JP2010217608A - Toner carrier, developing device, image forming method and image forming apparatus - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a toner carrier that can stably form toner cloud in a long period of time and develop an electrostatic latent image, to provide a developing device with the toner carrier, and to provide an image forming apparatus. <P>SOLUTION: A hopping developing device is provided, which allows a toner carried by a toner carrying member to hop by an electric field formed by a plurality of electrodes and to develop an electrostatic latent image on a photoreceptor surface. The toner is a droplet solidified toner in a vapor phase, which is produced by forming droplets from a toner composition liquid in a vapor phase, the composition liquid being prepared by dissolving or dispersing a toner composition containing at least a resin, a colorant, and a release agent in a solvent, and subsequently solidifying the droplets. The toner carriers array in a conveyance direction of the toner on an insulating support, and have a surface layer covering the electrodes, wherein the surface layer contains a structural unit expressed by formula (1). In formula (1), R<SP>1</SP>and R<SP>2</SP>each represents a hydrogen atom or an alkyl or aryl group, or R<SP>1</SP>and R<SP>2</SP>form a 5-8C cyclic hydrocarbon residue; R<SP>3</SP>and R<SP>4</SP>each represents a hydrogen or halogen atom or an alkyl or aryl group; a and b are integers of 1 or 2 and respectively represent numbers of R<SP>3</SP>and R<SP>4</SP>substituting in the benzene rings; and when a=2, two of R<SP>3</SP>may be identical or different from each other; when b=2, two of R<SP>4</SP>may be identical or different from each other; and the alkyl groups or aryl groups may have a substituent. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a toner carrier, a developing device including the toner carrier, and an image forming apparatus such as a copying machine, a printer, and a facsimile including the developing device.

In an image forming apparatus such as a copying machine or a printer, a developing device using an electrophotographic process is used. Among such developing devices, a non-contact type developing device that performs development without bringing a toner carrier that conveys developer (toner) into contact with a photosensitive member on which an electrostatic latent image is formed has attracted attention. ing. Examples of non-contact methods include powder round methods, jumping methods, methods using electric field curtains, etc., and toner is caused to fly by an alternating electric field applied to the surface of the toner carrying member facing the surface of the photosensitive member. There is known a hopping development in which a cloud of toner, that is, a cloud, is generated, and toner is supplied from the cloud to an electrostatic latent image on the surface of a photoreceptor to develop the electrostatic latent image.
For example, in Patent Document 1, a toner electric field curtain is formed on the surface of a roller-shaped toner carrier by applying an alternating voltage to a plurality of electrodes arranged at predetermined intervals on an insulating support. A hopping development technique for supplying toner from the electric field curtain to the surface of the photoreceptor is disclosed. We have been engaged in research on such hopping development technology for many years, and many proposals (for example, Japanese Patent Application Laid-Open No. 2004-198675 of Patent Document 2, Japanese Patent Application Laid-Open No. 2007-133388, Patent Document 4). Japanese Patent Laid-Open No. 2008-070674).

However, when the above-described toner cloud is generated, depending on the material constituting the surface layer, the charged toner does not sufficiently hop, and the toner cloud is not formed or even if it is formed, a problem has occurred. .
The present invention has been made in view of the above circumstances, and stably forms a cloud of toner for a long period of time, and supplies the toner to the electrostatic latent image on the surface of the photoreceptor to develop the electrostatic latent image. An object of the present invention is to provide a toner carrier that can be used, a developing device including the toner carrier, and an image forming apparatus.

The present invention provides a surprising combination of a hopping developing device using a specific toner carrier and a specific toner, which is surprisingly unexpected, as compared with many other combinations. As a result of verification, we have come to know that the results of image generation prevention are given. The present invention is based on the findings.
Thus, the above-mentioned problem is (1) “the photosensitive member that faces the toner carrier by hopping the toner carried on the toner carrier by an electric field formed by a plurality of electrodes of the toner carrier. In the hopping developing apparatus for developing the electrostatic latent image on the surface, the toner includes a toner composition solution in which a toner composition containing at least a resin, a colorant, and a release agent is dissolved or dispersed in a solvent. A solidified toner in a gas phase produced by solidifying the droplets and then solidifying the droplets, wherein the toner carrier comprises an insulating support and transport of the toner onto the insulating support An electrode that is arranged in a direction and generates the electric field; and a surface layer that covers the electrode, the surface layer containing a polymer compound that includes a structural unit represented by the following general formula (1) Hoppin characterized by being A developing device;

