JPS59116751A - Printing plate for electrostatic printing - Google Patents

Abstract

PURPOSE:To improve fixability by disposing a photoconductive layer formed by dispersing phthalocyanine and zinc oxide in a binder resin to form a photosensitive body, and developing the electrostatic latent image formed on the photosensitive body with a conductive toner. CONSTITUTION:A photoconductive layer 2 formed by dispersing a mixture composed of epsilon type copper phthalocyanine (A) and phthalocyanine deriv. (B) as well as zinc oxide in a binder is disposed on a conductive base 1, whereby a photosensitive body 3 is obtd. The body 3 is electrostatically charged by corona irradiation, etc. and is thereafter exposed by laser light 4 modulated by an electrical signal to form an electrostatic latent image thereof. Said latent image is subjected to reversal development or positive development by a conductive toner 5, and is fixed, whereby an electrostatic printing plate 8 consisting of a conductive part 6 and an insulating part 7 and having high sensitivity is formed. The mixing ratio by weight of the epsilon type copper phthalocyanine (A) and the phthalocyanne deriv. (B) is preferably 100/0.1-60. The mixing ratio of the phthalocyanine mixture and zinc oxide is preferably 20-60wt%. A resin such as melamine resin or the like having an insulating characteristic of >=10OMEGAcm specific volume resistivity is used as the binder resin.

Description

DETAILED DESCRIPTION OF THE INVENTION It relates to a printing plate for electrostatic printing, suitable for obtaining printed matter, and includes a semiconductor laser, which is unprecedented in the art, with a specific phthalocyanine mixture and zinc oxide dispersed in a binder resin. The present invention relates to a printing plate for electrostatic printing that is manufactured using a photoreceptor that has sufficient sensitivity to light.

That is, one of the objects of the present invention is to create a printing plate for electrostatic printing by writing information inputted by an electric signal using a semiconductor laser beam, and to write information inputted by an electric signal using a semiconductor laser beam, and to write information inputted by an electric signal using a semiconductor laser beam.
It is an object of the present invention to provide a printing plate for electrostatic printing that can easily achieve high quality reproduction of about 1,000 copies.

Recently, with the streamlining of office work, Japanese word processing sensors have become popular. Conventional typewriters print each character one by one, but with word processing sensors, the typed character stripes are recorded in an electrical storage device (memory) without being printed immediately. In addition, since the image is only displayed on the cathode ray tube, corrections and additions can be made easily. In addition, Japanese word processing sensors use inkjet type, thermal recording method,
There are wire tod methods and electrophotographic methods that use lasers. Among electrophotographic methods using lasers, those using semiconductor lasers are becoming popular.

The reason is that the light output power of semiconductor lasers in continuous operation ranges from several mW to several +771. Although it is relatively small (w), compared to other solid-state lasers and gas lasers, it is ultra-small, has high efficiency, low voltage, and low power consumption, and can perform high-speed direct modulation exceeding 1GH7° with a single shaft current. This is because they have many advantages, such as good compatibility with peripheral semiconductor circuits such as ICs, high reliability inherent to semiconductors, and the possibility of reducing costs through mass production.

Therefore, currently, as a semi-integrated laser, Al e a A
s laser (visible light and short wavelength laser) and In0aAs
Although P lasers (long wavelength lasers) have been put into practical use, A, 5GaAs lasers are used for optical information processing, and visible light lasers with a wavelength of 076 to 08 μm have a wavelength of 083 to 088 μm.
Either a short wavelength laser of μm is used.

However, in laser printers using semi-integrated lasers, the output of the semiconductor laser is higher than that of other gas lasers (Ar = He).
-Ne, He-Cd, etc.), and the sensitivity of currently used photoreceptors is low relative to semiconductor lasers, making it impossible to increase the copy speed by 1.

The present invention aims to eliminate the above-mentioned drawbacks, and particularly relates to improvements in the photoreceptor used. That is, in the present invention, information is written directly onto the photoreceptor using semiconductor laser light.

The photoreceptor is used as an electrostatic printing plate to perform high-speed electrostatic printing and meet the needs for large-scale duplication.

