JPH0157907B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a method of developing an electrostatic image formed on the surface of an electrostatic image carrier, and particularly to a method of forming and developing a thin and uniform insulating nonmagnetic toner layer on a toner carrier. Conventionally, the following methods are known as developing methods using a one-component non-magnetic toner. A movable developer carrying means carrying and conveying the developer and supplying it to the latent image carrier, a developer replenishing means, and a developer supplied from the developer replenishing means and supplying the developer to the movable developer carrying means. A movable applicator for coating, which has a fiber brush that carries a developer on its surface, contacts the movable developer carrier, and moves a movable developer in the same direction as the movable developer carrier at this abutting portion. A method in which toner is uniformly applied to the surface of the movable developer carrier means using a movable coating means that moves at a higher speed than the developer carrier means, and development is carried out by bringing this coated layer close to the electrostatic latent image area, or a one-component system. A rotatable magnetic roller that attracts a magnetic carrier to form a magnetic brush for charging non-magnetic toner particles, and a rotatable magnetic roller that transfers the toner particles from the roller to develop an electrostatic image on an electrostatic image carrier. The electrostatic image is developed by maintaining a gap between the electrostatic image holder and the developing roller in the developing section, and setting the gap length to be larger than the thickness of the toner coating layer on the developing roller. Method and an electrostatic image developing method in which a developer holder holding a developer on its surface is opposed to an electrostatic image carrier to develop an electrostatic image on the surface of the carrier, wherein the developer is stored in a developer storage means. When pumping up the developer under the developer holder onto the developer holder, vibration is applied to only the developer in the pumped up portion to activate it, thereby forming a developer layer of a predetermined thickness on the surface of the developer holder. There is a developing method in which a film is formed and then subjected to development. However, in the method of developing these insulating non-magnetic toners by supporting them on a carrier using non-magnetic force in the developing section, the force that causes the non-magnetic toner to be supported on the toner carrier in the vicinity of the developing section is mainly electrostatic attraction. and physical adhesion is dominant,
In this respect, various disadvantages arise compared to the conventional developing method using insulating magnetic toner in which toner is supported on a carrier by magnetic force, electrostatic force, etc. For example, a phenomenon occurs that many toners are not applied relatively thinly and uniformly on the carrier. Furthermore, for example, so-called background fog occurs in which toner adheres to non-image areas even though the toner is applied relatively uniformly.
Furthermore, even though the toner is applied thinly and uniformly, the amount of toner adhering to the image area is insufficient, resulting in an image with low density. Additionally, many toners produce very poor images with low fidelity and low resolution even though they are applied thinly and evenly. Furthermore, repeated use of more toner results in decreased image density and lower quality images. Furthermore, many toners have the disadvantage that they sometimes cause a decrease in image density when exposed to environmental changes such as high temperature and high humidity, low temperature and low humidity, and sometimes cause background fog. In addition, in the development method using one-component magnetic toner, since the magnetic toner particles contain a large amount of magnetic powder, it is not only more expensive than non-magnetic toner, but also produces beautiful colors. was difficult. An object of the present invention is to provide a new developing method using an insulating non-magnetic toner, which improves the above-mentioned drawbacks. That is, an object of the present invention is to provide a developing method with high fidelity and stable image quality. Another object of the present invention is to provide a developing method that eliminates the background fog phenomenon and provides a high-resolution image that is uniform and has sufficient density in the image area. Another object of the present invention is to provide a developing method with excellent durability such as continuous use characteristics. Another object of the present invention is to provide a developing method that is stable against environmental changes such as high temperature and high humidity, and low temperature and low humidity. Another object of the present invention is to provide a developing method that provides images with sharp hues. Specifically, the present invention provides an electrostatic image carrier that holds an electrostatic image on its surface, and a positively charged insulator that has on the surface of toner particles silicic acid fine powder treated with silicone oil having an amine in its side chain. A toner carrier carrying a non-magnetic toner on its surface is arranged with a certain gap in a developing section, and positively charged insulating non-magnetic toner is carried on the toner carrier to a thickness thinner than the gap. , relates to a