（一般式（１）において、Ｒ^１、Ｒ^２は水素原子、アルキル基、アリール基、Ｒ^１とＲ^２で形成する炭素数５〜８の環状炭化水素残基を表し、Ｒ^３、Ｒ^４は水素原子、ハロゲン原子、アルキル基、アリール基を表す。また、ａ、ｂは１又は２の整数であり、各々ベンゼン環に置換しているＲ^３、Ｒ^４の個数を表し、ａ＝２のときＲ^３は同一でも異なっていてもよく、ｂ＝２のときＲ^４は同一でも異なっていてもよい。ここで、前記のアルキル基、アリール基は置換基を有していてもかまわない。）」、
（２）「前記トナー担持体の他に、前記トナーを帯電させるトナー帯電手段を有することを特徴とする前記第（１）項に記載の現像装置」、
（３）「前記トナーは、その粒度分布（重量平均粒径／数平均粒径）が１．００〜１．１５であることを特徴とする前記第（１）項又は第（２）項に記載の現像装置」、
（４）「前記トナーは、離型剤を含むものであり、その含有量が樹脂１００質量部に対して０．２〜２０質量部であることを特徴とする前記第（１）項乃至第（３）項のいずれかに記載の現像装置」、
（５）「前記トナーの重量平均粒径が３μｍ〜１０μｍであることを特徴とする前記第（１）項乃至第（４）項のいずれかに記載の現像装置」、
（６）「前記トナー担持体の前記電極は、絶縁性支持体と、前記絶縁性支持体上にトナーの搬送方向に配列され、電界を発生させるものであることを特徴とする前記第（１）項乃至第（５）項のいずれかに記載の現像装置」、
（７）「前記トナー担持体は、前記感光体と空間を有して対面する非接触状態に配置されるものであることを特徴とする前記第（１）項乃至第（６）項のいずれかに記載の現像装置」、
（８）「前記トナー担持体が有する複数の相対する電極が櫛歯に配置されたものであることを特徴とする前記第（１）項乃至第（７）項のいずれかに記載の現像装置」、
（９）「前記トナー担持体が有する複数の相対する電極のうち、一方が下部支持体であり、他方がその上部に絶縁層を介して設けられた複数の電極であることを特徴とする前記第（１）項乃至第（７）項のいずれかに記載の現像装置」；
（１０）「像担持体上に静電潜像を形成する静電潜像形成工程、及び、トナー担持体に担持されたトナーを、該トナー担持体が有する複数の電極が形成する電界によってホッピングさせ、該トナー担持体と対面する感光体表面の静電潜像を現像するホッピング現像工程を含む画像形成方法において、前記トナーは、少なくとも樹脂、着色剤、離型剤を含有するトナー組成物を溶媒に溶解乃至は分散させたトナー組成液を、気相中で液滴化し、次いで該液滴を固化して製造された気相中での液滴固化トナーであり、前記トナー担持体は、絶縁性支持体と、前記絶縁性支持体上にトナーの搬送方向に配列され、前記電界を発生させる電極と、該電極を被覆する表面層とを有し、該表面層は、上記一般式（１）で示される構造単位を含む重合化合物を含有しているものであることを特徴とする画像形成方法；
（１１）「像担持体上に静電潜像を形成する静電潜像形成手段、及び、トナー担持体に担持されたトナーを、該トナー担持体が有する複数の電極が形成する電界によってホッピングさせ、該トナー担持体と対面する感光体表面の静電潜像を現像するホッピング現像手段を含む画像形成装置において、該ホッピング現像手段が前記第（１）項乃至第（９）項のいずれかに記載の現像装置であることを特徴とする画像形成装置」により解決される。

(In the general formula ^(1), R 1, ^{R 2} represents a hydrogen atom, an alkyl group, an aryl group, a cyclic hydrocarbon residue having a carbon formed by ^{R 1} and ^{R 2 5~8, R 3, R} 4 Represents a hydrogen atom, a halogen atom, an alkyl group or an aryl group, and a and b are integers of 1 or 2, each representing the number of R ³ and R ⁴ substituted on the benzene ring, and a = 2 In this case, R ³ may be the same or different, and when b = 2, R ⁴ may be the same or different, wherein the alkyl group and aryl group may have a substituent. .) ",
(2) “Developing device according to item (1), further including toner charging means for charging the toner in addition to the toner carrier”;
(3) In the item (1) or item (2), the toner has a particle size distribution (weight average particle size / number average particle size) of 1.00 to 1.15. The developing device ",
(4) “The toner includes a release agent, and the content thereof is 0.2 to 20 parts by mass with respect to 100 parts by mass of the resin. (3) the developing device according to any one of items
(5) “The developing device according to any one of (1) to (4) above, wherein the toner has a weight average particle diameter of 3 μm to 10 μm”;
(6) “The electrode of the toner carrying member is an insulating support, and is arranged in the toner transport direction on the insulating support to generate an electric field. ) To the developing device according to any one of (5) to "
(7) Any of the above-mentioned items (1) to (6), wherein the toner carrying member is disposed in a non-contact state facing the photoconductor with a space. The developing device according to
(8) “The developing device according to any one of (1) to (7) above, wherein a plurality of opposing electrodes of the toner carrier are arranged in a comb tooth. "
(9) “One of the plurality of opposing electrodes of the toner carrying member is a lower support, and the other is a plurality of electrodes provided on the upper portion with an insulating layer interposed therebetween. The developing device according to any one of items (1) to (7);
(10) “An electrostatic latent image forming step for forming an electrostatic latent image on an image carrier, and hopping the toner carried on the toner carrier by an electric field formed by a plurality of electrodes of the toner carrier. And a toner composition containing at least a resin, a colorant, and a release agent in the image forming method including a hopping development step of developing an electrostatic latent image on the surface of the photoreceptor facing the toner carrier. A toner composition liquid dissolved or dispersed in a solvent is formed into droplets in the gas phase, and then solidified into the droplets, and is solidified in the gas phase. The toner carrier comprises: An insulating support; an electrode arranged on the insulating support in a toner transport direction; for generating the electric field; and a surface layer for covering the electrode. 1) Polymerized compound containing the structural unit Image forming method which is characterized in that those containing;
(11) “Electric latent image forming means for forming an electrostatic latent image on an image carrier, and toner carried on the toner carrier by hopping by an electric field formed by a plurality of electrodes of the toner carrier. In the image forming apparatus including the hopping developing unit that develops the electrostatic latent image on the surface of the photosensitive member facing the toner carrier, the hopping developing unit is any one of the items (1) to (9). The image forming apparatus characterized in that it is a developing device described in 1).

