JPH0561232A - Photosensitive body - Google Patents

Abstract

PURPOSE:To restrain occurrence of image defects, such as black spots, and to obtain sufficient sensitivity to comparatively long wavelength lights, such as semiconductor laser beams, and superior characteristics, such as printing resistance, potential stability, and residual potential. CONSTITUTION:The photosensitive body comprises a conductive substrate 1 and on this substrate 1 at least an undercoat layer 7 and a photosensitive layer 8. This undercoat layer 7 is made of a radiation-curing resin having radiation- sensitive acrylic, allyl, or maleic type unsaturated double bonds and/or a polymer composed of their prepolymer or oligomer, and this polymer has a main skeleton composed of polyvinyl alcohol type, ketal type, cellulose type, or the like structure, thus permitting a barrier against local injection of carriers from the substrate 1 to be formed by the presence of this undercoat layer 7 and accordingly, loss or drop of surface electric charge to be hindered.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a photoconductor, particularly an electrophotographic photoconductor.

[Background of the Invention]

 In the Carlson electrophotographic copying method, after the surface of the photoconductor is charged, an electrostatic latent image is formed by exposure, the electrostatic latent image is developed with toner, and then the visible image is formed. Transfer and fix to paper. At the same time, the photoconductor is subjected to removal of adhered toner, charge removal, and surface cleaning, and is repeatedly used over a long period of time.

 Therefore, as an electrophotographic photosensitive member, of course, it has not only electrophotographic characteristics such as good charging characteristics and good sensitivity and small dark decay, but also printing durability, abrasion resistance, moisture resistance after repeated use. It is also required to have good physical properties and resistance to ozone generated during corona discharge and ultraviolet rays during exposure (environmental resistance).

 Conventionally, as an electrophotographic photoreceptor, an inorganic photoreceptor having a photoreceptor layer containing an inorganic photoconductive substance such as selenium, zinc oxide, or cadmium sulfide as a main component has been widely used.

 On the other hand, the use of various organic photoconductive substances as materials for the photoconductor layer of an electrophotographic photoconductor has been actively researched and developed in recent years.

 However, the sensitivity and durability are not always satisfactory.

 For this reason, in the photosensitive layer, by separating the carrier generation function and the carrier transport function into different substances, so-called function-separated type having high sensitivity and high durability, and further each functional layer was laminated. Attempts have been made to develop organic photoconductors.

 In such a function-separated type electrophotographic photoconductor, since substances exhibiting each function can be selected from a wide range of substances, it is relatively easy to obtain an electrophotographic photoconductor having arbitrary characteristics. It is possible to make it. Therefore, it is expected that an organic photoreceptor having high sensitivity and high durability can be obtained.

 2 and 4 show a function-separated laminated electrophotographic photosensitive member using such an organic photoconductive material.

 Further, FIG. 3 shows a function-separated single-layer electrophotographic photosensitive member.

 The electrophotographic photoreceptor of FIG. 2 is constructed by sequentially laminating an undercoat layer (UCL) 7, a carrier generation layer (CGL) 6, and a carrier transport layer (CTL) 4 on a conductive support 1. It is used for negative charging. That is, the photosensitive layer (PCL) 8 is composed of CGL 6 and CTL 4.

 In the electrophotographic photoreceptor having such a layer structure, since the mobility of holes is larger than that of electrons when it is negatively charged, a hole-transporting photoconductive material having good characteristics is used. It is possible and advantageous in terms of light sensitivity and the like.

 Next, FIG. 4 shows a photoconductor for positive charging. In such a layered type photoconductor, particularly a photoconductor using an organic photoconductive substance, non-uniform carrier (hole) injection from the conductive support or the lower layer side is likely to occur during negative charging, which results in surface charge. Microscopically disappears or decreases. In particular, this causes black spot-like image defects (black spots) in the reverse developing method, and significantly deteriorates the image quality.

 The problem of such black spots is a phenomenon peculiar to a photoconductor using an organic photoconductive material having a high hole mobility, and it is considered that the cause is that the above-mentioned carrier injection is uneven.

 Therefore, it has been proposed to provide UCL between the conductive support 1 and PCL to block carrier injection.

 Conventionally, as materials constituting UCL7, polyester-based, polyurethane-based, polyamide-based, epoxy resin-based, polycarbonate-based, vinyl polymer-based such as polyvinyl pyridine acrylic resin, cellulose-based, polyketal-based, condensation polymerization-based, for example, phenol Resins, melamine resins, etc. are known.

 However, the above-mentioned known undercoat layer does not have a sufficient black spot suppressing effect. Moreover, it has not been possible to improve both the blocking property and the sensitivity as a photoconductor. In other words, among the resins that have been conventionally used, those that are considered to have effective blocking properties and black spot suppression effects have poor sensitivity, and conversely, when trying to improve sensitivity, the blocking properties become insufficient. Black spots cannot be sufficiently suppressed.

 Furthermore, problems arise during the multi-layer coating process. If the solubility of the polymer in the upper layer is similar to that in the lower layer, a part of the lower layer will elute during coating of the upper layer, and the interface between the upper and lower layers will be disturbed, and coating will not be possible. Contamination with the components of the subordinate layers shortens the life of the expensive coating liquid for the upper layer, and also deteriorates the potential characteristics of the photoreceptor. These impose strict formulation restrictions on the upper layer and lower layer polymers and solvents.

 There are some cases where thermosetting resin is applied to UCL, but productivity is deteriorated because a high curing temperature (at least 110 ° C or higher) and a relatively long time (30 minutes or longer) are required. Further, the stability of the coating liquid containing the curing agent is essentially deteriorated.

 Further, the adhesiveness is not yet sufficient, and in addition to the adhesiveness between the support and UCL, the adhesiveness between the UCL and the upper layer is not good.

 Further, in recent years, a semiconductor laser light source is used in an electrophotographic copying method, which is inexpensive, small in size, and directly modulated. At present, gallium-aluminum-arsenic (Ga-Al-As) -based light emitting devices, which are widely used as semiconductor lasers, have an oscillation wavelength of about 750 nm or more.

