DE3943094C2 - Electrophotographic imaging process - Google Patents

Description

The present invention relates to an improved electrophoretic image forming method which provides steadily, stably and repeatedly high-quality full-color images which excel in resolution and sound reproduction. More particularly, the invention relates to an improved electrophotographic imaging process comprising (i) an amorphous silicon electrophotographic recording element having a photoconductive layer, a charge image bearing layer and a developed image support layer, and (ii) a fine particle isolation toner has a bulk average fineness of 4.5 to 9 μm and an apparent viscosity of 1 x 10 ⁴ to 2 x 10 ⁵ dPa · s at 100 ° C, where it is possible to continuously and repeatedly draw full-color graphic or pictorial images of High quality with high speed to produce, which are excellent in their resolution and sound reproduction.

Electrophotographic recording elements of an amorphous Si have already been used silicon system, hereinafter referred to as "amorphous silicon recording Element "are provided in quite a number beat. They were considered for electrophotographic recording suitable for use not only in electrophotographic copiers, the work at high speed, but also in lasers jet printers, since they have a high surface hardness aufwei sen, highly sensitive to long wave light, such as egg a semiconductor laser beam (770 nm-800 nm), and Hardly be affected even if they are for a lan period are used repeatedly.

FIG. 3 shows a schematic cross section of a typical structure of such an amorphous silicon recording element comprising an electrically conductive support 301 made of a suitable material such as aluminum, and a photoconductive layer consisting of a charge injection blocking layer 302 which is capable of To prevent injection of a charge from the side of the carrier 301 , a photoconductive layer (photoresist layer) 303 , which has a photoconductivity, and a surface protection layer 304 is made.

In DE-A 36 00 419, moreover, between the photoconductive Layer and the surface protection layer provided an intermediate layer, the by forming an optical energy gap serves that the accumulate generated charges in the underlying photoconductive layer.

The image formation using this light receiver is carried out, for example, as follows by means of a geeigne th electrophotographic copying machine, which is shown in Fig. 4, executed.

This Fig. 4 schematically shows an illustration of the structure of a conventional electrophotographic copying machine. According to Fig. 4 are close to a cylindrical recording element (a copying drum) 401 or having the ge in Fig. 3 showed structure and rotates in the direction giving by an arrow NEN direction, a main corona charger 402, a Me mechanism 403 for Generation of a charge image, a developing device 404 , a Bildzufufeblatt or Trans ferblatt supply device 405 , a transfer charger 406 (a), a separation charger 406 (b), a Reinigungsvorrich device 407 , a transfer sheet transport device 408 and a charge removal lamp 409 arranged.

The copying drum 401 is held at a predetermined temperature by a heater 423 . The copying drum 401 is uniformly charged by the main corona charger 402 to which a predetermined voltage is impressed. Then, resting on a contact lens 411 template 412 with light from the light source 410 , example, a halogen lamp or a fluorescent tube, irradiated through the contact glass 411 therethrough. The resulting reflected light is projected by mirrors 413 , 414 and 415 , a lens system 417 including a filter 418 , and a mirror 416 onto the surface of the copier drum 401 to form one of the original 412 of the charge image.

This charge image is developed by a toner supplied from the developing device 404 to form a toner image. By the transfer sheet feeding device 405 comprising a transfer sheet guide 419 and a pair of tact feed rollers 422 , a transfer sheet or paper P is supplied so that this sheet P is in contact with the surface of the recording receiver 401 is brought. A corona discharge having the polarity different from that of the toner is caused from the back side of the transfer sheet P by the transfer charger 406 (a) to which a predetermined voltage is applied to apply the toner image to the transfer sheet P. transfer. The transfer sheet P, the transferred toner image having electrostatically from the cylindrical recording member 401, that AC voltage is impressed from the copier drum through which charge-clearing effect of the separation corona charger 406 (b) to which a vorbe true, removed, and then through the transfer sheet conveying device 408 of the Fixing device 420 supplied. The residual toner on the upper surface of the copying drum 401 is removed by a cleaning blade 421 at its arrive on the cleaning device 407, and the removed toner is discharged by means of an excess toner removal device (conveying screw) 424th Thereafter, the copying drum 401 thus cleaned is wholly exposed to light by the discharge eliminating lamp 409 to extinguish the remaining charge, whereupon it is recirculated.

The electrophotographic recording element i. the copying drum, those in the above picture production process has the advantages mentioned above: For example, it shows a high sensitivity to long-wave light (Sensitive peak near 680 nm and sensitivity range of 400 to 800 nm), and it is satisfactory in practice lend, since in fact acceptable pictures without the Be gliding phenomenon of a jitter line picture or a washed-out or veiled line image re can be produced as long as usual documents be copied. However, she is not sufficiently satisfied pointing to recently raised demands with regard to the production of high-quality images, the one printed, obtained by a printing press Image are equivalent to fulfill.  

In other words, that if it is attempted a template, the superfine lines of 100 / μm width or darun contains, by the above-mentioned images generating method, wherein such a recording element of a amorphous silicon system as described above is used to reproduce, often unwanted fet te or thick lines or unwanted washed-out lines occur on the resulting copied lines. the same If an attempt is made, a template that com Plicated Chinese characters (in Japanese KANZI) with a size of 2 mm or below by the top of it thought to reproduce imaging methods that resul often dubbed copied Chinese characters have line or blurred line images, the can not be distinguished without difficulty.

Therefore, it is generally recognized that the aforesaid image Production method in which a copying drum of a amorphous silicon system is used, not for egg ne reproduction of such templates as mentioned above for example for catalogs or manuals from Items for sale, etc., is suitable, and that at all because of the insufficient resolution.

The mentioned problem is apparently caused when the imaging process under a high humidity environment is accomplished. To this problem too A procedure was proposed according to which the Light receiver (the copying drum) of the amorphous silicon is heated. However, it is still difficult desired copied pictures from such templates too get the superfine lines or complex chinesi include characters.  

Further, in recent years, full-color copies have become common of catalogs or manuals of sales items, etc. used, and there is an increased Need or an increased need for a wide improvement in the durability of a recording element, as an organic photosensitive element, a electrophotographic recording element of a selenium or selenium-tellurium System used in a full color electrophotographic Copier is to use. To fulfill this requirement len, the proposal was made instead of such Recording elements a recording element of an amor Phen silicon system (amorphous silicon recording element) to use.

In the conventional full-color graphic image forming Furthermore, the pictorial full-color images are processed using a cyan toner (C), magenta toner (M) and yellow toner (Y) and, if necessary, a black toner (B), wherein the toner on an image receiving sheet or transfer sheet ge melted and mixed, whereupon fixing connects to the full-color graphic pictures deliver. For these color toners, resins are used in one low temperature dissolve or dissolve and completely within a narrow temperature range ge can be melted used. These resins are used in the hereinafter referred to as "fast melt resins".

On the other hand, in the conventional image forming apparatus driving using an amorphous silicon recording element, the image forming process is executed during this recording element at a high temperature of 40 to 50 ° C gehal will be. Because of this, problems often arise when the aforementioned color toner in these image forming methods be used that these toners not only in the development  Mechanism but also in the cleaning mechanism ge become molten, blocking these mechanisms and as a result it becomes impossible to graph full to get color pictures.  

About in an electrophotographic image forming method usable toner is none in the prior art clear picture. For example, EP-A 02 75 636 describes the Using a two-component color toner with a Mean fineness of 11.0 to 14.0 μm and an apparent Viscosity at 100 ° C of 5 · 10⁴ to 5 · 10⁶ dPa · s. The GB-A 21 14 310 proposes the use of a toner, which a mean particle size in the volume title substantially from 6 to 10 microns, with a majority of the particles in the Number average a distribution in the range of 5 to 8 microns have.