Here, currently, as conventional optical semiconductors sensitive to semiconductor laser light, Cd, S-Cu, Se
- There are T e / S e, amorphous S1, phthalocyanine photoreceptor, etc., but considering that they are disposable as electrostatic printing plates, they are unsuitable from the viewpoint of toxicity and material cost. It is.

Therefore, photoreceptors suitable for use in the present invention include:
Phthalocyanine photoreceptors are preferred, but phthalocyanine pigments have a small average particle size of 0.05 μm and have poor charge retention (・
Therefore, in order to use it as a photoreceptor, it is necessary to increase the ratio of the binder resin component, and if a photoreceptor is made with phthalocyanine alone, the surface of the photosensitive layer is very smooth, so the toner fixing properties are poor. If an image is formed on this photoreceptor using conductive toner and fixed, the toner will peel off during the electrostatic printing process, making it unusable as an electrostatic printing plate. Ta.

Therefore, the present inventors investigated the fixing tendency of toner on the photoreceptor.
As a result of intensive research to find the second improvement, we discovered that the improvement could be achieved by making the surface of the photoreceptor matte.
. Therefore, various fillers (F161er) were added to a phthalocyanine pigment-resin type photoreceptor, and the toner fixability was tested. When we tested fillers such as titanium oxide, calcium carbonate, cadmium carbonate, magnesium oxide, and zinc oxide, we found that while the fixing properties were improved compared to phthalocyanine pigment-resin photoreceptors, there was a marked decrease in photosensitivity and charge retention. It was confirmed that this caused an increase in dark decay. However, in the case where zinc oxide was selected as the filler, although there was a slight decrease in photosensitivity, the charge retention and dark decay characteristics did not deteriorate significantly. In addition, the average particle size of zinc oxide is 0.3μ, which is an order of magnitude larger than that of phthalocyanine pigments, and its excellent charge retention properties make it possible to reduce the binder resin component ratio compared to when using only phthalocyanine pigments. The surface becomes matte. The matte surface has an increased surface area, which improves toner adhesion.

Next, the inventors aimed to improve photosensitivity. The present invention was then completed by improving the phthalo/anine phase of the photoreceptor, which is sensitive even to semiconductor laser light, to one with extremely high sensitivity, and adding zinc oxide as a filler.

That is, the photoreceptor and l~ are placed on a conductive acidic support with ε
Acid-pasted phthalocyanine derivatives tB) of phthalocyanines with electron-withdrawing groups or mixtures of phthalo-7-anines with electron-withdrawing groups and other phthalo/anines and oxidation Zinc is dispersed in a binder resin (a photovoltaic layer is provided).

In the present application, the above-mentioned photoreceptor is charged, and a semiconductor laser beam or the like is used to charge it.
This is a printing plate for electrostatic printing, which is formed by exposing to light to form a latent r-image, and then developing the a1-image using conductive toner and fixing it.

In the following, a detailed description of the present invention will be given. As shown in FIG. After a photoreceptor (3) comprising a photoconductive layer (2) in which zinc oxide is dispersed in a binder and a resin is charged by corona irradiation with a charging device, an electric signal is generated as shown in Fig. 2. A static a1 image is formed by exposure with semiconductor laser light (4) modulated by , and reverse development is performed with conductive toner (5) as shown in FIG. 4. , normal (as shown in Fig. 5) is fixed as shown in Fig. 6, and an electrostatic printing plate (8) consisting of a conductive part (6) and an insulating part (7) is produced.

In the present invention, ε-type steel phthalocyanine (A When the line diffraction angle is measured 1-, the strongest line corresponds to the interplanar spacing of 9728, the nodal line is at 1163A, 624, 5.13
4 ro 5, 4 1 9, 5 8 7
, Roro 6.628, and 303A have no weaknesses. It is known from Japanese Patent Publication No. 52-1667 that this ε-type steel phthalo/anine (A) exhibits excellent effects as a light guide element for electrophotographic plates.

In E.5 of the present invention, the above-mentioned ε-type copper phthalonanine (
A) is characterized by the use of a photoreceptor in which the core anine derivative CB+ is mixed and zinc oxide is further added to the lid. Due to the presence of the phthalocyanine derivative CDI having an electron-withdrawing group, it was possible to further improve electrophotographic properties such as photosensitivity.