  According to the present invention, a combination of a hopping developing apparatus using a specific toner carrier and a specific toner, that is, an electric field formed by a plurality of electrodes of the toner carrier, which is the toner carried on the toner carrier. In the hopping developing apparatus for developing the electrostatic latent image on the surface of the photoreceptor facing the toner carrier, a toner composition containing at least a resin, a colorant, and a release agent is dissolved in a solvent as the toner. Or a dispersed solidified toner in the gas phase produced by forming the dispersed toner composition liquid into droplets in the gas phase and then solidifying the droplets, and the toner carrier has an insulating support. And an electrode for generating the electric field, and a surface layer covering the electrode. The surface layer is represented by the following general formula (1). Structure shown The hopping development, characterized in that those containing the polymerizable compound containing the developing device for a long period of time stably capable of forming a cloud of toner.

（一般式（１）において、Ｒ^１、Ｒ^２は水素原子、アルキル基、アリール基、Ｒ^１とＲ^２で形成する炭素数５〜８の環状炭化水素残基を表し、Ｒ^３、Ｒ^４は水素原子、ハロゲン原子、アルキル基、アリール基を表す。また、ａ、ｂは１又は２の整数であり、各々ベンゼン環に置換しているＲ^３、Ｒ^４の個数を表し、ａ＝２のときＲ^３は同一でも異なっていてもよく、ｂ＝２のときＲ^４は同一でも異なっていてもよい。ここで、前記のアルキル基、アリール基は置換基を有していてもかまわない。）

(In the general formula ^(1), R 1, ^{R 2} represents a hydrogen atom, an alkyl group, an aryl group, a cyclic hydrocarbon residue having a carbon formed by ^{R 1} and ^{R 2 5~8, R 3, R} 4 Represents a hydrogen atom, a halogen atom, an alkyl group or an aryl group, and a and b are integers of 1 or 2, each representing the number of R ³ and R ⁴ substituted on the benzene ring, and a = 2 In this case, R ³ may be the same or different, and when b = 2, R ⁴ may be the same or different, wherein the alkyl group and aryl group may have a substituent. .)

  Thus, it is possible to provide a toner carrier capable of developing the electrostatic latent image for a long period of time by supplying toner to the electrostatic latent image on the surface of the photoreceptor, and a developing device and an image forming apparatus including the toner carrier. it can.

1 is a cross-sectional view illustrating a schematic configuration of a developing device according to an embodiment of the present invention. It is explanatory drawing of the state of an electric field change of the example of a comb-tooth-type toner carrier in this invention, and the shape of an electrode. FIG. 2 is a perspective view illustrating a configuration of an example of a developing device illustrated in FIG. 1. FIG. 2 is a schematic diagram illustrating a cloud state of toner in the example of the developing device illustrated in FIG. 1. 1 is a diagram illustrating an embodiment of a developing device for two-component development in the present invention. It is explanatory drawing of the state of an electric field change of the example of an upper-and-lower electrode type toner carrier in this invention, and the shape of an electrode.

Hereinafter, embodiments of the present invention will be described in detail with reference to the drawings.
FIG. 1 is a diagram illustrating a schematic configuration example of a developing device (and an image forming apparatus using the same) according to an embodiment of the present invention.
In FIG. 1, (1) is a drum-shaped photoconductor rotating in the direction of the arrow (A), (2) is a charging roller for uniformly charging the surface of the photoconductor (1), and (3) is for image information. An exposure device that irradiates the surface of the photoreceptor (1) with laser light or the like, and (4) is a developing device that supplies toner to the electrostatic latent image formed on the surface of the photoreceptor (1). (5) is a transfer roller for transferring the toner image formed by the developing device (3) on the surface of the photoreceptor (1) onto a transfer material (P) such as transfer paper, and (6) is on the transfer material (P). The cleaning device removes toner remaining on the surface of the photoreceptor (1) from the surface of the photoreceptor (1) after transferring the toner image. (7) is a fixing device that heats and presses the unfixed toner image transferred onto the transfer material (P) and fixes it on the transfer material (P).

