JPH03237465A - Image forming method - Google Patents

Abstract

PURPOSE:To lessen the degradation in image quality by repetitive use while substantially eliminating the influence of external environment by using a phthalocyanine pigment contg. many water molecules as the photoconductive material of the photosensitive layer of an image carrying member and applying alternately oscillating electric fields to a developing region while maintaining the photosensitive layer in a contactless state. CONSTITUTION:The phthalocyanine pigment is different in the flocculating state of pigment crystals from heretofore and further the many water molecules are incorporated therein in the number of molecules in the analysis of the gaseous adsorption components in a vacuum so that the pigment has the flocculating state in which the visual and near IR absorption spectra exhibit the max. absorption at 780 to 860nm. This pigment can exhibit a high-sensitivity characteristic to a semiconductor laser beam, etc. Development is executed by a contactless development method. The DC bias voltage and/or AC voltage is impressed to a developing sleeve 41 by a bias power source 52 and a developer layer past a developing area E is removed from the developing sleeve 41 by a cleaning blade 45 and is returned to a developer pool 43. The influence of the external environment is substantially eliminated in this way even in the contact developing system and the degradation in the image quality by the repetitive use at and under a high temp. and high humidity is obviated.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to an image forming method, for example, a multicolor image forming method in which toner images of different colors are sequentially formed on a photoreceptor as an image carrier to obtain a multicolor image. The present invention relates to an image forming method suitable for an image forming apparatus (color copy), that is, a color printer or an electrophotographic copying machine.

[Prior art 1] In the conventional multicolor image forming method, the development method employed to develop the latent image on the photoreceptor is to sequentially rotate the image carrier with a developer layer formed on a developer transport carrier. magnetic brush development method, in which toner particles are attached to the latent image using a magnetic brush, and non-contact development method, in which the developer layer is held in a state where it does not come into contact with the image carrier, and toner particles are caused to fly from the developer layer and adhere to the latent image. There is.

In the magnetic brush development method, the magnetic brush of the developing device that is not used for development scrapes off the toner image already formed on the photoreceptor, which not only tends to deteriorate the image but also allows other types of toner to get mixed into the developing device. easy. Furthermore, fogging is likely to occur. Therefore, in the magnetic brush development method, it is necessary to remove the magnetic brush of the developing device that is not used for development from the developer transport carrier, or to prevent it from coming into contact with the image forming body.

In the non-contact development method, for example, Japanese Patent Application Laid-Open No. 55-1865
As disclosed in Publication No. 6, an alternating oscillating electric field (AC voltage) is applied to the developer transport carrier in order to cause toner particles to fly from the non-contact developer layer and adhere to the latent image on the image carrier. is applied. In such a non-contact development method, the toner image is not scraped off unlike in the case of the magnetic brush development method, and it is also possible to prevent so-called fogging, in which toner adheres to non-image areas. (See the jumping development method described in Japanese Patent No. 9475).

[Issues that the defense aims to solve 1 Shikajina 7] Washi et al., non-contact development method, especially ditonbing development method (J, susceptible to the influence of external environment (t), especially under high temperature and high humidity conditions, the photoreceptor is repeatedly used) Due to use and repeated use, the charging ability of the corona electrode decreases due to scattering of particles, etc., resulting in a decrease in image quality, and in particular, a decrease in resolution and the appearance of blurred images become noticeable. .

Therefore, an object of the present invention is to provide an image forming method that is less susceptible to the influence of the external environment even in non-contact development and that improves the deterioration in image quality due to repeated use under high temperature and high humidity conditions.

[Means for Solving the Problems] In view of the above-mentioned problems, the present inventors have found, as a result of i52 Yu research, that the above-mentioned object of the present invention is to reduce the electrostatic potential on an image bearing member by charging and (!J! exposure). In an image forming method in which an image is formed and this electrostatic latent image is visualized, the photoconductive material of the photosensitive layer of the image bearing member is a molecule in the adsorbed gas component determined by an adsorbed gas component analysis in vacuum. A phthalocyanine face v1 containing the largest number of water molecules is used, and the image carrier and the developer transporting carrier therefor are kept in a non-contact state during development for visualizing the electrostatic latent image. However, it has been found that this can be achieved by an image forming method characterized by applying an alternating oscillating electric field to the developing area.

The present invention will be explained in more detail below.