 The technical system using such a laser beam is expected to be applied to a printer, but at present, a photoreceptor having high sensitivity to long wavelength light has not yet been developed.

[Object of the Invention]

 An object of the present invention is to provide a photoconductor capable of suppressing image defects such as black spots and having sufficient sensitivity to light having a relatively long wavelength such as a semiconductor laser.

 Another object of the present invention is to provide a photoreceptor having excellent printing durability, potential stability and residual potential characteristics.

Still another object of the present invention is to provide a photoreceptor having good coatability and adhesiveness in a photoreceptor having at least UCL and PCL provided on a conductive support.

[Constitution of the invention and its function and effect]

 The photoconductor of the present invention includes: (1) In a photoconductor in which at least UCL and PCL are provided on a conductive support, the UCL is a radiation-sensitive unsaturated double bond, an acrylic double bond, or allyl. A radiation-curable resin having at least one of a double bond and a maleic double bond, and / or a polymer composed of a prepolymer and an oligomer thereof.

 Further, in the aspect of the present invention: (2) The main skeleton portion of the polymer is polyvinyl alcohol, ketal resin, cellulose resin, pullulan resin, alkyd resin, polycaprolacte resin, spirane resin, condensation It preferably has a structure selected from polymerized resins.

 By adopting the configuration of the present invention, 1. 2. Good multi-layer coating. 2. No contamination of other coating liquids, 3. The range of prescription choices increases because it cannot be dissolved by other coating solutions. 4. It has good blocking properties and black dots do not appear. It has advantages such as good adhesiveness with the lower layer.

 As described above, this polymer has a blocking function that effectively prevents non-uniform injection of holes from the support, which tends to occur when an organic photoconductive substance having a high hole mobility is used for PCL. ing.

 Therefore, it is considered that the presence of this undercoat layer can provide a barrier against local carrier injection from the support side and prevent the disappearance and reduction of surface charges due to local carrier injection. Therefore, especially when reversal development is performed, black spots do not occur on the image, white spots, screen roughening, pinholes do not occur, and a high quality image without image defects is obtained. It can be effective.

 Examples of the radiation-curable resin used in the present invention include coating resins having a skeleton as shown below. By the method described below, an acrylic double bond, a maleic acid double bond, It is possible to introduce an allylic double bond and convert it into a radiation-curable resin.

1. As the polyvinyl alcohol-based resin, partially saponified polyvinyl alcohol, completely saponified polyvinyl alcohol, 1. Examples of the ketal resin include butyral resin, acetal resin and formal resin.

3. Cellulosic resins include methyl cellulose, ethyl cellulose, methyl ethyl cellulose, hydroxyethyl cellulose, cyanoethyl cellulose, nitro cellulose.

4. Examples of pullulan resins include acetyl pullulan and nitro pullulan.

5. Examples of the polycaprolactone-based resin include Praxel, 205, 210, 303 and 330 manufactured by Daicel Corporation.

6. Examples of the condensation polymerization resin include phenol resin, nopolak resin, cresol resin and melamine resin.

7. The spirane resin has a spiro acetal bond in the molecule, for example, unsaturated aldehyde, generally acrolein and polyvalent alcohol, for example, trimethylolamine, pentaerythritol, sorbitol, etc. Some polymers have been introduced.

 The radiation sensitivity is specifically acrylic double bonds having an unsaturated double bond having radical polymerizability, acrylic double bonds such as acrylic acid or methacrylic acid or their ester compounds, and allyl type double bonds such as diallyl phthalate. Introducing into the molecule a bond, a maleic acid, an unsaturated bond such as a maleic acid derivative, etc., which is crosslinked by irradiation or polymerized and dried.

 In addition, any unsaturated double bond that undergoes cross-linking polymerization upon irradiation with radiation can be used.

 A more specific radiation-sensitive modification method is performed as follows.

I. A thermoplastic resin or a thermoplastic resin having at least one hydroxyl group in the molecule, a prepolymer in which one molecule is reacted with one or more molecules of an isocyanate group of a polyisocyanate compound, and then a group which reacts with an isocyanate group and radiation. Reaction of one molecule of toluene diisocyanate for each hydroxyl group of a reaction product with one or more molecules of a curable unsaturated double bond, for example, saponified vinyl chloride-vinyl chloride copolymer (VAGH manufactured by UCC) And a vinyl chloride-based copolymer resin obtained by reacting one molecule of 2-hydroxyethyl methacrylate with the acrylic double bond in the form of a bendant.

 The polyisocyanate compounds used here include 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, 1,3-xylene diisocyanate, 1,4-xylene diisocyanate, m-phenylene diisocyanate and p-phenylene diisocyanate. Examples include diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, Desmodur L, Desmodur 1L (made by Bayer Bayer GmbH).

 Examples of monomers having a group that reacts with an isocyanate group and a radiation-curable unsaturated double bond include hydroxyl groups such as 2-hydroxyethyl ester, 2-hydroxypropyl ester and 2-hydroxyoctyl ester of acrylic acid or methacrylic acid. Esters that have; monomers that have active hydrogen that reacts with isocyanate groups such as acrylic amide, methacrylic amide, N-methylol acrylic amide, and that contain an acrylic double bond; and allyl alcohol, maleic acid Polyhydric alcohol ester compound, long-chain fatty acid monounsaturated with unsaturated double bonds, or diglyceride, etc. Contains active hydrogen that reacts with the sisocyanate group and contains unsaturated double bonds with radiation curability Monomers are also included.

II. Radical polymerization of a reaction product of one molecule of a compound containing one or more epoxy groups in the molecule with one or more molecules of a group reactive with an epoxy group and a radiation-curable unsaturated double bond, for example, glycidyl methacrylate. The resulting thermoplastic resin containing an epoxy group is reacted with acrylic acid, and a ring-opening reaction between a carboxyl group and an epoxy group results in a resin, a prepolymer or a resin in which an acrylic double bond is bent in the molecule. Examples thereof include oligomers, and resins, prepolymers, and oligomers having a radiation-curable unsaturated double bond in the molecular skeleton by ring-opening reaction of a carboxy group and an epoxy group by reacting maleic acid.