Here, the phthalocyanine having an electron-withdrawing group includes a diI-lo group, /ano group, halogen atom-sulfone group, carboxyl group, sulfamide group, carboxamide group on the benzene nucleus in the molecule of metal-free or various metal phthalocyanines. Substituted with an electron-withdrawing group such as This phthalonanine derivative is produced by using phthalonitrile, phthalic acid, phthalic anhydride as raw materials for phthalocyanine, and phthalonitrile, phthalic acid, phthalic anhydride, and phthalimide substituted with the above substituents as phthalimide during phthalocyanine synthesis.・It can be obtained by using some of them together. The method for producing the phthalo-77ine derivative is not particularly limited. Further, the number of substituents in one molecule of the phthalocyanine derivative is 1 to 16.

The above-mentioned phthalonanine having an electron-withdrawing group is optionally subjected to an anod-pasting treatment together with another phthalocyanine having one or no electron-withdrawing groups to obtain a phthalocyanine derivative (B). By the way, acid pasting treatment is to treat phthalonanine or phthalocyanine having two electron-withdrawing groups with sulfuric acid, orthosulfuric acid, pyrophosphoric acid, chlorosulfonic acid, hydrochloric acid, hydroiodic acid, hydrofluoric acid, or odor. This is a treatment method in which a salt is formed with an inorganic acid such as hydrohydric acid, and the phthalocyanine derivative is poured into water as known in the organic pigment industry, and the precipitated phthalocyanine derivative is filtered, washed with water, and dried. Get 1.

ε type steel phthalocyanine (A+ and phthalocyanine derivative t
The mixing weight ratio with B) is 1oo10. o1 to ioo, preferably 1oO101 to 60, and the total number of phthalocyanine units mixed with carbon is -00
0.01 or more, preferably 0.01 or more and 2 or less.

The photoreceptor used in this application is prepared by uniformly dispersing the above phthalo/anine mixture together with a binder resin, a solvent, etc. using a cross-dispersion machine such as a Bo)+, mill, or A) lighter, and then adding zinc oxide powder. , uniformly dispersed using a similar crosstalk dispersion machine,
A photoconductive layer is formed by coating ffi on a conductive support.

Note that it is also effective to provide a barrier layer between the conductive support and the photoconductive layer.

In addition, zinc oxide can be used as a filler, or any powder commonly used for electrophotography can be used.

The mixing ratio of the phthalocyanine mixture and zinc oxide is such that the photosensitivity to the phthalocyanine mixture/zinc oxide of 20 to 60 wt% is insufficient, and on the other hand, if it exceeds 60 wt%, the fixing properties of the conductive toner deteriorate.

Of course, the above matters are greatly influenced by the amount of binder resin added. The binder resin ratio is phthalo-7-anine mixture/binder resin -25 to
Good results were obtained when the content was 50 wt%.

Examples of binder resins include melamine resins, epoxy resins, silicone resins, polyurethane resins, polyester resins, acrylic resins, xylene resins, vinyl chloride-vinyl acetate copolymer resins, polycarbonate resins, and cellulose derivatives with a volume resistivity of io. A known material with insulation properties of Ω or higher is used.

In addition, as a solvent, benzene, toluene, xylene,
Aromatic hydrocarbons such as chlorobenzene, ketones such as acetone, methyl ethyl ketone, and cyclohexanone, alcohols such as methanol, ethanol, and isopropanol, esters such as ethyl acetate and methyl cellosolve, and carbon halides such as carbon tetrachloride, chloroform, and dichloromethane. Hydrogen, tetrahydrofuran, ethers such as dioxane, and dimethylformamide, dimethyl sulfoxide, etc. are used.

Conductive supports include aluminum, brass, copper,
Metal plates such as stainless steel or metal sheets, plates on which aluminum, palladium, metal oxides, etc. are vacuum-deposited on plates, plastinoch plates, conductive treated paper, and metal oxide plates can be used. .