The object of the invention is an electrophotographic To provide imaging processes which images with super fine lines and tiny, possibly complicated High resolution characters even after multiple Copy at high speed and high quality too reproduce. The electrophotographic image forming method should also be suitable for full-color illustrations, d. H. for image forming processes using toner with different colors are used.

The object is achieved by an electrophotographic An image forming method according to claim 1 or claim 5.  

The invention will with reference to the drawings he purifies. Show it:

Figs. 1 (A) and 1 (B) are respectively schematic diagrams showing the typical layer structure of a representative amorphous silicon recording element used in the invention;

Fig. 2 (a) and 2 (b) are respectively schematic diagrams showing the structure of an electrophotographic copying system, which is suitable for implementing the inven tion proper imaging method in the Pra xis;

Fig. 3 is a schematic representation of the layer structure of a conventional electrophotographic recording element;

Fig. 4 is a schematic representation of the structure of a forth conventional electrophotographic copying system;

Fig. 5 is a schematic representation of a manufacturing device for manufacturing an amorphous silicon recording element, which comes in the invention for use;

Fig. 6 is a schematic representation of a map for the evaluation of a resolution used in later-described experiments;

Fig. 7 (a), respectively curves Zvi rule the interrelationships of the volume means fineness of the toner Parti angle and the resolutions obtained in the later be written Example 1 and Comparative Example 1 represent;

Fig. 7 (b) shows curves respectively showing the relationships between the volume average fineness of toner particles and the sound reproducibility obtained in Example 1 and Comparative Example 1 described later;

Fig. 8 shows graphs each showing the interrelationships between the apparent viscosities of a toner and sound as obtained in the later-described Example 2 and Comparative Example 2;

Figures 9 are graphs, each of which solutions the interaction between the apparent viscosities of a toner and the background, which were obtained in the later-described game At 3 and Comparative Example 3,.;

FIG. 10 shows graphs each showing the correlations between the apparent viscosities of a toner and the uneven image densities obtained in Example 4 and Comparative Example 4.

The inventors have extensive studies through experiments performed to the above mentioned disadvantages, which in the known image forming process occur to eliminate and achieve the objects of the invention. When Result was found that if a specific Amorphous silicon recording element and a specific fine Particle Isolation Toners are used together Objectives of the invention can be effectively achieved. in the special was the invention based on the Er results of the experiments still to be explained as complete completed confirmed.

The electrophotographic image forming method according to The invention makes it possible, stable, steady and again gets copied full-color graphic images from high High speed quality under any order conditions to be created in relation to resolution and sound reproduction are excellent.  

The reason why these excellent effects are due to the combined use of a special amorphous silicon Light receiving layer and a special fast melting the fine particle isolation toner is induced ultimately not very clear. It may, however, be the result sen of the experiments described below are recognized, that's probably due to the interaction of the following Factors is due to the fact that the amorphous silicon record element with the charge image bearing layer under the developed Charge image bearing layer is provided, is effective and powerful a desired latent image without ne gative influences due to changes in the environmental condition go back, made; because the latent image through the developed charge image bearing layer using the specifi fast-melting fine particle isolation toner ent is wound, a Coulomb force effectively acts between the latent image and the specific fast melting fine particle isolation toner; and the amorphous silicon Recording element is not heated by a heater deliberately heated, as in the case of the conventional graphic full-color image generation process happens.

In the following the invention in its details he purifies.

Light receiving element (copying drum)

Figs. 1 (A) and 1 (B) are respectively schematic cross sections illustrating the layer structure of the recording element to be used in the invention.

Fig. 1 (A) shows a layered structure of the recording element used in the invention which includes a support 101 made of an electrically conductive material such as aluminum and a layer 102 'disposed thereon. This layer 102 'comprises a charge injection barrier layer 106 formed of an amorphous material comprising silicon atoms (Si) as a matrix and hydrogen atoms (H) and / or halogen atoms (X) and atoms of a V group element (excluding N ) contains. Further, the layer 102 'comprises a photoconductive layer 103 of a-Si (H, X), a latent image carrier layer 104 of a-SiC: M (H, X) wherein M represents atoms of III. Group of the periodic table, and a developed image support layer 105 of a-SiC (H, X), which are applied in this order from the side of the carrier 101 from.

Fig. 1 (B) shows still another layer structure of the recording element used in the invention. This layer structure comprises the mentioned carrier 101 as well as a layer 102 "arranged on this carrier. The layer 102 "contains a long-wavelength light absorption layer 107 , hereinafter referred to as" IR absorption layer ", of an amorphous material containing silicon atoms (Si) as a matrix, hydrogen atoms (H) and / or halogen atoms (X). , Germanium atoms (Ge) and / or tin atoms (Sn) and, optionally, at least one kind of atoms consisting of the elements carbon, a III group element, a V group element (excluding N) and a VI group element (O only) are selected, and further optionally at least one kind of atoms selected from nitrogen atoms (N) and oxygen atoms (O), said amorphous material hereinafter referred to as "a-Si (Ge, Sn) (H, X ) (C, M ') (N, O) ", wherein M' represents atoms of a III. Group element, a V. group element (excluding N) or a VI. Group element (excluding O). Further, the layer 102 "comprises a charge-injection blocking layer 106 of a-Si as in the layer 102 ' , a photoconductive layer 103 of a-Si (H, X), a latent-image carrying layer 104 of a-SiC: M (H , X) and a developed image carrier layer 105 of a-SiC (H, X) deposited in this order from the side of the carrier 101 .

The photoconductive layer 103 is basically formed of a-Si (H, X) as described above, but it may contain at least one kind of atoms composed of the elements carbon (C), nitrogen (N), oxygen ( O), germanium (Ge), tin (Sn), a III. Group element, a V. group element (excluding N), and a VI. Group element (excluding O) are selected, if necessary.

As for the hydrogen atoms (H) and / or the halogen atoms (X) to be included in the photoconductive layer 103 , it is desirable to control the amount of hydrogen (H), the amount of halogen atoms (X), or the sum of amounts at hydrogen atoms and halogen atoms (H + X) in the range of 0.1 to 40 atomic%.

In the case where the photoconductive layer 103 contains atoms of III. Group element, the amount of atoms is desirably controlled to one corresponding to one-fifth of the amount of atoms of a III. Group element present in the latent image-bearing layer 104 is included.

The photoconductive layer 103 preferably has a thickness of 1 to 100 μm.

The latent image carrier layer 104 is basically formed of a-SiC: M (H, X), but it may contain at least one kind of atoms composed of the elements germanium (Ge), tin (Sn), nitrogen (N), and oxygen (O) V. group element (excluding N) and are selected, if necessary.

The amount of carbon atoms (C) to be incorporated in the latent image carrier layer 104 is preferably set to be in the range of 1-90 at%. As far as the atoms of a III. Group element to be incorporated in the latent image carrier layer 104 are concerned, they are desirably in the range of 1 to 5 × 10 ⁴ atomic ppm.

For the hydrogen atoms (H) and / or the halogen atoms (X) which are to be included in the latent image carrier layer 104 , the amount of hydrogen atoms (H), the amount of Ha logenatomen (X) or the sum of the amounts of hydrogen and halogen atoms (H + X) desirably range from 0.1 to 70 at%.

The latent image carrier layer 104 preferably has a thickness of 0.003 to 30 μm.

The developed image carrier layer 105 is basically formed of a-SiC (H, X), but it may contain at least one kind of atoms composed of the elements germanium (Ge), tin (Sn), a III. Group element, nitrogen (N), oxygen (O), a V. group element (excluding N) and a VI.-Gruppenele element (only O) are selected, if necessary.

The amount of carbon atoms (C) to be incorporated in the developed image-receiving layer 105 is desirably set in the range of 1 to 90 atomic%. In a most preferred embodiment in this regard, the amount of carbon atoms (C) is desirably greater than that contained in the latent image carrier layer 104 .