developing method characterized in that the positively charged insulating non-magnetic toner is transferred to the electrostatic image holder in a developing section for development. Preferably, in the developing section, the toner is transferred from the toner carrier to the electrostatic image carrier while applying an alternating current and/or direct current bias between the toner carrier and the electrostatic image carrier, as necessary. is good. The present inventors have studied various developing methods using conventionally known non-magnetic toners, and found that in order to solve the above-mentioned drawbacks, compared to developing methods using magnetic toners, it is necessary to use a toner carrier in the developing section. We have found that more precise control of the amount of electrostatic charge that the above toner has is necessary. For example, if the amount of charge is low, a phenomenon occurs in which the toner is not evenly applied onto the carrier, and development cannot be achieved. Next, even if the amount of charge is increased to create a condition where the toner is evenly coated, if the value is not appropriate, background fogging will easily occur, and conversely, if the value is too high, electrostatic attraction with the toner carrier will cause is too strong, making it difficult for the toner to transfer to the electrostatic image carrier, resulting in a decrease in image density,
This may lead to the appearance of low-quality images. Furthermore, for the same reason, these developing methods have an extremely large effect on the image due to changes in the toner charge amount during repeated use or environmental changes, and ensuring the stability of the charge amount is more important than ever. In these development methods, the physical adhesion between the toner and the toner carrier is
This obviously affects the transfer of toner from the toner carrier. For example, when the degree of freedom of each toner is small and the toner coating density in the toner layer on the carrier is high, the image density is low and the resolution is low. We have learned that it is extremely important to prevent the physical adhesion from increasing, which would result in poor quality images. The present invention achieves these characteristic requirements due to the method of developing an insulating non-magnetic toner by supporting it on a carrier using non-magnetic force in a developing section by using a toner containing a specific fine silica powder. It is something to do. As the silicic acid fine powder constituting a component of the developer used in the developing method of the present invention, silicic acid fine powder produced by a dry method or a wet method can be used. The dry method mentioned here is a method for producing fine silica powder produced by vapor phase oxidation of a silicon halide compound. For example, this method utilizes a thermal decomposition oxidation reaction of silicon tetrachloride gas in an oxyhydrogen flame, and the basic reaction formula is as follows. SiCl ₄ +2H ₂ +O ₂ →SiO ₂ +4HCl Also, in this manufacturing process, for example, by using other metal halide compounds such as aluminum chloride or titanium chloride together with silicon halide, a composite fine powder of silica and other metal oxides can be produced. It is also possible to obtain a body, and it includes these as well. Commercially available silica fine powder produced by vapor phase oxidation of a silicon halogen compound used in the present invention includes, for example, those commercially available under the following trade names. AEROSIL 130 (Japan Aerosil Co., Ltd.) 200 300 380 OX50 TT600 MOX80 MOX170 COK84 Ca-O-SiL M-5 (CABOT Co.) MS-7 MS-75 HS-5 EH-5 Wacker HDK N 20 (WACKER-CHEMIE GMBH Dow Corning Co.) V15 N20E T30 H40 D-C Fine Silica (Dow Corning Co.) Fransol (Fransil Co.) On the other hand, the method for producing the silicon fine powder used in the present invention by the immersion method can be performed using various conventionally known methods. is applicable. For example, there is a method of decomposing sodium silicate with an acid, and the reaction formula is shown below. Na ₂ O・XSiO ₂ +HCl+H ₂ O→SiO ₂・nH ₂ O+
NaCl Other methods include decomposition of sodium silicate with ammonia salts or alkali salts, generation of alkaline earth metal silicate from sodium silicate and then decomposition with acid to produce silicic acid, method of converting sodium silicate solution into ion exchange resin There are methods such as using silicic acid, and using natural silicic acid or silicate. As the silicic acid fine powder referred to herein, any of anhydrous silicon dioxide (silica) and other silicates such as aluminum silicate, sodium silicate, potassium silicate, magnesium silicate, and zinc silicate can be used. Commercially available fine silicic acid powders synthesized by the immersion method include those sold under the following trade names, for example. Carplex Shionogi & Co., Ltd. Neve Seal Nippon Silica Toxil, Fine Seal Tokuyama Soda Vita Seal Taki Hi Shilton, Silnetx Mizusawa Kagaku Starsil Kamishima Kagaku Himezil Ehime Pharmaceutical Thyroid Fuji Davison Kagaku Hi-Sil Pittsburgh Plate Glass
Co. (Pittsburgh Plate Glass) Durosil Fiillstoff-Gesellschaft Ultrasil Marquart Manosil Hardman and Holden
(Hardman and Holden) Hoesch Chemische Fabrik Hoesch
K-G Sil-Stone Stoner Rubber
Co. (Stoner Lover) Nalco (Nalco) Nalco Chem.Co. (Nalco Chemical) Quso (Quos) Philadelphia Quarts Co. (Philadelphia Quartz) Santocell (Santocell) Monsanto.Chemical
Co. (Monsanto Chemical) Imsil (Imsil) Illinois Minerals Co. (Isonois Minerals) Calcium Silikat Chemische Fabrik Hoesch.