A method for forming a toner image on the transfer material (P) using this image forming apparatus will be described.
The surface of the photoreceptor (1) rotating in the direction of the arrow (A) is uniformly charged by applying a predetermined voltage by the charging roller (2). An electrostatic latent image is formed on the surface of the photoconductor (1) by irradiating the surface of the photoconductor (1) uniformly charged with laser light corresponding to desired image information from the exposure device (3). To do. Subsequently, toner is supplied from the developing device (4) to the electrostatic latent image formed in this way, and electrostatically attached to form the electrostatic latent image into a toner image. The toner image thus formed is biased while the surface of the photoreceptor (1) and the transfer material (P) are pressed against each other by the transfer roller (5) and the transfer material (P) is conveyed in the direction of the arrow (B). A voltage is applied to transfer from the surface of the photoreceptor (1) to the surface of the transfer material (P). Thereafter, the toner image transferred onto the transfer material (P) is heated and pressed by the heating roller (7a) and the pressure roller (7b) of the fixing device (7) to be fixed on the transfer material (P). The photosensitive member (1) having the toner image transferred onto the transfer material (P) in this way removes the toner remaining on the surface of the photosensitive member (1) by the cleaning device (6) and removes the toner on the photosensitive member (1). The surface is cleaned and again uniformly charged by the charging roller (2). Thereafter, as described above, an electrostatic latent image is formed by the exposure device (3), the electrostatic latent image is converted into a toner image by the developing device (4), and is transferred onto the transfer material (P) by the transfer roller (5). The operation of transferring the toner image and cleaning the surface of the photoreceptor (1) by the cleaning device (6) is repeated.

  As described above, the present invention is characterized by the developing device (4) that converts the electrostatic latent image formed on the surface of the photoreceptor (1) into a toner image with toner.

(Description of charging means for one-component development)
As shown in FIG. 1, the developing device (4) according to one embodiment of the present invention has a container (8) for storing toner (T), and a toner (photoreceptor (1)) and a container (8) opening. A developing roller (9), which is a toner carrier supplied from the section (8a), is rotatably mounted and is rotated in the direction of arrow (C) by a driving means (not shown). Then, the toner (T) is circulated while being stirred by the circulation paddle (10) to charge the toner (T), and the toner (T) is supplied to the surface of the developing roller (9).

(Description of charging means for two-component development)
FIG. 5 shows another embodiment of the present invention. The developing roller (9), which is a toner carrier, is in contact with the spikes of the two-component developer by an ordinary two-component developer (56). Specifically, a two-component developer in which a magnetic carrier powder having a particle size of 50 [μm] and a polyester toner having a particle size of about 6 [μm] are mixed in a weight ratio of 7 to 8 [wt%] The magnetic sleeve (57) containing the permanent magnet (56) is conveyed to the developing roller (9), and a part of the toner is applied to the DC sleeve between the magnetic sleeve (57) and the developing roller (9). The electric potential is supplied to the surface of the developing roller (9).

  The developing roller (9) supplied with the toner (T) in this manner is pumped up while holding the toner (T) on the surface thereof by electrostatic force, and has a predetermined distance from the developing roller (9). The amount of toner pumped up is regulated by the blade-like toner regulating member (11) attached to 8). As will be described later, an alternating electric field is applied to the developing roller (9) at the opening (8a) to form a cloud of toner (T). As a result, the toner (T) is electrostatically supplied from the cloud to the electrostatic latent image on the surface of the photoreceptor (1) to form a toner image. Reference numeral (12) in FIG. 1 denotes a toner supply port for supplying replenished toner.

  As shown in the configuration of the electrodes, there are two types of configurations as shown in FIGS.