The coating method is to adjust the viscosity by adding a solvent if necessary, and then form a film using an air knife coater, blade coater, rod coater, +) hearth roll coater, spray coulter, hot coater, or squeeze coater. Let's do it.

After application, drying is performed using a suitable drying device.

Furthermore, there are two types of conductive toner: liquid toner and powder toner.
- A conductive toner is dispersed in an electrically insulating carrier liquid with a boiling point of 100 to 200°C. The toner is composed of a conductive agent, a fixing agent, a charge control agent, etc. As a carrier liquid for a conductive liquid toner, an imparaffinic solvent having a boiling point of 120 to 2000 C is often used.

For positively charging conductive liquid toner, conductive carbon black or the like can be used as a conductive agent, but carbon black treated with nigrosine dye is also used to stabilize charge polarity. Fixing agents include alkyd resins, cyclized rubber, natural resins soluble in aliphatic hydrocarbons, asphalt, acrylic resins, copolymers of higher alkyl esters of methacrylic acid and various vinyl monomers, and charge control agents. For this purpose, fatty acids and metal salts such as naphthenic acid, higher fatty acids, antioxidants, etc. are used. Examples of the conductive agent for the negatively charged conductive liquid toner include furnace carbon black and grafted carbon black containing vinylpyrrolidone.

Fixing agents include cyclized rubber, acrylic resins, and acrylic resins copolymerized with monomers having highly electronegative phenolic hydroxyl groups, sulfone groups, and ester sulfate groups.Charge control agents include lecithin and oil-soluble sulfonates. etc. are used.

Powdered conductive toners include conductive powders such as copper, iron, aluminum, silver, zinc, black iron oxide, silver oxide, iodized steel, chloride steel, silver oxide, cobalt oxide, indium oxide, and carbon black. Body and styrene resin, epoxy resin,
Although suitable resins such as vinyl chloride resins, vinyl butyral resins, acrylic resins, waxes, etc. which exhibit adhesive properties under the application of heat or pressure can be used, -component conductive toners are generally known. -Component Conductive toner includes conductive non-magnetic toner and conductive magnetic toner.

The first phenomenon method for conductive non-magnetic toner was published in 1983.
There is a touchdown method proposed in Japanese Patent Publication No. 491 and Japanese Patent Publication No. 67-492, in which the surface of three 7 having a conductive surface is uniformly coated with conductive developer particles. In this method, the sleeve is brought into contact with an electrostatic charge image to produce an effect. The toner is made of powdered metal, graphite,
It is said that a particle size of 20 μm or less consisting of carbon blank and thermoplastic resin is desirable. Furthermore, as a developing method using conductive magnetic toner, there is a magneto-dry phenomenon method proposed in Japanese Patent Laid-Open No. 49-4532, in which conductive magnetic toner is placed on a magnetic sleeve having a grounded conductive surface. This is a method in which electrostatic charges are generated by uniformly magnetically coating the conductive magnetic toner and bringing the electrostatic charge into contact with the toner. The toner is composed of a thermoplastic resin, a magnetic material, and conductive fine particles, and the particle size is 1 to 50 μm, preferably 5 to 30 μm, and the conductivity is preferably 108 (1 cm to 102 Ω). , for example, paraffin wax, ethylene-
When using a one-component conductive magnetic toner such as vinyl acetate copolymer and black iron oxide (magnetite), generally 20~
30, it can be pressure-fixed by passing between the steel polished o-ru with the pressure of P/CTL.

Further, for example, the inner wall is a double wall made of a colloidal material and the outer wall is made of a mixed system of a hydrophobic resin and a pigment or dye, and the outer wall contains a magnetic liquid or semi-solid inside, and the outer wall has a volume resistivity of about 1010 Ω or less. Conductive magnetic microcapsule toners having the following properties can also be used.

Above, we have mainly described the use of semiconductor laser light as a total optical method for photoconductors, but the photoconductor used in the present invention has a far greater photosensitivity to semiconductor laser light than conventional products. The biggest feature is that it is high, but it is also 400 to 70. It also has excellent photosensitivity to Onm visible light, and can be sufficiently applied using conventional general exposure methods and light sources.