(Calcium Zilicart) K-G (Hiemitsussie Fabrik Hetsushu) Calsil Fiillstoff-Gesellschaft
Marquart
Marc Ort) Fortafil Imperial Chemical
Industries, Ltd. (Imperial Chemical Industries) Microcal Joseph Crosfield & Sons.
Ltd. (Jiecef Crossfield & Sons) Manosil (Manosil) Hardman and Holden
(Hardman and Holden) Vulkasil Farbenfabriken
Bryer, A.-G. Tufknit Durham Chemicals.Ltd.
(Doulham Chemicals) Silmos Shiraishi Kogyo Starex Kamishima Chemical Fricosil Takihii Among the above silicic acid fine powders, those with a specific surface area of 30 m ² /g or more due to nitrogen adsorption measured by the BET method, especially
Those within the range of 50-400m ² /g give good results. Conventionally, it is known that fine silica powder produced by vapor phase oxidation of a silicon halide compound is added to a developer. However, even in a developer containing a dye having positive charge control properties, when such silica is added, the chargeability changes to negative, making it unsuitable for visualizing a negative electrostatic charge image. As a result of researching the above phenomenon, it was discovered that fine silica powder produced by conventional vapor phase oxidation of silicon halogen compounds reduces the charge of positively charged developer or reverses the polarity.
As a result of detailed studies aimed at obtaining a developer that exhibits stable and uniform positive chargeability, we found that it is effective to treat fine silicic acid powder with silicone oil that has an amine in its side chain and incorporate it into the developer. I found it. As the silicone oil having an amine in its side chain, silicone oil containing a structural unit represented by the formula () can generally be used. (Here, R ₁ , R ₂ , R ₃ , and R ₄ may be any group as long as it does not impair chargeability, but preferably R ₁ is hydrogen, an alkyl group, an aryl group, or an alkoxy group. and R ₂ is an alkylene group and/or
or represents a phenylene group, and R ₃ and R ₄ represent hydrogen, an alkyl group or an aryl group. However, the above alkyl group, aryl group, alkylene group, and phenylene group may contain an amine, or may have a substituent such as a halogen within a range that does not impair chargeability. ) Preferred commercially available silicone oils having an amine in their side chains include, for example, amino-modified silicone oils represented by the following structural formula. it is (Here, R ₁ and R ₅ represent an alkyl group or an aryl group, R ₂ represents an alkylene group, a phenylene group, or an alkyl group containing an amine, and R ₃ represents hydrogen, an alkyl group, or an aryl group. m, (n is a number of 1 or more). Specifically, the following are preferred, and these may be used alone or in a mixture of two or more.

[Table] Manufactured by the company)
The amine equivalent in the present invention is the equivalent per amine (g/eqiv), which is the value obtained by dividing the molecular weight by the number of amines per molecule. In the present invention, as mentioned above, the amine equivalent is 320 to 8800 and the viscosity at 25°C is 20 to 3500 cps.
It is preferable to use a silicone oil having an amine in its side chain, which has the following properties: from the viewpoint of positive charge control, environmental stability, and development characteristics. In the present invention, the processing amount of silicone oil having an amine in the side chain is 0.2 to 70% by weight of the total amount of treated silicic acid fine powder, and 0.0001% in the developer.
It is preferable to adjust the amount to ~10% by weight.
