun. , 19
92, 1339, JP-A-8-239398). However, no attempt has been made so far for use intended for use in an electrophotographic photoreceptor as in the present invention.

DNA materials having a double helix structure are generally known to intercalate organic dye compounds between base pairs, and similar behavior has been found for DNA-lipid complexes ( J. Chem. Soc.,
Chem. Commun. , 1992, 1339, La
ngmuir, 1993, 9, 19). It has been reported that the photoelectron property is expressed by the interaction between the intercalated organic compound and the aromatic ring forming the base pair. However, it is generally said that even molecules that are easily intercalated do not enter between all base pairs,
It is considered that many of the photosensitive dyes and pigments used in the photoconductor of the present invention are difficult to intercalate because they have large molecules. Therefore, it is presumed that the improvement of the properties is not sufficient only by incorporating the photosensitive molecules by intercalating.

[0008]

SUMMARY OF THE INVENTION An object of the present invention is to solve the above-mentioned problems and a novel electron using a high molecular weight compound derived from DNA having a structure derived from a photosensitive dye as a part thereof in a photosensitive layer. To provide a photographic photoreceptor.

Another object of the present invention is to provide an electrophotographic photosensitive member having improved sensitivity and broadened sensitivity of photosensitive wavelength.

Still another object of the present invention is to provide a process cartridge and an electrophotographic apparatus having the above electrophotographic photosensitive member.

[0011]

According to the present invention, there is provided an electrophotographic photoreceptor having a photosensitive layer containing an organic solvent-soluble high molecular weight compound derived from DNA on a conductive support,
There is provided an electrophotographic photosensitive member characterized in that the high molecular weight compound has a structure derived from a photosensitive dye in a part thereof.

According to the present invention, there are also provided a process cartridge and an electrophotographic apparatus having the electrophotographic photosensitive member.

[0013]

BEST MODE FOR CARRYING OUT THE INVENTION Embodiments of the present invention will be described in detail below.

The high molecular weight compound derived from DNA used in the present invention is a known DNA-sodium salt or potassium salt extracted from the testes of fish such as salmon and herring or shellfish such as scallop by the above-mentioned known method. A water-soluble substance such as a compound having a long-chain alkyl group and a structure derived from a photosensitive dye
It is a DNA-lipid complex obtained by ion-exchange with a halide of a primary ammonium salt, etc., and is soluble or finely dispersible in an organic solvent such as alcohol or halogen.

DN extracted and purified from the above fish and shellfish
Although the molecular weight of A-sodium salt or potassium salt can be reduced to several million base pairs or less in the process of treatment, the average molecular weight is required for use as a high molecular weight compound derived from the organic solvent-soluble DNA of the present invention. Is preferably 50,000 base pairs or less, and particularly preferably 30,000 base pairs or less. When the average molecular weight exceeds 50,000 base pairs (hereinafter, base pairs are abbreviated as bp), the solution becomes highly viscous, and preparation of the lipid complex takes time, and the solubility of the obtained lipid complex in a solvent is high. It is difficult to use due to a decrease in. The molecular weight of DNA-sodium salt, potassium salt and the like can be measured by a gel electrophoresis method using a commonly used agarose gel.

In the present invention, the use of, for example, a quaternary ammonium salt having a structure derived from various photosensitive dyes, which will be described later, as a substituent in the DNA-lipid complex having a structure derived from the photosensitive dye. Can be obtained. The group of the dye structure may be directly bonded to the nitrogen atom of the ammonium group, but a group bonded to the nitrogen atom via a long-chain alkylene group is more preferable from the viewpoint of easy synthesis of the DNA-lipid complex. Examples of the long-chain alkylene group include aliphatic hydrocarbon groups having 6 or more carbon atoms, and particularly those having 8 to 23 carbon atoms are preferable. A part of the long-chain alkylene group may have 1 to 4 ether bonds or oxyethylene groups. One having one or two groups of the dye structure is suitable, but one having one is more preferable from the viewpoint of film-forming property. The dye structure to be selected is selected according to the desired wavelength, sensitivity and the like, and may be appropriately selected depending on the difficulty of lipid exchange.