The present invention will be explained below by giving examples. In the examples, "parts" indicate parts by weight.

(Preliminary Experiment) 40 parts of copper phthalocyanine and 05 parts of tetranitrocopper phthalocyanine were dissolved in 500 parts of 98% concentrated sulfuric acid with thorough stirring. The dissolved solution was poured into 5,000 parts of water to precipitate a composition of copper phthalocyanine and tetranitrocopper phthalocyanine, which was then washed with water and dried at 120° C. under reduced pressure. The composition [I] thus obtained was treated with ε-type copper phthalocyanine (LionolBlue ER) manufactured by Toyo Ink Manufacturing Co., Ltd.
Mix 100 parts to 100 parts, add 5oon of methanol
Part cH'tc was dispersed to obtain a uniformly mixed dispersion liquid. after that,
The mixture was passed through the mouth and dried at 120° C. under reduced pressure to obtain a mixture CII).

Next, 5 parts of the above mixture [■], 25 parts of acrylic polyol (Takelac UA-702, manufactured by Takeda Pharmaceutical Co., Ltd.), 2 parts of Epoquin resin (Epicoat +1007, manufactured by Shell Chemical Co., Ltd.), 26 parts of methyl ethyl ketone, and 2 parts of Cellsolve Acetate were added.
After 6 parts were kneaded in a porcelain ball mill for 48 hours, 16 parts of zinc oxide 5AZEX2000 manufactured by Sakai Chemical Co., Ltd. was added and kneaded for another 10 hours in a porcelain ball mill, and the coating liquid was mixed using a bar coater. Then, 13
The photoreceptor was coated to a thickness of μ and dried at 130° C. for 3 portions to obtain a photoreceptor.

Next, a commercially available electrostatic copying paper tester (manufactured by Kawaguchi Electric Co., Ltd. 5P4) was used.
28), after performing corona discharge of 4-6 kV to positively charge it (maximum surface potential -1-570■), 5P
Using the 2856° W lamp attached to the 428 in combination with Toshiba's sharp cut filter and interference filter, the sensitivity at 800 nm was determined to be 2° and 1 μJ/ffl. Furthermore, when exposed with only a W lamp without a filter at an illuminance of 10 Luxυ), the sensitivity was 3 Lux·sec.

Next, 150V was applied to the aluminum base side of the photoreceptor, and the photoreceptor was placed in EG Tevero tube (positive polarity conductive liquid toner) manufactured by Minolta Business Machine Sales Co., Ltd. for 60 seconds to create a bias voltage.
The surface resistance was measured using a Takeda Riken electrometer TR30QC power supply for insulation resistance measurement and a TR42 ultra-high resistance measurement sample box, which was 1.4 x 10'Ω. there were.

Next, even if negative corona discharge (±6 kV) is continuously applied to the photoreceptor that has undergone this bias phenomenon, its surface potential increases only by about +20 to +30 and -20 to -3 parts, respectively. Ta.

From the above experimental results, it is clear that conductive liquid toner allows A′lI
It is easy to understand that if an image is formed on the photoreceptor described above, the image area (a portion of the conductive liquid toner) and the non-rectangular area have greatly different acceptance potentials under corona discharge, and can be used as an electrostatic printing plate. Good morning.

(Comparative Example 1) ε type steel phthalocyanine (εCu,
Pc) 4.5 g and 7 Recon resin (manufactured by Shin-Etsu Chemical Co., Ltd., R21t) and acrylic resin (Aron 81001, manufactured by Toagosei Chemical Co., Ltd.) in solid weight ratio? = 1 mixed with 18.9, toluene 67.9 and dispersed in a ball mill for 10 hours, and then photoconductive zinc oxide (SAZ EX 200 D manufactured by Sakai Chemical Co., Ltd.) f/Additionally, mixed Mz dispersed in a ball mill for 6 hours, polynisdel film (Metalumi manufactured by Toshisha Co., Ltd.) u-, Ki2μ, which was vapor-deposited with aluminum Ramura using a bar coater.
εCu,
A photoreceptor with P c /Z n O = 0.5 (W t ) was obtained.