Furthermore, the appropriate amount of silicone oil to be treated with an amine in the side chain is determined by assuming that the weight part of this silicone oil is X for 100 parts by weight of the silicic acid fine powder before treatment with the silicone oil, When the specific surface area of the fine powder is bm ² /g and the amine equivalent of the silicone oil having an amine in the side chain is a, particularly good results are obtained when the relationship of formula () is satisfied. ab/30000≦x≦b/2…Formula () In the above equation, if x>b/2, the silicone oil having an amine in the side chain will be in large excess with respect to the silicic acid fine powder, and the amine in the side chain will be in excess. Problems such as oozing of silicone oil from the silicic acid fine powder may occur. Further, when x<ab/30000, the charging property is insufficient and it becomes difficult to achieve the object of the present invention. On the other hand, the viscosity at 25℃ of silicone oil having an amine in the side chain is preferably 5000 cps or less, especially
3000cps or less is preferable. If the viscosity is 5000 cps or more, the silicone oil having an amine in its side chain will not be sufficiently dispersed in the silicic acid fine powder, which may easily cause poor images such as fog. The above-mentioned treatment of fine silicic acid powder with silicone oil having an amine in its side chain can be carried out, for example, as follows. If necessary, stir vigorously with the silicic acid fine powder while heating, and then spray or vaporize the silicone oil or its solution having an amine in the side chain, or form the silicic acid fine powder into a slurry. This can be easily treated by adding a silicone oil having an amine in its side chain or a solution thereof while stirring the mixture. Furthermore, it is also preferable to perform a heat treatment thereafter at a temperature of about 50 to 400°C. In the present invention, one type or a mixture of two or more types of silicone oils may be used from among the above-mentioned silicone oils having amines in their side chains. In addition, the applied amount of these treated silicic acid fine powders exhibits an effect when the amount is 0.01 to 20% based on the weight of the developer, and particularly preferably when it is added in an amount of 0.03 to 3%, excellent stability is obtained. It exhibits positive chargeability. A preferred form of addition is that 0.01 to 5% by weight of the treated silicic acid fine powder based on the weight of the developer is attached to the surface of the toner particles. Further, the silicic acid fine powder used in the present invention may be treated with a silane coupling agent or a treatment agent such as an organosilicon compound for the purpose of hydrophobization, if necessary, and a known method may be used. and treated with the above-mentioned treatment agent that reacts with or physically adsorbs the silicic acid fine powder. Such treatment agents include, for example, aminopropyltrimethoxysilane, aminopropyltriethoxysilane, diethylaminopropyltrimethoxysilane, aminophenyltrimethoxysilane, dimethylaminophenyltriethoxysilane, dimethylsilicone oil, hexamethyldisilazane. , trimethylsilane, trimethylchlorosilane, trimethylethoxysilane, dimethyldichlorosilane, methyltrichlorosilane, allyldimethylchlorosilane, allyl phenyldichlorosilane, benzyldimethylchlorosilane, bromomethyldimethylchlorosilane, α-chloroethyltrichlorosilane , β-chloroethyltrichlorosilane, chloromethyldimethylchlorosilane, triorganosilylmercaptan, trimethylsilylmercaptan, triorganosilylacrylate, vinyldimethylacetoxysilane, dimethylethoxysilane, dimethyldimethoxysilane, diphenyldiethoxysilane, hexamethyldisiloxane , 1,3-divinyltetramethyldisiloxane, 1,3-diphenyltetramethyldisiloxane, and 2 to 12 siloxane units per molecule, each of which is bonded to one Si at the terminal unit. There are dimethylpolysiloxanes containing hydroxyl groups. These may be used alone or in a mixture of two or more. According to the present invention, when a developer containing fine silicic acid powder treated with silicone oil having an amine in the side chain is used, the triboelectric charging of the developer becomes stable and uniform positive charge is obtained even under various environments. It begins to show chargeability. Therefore, when the developer according to the present invention is used, it is possible to obtain a clear, high-density image without fog, and furthermore, the image does not deteriorate even after continuous use for a long period of time. Further, clear images can be obtained even under high temperature and high humidity conditions and under low temperature and low humidity conditions. Examples of the binder resin of the toner that can be used in the present invention include monopolymers of styrene and its substituted products such as polystyrene, polyP-chlorostyrene, and polyvinyltoluene; styrene-P-chlorostyrene copolymers, and styrene-propylene copolymers. Copolymer, styrene-vinyltoluene copolymer, styrene-vinylnaphthalene copolymer, styrene-methyl acrylate copolymer, styrene-ethyl acrylate copolymer, styrene-butyl acrylate copolymer, styrene-octyl acrylate Copolymer, styrene
Methyl methacrylate copolymer, styrene-ethyl methacrylate copolymer, styrene-butyl methacrylate copolymer, styrene-alpha chloromethyl methacrylate copolymer, styrene-acrylonitrile copolymer, styrene-vinyl methyl ether copolymer combination, styrene-vinyl methyl ketone copolymer,
Styrene-butadiene copolymer, styrene-isoprene copolymer, styrene-acrylonitrile
Styrenic copolymers such as indene copolymer, styrene-maleic acid copolymer, and styrene-maleic ester copolymer; polymethyl methacrylate, polybutyl methacrylate, polyvinyl chloride, polyvinyl acetate, polyethylene, polypropylene, polyester , polyurethane, polyamide, polyvinyl butyral, polyacrylic acid resin, rosin, modified rosin, terpene resin, phenolic resin, aliphatic or alicyclic hydrocarbon resin, aromatic petroleum resin, chlorinated paraffin, paraffin wax, etc. Alternatively, they can be used in combination. Colorants used in the toner used in the present invention include known dyes and pigments such as carbon black,
Phthalocyanine blue, indanthrene blue,
Peacock blue, permanent red, lake red, rhodamine lake, Hansa yellow, permanent yellow, benzidine yellow, etc. can be widely used. The present invention will be explained in detail below using figures and examples. FIG. 1 is an explanatory diagram showing an example of an embodiment of an electrostatic latent image developing method using an insulating nonmagnetic toner.