The phthalocyanine pigment according to the present invention is different from conventionally known phthalocyanine pigments in the agglomeration state of pigment crystals, and furthermore, it has the characteristic that water molecules are contained in the largest number of molecules in the adsorbed gas component analysis in vacuum. It has an agglomerated state in which the visible and near-infrared absorption spectra exhibit maximum absorption in the range of 780 nm to 860 nm, and exhibits extremely high 5i properties for semiconductor laser light and the like.

In the present invention, the adsorbed gas component analysis of the phthalocyanine pigment is carried out by the following method.

An ampoule containing phthalocyanine pigments o and sg sealed in a glass tube with an internal volume of 3.0 cm3 under atmospheric humidity conditions of 60% was installed in the measurement chamber, and the degree of vacuum in a constant atmosphere of 1tll was set to 2.
Breaking the ampoule at X 10-8 Torr,
Component analysis is performed by measuring the molecular weight of the gas released from the ampoule using a four-m&n-bar analysis tube.

As a result of this component analysis, the phthalocyanine pigment contains water,
Although various molecules such as hydrogen, nitrogen, oxygen, and carbon dioxide are detected, the phthalocyanine pigment according to the present invention is characterized by containing the largest amount of water molecules.

Further, it is preferable that the phthalocyanine pigment according to the present invention has an endothermic peak between 80° C. and 120° C. in differential thermal analysis from the viewpoint of sensitivity and repeatability.

Here, the above differential thermal analysis shows that the phthalocyanine pigment 10+
11 (1) was carried out under the conditions of atmospheric humidity of 60% and temperature increase rate of 10° C. per minute, and the endothermic peak mentioned above refers to an endothermic peak with a half-width of 30 degrees or more.

Specific examples of the phthalocyanine pigment according to the present invention include, but are not limited to, metal-free phthalocyanine, titanyl phthalocyanine, vanadyl phthalocyanine, lead phthalocyanine, chlorindium phthalocyanine, and tin phthalocyanine. In the present invention, titanyl fucrocyanine pigments and vanadyl phthalocyanine pigments can be preferably used. Particularly preferred is a chichnylphthalocyanine pigment whose X-ray diffraction spectrum for Cu-α rays has peaks at 95°±0.2° and 27.2°±02° of the Bragg angle 2θ.

The basic structure of the titanyl phthalocyanine pigment used in the present invention is expressed in the following format.

In the formula, x+, X2, X3 and x4 each represent a hydrogen atom, a halogen atom, an alkyl group or an alkoxy radical, and n, m, Q and k each represent an integer of O to 4.

An example of the method for producing the titanyl phthalocyanine used in the present invention will be described below. That is, 1,3-diiminoisoindoline and sulfolane are mixed, titanium tetrapropoxide is added to the mixture, and the mixture is reacted in a nitrogen atmosphere. The reaction temperature is 80°C to 300°C, especially 1
A temperature of 00°C to 260"C is preferable. After completion of the reaction, the precipitate is observed after cooling and titanyl phthalocyanine can be obtained. Next, by treating this with a warm solvent, the desired titanyl phthalocyanine can be obtained. However, in addition to the general W! stirring table apparatus, a homomixer, a disperser, an agitator, a ball mill, a sand mill, an attritor, etc. can be used for the treatment.

In the present invention, in addition to the above-mentioned phthalocyanine pigment according to the present invention, other carrier-generating substances may be used in combination as a carrier-generating substance within a range that does not impair the effects of the present invention. Carrier generating substances that can be used in combination include those that differ in crystal form from the phthalocyanine according to the present invention, such as α type and β type.
Examples include titanyl phthalocyanine of type, α, β mixed type, and amorphous type, as well as azo pigments, anthraquinone pigments, perylene pigments, polycyclic quinone pigments, and squareium pigments.

In order to produce an image bearing member, that is, a photoreceptor in the present invention, for example, the phthalocyanine pigment according to the present invention is mixed and dispersed in a solution in which a binder resin is dissolved in a solvent, and the carrier transport substance described below is dissolved therein. The resulting coating solution is coated onto a conductive support provided with an intermediate layer (subbing layer) in advance, if necessary, by a method such as dip coating, spray coating, or spiral coating. By such a method, the figure 4 or 5! A photoconductor having an i-containing configuration is obtained. In addition, 71+@ in the diagram
The conductive support, 74'' is a single-layer photosensitive layer, and 75 is an intermediate layer.

