JPH0240661A - Copper phthalocyanine photosensitive body and manufacture thereof - Google Patents

Abstract

PURPOSE: To obtain a photoreceptor having high sensitivity by using copper phthalocyanine treated with gaseous iodine as an electric charge generating material and forming a photosensitive layer on an electrically conductive substrate by coating with the electric charge generating material together with an electric charge transferring material or with the materials in a separate state. CONSTITUTION: An electrically conductive substrate is coated with copper phthalocyanine, the resultant copper phthalocyanine layer is treated with gaseous iodine so that the ratio of iodine to copper phthalocyanine is regulated from 0.01 to 1.0 and the layer is coated with an electron hole transferring material to form a photosensitive layer. In other way, an Al material as a substrate is coated with a polyamide resin soln. and dried to form a bonding layer and a suspension prepcl. by dispersing copper phthalocyanine in a polyvinyl butyral resin soln. is adhered on the bonding layer and dried to form an electric charge generating layer. After holding in gaseous iodine at 20-90 deg.C for 1-120min, the electric charge generating layer is coated with an electric charge transferring layer formed by dispersing an electron hole transferring material such as a mixture of a hydrazone compd., a pyrazoline compd., etc., in a bonding layer to produce the objective photoreceptor.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] This invention relates to a copper phthalocyanine photoreceptor and a method for manufacturing the same.

[Conventional technology]

Generally, in electrophotography, the surface of the photosensitive layer of a photoreceptor is charged and exposed to form an electrostatic latent image, which is developed with a developer to make it visible, and the visible image is directly transferred onto the photoreceptor. A method is used in which a copy image is obtained by fixing the image, or a visible image on a photoreceptor is transferred onto a transfer paper such as paper, and the transferred image is fixed to obtain a copy image. These methods are mainly applied to electronic printers and laser printer facsimiles.

Conventionally, amorphous selenium, cadmium sulfide, or zinc oxide has been widely used as a photoconductive material to form a photosensitive layer of an electrophotographic photoreceptor used for this type of purpose.

However, amorphous selenium is difficult to manufacture because it requires vapor deposition on a conductive support, and the vapor-deposited film is not flexible and is highly toxic, so it must be handled with care.
It has the disadvantage of being expensive. On the other hand, the sensitivity of cadmium sulfide and zinc oxide is significantly affected by the mixing ratio with the binder that binds them onto the substrate, so it is necessary to reduce the ratio of the binder in order to obtain practical sensitivity. I have no choice but to
As a result, mechanical strength such as flexibility, smoothness, hardness, and abrasion resistance is low, and in addition, its properties deteriorate due to ozone generated due to corona charging, and it is toxic and pollutes the environment. There were also hygiene problems, such as the possibility of the occurrence of In order to solve these shortcomings and problems,
In recent years, organic photoreceptors with excellent processability and no hygienic problems such as toxicity or environmental pollution have been rapidly developed and become popular.

In terms of structure, organic photoreceptors are generally classified into single-layer types and multi-layer types. The single-layer type is formed by coating a conductive substrate with a photosensitive layer consisting of a charge-generating material, a charge-transmitting material, and a binder. In the multi-layer type, a charge-generating substance is coated on a conductive substrate by vapor deposition or coating, and then a suspension consisting of a charge-transmitting substance and a binder is further applied on the formed charge-generating layer. The coating is dried. Once such a photoreceptor is exposed to light, charge pairs are generated from the charge-generating material, and due to the action of the electric field, electrons are released via the conductive substrate, while electron holes pass through the charge-transfer material and are exposed to light. It can be transmitted to the body surface to neutralize its negative charge and form an electrostatic latent image.

The charge generating materials used in organophotoreceptors are typically photoconductive organic pigments. For example, bisazo pigments,
Examples include anthrahydroquinone pigments, thioindigo pigments, and phthalocyanine pigments. Among them, especially copper phthalocyanine, which belongs to phthalocyanine pigments,
It is currently the most widely used blue organic pigment because it has excellent coloring power, light resistance, heat resistance, and chemical resistance, has no toxicity problems, and is low in cost.