In the same figure, reference numeral 1 denotes a cylindrical electrostatic image carrier, on which an electrostatic latent image is formed by, for example, a known electrophotographic method such as the Carlson method or the NP method, and a hopper, which is a toner supply means, is used. Applying means 4 applies the insulating non-magnetic toner 5 in 3 onto the toner carrier 2.
The layer thickness of the toner layer is regulated by the applied toner 5 for development. The toner carrier 2 is a cylindrical developing roller made of stainless steel. The developing roller may be made of aluminum or other metals. Alternatively, a metal roller coated with resin or the like may be used in order to triboelectrically charge the toner to a desired polarity. Further, the toner applying means 4 may be a blade as shown in FIG.
An elastic roller may also be used. When the application means 4 is an elastic roller, the amount of toner charge on the carrier can be changed by changing the pressing pressure of the elastic roller against the toner carrier. Further, it is preferable that the distance between the electrostatic image holder 1 and the toner carrier 2 is set to be greater than or equal to the thickness of the toner layer coated on the toner carrier 2. Furthermore, it is preferable that a bias power source as shown in 6 is provided and a developing bias is applied between the electrostatic image carrier 1 and the toner carrier 2. FIG. 2 is another explanatory diagram. In the same figure, 1
2 is an electrostatic image carrier, 2 is a toner carrier, 5 is a toner, 3 is a hopper, 16 is a vibration member, 17 is a vibration generating means, 16a is a permanent magnet, 19 is a cleaning plate, and 10 is a toner supply member. That is, the vibrating member 16 is vibrated with an appropriate amplitude and frequency to form a uniform toner coating layer on the toner carrier 2 rotating at a constant speed, and the toner carrier 2 and the electrostatic image carrier 1 are The electrostatic image is developed by facing the electrostatic image with a gap larger than the thickness of the toner coating layer, and causing the non-magnetic toner to fly onto the electrostatic image. The vibration of the vibrating member 16 may be at any level as long as it does not come into direct contact with the toner carrier 2. It is also possible to apply an AC and/or DC developing bias voltage between the toner carrier 2 and the electrostatic image holder 1. FIG. 3 is an explanatory diagram of another example. In the figure, 1 is an electrostatic image carrier, 2 is a toner carrier,
35 is a coating roller, 36 is a fiber brush fixed to its surface, 6 is a developing bias power source, 38 is a developing device, 9 is a toner cleaning member, and 40 is a coating bias source. That is, toner No. 5 is uniformly applied onto the toner carrier 2 by rotating an application roller No. 35 and conveyed by a brush No. 36, and is caused to fly onto the electrostatic image No. 1 to be developed. The gap between the toner carrier 2 and the application roller 35 may be adjusted so as to form a uniform toner layer on the toner carrier 2, and a bias voltage indicated by 40 may be applied to uniformly apply the toner. The gap between the electrostatic image carrier 1 and the toner carrier 2 may be made larger than the above-mentioned toner layer thickness, and a developing bias of 6 may be applied during development. FIG. 4 is an explanatory diagram of another example. In the figure, 1 is an electrostatic image carrier, 2 is a toner carrier, and 4 is a toner carrier.
3 is a developing device, 5 is one-component non-magnetic toner, 6 is a bias power supply, 48 is a magnetic roller, 49 is a non-magnetic sleeve, 50 is a magnet, 52 is a magnetic brush, 53
represents a one-component non-magnetic toner or a two-component developer in which a non-magnetic toner and a magnetic carrier are mixed. That is, by magnetically holding a magnetic carrier on a non-magnetic sleeve 49 to form a brush, and rotating 49, 53 draws up toner or developer with the carrier brush and applies it on the toner carrier 2 in contact with it. This forms a uniform toner layer. At this time, since the carrier is held on the toner carrier 48 by magnetic force, it does not move onto the toner carrier 2. Next, the non-magnetic toner is transferred to the toner carrier 2.