As far as the hydrogen atoms (H) and / or the halogen atoms (X) to be included in the developed image-receiving layer 105 are concerned, it is desirable to have the amount of hydrogen atoms (H), the amount of halogen atoms (X) or the sum the amount of hydrogen and halogen atoms (H + X) in the range of 0.1 to 70 atom% is turned. Further, in the case where the developed image carrier layer contains 105 atoms of a III. Group element, the amount of atoms is set to one-tenth the amount of the atoms of a III. Group element in the latent image carrier layer 104 is included corresponds.

As for the developed image base layer 105 , it is of special importance that these are high in view of preventing the recording element from being adversely affected by changes in environmental conditions and stably maintaining the electrophotographic characteristics or characteristics to constantly copied images To produce quality, designed for a specific resistance of 10 ¹² to 10 ¹⁶ Ω × cm. A control of the resistivity of the developed image-receiving layer 105 which is in the above range can be carried out by controlling the mixing or composition ratio of the components of this layer to a predetermined value by controlling the flow rate of the film-forming raw material in the formation of the layer ,

The charge injection blocking layer 106 preferably has a thickness of 0.03 to 15 μm.

The infrared absorption layer 107 formed of a-Si (Ge, Sn) (H, X) (C, M ') (N, O) preferably has a thickness of 0.05 to 25 μm.

In each of the above cases, the halogen atoms can (X) contain fluorine, chlorine, bromine and iodine. Under these Halogen atoms, fluorine and chlorine are particularly preferred. Likewise, the mentioned III. Group element B (boron),  Al (aluminum), Ga (gallium), In (indium) and Tl (Thallium). Among these elements are B, Al and Ga are particularly preferred. The mentioned V. groupele P (phosphorus), As (arsenic), Sb (antimony) and Bi (Bismuth). Of these elements, P and As particularly preferred. Finally, the mentioned VI.- Group element S (sulfur), Se (selenium), Te (tellurium) and Include Po (polonium). These elements become S and Se are particularly preferred.

In the following, the method for producing the recording receiving elements, which in the invention for use comes, explains.

Each of the above-mentioned layers for forming the layer 102 , 102 'or 102 "of the recording element may be suitably formed by any of the well-known vacuum evaporation methods wherein the film forming parameters are appropriately set. Specifically, special mention may be made of a hot cathode method such as an AC glow discharge PCVD method, ie, a low-frequency PCVD method, a high-frequency PCVD method, a microwave PCVD method, and a DC glow discharge PCVD method ; an ECR PCVD method; drive a reactive Ionenstrahlzerstäubungsver; a thermally induced CVD process; an ion plating method; a photo-induced CVD method. Besides these methods, the HR-CVD method (Hydrogen Radical Assisted CVD method) and the FO-CVD method (Fluoroxidation CVD method) are also mentioned.

The HR-CVD method denotes such, wherein an ak tive species (A), formed from a raw material gas, such as  Hydrogen gas, and another active species (B), the with said active species (A), which consists of a film-forming raw material gas, is reactive, introduced separately into a film forming room and the akti species (B) with the active species (A) for reaction be brought to thereby a film on a support, which is maintained at a desired temperature, down strike. The FO-CVD method refers to such after which a film-forming raw material gas and a halogen gas, which is capable of producing the film-forming raw material gas for oxy To bring dation, separated in a film education room be guided and the film-forming raw material gas with the Halogen gas is reacted to thereby a Film on a kept at a desired temperature Knock down the substrate.

These film-forming methods can be selected depending on your choice certain factors, such as the manufacturing conditions, the required investment the production scale and the light receiving element ment, which is to be produced, required property The hot cathode method, the reactive ion beam sputtering, the ion plating process, the HR CVD and the FO CVD method are suitable because the Kon control the conditions when forming the layers, have the desired properties, relatively easy are and hydrogen, halogen and other atoms without Difficulties together with silicon atoms in one never the film to be slipped can be introduced. These Film forming processes can be in an identical system be applied together.

The following is an explanation for the case, that the recording element used in the invention to apply  tion by means of a high-frequency PCVD method rens (HF-PCVD method) is produced.

For the implementation of the RF-PCVD method in practice, a suitable HF PCVD device having the structure shown in FIG. 5 can be used.

Referring to Fig. 5, gas containers 571 , 572 , 573 , 574 , 575 , 576 and 577 are charged with gaseous starting materials to form the respective layers for forming the layers 102 , 102 'or 102 "of the recording element used in the invention , In example SiH ₄ gas is in the container 571 , H ₂ gas in the container 572 , CH ₄ gas in the container 573 , PH ₃ gas which is diluted with H ₂ gas and hereinafter referred to as "PH ₃ / H ₂ gas ", in vessel 574 , B ₂ H ₆ gas diluted with H ₂ gas, hereinafter referred to as" B ₂ H ₆ / H ₂ gas ", in vessel 575 , NO. Gas in the tank 576 and Ar gas in the tank 577 .

For the respective gases manometer 561 , 562 , 563 , 564 , 565 , 566 and 567 are arranged in the wegfüh from the containers 571-577 -generating lines.

Prior to introducing these gases into a film forming chamber 501 , it is checked that the valves 551-557 for the gas tanks 571-577 and a leak or drain valve 515 closed, and the inlet valves 531-537 , the exhaust valves 541-547, and a valve HiIfsventil 518 are open. Then, first, a main valve 516 is opened to reuse the interior of the film forming chamber 501 and the interiors of the gas passages by a suction pump (not shown) to evacuate.

Upon detection that the reading on a vacuum gauge 517 has reached a predetermined vacuum level, then the auxiliary valve 518 and the exhaust valves 541-547 are closed.

In the film forming chamber 501 , a cylindrical support 505 on which a film is to be formed is mounted on a rotatable cylindrical support holder 506 provided with an electric heater 514 in its interior. Further, in the film-forming chamber 501 in the longitudinal direction of a plurality of gas supply pipes 508 arranged on, each of which is provided with a plurality of gas discharge holes 509 , which are capable of uniformly deliver a filmbil Dendes raw material gas to the cylindrical support 505 out. Each of the gas supply tubes 508 is connected through an attached to a bottom wall 503 of the film-forming chamber 501 releasable sealing means 510 with a gas supply line 511, which container is connected 571-577 to each of the gas.

The film-forming chamber 501 is formed so that its peripheral wall can serve as a cathode. Similarly, the cylindrical support holder 506 to which the cylindrical support 505 is attached is formed so as to serve as an anode. For this purpose, the peripheral wall of the film-forming chamber 501 is electrically insulated by an insulator 502 . An adapter or junction box 512 is connected to an RF power source (not shown). When the RF power source is turned on to generate RF energy, this energy is transmitted through the junction box 512 between the peripheral wall (cathode) of the film forming chamber 501 and the cylindrical support 506 carrying the cylindrical support 505 (anode). to thereby cause an RF glow discharge in the film formation chamber 501 .

Before the start of film formation, the exhaust valve 547 and the sub-valve 518 are gradually opened to introduce Ar gas into the film-forming chamber 501 through the gas discharge holes 509 of the gas supply pipes 508 . The flow rate of the Ar gas is regulated to a predetermined value by means of a mass flow controller 527 . The gas pressure (internal pressure) of the film forming chamber 501 is set to a predetermined value by controlling the suction pump and the main valve 516 while observing the measured value on the vacuum gauge 517 . Then, the zy-cylindrical support 505 starts its rotation, and it is heated and maintained at a predetermined temperature by the electric heater 514 is operated. Subsequently, by closing the exhaust valve 547 and the auxiliary valve 518, the supply of Ar gas to the film-forming chamber 501 is stopped.

Hereupon, the formation of a constituent layer of the layer 102 , 102 'or 102 "of the recording element is carried out, for example, in the following manner. One or more kinds of a raw material gas are by opening the corresponding one of the exhaust valves 541 - introduced 547 and the auxiliary valve 518 in the film forming chamber 501, the respective flow rates of the raw material gas in a desired manner by the entspre sponding the mass flow controllers 521-527 in the same manner as in the case of the Ar gas above.