 Here, the compound containing one or more epoxy groups in the molecule is a homopolymer of an acrylate or methacrylic ester containing an epoxy group such as glycidyl acrylate or chrysyl methacrylate, or a copolymer with another polymerizable monomer. There are various other types of epoxy resin such as Shrimp Coat 828, Shrimp Coat 1001, Shrimp Coat 1007, Shrimp Coat 1009 (all manufactured by Ciel Chemical Co., Ltd.).

 Examples of the monomer having a group that reacts with an epoxy group and a radiation-curable unsaturated double bond include acrylic monomers containing a carboxyl group such as acrylic acid and methacrylic acid, methylaminoethyl acrylate, and methyl. In addition to acrylic monomers having primary or secondary amino groups such as aminomethacrylate, maleic acid, fumaric acid, crotonic acid, undecylenic acid, and other polybasic acids having radiation-curable unsaturated double bonds are used. A quantity can also be used.

III. A reaction product of one molecule of a compound containing one or more carboxyl groups in the molecule and one or more molecules of a group that reacts with a carboxyl group and one or more radiation-curable unsaturated double bonds, for example, methacrylic acid as a solution. Glycidyl methacrylate was reacted with a thermoplastic resin containing a carboxyl group obtained by polymerization, and an acrylic double bond was introduced into the molecule by ring-opening reaction of a carboxyl group and an epoxy group in the same manner as in Section II. Resins, prepolymers and oligomers can be mentioned.

 Examples of the compound containing one or more carboxyl groups in the molecule include polyesters in the above-mentioned resin containing a carboxyl group in the molecular chain or at the terminal of the molecule; acrylic acid, methacrylic acid, maleic anhydride, fumaric acid, etc. It is a homopolymer of a monomer having a radical polymerizable property and having a carboxyl group, or a copolymer with another polymerizable monomer.

 Examples of the monomer having a group reactive with a carboxyl group and a radiation-curable unsaturated double bond include glycidyl acrylate and glycidyl methacrylate.

 In addition to the resin that is crosslinked or polymerized by irradiation with radiation, another resin may be used in combination with the resin layer in order to modify the adhesiveness with PCL. Examples of such other resins include polycarbonate resin, polyacrylate resin, polyvinyl acetal resin, diallyl phthalate resin, silicone resin, polysulfone resin, acrylic resin, polyvinyl acetate resin, polyphenylene oxide resin, alkyd resin, styrene-anhydrous resin. Examples include maleic vinegar copolymer resin, phenolic resin, and paraffin wax. These other resins may be used alone or in combination of two or more.

 Next, a few examples will be shown as synthesis examples. Other polymers can be easily synthesized by the method described above.

Synthesis example 1. Synthesis of novolac acrylate Epicoat # 154 178g (equivalent) Acrylic acid 72g (1 mol) BDMA 0.2% Phenothiazine (inhibitor) 0.02% Take the above composition in a flask and react at 100-110 ° C for 2-5 hours while blowing air, It ends when the acid value becomes 2 or less.

2. Melamine Acrylate Cymel # 300 (Hexamethylol Melamine) 130g HEMA 173g (4 molar equivalents) 85% Phosphoric acid 0.5 HQ 0.1 The above composition is demethanol ether exchanged at 80-85 ° C for 2-3 hours in a flask with a water separation tube. The state where the amount of methanol removal does not increase ends.

3. Alkyd acrylate THPA (Mw.152) 152g (1mol) DEG (Mw.106) 212g (2mol) Acrylic acid (Mw72) 144g (2mol) Toluene 800ml Phenothiazine 5% reflux Azeotropic dehydration esterification reaction for 8hr After neutralization and water washing, distill off toluene.

 In using the compound of the present invention, a photopolymerization initiator may be added in order to accelerate the UV absorption rate and the curing rate. Examples of this include benzoin ether type, benzyl ketal type, α-hydroxyacetophenone type, chloroacetophenone type, α-aminoacetophenone type, acylphosphine oxide type, α-dicarbonyl type, α-acyl oxime ester. Etc.

 The radiation used includes ultraviolet rays, electron beams, X-rays, γ rays, etc., but ultraviolet rays and electron beams are preferable.

 Curing by ultraviolet irradiation is performed by irradiating ultraviolet rays having a wavelength of about 2000 to 4000 Å. A mercury lamp with an output of about 50 to 100 W / cm is suitable for the ultraviolet ray generator.

 The electron beam irradiation is carried out using an electron beam accelerator having an accelerating voltage of 100 to 750 KV, preferably 150 to 300 KV, so that the absorbed dose becomes 2 to 20 Mrad.

 There is no significant difference in the formulation between the use of ultraviolet rays and the use of electron beams when using ultraviolet rays, except that a photopolymerization initiator may be required.

 It is desirable that the UCL in the present invention has a thin film thickness of 2 μm or less in order to sufficiently exhibit the blocking performance, and to favorably maintain the photoreceptor performance such as suppression of residual potential. More preferably, it is 0.2 to 1.0 μm.

 The photoconductor of the present invention has, for example, the structure shown in FIG.

 In this photoconductor, the CGL 6 is provided on the conductive support (base) 1 via the UCL 7 described above, and the CTL 4 is provided on the CGL 6. 8 indicates PCL. Therefore, since the UCL 7 is provided between the CGL 6 and the support 1, the non-uniform injection of holes from the support side shown in FIG. Electrons, which are photocarriers, can be efficiently transported.

 In addition to the above-described structure (that is, CTL is laminated on CGL), the photoconductor of the present invention is a mixture of a carrier-generating substance (CGM) and a carrier-transporting substance (CTM) as shown in FIG. It may consist of a single layer of PCL8.