The image is transferred from above onto the electrostatic image holder 1 and developed. The gap between the toner carrier 2 and the electrostatic image carrier 1 is made larger than the toner layer thickness, and the gap between the toner carrier 2 and the electrostatic image carrier 1 is made larger than the toner layer thickness.
A developing bias voltage may be applied between the image carrier 1 and the electrostatic image holder 1 . FIG. 5 is an explanatory diagram of another example. In the figure, 1 is an electrostatic image carrier, 2 is a toner carrier, and 3 is a toner carrier.
is a hopper, 52 is a magnetic brush using a carrier toner mixture, 58 is a blade for regulating toner thickness,
50 is a fixed magnet, 6 is a developing bias, and 5 is a one-component non-magnetic toner. That is, the magnetic brush 52 formed on the toner carrier 2 is circulated by rotating the toner carrier 2, takes in the toner in the hopper 3, and uniformly coats the toner 2 in a thin layer. Next, toner carrier 2
and an electrostatic image carrier 1 are opposed to each other with a gap larger than the toner layer thickness, and the one-component non-magnetic toner 5 on 2 is developed by flying onto the electrostatic charge image on 1. The total amount of charge in the toner layer can be controlled by the size or carrier amount of the magnetic brush 52 and the regulating blade 58. The gap between 1 and 2 may be made larger than the toner layer thickness, and a developing bias of 6 may be applied. Example 1 Styrene-butyl methacrylate-dimethylaminoethyl methacrylate (weight ratio 7:2.5:
0.5) Mix 100 parts by weight of copolymer, 10 parts by weight of phthalocyanine blue pigment, and 3 parts by weight of polyethylene wax, and melt-knead with a roll mill. After cooling, it is roughly pulverized in a hammer mill, and then finely pulverized in a jet pulverizer. The mixture was then classified using an air classifier to obtain blue fine powder (toner) having a particle size of approximately 5 to 20 μm. On the other hand, silicic acid fine powder (product name: Aerosil #130, specific surface area approximately 130 m ² /g,
While stirring 100 parts by weight of silicone oil (manufactured by Aerosil), the temperature was maintained at approximately 250°C,
20 parts by weight of amine equivalent (830) was sprayed and treated for 10 minutes. To 100 parts by weight of the blue fine powder, 0.4 parts by weight of the silicic acid fine powder treated with silicone oil having an amine in the side chain was added and mixed to form a positively charged insulating non-containing powder having the treated silicic acid fine powder on the surface of the toner particles. A magnetic toner was prepared. On the other hand, 100 parts by weight of zinc oxide, 20 parts by weight of styrene-butadiene copolymer, n-butyl methacrylate
A mixture consisting of 40 parts by weight, 120 parts by weight of toluene, and 4 parts by weight of 1% rose bengal methanol solution was dispersed and mixed in a ball mill for 6 hours. This is 0.05mm
A zinc oxide binder-based photoreceptor was prepared by coating a thick aluminum plate with a wire bar to a dry coating thickness of 40 μm and evaporating the solvent with hot air, and forming it into a drum shape. This photoreceptor was subjected to -6 KV corona discharge to uniformly charge the entire surface, and then an original image was irradiated to form an electrostatic latent image. The above toner was put into a developing device as shown in FIG. 1, and the electrostatic latent image described above was developed. Here, the toner carrier was a stainless steel cylindrical sleeve with an outer diameter of 50 mm, the distance between the photosensitive drum surface and the sleeve surface was set to 0.25 mm, and an alternating current of 400 Hz, 1000 V, and a direct current bias of -150 V were applied to the sleeve. Next, the powder image was transferred while irradiating -7 KV direct current corona from the back side of the transfer paper to obtain a copied image. Fixing was carried out using a commercially available plain paper copying machine (trade name: NP-5000, manufactured by Canon). The resulting transferred image had a sufficiently high density of 1.45, no fogging, no toner scattering around the image, and a good blue image with high resolution was obtained. Durability was continuously investigated using the above developer.