The gas pressure (internal pressure) of the film-forming chamber 501 is adjusted as desired by controlling the suction pump and the main valve 516 while observing the measured value on the vacuum gauge 517 .

After all raw material gas flow rates and internal pressure have become stable, a predetermined RF energy is introduced through the junction box 512 into the film forming chamber 501 to produce an RF glow discharge, causing the cylindrical support 505 to be at a desired temperature is held, a dejected film is formed.

If the component layer with a desired thickness is formed, the exhaust valves and the Hilfsven closed til. A following, involved in the construction Layer is issued by repeating the above operations staltet. In any case, if the constituent layer is formed, the respective throughputs of the Rohma terialgase using a microcomputer od. Like. controlled so that the gas pressure in the Filmbildungskam can be stabilized to stable, steady film conditions of education.

All exhaust valves except those necessary for the formation of the respective layers are of course closed. Further, in the formation of the respective layers, the interior of the system is once evacuated to a high vacuum level as required by closing the exhaust valves 541-547 while the auxiliary valve 518 is opened and the main valve 516 is fully moved to the open position in order to avoid that gases used for the previous layer remain in the film-forming chamber 501 and also in the gas lines.

In order to form a desired layer of uniform thickness on the zy-cylindrical support 505, it is possible to displace the cylindrical support 505 during the formation of layers by rotating the substrate holder 506 by means of a (not shown) in engine revolution.

Developer (Isolation Toner)

As described above, in the present invention, a fine particle isolation toner having a volume average fineness of 4.5-9 μm and an apparent viscosity of 1 × 10 ⁴ to 2 × 10 ⁵ dPa · s at 100 ° C is used dissolved at a low temperature and can be completely melted within a narrow temperature range, that is, it uses a fine particle fast-melting isolation toner used.

This fast melting isolation toner used in the invent used, contains a suitable binder resin.

Examples of such a binder resin are: Homopolyme of styrene and its derivatives, such as polystyrene, chlorine polystyrene, poly-α-methylstyrene; Styrene copolymers, such as Styrene-chlorostyrene copolymers, styrene-propylene copolymer, Styrene-butadiene copolymer, styrene-vinyl chloride copoly merisate, styrene-vinyl acetate copolymer and styrene-maleic acid säurecopolymerisat; Styrene-acrylate copolymers, such as Styrene-methyl acrylate copolymer, styrene-ethyl acrylate copolymer, styrene-butyl acrylate copolymer, styrene Octyl acrylate copolymer and styrene-Phenylacrylatcopolyme risat; Styrene-methacrylic acid ester copolymers, such as Sty rol-Methylmethacrylatcopolymerisat, styrene-Äthylmethacry latcopolimerisat, styrene-Buylmethacrylatcopolimerisat and Styrene Phenylmethacrylatcopolimerisat; Styrene-α-methyl chloracrylate; Styrene resins, such as styrene-chloroacrylonitrile acrylatcopolimerisat; vinyl acetate; Maleic resins with Rosin modified; Phenol resins; epoxy resins; poly esterharze; Low molecular weight polyethylene resins;  Low molecular weight polypropylene resins; Silicone resins; ketone resins; Ethylene Äthylacrylatcopolymerisat; Xylene resins and Polyvinyl butyral resins and the like. Resins.

Of these polymers and resins in practice he Wanted examples of copolymers of styrene-acrylate stems and polyester resins.

Especially preferable examples of the above binder resins are polyester resins, the condensation products of a Bisphenol derivative, represented by the following structural formula is shown, or a substituted component there of, such as a diol component and a carboxyl component, which are selected from the group consisting of acids be which have two or more carboxyl groups, such as Fumar acid, maleic acid, phthalic acid, terephthalic acid, tri mellitic acid and pyromellitic acid, anhydrides of said Acids and lower alkyl esters of these acids.

(wherein R is an ethylene group or a propylene group, x and y are each an integer of 1 or above and x + y = 2 to 10 in a middle value.) The fine particle isolation toner used in the invention can be used either a magnetic or non-magnetic toner. The magnetic fine particle Isolation toner can be generated in a suitable manner by one or more necessary components and magnet powder in the aforesaid binder resin by a conven be mixed. Than magnetic powders can be mentioned, for example:  

Magnetic powder of non-oxidised iron, iron with one oxidized surface, ferrite, nickel, copper, rare earth metals, alloys of two or more of these metals or oxides of these metals.

Basically, the fine particle isolation toner, the is used in the invention, by mixing a ge Suitable dye produced in the aforementioned binder resin. As a coloring substance, a known dye and / or a known pigment can be used. As dyes are, for example, basic dyes, oil-soluble dye fe etc. usable. As a pigment, for example, diazo Yellow compounds, insoluble azo compounds, copper phthalocyanines, etc. can be used.

Besides these coloring substances, any of the above-mentioned magnetic powders capable of, as a coloring substance, of choice as well as the Dye can be used.

Specific examples of the usable dye used in the fine particle isolation toner for use in the Invention are: C.I. Solvent Red 49, C.I. Solvent Red 52, C.I. Solvent Red 109, C.I. basic Red 12, C.I. Basic Red 1 and C.I. Basic Red 36.

Specific examples of the usable, in the Feinpartikel- Isolation toner for the invention to be included Pig are: C.I. Pigment Yellow 17, C.I. Pigment Yellow 15, C.I. Pigment Yellow 13, C.I. Pigment Yellow 14, C.I. Pig ment Yellow 12, C.I. Pigment Red 5, C.I. Pigment Red 3, C.I. Pigment Red 2, C.I. Pigment Red 6, C.I. Pigment Red 7, C.I. Pigment Blue 15 and C.I. Pigment Blue 16.  

Specific examples of the copper phthalocyanine are: copper phthalocyanine-Ba salts containing two or three carboxybenzoyls methyl group substituents on the phthalocyanine nucleus sen, as represented by the following structural formula 2 is.

The fine particle Isola to be used in the invention tiontoner may contain one or more arbitrary additives, such as a charge state regulator, a lubricant Abrasive or polishing agents, a means of improvement flowability, etc. included.

In any case, the fine particle isolation toner used in the present invention is required to have a volume average unit of 4.5 to 9 μm and an apparent viscosity of 1 x 10 ⁴ to 2 x 10 ⁵ dPa · s at 100 ° C and has dissolved at low temperature and completely melted within a narrow temperature range who can. The use of this toner in conjunction with the aforementioned special recording element results in improvement in the fixing properties, high-temperature displacement property and toner mixing efficiency, so that a desired full-color graphic or pictorial image is formed.

The measurement of the apparent viscosity in the production of this fine particle isolation toner is carried out using a Flow Tester CFT-500 (a product of Shimazu Seisakusho Ltd.). That is, about 1.0-1.5 g of a test specimen obtained by sieving with a mesh size of about 0.25 mm (60 mesh) is taken out and buried under a load of 980 N / cm ² (100 kg / cm ² ) Use of a molding device presses ge, and the resulting pressed specimen is subjected to the measurement by the said flow tester at normal temperature and normal humidity under the conditions mentioned below, thereby obtaining a viscosity-related curve (continuous curve) ,

Temperature change: 6.0 (° C / 1 min) Set temperature: 70.0 ° C maximum temperature: 200.0 ° C Interval: 3.0 ° C preheating: 300.0 s Burden: 197 Nm (20.0 kgf) Shape (diameter): 1.0 mm Shape (length): 1.0 mm Piston: 1.0 cm²

An apparent viscosity at 100 ° C will be from the steady course ve obtained and as viscosity of the sample for the Temperature viewed.

In order to obtain an apparent viscosity of 1 × 10 ⁴ to 2 × 10 ⁵ dPa · s for the fine particle insulating toner, the aforementioned binder resin and various additives are appropriately selected and mixed as required, while the above measurement of the apparent Viscosity aiming at the above-mentioned range of apparent viscosity and based on the results, the kind of the binder resin and the kinds of the various additives to be used as required, and the mixing ratio thereof is determined.

