JPH1115178A - Image forming method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an image forming method by which a stable copying image having high image quality for a long period is obtainable. SOLUTION: This image forming method uses at least a brush roller in a stage for removing the toners remaining on an org. photoreceptor provided with a photosensitive layer contg. at least oxytitanyl phthalocyanine on a conductive base after transferring the toner image formed on the photoreceptor to a recording material. The ten point average surface roughness Rz of the conductive base described above is 0.4 to 2.5 μm and the oxytitanyl phthalocyanine has the max. peak at 27.2 deg.±0.2 deg. of a Bragg angle 20 for the Cu-Kα line.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an image forming method used for a copying machine, a printer, light printing, and the like.

[0002]

2. Description of the Related Art Conventionally, in an electrophotographic copying machine of the Carlson method, after a photosensitive member is uniformly charged, an electric charge is erased imagewise by exposure to form an electrostatic latent image, and the electrostatic latent image is formed. The image is developed and visualized with toner, and then the toner image is transferred and fixed to a recording material such as paper to form an image.

On the other hand, not all of the toner on the photosensitive member is transferred, and some of the toner remains on the photosensitive member. When an image is repeatedly formed in this state, the latent image formation is disturbed by the influence of the residual toner, so that a high-quality copy without contamination cannot be obtained. Therefore, it is necessary to remove the residual toner. The cleaning means is typically a fur brush, a magnetic brush, a blade, or the like, but a blade is mainly used in terms of performance, configuration, and the like. At this time, a plate-shaped rubber elastic body is generally used as the blade member.

The electrophotographic photoreceptor used in the above situation has good electrophotographic properties such as good charging characteristics and sensitivity and low dark decay, as well as printing durability and abrasion resistance in repeated use. It is also required to have good physical properties such as resistance and scratch resistance, and good resistance to ozone, NOx generated during corona discharge, ultraviolet rays during exposure, and the like.

Conventionally, selenium,
Inorganic photoreceptors containing an inorganic photoconductive substance such as zinc oxide and cadmium sulfide as a main component of a photosensitive layer have been widely used. However, these inorganic photoreceptors are harmful to the human body, and thus pose a problem in their disposability.

In recent years, organic photoreceptors using non-polluting organic substances have been actively developed and put to practical use. Above all, charge generation function and charge transport function are shared by different substances,
The development of a function-separated type photoreceptor capable of selecting a substance exhibiting each function from a wide range in view of desired characteristics has been actively developed, and there is a trend to commercialize an organic photoreceptor having high sensitivity and durability.

In recent years, printers and digital copiers using semiconductor lasers as exposure light sources have become widespread in place of analog exposure copiers such as halogen lamps. However, when such a coherent light is used as a light source in the conventional analog exposure, the light reflected from the substrate (conductive support) and the light reflected from the surface of the film or the interface of the film laminated for separating functions are used. So-called interference fringes due to interference appear in the image. As means for preventing this, means for increasing the surface roughness of the conductive support and scattering laser light is employed.

[0008] However, when a coating film is formed on a conductive support having such a large surface roughness, the surface of the photosensitive layer also loses its smoothness. As a result, when the toner remaining after the transfer is to be cleaned only with the elastic rubber blade, toner external additives such as silica and paper powder such as talc enter the recesses on the surface, so that the blade slips through the blade. Occurs. Such poor cleaning is unlikely to cause a problem on an image in a normal use environment, but is particularly problematic in a high-temperature and high-humidity environment such as a character flow and an image blurring.

On the other hand, an undercoat layer is often provided between the conductive support and the photosensitive layer for the purpose of preventing image defects due to charge injection from the conductive support and improving the charging performance of the photosensitive body. In particular, in the reversal development process often used in digital machines, image defects such as minute black spots (black spots in a solid black image in the case of regular development) or transfer memories often appear on a white image. In order to prevent these problems, an undercoat layer having more excellent performance is desired. Conventionally, polyamide, polyester, polyurethane and the like have been often used as the undercoat layer. However, as a means for solving the above-mentioned problem, an organic metal based undercoat that forms a cured film by combining a metal chelate compound and a silane coupling agent is used. Coating layers have been used.

[0010] The undercoat layer of such a cured film is characterized in that it is hardly eroded by a solvent when a layer having another function is applied thereon, and the film interface is maintained well. . This feature is very advantageous from the viewpoint of electrophotographic performance because there is no disturbance of the interface between the functional layers. However, on the other hand, since there is no disturbance at the interface, the irregularities of the substrate are reflected as it is to the upper layer, and irregularities also appear on the outermost surface of the photoconductor,
Smoothness is impaired.

As described above, when a coating film is formed on a conductive support having a large surface roughness by using a cured organometallic film as an undercoat layer, the surface of the photosensitive layer also has a smooth surface. Is impaired. As a result, when an attempt is made to clean the toner remaining after the transfer using only the elastic rubber blade, a toner external additive such as silica or paper powder such as talc enters the recesses on the surface, and the blade tends to slip through, resulting in poor cleaning. Becomes stronger.

In order to solve these problems, means for forcibly shaving the photosensitive layer and always exposing a clean surface of the photosensitive member has been adopted. Means for shaving the photoreceptor include increasing the abrasion speed by increasing the contact load of the blade, and bringing a urethane roller with an abrasive added into contact with the photoreceptor. However, when the amount of wear is increased in this way, although the image failure due to poor cleaning is improved, the sensitivity and the charging potential are reduced due to the wear, and the life is shortened as compared with the inorganic photoreceptor. It is the main cause of inhibition.

[0013]

SUMMARY OF THE INVENTION An object of the present invention is to provide an image forming method capable of obtaining a high-quality and stable copy image for a long period of time.

[0014]

The above object of the present invention has been attained by the following constitutions.

(1) After transferring a toner image formed on an organic photoreceptor having a photosensitive layer containing at least oxytitanyl phthalocyanine on a conductive support to a recording material,
The image forming method using at least a brush roller in the step of removing the toner remaining on the photoconductor, wherein the ten-point average surface roughness Rz of the conductive support is 0.4 μm or more and 2.5 μm or less and the oxy 27. titanyl phthalocyanine having a Bragg angle of 2θ with respect to Cu-Kα ray;
An image forming method having a maximum peak at 2 ° ± 0.2 °.

(2) A toner image formed on an organic photoreceptor obtained by laminating an undercoat layer and a photosensitive layer containing at least oxytitanyl phthalocyanine on a conductive support is transferred to a recording material, and then transferred to a recording material. In an image forming method using at least a brush roller in a step of removing toner remaining on the conductive support, the ten-point average surface roughness Rz of the conductive support is 0.4 μm.
m or more and 2.5 μm or less, and the undercoat layer is an organometallic resin comprising at least one reaction product selected from a metal alkoxide, an organometallic chelate and a silane coupling agent, and the oxytitanyl 27. Phthalocyanine has a Bragg angle of 2θ with respect to Cu-Kα ray.
An image forming method having a maximum peak at 2 ° ± 0.2 °.