The transferred image after 50,000 copies was also completely neutral compared to the initial image. In addition, when the environmental conditions were set to 30℃ and 90%, the image density was 1.40, a value that was almost unchanged from normal temperature and humidity, and a clear blue image was obtained without fogging or scattering, and the durability was almost 50,000 sheets. There was no change. Next, a transferred image was obtained at a low temperature of 10°C and 10% humidity, and the image density was as high as 1.40, solid black was developed and transferred extremely smoothly, and the image was excellent with no scattering or hollow spots. When durability tests were carried out under these environmental conditions, the density fluctuation was ±0.2 up to 50,000 sheets, which was sufficient for practical use even though continuous and intermittent copying was performed. Example 2 Styrene-butyl methacrylate-dimethylaminoethyl methacrylate (weight ratio 7:2.5:
0.5) A fine powder was prepared in the same manner as in Example 1, except that 100 parts by weight of the copolymer, 10 parts by weight of the phthalocyanine blue pigment, and 4 parts by weight of polyethylene wax were used. Furthermore, silicic acid fine powder synthesized by dry method (trade name, Aerosil 0x-50, specific surface area approximately 50
m ² /g, manufactured by Aerosil) 100 parts by weight of silicone oil with amine in the side chain (viscosity at 25°C)
Example 1 using 1 part by weight of 60 cps, amine equivalent 360)
It was processed in the same way. To 100 parts by weight of the fine powder, 1 part by weight of the silicic acid fine powder treated with the silicone oil having an amine in the side chain was added to prepare a toner. When this toner was evaluated in the same manner as in Example 1, a clear blue image without fogging was obtained. It also performed well under both high temperature and high humidity, and low temperature and low humidity. Example 3 Styrene-butyl methacrylate-dimethylaminoethyl methacrylate (weight ratio 7:2.5:
0.5) 80 parts by weight of copolymer, 20 parts by weight of styrene-butadiene (weight ratio 85:15) copolymer, 6 parts by weight of phthalocyanine blue, 4 parts by weight of low molecular weight polypropylene
A blue fine powder having a particle size of about 5 to 20 μm was obtained using the same parts by weight as in Example 1. On the other hand, 100 parts by weight of silicic acid fine powder (trade name, Aerosil #200, specific surface area approximately 200 m ² /g, manufactured by Aerosil Co., Ltd.) synthesized by a dry method was used as a silicone oil with an amine in the side chain (viscosity at 25°C: 3500 cps). ,
The treatment was carried out in the same manner as in Example 1 using 100 parts by weight of amine equivalent (3800). When this toner was evaluated in the same manner as in Example 1, good results were obtained. Example 4 100 parts by weight of silicic acid fine powder with a specific surface area of about 90 m ² /g synthesized by a wet method and silicone oil having an amine in the side chain (viscosity, 1300 cps, amine equivalent)
1700) was carried out in substantially the same manner as in Example 1, except that 10 parts by weight was used, and a clear image without fog was obtained. Example 5 100 parts by weight of silicic acid fine powder synthesized by a dry method (trade name, Aerosil #380, specific surface area approximately 380 m ² /g, manufactured by Aerosil) and silicone oil having an amine in the side chain (viscosity 750 cps, amine Equivalent weight 1900) 40
The procedure was carried out in substantially the same manner as in Example 1 except that parts by weight were used, and a clear image without fogging was obtained. Example 6 Specific surface area synthesized by wet method is approximately 120 m ² /g
100 parts by weight of fine silicic acid powder and silicone oil with amine in the side chain (viscosity 1200 cps, amine equivalent
3500) was carried out in substantially the same manner as in Example 1 except that 15 parts by weight was used, and a clear image without fogging was obtained. Examples 7-13 The viscosity and amine equivalent were (250 cps, 7600),
(3500cps, 2000), (1700cps, 3800), (90cps,
4000), (20cps, 320), (90cps, 8800),
(2300 cps, 3800 cps) Except for using a silicone oil having an amine in the side chain, the same procedure as in Example 1 was conducted, and good results were obtained. Example 14 The same procedure as in Example 1 was conducted except that 98 parts by weight of a silicone oil having an amine in the side chain with a viscosity of 60 cps and an amine equivalent of 22,500 was used. However, good images were obtained. The image density was 0.83. Comparative Example 1 The same procedure as in Example 1 was carried out using untreated silicic acid fine powder instead of using silicic acid fine powder treated with silicone oil having an amine in the side chain, but only a poor image was obtained. I couldn't get it. The image density is
It was 0.18. Comparative Example 2 A test was carried out in the same manner as in Example 1, except that an aminosilane coupling agent was used instead of the silicone oil having an amine in the side chain. An image of 0.85 was obtained, but in a high temperature and high humidity environment, the image density decreased significantly to only 0.30, and only a poor image was obtained. The image density under each environment in the above examples is as shown in the table below. Comparative Example 3 A developer was prepared in the same manner as in Example 1 except that fine silicic acid powder treated with dimethyl silicone oil (viscosity 50 cps at 25°C) was used instead of silicone oil having an amine in the side chain. Then, image printing was carried out in the same manner as in Example 1.