(Comb electrode application method)
As shown in FIGS. 2A and 2B (FIG. 2A is a cross-sectional view taken along the line AA ′ in the top view of FIG. 2B), the developing roller 9 is as shown in FIG. A first electrode pattern (9bA) having a plurality of linear electrodes (9bAa) and a second electrode pattern (9bB) having a plurality of linear electrodes (9bBb) include an electrode (9bAa) and an electrode (9bBb). Are alternately formed parallel to the axial direction of the developing roller. The electrode patterns (9bA) and (9bB) were formed by depositing a copper thin film on the peripheral surface of a cylindrical support (93) having a rotating shaft (9d) in FIG. It is possible by processing into a desired shape by a photoresist method from
The method for forming the electrode is not particularly limited, and the electrode may be formed by drawing using, for example, an ink jet apparatus in addition to patterning using a photoresist method. Moreover, there is no limitation in particular about the magnitude | size of a resin support body (93), What is necessary is just to use what the practitioner of this invention selected suitably. Also, the width (d) of each of the electrode (9bAa), the electrode (9bBa), and the electrode (9bBb) and the distance (D) between the electrode (9bAa) and the electrode (9bBb) are not particularly limited. The practitioner may determine as appropriate.
As the support (93), a cylindrical insulating support formed from a synthetic resin such as polyimide, polycarbonate, nylon, fluororesin, polyacetal, phenol, polystyrene, or aluminum, aluminum alloy, nickel, titanium, A cylindrical metal conductive support (9a) obtained by cutting or polishing stainless steel or the like and processing the metal can be used.
Further, a surface layer (9c) for covering and protecting these electrodes (9bA) and (9bB) is formed on the electrode patterns (9bA) and (9bB).

  In the present invention, as a result of an eager search for a toner carrier surface layer constituent material capable of stably forming a toner cloud for a long period of time, the inventors have found that a polymer compound containing the structural unit represented by the general formula (1) is a surface layer. When it is contained in (9c), the detailed principle has not been clarified, but it has been found that a toner cloud can be stably formed for a long period of time.

In the general formula (1), R ¹ and R ² represent a hydrogen atom, an alkyl group, an aryl group, a cyclic hydrocarbon residue having 5 to 8 carbon atoms formed by R ¹ and R ² , and R ³ and R ⁴ are A hydrogen atom, a halogen atom, an alkyl group, or an aryl group is represented. A and b are integers of 1 or 2, each representing the number of R ³ and R ⁴ substituted on the benzene ring, and when a = 2, R ³ may be the same or different; b = 2 In this case, R ⁴ may be the same or different. Here, the alkyl group and aryl group may have a substituent.

  Although the specific example of the structure contained in General formula (1) is shown to the following (M-1)-(M-19), the material which can be used for this invention is not limited to these.

The molecular weight of the polymerization compound is preferably 30,000 to 60,000 because it is easy to handle when dissolved in a solvent.
Further, the surface layer may contain a leveling agent as an additive in the polycarbonate resin.
As the leveling agent, known materials can be used, but a silicone oil leveling agent capable of imparting high smoothness in a small amount is particularly preferable. Examples of silicone oils include dimethyl silicone oil, methyl phenyl silicone oil, methyl hydrogen polysiloxane, cyclic dimethyl polysiloxane, alkyl-modified silicone oil, polyether-modified silicone oil, alcohol-modified silicone oil, fluorine-modified silicone oil, amino-modified Examples include silicone oil, mercapto-modified silicone oil, epoxy-modified silicone oil, carboxyl-modified silicone oil, higher fatty acid-modified silicone oil, and higher fatty acid-containing silicone oil.
In addition, an appropriate amount of additives such as a plasticizer and an antioxidant can be added to the surface layer.
The surface layer can be formed by a commonly used coating method such as a dip coating method or a spray coating method using one or more solvents soluble in a polycarbonate resin such as tetrahydrofuran.

  The film thickness of the surface layer (c) may be any as long as it can form a toner electric field curtain on the surface of the toner carrier, and the electrode (9b) can prevent exposure to the surface of the toner carrier. The thickness is preferably 100 μm or less.

  The surface layer and the insulating layer may each comprise a plurality of layers, but the outermost layer of the surface layer must contain a polymer compound containing the structural unit represented by the general formula (1).

  As shown in FIG. 3, the electrodes (9bA) and (9bB) of the electrode pattern (9b) are formed so that the opposing end portions are long, and the long ends (9bA1) and (9bB1) These portions may be exposed and electrically connected to terminals (13A) and (13B) respectively attached to the opening (8a) side of the container (8). An alternating voltage (14) is applied to the terminals (13A) and (13B), and a plurality of electrodes (9bA) and (9bA) of the electrode pattern (9b) are generated by the alternating electric field applied from the terminals (13A) and (13B). The electric field between 9bB) changes with time. As a result, the toner (T) held on the surface layer (9c) of the developing roller (9) by the electric field applied between the electrodes (9bA) and (9bB) of the electrode pattern (9b) is shown in FIG. As shown, a cloud is formed by flying between the surface of the photoreceptor (1) and the surface layer (9c) of the developing roller (9), and the toner (T) of this cloud is the surface of the photoreceptor (1). A toner image is formed by electrostatically attracting and adhering to the electrostatic latent image formed on the toner.

