JPS5995548A - Manufacture of electrostatic printing plate - Google Patents

Abstract

PURPOSE:To manufacture efficiently an electrostatic printing plate with high sensitivity by using a specified photosensitive body and by applying a system for writing information inputted as electric signals with semiconductor laser. CONSTITUTION:A photoconductive layer 2 contg. powdered zinc oxide (A) and a phthalocyanine pigment (B) such as epsilon-form copper phthalocyanine dispersed in a binding resin (C) such as polyester resin is formed on an electrically conductive support 1 to form a photosensitive body 3. The amount of the component B to be dispersed is about 20-60wt% of the amount of the component A. The body 3 is electrostatically charged and exposed to semiconductor laser light 4 modulated with electric signals. The resulting electrostatic latent image is developed with an electrically conductive toner 5 and fixed to manufacture an electrostatic printing plate 8 consisting of electrically conductive parts 6 and insulating parts 7.

Description

[Detailed Description of the Invention] The present invention is directed to small pieces of about 100 to 1,000 parts.
This invention relates to a method for producing an electrostatic printing plate suitable for obtaining printed matter, and particularly relates to a method for producing an electrostatic printing plate using an electric signal.

In other words, is the purpose of the present invention to obtain hexagonal information using electrical signals? An object of the present invention is to provide a method for producing an electrostatic printing plate by which the electrostatic printing plate is made by deep inscription using a semiconductor laser, and reproduction of about 100 to 1,000 copies can be easily achieved in good quality by the electrostatic printing method.

Recently, with the rationalization of office work, 1 Japanese word processing sensors have become popular. In conventional typewriters, each character is printed one by one for each type of minus character, but in word glossosaurs, the typed characters are not printed immediately, but are recorded in an electrical storage device (memory) and It is easy to make corrections and additions to the letters displayed on the fluoroun tube.In addition, the cylinder with the letters E1 word processor uses inkjet type, heat-sensitive recording method, wire 1-node type, and Rayleigh. There is an electrophotographic method that uses a laser.The electrophotographic method that uses a semiconductor laser is becoming popular.

The semiconductor laser has a continuous operation optical output of several meters to l.
It is relatively small at only a few tens of mW, or is ultra-small compared to other solid-state lasers or cass lasers, and has high efficiency, low voltage, and low power consumption.The drive current allows for high-speed direct modulation exceeding IGIIz, and it can be used for Ic, etc. Good compatibility with peripheral semiconductor circuits (
This is because it has many advantages, such as the high reliability inherent in semiconductors and the possibility of reducing costs through mass production.

Therefore, currently, as a semiconductor laser, A stone G a A
s laser (visible light and short wavelength laser) and I n G
Although aAsP lasers (long wavelength lasers) have been put into practical use, A-gGaAs lasers are used for optical information processing, and visible light lasers with a wavelength of 076 to 08 μm are used for optical information processing.
Either a short wavelength laser of 6 to 0.88 μm is used.

However, in laser printers that use semiconductor lasers, the output of the semiconductor laser is similar to that of other gas lasers (Arb l-
Copying speed cannot be increased because the photoreceptor currently in use has lower sensitivity than a semiconductor laser.

The present invention aims to eliminate the above-mentioned drawbacks, and particularly relates to improvements in the photoreceptor used. That is, the present invention writes information directly onto a photoreceptor using a semiconductor laser, uses the photoreceptor as an electrostatic printing plate, performs high-speed electrostatic printing, and meets the need for large-scale duplication.

Currently, as conventional optical semiconductors sensitive to semiconductor lasers, Cd5-Cu, 5e-T
e/Se, amorphous s1. There are phthalocyanine photoreceptors, but considering that they are disposable as electrostatic printing plates, materials other than phthalocyanine are toxic and are unsuitable from the viewpoint of material cost. Therefore, as a photoreceptor suitable for use in the present invention, a phthalonanine photoreceptor is preferable, but since the surface of the photosensitive layer of this photoreceptor is very smooth, toner fixing properties are extremely poor, and When an image is formed with electroconductive toner and fixed,
In the electrostatic printing process, the toner peels off, which has the disadvantage that it cannot be used as an electrostatic printing plate.