 Further, as shown in FIG. 4, the layer structure (for positive charging) in which the CGL 6 and the CTL 4 are turned upside down may be used.

 Further, in the photoreceptor of the present invention, a protective layer (protective layer; OCL) may be formed on the surface of the photoreceptor for improving printing durability and the like, for example, a synthetic resin film may be coated.

 Next, CGM used in the photoreceptor of the present invention is represented by a general formula.

1. Polycyclic quinone pigment (1) Antoanthrone pigment General formula [G1]: (2) Dibenzprenequinone pigment General formula [G2]: (3) Plantron pigment General formula [G3]: In the above, X: a halogen atom, a nitro group, a cyano group, an acyl group, or a carboxyl group.

 n = 0 to 4 m = 0 to 6 2. Azurenium Compound The azurenium compound is, for example, a compound described in the following publication.

 (A) JP-A-61-1547 (b) same 61-1548 (c) same 61-15147 (d) same 61-15150 (e) same 61-15151 Specific examples of azurenium compounds include, for example: There are things.

General formula [G4]: However, in said general formula, R < ¹¹ >, R < ¹² >, R <^13> , R <^14> , R < ¹⁵ >, R <^16> , R is shown.
¹⁷ : represents a hydrogen atom, a halogen atom, or an organic residue. Also, substituted with any one of the combinations of R ¹¹ and R ¹² , R ¹² and R ¹³ , R ¹³ and R ¹⁴ , R ¹⁴ and R ¹⁵ , R ¹⁵ and R ¹⁶ , and R ¹⁶ and R ^17. Alternatively, it may form an unsubstituted fused ring.

Ar ¹ , Ar ² : represents an aryl group.

R ¹⁸ and R ^{19 represent a} substituted or unsubstituted group of the following three groups; an alkyl group, an aryl group and an aralkyl group. Further, R ¹⁸ and R ¹⁹ may form a ring together with the nitrogen atom.

L ^θ : represents an anion residue.

 Typical examples of such an azurenium salt include the following.

(1) 3. Cyanine Dyes Cyanine dyes are known, and examples thereof include compounds described in JP-A-58-1 18650, JP-A-58-224354, and JP-A-59-14606.

4. Phthalocyanine compound It is known that the phthalocyanine compound, which is one of the organic photoconductive materials, has a light-sensitive region expanded to a longer wavelength region than other compounds. Various crystalline forms of phthalocyanine compounds have been found in the process of converting α-type phthalocyanine compounds into crystalline stable β-type phthalocyanine compounds. Examples of these phthalocyanine compounds exhibiting photoconductivity include X-type metal-free phthalocyanine compounds described in JP-B-49-4338, τ described in JP-A-58-182639 and JP-A-60-19151. In addition to the τ ′, η, η ′ type metal-free phthalocyanine compounds, the phthalocyanine compounds described in JP-A-63-148269, various metal phthalocyanine compounds are exemplified.

For example, there is a tital phthalocyanine compound described in Japanese Patent Application No. 62-241938. In addition to these, phthalocyanine compounds particularly suitable for semiconductor lasers are exemplified.

General formula [G5]: 5. Azo Compound Examples of the disazo compound include those represented by the following general formula.

General formula [G6]: Cp-N = M-D-N = N-Cp However, as D, Etc.

 Other azo compounds include those represented by the following general formulas.

General formula [G7]: Formula ^{[G8]: Cp-N = N-Ar} 3 -N = N-Ar 4 -N = N-C
p general formula ^{[G9]: Cp-N = N-Ar} 3 -N = N-Ar 4 -N = N-A
r ⁵ -N = N-Cp where Ar ³ , Ar ⁴ , and Ar ⁵ are each a substituted or unsubstituted group of the following two types; a carbocyclic aromatic ring group, and a heterocyclic aromatic ring Represents a group.

Furthermore, exemplifying specific examples of Ar ³ , Ar ⁴ , and Ar ⁵ are: The Cp (coupler) is, for example, as follows.

However, as A, In CGL, the content ratio of CGM to the binder substance is preferably 5/1 to 1/10, and more preferably 3/1 to 1/3.

 If the CGM content ratio is larger than the above range, black spots and the like are likely to appear. However, if the ratio of CGM is too small, the photosensitivity and the like will rather deteriorate.

 The film thickness of CGL is preferably 0.1 to 10 μm or more, more preferably 0.2 to 5 μm. The thickness of the CTL is preferably 10 μm or more.

 The thickness of the entire photosensitive layer is preferably in the range of 10 to 40 μm, more preferably 15 to 30 μm. If the film thickness is smaller than the above range, the film thickness is thin and the charging potential becomes small, so that the printing durability tends to be deteriorated. On the other hand, when the film thickness is larger than the above range, the residual potential is rather increased, and moreover, as in the case where the above-mentioned CGL is too thick, it is caught in the trap site during carrier movement and it becomes difficult to obtain sufficient transport ability. There is a tendency that the residual potential is likely to rise during repeated use.

 It is also possible to include CTM in CGL.

 In the case of forming PCL by dispersing granular CGM, the CGM is preferably a powder having an average particle diameter of 2 μm or less, preferably 1 μm or less, more preferably 0.5 μm or less.

 Further, in the carrier transport layer, the carrier transport material preferably has excellent compatibility with the binder substance.

 As a result, turbidity and opacity do not occur even if the amount of the binder material is increased, so that the mixing ratio with the binder material can be made extremely wide, and the charge generation is excellent because of the excellent compatibility. It is possible to obtain a photoreceptor in which the green layer is uniform and stable, and as a result, the sensitivity and charge characteristics are improved, and a clear image can be formed with higher sensitivity.

 Further, when it is used especially in repetitive transfer type electrophotography, it is possible to obtain the effect that fatigue deterioration is less likely to occur.