The formation of such a cloud is influenced by the width (d), interval (D), alternating voltage, and the like of the electrodes (9bA) and (9bB) of the electrode pattern (9b). Although there is no particular limitation on the size of the electrode pattern, in order to form a good cloud in the developing roller of FIG. 3, the width (d) and interval (D) of the electrodes (9bA) and (9bB) of the electrode pattern (9b) May be set to a width of 40 μm to 250 μm and an interval of 85 μm to 500 μm, respectively. Moreover, as an alternating voltage, frequency 100Hz-5KHz and 100V-3KV are suitable.
In the developing roller (9) in this embodiment, a single-phase alternating voltage is used as the alternating voltage power supply, but a plurality of alternating voltage power supplies having different periods can also be used. In this case, as the electrode pattern (9b), a plurality of electrodes (9b) having different end lengths are formed adjacent to each other corresponding to the period, and a plurality of terminals connected at the end portions having the same length are attached. Alternatively, alternating voltages of different phases may be applied from each terminal. When such a plurality of alternating voltage power supplies having different periods are used, a traveling wave cloud can be formed.

(Upper and lower electrode application method)
FIG. 6 shows an upper and lower electrode application method as another example. The same reference numerals as those in FIG. 2 represent the same meaning. However, in this example, the support (conductive) is grounded, the support (91A) is made conductive instead of the electrode (9bAa), and an electrode pair is provided between this electrode and the upper electrode (9bB). Is formed. As shown in FIG. 6 of the electrode, the conductive support may be the A phase, and the electrode formed by the photoresist method may be the B phase. A crucial difference from the comb-teeth electrode application method is that the support is not an insulating support, but a conductive support covered with an insulating film.
That is, as shown in FIGS. 6A and 6B (note that FIG. 6A is a cross-sectional view taken along line AA ′ in the top view of FIG. 6B), a conductive support ( 9bA), using a support provided with an insulating layer (95) on it, the conductive support (91A) has the function of one of the two electrodes (9bA) and (9bB) of the comb electrode system. The conductive support (91A) is the A phase, and the electrode pattern (9b) having a plurality of linear electrodes (9bB) formed on the insulating layer (95) and protected by the surface layer (9c) is the B phase. The toner particles are hopped by a potential difference between the conductive support (91A) and the electrode (9bB) to form a toner cloud. The electrode (91bB) is covered with a surface layer (9c). As the conductive support (91A), a support made of a material having excellent conductivity such as aluminum or an aluminum alloy can be used. In addition, a conductive film made of a material having excellent conductivity such as aluminum or aluminum alloy is coated on a support formed from a synthetic resin such as polyimide, polycarbonate, nylon, fluorine resin, polyacetal, phenol, or polystyrene. A thing may be used. Moreover, there is no limitation in particular about the magnitude | size of an electroconductive support body (91A), What is necessary is just to use what the practitioner of this invention selected suitably. Further, the width (d) of the electrode (9bB) and the distance (D) between the electrodes (9bB) (9bB) are not particularly limited, and may be determined as appropriate by the practitioner of the invention.

  The surface layer (9c) described above may be formed of a polycarbonate resin having the general formula (1) added with an acceptor that accepts the charge on the charged toner surface. The thickness of the surface layer (9c) is not particularly limited, but the film thickness is preferably 3 μm or more and 20 μm or less so that no leakage occurs between the electrode and the toner and the electric field strength does not become too weak. . By setting the surface layer (9c) to such a film thickness, it becomes difficult for toner cloud to become unstable due to a decrease in hopping electric field strength.

Examples of the acceptor include naphthalene tetracarboxylic acid diimide, chloroanil, bromoanil, tetracyanoethylene, tetracyanoquinodimethane, 2,4,7-trinitro-9-fluorenone, 2,4,5,7-tetranitro. -9-fluorenone, 2,4,5,7-tetranitroxanthone, 2,4,8-trinitrothioxanthone, 2,6,8-trinitro-4H-indeno [1,2-b] thiophen-4-one , 1,3,7-trinitrodibenzothiophene-5,5-dioxide, and diphenoquinone derivatives.
These electron accepting substances can be used alone or as a mixture of two or more. The content of the electron-accepting substance in the surface layer is not particularly limited, but it is preferably contained at a concentration of about 40 wt% so that the surface potential of the developing roller immediately after the toner cloud formation becomes the initial value (0 V). .

  In addition, the insulating layer (95) is composed of the polycarbonate resin of the general formula (1), polyester, polyimide, other types of polycarbonate, nylon, fluororesin, polyacetal, phenol, polystyrene and other synthetic resins, polyvinyl alcohol, Case-in, water-soluble resins such as sodium polyacrylate, alcohol-soluble resins such as copolymer nylon and methoxymethylated nylon, curable resins that form a three-dimensional network structure such as polyurethane, melamine resin, alkyd resin, and epoxy resin You may use together the material which has 1 or 2 or more insulating properties selected from the inside.

  The toner in the present invention may or may not contain a wax. In order to suppress a significant change in the surface potential of the toner carrier due to charge transfer that occurs when the toner and the surface of the toner carrier are in contact with each other, the ionization potential of the surface layer (9c) is set to 0 less than the ionization potential of the toner. It is preferable to increase it by 2 eV or more.