The fine particle insulation to be used in the invention Toner can be conveniently removed by a conventional toner be produced with a suitable Mixture from which the fine particle ionizing toner is obtained is processed, and the mixture of a grinding granulation is subjected. The above mentioned mixture can also be found in a suitable manner by a conventional method For example, a method wherein components be dispersed in a binder resin solution and the resulting liquid is spray-dried, or a process wherein an emulsion, the monomers, the are capable of forming a binder resin, and erforder contains certain components, first produced, the Emul subjected to polymerization and the result in Spray process is dried. In addition to these procedures can the fine particle insulation to be used in the invention toner are also produced by a process where in toner microcapsules, each one core and one Covering material comprises, produced, dried by spraying net and then classified.

The following are examples of the production of the fine given particle isolation toner.

The following examples are for illustrative purposes only and in no way limit the scope of the invention.  

Unless otherwise indicated, parts and% indicate each Parts by weight and wt .-%.

Example 1 for toner production

Polyester resin obtained by a condensation polymerization a bisphenol derivative, the diol substituent and fumaric acid contains, was received,

as the binder resin 100 parts Magnetite powder (as the coloring matter and also as the magnetic powder) 60 parts Nigrosine (as the charge state regulator) 2 parts Polypropylene (as the lubricant) 3 parts

The above ingredients were in a Henschel mixer mixed thoroughly to get a mixture.

The mixture was melted at 180 ° C by means of a roller mill kneaded. The kneaded product was cooled by means of a Hammer mill to a particle size of about 1-2 mm coarse crushed, then to a particle size of about 40 microns or including by means of a micro mill, in which an air jet stream was used, finely pulverized and using of a MIKROPLEX 400 MP classifier (a product of ALPINE Co., Ltd.), the device being adjusted was that particles with a particle exceeding 9 microns size were separated. The first classification by this Classified fine particles obtained were again analyzed under Ver use of a MICROPLEX 132 MP classifier (a product from ALPINE Co., Ltd.), the device being so was set that particles with a size below 4.5 microns were separated, whereby toner fine particles with a Volume average fineness of 4.5 to 9 microns were obtained.  

The test result of the apparent viscosity at 100 ° C of the toner fine particles formed by the above method of measuring the apparent viscosity showed that they had such as 3 × 10 ⁴ dPa · s.

Example 2 for toner production

There were prepared four kinds of fine particle color toners having a volume average resolution of 4.5 to 9 μm and an apparent viscosity at 100 ° C of 1 x 10 ⁴ to 2 x 10 ⁵ dPa · s in the manner described below As the binder resin, 100 parts of polyester resin obtained by a condensation polymerization of a propoxy-bisphenol derivative and fumaric acid were used. As the other ingredients, the respective coloring substances and charging state control agents were used in the respective amounts shown in the attached Table 1.

In each case, the binder resin became the coloring substance and the state of charge control thoroughly in a Henschel Mixer mixed to obtain a mixture by means of a three-roll mill was twice melt-kneaded. The Kneaded product was cooled by means of a hammer mill roughly crushed to a particle size of 1 to 2 mm, then to particle sizes of about 40 microns or below fine means a Feinstmühle using a jet air stream pulverized and by means of a MICROPLEX 400 MP classifier (a product of ALPINE Co., Ltd.) classified, wherein the System was set so that particles with a size above 9 microns were separated. The by the mentioned first class were obtained using a MIKROPLEX 132 MP classifier (a product of ALPINE Co., Ltd), with this system being set up again was that separated particles with a size less than 4.5 microns were used, producing toner fine particles with a volume means purity of 4.5 to 9 microns were obtained.  

To 100 parts of the toner fine particles thus obtained were added 0.5 part of fine powdery silica treated with hexamethyldisilazane to thereby obtain color toner fine particles. In this way, four kinds of color toners were obtained. Then, as the flowability improving agent, a ferrite carrier of Cu-Zn-Fe system (particle size: 58 μm, 250 mesh (about 0.058 mm) passage and 350 mesh (about 0.04 mm) holding at 85 wt% and true density of 4.5 g / cm ³ ) coated with about 5% of a mixture consisting of vinylidene fluoride / tetrafluoroethylene copolymer (copolymerization ratio of 8: 2) and styrene / 2-ethylhexyl acrylate-methyl methacrylate copolymer (copolymerization ratio of 45: 20: 35 ) in a quantitative ratio of 50: 50 is generated.

To 8-12 parts of each of the above four color Toner was the above-mentioned improver for the Flowability in an amount added that the total amount was 100 parts, and the product was mixed thoroughly, to thereby obtain a developer.

In this way, four types of developers were obtained.

Example 3 for toner production

100 parts of a styrene-acrylic resin as the binder resin, 3 parts of CI Pigment Red 5 as the coloring substance and 3.5 parts of a Cr-salicylate complex as the charge state control agent were thoroughly mixed, whereupon this mixture was introduced into toluene to form a microcapsule Dispersion containing 10% of solid materials (core materials). The microcapsule dispersion was introduced into a Niro Atomizer, which has two nozzles and is a product of Ashizawa Tekkojo Kabushiki Kaisha, in which they are heated using hot air at 100 ° C and a pressure of 392 Pa (4 kg / cm ² ). was spray-dried to obtain toner microcapsules. The particle size of the toner microcapsules thus obtained was measured with a Coulter counter of 100 μm in aperture size, and as a result, they were found to be in the range of 0.1 to several hundreds of μm. The toner microcapsules were classified by the mentioned MICROPLEX 400 MP classifier and then by the mentioned MICROPLEX 132 MP classifier in the same manner as in the example 1 for toner production, so that toner fine particles having a volume average resolution of 4.5 up to 9 μm were obtained.

The result of the examination of the resulting toner fine particles by the above-mentioned apparent viscosity measuring method revealed that they had an apparent viscosity of about 3 × 10 ⁴ dPa · s at 100 ° C.

Then, as the flowability improving agent, a ferrite carrier of a Cu-Zn-Fe system (average particle size: 48 μm, 250 mesh passage and 350 mesh hold at 89 wt% and true density of 4.5 g / cm ³ ), coated with about 5% of a mixture consisting of vinylidene fluoride-tetrafluoroethylene copolymer (copolymerization ratio of 8: 2) and styrene / 2-Äthylhexylacrylat / Methylmethacrylatcopolymerisat (copolymerization ratio of 45: 20: 35) produces.

To 10 parts of the above toner fine particles was added the flowability improving agent in an amount added that the total amount was 100 parts, whereupon a thorough mixing was done to get a developer.

Imaging process

The electrophotographic image forming method according to the invention can be practiced in a suitable electrophotographic copying machine having, for example, the structure shown in Figs. 2 (a) or 2 (b).

The structure of the copying machine shown in Fig. 2 (a) is substantially the same as that of the electrophotographic copying machine of Fig. 4 except that the former is provided with a magnetic roller 227 in the cleaning apparatus, with a special amorphous silicon recording element (Copying drum 201 ) according to the invention and a development device 204 , which is charged with a special fine particle insulation toner according to the invention is provided, but has no heating device for the recording element.

As shown in FIG. 2 (a), near the cylindrical amorphous silicon copying drum 201 having the structure shown in FIG. 1 and rotating in the direction indicated by an arrow, a main corona charger 202 , an electrostatic latent image Generating mechanism 203 , the developing device 204 , charged with the fine particle isolation toner having a volume average unit of 4.5 to 9 μm and an apparent viscosity at 100 ° C of 1 × 10 ⁴ to 2 × 10 ⁵ dPa × s, an image receiving unit. or transfer sheet feeding device 205 , a transfer charger 206 (a), a separation charger 206 (b), a cleaning device 207 , a transfer sheet transporting device 208 , a charge eliminating lamp 209, and a fixing device 228 .