(3) The oxytitanyl phthalocyanine has a Bragg angle 2θ of 27.2 ゜ ± with respect to Cu-Kα radiation.
The maximum peak at 0.2 ° and 9.5 ± 0.2 ° or 9.
The image forming method according to (1) or (2), which has a peak at 0 ° ± 0.5 °.

(4) The single fiber thickness of the brush of the brush roller is 6 denier to 30 denier, and the fiber density is 4.5 × 10 ² f / cm ² (number of filaments per square centimeter). The image forming method according to (1) or (2), wherein the density is 5 × 10 ² f / cm ² or less.

The material of the conductive support used in the present invention is mainly aluminum, copper, brass, steel,
A belt-shaped or drum-shaped metal material such as stainless steel or another plastic material is used. Above all, aluminum excellent in cost, workability and the like is preferably used, and a thin-walled cylindrical aluminum tube which is usually formed by extrusion or drawing is used.

The surface of the conductive support used in the present invention has a ten-point average surface roughness Rz of 0.4 μm or more.
One having a size of 5 μm or less is used. More preferably 0.6 μm
It is 1.5 μm or less. The outline of the method of calculating the ten-point average roughness Rz is shown in FIG. Rz is the difference between the average height of five peaks and the average height of five valleys between lengths L (250 μm in the present invention).

The ten-point average roughness Rz was measured by an optical stylus type surface roughness measuring device Sircom 470A (Tokyo Seimitsu Co., Ltd.) incorporating an optical stylus type pickup E-DT-SL024.

If the ten-point average surface roughness Rz is less than 0.4 μm, the moiré prevention effect is insufficient and is not practical. When Rz exceeds 2.5 μm, there is a problem that a processed streak appears in an image.

As a method for roughening the surface of the conductive support, in the case of a metal tube made of aluminum or the like, a metal surface is mirror-polished and then finely grooved with a diamond bite or the like, or the metal tube is sandblasted. A method of roughening the surface is preferable, but the present invention is not limited to these methods.

The structure of the photoreceptor used in the present invention is as follows.

As the charge generation material (CGM), oxytitanyl phthalocyanine (TiOPc) is used. When an oxytitanyl phthalocyanine having a maximum peak at a Bragg angle 2θ of 27.2 ° ± 0.2 ° with respect to Cu-Kα radiation is used in the electrophotographic photoreceptor of the present invention, sensitivity, durability and image quality are remarkably improved. The effect is shown.

The basic structure of TiOPc is represented by the following general formula.

[0027]

Embedded image

In the formula, X ¹ , X ² , X ³ and X ⁴ each represent a hydrogen atom, a halogen atom, an alkyl group or an alkoxy group, and n, m, l and k each represent an integer of 0-4.

Among them, those in which X ¹ , X ² , X ³ and X ⁴ are all hydrogen atoms are preferred.

The crystal form of TiOPc is A,
There are many types such as B and Y types, and the crystal type of the present invention has an X-ray diffraction spectrum (Bragg angle 2θ) of 9.
5 ± 0.2 ° or 9.0 ± 0.2 ° and 27.2 ±
Those having a peak at 0.2 ° are particularly preferred.

The charge transport material (CTM) according to the present invention is not particularly limited, but includes, for example, oxazole derivatives, oxadiazole derivatives, thiazole derivatives, thiadiazole derivatives, triazole derivatives, imidazole derivatives, imidazolone derivatives, imidazolidine derivatives,
Bisimidazolidine derivatives, styryl compounds, hydrazone compounds, pyrazoline derivatives, amine derivatives, oxazolone derivatives, benzothiazole derivatives, benzimidazole derivatives, quinazoline derivatives, benzofuran derivatives,
Acridine derivative, phenazine derivative, aminostilbene derivative, poly-N-vinylcarbazole, poly-1-
Vinylpyrene and poly-9-vinylanthracene.

Further, as the charge transporting substance, those which are excellent in the ability to transport holes generated upon light irradiation and which are suitable for combination with oxytitanyl phthalocyanine are preferable.

Since the charge generating substance and the charge transporting substance by themselves have poor film-forming ability, the photosensitive layer may be formed using various binders.

Although any binder resin can be used for forming the photosensitive layer, it is preferable to use a film-forming polymer which is hydrophobic, has a high dielectric constant, and is electrically insulating. . Examples of such a polymer include polycarbonate, polyester, methacrylic acid resin, acrylic resin, polyvinyl chloride, polyvinylidene chloride, polystyrene, polyvinyl acetate, styrene-butadiene copolymer, vinylidene chloride-acrylonitrile copolymer, Vinyl chloride-vinyl acetate copolymer, vinyl chloride-vinyl acetate-maleic anhydride copolymer, silicone resin, silicone-alkyd resin, phenol formaldehyde resin, styrene-alkyd resin, poly-N-vinylcarbazole, polyvinyl acetal (for example, Polyvinyl butyral) and the like. These binder resins can be used alone or as a mixture of two or more.

An antioxidant can be added to the photosensitive layer for the purpose of preventing ozone deterioration. As antioxidants,
Hindered phenol, hindered amine, paraphenylenediamine, arylalkane, hydroquinone, spirochroman, spiroidanone and derivatives thereof,
Organic sulfur compounds, organic phosphorus compounds and the like can be mentioned.

[0036] These specific compounds are disclosed in
Nos. 3-14154, 63-18355, 63-4
No. 4662, No. 63-50848, No. 63-5084
9, No. 63-58455, No. 63-71856,
Nos. 63-71857 and 63-146046.

The amount of the antioxidant to be added is 0.1 to 100 parts by weight, preferably 1 to 50 parts by weight, particularly preferably 5 to 25 parts by weight, per 100 parts by weight of CTM.

Solvents or dispersion media used for forming the charge generation layer and the charge transport layer include butylamine, diethylamine, ethylenediamine, isopropanolamine, triethanolamine, triethylenediamine, and the like.
N, N-dimethylformamide, acetone, methyl ethyl ketone, cyclohexanone, benzene, toluene, xylene, chloroform, 1,2-dichloroethane, 1,
2-dichloropropane, 1,1,2-trichloroethane, 1,1,1-trichloroethane, trichloroethylene, tetrachloroethane, dichloromethane, tetrahydrofuran, dioxane, methanol, ethanol, isopropanol, ethyl acetate, butyl acetate, dimethyl Sulfoxide, methylcellosolve and the like.

The organic photoreceptor is provided on a support with a charge generation layer (C
GL), a charge transport layer (CTL), and if necessary,
Auxiliary layers such as a protective layer and an undercoat layer may be laminated.

The undercoat layer functions as an adhesive layer or a blocking layer. Conventionally, in addition to the binder resin, for example, polyvinyl alcohol, ethyl cellulose,
Carboxymethylcellulose, casein, copolymerized nylon, N-alkoxymethylated nylon, starch and the like were often used.