However, a photoreceptor with high sensitivity and high durability is
From the above, it is preferable to use a functionally separated type photoreceptor having the layer structure shown in FIGS. 6 to 9. In this case, a female heavy liquid prepared by mixing and dispersing the pigment 8 in a solution in which a binder resin is dissolved is coated on the conductive support 71 having the intermediate layer 75 as necessary. After forming 72, a coating liquid containing a carrier transporting substance is applied onto the carrier generation layer 72 to form a carrier transporting layer 73.
A photosensitive layer 74 (FIGS. 6 and 8) having a duck structure or a photosensitive layer 74' (FIGS. 7 and 9) having a layer structure opposite thereto is formed. The following description will focus on a photoreceptor having a two-layered photosensitive layer.

In the case of forming a two-layered photosensitive layer, the carrier generation layer 72 and the carrier transport layer 73 can be provided by the following method.

(a) A method of applying a solution in which a carrier generating substance and a chitria transporting substance are respectively dissolved in a suitable solvent, or a solution in which a binder is added and mixed and dissolved.

(b) A method in which a carrier-generating substance and a carrier-transporting substance are made into fine particles in a dispersion medium using a ball mill, a homomixer, an ultrasonic wave, etc., and a binder is added as necessary to mix and disperse the obtained dispersion, and the resulting dispersion is applied.

Examples of the solvent or dispersion medium used for forming the carrier generation layer and the carrier transport layer include butylamine, N,N-dimethylformamide, acetone, butyl ethyl ketone, cyclohexanone, benzene, toluene, xylene, chloroform, 1 , 2-dichloroethane, dichloromethane,
Tetrahydrofuran, dioxane, methanol, ethanol, isopropanol, ethyl acetate, butyl acetate, dimedelsulfoxide and the like can be mentioned. When a binder is used to form the carrier generation layer or the carrier transport layer, any binder can be used, but particularly polymeric polymers that are hydrophobic, have a high dielectric constant, and have the ability to form an electrically insulating film are used. Combination is preferred. Examples of such polymers include, but are not limited to, the following.

1) Polycarbonate 2) Polyester 3) Methacrylic resin 4) Acrylic resin 5) Polyvinyl chloride 6) Polynylidene chloride 7) Polystyrene 8) Polyvinyl acetate 9) Styrene-butadiene copolymer 10) Vinylidene chloride-acryloni 1-lyl Copolymer 1
1) Vinyl chloride-vinyl acetate copolymer 12) Vinyl chloride-vinyl acetate-maleic anhydride copolymer 13) Silicone resin 14) Silicone-alkyd resin 15) Phenol-formaldehyde resin 16> Styrene-acrylic copolymer resin 17) Styrene-alkyd resin 18) Poly-N-vinyl carbazole 19) Polyvinyl butyral 20) Polycarbonate Za1 resin These binders can be used alone or in a mixture of two or more.

The ratio of the carrier generating substance to the binder resin is preferably 10 to 600%, more preferably 50 to 600%.
It is assumed to be 400% by weight.

It is preferable that the thickness of the 4-Yaria generation chamber 72 formed in this way is 0.01 to 20 μm, and more preferably 0.05 to 5 μm.

The carrier generating layer 7 is made by dispersing the carrier generating substance.
2, the carrier-generating substance is preferably in the form of powder having an average particle size of 2 μm or less, preferably 1 μm or less. In other words, if the particle size is too large, dispersion in the layer will be poor, and some of the particles will protrude from the surface, resulting in poor surface smoothness. Toner particles tend to adhere to the toner, causing a toner filming phenomenon.

Various carrier transport substances can be used, but typical examples include nitrogen-containing heterocyclic nuclei and fused rings thereof, such as oxazole, oxadiazole, ditazole, thiadiazole, and isodazole. Compounds having a nucleus, (1), 1-aryl alkane compounds,
Pyrazoline compounds, hydrazone compounds, triarylamine compounds, styryl compounds, styryltriphenylamine compounds, α-phenylstyryl 1-rifenylamine compounds, butadiene compounds, hexatriene compounds, carbazole compounds, Examples include fused polycyclic compounds.

Specific examples of these carrier-transporting substances include carrier-generating substances described in Mochima Sho 61-107356.

The ratio of the carrier transport substance to the binder resin is preferably 10 to 500% by weight, and the thickness of the carrier transport layer is preferably 1 to 100 μm, more preferably 5 to 30 μm.