Examples of the quaternary ammonium salt having a structure derived from the photosensitive dye used in the present invention include charge generating functional groups shown in the following (1-1) to (1-8). A structure derived from a group,

[0018]

[Chemical 1]

[0019]

[Chemical 2]

Alternatively, the structures derived from the charge-transporting functional groups shown in the following (2-1) to (2-5)

[0021]

[Chemical 3]

Examples thereof include those represented by the following formula (1) or formula (2) having a part of the above long-chain alkyl group.

[0023]

[Chemical 4]

Where R₁And R₃Is (1-1) to (1
-8) and (2-1) to (2-5)
Indicates a functional group, R₂And R_FourIs a long-chain alkylene group
And R _FiveRepresents a long-chain alkyl group. X is a single bond, O,
S, NH, CO, CO₂, OCO ₂, SO, SO₂, CO
A bonding group such as NH or COONH is shown.

The quaternary ammonium salt represented by the above formula (1) or formula (2) is used as a halide to obtain a DNA-lipid complex as described later.

More specifically, the following (3-1) to (3)
-3) can be mentioned, but not limited to these.

[0027]

[Chemical 5]

In the present invention, a DNA containing a halide of a quaternary ammonium salt having the above structure is used.
-By exchanging lipid with sodium salt or the like, a DNA-lipid complex having a structure derived from a photosensitizing dye in a part thereof can be obtained.

The advantages of using such a DNA-lipid complex are considered as follows. That is, when dispersed and mixed with a normal binder polymer, it is considered that the dye material has a disordered mixed state in the system, but in this case, the dye material has a higher-order structure of a DNA chain having a double helix structure. That is, photosensitive groups are aligned and ordered to induce anisotropic orientation, and as a result, an improvement in photosensitive characteristics (improvement in sensitivity) is exhibited. Further, in the case of a combination in which it is difficult to increase the concentration of the dye material depending on the compatibility of the DNA-lipid complex and the photosensitizing dye material, and a mixing failure is likely to occur, such problems can be avoided by integrating the above structure. Therefore, the effect of being able to obtain a photosensitive layer with improved sensitivity can be expected. Further, with the structure as described above, the photosensitive wavelength can be set to a long wavelength region and the selectivity of the photosensitive wavelength can be widened.

In the present invention, the quaternary ammonium salt described below can be used in combination with the quaternary ammonium salt having a photosensitive dye structure of the present invention at the time of lipid exchange, and is preferable in that the film-forming property is improved. That is, examples of the long-chain alkyl group of the quaternary ammonium salt having a long-chain alkyl group include an aliphatic hydrocarbon group having 6 or more carbon atoms,
It is particularly preferable that the carbon number is 8 to 23. That is,
A DNA-lipid complex using a quaternary ammonium salt having one or two alkyl groups having 8 to 23 carbon atoms is preferable. Specifically, n-hexyltrimethylammonium chloride, n-heptyltrimethylammonium chloride, n-octyltrimethylammonium chloride, n-nonyltrimethylammonium chloride, n
-Decyltrimethylammonium chloride, n-undecyltrimethylammonium chloride, lauryltrimethylammonium chloride, n-tridecyltrimethylammonium chloride, myristyltrimethylammonium chloride, n-pentadecyltrimethylammonium chloride, cetyltrimethylammonium chloride, n-heptadecyltrimethyl Ammonium chloride, stearyl trimethyl ammonium chloride, n-nonadecyl trimethyl ammonium chloride, arachidyl trimethyl ammonium chloride,
n-heneicosyltrimethylammonium chloride,
Quaternary ammonium salts having one long chain alkyl group such as behenyltrimethylammonium chloride, n-tricosyltrimethylammonium chloride and their bromides; di-n-hexyldimethylammonium chloride, di-n-heptyldimethylammonium chloride, di-n-hexyldimethylammonium chloride -N-octyldimethylammonium chloride, di-n-nonyldimethylammonium chloride,
Di-n-decyldimethylammonium chloride, di-
n-undecyldimethylammonium chloride, dilauryldimethylammonium chloride, di-n-tridecyldimethylammonium chloride, dimyristyldimethylammonium chloride, di-n-pentadecyldimethylammonium chloride, dicetyldimethylammonium chloride, di-n- Heptadecyldimethylammonium chloride, distearyldimethylammonium chloride, di-n-nonadecyldimethylammonium chloride, diarachidyldimethylammonium chloride, di-n-heneicosyldimethylammonium chloride, dibehenyldimethylammonium chloride, di-n-trico 2 long-chain alkyl groups such as sildimethylammonium chloride and their bromides
A quaternary ammonium salt having one; an ether bond or an oxyethylene group in a part of the above-mentioned one or two long-chain alkyl groups
Aromatic ring-containing quaternary ammonium salts such as phenyl dimethyl cetyl ammonium chloride, benzyl dimethyl cetyl ammonium chloride and bromides thereof having 1 to 4 quaternary ammonium salts; quaternary pyridinium salts such as cetyl pyridinium chloride and their bromides Is mentioned.