Image density under normal temperature and humidity (20℃, 60%) environment
The value was 0.25, and the entire image was pale and had a lot of blur. Under a high temperature, high humidity (30°C, 90%) environment, the image density was even lower, 0.16, and under a low temperature, low humidity (10°C, 10%) environment, the image density was 0.24.

【table】

[Table] Example 15 The toner of Example 1 was put into the device shown in Fig. 2, the vibrating member 16 was vibrated at a frequency of about 50 Hz and an amplitude of 0.2 mm, and the toner carrier 2 was vibrated at a circumferential speed of 120 mm/sec. When rotated, a uniform toner coating layer with a thickness of about 50 μm was formed on the toner carrier. The toner carrier 2 and the electrostatic image holder 1 are placed facing each other with a gap of about 300μ maintained, and the toner carrier 2 has a frequency of 100 to several kilohertz.
Similar good results were obtained when development was carried out by applying a bias AC electric field with a negative peak value of -600 to -1200V and a positive peak value of +400 to +800V. Example 16 The toner shown in Example 1 was applied with a gap between the toner carrier 2 and the application roller 35 of about 2 mm, and a fiber brush 36.
The toner was placed in the developing device shown in Figure 3 whose length was set to approximately 3 mm, the gap between the developing roller and the electrostatic image holder was maintained at 300 μ, and a toner layer of approximately 80 μ was formed on the developing roller. The waveform has a frequency of 200Hz and a DC component of 250V is added to the voltage peak value ±450V.
Similar good results were obtained when developing at peak voltages of +700V and -200V. Example 17 The toner of Example 1 was put into the developing device shown in FIG. 4, which was set so that the gap between the toner carrier 2 and the magnetic roller 48 was about 2 mm, and the maximum thickness of the magnetic brush 52 was about 3 mm. The gap between the developing roller and the electrostatic image holder is maintained at 300μ, a toner layer of approximately 80μ is formed on the developing roller, and the frequency is expressed as an AC waveform.
200Hz, voltage peak value ±450V and DC component 250V
Similar good results were obtained by applying peak voltages of +700V and -200V. Example 18 20g of the toner of Example 1 was placed in an iron powder carrier in advance.
20g and the mixture is passed through the regulation blade 58
The toner is placed in the developing device shown in Fig. 5, which is set so that the gap between the toner and the electrostatic image holder 2 is approximately 250μ, and the gap between the developing roller and the electrostatic image holder 2 is maintained at 300μ.
A toner layer of 80μ is formed on the developing roller, and the frequency is 200Hz as an AC waveform, and the voltage peak value ±
Similar good results were obtained when developing by adding a direct current component of 250 V to 450 V to give voltage peak values of +700 V and -200 V.

[Brief explanation of drawings]

1 to 5 are explanatory views showing examples of embodiments of a developing method using insulating nonmagnetic toner. 1...Electrostatic image holder. 2...Toner carrier. 4... Application means. 5...Toner. 6...Bias power supply.

Claims (1)

[Claims] 1. An electrostatic image carrier that holds an electrostatic image on its surface, and a positively charged insulating non-containing material having on the surface of toner particles silicic acid fine powder treated with silicone oil having an amine in its side chain. A toner carrier carrying magnetic toner on its surface is arranged with a certain gap in the developing section, and a positively charged insulating non-magnetic toner is carried on the toner carrier to a thickness thinner than the gap. A developing method comprising transferring positively charged insulating non-magnetic toner to the electrostatic image holder in a developing section for development. 2. The developing method according to claim 1, wherein in the developing section, an alternating current and/or direct current bias is applied between the toner carrier and the electrostatic image holding surface. 3 Silicone oil with amine in the side chain is
The following structural units [In the formula, R ₁ represents hydrogen, an alkyl group, an aryl group, or an alkoxy group, R ₂ represents an alkylene group or a phenylene group, and R ₃ and R ₄ represent hydrogen, an alkyl group, or an aryl group. ] The developing method according to claim 1 or 2, which has the following. 4 Silicone oil with amine in the side chain is
Amine equivalent 320~8800 and viscosity at 25℃ 20~
Claims 1 to 3 having 3500 cps
The developing method described in any of the paragraphs.