The undercoat layer (UCL) used in claim 2 of the present invention comprises an organic metal chelate of a metal alkoxide represented by the following general formula (1) (hereinafter sometimes referred to as an organometallic compound) and the following general formula ( It is formed from those containing the silane coupling agent represented by 2).

In the formula (1), R represents an alkyl group, M represents titanium, zirconium or aluminum;
X represents a chelating group and represents an acetoacetic acid ester or a β-diketone residue, and m and n each represent an integer of 1 or more. Where M
Is m + n is 4 when is titanium or zirconium, and m + n is 3 when M is aluminum.

In the formula (2), Z represents a hydrolyzable group representing an alkoxy group, a halogen atom or an amino group, A represents an alkyl group or an aryl group, and Y represents an organic functional group having a terminal methacryloxy or amino group. , That is, -BOOC
(R ′) represents C ＝ CH ₂ , —BNHR ″ or —BNH _2. R ′ represents an alkyl group, R ″ represents an alkyl group or an aryl group, and B represents an alkylene group or —O—, —NH.
-Represents an alkylene group containing -CO-. a and c are 1
B represents an integer of 0 or more and a + b + c
Is 4.

The general formula _{(1) (RO) m MX} n Formula _{(2) Z a A b Si} Y c curable undercoat layer according to the present invention, as described above, the organometallic compound and the silane coupling agent Those consisting of reaction products are considered to be preferred. Most preferably, the reaction product is a 100% reaction product. For example, a case where the reaction product contains a raw material and other components is also preferably employed in the present invention.

First, the organometallic compound, which is one of the raw materials for the curable undercoat layer, is preferably composed of a compound having an alkoxy group and at least one chelating group. When a photoreceptor is formed using a metal alkoxide consisting of only an alkoxy group such as tetraalkoxytitanium, image defects such as white spots (or black spots) may occur. Therefore, it was found that it is more preferable to have at least one chelating group. The following are known chelating groups (see JP-A-4-247461).

(1) β-diketone such as acetylacetone, 2,4-heptanedione, etc. (2) Ketoester such as methyl acetoacetate, ethyl acetoacetate, propyl acetoacetate, butyl acetoacetate, etc. (3) Lactic acid, salicylic acid, malic acid, etc. (4) Hydroxycarboxylic acid esters such as methyl lactate, ethyl lactate, ethyl salicylate and ethyl malate (5) Glycols such as octanediol and hexanediol (6) 4-hydroxy-4-methyl-2-pentanone (7) Amino alcohol such as triethanolamine As a result of various studies by the present inventors on these, (3)
Β-diketone of (1) and acetoacetate of (2) as compared with (7), the potential characteristics, film formability, adhesion to photosensitive layer, image characteristics, pot life of coating solution, It was found that all the characteristics satisfied better characteristics.

The study also revealed that the number of chelating groups in the organometallic compound has an appropriate range. When the organometallic compound does not have an alkoxy group but has only a chelate group, the residual potential is relatively large, so it is preferable that the organometallic compound contains at least an alkoxy group.If possible, the number of chelate groups in the compound is the same as the number of alkoxy groups. It is particularly preferred that they are the same or less. By doing so, the residual potential can be suppressed particularly low.

Next, zirconium, titanium and aluminum are particularly preferred as the kind of metal of the organometallic compound. For other metals, the versatility is low and the establishment of a manufacturing method as a compound is insufficient, the cost is high, the potential characteristics, the image characteristics are insufficient,
In some cases, there may be problems in practical use as compared with those of the present invention.

Further, the above-mentioned zirconium, titanium,
Among aluminum, titanium and aluminum are also excellent in the stability of the coating solution, and can be said to be particularly preferable in this regard.

Among the particularly preferred organometallic compounds used in the present invention, titanium chelate compounds having an acetoacetate ester chelate group include diisopropoxytitanium bis (methylacetoacetate) diisopropoxytitanium bis (ethylacetoacetate) ) Diisopropoxytitanium bis (propylacetoacetate) diisopropoxytitanium bis (butylacetoacetate) dibutoxytitanium bis (methylacetoacetate) dibutoxytitanium bis (ethylacetoacetate) triisopropoxytitanium (methylacetoacetate) triiso Propoxy titanium (ethyl acetoacetate) Tributoxy titanium (methyl acetoacetate) Tributoxy titanium (ethyl acetoacetate) Isopropoxytitanium tri (methylacetoacetate) isopropoxytitanium tri (ethylacetoacetate) isobutoxytitanium tri (methylacetoacetate) isobutoxytitanium tri (ethylacetoacetate) As a titanium chelate compound having a β-diketone chelating group Is diisopropoxytitanium bis (acetylacetonate) diisopropoxytitanium bis (2,4-heptanedionate) dibutoxytitanium bis (acetylacetonate) dibutoxytitanium bis (2,4-heptanedionate) triiso Propoxy titanium (acetylacetonate) Triisopropoxy titanium (2,4-heptanedionate) Tributoxy titanium (acetylacetonate) Titanium (2,4-heptanedionate) isopropoxytitanium tri (acetylacetonate) isopropoxytitanium tri (2,4-heptanedionate) isobutoxytitanium tri (acetylacetonate) isobutoxytitanium tri (2,4- Heptane dionate) Aluminum chelate compounds having an acetoacetate ester chelate group include diisopropoxyaluminum (methylacetoacetate) diisopropoxyaluminum (ethylacetoacetate) diisopropoxyaluminum (propylacetoacetate) diisopropoxyaluminum (butyl) Acetoacetate) dibutoxyaluminum (methylacetoacetate) dibutoxyaluminum (ethylacetoacetate) isopropoxya Minium bis (methylacetoacetate) isopropoxyaluminum bis (ethylacetoacetate) isobutoxyaluminum bis (methylacetoacetate) isobutoxyaluminum bis (ethylacetoacetate) As an aluminum chelate compound having a β-diketone chelate group, diisopropoxyaluminum (Acetylacetonate) diisopropoxyaluminum (2,4-heptanedionate) dibutoxyaluminum (acetylacetonate) dibutoxyaluminum (2,4-heptanedionate) isopropoxyaluminum bis (acetylacetonate) isopropoxyaluminum Bis (2,4-heptanedionate) isobutoxyaluminum bis (acetylacetonate) isobutoxyaluminium Bis (2,4-heptanedionate) but the like but is not limited thereto.

The following zirconium-based compounds are preferred next to titanium and aluminum-based compounds.