Therefore, the inventors of the present invention sought to improve the toner fixing properties of this photoreceptor (as a result of intensive research, they discovered that the improvement could be achieved by matting the surface of the photoreceptor. Therefore, the phthalocyanine pigment - Various fillers (fillcr) were placed in a resin-based photoreceptor and the toner fixability was tested.The fillers used in the tests included titanium oxide, calcium carbonate, cadmium carbonate, hismagnesium oxide, and zinc oxide. As a result, the inventors confirmed that fillers other than zinc oxide cause a significant decrease in photosensitivity compared to phthalocyanine pigment-resin photoreceptors. The present invention was completed by selecting a photoreceptor made of a highly sensitive phthalocyanine pigment, zinc oxide as a filler, and a resin.In other words, the present invention is a photoreceptor consisting of a conductive material, a support material, and a conductive material. A photoconductive layer on which a phthalocyanine pigment and/or zinc oxide are dispersed in a binder resin is used, the photoreceptor is charged, and a latent image is formed by semiconductor laser light modulated by an electrical signal. This is a method for producing an electrostatic printing plate, which comprises developing and fixing the latent image using a conductive toner.

Hereinafter, the present invention will be explained in detail with reference to the drawings.

As shown in FIG. 1, a charging device is placed on a photoreceptor (3) comprising a conductive support (1) and a photoconductive layer (2) in which a phthalocyanine pigment and zinc oxide are dispersed in a binder resin. After being charged by corona irradiation or the like, it is exposed to semiconductor laser light (ll) modulated by an electric signal as shown in FIG. 2 to form an electrostatic latent image. The electroconductive toner (5) is used for reversal development or normal development as shown in FIG. 4, and is fixed as shown in FIG. : An electrostatic printing plate (8) consisting of:

Here, the conductive support used in the present invention is made of aluminum, brass, stainless steel, metal plate or sheet, plastic sheet on which aluminum, palladium, metal oxide, etc. are vacuum-deposited, Plastic plates, paper etc. treated with electrical conductivity, metal oxide plates, etc. can be used.

In addition, the zero phthalocyanine pigment used in the present invention has
Type metal-free phthalocyanine, ε-type copper phthalocyanine, α-type copper phthalocyanine, β-type copper phthalocyanine, α-type metal-free phthalocyanine, β-type meckle-free phthalocyanine, vanadyl phthalocyanine, etc.

Also, zinc oxide as a filler is the one commonly used for electrophotography in powder form.

You can use either. It should be noted that the mixing ratio of the phthalocyanine pigment and zinc oxide was good when the phthalocyanine pigment/zinc oxide = 20 to 60 wt%.In other words, when the phthalocyanine pigment was less than 20 wt%, the sensitivity to semiconductor laser was insufficient; If it exceeds 60 wt%, the fixing properties of the conductive toner will be poor.

On the other hand, the binder resin used in the present invention includes polyester resin, polystyrene, polyvinyl chloride, polyvinyl acetate, vinyl chloride-vinyl acetate copolymer, polyvinyl acecool, alkyd resin, acrylic resin, polyacrylonitrile,
Polycarbonate, polyamide, polyketone, polyacrylamide.

Known materials such as thermoplastic resins such as butyral resins, thermosetting resins such as polyurethane, epoxy resins, and phenolic resins can be used. Also, the solvent! Z Sea C
Aromatic hydrocarbons such as benzene, toluene, chlorobenzene, and acetone.

Ketones such as methyl ethyl ketone and cyclohexanone,
Alcohols such as methanol, ethanol, and isopropanol, esters such as ethyl acetate and methyl cellosolve, halogenated hydrocarbons such as carbon, chloroform, and citalolmethane, ethers such as tetrahydrofuran and dioxane, and esters such as ethyl acetate and methyl cellosolve. Formamide, dimethyl sulfoxide, etc. are used.

In addition, there are various methods of manufacturing the photoreceptor used in the present invention. For example, a phthalocyanine pigment, a binder, a binder, and a solvent are dispersed in a ball mill for 10 hours, and then zinc oxide is dispersed in a ball mill for 10 hours. There is a method of adding powder, dispersing for another 6 hours, and applying the obtained photosensitizer to a conductive support.Dispersion methods include the above-mentioned ball mill, paint conditioner, ultrasonic dispersion, etc. Application methods include applicator, spray coater, and bar coater.

There are methods using a dip coater, a doctor blade, etc.

Further, as the conductive toner, there are liquid toner and powder toner, and the liquid toner will be explained first.

The conductive liquid toner is a conductive toner dispersed in an electrically insulating carrier liquid having a boiling point of IOOO to 200'C. The toner is composed of a conductive agent, a fixing agent, a charge control agent, and the like. Isoparaffinic solvents having a boiling point of 120 to 20[deg.] C. are often used as carrier liquids for conductive liquid toners.