Next, a commercially available electrostatic copying paper tester (manufactured by Kawaguchi Electric Co., Ltd. 5P4) was used.
28) was charged positively by corona discharge at -1-6 kV at ℃, then 285, which belongs to 5P428, was charged.
Using a W lamp at 6° in combination with Toshiba's 7-year filter and interference filter, the 800nm
The sensitivity was found to be 52 μJ/d.

(Comparative Example 2) β-type copper phthalocyanine (βC11
, 'P c ) 10 g, 215 g of a mixture of silicone resin (KR211 manufactured by Shin-Etsu Chemical Co., Ltd.) and acrylic resin (Aron S1004 manufactured by Toagosei Chemical Co., Ltd.) at a solid weight ratio of 9:1, and 76 g of l.ruene. After dispersing in a hole mill for 10 hours, 10 g of photoconductive zinc oxide (5AZEX 2000 manufactured by Sakai Chemical Co., Ltd.) was added, and the ball mill solution was further applied for 6 hours using a bar coater to form a polyester film on which aluminum was vapor-deposited. (Metal Me manufactured by Toshisha)” - 1
Coated to a thickness of 2μ, dried at 50°C for 8 hours, and βC
A photoreceptor with u P c /7+ no=(1.5 (wt)) was obtained.

Next, a commercially available electrostatic copying paper test and testing device (SP manufactured by Kawaguchi Electric Co., Ltd.
42B), perform a +6 kV corona discharge to positively charge it, and then apply it to SP428.
Using a W lamp at 6° in combination with Toshiba's sharp cut filter and interference filter, 8 DO
The sensitivity at n rn was found to be 45μ=r/'c
It was r&.

(Example 1) Semiconductor laser beam printer LBP manufactured by Canon
-10 was modified, the photoconductor tram was replaced with an aluminum drum, and the photoconductor used in the preliminary experiment was replaced with an aluminum tram & I grounded it and pasted it. The same positive polarity conductive liquid toner used in the preliminary experiment and the first experiment was placed in the developing device.

Next, an electric signal was input to operate the machine, and the steps of charging, exposure of one quadrant of the image using semiconductor laser light, and reversal development using conductive liquid toner were completed. Next, the imaged photoreceptor was removed from the aluminum tram, dried with warm air, and a conductive electrostatic mark was uniformly applied to the image area (~, negative type 1-ner Liof manufactured by Toyo Ink Mfg. Co., Ltd.). A developer consisting of 'ax N-1 and Carrier EF 150/250 manufactured by Nippon Tetsuko Co., Ltd. was developed using a magnetic brush method, paper was placed on the paper, and a positive corona discharge (+6 kV) was applied to the paper. give,
The toner was electrostatically transferred onto paper and fixed by heating to obtain a printed matter.

(Example 2) Corona discharge (+61 (■
) to form an electrostatic latent iron on the photoreceptor by projecting a positive film original image in reverse one image for 15 seconds at 10 Lux using a ioow tungsten light source for enlargement, and then forming a one-component conductive film with the following composition. A visible image was obtained with magnetic toner.

The average particle size was 15 microns, and the pressed powder had a resistance of about io 5 ohms.

This -component conductive magnetic toner adhered to the electrostatic a11 portion. Next, heating was applied to melt and fix the -component conductive magnetic toner. This was used as a printing plate for electrostatic printing.

Using this printing plate for electrostatic printing, a printed matter was obtained by electrostatic printing using the same method and materials as in Example 1.

(Example 6) 40 parts of metal-free phthalocyanine and 15 parts of mononitro flfll phthalonanine were dissolved in 98 i o o o parts of sulfuric acid with thorough stirring. Pour the dissolved liquid into 1ooooo of water.
After pouring the phthalocyanine composition into
It was filtered, washed with water, and dried at 120°C under reduced pressure.

Composition [11] thus obtained and ε-type copper phthalocyanine (Liono, d Blue ER) 100
100 parts to 100 parts, and dispersed in 5,000 parts of 71 tanoyl to obtain a uniformly mixed dispersion liquid. Thereafter, it was passed through the mouth and dried under reduced pressure at 12[]'C to obtain a mixture [11].