The mentioned cylindrical amorphous silicon recording element 201 is uniformly charged by the main corona charger 202 , which is impressed with a predetermined voltage. Then, a template 212 to be copied is placed on a contact glass 211 , irradiated through the contact glass with a light from a light source 210 , whereupon the resulting reflected reflected light by mirror 213 , 214 and 215 , by a filter 218 containing a lens system 217 and a Mirror 216 is projected onto the surface of the cylindrical amorphous silicon copying drum 201 to produce an electrostatic image corresponding to the original 212 .

This electrostatic latent image is developed with the above-mentioned fine particle isolation toner supplied by the developing device 204 to form a toner image. A transfer sheet P is fed by the transfer sheet feeding apparatus 205 including a transfer sheet guide 219 and a pair of tact feed rollers 222 so that the transfer sheet P is brought into contact with the upper surface of the amorphous silicon copying drum 201 . A corona discharge having a polarity different from the polarity of the toner is effected from the back of the transfer sheet P by the transfer charger 206 (a) to which a predetermined voltage is applied to transfer the toner image to the transfer sheet P. The transfer sheet P, the transferred toner image containing will of the copying drum 201 by the Ladungsbeseiti supply effectively the separating corona charger 206 (b), when a predetermined AC voltage is impressed away and then conveyed by the transfer sheet conveying device 208 to the fixing device 228, a pair of Heated rollers and a mechanism for supplying a toner replacement preventing oil to each of the rollers and in which the toner image is fixed to the transfer sheet P, and discharged from the system.

The amorphous silicon copying drum 201 then passes to the cleaning device 207 which includes a cleaning blade 221 , the magnet roller 227, and a screw feeder 226 . Here, the magnetic particles contained in the residual toner on the copying drum are first removed by the action of the magnetic brush 227 formed on the toner brush, and then the copying drum is polished by the cleaning blade 221 , thereby further, on the surface of the drum bene Fene materials without a Abrasion of the surface layer of the amorphous silicon copying drum cause, eliminate.

The thus removed magnetic and other Ma materials are discharged through the screw conveyor 226 .

Subsequently, the thus cleaned Kopiertrom mel 201 is exposed on its surface entirely to the light from the La tion eliminating lamp 209 to delete the remaining La dung, and put back into circulation.

The above-mentioned magnetic roller 227 to be contained in the cleaning device 207 comprises a spindle made of a metal such as aluminum. Its surface is coated with magnetic ferrite materials by a conventional method or by a composition of a binder resin and magnetic ferrite powder by applying an emulsion containing the binder resin and the magnetic ferrite powder to this surface by means of an injection molding apparatus. The magnetic force on the surface of the magnetic roller is desirably 900 to 1000 Gauss.

The electrophotographic copying machine shown in Fig. 2 (b) is particularly suitable for putting the electrophotographic image forming method into practice, so that pictorial, copied full-color images are obtained.

The copying machine shown in Fig. 2 (b) has the same structure as that of Fig. 2 (a) except that the developing device 204 of Fig. 2 (a) has been replaced by a developing device 223 including four developing mechanisms . This includes a yellow toner-loaded developing mechanism Y, a magenta toner-loaded developing mechanism M, a cyan toner-fed developing mechanism C, and a black toner-fed developing mechanism B. The transfer charger 206 (a) and the separation corona charger 206 (b) of FIG. 2 (a) are replaced by a transfer drum 224 containing a transfer charger 225 . Instead of the filter 218 of Fig. 2 (a), there is provided a rotatable filter 218 'having the structure shown in Fig. 2 (b), which includes four filters: a blue filter, a green filter, a red filter, and a color correction filter. The filter 218 'is adapted to be rotated by means of a rotary device (not shown) to selectively apply a suitable filter depending on the type of developer to be used.

In the electrophotographic copying apparatus shown in Fig. 2 (b), the image forming process is carried out in the same manner as in the case of the copying apparatus shown in Fig. 2 (a) except that the developing device 223 is rotated by means of a rotary device (not shown) is rotated so that image development is carried out using a suitable developing mechanism which includes a developer corresponding to the color filter of the rotary filter 218 'to be used. The transfer drum 224 is rotated ge in the direction indicated by an arrow to wind on this a transfer sheet P, so that on this sheet P a toner image is transferred, followed by fixing followed.

Trial 1

Ten cylindrical patterns of recording elements (copying drums) having the structure shown in Fig. 1 (A) were prepared, comprising a cylindrical support 101 and a layer 102 '. This layer 102 'contains a charge injection blocking layer 106 , a photoconductive layer 103 , a latent image carrying layer 104, and a developed image carrying layer 105 , which are applied on the cylindrical support in this order and made in accordance with the above-mentioned layer forming method. using the RF plasma CVD apparatus of Fig. 5 and under the film forming conditions set forth in the attached Table 2, wherein as a cylindrical support, an aluminum cylinder of 108 mm in outer diameter, 358 mm in length and 5 mm in thickness was used.

Separately, a plurality of fine particle insulation materials were prepared produced, each of which is a different one Volume median fineness with an interval of 1.5 μm Range of about 3 microns to about 12 microns, through Repeat the procedures of Example 1 to Tonerher position.

The electrophotographic image forming method has been modified by employing each of the resulting copying drum patterns in a modification for use in a commercially available CANON NP-7550 electrophotographic copying machine, basically the same construction as shown in Fig. 2 (a) and in which the development mechanism was charged with each of the resulting fine particle isolation toners, where the above-mentioned image forming operations were repeatedly repeated by using the image forming system shown in Fig. 2 (a).

In any case, images were reproduced to determine the resolution solution and sound reproduction in the interrelationships between the used pattern of the copying drum (cylindrical Recording element) whose surface temperature at the Formation of an image and the fine particle To evaluate isolation toners.  

For evaluating the resolution, a test chart was used which has a plurality of black color portions of a regular width a and a plurality of white color portions of a regular width a arranged alternately and regularly as shown in Fig. 6 are. Each width a of the white-colored part between each pair of black-colored parts on the inspection chart was narrowed, and the inspection card was subjected to reproduction to thereby evaluate its minimum width a that can be resolved. In other words, if each width a of the white-colored part between each pair of black-colored parts on the probe card is narrowed to a certain width or less, and the probe card is subjected to reproduction, the resultant image becomes such that it becomes minute include unfocused or blurred images of the contours or contours of the adjacent black-colored parts that are overlapped. This case means that the resolution is practically impossible. For this reason, if the width a of the white-colored part makes a resolution of the image impossible, it has become a value for the resolution.

When evaluating the sound reproduction became a probe card used on the three black full or compact circles each with an optical density of 0.3 or 0.5 or 1.1 are arranged. The inspection card became a reproduction subjected such that a black full circle image with an optical density of 0.3 or a black solid circular image with an optical density of 1.1, which each with the original black full circle with one optical density of 0.3 and the original black Full circle with an optical density of 1.1, were obtained.  

The evaluation of sound reproduction was based on the resulting, from the remaining original black Full circle reproduced with an optical density of 0.5 Figure executed. This means that the absolute value of a Difference of the optical density difference between the optical density of 0.5 for the original black Full circle and the optical density of the black circle, which was reproduced as a value for the sound again was taken.

The evaluated results obtained with respect to the resolution are collectively shown in Fig. 7 (a), wherein each of the plotted values is a mean value among the values obtained for the ten patterns of the light-receiving elements.

The evaluated results obtained with respect to the sound reproduction are shown together in Fig. 7 (b), wherein each of the plotted values is a middle value among the values obtained for the ten patterns of light-receiving elements.

All the values plotted in each of Figs. 7 (a) and 7 (b) are relative values obtained when the value for the resolution and the value for the sound reproduction described in the following comparative experiment 1, wherein the fine particle isolation toner was used with about 12 microns volume median, equal to 1.