For positively charging conductive liquid toner, conductive carbon black or the like can be used as a conductive agent, and carbon black treated with a 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, higher argyle esters and various vinyl monomer tonocopolymers, and antistatic agents include fatty acids and Metal salts such as nantenic acid, higher fatty acids, acid inhibitors, etc. are used. Negatively charged conductive liquid 1.
As a conductive agent, furnace-based carbon black,
There are kraft carbon blacks containing vinylpyrrolidone and the like. Fixing agents include cyclized comb, acrylic resins, phenolic hydroxyl a with high electronegativity, acrylic resins copolymerized with heptamers having sulfone groups and ester sulfate groups, and charge control agents such as lecithin and oil. Soluble sulfonates and the like are used.

Powder conductive toners include copper, iron, aluminum, copper, zinc, black iron oxide, copper oxide, copper iodide, copper chloride, silver monoxide, cobalt oxide, indium oxide, carpumpsic, etc. Conductive powder and a suitable resin that exhibits adhesive properties under the application of heat or pressure, such as styrene resin, epoxy resin, vinyl chloride resin, vinyl butyral resin, acrylic resin, waxes, etc., can be used. - Ingredients of conductive toners are generally well known. -Component Conductive toners include conductive non-magnetic toners and conductive magnetic toners. As a developing method for conductive non-magnetic toner,
7-491 and Japanese Patent Publication No. 37-492, there is a development method [well known for touchdown] which is a method in which conductive developer particles are uniformly coated on the surface of a sleeve having a conductive surface. This is a development delay method in which the sleeve is brought into contact with the electrostatic charge image. The toner is made of powdered metal, graphite,
It is said that particles composed of carbon black and thermoplastic resin with a particle size of 20 μm or less are desirable. Furthermore, as a developing method using conductive magnetic toner, there is a magneto-dry developing method proposed in Japanese Patent Laid-Open No. 49-4552. This is a method in which electroconductive magnetic toner is coated uniformly on the toner and developed by bringing the electroconductive magnetic toner into contact with the static iL particles. The toner is composed of thermoplastic material (1), raw resin (2), magnetic material (2), and electrically conductive fine particles, and the particle size is 1 to 50 μm, preferably 5 to 50 μm.
30 knots, and its conductivity is 108ΩC7rL~1
02b is good. Also, for example, paraffin wax,
When using a single-component conductive magnetic toner made of ethylene-vinyl acetate copolymer and black iron oxide (magnetite), it is generally pressure-fixed by passing it between steel polishing rolls at a pressure of 20 to 50 Kq/Cm. Furthermore, for example, the inner wall is a colloidal substance and the outer wall is a double wall σ from a mixed system of a hydrophobic water resin and a dye.
It is also possible to use a conductive magnetic micro toner that contains a magnetic liquid or semi-solid inside and has a volume resistivity of less than 100Ω, 1Q10Ω, and 10Ω.

Next, examples of preliminary experiments conducted to arrive at the present invention will be shown to further explain the principle of the present invention.

(Preliminary experiment 1) ε-type copper phthalocyanine (Eeol) manufactured by Toyo Ink Manufacturing Co., Ltd.
'c) 4.5 g- and Shinjyen's Silicon Klt211 made by Gakusha and Aron 3io made by Touya Gosei Kagaku Co., Ltd.
o'+ is the solid content 411. 67 g of toluene was added to the mixture at a ratio of 9:1 to 181. After dispersing in a hall mill for 10 hours, zinc oxide SAZEX, 200 o manufactured by Sakai Shigakusha was added to 159. In addition, the mixed solution dispersed in a vtC6++ near ball mill was applied to a thickness of 12 μm on a polyester film (Metal Me, manufactured by Toshisha Co., Ltd.) on which aluminum was vapor-deposited. Dry at 50°C for 8 hours and
(: u 1.' c/ Z n Q =0.5 (w
I paid 4 yen for the photoreceptor.

Next, a commercially available electrostatic copying paper tester (manufactured by Kawaguchi Electric Co., Ltd. 5P4) was used.
2B), perform a corona discharge of +l (V to positively charge it, then use the W lamp at 2856° belonging to 5P428 in combination with Toshiba's 7Yapkanoto filter and interference filter. The sensitivity at 800 nm was found to be 52 μJ'/cr.

Next, +50V was applied to the aluminum base side of this photoreceptor, and it was placed in a liquid toner developer manufactured by Company A for 60 seconds for bias development, left to dry at room temperature, and its surface resistance was measured by Kukeda Buken Co., Ltd. Lectronota manufactured by 'J) T(, 300C
Power supply for insulation resistance measurement, T It 42 Super High 41 (measured with a combination of resistance measurement sample box).