  In the above embodiment, a rotating roller is used as the toner carrier. However, the toner carrier according to the present invention is not limited to a roller, and a plurality of electrodes are arranged at predetermined intervals on an insulating support. It is also possible to use an endless belt having a surface layer coated with a plurality of electrodes, and to rotate and transfer the endless belt over the opening (8a) of the developing device (4). Further, a plurality of electrodes are arranged on the insulating support at predetermined intervals, and an arcuate support having a surface layer covering the plurality of electrodes is formed on the opening (8a) of the developing device (4). Even if they are fixedly arranged, the same actions and effects can be achieved.

  In addition, in the present invention, as a result of earnestly searching for a toner that can stably form a cloud of toner for a long period of time, the inventor dissolved or dissolved a toner composition containing at least a resin, a colorant, and a release agent in a solvent. It has been found that when a dispersed toner composition liquid is formed into droplets in the gas phase and then the toner produced by solidifying the droplets is used, a toner cloud can be stably formed for a long period of time. .

(toner)
The toner has a particle size distribution (weight average particle diameter / number average particle diameter) of 1.00 to 1.15. The toner material used for the toner is the same as that of a conventional electrophotographic toner. Can be used. That is, a graft polymer that dissolves a toner binder such as a styrene acrylic resin, a polyester resin, a polyol resin, and an epoxy resin in various organic solvents, disperses a colorant, and is a release agent and a dispersion stabilizer. The desired toner particles can be produced by dispersing or dissolving the particles and then drying and solidifying them as fine droplets by the toner production method. It is also possible to obtain the desired toner by drying and solidifying a liquid obtained by dissolving or dispersing the kneaded material obtained by hot-melt kneading the above materials in various solvents once into fine droplets by the toner production method. is there. By adding a release agent and a graft polymer to the toner, offset resistance is improved, and the dispersed particle size of the release agent can be reduced and re-aggregation can be prevented, thereby preventing nozzle clogging. be able to.

(Toner composition)
The toner composition contains at least a resin, a colorant, a release agent, and, if necessary, the graft polymer. Further, if necessary, a charge control agent, a magnetic material, a fluidity improver, a lubricant, Contains other components such as cleaning aids and resistance adjusters.
A toner composition liquid in which the toner composition is dissolved or dispersed in a solvent is discharged from a nozzle to form droplets to produce toner particles.

(solvent)
The solvent is preferably an organic solvent, and the organic solvent is not particularly limited. However, since it is easy to remove, the boiling point is preferably less than 150 ° C., for example, toluene, xylene, benzene, carbon tetrachloride, chloride. Examples include methylene, 1,2-dichloroethane, 1,1,2-trichloroethane, trichloroethylene, chloroform, monochlorobenzene, dichloroethylidene, methyl acetate, ethyl acetate, methyl ethyl ketone, and methyl isobutyl ketone. . Among them, since the solubility of the polyester resin is excellent, the organic solvent preferably has a solubility parameter of 8 to 9.8 (cal / cm ³ ) ^1/2 , and 8.5 to 9.5 (cal / cm). ³ ) ^1/2 is more preferable. Furthermore, since the interaction with the modifying group of the release agent is large and the crystal growth of the release agent can be effectively suppressed, ester solvents and ketone solvents are preferable, and removal is easy. Therefore, ethyl acetate and methyl ethyl ketone are particularly preferable.

(resin)
Examples of the resin include at least a binder resin. The binder resin is not particularly limited, and a commonly used resin can be appropriately selected and used. For example, from a styrene monomer, an acrylic monomer, a methacrylic monomer, etc. Vinyl polymers, copolymers of these monomers or two or more types, polyester polymers, polyol resins, phenol resins, silicone resins, polyurethane resins, polyamide resins, furan resins, epoxy resins, xylene resins, terpenes Examples thereof include resins, coumarone indene resins, polycarbonate resins, and petroleum resins.

  Examples of the styrene monomer include styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, p-phenylstyrene, p-ethylstyrene, 2,4-dimethylstyrene, and pn-. Amyl styrene, p-tert-butyl styrene, pn-hexyl styrene, pn-octyl styrene, pn-nonyl styrene, pn-decyl styrene, pn-dodecyl styrene, p-methoxy styrene , Styrene such as p-chlorostyrene, 3,4-dichlorostyrene, m-nitrostyrene, o-nitrostyrene, p-nitrostyrene, or derivatives thereof.

  Examples of the acrylic monomer include acrylic acid, methyl acrylate, ethyl acrylate, propyl acrylate, n-butyl acrylate, isobutyl acrylate, n-octyl acrylate, n-dodecyl acrylate, and acrylic. Examples include 2-ethylhexyl acid, stearyl acrylate, 2-chloroethyl acrylate, acrylic acid such as phenyl acrylate, or esters thereof.

  Examples of the methacrylic monomer include methacrylic acid, methyl methacrylate, ethyl methacrylate, propyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, n-octyl methacrylate, n-dodecyl methacrylate, and methacrylic acid. And methacrylic acid or esters thereof such as 2-ethylhexyl, stearyl methacrylate, phenyl methacrylate, dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate, and the like.