First, zirconium chelate compounds having an acetoacetate ester chelate group include diisopropoxy zirconium bis (methyl acetoacetate) diisopropoxy zirconium bis (ethyl acetoacetate) diisopropoxy zirconium bis (propyl acetoacetate) diiso Propoxy zirconium bis (butyl acetoacetate) dibutoxy zirconium bis (methyl acetoacetate) dibutoxy zirconium bis (ethyl acetoacetate) triisopropoxy zirconium (methyl acetoacetate) triisopropoxy zirconium (ethyl acetoacetate) tributoxy zirconium (methyl acetoacetate) Acetate) Tributoxy zirconium (ethyl acetoacetate) Isopropoxy zircon Tri (methylacetoacetate) isopropoxyzirconium tri (ethylacetoacetate) isobutoxyzirconium tri (methylacetoacetate) isobutoxyzirconium tri (ethylacetoacetate) As a zirconium chelate compound having a β-diketone chelate group, diisopropoxyzirconium Bis (acetylacetonate) diisopropoxyzirconium bis (2,4-heptanedionate) dibutoxyzirconium bis (acetylacetonate) dibutoxyzirconium bis (2,4-heptanedionate) triisopropoxyzirconium (acetylacetonate ) Triisopropoxy zirconium (2,4-heptanedionate) Tributoxy zirconium (acetylacetonate) Tributy Zirconium (2,4-heptanedionate) isopropoxy zirconium tri (acetylacetonate) isopropoxy zirconium tri (2,4-heptanedionate) isobutoxy zirconium tri (acetylacetonate) isobutoxytitanium tri (2,4- Heptandionate) and the like, but are not limited thereto.

These compounds are mentioned as being able to achieve the object of the present invention at a particularly high level, and there are many other compounds which can also achieve the object of the present invention.

The silane coupling agent which is another essential element for forming the undercoat layer is represented by the formula (2).

Known documents, for example, Japanese Patent Application Laid-Open No. 4-247461
In the above, Z represents an alkoxy group such as a methoxy group, an ethoxy group, a propoxy group or a butoxy group, and A represents an alkyl group such as a methyl group, an ethyl group, a propyl group, or a butyl group, or an aryl group such as a phenyl group. The following are listed as the terminal groups of the organic functional group Y.

[0056]

Embedded image

As a result of the study by the present inventors, it has been found that, by selecting a terminal group of the organic functional group Y of the silane coupling agent having a methacryloxy group or an amino group, film forming properties, image characteristics and potential characteristics are rare. It was found that excellent performance was obtained.

The methacryloxy group is CH ₂ ＣC (R ')
It is represented by COO-, and R 'is an alkyl group. Preferably a C ₃ or less alkyl groups. Specific examples of these silane coupling agents having a methacryloxy group include the following.

Γ methyl methacryloxypropyl trimethoxy silane γ methyl methacryloxy propyl triethoxy silane γ ethyl methacryloxy propyl trimethoxy silane γ methyl methacryloxy propyl methyl dimethoxy silane γ methyl methacryloxy propyl methyl diethoxy silane However, the present invention is not limited to this.

With the silane coupling agent having a methacryloxy group, an undercoat layer having excellent film forming properties and image characteristics could be obtained. A notable silane coupling agent having a terminal methacryloxy group is the stability of the potential. Even under repeated use, an undercoat layer having very stable performance with little increase in residual potential could be obtained.

Among the silane coupling agents, those exhibiting excellent performance include those having a methacryloxy group at the terminal of the organic functional group Y or an amino group, ie, --NH ₂ or --NH
It has an R "structure. R" represents an alkyl group or an aryl group, preferably an alkyl group having a carbon number of ₆ or less or an aryl group having a carbon number of ₈ or less.

The silane coupling agent having an amino group at the terminal has a higher reactivity than other silane coupling agents not having the structure at the terminal, and is polymerized with a metal compound at the time of forming an undercoat layer film. It has been found by the present inventors that the network structure is easily progressed by the present invention. This high reactivity causes image defects, specifically white spots (or black spots).
It is presumed that this greatly contributed to the suppression of the silane coupling agent, and in this regard, superior performance was obtained as compared with many other silane coupling agents.

From the viewpoint of reactivity, the reactivity of primary or secondary amino groups is high, and particularly, the primary amino group —NH ₂ exhibits very high reactivity, and the ability to suppress image defects is high. Are better.

Specific examples of the organic functional group having a terminal of —NH ₂ include a γ-aminopropyl group, a β-aminoethyl group, and a γ-aminobutyl group. Examples of the ring agent include γ-aminopropyltrimethoxysilane γ-aminopropyltriethoxysilane γ-aminopropylmethyldimethoxysilane γ-aminopropylmethyldiethoxysilane β-aminoethyltrimethoxysilane γ-aminobutyltrimethoxysilane But are not limited to these.

The structure of the organic functional group is not particularly limited except for the terminal amino group. Other than those having only the alkylene group-(CH ₂ ) _n- as exemplified above,
_{- (CH 2) m -NH- (} CH 2) n -, - (CH 2) n -N
Those containing another type of structural unit such as an amino group, a carbonyl group or an oxygen atom such as H-CO- may be used. m and n are preferably integers of 10 or less.

Specific examples of such organic functional groups include N-β (aminoethyl) γ-aminopropyl group N-β (aminopropyl) γ-aminopropyl group N-β (aminoethyl) γ-amino Butyl group γ-ureidopropyl group and the like. Examples of the silane coupling agent having an organic functional group include N-β (aminoethyl) γ-aminopropyltrimethoxysilane N-β (aminoethyl) γ-aminopropyl Triethoxysilane N-β (aminoethyl) γ-aminopropylmethyldimethoxysilane N-β (aminoethyl) γ-aminopropylmethyldiethoxysilane N-β (aminopropyl) γ-aminopropyl metrimethoxysilane N-β ( Aminoethyl) γ-aminobutyltrimethoxysilane γ-ureidopropyltrimethoxysilane γ-U Examples include, but are not limited to, raidopropyltriethoxysilane.

However, when repeatedly mounted on an image forming apparatus having a high linear velocity and used repeatedly, the aliphatic hydrocarbon chain-(CH
₂ ) It was also found by the present inventors that the device composed only of _n − can provide excellent potential performance with a smaller sensitivity such as a rise in residual potential.

Examples of the aliphatic or aromatic hydrocarbon group to be introduced into the amino group include alkyl groups such as methyl group, ethyl group, propyl group and butyl group, and unsaturated aliphatic hydrocarbon groups such as vinyl group and allyl group. Examples of the residue include, but are not limited to, an aryl group such as a phenyl group, a tolyl group, a xylyl group, and a naphthyl group. Further, these may be substituted with any substituent.

Specific examples of the organic functional group having a secondary amino group at its terminal include N-methyl-γ-aminopropyl group N-ethyl-γ-aminopropyl group N-vinyl-γ-aminopropyl group Allyl-γ-aminopropyl group N-phenyl-γ-aminopropyl group N-tolyl-γ-aminopropyl group, etc. Examples of the silane coupling agent having this organic functional group include N-methyl-γ-aminopropyl Trimethoxysilane N-ethyl-γ-aminopropyltrimethoxysilane N-vinyl-γ-aminopropyltrimethoxysilane N-allyl-γ-aminopropyltrimethoxysilane N-phenyl-γ-aminopropyltrimethoxysilane N-tolyl -Γ-aminopropyltrimethoxysilane and the like, but are not limited thereto. There.