As the photosensitive layer, a layered type of a function-separated type including a charge generation layer and a charge transport layer, or a single layer type in which charge generation and charge transport are performed in the same layer is used.

In the present invention, the DNA obtained as described above
-The lipid complex can be used for the charge generation layer and / or the charge transport layer, but when the volume resistivity of the obtained DNA-lipid complex is about 10 ⁵ to 10 ¹³ Ω · cm, the charge generation layer. It is preferable that the volume resistivity is 10 ¹³
When it is Ω · cm or more, it can be used for any layer.

Examples of the charge-generating photosensitive dye used in the present invention include polycyclic quinone type, phthalocyanine type, anthraquinone type, squarylium type, azurenium type,
Pyrylium-based, thiopyrylium-based, azo-based, trisazo-based, disazo-based, indigo-based, dioxazine-based, quinacridone-based, and cyanine-based pigments and dyes that are known as charge generation materials can be mentioned.

The charge transporting photosensitive dyes include polycyclic aromatic compounds such as pyrene and anthracene, heterocyclic compounds such as carbazole, indole, oxazole, thiazole, oxathiazole, pyrazole, pyrazoline, thiadiazole and triazole, tria. Lille amine compound, p-diethylaminobenzaldehyde-
Hydrazone compounds such as N, N-diphenylhydrazone and N, N-diphenylhydrazino-3-methylidene-9-ethylcarbazole, α-phenyl-4′-N, N
-Styryl compounds such as diphenylaminostilbene,
Examples of the charge transport material include triallylmethane compounds and benzidine compounds.

The charge generation layer and the charge transport layer are preferably formed by dissolving the above-described DNA-lipid complex having a photosensitizing function in a suitable solvent. It is also preferable that the charge generation material and the charge transport material described above are used together and dissolved in an appropriate solvent. In addition, a DNA-lipid complex is used in either the charge generation layer or the charge transport layer, and is usually used as a binder resin in any other layer, such as polyarylate resin, polysulfone resin, polyamide resin, and acrylic resin. Resin, acrylonitrile resin, methacrylic resin,
Vinyl chloride resin, vinyl acetate resin, phenol resin, epoxy resin, polyester resin, alkyd resin, polycarbonate resin, polyurethane resin and copolymer resin (for example, styrene-butadiene copolymer, styrene-acrylonitrile copolymer and styrene-maleic acid copolymer, etc.) ) Can also be used. In addition to such insulating polymers, organic photoconductive polymers such as polyvinylcarbazole, polyvinylanthracene and polyvinylpyrene can also be used. Furthermore, in either the laminated type or the single layer type, the DNA-lipid complex and the binder resin may be mixed and used together.

In the present invention, the above-mentioned charge-generating or charge-transporting photosensitive dyes may be mixed and contained in the DNA-lipid complex having the above-mentioned photosensitive dye-derived structure as a part thereof. Further, the blending ratio of the DNA-lipid complex or binder resin to the charge generating material or charge transporting material may be appropriately selected within the range of 10 to 500 parts by weight of the charge generating material or charge transporting material per 100 parts by weight of the former. .