The photosensitive layer of the photoreceptor in the present invention can contain an electron-accepting substance for the purpose of improving sensitivity, reducing residual potential, or reducing fatigue during repeated use. Examples of such electron-accepting substances include succinic anhydride, maleic anhydride, dibromo succinic anhydride, phthalic anhydride, tetrachlorophthalic anhydride, tetrabromo phthalic anhydride,
3-ditro phthalic anhydride, 4-di phthalic anhydride,
Pyromellitic anhydride, mellitic anhydride, tetracyanoethylene, tetracyanoquinodimethane, 0-dinitrobenzene, m-dinitrobenzene, 1,3.

5-trinitrobenzene, p-nitrobenzonitrile,
Vicrylchloride, quinone chlorimide, chloranil, bromanil, dichlordicyano-p-benzoquinone,
Anthraquinone, dinitroanthraquinone, 9-fluorenylidenemalonodinitonol, polynitro-9-fluorenylidenemalonodinitrile, picric acid, 0-nitrobenzoic acid, p-nitrobenzoic acid, 3,5-dinitrobenzoic acid, pentafluoro Examples include benzoic acid, 5-nitrosalicylic acid, 3.5-dinitrosalicylic acid, phthalic acid, Melitron, and other compounds with high electron affinity. The electron-accepting substance is added to the carrier-generating substance.
0.01~.00 weight ω. 200 min. is desirable, and 0.1 to 100 min. is more preferred.

Further, the photosensitive layer may contain deterioration inhibitors such as oxidation inhibitors and light stabilizers for the purpose of improving storage stability and durability.

In the single-layer photoreceptor shown in FIGS. 4 and 5, the carrier-generating material used in the photosensitive layer 74'' is the phthalocyanine face 11 according to the present invention, and the carrier-transporting material is the one described above. The binder resin and other additives for the photosensitive FW 74'' may also be the same as those described above.

As the conductive support, a metal plate, a metal drum, etc. are used, and a thin layer of a conductive polymer, a conductive compound such as indium oxide, or a metal such as aluminum or palladium is coated, vapor-deposited, laminated, etc. Depending on the situation, a material provided on paper, plastic film, etc. is used.

The intermediate layer 75, which functions as an adhesive layer or a barrier layer, may be made of a high molecular weight material such as a high molecular weight polymer, polyvinyl alcohol, ethyl cellulose, carboxymethyl cellulose, polyamide, etc., or an oxidized polymer as explained above as the binder resin. A material made of aluminum or the like is used.

The present invention provides an image forming method in which an electrostatic latent image is formed on an image carrier by charging and image exposure, and this tf\' electrostatic latent image is visualized. Using a specific phthalocyanine pigment as described above as a sexual substance,
and applying an alternating oscillating electric field to the developing area while maintaining the image bearing member and the developer transporting carrier therewith in a non-contact state during development for visualizing the G11 latent image. The present invention relates to an image forming method characterized by:

In the present invention, in order to effectively implement this method, a charging means, a digital (dot) exposure means, and a developing means are arranged, and the developing means is in a non-contact state with respect to the image carrier. An image-forming 1512 pack can be used that has a developer transport carrier held in the developer area and an oscillating field supply that applies an alternating oscillating electric field to the development area.

An example of an image forming apparatus (for example, a digital copy type multicolor image forming apparatus) that can be used in the present invention will be described with reference to FIGS. 1 to 3.

FIG. 1 is a schematic cross-sectional view of a copy amount that is an image forming apparatus that can be used in the present invention. According to the apparatus shown in FIG. 1, the original 1 placed on the original table 19 in the image reading section LE.
8 receives light from an illumination light source 13 moving in the X direction, and the reflected light 2 passes through a tfi mirror 1, a lens 15, and a color separation filter 16 to each CCDI for red, green, and blue.
The image is formed on image elements 17R117G and 17B. These CCD1fi image elements convert the optical information into time-series electric signals and send them to the image data processing section TR+ (see FIG. 2), where recording image data is formed. In the laser optical system 10, the laser beam of the semiconductor laser 21 is modulated in the modulation section MD based on the recorded image data from the video signal processing section TR2 (in the figure, 22 is a polygon mirror). On the other hand, the surface of the image carrier 1 is uniformly charged by the scorotron charging electrode 2. Next, image exposure from the laser optical system 10 is applied onto the image carrier (photosensitive drum) 1. In this way, an electrostatic latent image is formed. For example, a blue filter is set as the color separation filter 16. In this case, this acid-N latent image is reversely developed by the developing device 31 containing yellow toner.The image carrier 1 on which the toner image has been formed is uniformly charged again by the scorotron charging electrode 2. For example, when a green filter is set as the color separation filter 16, image exposure is performed based on optical information read through this filter. On the other hand, the recording paper P is reversely developed by the developing device 32 located at the paper feed roller 23.
is fed into the drum-shaped transfer unit 1-63 by
The tip is gripped by the gripper 64 and moved as the transfer unit 63 rotates in the direction of the arrow.