Already known copper phthalocyanine is α-1β-2T-1δ-1π-β-1χ-ε-
There are eight types. Among them, three types, α, β- and ε-, are mass-produced and widely used. In particular, ε-type copper phthalocyanine exhibits high absorption of light with a long wavelength (approximately 780 nm) such as that produced by semiconductor lasers, and is thought to be applicable to laser printers and facsimile machines that are developed using electrophotography. Attention has been paid. However, the conventional ε-type copper phthalocyanine lacks sensitivity as a charge-generating substance, and the required light energy from exposure until the surface potential attenuates by half is too high, and when applied to photoreceptors, The potential difference of the latent image becomes insufficient, making it difficult to form a clear copy image.

There is a method of increasing the sensitivity by coating the surface of ε-type copper phthalocyanine with a dye sensitizer (see Japanese Patent Laid-Open No. 55161.249). However, this method only works in the infrared wavelength range (780 nm).
It has the disadvantage that the absorption wavelength is varied so that the sensitivity disappears in the vicinity of (around m).

[Problem to be solved by the invention]

The present invention improves the manufacturing method so that a photoreceptor made of copper phthalocyanine as a charge generating substance has high sensitivity in the infrared wavelength range, and is applicable to laser printers, facsimile machines, and electronic printers that are developed by electrophotography. The purpose is to become a body.

[Means for Solving the Problems] In order to achieve the above object, the present invention uses copper phthalocyanine treated with iodine gas as a charge generation material, and together with or separately from a charge transfer material,
By coating a conductive substrate to form a photosensitive layer,
Manufacture a copper phthalocyanine photoreceptor.

That is, the manufacturing method of the present invention includes, for example, a binding layer forming step in which a conductive substrate is coated with a binder and then dried, and a binding layer forming step in which copper phthalocyanine is dispersed in the binder. a charge generation layer forming step in which the charge generation layer formed in the charge generation layer formation step is coated and dried after being coated on the binding layer formed in the step; an iodine treatment step in which the charge generation layer formed in the charge generation layer formation step is treated with iodine gas; One example is a method comprising a charge transmission layer forming step of dispersing a transmission substance in a binder and coating it on the charge generation layer treated in the iodine treatment step.

By such a method, the present invention provides an organic photoreceptor in which a conductive substrate is coated with a charge-generating substance and a charge-transferring substance as a photosensitive layer, and in particular, an organic photoreceptor in which a copper phthalocyanine treated with iodine gas is used as the charge-generating substance. A photoreceptor can be provided.

Copper phthalocyanine is suitable as the above-mentioned charge-generating substance, but it is desirable to use three types, α-1β- and ε-, with the ε-type being the most preferable.

The above-mentioned charge transfer substance is preferably a so-called electron hole transfer substance, such as a hydrazone compound, a birapurine compound,
Examples include oxazole compounds, thiazole compounds, and triallylmethane compounds. As a hydrazone compound, p-diethylaminobenzaldehyde-N
, N-diphenylhydrazone, p-diethylaminobenzaldehyde-N-α-naphthyl-N-phenylhydrazone, p-(1-pyrrolidinyl)-henzaldehyde N, N-diphenylhydrazone, 1.3゜3-trimethylindoleene- ω-aldehyde-N,N-diphenylhydrazone, p-diethylaminobenzaldehyde-
Examples include 3-methylbenzthiazolinone-2-hydrazone. As a pyrazoline compound, 1-phenyl-3
-(p-diethylaminostyryl)-5-(p-diethylaminophenyl)pyrazoline, 1-[quinolyl (2))
-3-(p-diethylaminostyryl)-5-(p-diethylaminophenyl)pyrazoline, 1-[pyridyl(
2))-3-(p-diethylaminostyryl)-5-(
Examples include p-diethylaminophenyl) pyrazoline.

Further, as oxazole compounds, 2-(p-diethylaminostyryl)-6-dinithylaminobenzoxazole, 2-(p-diethylaminophenyl)-4=
(p-'; Methylaminophenyl (2-chlorophenyl) oxazole, thiazole compounds include 2-
(p-diethylaminostyryl)-6-dinithylaminobenzothiazole and triallylmethane compounds include bis(4-diethylamino-2-methylphenyl)-
Examples include phenylmethane.