The organic solvent which dissolves the above-mentioned DNA-lipid complex, binder resin and the like is selected in consideration of the solubility of the photosensitive dye and resin, and in the case of a laminated electrophotographic photoreceptor, the lower layer is It is preferable to select one that does not dissolve. As the organic solvent, alcohols such as methanol, ethanol and isopropanol; halogenated alcohols such as hexafluoroisopropanol; acetone,
Ketones such as methyl ethyl ketone and cyclohexanone; Amides such as N, N-dimethylformamide and N, N-dimethylacetamide; Pyrrolidones such as N-methylpyrrolidone; Sulfoxides such as dimethyl sulfoxide; Tetrahydrofuran, dioxane and ethylene glycol monomethyl ether And the like; aliphatic halogenated hydrocarbon compounds such as chloroform, methylene chloride, dichloroethane, dichloroethylene, carbon tetrachloride and trichloroethylene, and aromatic compounds such as toluene, xylene, monochlorobenzene and dichlorobenzene.

The coating can be carried out by a method such as a dip coating method, a spray coating method, a spinner coating method, a blade coating method, a Meyer bar coating method, a roller coating method or a curtain coating method. Drying can be performed at room temperature or by heat drying depending on the boiling point of the solvent used. The heat-drying can be performed in a temperature range of 30 to 200 ° C. for about 5 minutes to 2 hours in a static or blown state according to a predetermined dry state, but the drying of the DNA material is preferably room temperature to 150 ° C. The temperature is more preferably room temperature to 100 ° C, and further preferably room temperature to 80 ° C. This is because at a temperature of higher than 150 ° C., film properties may be impaired due to dissolution of lipids, decomposition of DNA chains, and the like.

A function-separated charge generation layer and a charge transport layer 2
When it is composed of layers, the charge transport layer may be laminated either above or below the charge generation layer, depending on whether it is positively charged or negatively charged. In the laminated electrophotographic photoreceptor of the present invention, a layer structure in which a charge transport layer is laminated on the charge generation layer is preferable in terms of electrophotographic characteristics.

The support on which the photosensitive layer is formed is, for example, aluminum, aluminum alloy, copper, zinc, stainless steel, vanadium, molybdenum, chromium, titanium, nickel, magnesium, indium, gold, platinum, silver or iron. Used. Further, a plastic (for example, polyethylene, polypropylene, polyvinyl chloride, polyethylene terephthalate, acrylic resin, polyfluorinated ethylene, etc.) having a conductive layer formed by film-forming such a metal or alloy by a vacuum deposition method or the like, a composite thereof, etc. Is mentioned.

An undercoat layer having an injection blocking function and an adhesive function may be provided between the conductive support and the photosensitive layer. The subbing layer can be formed of casein, polyvinyl alcohol, polyethylene oxide, ethyl cellulose, nitrocellulose, ethylene-acrylic acid copolymer, polyvinyl butyral, phenol resin, alcohol-soluble polyamide, polyurethane or gelatin.

FIG. 1 shows a schematic structure of an electrophotographic apparatus provided with a process cartridge having the electrophotographic photosensitive member of the present invention.

In FIG. 1, reference numeral 1 is a drum-shaped electrophotographic photosensitive member of the present invention, which is rotationally driven around a shaft 2 in a direction of an arrow at a predetermined peripheral speed. In the rotating process, the electrophotographic photosensitive member 1 is uniformly charged with a positive or negative predetermined potential on its peripheral surface by the primary charging unit 3, and then from an exposing unit (not shown) such as slit exposure or laser beam scanning exposure. The exposure light 4 intensity-modulated corresponding to the time-series electric digital image signal of the output target image information is received. In this way, electrostatic latent images corresponding to target image information are sequentially formed on the peripheral surface of the electrophotographic photosensitive member 1.

The formed electrostatic latent image is then developed by the developing means 5.
Toner is developed by the electrophotographic photosensitive member 1 and is transferred between the electrophotographic photosensitive member 1 and the transfer unit 6 from a sheet feeding unit (not shown) in synchronism with the rotation of the electrophotographic photosensitive member 1. The toner images formed and carried on the surface of the photoconductor 1 are sequentially transferred by the transfer unit 6.

The transfer material 7 to which the toner image has been transferred is separated from the surface of the electrophotographic photosensitive member and introduced into the image fixing means 8 to undergo image fixing, thereby being printed outside the apparatus as an image formed product (print, copy). Will be out.