The developed toner image is transferred onto the recording paper P by a transfer device 5 provided in the transfer unit 1-63. In the case of monochrome image copying, the recording paper P is immediately separated from the transfer unit 63 by the operation of the separation claw 66, sent to the heat fixing roller 9, where the toner image is fixed, and then discharged from the apparatus. In the case of multicolor image copying of two or more colors, the separation claw 66 does not operate, and the recording MP rotates while being held in the transfer unit 63. Before the transfer by the transfer device 5, exposure for promoting transfer may be performed.

The surface of the image carrier onto which the toner image has been transferred is cleaned of residual toner by a cleaning device 8 (if necessary, the charges may be removed before cleaning), and the surface is prepared for the next image forming process. In the case of a multicolor image a+copying of two or more colors, the toner images 1 to 1 are transferred to overlap the toners and toner images at the front of the recording paper P held in the transfer unit 63. As a result, a two-color image is formed on the recording paper P, and in the case of a two-color image @copying, the separation claw 66 is activated at this point and the recording paper P is
The toner image is separated from the transfer unit 63, the toner image is fixed in the same manner as in the case of monochrome, and then the toner image is discharged.

In the case of three-color image copying, the separation claw 66 is not activated yet, and furthermore, the formation of electrostatic latent images of different color separations on the image carrier 1 and the development by another image processing are performed as before. It was done and that l.
The separation claw 6G is activated only when the toner image is transferred to the recording paper P in the same manner as before. After that, the recording paper P is discharged without fixing the toner image, as in the case of monochrome or two-color printing. The developing units 33 and 34 are used for development with cyan 1-toner and black 1-toner, respectively, and when these are used, a four-color toner image is formed on the image carrier 1.

Although FIG. 2 does not show a block diagram of the copying operation of the copying machine shown in FIG. 1, according to this, the control section CT is actuated by the operation section OP, and the @reading section LE whose operation is controlled by this control section , the optical information of the original 18 is converted into color-based time-series signals, the converted data is processed in an image data processing section TR+, and further converted into data suitable for recording in a video signal processing section TR2.

The image forming section RE executes the above-described process for forming an image based on the control signal, and transfers the toner (image) onto copy paper to form a recorded matter.This image forming section RE employs an electrophotographic method. It is something.

In addition to the above, various preset information, especially data on functional operation contents such as the copy magnification and color described above, can be stored in the ROM (Re
ad Qn! y MIJOry>, 70 tshi-7'isk, magnetic tape, etc., and the information in the image memory ME can be taken out and output to the image forming section RE as necessary.

In the above-mentioned apparatus, as the developing units 31 to 34, a base-structured developing unit as shown in an enlarged view in FIG. 3 is used. In each of these developing devices, a non-magnetic developing sleeve 41 serving as a developer transport carrier rotates counterclockwise, and an internal magnet body 42 rotates clockwise to transfer the developer 50 in the developer reservoir 43 onto the surface of the developing sleeve 41. It attracts and conveys it in the direction opposite to the rotation of the magnet body 42. The thickness of the developer conveyed on the developing sleeve 41 is regulated by a layer thickness regulating blade 44 on the way, thereby forming a developer layer.

When performing development, a bias power supply 52 applies a DC bias voltage and/or an AC voltage to the development sleeve 41 . As a result, development is performed in the development area E, and the developer layer that has passed through the development area E is removed by the cleaning blade 45.
The developer is removed from the developing sleeve 41 by
It is reduced to 3. The developer reservoir 43 is supplied with toner from a toner hopper (not shown) by a toner supply row. In addition, the developer 5 in the developer reservoir 43
0 are uniformly agitated by the stirring or conveying means 46, 47, 48 and the toner particles are given sufficient charge.

In the above, the developer layer may be conveyed by rotating the developing sleeve 41 stationary or clockwise, or by rotating the magnet body 42 counterclockwise or stationary.