These compounds are intended to achieve the object of the present invention at a particularly high level, and many other compounds also achieve the object of the present invention.

In the present invention, the undercoat layer comprises at least one of the above-mentioned organometallic compound and silane coupling agent.
It is preferable to contain a species, and if necessary, a mixture of two or more species can be used, from among the above-mentioned species alone, or a species other than the above-mentioned species.

Further, if necessary, other compounds such as resins can be contained in necessary amounts.

The undercoat layer according to the present invention is obtained by forming a constituent material of the undercoat layer, that is, a solution obtained by dissolving an organometallic compound and a silane coupling agent in a solvent (the above-mentioned coating solution) on a conductive support. And dried and cured. Examples of the solvent include alcohols such as methanol, ethanol, propanol and butanol, aromatic hydrocarbons such as toluene, ethylene glycols and glycols such as propylene glycol, but are not limited thereto. Absent. These may be used alone or as a mixture. Further, water may be mixed as necessary.

As a method of applying the coating solution, a dip coating method, a spray coating method, a blade coating method, a spinner coating method, a bead coating method, a curtain coating method, or the like can be used.

The drying condition of the coating film is as follows.
The drying can be performed by air drying or still drying at 0 to 250 ° C, preferably 90 to 200 ° C, for a drying time of 5 minutes to 5 hours, preferably 20 minutes to 2 hours.

Next, the form of the organic photoreceptor is shown in FIGS.
An example is shown in (6).

As shown in FIGS. 2A and 2B, the organic photoreceptor includes a conductive support 21 on which CGL 22 containing CGM as a main component and CTL 23 containing CTM as a main component. Is provided.

As shown in FIGS. 3 (3) and 4 (4), in the invention of claim 2, the photosensitive layer 24 is made of the conductive support 2.
1 may be provided via an undercoating layer 25 provided on the substrate.

Thus, when the photosensitive layer 24 has a two-layer structure, an electrophotographic photosensitive member having excellent electrophotographic characteristics can be obtained.

Also, in the present invention, as shown in FIGS.
A photosensitive layer 24 in which fine-grained CGM 27 is dispersed may be provided directly on the conductive support 21 or via an undercoat layer 25.

Further, a protective layer may be provided on the photosensitive layer 24 if necessary.

Here, when the photosensitive layer 24 has a two-layer structure as shown in FIG. 2A, the CGL 22 can be formed by the following method.

(1) Vacuum evaporation method (2) Method of applying a solution in which CGM is dissolved in an appropriate solvent (3) CGM is made into fine particles in a dispersion medium by a ball mill, sand grinder, or the like, and if necessary, a binder is used. And applying a dispersion obtained by mixing and dispersing.

That is, vacuum deposition, sputtering, CVD
Or a coating method such as dipping, spraying, blade, or roll method.

The thickness of the CGL thus formed is preferably 0.01 to 5 μm, more preferably 0.05 to 3 μm.

The CTL 23 can be formed in the same manner as the CGL 22.

The composition ratio in this CTL is CTM1
The binder is preferably used in an amount of 0.1 to 5 parts by weight based on the weight of the photosensitive layer 24 in which fine particle CGM is dispersed.
Is preferably used in an amount of 5 parts by weight or less with respect to 1 part by weight of CGM.

The brush roller used in the present invention is shown in FIG.
As shown in (1), it is preferable that a fur brush is provided on the surface of a columnar support via an adhesive layer.

FIG. 3 is a schematic sectional view for explaining the cleaning step of the present invention.

As shown in FIG. 3, the brush used in the present invention preferably has a configuration in which a fur brush 17 is provided on the surface of a cylindrical support 16 via an adhesive layer.

Further, if necessary, a member (flicker) for knocking off the toner and foreign matters adhering to the brush roller 15 from the brush may be provided.

In the present invention, it is preferable that the elastic rubber blade is provided so as to have a free end on the support member in addition to the brush roller.

In FIG. 3, reference numeral 4 denotes a photosensitive drum, 15 denotes a brush roller, 13 denotes an elastic rubber blade, and 19 denotes a support member.

It is preferable that the free end of the elastic rubber blade is pressed against the opposite side (counter) of the photosensitive drum in the rotation direction.

The rubber hardness of the elastic rubber blade is JIS.
A 30-90 °, rebound resilience 30-70%, Young's modulus 30-60 kgf / cm ² , thickness 1.5-5.0
mm, free length is 7 to 12 mm, and pressing force on the photoreceptor is 18
g / cm or less is preferable.

As the constituent material of the brush according to the present invention, any material can be used, but it is preferable to use a fiber-forming polymer having hydrophobicity and a high dielectric constant.
Examples of such high-molecular polymers include rayon, nylon, polycarbonate, polyester, methacrylic resin, acrylic resin, polyvinyl chloride, polyvinylidene chloride, polypropylene, polystyrene, polyvinyl acetate, styrene-butadiene copolymer, and vinylidene chloride. -Acrylonitrile copolymer, vinyl chloride-vinyl acetate copolymer, vinyl chloride-vinyl acetate-maleic anhydride copolymer, silicone resin, silicone-alkyd resin, phenol formaldehyde resin, styrene-alkyd resin, polyvinyl acetal (for example, polyvinyl acetal) Butyral) and the like. These binder resins can be used alone or as a mixture of two or more. Particularly preferred are rayon, nylon, polyester, acrylic and polypropylene.

The brush may be conductive or insulative, and may be a material in which a constituent material contains a low-resistance substance such as carbon and the resistance is adjusted to an arbitrary value.

The single fiber thickness of the brush is 6 denier or more.
30 denier or less is preferable. It is preferable to use one in this range, since there is no sufficient rubbing force to remove surface deposits, or the fibers become rigid, so that the surface of the photoconductor is not damaged and the life of the photoconductor is shortened.

The term “denier” as used herein refers to a value obtained by measuring the weight of 9000 m of the fibers constituting the brush in g (gram) units.

The fiber density of the brush was 4.5 × 10 ² f /
cm ² or more and 15.5 × 10 ² f / cm ² or less. In this range, the abrasion becomes uneven and the attached matter cannot be uniformly removed, or the toner and foreign matter that have entered between the brush fibers cannot be completely removed, so that packing does not occur and the characteristics of the brush are not lost.

The support used in the brush of the present invention is mainly made of metal such as stainless steel or aluminum, paper, or the like.
Plastic or the like is used, but is not limited thereto.

The developer according to the present invention is not particularly limited, whether it is a one-component system containing only a toner as a main component or a two-component system using a toner and a carrier. Usually, a two-component system is used.

As the resin used for forming the toner, polyester-based or styrene-acrylic-based resins can be mainly used.