 CTMs usable in the present invention include carbazole derivatives, oxazole derivatives, oxadiazole derivatives, thiazole derivatives, thiadiazole derivatives, triazole derivatives, imidazole derivatives, imidazolone derivatives, imidazolidine derivatives, bisimidazolidine derivatives, styryl compounds, hydrazos. Compounds, pyrazoline derivatives, oxazolone derivatives, benzothiazole derivatives, benzimidazole derivatives, quinazoline derivatives, benzofuran derivatives, acridine derivatives, phenazine derivatives, aminostilbene derivatives, triarylamine derivatives, phenylenediamine derivatives, stilbene derivatives, poly-N It may be one or more selected from -vinylcarbazole, poly-1-vinylpyrene, poly-9-vinylanthracene and the like.

 Specific examples of such carrier transporting substances are described in JP-B-63-50851.

 The general formula is given below.

 A styryl compound represented by the following general formula [T1] or [T2] can be used as a carrier-transporting substance.

General formula [T1]: However, in this general formula, R ²¹ and R ²² : two types of groups, substituted or unsubstituted, represent an alkyl group or an aryl group, and as the substituent, an alkyl group, an alkoxy group, a substituted amino group, a hydroxyl group, a halogen atom , An aryl group is used.

Ar ¹⁵ and Ar ¹⁶ represent a substituted or unsubstituted aryl group, and an alkyl group, an alkoxy group, a substituted amine group, a hydroxyl group, a halogen atom or an aryl group is used as a substituent.

R ²³ , R ²⁴ : Substituted or unsubstituted aryl group, represents a hydrogen atom, and as a substituent, an alkyl group, an alkoxy group, a substituted amino group, a hydroxyl group, a halogen atom, or an aryl group is used.

General formula [T2]: However, in this general formula, R ²⁵ : a substituted or unsubstituted aryl group, R ²⁶ : a hydrogen atom, a halogen atom, a substituted or unsubstituted three kinds of groups; an alkyl group, an alkoxy group, an amino group, and Hydroxyl group, R ²⁷ : two types of substituted or unsubstituted groups; an alkyl group and a heterocyclic group.

 As the CTM, a hydrazone compound represented by the following general formula [T3], [T4], [T4a], [T4b] or [T5] can also be used.

General formula [T3]: However, in this general formula, R ²⁸ and R ²⁹ are each a hydrogen atom or a halogen atom, R ³⁰ and R ³¹ are each a substituted or unsubstituted aryl group, and Ar ^{17 is a} substituted or unsubstituted aryl group.

General formula [T4]: However, in this general formula, R ^{32 represents a} substituted or unsubstituted group, a carbazolyl group, or a heterocyclic group, and R ³³ , R ^34, and R ^{35 are a} hydrogen atom, an alkyl group, an aryl group, a substituted or unsubstituted group. Two types of substituted groups; an aryl group and an aralkyl group.

General formula [T4a]: However, in this general formula, R ³⁶ : methyl group, ethyl group, 2-hydroxyethyl group or 2-chloroethyl group, R ³⁷ : methyl group, ethyl group, benzyl group or phenyl group, R ³⁸ : methyl group, ethyl group , Benzyl group or phenyl group.

General formula [T4b]: However, in this general formula, R ³⁹ is a substituted or unsubstituted naphthyl group; R ⁴⁰ is a substituted or unsubstituted aralkyl group, aralkyl group, or aryl group; R ⁴¹ is a hydrogen atom, an alkyl group, or an aryl group; R ⁴² and R ⁴³ represent the same or different groups consisting of a substituted or unsubstituted alkyl group, aralkyl group or aryl group.

General formula [T5]: However, in this general formula, R ⁴⁴ : two types of substituted or unsubstituted groups; aryl group, heterocyclic group, R ⁴⁵ : hydrogen atom, two types of substituted or unsubstituted groups; alkyl group, aryl group, Q : Hydrogen atom, halogen atom, alkyl group, substituted amino group, alkoxy group or cyano group, S: represents an integer of 0 or 1.

 Further, as the CTM, a piezoline compound represented by the following general formula [T6] can also be used.

General formula [T6]: However, in this general formula, 1: 0 or 1, R ⁴⁶ and R ⁴⁷ : a substituted or unsubstituted aryl group, R ⁴⁸ : a substituted or unsubstituted aryl group or a heterocyclic group, R ⁴⁹ and R ⁵⁰ : a hydrogen atom An alkyl group having 1 to 4 carbon atoms, or a substituted or non-substituted aryl group or aralkyl group (provided that R ⁴⁹ and R ⁵⁰ are not both hydrogen atoms, and 1 is 0). In this case, R ⁴⁹ is not a hydrogen atom.) Furthermore, the amine derivative represented by the following general formula [T7] can also be used as CTM.

General formula [T7]: However, in this general formula, Ar ¹⁸ and Ar ¹⁹ represent a substituted or unsubstituted phenyl group, and a halogen atom, an alkyl group, a nitro group or an alkoxy group is used as the substituent.

Ar ²⁰ : a substituted or unsubstituted phenyl group, a naphthyl group, an anthryl group, a fluorenyl group, or a heterocyclic group, and the substituent is an alkyl group, an alkoxy group, a halogen atom, a hydroxyl group, an aryloxy group, an aryl group. , An amino group, a nitro group, a piperidino group, a morpholino group, a naphthyl group, an anthryl group and a substituted amino group are used.

 However, an acyl group, an alkyl group, or an aryl group is used as the substituent of the substituted amino group.

 Further, the compound of the following general formula [T8] can also be used as CTM.

General formula [T8]: However, in this general formula, Ar ²¹ represents a substituted or unsubstituted arylene group, and R ⁵¹ , R ⁵² , R ^53, and R ⁵⁴ are three types of substituted or unsubstituted groups; an alkyl group, an aryl group, and an aralkyl. Represents a group.

 Further, the compound of the general formula [T9]: can also be used as CTM.