Although a one-component developer made of magnetic toner particles can be used as the developer 50, a two-component developer made of a mixture of magnetic carrier particles and non-magnetic toner particles has a color (Y magnetic, j~lunar charge 1). It is preferably used from the viewpoint of .11 m.

The development using the developing device shown in Fig. 3 is carried out by non-contact development based on the present invention, but the detailed development conditions were described in Japanese Patent Laid-open No. 5
No. 7-147652 or No. 59-181362 (however, both use a two-component developer) and I
It may be like i'il. In addition, when using a -component developer, JP-A No. 55-18656 or equity Il: 4
It may be the same as that described in Publication No. 44-9475q.

During development by the developing units 31 to 34, a bias voltage is applied to the developing sleeve 41 to control the flight of one hener to two.
1+ For effective implementation, image bearing member 1 and developing sleeve 4 are required.
It is preferable that the alternating electric field applied between 1 and 1 is set to 100 V to 5 KV, and the DC bias is 100 V to 2 KV.

Further, there is a gap E'A 5 between the image carrier 1 and the developing sleeve 41.
11. It is preferable that the thickness of the developer layer is in the range of 110 to 2000 L1 m, and therefore the thickness of the developer layer regulated by the layer thickness regulating blade 44 is thinner than the above gap.

By using the above-mentioned preferable conditions for the developing units 31 to 34, it is possible to clearly develop electrostatic latent images for each color using each developing unit without fogging. Therefore, a clear monochrome image or a multicolor image is recorded on the recording paper P.

Note that when the developer 50 is made of two components, the particle diameters of the carrier and toner are preferably 5 to 100 μm for the former and 20 μm or less for the latter. As the carrier, a magnetic carrier or an insulating carrier coated with an insulating material can be used.

When the developer 50 is made of one component, a known insulating toner can be used.

Furthermore, the present invention is of course applicable not only to the above-mentioned apparatus but also to other types of copying machines. Development is not limited to reversal development, but regular development is also possible.

[Example 1 Hereinafter, the present invention will be explained in more detail with reference to Examples.

First, examples of synthesis of various phthalocyanine pigments will be described.

(Synthesis Example 1) 292 g of 1.3-diiminoisoindoline and 200 g of sulfolane. , i2 was wetted, 170 g of titanium tetraisopropoxide was added, and the mixture was heated at 140°C under a nitrogen atmosphere for 2 hours.
I got a reaction when I heard it. After cooling, the precipitate was collected by filtration, washed with chloroform, and further washed with a 2% aqueous hydrochloric acid solution. Next, the product was washed with water and methanol, and then dried to obtain 25.5 g (88.5%) of titanyl phthalocyanine. Dissolve 100 g of the product in 2 k (l) of concentrated sulfuric acid,
The mixture was poured into 0.01 water to precipitate and collected by filtration to obtain a wet paste in an amorphous state.

To this wet paste 2Q, add a mixed solvent of 1,2-dichloroethane 20 (hR) and methanol 100 nQ,
3 rRIK stirring was performed under i4. Diluted with MetaTsuru, filtered, washed with methanol, and dried to a Bragg angle of 2θ of 9.5°±0.2”, 27.2′±02
A crystal with an X-ray diffraction spectrum having a peak at ° was obtained. Note that the X-ray diffraction spectrum was obtained using an X-ray diffraction instrument fa J
It was measured using DX-8200 (manufactured by JEOL Ltd.) under the following conditions (the same applies hereinafter).

X-ray tube Cu (α rays to C1J-) voltage
40.0 KV Lightning current 100.0 mA Start angle 6.00 deg Stop angle 35.00 deg.

Step angle 0.02 (l deg measurement time
0.50 deg.

Further, in differential thermal analysis of this crystal, a differential thermal curve shown in FIG. 10 was obtained, and an endothermic peak was observed at 99.6°C. Differential thermal analysis followed the method described above (the same applies below).

(Synthesis Example 2) 29.2 g of 1,3-diiminoisoindoline and 200 d of sulfolane were mixed, 17.0 (l) of titanium tetraisopropoxide was added, and the mixture was heated at 140°C under a nitrogen atmosphere for 2 hours.
Allowed time to react. After cooling, the precipitate was collected by filtration, washed with chloroform, and further washed with a 2% aqueous hydrochloric acid solution. Next, after washing with water and methanol, it was dried for 25 minutes.
．． 5 g (88.5%) of titanyl phthalocyanine were obtained.