As the colorant used in the toner of the present invention, carbon black, magnetic substance, dye, pigment and the like can be arbitrarily used. As the carbon black, channel black, furnace black, acetylene black, thermal black lamp and the like can be used. Black or the like is used. As the magnetic material, ferromagnetic metals such as iron, nickel and cobalt, alloys containing these metals, compounds of ferromagnetic metals such as ferrite and magnetite, alloys which do not contain ferromagnetic metals but show ferromagnetism by heat treatment, For example, an alloy of a type called a Heusler alloy such as manganese-copper-aluminum, manganese-copper-tin, chromium dioxide, or the like can be used.

As the dye, C.I. I. Solvent Red 1, 49, 52, 58, 63, 111, 1
22, C.I. I. Solvent Yellow 19, 44, 7
7, 79, 81, 82, 93, 98, 10
3, 104, 112, 162, C.I. I. Solvent Blue 25, 36, 60, 70, 93, 9
5 and the like, and mixtures thereof can also be used. Examples of the pigment include C.I. I. Pigment Red 5,
48: 1, 53: 1, 57: 1, 122, 1
39, 144, 149, 166, 177, 1
78, 222, C.I. I. Pigment Orange 31, 43 and C.I. I. Pigment Yellow 14, 17, and 9
3, 94, 138, C.I. I. Pigment Green 7, C.I. I. Pigment Blue 15: 3, 60 and the like, and mixtures thereof can also be used.

Further, low molecular weight polypropylene (number average molecular weight = 1500 to 9000) or low molecular weight polyethylene as a fixing property improving agent may be added. Further, an azo-based metal complex, a quaternary ammonium salt, or the like may be used as a charge control agent.

The toner particles used in the present invention can be mainly produced by a pulverization method or a polymerization method.

From the viewpoint of imparting fluidity, inorganic fine particles and organic fine particles may be added to the toner. in this case,
It is preferable to use inorganic fine particles, and it is preferable to use inorganic oxide particles such as silica, titania, and alumina. Further, it is preferable that these inorganic fine particles have been subjected to a hydrophobic treatment with a silane coupling agent, a titanium coupling agent, or the like.

The particle size of the toner itself of the present invention is arbitrary, but a small particle size tends to exert the effects of the present invention, and a volume average particle size of 2 to 15 μm is preferable, and particularly 3 to 9 μm.
m is preferred. The particle size can be controlled by the concentration of the coagulant, the amount of the organic solvent added, and the composition of the polymer itself. The volume average particle size of the colored particles is measured with a Coulter Counter TA-II or Coulter Multisizer.

As the carrier constituting the two-component developer, a resin-coated carrier obtained by coating the surface of magnetic material particles such as iron and ferrite with a resin or the like is preferably used. The average particle size of this carrier is 30 to 150 μm in volume average particle size.
Is preferred. The resin for coating is not particularly limited.

For example, silicone compounds, fluorine resins, styrene-acryl resins, acrylic resins, olefin resins, vinylidene fluoride resins, olefin resins, and the like can be used.

Next, although not limited to this, FIG. 4 shows an example of a digital copying machine adopting the image forming method, and the image forming process of the present invention will be described.

As described above, the image forming process of the present invention is particularly effective in an image forming method including reversal development such as a printer and a digital copying machine.

In the image forming apparatus shown in FIG. 4, although not shown in the figure, the original is irradiated with light from a light source, the reflected light is converted into an electric signal by an image reading section, and this image data is converted into an image by the image writing section 1. To 3 (1 is a laser light source,
2 is a polygon mirror, and 3 is an fθ lens).

On the other hand, the photosensitive drum 4 for forming an image is uniformly charged by corona discharge in the charging unit 5, and subsequently, the image light is irradiated onto the photosensitive drum 4 from the laser light source 1 in the image writing section. Then, the image is reverse-developed in the next developing unit 6 and is transferred to recording paper (recording material) by the transfer pole 7. The recording paper (recording material) 8 is separated from the photosensitive drum by the separation pole 9 and fixed by the fixing device 10. On the other hand, the photosensitive drum 4 is cleaned by a cleaning device. Reference numeral 12 denotes a pre-charging exposure lamp, which may be provided after the separation pole 9 and before the cleaning device.

After the transfer of the toner image onto the transfer material, the toner remaining on the photosensitive member is removed by cleaning, and the photosensitive member is repeatedly used in the next process.

As described above, the cleaning mechanism in the present invention is preferably a cleaning system using a so-called brush roller 15 and an elastic rubber blade 13. 1
1 is an elastic rubber blade unit and 14 is a brush roller unit.

As a material forming the elastic rubber blade 13, an elastic material such as silicone rubber or urethane rubber can be used.

In the above description, the process using a single color has been described. However, in some cases, an image of a plurality of colors such as two colors may be used. The process of charging, image writing by laser light exposure, and developing the corresponding color toner is repeated by applying the signal for each color separated at the time of image reading, and the four color toners of yellow, magenta, cyan, and black toner are repeated. The image may be formed on the photoreceptor and transferred to the recording material at one time.

The method of forming the toner image and the method of transferring the toner image to the recording material may be different.

Further, in addition to the above, image information is previously stored in RO
The information can be stored in an image memory such as an M or a floppy disk, and the information in the image memory can be extracted as needed and output to an image forming unit. Therefore, an apparatus that does not have an image reading unit but stores information from a computer or the like in a memory and outputs the information to an image forming unit as in this example is also included in the image forming apparatus of the present invention. The most common of these are LED printers and LBPs (laser beam printers).

[0122]

EXAMPLES The present invention will be described below in detail with reference to examples, but embodiments of the present invention are not limited thereto.

Example 1 (Example 1-1) Polyamide resin Amilan CM-800
30 g of 0 (manufactured by Toray Industries, Inc.) was charged into a mixed solvent of 900 ml of methanol and 100 ml of 1-butanol, and dissolved by heating at 50 ° C. This liquid was applied on a cylindrical aluminum conductive support having an outer diameter of 80 mm and a length of 360 mm,
A thick undercoat layer was formed.

The surface roughness of the conductive support at this time was Rz
Was 1.2 μm.

Next, 10 g of a silicone resin KR-5240 (manufactured by Shin-Etsu Chemical Co., Ltd.) was dissolved in 1000 ml of t-butyl acetate, and as shown in FIG. TiOPc (Y-type T
10 g of iOPc) was mixed and dispersed using a sand mill for 20 hours to obtain a charge generation layer coating liquid (CGL liquid-1). This liquid was used to coat the undercoat layer to form a 0.3 μm thick charge generation layer.

Next, CTM (the following compound T-1) 150
g and 200 g of polycarbonate resin Iupilon Z-200 (manufactured by Mitsubishi Gas Chemical Company) in 1,2-dichloroethane 10
Dissolve in 100 ml and apply to the charge transport layer coating solution (CTL solution-1)
I got Using this solution, coating was performed on the charge generation layer, and the coating was dried at 100 ° C. for 1 hour to form a charge transport layer having a thickness of 20 μm.