General formula [T9]: However, in this general formula, R ⁵⁵ , R ⁵⁶ , R ⁵⁷ and R
⁵⁸ is a hydrogen atom, a substituted or unsubstituted alkyl group, a cycloalkyl group, an alkenyl group, an aryl group, a benzyl group or an aralkyl group, and R ⁵⁹ and R ⁶⁰ are a hydrogen atom, a substituted or unsubstituted group, respectively. An alkyl group having 1 to 40 carbon atoms, a cycloalkyl group, an alkenyl group, a cycloalkenyl group, an aryl group or an aralkyl group (provided that R ⁵⁹ and R ⁶⁰ are combined to form a saturated group having 3 to 10 carbon atoms or It may form an unsaturated hydrocarbon ring.) R ⁶¹ , R ⁶² , R ⁶³ and R ⁶⁴ are each a hydrogen atom, a halogen atom, a hydroxyl group, a substituted or unsubstituted alkyl group, cyclo It is an alkyl group, an alkenyl group, an aryl group, an aralkyl group, an alkoxy group, an amino group, an alkylamino group or an arylamino group.

 An antioxidant can be contained in CTL and CGL.

 As a result, the effect of ozone generated by discharge can be suppressed, and the increase in residual potential and the decrease in charging potential during repeated use can be prevented.

 Examples of antioxidants include hindered phenols, hindered amines, paraphenylenediamines, aryl alkanes, hydoquinones, spirochromans, spiroindanones and their derivatives, organic sulfur compounds, and organic phosphorus compounds.

 Specific examples of these compounds include JP-A-63-44662, 63-14153, 63-50849, 63-18355, 63-58455, 63-71856, 63- 71855 and 66-146046.

 It is also possible to incorporate a polymer semiconductor in the photosensitive layer.

 Among these polymer organic semiconductors, poly-N-vinylcarbazole or its semiconductor has a great effect and is preferably used. Such a poly-N-vinylcarbazole derivative means that all or part of the carbazole ring in the repeating unit is substituted with various substituents, for example, an alkyl group, a nitro group, an amino group, a hydroxy group or a halogen atom. It is a thing.

 Also, at least one electron-accepting substance may be contained in the photosensitive layer for the purpose of improving sensitivity, reducing residual potential or reducing fatigue during repetitive use.

Examples of electron-accepting substances that can be used in the photoreceptor of the present invention include succinic anhydride, maleic anhydride, dibromomaleic anhydride, phthalic anhydride, tetrachlorophthalic anhydride, tetrabromophthalic anhydride, 3- Nitrophthalic anhydride, 4-Nitrophthalic anhydride, Pyromellitic anhydride, Mellitic anhydride, Tetracyanoethylene, Tetracyanoquinodimethane, o-Dinitrobenzene, m-Dinitrobenzene, 1,3,5-Trinitrobenzene, Paranitrobenzonitrile, picryl chloride, quinone chlorimide, chloranil, bulmannyl, 2-methylnaphthoquinone, dichlorodicyanoparabenzoquinone, anthraquinone, dinitroanthraquinone, trinitrofluorenone, 9-fluorenylidene- [dicyanomethylene malonodinitrile ], Pyrinitro-9-fluorenyl -[Dicyanomethyline malonodinitrile], picric acid, o-nitrobenzoic acid, p-nitrobenzoic acid, 3,5-dinitrobenzoic acid, pentafluorobenzoic acid, 5-nitrosalicylic acid, 3,5-dinitrosalicylic acid One or more of acids, phthalic acid, mellitic acid, and other compounds having a high electron affinity can be cited. Among these, fluorenone type, quinone type, and benzene derivatives having an electron-withdrawing substituent such as Cl, CN, and NO ₂ are particularly preferable.

 Further, a silicone oil or a fluorine-based surfactant may be present as a surface modifier. Further, an ammonium compound may be contained as a durability improver.

 Further, an ultraviolet absorber may be used.

 Preferred UV absorbers include nitrogen-containing compounds such as benzoic acid, stilbene compounds and their derivatives, triazole compounds, imidazole compounds, triazine compounds, coumarin compounds, oxadiazole compounds, thiazole compounds and their derivatives. ..

 Examples of the binder resin that can be used in the constituent layers of the photoconductor include polyethylene, polypropylene, acrylic resin, methacrylic resin, vinyl chloride resin, vinyl acetate resin, epoxy resin, polyurethane resin, polyester resin, alkyd resin, and polycarbonate. Resins, melamine resins, methacrylic resins, acrylic resins, polyvinylidene chloride, polystyrene, etc., addition polymerization resins, polyaddition resins, polycondensation resins and copolymer resins containing two or more of these repeating units, Insulating resins such as vinyl chloride-vinyl acetate copolymer resins, styrene-butadiene copolymer resins, vinylidene chloride-acrylonitryl copolymer resins, etc., and polymer organic semiconductors such as N-vinyl cambazole, modified silicones. Examples thereof include resins.

 The above binders can be used alone or as a mixture of two or more kinds.

As the binder for the protective layer provided as necessary, a transparent resin having a volume resistance of 10 ⁸ Ω · cm or more, preferably 10 ¹⁰ Ω · cm or more, more preferably 10 ¹³ Ω · cm or more is used.

 Further, the binder may be a resin which is hardened by heat. Examples of the resin which is hardened by heat include thermosetting acrylic resin, epoxy resin, urethane resin, urea resin, polyester resin, alkyd resin and melamine resin. , Or these copolymers or condensation resins, and all of the other thermosetting resins used for electrophotographic materials can be used.

 If necessary, the protective layer may contain less than 50 wt% of a thermoplastic resin for the purpose of improving workability and physical properties (preventing cracks, imparting flexibility, etc.). Examples of the thermoplastic resin include polypropylene, acrylic resin, methacrylic resin, vinyl chloride resin, epoxy resin, polycarbonate resin or copolymer resins thereof, polymer organic semiconductors such as poly-N-vinylcarbazole, and the like. All of the thermoplastic resins used in electrophotographic materials are used.

 The CGL can be provided by the following method.

(A) A method in which a binder and a solvent are added to CGM or the like and the solution is mixed and dissolved to be applied.