16XIQ"Ω. Similarly, -50~r was applied to the aluminum base side of this photoreceptor, and it was placed in a conductive liquid toner developer manufactured by Company B for 50 seconds for bias development, and then left at room temperature. The surface resistance was measured in the same manner and found to be 1.5×10 7 Ω.

Next, a negative corona discharge (-6K V
) is shown in Figure 7 (al f
b) Shown in jcl. In the figure, the vertical axis is the surface potential (X
A.

The 4J+¥ axis shows the charging time (V), the horizontal axis shows the charging time (minutes), and (a) shows the above-mentioned ', 'CuPc/Zn (C-0,
3 (wt) photoreceptor.

In (I)), liquid l/ner manufactured by Company A was deposited on the photoreceptor lid of photoreceptor (a), and its surface resistance was 1.6
1013Ω photoreceptor, (c) is a lY & photoreceptor whose surface resistance is 1.5×10′Ω by depositing 15 electrolyte liquid toner manufactured by Company B on the photoreceptor layer of photoreceptor (21). This shows the results.

In addition, measurements were performed using a commercially available electrostatic copying paper testing device (Kawaguchi Denki Fu'j).
C, 1) S P 712 s) was carried out using the Taiminota method.

From I) and (c) in the figure, if an image f34 is formed on the photoreceptor with ε (IJPc/ZnO = 0.5 (w t )) using conductive liquid toner, the image area (part of the conductive liquid toner) It will be easily understood that the non-image area has a significantly different acceptance potential under negative corona discharge and can be used as an electrostatic printing plate.

(Ji# Experiment 2) β1M copper lid cyanine (βCu
Pc) 107 and Silicon 1.1 manufactured by Shin-Etsu Chemical Co., Ltd.
215fVc, which is a mixture of 211 and Aron 31001 manufactured by Toagosei Kagaku Co., Ltd. in a solid content weight ratio of 921,
After complete processing and dispersion in a ball mill for 〇 hours, zinc oxide 5AZEX2o manufactured by Sakai Chemical Co., Ltd.
The mixture was further dispersed in a ball mill for 6 hours, and the mixture was coated with a percoater to a thickness of 12μ on an aluminum-deposited polyester film (Metal Me, manufactured by Toshisha Co., Ltd.), and heated at SO℃. After drying for 8 hours, a photoreceptor with βCu P c /Z n○=0.5 (wt) was obtained.

Next, a commercially available electrostatic copying paper tester (Riji Kawa [S
P428), perform a corona discharge of -1-6J (V to positively charge it, then attach Toshiba's Sharp Cut 1 filter and interference filter to the 2856° W run that comes with 5P428. Sensitivity at 800 nm was determined using a combination of

It was 45 μJ/c.

Next, add +1o to the aluminum base side of this photoreceptor.

V was applied, placed in a liquid toner developer manufactured by Company A for 5 degrees for bias development, left to dry at room temperature, and its surface resistance was measured using an electrometer manufactured by Tagada Buken, T H, 3-hole C insulation resistance. Combine measurement power supply and i''R42 ultra-high resistance measurement sample box to measure
Similarly, a voltage of 1100 V was applied to the aluminum base side of this photoreceptor, and bias development was performed by placing it in a conductive liquid toner developer manufactured by Company 13 for 60 seconds, and then it was left at room temperature. After drying, the surface resistance was measured in the same manner and found to be 7.7 x 10 Ω.

Next, a positive corona discharge (+6 K-
Figure 8 shows the charging characteristics when V ) is applied continuously.
(1)L Shown in (c). In the figure, the vertical axis shows the surface potential (~0°; the horizontal axis shows the charging time (minutes); b) The photoconductive layer of the photoreceptor in (a) was prepared using a liquid toner manufactured by Company A.

The photoreceptor has a surface resistance of 56 x 1013 Ω, and (C) is a conductive l-ner made by Company B on the photoconductive layer of the photoreceptor in (a), whose surface resistance is 7.7 x 105 Ω. This shows the results for the photoreceptor. In addition, the measurement was carried out using a commercially available electrostatic copying paper testing device (SI 42B manufactured by Kodenki Co., Ltd.).
) using a dynamic method. same figure fa)
and (c), βCu P c
/ When an image is formed on a photoreceptor of 0.5 (wt) Z n O2, one image area (part of the conductive liquid toner) and the non-image area have significantly different response potentials under positive corona charging, and static The words available as a printed version will be easily understood.