The binder is not particularly limited, and commonly used resins can be used. Examples include poly(vinyl butyral), poly(vinyl acetate), polyester, polycarbonate, phenoxy resin, acrylic resin, polyacrylamide, polyamide, polyvinylpyridine, cellulose resin, urethane resin, epoxy resin, casein, poly(vinyl alcohol) ) etc.

Methods for iodine treatment include a method of treatment with saturated iodine gas in a closed container and a method of treatment using a vacuum evaporation apparatus. The treatment conditions are such that the ratio of iodine placement to amount of charge generating material in the treated charge generating material is 0.01 to 1.
It suffices if it is 0. For example, 20℃~9
What is necessary is just to process at the temperature of 0 degreeC for 1 to 120 minutes. If the ratio is less than 0.01, there will be no improvement in sensitivity, but if it is more than 1.0, the dark decay characteristic will be too large and static charges cannot be absorbed sufficiently.

[For production]

According to the present invention, copper phthalocyanine treated with iodine gas is used as a charge-generating substance and coated on a conductive substrate together with or separately from a charge-transfer substance to form a photosensitive layer. Sensitivity can be increased without affecting the wavelength absorption range of the photoreceptor.

〔Example〕

The present invention will be further explained below with reference to Examples.

An aluminum plate with a diameter of 0.2 m x 260 m x 80 mm was used as a substrate, and this was immersed in a methanol solution of polyamide resin (solid content: 7%), and then dried in an oven at 60°C for about 30 minutes. The thickness of the dried resin binding layer was 1.0 g/m.

Meanwhile, 0.22 g of polyvinyl butyral was completely dissolved in 10 g of cyclohexanone solvent, and 0.22 g
After adding copper phthalocyanine (manufactured by BASF, trade name: Halogen Blue L 6700), the mixture was polished for 1 hour using a pulverizer (manufactured by Macron Research Associated Limited) to obtain a suspension.

The above substrate is yL! , immersed in the suspension and dried in an oven at 60° C. for about 30 minutes. The thickness of the dried charge generation layer was 0.3 g/m.

Next, the substrate was treated with iodine for 15 minutes at 35° C. in a closed container into which a predetermined amount of iodine gas was constantly introduced. The iodine uptake of the treated substrate is approximately 7.5X10-
It was 3g/i.

The substrate was then cooled to room temperature. The cooled substrate was immersed in the charge transfer layer composition described below and then dried in an oven at 90° C. for about 60 minutes. The thickness of the dried charge transport layer was 16jnn. The components of the charge transfer layer composition used are shown below.

Toluene 330g The sensitivity of the photoreceptor obtained above was measured using a photoconductivity tester EPA-8100 (manufactured by Kawaguchi Denki, Japan). The measured light energy demand is 5.4 lux・sec when the light source is a halogen lamp, and 0.11 u when a light source filtered with a 780 mm filter glass is used.
x-sec・Charcoal 1 Same as Example 1, 0.2 m x 260 mm x 8 (
A Bm aluminum plate was used as a substrate, immersed in a methanol solution of polyamide resin (solid content 7%), and dried in an oven at 60° C. for about 30 minutes. The thickness of the dried resin binding layer was 1.0 g/m.

Meanwhile, 0.22g of polyvinyl butyral was completely dissolved in IOg of cyclohexanone solvent, and 0.22g of
After adding copper phthalocyanine (manufactured by BASF, trade name: Halogen Blue L 6700), the mixture was ground for 1 hour using a pulverizer (manufactured by Ma Nokron Research Associates Sodorimisoted) to obtain a suspension.

The substrate was immersed in the suspension and dried in a 60°C oven for about 30 minutes. The thickness of the dried charge generation layer was 0.3 g/m.

Next, in a closed container filled with saturated iodine vapor, 2
The substrate was iodine treated for 60 minutes at 7.5°C. The iodine uptake of the treated substrate was approximately 1 x 10-'' g/m.