Thus, a photoreceptor sample (OPC1-1) comprising an undercoat layer, a charge generation layer, and a charge transport layer was obtained.

[0128]

Embedded image

The photoreceptor produced as described above was incorporated in a remodeled digital copier Konica 7050 (manufactured by Konica).

At this time, the rubber hardness of the cleaning member was JIS A 65 °, the rebound resilience was 40%, and the thickness was 1.9 m.
m, an elastic rubber blade having a free length of 9 mm at a contact angle of 20 ° and a pressing force of 18 g /
cm.

Further, an acrylic brush having a single fiber thickness of 15 denier and a fiber density of 9.3 × 10 ² f / cm ^{2 was} coated with a 6-diameter fiber.
and a roller manufactured so as to have an outer diameter of 15 mm on a SUS cored bar having a diameter of 15 mm is installed at an upstream portion of the blade so as to have a bite amount of 1 mm with respect to the photosensitive drum as shown in FIGS. Rotation speed of 500rpm
To rotate in synchronization with the photoreceptor. Also, at this time, the amount of bite into the brush is 1 mm,
A flicker was provided to knock off the toner.

In this state, room temperature and normal humidity (23 ° C., 60% R
H) A real-life test of 200,000 copies was performed in an environment to evaluate the quality of the copied image.

(Example 1-2) In Example 1-1,
A photoreceptor sample (OPC1-2) was prepared in the same manner except that the surface roughness of the conductive support was set to 0.4 μm in Rz.
A live-copy test of 10,000 copies was performed.

(Example 1-3) In Example 1-1,
A photoreceptor sample (OPC1-3) was prepared in the same manner except that the surface roughness of the conductive support was set to 2.5 μm in Rz.
A live-copy test of 10,000 copies was performed.

(Example 1-4) In Example 1-1,
A 200,000 copy live-action test was performed in the same manner except that the brush had a single fiber thickness of 6.2 denier.

(Example 1-5) In Example 1-1,
A 200,000 copy live-action test was performed in the same manner except that the thickness of the single fiber of the brush was changed to 30 denier.

(Example 1-6) In Example 1-1,
A 200,000 copy actual photography test was performed in the same manner, except that the brush had a fiber density of 4.5 × 10 ² f / cm ² and the material was nylon.

(Example 1-7) In Example 1-1,
A 200,000 copy actual photography test was performed in the same manner except that the brush fiber density was 15.5 × 10 ² f / cm ² and the material was nylon.

(Example 1-8) In Example 1-1,
A photoreceptor sample (OP) was prepared in the same manner except that the charge generating material was TiOPc (I-type TiOPc) having a maximum peak at 27.3 ° and a peak at 9.0 ° as shown in FIG. 5B.
C1-4) was produced. A 200,000 copy actual photographing test was performed in the same manner except that the brush was made of nylon.

(Comparative Example 1-1) In Example 1-1,
A photoreceptor sample (OPC1-5) was prepared in the same manner except that the surface roughness of the conductive support was set to 0.3 μm in Rz.
A live-copy test of 10,000 copies was performed.

(Comparative Example 1-2) In Example 1-1,
A photoreceptor sample (OPC1-6) was prepared in the same manner except that the surface roughness of the conductive support was changed to 2.7 μm in Rz.
A live-copy test of 10,000 copies was performed.

(Comparative Example 1-3) In Example 1-1,
A photoreceptor sample (OPC1-7) was prepared in the same manner except that the charge generating material was TiOPc (A-type TiOPc) having a maximum peak at 26.3 ° as shown in FIG. Was tested live.

The phenomena of each evaluation item are as follows.

Moire This is stripe-like unevenness that occurs at the time of laser exposure, and is visually recognized as shading unevenness at an intermediate density of a copied image.

Black Streaks The traces of the conductive support after the surface roughening process appear as black streaks of several mm in length on the white background of the copied image.

Slip-through The toner that cannot be completely removed by the cleaning blade affects the next image formation and appears as a linear or planar abnormal image on the copied image.

Image deletion Ozone generated during corona discharge, such as charging and transfer, to the deposits on the surface of the photosensitive layer. Also, a phenomenon in which a latent image is disturbed due to adsorption of moisture in the air and a decrease in surface resistance, causing characters and the like to flow in a copied image.

Density drop A phenomenon in which the density of a solid black portion of a copied image decreases during reversal development due to an increase in the residual potential of the photosensitive member.

Table 1 shows the results of the test.

[0150]

[Table 1]

：: Good up to 200,000 copies Δ: Good up to 100,000 copies Problem occurred from 100,000 copies to 200,000 copies ×: Problem occurred up to 100,000 copies.

As shown in Examples 1-1 to 8 in the present invention, good image quality is obtained from the initial stage to 200,000 copies.

On the other hand, in Comparative Examples 1-1 to 1-3, it can be seen that the image quality deteriorates due to repeated use, and there is a problem.

Example 2 (Example 2-1) Titanium chelate compound TC-750
200g (Matsumoto Pharmaceutical Co., Ltd.) and silane coupling agent KB
130 g of M-503 (manufactured by Shin-Etsu Chemical Co., Ltd.) was charged into 1000 ml of 2-propanol and dissolved. This liquid has an outer diameter of 80m.
m, coated on a 360 mm long cylindrical aluminum conductive support to form a 1.0 μm thick undercoat layer.

At this time, the surface roughness of the conductive support was Rz
Was 1.2 μm.

Next, 10 g of a silicone resin KR-5240 (manufactured by Shin-Etsu Chemical Co., Ltd.) was dissolved in 1000 ml of t-butyl acetate, and 10 g of Y-type TiOPc was mixed therein and dispersed for 20 hours using a sand mill. A liquid (CGL liquid-1) was obtained. This liquid was used to coat the undercoat layer to form a 0.3 μm thick charge generation layer.

Next, CTM (the compound T-1) 150
g and 200 g of polycarbonate resin Iupilon Z-200 (manufactured by Mitsubishi Gas Chemical Company) in 1,2-dichloroethane 10
Dissolve in 100 ml and apply to the charge transport layer coating solution (CTL solution-1)
I got Using this solution, coating was performed on the charge generation layer, and the coating was dried at 100 ° C. for 1 hour to form a charge transport layer having a thickness of 20 μm.

Thus, a photoreceptor sample (OPC2-1) comprising an undercoat layer, a charge generation layer and a charge transport layer was obtained.

The photoreceptor produced as described above was incorporated in a remodeled machine of a digital copying machine Konica 7050 (manufactured by Konica).

At this time, the cleaning member had a rubber hardness of JIS A 65 °, a rebound resilience of 40%, and a thickness of 1.9 m.
m, an elastic rubber blade having a free length of 9 mm at a contact angle of 20 ° and a pressing force of 18 g /
cm.