10g of the product was dissolved in 2kq of concentrated sulfuric acid, poured into 2Of of water, precipitated and collected by filtration to obtain an amorphous wet paste.

1,2-dichloroethane 2g to 2g of this wet paste
A mixed solvent of 001/ and acetone 1001Q was added and stirred at room temperature for 3 hours. Diluted with methanol, filtered, washed with methanol and dried to obtain a Bragg angle of 2θ of 9.
A crystal with an X-ray diffraction spectrum having peaks at 5°±0.2' and 27.2°±02° was obtained. Further, in the differential thermal analysis of this crystal, a differential thermal curve shown in FIG. 11 was obtained.

(Synthesis Example 3) 1,3-diiminoisoindoline 14.6Q (Oi
mole) and vanadium oxide acedelacetonate-1 to 7.9
547 (0.03 mol) was mixed in 1001N α-chloronaphthalene and reacted at 190° C. for 2 hours under a nitrogen stream. After cooling to room temperature, the precipitate was collected by filtration and washed with α-chloronaphthalene. Next, it was washed with chloroform, further washed with a 2% aqueous hydrochloric acid solution, washed with water, finally washed with methanol, and then dried to obtain 11.0 g of vanadyl phthalocyanine. The product was then added to 30 (8
m of concentrated sulfuric acid, poured into 300 times the volume of water, precipitated and collected by filtration to obtain an amorphous wet paste.

1,2-dichloroethane 2g to 2g of this wet paste
A mixed solvent of 00d and methanol 100iR was added and stirred for 3 g at room temperature. The mixture was diluted with methanol, filtered, washed with methanol, and dried to obtain crystals exhibiting the differential thermal curve shown in FIG. 12.

<Comparative Synthesis Example 1> After drying the wet paste in Synthesis Example 1, β-chloronaphthalene was heated and stirred.
type titanyl phthalocyanine was obtained. The X-ray diffraction spectrum is 9.3°±0.2° 106′± of Bragg angle 2θ.
0.2° 13°2″ ±0.2°, is, i°±
0.2°, 157°±02°16.1°±02°,
20.8°±0.2°, 23.3°±02''', 26
The peaks were at 3°±0.2° and 27.1°±02″. The differential thermal curve is shown in FIG.

When each of the titanyl phthalocyanine and vanadyl phthalocyanine prepared in Synthesis Examples 1 to 3 and Comparative Synthesis Example 1 was subjected to component analysis of adsorbed gas in vacuum according to the method described above, the following results were obtained.

Number of molecules % 2nd 20th Co N2 02 CO
2 go or synthesis 2.2 68.5 0.0 23
．． 3 4.2 1.8 Synthesis Example 2 2.0 59.3
0.0 31.3 5.6 1.8 Synthesis Example 3 2
,0 50.8 0.0 38.5 7.0 1.
7 Comparative Synthesis Example 1 0.0 2. G, 0.0 79
．． 5 13.9 4.0 It can be seen that titanyl phthalocyanine and vanadyl phthalocyanine obtained in Synthesis Examples 1 to 3 contain the largest amount of water molecules.

Example 1 Titanyl phthalocyanine 3 obtained in Synthesis Example 1
Part, silicone resin as binder resin (rKR-5
240 15% xylene-butanol solution (manufactured by Shin-Etsu Chemical Co., Ltd.) 35 parts, min i2I! 100 parts of methyl ethyl ketone as a medium was dispersed using a sand mill, and this was applied by dip coating onto an aluminum drum coated with a 0.3 μm thick polyamide resin layer to give a film thickness of 0.2 μm.
A carrier generation layer was formed. Next, 1,000 to 11 parts of the following carrier transport substance, 1,3 parts of polycarbonate resin "Nipiron Z200J (manufactured by Mitsubishi Gas Chemical Co., Ltd.)" and 10 parts of 1,2-dichloroethane were added to the silicone oil rKF-54J (manufactured by Shin-Etsu Chemical Co., Ltd.). A solution dissolved in the above was applied using a blade coater, and after drying, a carrier transport layer having a thickness of 20 μm was formed to obtain a photoreceptor sample.