The substrate was then cooled to room temperature. Example 1 of the cooled substrate
After being immersed in the same charge transfer layer composition as above, it was dried in an oven at 90° C. for about 60 minutes. The thickness of the dried charge transport layer was 161M.

The sensitivity of the photoreceptor obtained above was measured by photoconductivity test@EPA-8100 (manufactured by Kawaguchi Electric, Japan).

The measured light energy demand is 4.51 ux-sec when the light source is a full spectrum light source, which is 780 n+
When the light source of a was used, it was 0.11 ux-sec.

Comparison ■ Photoreceptors were prepared in the same manner as in Examples I and 2. However, no iodine treatment was performed here.

According to EPA-8100, the produced photoreceptor is
The photosensitivity was measured. The measured light energy demand is 12. when the light source is a full spectrum light source. Olux・se
c, and when the light source is 780 mm, it is 0.31 ux-
sec, which were both much higher than those of Examples 1 and 2.

An aluminum cylinder with a diameter of 30 mm and a length of 260 mm was used as a base, which was immersed in a methanolic solution of polyamide resin (solid content 7%) and dried in an oven at 60 °C for about 30 minutes. . The thickness of the dried resin binding layer is 1.
It was 0g/g.

Meanwhile, 6 g of polyvinyl butyral was completely dissolved in 200 g of cyclohexanone solvent, and 6 g of copper phthalocyanine (manufactured by BASF, trade name Halogen Blue L 67) was completely dissolved in 200 g of cyclohexanone solvent.
After adding 00) and 200 g of butanone, the mixture was dispersed for 72 hours using a ball mill to form a suspension.

The substrate was immersed in the suspension and dried in a 60°C oven for about 30 minutes. The thickness of the dried charge generation layer was 0.3 g/n.

Next, in a closed container filled with saturated iodine vapor, 2
The substrates were iodine treated for 30 minutes at 5°C.

The substrate was then cooled to room temperature. Example 1 of the cooled substrate
After being immersed in a charge transfer layer composition similar to the above, it was dried in an oven at 90°C for about 60 minutes. The thickness of the dried charge transport layer was 201 m.

The photoconductor created above is actually printed on a laser printer (
Canon LBP-81T), and a clear copy image was obtained.

A photoreceptor was prepared in the same manner as Example 3. However, no iodine treatment was performed here.

The prepared photoreceptor was actually used in a laser printer (Canon LBP-8JI), and a vague copy image was obtained.

〔Effect of the invention〕

According to the above Examples and Comparative Examples, the present invention has a method of forming a photosensitive layer by coating a conductive substrate with a charge-generating substance and a charge-transmitting substance made of copper phthalocyanine treated with iodine gas. The sensitivity of the photoreceptor can be greatly improved without affecting the image quality.

From now on, F sect E.

Claims (1)

[Scope of Claims] 1. An organic photoreceptor in which a conductive substrate is coated with a charge-generating material and a charge-transmitting material made of copper phthalocyanine treated with iodine gas as a photosensitive layer. 2. After coating a conductive substrate with copper phthalocyanine, this copper phthalocyanine layer is treated so that the value of the amount of iodine to the amount of copper phthalocyanine is from 0.01 to 1.0, and then the copper phthalocyanine layer is coated on the copper phthalocyanine layer. Copper phthalocyanine photoreceptor coated with electron hole transport material. 3. A binding layer forming step in which an aluminum material is coated with a polyamide resin solution as a substrate and then dried, and the binding layer is formed using a suspension obtained by dispersing ε-copper phthalocyanine in a polyvinyl butyral resin solution. A charge generation layer formation step in which the charge generation layer is coated on the binding layer formed in the formation step and then dried; and a charge generation layer formed in the charge generation layer formation step in an iodine gas atmosphere at a temperature range of 20° C. to 90°C. an iodine treatment step in which the charge generation layer is maintained for 1 to 120 minutes; and a hydrazone compound, a pyrazoline compound, an oxazole compound, a thiazole compound, a triallylmethane compound, and a mixture of two or more thereof. A method for producing a copper phthalocyanine photoreceptor, which comprises a step of forming a charge transport layer in which an electron hole transport material is dispersed in a binder and coated on the charge generation layer treated in the iodine treatment step.