Comparative experiment 1

Ten samples of cylindrical recording elements of the structure shown in FIG. 3 were made for comparison purposes, each of which includes a cylindrical support 301 and a layer comprising a charge injection blocking layer 302 , a photoconductive layer 303, and a surface layer 304 in accordance with FIG 5, and under the film-forming conditions shown in the attached Table 3. The layer forming method using the RF plasma CVD apparatus of FIG . As the cylindrical support 301 , an aluminum cylinder of 108 mm in outer diameter, 358 mm in length and 5 mm in thickness was used. With the comparative patterns of light receiving elements thus obtained, the electrophotographic image forming process was carried out in the same manner as in Experiment 1. Ratings of resolution and sound reproduction were also conducted in the same manner as in Experiment 1.

The obtained evaluated results are collectively shown in Fig. 7 (a) with respect to the resolution and Fig. 7 (b) with respect to the sound reproduction.

findings

From the results obtained in Experiment 1 and Comparative Experiment 1 shown in Figs. 7 (a) and 7 (b), it was recognized that when the specific amorphous silicon recording element according to the invention was used in conjunction with the special fine particle toner is used of about 4.5 to 9 .mu.m average particle size according to the invention, from extremely high quality formations, which are characterized both in the resolution as in the sound reproduction, stable, can be obtained stigt and repeatedly.

Experiment 2 and Comparative Experiment 2

Evaluation of sound reproduction was performed.

Trial 2

Ten patterns of cylindrical amorphous silicon recording elements of the structure shown in Fig. 1 (A) were prepared in the same manner as in Experiment 1 except that as the cylindrical support 101, an aluminum cylinder of 80 mm in outer diameter, 358 mm in length and 5 mm thickness was used.

As the electrophotographic copying machine, a modification for experimental purposes of a commercially available CANON Color Laser Copier PIXEL was used for image evaluation, which basically has the same structure as that shown in Fig. 2 (b).

As the four types of color toners, those obtained in Example 2 for toner production were used. For each of these four types of color toners, three different fine particle color toners were generated, each having a volume average fineness of about 4.5 μm, about 6 μm and about 9 μm. For each of these three different color toners, five different fine particle color toners were generated, each having an apparent viscosity at 100 ° C of about 5 x 10 ³ , about 1 x 10 ⁴ , about 2 x 10 ⁵ and about 3 x 10 ⁵ dPa x s have.

The same evaluation processes of sound reproduction as in Example 1 were performed using a CANON Test Sheet CA-4 repeated as a test sheet.

Comparative experiment 2

Ten samples of a cylindrical amorphous silicon recording element having the structure shown in Fig. 3 were prepared in the same manner as in Comparative Experiment 1 except that an aluminum cylinder of 80 mm in outer diameter, 358 mm in length and 5 mm in thickness was used as the cylindrical support 301 has been.

An evaluation of the sound reproduction was done in the same way such as 2 performed.  

The results obtained in Experiment 2 and Comparative Example 2 are collectively shown in Fig. 8 in the same manner as in the case of Fig. 7 (b), the plotted values being relative values obtained when in the case of Figs. since the fine particle color toner having an apparent viscosity of about 6 × 10 ⁴ dPa · s was used at 100 ° C., the value obtained was made the check value (1).

findings

From the results obtained in Experiment 2 and Comparative Example 2, it was found that when the specific amorphous silicon light-receiving element of the invention was used in conjunction with the special fine particle color toner having a volume average resolution of 4.5 to 9 μm and has a pseudo-viscosity at 100 ° C of 5 × 10 ³ to 2 × 10 ⁵ dPa · s, a large number of fine particle color toners are thoroughly melted and mixed to produce high-quality copied graphic color images which are extremely excellent in sound reproduction.

Experiment 3 and Comparative Experiment 3

An evaluation of the resolution was performed.

Trial 3

Ten patterns of cylindrical amorphous silicon recording elements of the structure shown in Fig. 1 (A) were prepared in the same manner as in Experiment 1 except that the cylindrical support 101 was an aluminum cylinder of 80 mm in outer diameter, 358 mm in length and 5 mm thickness was used.

As the electrophotographic copier to be used for the image evaluation, a modification was used for experimental purposes of a commercial CANON Color Laser Copier PIXEL, which basically has the same structure as the apparatus shown in Fig. 7 (b).

As the four types of color toners, those colorants obtained in Example 2 for toner production were used. For each of these four types of color toners, three different fine particle color toners each having a bulk average fineness of about 4.5 μm, about 6 μm and about 9 μm were provided. For each of these three different color toners, five different fine particle color toners each having an apparent viscosity at 100 ° C. of about 5 × 10 ³ , about 1 × 10 ⁴ , about 6 × 10 ⁴ , about 2 × 10 ⁵ and about 3 × 10 ⁵ dPa × s before seen.

The same evaluation processes of the resolution as in the example 1 were repeated using a CANON Test Sheet CA-4 has been.

Comparative experiment 3

Ten cylindrical amorphous silicon light receiving elements of the structure shown in Fig. 3 were prepared in the same manner as in Comparative Example 1 except that as the cylindrical support 301, an aluminum cylinder of 80 mm in outer diameter, 358 mm in length and 5 mm in thickness was used Application came.

An evaluation of the resolution was done in the same way as performed in Example 2.

The results obtained in Experiment 3 and Comparative Experiment 3 are collectively shown in Fig. 9 in the same manner as in the case of Fig. 7 (a), wherein the plotted values are relative values obtained when in the case of Figs. since the fine particle color toner having an apparent viscosity of about 6 × 10 ⁴ dPa · s was used at 100 ° C., the value obtained was made the control value (1).

findings

From the results obtained in Experiment 3 and Comparative Experiment 3, it can be seen that when the specific amorphosilicon light-receiving member of the invention is used in conjunction with the special fine particle color toner having a volume average particle size of 4.5 to 9 μm and an apparent viscosity at 100 ° C of from 1 x 10 ⁴ to 3 x 10 ⁵ dPa · s, a large amount of fine particle color toners are thoroughly melted and mixed to produce copied high quality pictorial solid color images comprising in the resolution are extremely outstanding.

Experiment 4 and Comparative Experiment 4

A judgment has been made on the situation wherein uneven image density or blackening is caused due to stains sticking to the corona wires associated with the corona charger 202 .

Trial 4

Ten cylindrical amorphous silicon recording elements of the structure shown in Fig. 1 (A) were prepared in the same manner as in Comparative Experiment 1 except that the cylindrical support 101 was an aluminum cylinder of 80 mm in outer diameter, 358 mm in length and 5 mm in thickness was used.

As an electrophotographic copying machine for image evaluation, a modification for experimental purposes of a commercial CANON Color Laser Copier PIXEL has basically the same structure as shown in Fig. 2 (b).

As the four types of color toners, those obtained in Example 2 for toner production were used. For each of these four types of color toners, three different fine particle color toners were provided, each having a volume average unit of about 4.5 μm, about 6 μm and about 9 μm. For each of these three different color toners, five different fine particle color toners each having an apparent viscosity at 100 ° C. of about 5 × 10 ³ , about 1 × 10 ⁴ , about 6 × 10 ⁴ , about 2 × 10 ⁵ and about 3 × 10 ⁵ dPa × s provided.

The critical review was done by the pictures in the above-mentioned laser-copier was to receive copied full-color pictorial pictures using a CANON Test Sheet BS-1 as a test sheet was and the received full-color pictures with the eyes were looked at to find the number of copies on which an uneven picture darkness in Erschei occurred. This number was related to the rating point of uneven image darkness to a ausge valued value.

Comparative experiment 4

Ten cylindrical amorphous silicon recording elements of the structure shown in Fig. 3 were prepared in the same manner as in Comparative Example 1 except that an aluminum cylinder of 80 mm in outer diameter, 358 mm in length and 5 mm in thickness was used as the cylindrical support 301 ,

A rating regarding the situation of a occur the uneven image darkness was in the same way as carried out in experiment 4.