After the image transfer, the surface of the electrophotographic photosensitive member 1 is cleaned by the cleaning means 9 to remove the transfer residual toner, and is further discharged by pre-exposure light 10 from pre-exposure means (not shown). After that, it is repeatedly used for image formation. If the primary charging means 3 is a contact charging means using a charging roller or the like, pre-exposure is not always necessary.

In the present invention, among the above-mentioned electrophotographic photosensitive member 1, primary charging means 3, developing means 5, cleaning means 9 and the like, a plurality of components are housed in a container and integrally combined as a process cartridge. The process cartridge may be detachably attached to the main body of the electrophotographic apparatus such as a copying machine or a laser beam printer. For example, at least one of the primary charging unit 3, the developing unit 5, and the cleaning unit 9 is integrally supported together with the electrophotographic photosensitive member 1 to form a cartridge, and the cartridge is attached to and detached from the apparatus main body by using a guide unit 12 such as a rail of the apparatus main body. The process cartridge 11 can be freely used.

Further, when the electrophotographic apparatus is a copying machine or a printer, the exposure light 4 is reflected light or transmitted light from an original document, or a document is read by a sensor, converted into a signal, and a laser is produced according to this signal. Beam scanning, LED
Light emitted by driving the array or driving the liquid crystal shutter array.

The electrophotographic photoreceptor of the present invention can be used not only in electrophotographic copying machines but also in laser beam printers,
It can be widely applied to electrophotographic application fields such as CRT printers, LED printers, FAX machines, liquid crystal printers, and laser plate making.

[0050]

EXAMPLES The present invention will be described more specifically below with reference to production examples and examples, but the present invention is not limited to these examples. In addition, "part" in an Example means a mass part.

<Production Example 1> The quaternary ammonium chloride (I) represented by the compound 3-3 (n = 16) having the thiapyrylium group represented by the compound 1-6 was synthesized as follows.

Under a stream of argon, 14.8 parts of magnesium was mixed with 5 parts of ethyl bromide in dry ether while stirring at 0 ° C.
0.4 part of a dry ether solution was added dropwise. Next, a mixture of 24.9 parts of phenylacetylene and 51.7 parts of 3-benzylethylphenylacetylene was added dropwise, and the mixture was stirred at room temperature for 3 hours. Next, 17.9 parts of ethyl formate was added dropwise at 0 ° C., and dry ether was added. 30 minutes later, 6N-at 0 ° C
Hydrochloric acid was added dropwise to terminate the reaction. The organic layer extracted with isopropyl ether was dried over anhydrous magnesium sulfate, concentrated under reduced pressure and purified by a silica gel column to give 1-phenyl-5.
(3-benzylethyl) -1,4-pentadiyne-3-
I got all (A). 31.1 parts of the obtained (A) was dissolved in acetone, and an aqueous solution of 25 parts of sodium dichromate and 33.3 parts of sulfuric acid was added dropwise under cooling and stirring at 10 ° C or lower.
After stirring at 10 ° C or lower, the reaction solution was poured into ice, extracted with chloroform, dried over anhydrous magnesium sulfate, concentrated under reduced pressure, and purified by silica gel column purification to give 1-phenyl-5 (3-
Benzylethyl) -1,4-pentadiyn-3-one (B) was obtained. Under an argon stream, 3.1 parts of sodium was dissolved in dry ethanol, 3.3 parts of sulfur and 3.8 parts of sodium borohydride were charged, and the mixture was heated under reflux and stirred for 2 hours. On the other hand, under an argon stream, 3.1 parts of sodium was dissolved in dry ethanol, 21.8 parts of (B) was added, and the mixture was stirred for 10 minutes and added to the above solution. After stirring for 30 minutes, the crystals were poured into ice and the precipitated crystals were filtered and washed with water. Dried under reduced pressure,
2-phenyl-6 (3-benzylethyl) phenyl-4
H-thiapyran-4-one (C) was obtained.