Next, add 46 parts of the above mixture [l(]) and lincon resin (
K R211 (manufactured by Shin-Etsu Chemical Co., Ltd.) and acrylic resin (Aron 51oo1, manufactured by Toagosei Chemical Co., Ltd.) at a weight ratio of 9 for one cylinder.
After adding 674 parts of toluene to 18 parts of a mixture of 1 and 1 and dispersing it in a magnetic ball mill, photoconductive zinc oxide (Sakai Ishigakusha SAZEX 2 [1 0 0
) was added and the mixture was further dispersed for 10 hours.
Using a coulter, apply aluminum-deposited polyester film (Metal Me, manufactured by Toshisha Co., Ltd.) to a thickness of 14 μm on 1., dry at 130”C for 3 sections, and then process the photosensitive layer. Ushita.

Using this photoreceptor, a printing plate for electrostatic printing was manufactured in the same manner as in Example 1 and by the same method as in Example 1.

(Example 4) 40 parts of copper phthalocyanine and 05 parts of tetracyanoco/(lutophthalocyanine were dispersed in 200 parts of ice vinegar,
10 parts of 98% sulfuric acid was added dropwise while stirring, and after stirring for 10 hours, the solid matter was separated, and ammonia gas was passed through it to precipitate the lid r+'/anine-based composition, which was then washed with water and heated for 120 minutes under reduced pressure. It was dried at C.

The composition [Ill] thus obtained was mixed according to my own recipe.

The magnetic properties of a composition such as (2)
After kneading at room temperature for 4 days, 15 parts of photoconductive zinc oxide (SAZ I Ba A mixture of 2 parts of Tesmodule +q-7s) was added using a no-coater to form a polyester resin film (Metal Me, manufactured by Ton Co., Ltd.) on which aluminum was vapor-deposited. ” Second, apply it to a thickness of 12μ,
A photoreceptor was obtained by placing it in an oven uniformly heated to 12 D'C for 30 minutes.

Next, in a machine similar to that of Example 1, the above-mentioned autophotoreceptor was attached to an aluminum drum with a ground connection.

The current test device was filled with the conductive liquid toner of positive electrode No. 1 used in the preliminary experiment.

Next, a drowsiness signal was input to turn off the machine, and the process of charging, image formation using semiconductor laser light (exposure, and positive development using conductive liquid toner) was performed. Take the developed Jt 1-layer photoreceptor from the drum and remove it from the drum.
Warm) Dry with lice 1 to conductive static electricity in non-image area [1] Report 1
We were able to produce 51 copies of IEp for J.

This printing plate for electrostatic printing has the old corona direction (+61 (■
) was uniformly applied, positive development was performed using the negative type toner and carrier used in Example 1 using a magnetic comb method, a piece of paper was placed, and a positive corona discharge was applied to the paper. (+6 kV), electrostatically transfers the toner onto the paper, heats it and fixes it, creating a printed matter.

(Example 5) Trinitrocopper phthalocyanine 50 units 98% concentrated sulfuric acid 6
The mixture was dissolved in 1.00 parts with sufficient stirring. The dissolved solution was poured into 6000 parts of water to precipitate a composition of α-type 1.1 nonitro@fil phthalocyanine, which was then filtered, washed with water, and dried at 120'C under reduced pressure. 100 parts of the composition thus obtained and 100 parts of ε-type copper phthalocyanine were dispersed in 5000 parts of methanol to form a uniform dispersion. Thereafter, it was passed through the mouth and dried at 120° C. under reduced pressure to obtain a mixture CIV].

3 parts of the above mixture [1v], 18 parts of acrylic resin (Arotap 41=3211 manufactured by Nippon Shokubai Chemical Co., Ltd.), 34.4 parts of methyl ethyl ketone, 17.2 parts of n-butyl alcohol, and 17.2 parts of Cellsolve Acetate. After 30 hours of dispersion using a ball mill manufactured by B,
Photoconductive zinc oxide (5AZEχ2ooo manufactured by Sakai Chemical Co., Ltd.)
Added 102 parts of the mixture and dispersed it for another 10 hours. Using a harcoater, the mixture was coated with 13μ of carbon paper (thickness: 173μ) coated with casein as a water-soluble resin.
The photoreceptor was coated to a thickness of 7 parts and dried at 7°C for 8 hours to obtain a photoreceptor.