(B) A method in which CGM or the like is coated with a dispersion liquid obtained by forming fine particles in a dispersion medium with a ball mill, homomixer, sand mill, ultrasonic disperser, attritor, etc., adding a binder and mixing and dispersing.

 In these methods, if the particles are dispersed under the action of ultrasonic waves, uniform dispersion becomes possible.

 The CTL can be formed by coating and drying the above-mentioned CTM alone or dissolved and dispersed with the above-mentioned binder resin.

 In this case, when CTM is contained in CGL, the method of dissolving or dispersing CTM in the solution of (a) or the dispersion of (b) in advance, that is, the method of adding CTM to CTL is used. is there. In this case, the amount of CTM added is preferably in the range of 1 to 100 parts by weight with respect to 100 parts by weight of the binder.

 In addition, there is a method in which a solution containing CTM is applied onto CGL, and CGL is swollen or partially dissolved to diffuse CTM into CGL. When this method is adopted, it is not necessary to add CTM into CGL as described above, but it is also possible to carry out the above two methods at the same time.

 Solvents or dispersion media used for layer formation include butylamine, diethylamine, ethylenediamine, isopropanolamine, triethanolamine, triethylenediamine, N, N-dimethylformamide, acetone, methylethylketone, cyclohexanone, benzene, toluene, xyleamine. And chloroform, 1,2-dichloroethane, dichloromethane, tetrahydrofuran, dioxane, methanol, ethanol, isopropanol, ethyl acetate, butyl acetate, dimethyl sulfoxide and the like.

 The PCL, UCL, OCL and the like can be provided by, for example, blade coating, dip coating, spray coating, roll coating, spiral coating, or the like.

 The conductive support may be a metal plate, a metal drum, or a conductive polymer, a conductive compound such as indium oxide, or a conductive thin layer made of metal such as aluminum, palladium, or gold, and may be applied by vapor deposition, laminating, or the like. Therefore, the one provided on a substrate such as paper or plastic film is used.

 Next, FIG. 5 shows an example of a recording apparatus using the photoconductor of the present invention.

 FIG. 6 is a flow chart of the reversal development method in electrophotography.

 In the apparatus shown in FIG. 5, reference numeral 23 denotes the above-mentioned organic photoelectric substance PCL8 and UCL7, a drum-shaped image bearing member rotating in the direction of the arrow, 22 an image bearing member, and the surface of 23 is uniformly charged. A charger, 24 is an image exposure unit, and 15 is a developing unit.

 Reference numeral 20 is a pre-transfer exposure lamp that is provided as necessary to facilitate the transfer of an image having a toner image formed on the image carrier 23 to the recording body P, 21 is a transfer device, 19 is a separation corona discharge device, A fixing device 12 fixes the toner image transferred onto the recording medium P.

 13 is a static eliminator comprising one or a combination of a static eliminator lamp and a corona discharger for static eliminator, and 14 is a cleaning blade or a fur brush for removing the residual toner on the surface of the image carrier 23 after the image is transferred. Is a cleaning device.

 When the image exposure is performed by the semiconductor laser, when the drum-shaped image carrier 23 is used as in the recording device of FIG. 2, the image exposure 24 is preferably performed by the laser beam scanner.

 Further, in a recording device in which the image carrier can take a flat state like a belt, the image exposure can be flash exposure.

 The recording apparatus as described above can perform the method as shown in FIG.

 Fig. 6 shows that an electrostatic image is formed by the electrostatic image forming method in which the image exposed portion becomes an electrostatic image having a lower potential than the background portion, and after development is electrostatically charged to the same polarity as the background portion potential. An example of reversal development performed by toner adhesion is shown.

 That is, first, the surface of the image carrier 23 in the initial state in which the electric charge is removed by the charge remover 13 and cleaned by the cleaning device 14 and the potential is 0 is uniformly charged by the charger 22. Image exposure 24 is projected onto the charged surface to perform image exposure so that the potential of the electrostatic image portion becomes substantially 0, and the obtained electrostatic image is developed by the developing device 15 (toner T).

 The image forming method can be applied to various light sources such as a halogen lamp, a tungsten lamp, an LED (light emitting diode), a gas laser such as helium-neon, argon, and helium-cadmium, and a semiconductor laser.

 The image forming method of the present invention has various uses such as an electrophotographic copying machine and a printer.

〔Example〕

 Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited thereto, and naturally includes various modified examples.

 First, as shown in Table 1, a total of four coating solutions of UCL No. UCL-1Z to 4Z were prepared, and each was filtered through a 0.6 μm filter to obtain a UCL coating solution.

An aluminum drum (for Konica LP-3010 laser printer) was dipped in these UCL coating solutions and the pulling rate was adjusted to 4 mg / dm ² to form UCL.

 UCL-1Z is a rosin-modified phenolic resin and is a blank.

For UCL-2Z and UCL-3Z, after dipping, slowly rotate the drum and irradiate ultraviolet rays for 60 seconds to a concentrating medium-pressure mercury lamp with an output of 80W / W / cm from a distance of about 50cm for a coating amount of 4mg. UCL was formed to be / dm ² .

For UCL-4Z, after dip coating, using an electron beam accelerator of ESI (curtain type method) with an accelerating voltage of 300 KV and a beam current of 10 to 15 mA while rotating the drum, the absorbed dose is within the range of 3 to 10 Mrad. It was irradiated with rays to form UCL so as to have a dose of 4 mg / dm ² .

 Each of these UCL-coated drums was coated with two drums, one was subjected to the following CGL multilayer coating, and the other was subjected to an adhesiveness test (cross-cut test) and a solvent resistance test described later.

Next, 40 g of each CGM shown in Table 2 was added to 40 g of each binder and 200 ml of each solvent in the polymer solution and dispersed for 12 hours with a sand grinder to prepare a CGL dispersion liquid.

A cylinder having the above UCL was immersed in this dispersion liquid, and the coating speed was adjusted so that the amount of CGL was 5 mg / dm ² .