Next, examples of the present invention will be described below.

[Example 1] Canon ■ semiconductor laser beam printer 1.13
P10 was modified, the photosensitive drum was replaced with an aluminum drum, and only the glass charger, exposure device, and developing device were functional. A photoconductor of 3 (wt) was grounded and attached to an aluminum drum.For the developing device, the same 13 (wt) photoreceptor used in preliminary experiment 1 was used.
Add conductive liquid toner manufactured by the company. Next, an electric signal is input to operate the machine, and the steps of charging, exposing an image area using a semiconductor laser, and reversing development using a conductive liquid toner are completed. Next, the developed photoreceptor was removed from the aluminum drum and dried with 61M air to produce an electrostatic printing plate with conductive image areas.

A negative corona radiation of 1 u (6K ■) was uniformly applied to this static printing plate.1. Toyo Ink Manufacturing Co., Ltd.'s Negative Quiptoner Irrio Fax N-1 and 1" Iron Powder M
Reversal development was carried out using a magnetic push method using a developer made of Carrier E I"
The toner is electrostatically transferred onto a sheet of paper, and the printed matter is heated and fixed.
j.

[Example 2] βCu used in preliminary experiment 2 was used in a machine similar to Example 1.
Pc/ZnO-: 0.5 (wt)
Glue and ground the photoreceptor to the aluminum drum and raise the chair. The conductive liquid l/ner manufactured by Company 13, which was also used in Preliminary Experiment 2, was placed in the developing device. Next, an electric signal is input to operate the machine, and the steps of charging, image exposure using a semiconductor laser, and positive development using conductive liquid toner are completed. Next, the developed photoreceptor was removed from the aluminum drum and dried with warm air to produce an electrostatic printing plate with conductive non-image areas.

A positive corona discharge (+6 KV) is applied to this electrostatic printing plate.
Apply it uniformly and use Negative Type Toner D manufactured by Tomoe Paper Manufacturing Co., Ltd.
N--io and carrier E F ■15 made by Nippon Tetsuko Hayashi Co., Ltd.
Positive development was performed using a magnetic brush method using a developer consisting of 0/250, and a sheet of paper was placed on the paper and a positive corona discharge (-) of -6K was applied to the paper.
V) was applied, and Totsuichi was electrostatically transferred onto paper and fixed by heating to obtain a printed matter.

[Example 3] Using the same machine and photoreceptor as in Example 1, operate the machine, charge, and expose the non-image area with a semiconductor laser s2D
By positive development with electrolytic liquid toner.

An electrostatic printing plate is produced whose image areas are electrically conductive.

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

[Example 4] Using the same machine as in Example 1 and the same photoreceptor as in Example 2, the machine was operated, and by charging, exposing the non-image area with a semiconductor laser, and reversing development with a conductive liquid toner,
An electrostatic printing plate is produced in which the non-image areas are electrically conductive.

Using this electrostatic printing plate, a printed matter was obtained by electrostatic printing using the same method and materials as in Example 2.

[Brief explanation of drawings]

[The drawings show one embodiment of the present invention; FIG. 1 is an explanatory diagram showing a state in which a phthalocyanine pigment/zinc oxide photoreceptor is charged by corona irradiation, and FIG. Explanatory diagram showing a state in which an image is formed, No. 6
The figure is an explanatory diagram showing a photoconductor that has been reversely developed with conductive toner, Figure 4 is an explanatory diagram showing a photoconductor that has been developed with conductive toner, and Figures 5 and 6 are Explanatory diagrams showing the fixed photoreceptor, Figures 7 and 8g8 are diagrams showing the continuous charging characteristics of a phthalocyanine pigment/zinc oxide photoreceptor and when liquid toner is placed on the photoreceptor. This shows the relationship between potential and continuous charging time. [1,1... Conductive support (2)... Photoconductive layer
(3)...Phthalocyanine pigment/zinc oxide-photoreceptor
(・1)...Semiconductor V-The Light (51...Conductive toner (G)...Conductive part (7)...Insulating part (8)...Electrostatic printing plate patent publication IPJ 1 person letterpress stamp 11” Co., Ltd.

Claims (1)

[Claims] As the photoreceptor, a photoconductive layer in which a phthalocyanine pigment and zinc oxide are dispersed in a binder resin is provided on a conductive support, and the photoreceptor is charged and a semiconductor laser modulated by an electric signal is used. By light? A method for producing an electrostatic printing plate, which comprises forming a h-image, developing and fixing the latent image using a conductive toner.