Under an argon stream, 1.15 parts of magnesium was charged and 4-bromo-N, N-dimethylaniline was added.
5 parts of dry THF solution was added dropwise. After refluxing for 2 hours, the mixture was cooled to room temperature, and 10 parts of (C) dry THF solution was added dropwise.
After refluxing for 3 hours, it was cooled to room temperature and 16 ml of perchloric acid / water 3
After pouring into 10 ml and stirring, the precipitated crystals were filtered and washed with water. The crystals dried under reduced pressure were dissolved in ethanol, 5 parts of 16-chlorohexadecamethylenedimethylamine were reacted, and then methyl bromide was added and stirred at room temperature. The obtained crystals were dissolved in acetonitrile, ether was added to reprecipitate, and the crystals were washed with ether. After drying under reduced pressure, quaternary ammonium chloride (I) was obtained.

250 mg of salmon sperm-derived DNA-sodium salt (average molecular weight 3000 bp) was dissolved in 25 ml of water. This DNA aqueous solution was stirred under ice-cooling with the above (I) and cetyltrimethylammonium chloride (n-C16N).
And were mixed in the ratio shown in Table 1 and added to the aqueous solution.
710 mg (A-1) to 250 mg (A-5) 25 m
It was added to an aqueous solution dissolved in 1 l of water. The resulting precipitate was collected by a centrifuge, washed with water and diethyl ether, and then vacuum dried to obtain a powdery DNA-lipid complex (A-1).
~ A-5) was obtained.

On a comb-shaped electrode of a polyethylene terephthalate substrate, a 5% by mass solution of chloroform / ethanol (4/1 mass ratio) of (A-1 to A-5) above was formed into a film by the Meyer bar coating method, and the film thickness was 2 μm. When a thin film sample of 1 was prepared and 10 V was applied between the electrodes to measure the volume resistivity, the values shown in Table 1 were obtained according to the ratio.

<Production Example 2> 23 parts of sodium hydroxygallium phthalocyanine disulfonate and 5 parts of 16-chlorohexadecamethylenedimethylamine were reacted, and then methyl bromide was added and stirred at room temperature. After distilling off the solvent, the compound 3-2 (n = 1) having a dye structure is separated by column separation.
5, a quaternary ammonium salt (II) represented by Me: GaOH, X: Br) was synthesized.

Powdery DNA-lipid complexes (B-1 to B-3) were obtained in the same manner as in Production Example 1 except that the quaternary ammonium chloride (I) was replaced with the above (II). The volume resistivity measured in the same manner as in Production Example 1 was the value shown in Table 1.

Example 1 An alcohol-soluble copolyamide (trade name: Amilan CM-8000, manufactured by Toray Industries, Inc.) 5 as an undercoat layer on an aluminum cylinder.
A solution in which 95 parts of methanol was dissolved was applied by a dip coating method. It was dried at 80 ° C. for 10 minutes to form an undercoat layer having a film thickness of 1 μm.

Next, 4 parts of the DNA-lipid complex (A-1 to A-4) obtained in Production Example 1 and 46 parts of chloroform / ethanol (mass ratio 4/1) were mixed, dissolved and dispersed. A coating solution (III) was prepared, and the coating solution was applied onto the undercoat layer by a dip coating method so that the film thickness after drying was 0.5 μm, and the coating solution was dried at 60 ° C. for 30 minutes to obtain a charge. A generator layer was formed.

Then, 5 parts of p-diethylaminobenzaldehyde-N-phenyl-N-naphthylhydrazone and 5 parts of a polycarbonate resin (Mw = 25000, molecular weight measured by GPC (gel permeation chromatography) method) and 50 parts of monochlorobenzene. To prepare a coating liquid (IV), and the coating liquid is applied onto the charge generation layer by a dip coating method so that the film thickness after drying is 15 μm. Was dried for 1 hour to form a charge transport layer, and an electrophotographic photosensitive member was produced.

The electrophotographic photosensitive member thus produced was corona-charged (V ₀ ) at -5 kV by the static method using an electrostatic copying paper tester (SP-428) manufactured by Kawaguchi Electric Co., Ltd., and E _{1 / 2} (exposure amount that reduces the charging potential to 1/2,
Microjoule / cm ² ) was measured. As a light source
A semiconductor laser with an oscillation wavelength of 680 nm was used. The results are shown in Table 2.