Further, 200 g of CTM shown in Table 3 and 450 g of the resin shown in Table 3 were dissolved in 1500 ml of 1,2-dichloroethane, and each of the drums coated with the CGL was dipped in the obtained solution to obtain a film thickness of 200 μm. The coating speed was adjusted so as to obtain the above coating, and the coating was dried at 100 ° C. for 1 hour to form CTL, thereby preparing a laminated photoreceptor.

 The final laminated form of the photoreceptor is shown in Table 4 and also described below.

The electrophotographic characteristics and physical properties measured by the measuring method are also shown.

[Characteristic evaluation]

Mounted on the respective color of each of the photosensitive materials of Examples and Comparative Examples, "LP -3 010" (manufactured by Konica Corp.) remodeled machine (the semiconductor laser beam source mounted), grid so V _M becomes -600 ± 10 V! The voltage was adjusted, the potential on the exposed surface at the time of irradiation of 0.7 mW was set to _VL, and reversal development was performed at a developing bias of -500 [V], and black spots on the white background portion of the image were evaluated.

In addition, performs a 5000 times of print, _V M after the 5000 time of print, the _{V L} was set to ^{_{V M 5000, V L ■ 5000}} .

Then, the displacement amounts of V _M and V _L from the initial stage were set to ΔV _M ⁵⁰⁰⁰ and ΔV _L ⁵⁰⁰⁰ , respectively.

Therefore, ΔV _M ⁵⁰⁰⁰ = (V _M ⁵⁰⁰⁰ +600, ΔV
_L ⁵⁰⁰⁰ = (V _L ⁵⁰⁰⁰ −V _L ).

The black spots (black spots) were evaluated by measuring the particle size and number of the black spots using the image analysis device "Omnicon 3000" (manufactured by Shimadzu Corp.), and measuring the black (φ) of 0.05 mm or more. Judgment was made based on how many spots per 1 cm ² . The criteria for black dot evaluation are as shown in the table below.

It should be noted that if the result of the black spot determination is ⊚ or ◯, it is practical, but Δ is not suitable for practical use, and if it is ×, it is not suitable for practical use.

 Further, in order to check the solvent resistance of UCL, after coating and drying UCL, it was immersed in methyl ethyl ketone for 30 seconds and then observed with an electron microscope (SEM). The one in which the UCL on the immersion surface remains homogeneous is indicated by ⊚, and the one in which the UCL is inhomogeneous or dissolved or peeled is indicated by Δ or ×.

 The adhesiveness between UCL and PCL was evaluated by a substrate test. That is, using a cutter guide with a gap of 1 mm between adjacent gaps, the cutter scratches 11 conductive lines in parallel vertically and horizontally to form 100 squares (base). Stick a cellophane tape with a width of 24 mm on it and peel it off from one end. The number of squares peeled off at that time was counted, and the number of squares remaining in 100 was displayed.

 As a measure of adhesiveness, 100/100 is regarded as good adhesiveness, and 0/100 is regarded as poor.

 According to the results shown in Table 4, when the resin according to the present invention is used, it is possible to obtain a good image having no charging effect and sensitivity, a good image without black spots, and a good adhesive property when repeatedly used. You can see that it can be provided.

 On the other hand, when the binder resin for comparison was used, after coating the CGL solution, a part of UCL was dissolved, resulting in poor multi-layer coating property and many black spots.

 Next, each photosensitive member similar to that of the above-described example was prepared by a drum size for DC-8010 (manufactured by Konica). An image was formed on each of these photoconductors using DC-8010 under the following developing conditions, and no matter what photoconductor was used under each developing condition, a good image without black spots was obtained. Was obtained.

The development was so-called two-component non-contact jumping development.

Development conditions 70 wt% of magnetite powder having an average particle size of 0.1 μm and 30 wt% of polyester resin as a binder resin were mixed, kneaded, crushed and granulated, and then classified to a particle size of 20 to 30 μm to obtain a carrier. The specific gravity of this carrier was about 3.5 or less. U-Bix1800 (Konika Co.) copier toner (toner containing carbon in polyester resin) was mixed with this carrier to a toner concentration of 20 wt%, and copying was performed under the following conditions. It was

 The peripheral speed of the image bearing member was 60 mm / sec, the gap between the image bearing member and the developing sleeve was 0.3 mm, the developer layer thickness was 0.05 mm, the developing sleeve diameter was 24 mm, and the rotation speed was 200 rpm.

 The developing bias and the like were set under the following three conditions.

[Brief description of drawings]

 FIGS. 1 to 7 are for explaining the embodiment, and FIGS. 1 (A) and 1 (B) each schematically show the movement of the carrier by using the hand model. Schematic views, FIG. 2, FIG. 3, and FIG. 4 are sectional views of a part of each photoconductor used in the present invention, FIG. 5 is a schematic view of an image forming apparatus, and FIG. 6 shows an image forming process. A flow chart, FIG. 7 is a partial cross-sectional view showing a conventional photoconductor. FIG. 8 is an enlarged sectional view showing a part of another conventional photoconductor. In the drawings, reference numerals 1 ... Conductive substrate 4 ... Carrier transport layer (CTL) 6 ... Carrier generation layer (CGL) 7 ... Undercoat layer (UCL) 8 ... Photosensitivity Layer (PCL).

Claims (2)

[Claims] 1. A photoreceptor having a conductive support and at least an undercoat layer and a photosensitive layer provided thereon, wherein the undercoat layer is an acrylic double bond of a radiation-sensitive unsaturated double bond, allyl. A photoconductor characterized by being formed from a polymer comprising a radiation curable resin having at least one of a double bond and a maleic double bond and / or a prepolymer thereof or an oligomer. 2. The main skeleton portion of the polymer is selected from polyvinyl alcohol-based, ketal resin-based, cellulose-based resin, pullulan-based resin, alkyd resin, polycaprolact-based resin, spirane-based resin, and condensation-polymer resin. The photoconductor according to claim 1, which has a structure.