Next, the above photoreceptor was attached to the same machine as in Example 1. The positive conductive liquid toner used in the preliminary experiment was placed in the developing device. Next, a printing plate for electrostatic printing in which the image area is electrically conductive was produced by using a machine to produce a regular image using light and electrically conductive liquid toner.

(Example 6) Tetranitrocopper phthalocyanine was prepared in the same manner as in Example 5, and a mixture [v] was prepared.

3 parts of the above mixture [V], 15 parts of acrylic resin (Arotap +3211 manufactured by Nippon Shokubai Chemical Co., Ltd.), 65 parts of methyl ethyl ketone, 184 parts of n-butyl alcohol, and 1-18.4 parts of Celnorb acetate were added in a porcelain ball mill. After dispersing for 30 hours, 10.2 parts of photoconductive zinc oxide (5AZEX2000 manufactured by Sakai Chemical Co., Ltd.) was added, and the mixture was dispersed for another 10 hours using a bar coater.
Coated to a thickness of 15μ on carbon paper (thickness 170μ) coated with casein as a water-soluble resin, and heated at 70°C.
The photoreceptor was dried for 8 hours to obtain a photoreceptor.

Next, the photoreceptor was attached to a machine similar to that in Example 1, and the positive polarity conductive liquid l/ner used was placed in the υ phenomenon device. Next, the machine was operated, and a printing plate for electrostatic printing in which the non-orthogonal area was conductive was manufactured by charging, exposing the non-image area to semiconductor laser light, and reversing development with conductive liquid toner.

When comparing the photoreceptors of Comparative Examples 1 and 2 and Examples 1 to B,
A remarkable difference was observed in terms of photosensitivity, and the results are shown in Table 1. The samples were measured using an electrostatic copying paper tester (
After applying a +6 kV corona discharge at a charging speed of 1 on/min using Kawaguchi Electric Co., Ltd.'s 5P42B), 10 seconds later, a W lamp at 2856° was combined with Toshiba's Nyapukanoto filter and interference filter. and use 4
Photosensitivity was determined by applying a light energy of μW/CIIt and measuring the time until the surface potential was halved.

Table 1 Spectral sensitivity characteristics (μJ/crit)

[Brief explanation of the drawing]

The drawings show one embodiment of the present invention. Fig. 1 is an explanatory diagram showing a state in which a photoreceptor is charged by corona irradiation, and Fig. 2 is an explanatory diagram showing a state in which a photoreceptor is charged by corona irradiation, and Fig. 2 is an explanatory diagram showing a state in which a photoreceptor is charged by corona irradiation. FIG. 3 is an explanatory diagram showing the photoconductor that has been reversely developed with conductive toner, FIG. 4 is an explanatory diagram that shows the photoconductor that has been normally developed with conductive toner, and FIGS.
The figure is an explanatory view showing a fixed photoreceptor. il+... Conductive support (2) Mountain photoconductive layer (3)
... Photoreceptor (4) ... Semiconductor - The light (
5) Conductive toner (6) Conductive portion (7
)... Insulating portion (8)... Printing plate patent applicant for electrostatic printing Toppan Printing Co., Ltd. (and one other person)

Claims (1)

[Claims] (1) As a photoreceptor, acid pasting treatment of ε-type copper phthalocyanine (A), phthalocyanine having an electron-withdrawing group, or a mixture of phthalocyanine having an electron-withdrawing group and other phthalocyanines is applied to a conductive support. Using a photoconductive layer in which a mixture of the phthalocyanine derivative (B) and zinc oxide are dispersed in a binder resin, the photoreceptor is charged and exposed to form an electrostatic latent image; The electrostatic latent phenomenon is visualized using conductive toner,
A printing plate for electrostatic printing that is fixed. (2. A printing plate for electrostatic printing, characterized in that semiconductor laser light modulated by an electric signal is used for exposure as described in claim 11.1.