Further, an acrylic brush having a single fiber thickness of 15 deniers and a fiber density of 9.3 × 10 ² f / cm ² was used with a diameter of 6
A SUS cored bar having a diameter of 15 mm was provided with a roller having an outer diameter of 15 mm, which was installed below the blade so that the amount of bite into the photosensitive drum was 1 mm, and the number of rotations of the photosensitive drum in the forward direction was 500 rpm. It was set to operate in synchronization with the photoconductor. At this time, a flicker for knocking off the toner was provided so that the amount of bite into the brush was 1 mm.

In this state, high temperature and high humidity (30 ° C., 80% R
H) An actual shooting test of 200,000 copies was performed in an environment, and the quality of the copied image was evaluated from the viewpoints of moire, black stripes, slip-through, image deletion, and density reduction.

(Example 2-2) In Example 2-1
A photoreceptor sample (OPC2-2) was prepared in the same manner except that the surface roughness of the conductive support was set to 0.4 μm in Rz.
A live-copy test of 10,000 copies was performed.

(Example 2-3) In Example 2-1.
A photoreceptor sample (OPC2-3) was prepared in the same manner except that the surface roughness of the conductive support was set to 2.5 μm in Rz.
A live-copy test of 10,000 copies was performed.

(Example 2-4) In Example 2-1,
A photoconductor sample (OPC2-) was prepared in the same manner except that the silane coupling agent was KBM-903 (manufactured by Shin-Etsu Chemical Co., Ltd.).
4) was produced. In addition, an actual photographing test of 200,000 copies was performed in the same manner as in Example 2-1 except that the thickness of the single fiber of the brush was changed to 6.2 denier.

(Example 2-5) In Example 2-4,
A 200,000 copy live-action test was performed in the same manner except that the thickness of the single fiber of the brush was changed to 30 denier.

(Example 2-6) In Example 2-1,
The chelate compound is replaced with a zirconium chelate compound ZC-5.
40 (Matsumoto Pharmaceutical Co., Ltd.) with silane coupling agent KB
A photoconductor sample (OPC2-5) was prepared in the same manner except that M-603 (manufactured by Shin-Etsu Chemical Co., Ltd.) was used. A 200,000 actual copy test was performed in the same manner as in Example 2-1 except that the brush fiber density was 4.5 × 10 ² f / cm ² and the material was nylon.

(Example 2-7) In Example 2-6,
A 200,000 copy actual photography test was performed in the same manner except that the fiber density of the brush was 15.5 × 10 ² f / cm ² .

(Example 2-8) In Example 2-1,
A photoreceptor sample (OPC2-6) was prepared in the same manner except that the charge generating substance was changed to I-type TiOPc. In addition, a 200,000 copy actual photographing test was performed in the same manner as in Example 2-1 except that the brush was made of polypropylene.

(Comparative Example 2-1) In Example 2-1.
A photoreceptor sample (OPC2-7) was prepared in the same manner except that the surface roughness of the conductive support was changed to 0.3 μm in Rz.
A live-copy test of 10,000 copies was performed.

(Comparative Example 2-2) In Example 2-1,
A photoreceptor sample (OPC2-8) was prepared in the same manner except that the surface roughness of the conductive support was set to 2.7 μm in Rz.
A live-copy test of 10,000 copies was performed.

(Comparative Example 2-3) In Example 2-1,
A photoreceptor sample (OPC2-9) was prepared in the same manner except that the charge generating substance was changed to A-type TiOPc, and a 200,000 copy actual photographing test was performed.

Evaluation was performed in the same manner as in Examples 1-1 and below, and the results of the test are shown in Table 2.

[0174]

[Table 2]

：: Good up to 200,000 copies Δ: Good up to 100,000 copies × Problems occurred from 100,000 copies to 200,000 copies ×: Problems occurred up to 100,000 copies.

As shown in Examples 2-1 to -8, in the present invention, good image quality from the initial stage to 200,000 copies is obtained.

On the other hand, in Comparative Examples 2-1 to 3, it can be seen that there is a problem that the image quality is deteriorated by repeated use.

[0178]

According to the present invention, it is possible to provide an image forming method capable of obtaining a high-quality and stable copy image for a long period of time.

[Brief description of the drawings]

FIG. 1 is a diagram illustrating a method for calculating Rz (ten-point average surface roughness).

FIG. 2 is a diagram illustrating an embodiment of an organic photoreceptor according to the present invention.

FIG. 3 is a schematic sectional view illustrating a brush and blade cleaning according to the present invention.

FIG. 4 is a schematic sectional view illustrating an example of the image forming apparatus of the present invention.

FIG. 5 is an X-ray diffraction spectrum of TiOPc (Y-type TiOPc).

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Laser light source of image writing part 4 Photoreceptor drum 5 Charging unit 6 Developing unit 7 Transfer pole 9 Separation pole 10 Fixing unit 11 Elastic rubber blade unit 12 Exposure lamp (PCL) before charging 13 Elastic rubber blade 14 Brush roller unit 15 Brush roller

Claims (4)

[Claims] 1. After transferring a toner image formed on an organic photoreceptor having a photosensitive layer containing at least oxytitanyl phthalocyanine on a conductive support to a recording material, the toner remaining on the photoreceptor is removed. In the image forming method using at least a brush roller in the step of performing, the ten-point average surface roughness Rz of the conductive support is 0.4 μm or more.
An image forming method wherein the oxytitanyl phthalocyanine has a maximum peak at 27.2 ° ± 0.2 ° of Bragg angle 2θ with respect to Cu-Kα ray. 2. A toner image formed on an organic photoconductor obtained by laminating an undercoat layer and a photosensitive layer containing at least oxytitanyl phthalocyanine on a conductive support, is transferred to a recording material, and then transferred to a recording material. In an image forming method using at least a brush roller in the step of removing toner remaining on the
The ten-point average surface roughness Rz of the conductive support is 0.4 μm or more and 2.5 μm or less, and the undercoat layer is at least one selected from a metal alkoxide, an organic metal chelate, and a silane coupling agent. Wherein the oxytitanyl phthalocyanine has a maximum peak at a Bragg angle 2θ of 27.2 ° ± 0.2 ° with respect to Cu-Kα radiation. 3. The method according to claim 1, wherein the oxytitanyl phthalocyanine is C
27.2 ゜ ± 0.2 at Bragg angle 2θ for u-Kα ray.
2. A peak having a maximum peak of 2 ° and a peak at 9.5 ° ± 0.2 ° or 9.0 ° ± 0.5 °.
Or the image forming method according to 2. 4. The brush of the brush roller has a single fiber thickness of 6 deniers or more and 30 deniers or less, and a fiber density of 4.5 × 10 ² f / cm ² (the number of filaments per square centimeter) or more and 15.5 or more. 3. The image forming method according to claim 1, wherein the density is not more than × 10 ² f / cm ² .