The results obtained in Test 4 and Comparative Experiment 4 are collectively shown in Fig. 10 in the same manner as in the case of Fig. 7, wherein the plotted values obtained are relative values, when in the case where the fine particle color toner has a Visible viscosity was used at 100 ° C of about 6 × 10 ⁴ dPa × s, the value obtained was made to the test value (1).

findings

From the results obtained in Experiment 4 and Comparative Experiment 4, it was found that when the specific amorphous silicon recording element according to the invention together with the special fine particle color toner having a volume average particle size of 4.5 to 9 μm and an apparent viscosity at 100 ° C of from 1 × 10 ⁴ to 2 × 10 ⁵ dPa × s, high quality pictorial full color images are extremely useful which are extremely distinctive in both sound reproduction and resolution without the concomitant of any uneven Image density can be steadily and repeatedly obtained, even if the image forming process is repeated over a long period of time.

Total determination

In addition to the observations in the aforementioned experiments and Comparative tests have the following results also shown.

By experiment 1 and comparative experiment 1 gefun was that the electrophotographic imaging process, in which the aforesaid special amorphous silicon recording element and the aforementioned fine particle toner together be used, allows, steady, stable and again Brings high quality images to reproduce themselves extremely high in sound reproduction as well as the resolution and are equivalent to the original, with a Coulomb's Force effectively between the latent image carrier layer of the recording element and the fine particle toner. Through Experiments 2 to 4 and Comparative Experiments 2 to 4 has then been found that the electrophotographi image processing method using the above-mentioned special amorphous silicon recording element and the aforementioned special fine particle toner [yellow toner (Y)]  Magenta toner (M), cyan toner (C) and black toner (B)] light, stable and repeatedly illustrated or pictorial Reproduce full-color illustrations of high quality, which are extremely in both the sound reproduction and in the Resolution and are equivalent to the original, even if the imaging process for a long time space is repeated without this case the corona wire with Oil is polluted, which is used to the occurrence to prevent dislocation while in the herkömmli The image forming method of Comparative Examples the corona wires are soiled, so that the resultie Illustrated uneven image blackening images and the reproduced illustrations are completely open visibly against any illustrations in the verse were inferior.

Preferred embodiments

The present invention will be more specifically described with reference to FIG to examples, wherein the invention none It is limited to these examples only is.

example 1

The cylindrical recording element manufactured in Experiment 1 was used in a commercial CANON Color Laser Copier PIXEL basically having the same structure as shown in Fig. 2 (b), and in which the four kinds of fine particle isolation color toners described in U.S. Pat Example 2 were obtained for toner production, were used. The electrophotographic image forming method was conducted under normal environmental conditions (23 ° C, humidity 60%) using a CANON Test Sheet CA-4 as a test sheet for image evaluation in accordance with the aforementioned image forming processes using the electrophotographic copying apparatus of Fig. 2 (b). was used to reproduce images of the templates.

As a result of the evaluation of the resulting pictures has been shown to be both in resolution as well in sound reproduction without the accompaniment of any an uneven picture blackening and some fuzziness picture and the originals of the test sheet are equivalent.

Then, the above electrophotographic image forming apparatus was prepared continuous production of 500 000 copies repeated. The reproduced pictures on the last ko pie were evaluated. As a result, it has been shown that they those who were received in the initial stage, the same valuable and still the originals of the test sheet are equivalent.

Example 2

The cylindrical recording element prepared in Experiment 1 was used in a commercial CANON Color Laser Copier PIXEL, which basically has the same structure as shown in FIG. 2 (b), wherein the four types of fine particle insulation color toners described in Example 3 for Tonerher were used to charge the device. The electrophotographic image forming method was conducted under high humidity conditions (23 ° C, 85% humidity) using a CANON Test Sheet CA-4 as a test sheet for image evaluation, in accordance with the above-mentioned electrophotographic image forming processes Copy system of Fig. 2 (b) is used to thereby reproduce images of the original.

As a result of an evaluation of the resulting images It has been shown that without the concomitant phenomenon an uneven picture blackening and any fuzzy Picture in both resolution and sound reproduction as well as the templates of the test sheet are valuable.

The above electrophotographic image forming process has been then continuously to make 500,000 copies again get. The reproduced on the last copy Illustrated pictures. As a result, it has been found that they are equivalent to the copies obtained in the initial stage and still equivalent to the originals of the test sheet are.  

Claims (8)

An electrophotographic image forming method comprising an electrophotographic recording element having the following layers stacked on a support in the order named:

• a charge injection barrier layer comprising amorphous silicon as matrix material and hydrogen and / or halogen atoms introduced into the matrix material and atoms of an element of group V of the periodic table,
• a photoconductive layer with amorphous silicon as the matrix material and hydrogen and / or halogen atoms introduced into the matrix material,
• - A charge image bearing, translucent for the image light layer with amorphous silicon as a matrix, in the carbon atoms, atoms of an element of III. Group of the Periodic Table and hydrogen and / or halogen atoms are introduced, and
• - A developed a charge image, transparent to the image light layer with amorphous silicon as a matrix and introduced into the matrix carbon atoms and hydrogen and / or halogen atoms
• - electrostatically charged,
• exposed to image light to form a latent electrostatic image,
• - transferred with the electrostatic latent image in a development station, in which the electrostatic latent image is developed with an insulating toner containing a dye and a binder, an apparent viscosity of 1 · 10⁴ dPa · s to 2 · 10⁵ dPa · s at 100 ° C and in the volume average has an average particle size of 4.5 to 9 microns, and in the
• - The recording element is transferred with the toner image in a transfer station, in which the toner image is transferred to an image-receiving sheet.

2. Image forming method according to claim 1, characterized characterized in that the developed charge image supporting layer has a thickness of 3000 to 10,000 Å. The image forming method according to claim 1, characterized in that the layer bearing the developed charge image has a resistivity of 10 ¹² to 10 ¹⁶ Ω · cm. 4. image forming method according to claim 1, characterized characterized in that the recording element is a layer which absorbs longwave light and which intercepts the carrier and the charge injection blocking layer is. 5. An electrophotographic color image forming process comprising exposing an electrophotographic recording element to the following layers superimposed on a support in the order given:

• a charge injection barrier layer comprising amorphous silicon as matrix material and hydrogen and / or halogen atoms introduced into the matrix material and atoms of an element of group V of the periodic table,
• a photoconductive layer with amorphous silicon as the matrix material and hydrogen and / or halogen atoms introduced into the matrix material,
• - A charge image bearing, translucent for the image light layer with amorphous silicon as a matrix, in the carbon atoms, atoms of an element of III. Group of the Periodic Table and hydrogen and / or halogen atoms are introduced, and
• - A developed a charge image, transparent to the image light layer with amorphous silicon as a matrix and introduced into the matrix carbon atoms and hydrogen and / or halogen atoms
• - is charged electrostatically,
• to image latent electrostatic images of the same original successively with image light of different colors,
• with the respective electrostatic latent image being transferred to a development station where the sequentially generated charge images of the original of different color ink-resisting original are developed, the toner each containing a different colorant dye and a binder having an apparent viscosity of 1 × 10⁴ dPa · s to 2 · 10⁵ dPa · s at 100 ° C and in the volume average has an average particle size of 4.5 to 9 microns, and in the
• - The recording element is transferred with the toner image in a transfer station, in which the toner image for producing a full-color image are transferred to an image-receiving sheet.

6. The method according to claim 5, characterized in that the layer bearing the developed charge image has a thickness from 3000 to 10 000 Å. 7. The method according to claim 5, characterized in that the developed charge image bearing layer has a resistivity of 10 ¹² to 10 ¹⁶ Ω × cm. 8. The method according to claim 5, characterized in that the recording element comprises a layer which long-wavelength light is absorbed and that between the substrate and the charge injection blocking layer is disposed.