Example 2 The DNA-lipid complex (A-1 to A) of the coating solution (III) used for the charge generation layer in Example 1
-4) is the DNA-lipid complex (B-
1 to B-3) except that the coating liquid (V) was used in place of 1 to B-3), an electrophotographic photosensitive member was produced in the same manner as in Example 1, and the characteristics were measured. The results are shown in Table 2.

(Example 3) An electrophotography was carried out in the same manner as in Example 1 except that the coating solution (VI) used in Example 2 was replaced with hexafluoroisopropanol. A photoconductor was prepared and its characteristics were measured. The results are shown in Table 3.
Shown in.

Example 4 In the coating liquid (III) used for the charge generation layer in Example 1, the DNA-lipid complex A-3 was used.
3 parts, thiapyrylium dye 2 parts, and chloroform / ethanol (mass ratio 4/1) 45 parts are mixed to obtain a coating solution (VI
An electrophotographic photosensitive member was prepared and the characteristics were measured in the same manner as in Example 1 except that it was changed to I). The results are shown in Table 3.

Comparative Example 1 D obtained by lipid exchange with n-C16N as the quaternary ammonium salt in Production Example 1
Example 1 except that the NA-lipid complex (A-5) was used.
An electrophotographic photosensitive member was produced in the same manner as in, and the characteristics were measured. The results were not sensitive as shown in Table 2.

[0066]

[Table 1]

[0067]

[Table 2]

[0068]

[Table 3]

[0069]

As described above, according to the present invention, a DNA material, whose use is limited to health foods and the like, is in little demand and most of it is a waste, is electrophotographic photosensitive member and electrophotographic photosensitive member. It is possible to apply to a process cartridge having a body and an electrophotographic apparatus, and by forming a composite of an organic photosensitive dye, the film-forming property and the sensitivity are improved, and the electrophotographic photosensitive member and the process cartridge having a wide selection of photosensitive wavelengths. And it has become possible to provide an electrophotographic apparatus.

[Brief description of drawings]

FIG. 1 is a diagram showing an example of a schematic configuration of an electrophotographic apparatus provided with a process cartridge having an electrophotographic photosensitive member of the present invention.

[Explanation of symbols]

1 Electrophotographic photoreceptor 2 axes 3 charging means 4 exposure light 5 Developing means 6 Transfer means 7 Transfer material 8 fixing means 9 Cleaning means 10 Pre-exposure light 11 Process cartridge 12 guidance means

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Claims (5)

[Claims] 1. An electrophotographic photoreceptor having a photosensitive layer containing a DNA-derived high molecular weight compound on a conductive support, wherein the high molecular weight compound partially has a structure derived from a photosensitive dye. An electrophotographic photosensitive member. 2. A DNA-derived high-molecular weight compound obtained by lipid exchange between water-soluble DNA and a quaternary ammonium salt, wherein a structure derived from a photosensitizing dye is part of a lipid of the quaternary ammonium salt. The electrophotographic photosensitive member according to claim 1, further comprising: 3. The photosensitive layer according to claim 1, wherein the photosensitive layer is composed of a single layer or two or more layers, and either of the layers contains a charge-generating or charge-transporting photosensitive dye or both of them. Electrophotographic photoreceptor. 4. A charging unit for charging the electrophotographic photosensitive member according to claim 1,
With at least one means selected from the group consisting of a developing means for developing the electrophotographic photosensitive member on which an electrostatic latent image is formed with toner and a cleaning means for recovering the toner remaining on the electrophotographic photosensitive material after the transfer step. A process cartridge which is integrally supported and is detachable from the main body of the electrophotographic apparatus. 5. The electrophotographic photosensitive member according to claim 1, a charging unit that charges the electrophotographic photosensitive member, and the charged electrophotographic photosensitive member is exposed to form an electrostatic latent image. An electrophotographic apparatus comprising an exposing means, a developing means for developing with a toner on an electrophotographic photosensitive member on which an electrostatic latent image is formed, and a transferring means for transferring a toner image on the electrophotographic photosensitive member onto a transfer material. .