-1 Color copy D of the sample obtained as above
4 for C-8010 (manufactured by Konica: uses two-component developer)
It was installed in a modified machine equipped with a 00 dpi optical system, and the image quality was mainly evaluated for copied images. However, the development method was non-contact jumping development using a reversal development method. The development conditions were as follows. Image quality evaluation is based on resolution,
Testing was conducted from two points of ground yellowtail at 33°C and 80% relative conditions at the initial stage and after 1 to 50,000 pudding.

The results are shown in Table 1. The evaluation criteria were set as follows.

Development conditions/image forming body 150φ drum/linear speed
70mm/S・V++ -6
00V ・Sleeve linear speed (φ20 25Orpm>260mm
/ 5ec 500μm 300μm Density 7 balls are % 50v 1.2KVp-p (3KHz) ・Development gap・Developer layer thickness・Developer]・DC bias・AC bias (planning method) Resolution...per 1 mm, etc. 40, 50 vertical lines at intervals
There were 60, 7.0, and 8.0 lines, and the blades with vertical lines that could be distinguished were displayed as the resolution.

Land strength: Image samples obtained by copying blank paper using a modified Konica 8010 machine were visually evaluated.

○: No background fog occurred. ×: Background fog occurred. However, when using the above-mentioned DC-8010, the evaluation of the copied image was performed using the above-mentioned 10-level and resolving power chart.

(Comparative Example 1) A comparative photoreceptor sample was prepared in the same manner as in Example 1 except that the titanyl phthalocyanine of Comparative Synthesis Example 1 was used in place of the titanyl phthalocyanine of Synthesis Example 1.

Further, development was performed in the same manner as in Example 1, and resolution and blurring were evaluated. The results are shown in Table 1.

(Comparative Example 2) Using a photoreceptor sample obtained in the same manner as in Example 1,
Development was carried out in the same manner as in Example 1, except that the developer layer and the photoconductor were brought into contact with each other, and wf image strength and ground force blur were evaluated. The developing conditions were as follows.

The results are shown in Table 1.

Developing device ('r, image forming body, l!i! speed, surface potential, sleeve linear speed, development gap, developer layer thickness, DC bias 00V 150φ drum 70mm/s VH= 260mm/ 5 500μm 600μm 60V Table 1 Table Using the phthalocyanine photoreceptor according to the present invention from 1,
By performing development using a non-contact development method, 33℃, 8
It was found that even after repeated use of 50,000 prints under the high temperature and high humidity conditions of 0% R1 mouth, high resolution was obtained and the occurrence of soil blurring was improved.

[Effects of the Invention] As described in detail above, the image forming method of the present invention is less susceptible to the influence of the external environment even in the contact development method, and improves image quality deterioration due to repeated use under high temperature and high humidity conditions. I can do it.

[Brief explanation of drawings]

FIG. 1 is a schematic sectional view of a copying machine which is an example of an image forming apparatus used in the present invention, FIG. 2 is a block diagram of the copying operation of the copying machine shown in FIG. 1, and FIG. 2 is a sectional view of a main part of the developing device of the copying machine shown in FIG. 1. FIG. Further, FIGS. 4 to 9 are cross-sectional views illustrating the layer structure of the photoreceptor according to the present invention, and FIGS. 10 to 12 are differential thermal curve diagrams of the phthalocyanine pigment according to the present invention, respectively. , FIG. 13 is a differential thermal curve diagram of a β-type titanyl phthalocyanine pigment. In addition, in the symbols shown in the drawings, 1... Photoreceptor 2... Electric appliance 5... Transfer pole 8... Cleaning device 9... Fixing roller 10... Laser optical system 17R, 17G, 17B...CCD image carrier element 18...
・Documents 31, 32, 33, 34...Developer 41...Developing sleeve 42...Magnet 43...Developer reservoir 44...Layer thickness regulating blade 63...Transfer unit 71... - Conductive support 72...Carrier photogenerating layer 73...Carrier transport layer 74, 74' 75...Intermediate layer...Image exposure E...Development area.

Claims (1)

[Claims] In an image forming method in which an electrostatic latent image is formed on an image carrier by charging and image exposure, and this electrostatic latent image is made into a visible image,
As the photoconductive substance of the photosensitive layer of the image carrier, a phthalocyanine pigment containing the largest number of water molecules among the adsorbed gas components determined by an adsorbed gas component analysis in vacuum is used, and
During the development for visualizing the electrostatic latent image, an alternating oscillating electric field is applied to the development area while maintaining the image carrier and the developer transport carrier therewith in a non-contact state. image forming method.