The following (1)-(18) is mentioned as an example of the other monomer which forms the said vinyl polymer or a copolymer.
(1) Monoolefins such as ethylene, propylene, butylene, isobutylene;
(2) Polyenes such as butadiene and isoprene;
(3) Vinyl halides such as vinyl chloride, vinyl chloride, vinyl bromide and vinyl fluoride;
(4) Vinyl esters such as vinyl acetate, vinyl propionate and vinyl benzoate;
(5) Vinyl ethers such as vinyl methyl ether, vinyl ethyl ether, vinyl isobutyl ether;
(6) Vinyl ketones such as vinyl methyl ketone, vinyl hexyl ketone, methyl isopropenyl ketone;
(7) N-vinyl compounds such as N-vinylpyrrole, N-vinylcarbazole, N-vinylindole, N-vinylpyrrolidone;
(8) vinyl naphthalenes;
(9) Acrylic acid or methacrylic acid derivatives such as acrylonitrile, methacrylonitrile, acrylamide, etc .;
(10) unsaturated dibasic acids such as maleic acid, citraconic acid, itaconic acid, alkenyl succinic acid, fumaric acid, mesaconic acid;
(11) unsaturated dibasic acid anhydrides such as maleic acid anhydride, citraconic acid anhydride, itaconic acid anhydride, alkenyl succinic acid anhydride;
(12) Maleic acid monomethyl ester, maleic acid monoethyl ester, maleic acid monobutyl ester, citraconic acid monomethyl ester, citraconic acid monoethyl ester, citraconic acid monobutyl ester, itaconic acid monomethyl ester, alkenyl succinic acid monomethyl ester, fumaric acid Monoesters of unsaturated dibasic acids such as monomethyl esters, mesaconic acid monomethyl ester;
(13) Unsaturated dibasic acid esters such as dimethylmaleic acid and dimethylfumaric acid;
(14) α, β-unsaturated acids such as crotonic acid and cinnamic acid;
(15) α, β-unsaturated acid anhydrides such as crotonic acid anhydride and cinnamic acid anhydride;
(16) Monomers having a carboxyl group such as anhydrides of the α, β-unsaturated acid and lower fatty acids, alkenylmalonic acid, alkenylglutaric acid, alkenyladipic acid, acid anhydrides and monoesters thereof;
(17) Acrylic acid or methacrylic acid hydroxyalkyl esters such as 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate;
(18) Monomers having a hydroxy group such as 4- (1-hydroxy-1-methylbutyl) styrene and 4- (1-hydroxy-1-methylhexyl) styrene.

  In the toner of the present invention, the vinyl polymer or copolymer of the binder resin may have a crosslinked structure crosslinked with a crosslinking agent having two or more vinyl groups. Examples of the crosslinking agent used in this case include aromatic vinyl vinyl compounds such as divinylbenzene and divinylnaphthalene. Examples of diacrylate compounds linked by an alkyl chain include ethylene glycol diacrylate, 1,3-butylene glycol diacrylate, 1,4-butanediol diacrylate, 1,5-pentanediol diacrylate, and 1,6. And xanthdiol diacrylate, neopentyl glycol diacrylate, and those obtained by replacing acrylates of these compounds with methacrylate. Examples of diacrylate compounds linked by an alkyl chain containing an ether bond include diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, polyethylene glycol # 400 diacrylate, polyethylene glycol # 600 diacrylate, and dipropylene. Examples include glycol diacrylate and those obtained by replacing acrylate of these compounds with methacrylate.

  Other examples include diacrylate compounds and dimethacrylate compounds linked by a chain containing an aromatic group and an ether bond. Examples of polyester diacrylates include trade name MANDA (manufactured by Nippon Kayaku Co., Ltd.).

Examples of the polyfunctional crosslinking agent include pentaerythritol triacrylate, trimethylol ethane triacrylate, trimethylol propane triacrylate, tetramethylol methane tetraacrylate, oligoester acrylate, and acrylates of the above compounds in place of methacrylate, triallyl cyanide. Examples include nurate and triallyl trimellitate.
These cross-linking agents are preferably used in an amount of 0.01 to 10 parts by mass, and 0.03 to 5 parts by mass, with respect to 100 parts by mass of the other monomers forming the vinyl polymer or copolymer. More preferred. Among these crosslinkable monomers, diacrylates bonded to a toner resin from a bond chain containing an aromatic divinyl compound (particularly divinylbenzene), an aromatic group, and an ether bond from the viewpoint of fixability and offset resistance. Preferred examples include compounds. Among these, a combination of monomers that becomes a styrene copolymer or a styrene-acrylic copolymer is preferable.

  Examples of the polymerization initiator used in the production of the vinyl polymer or copolymer of the present invention include 2,2′-azobisisobutyronitrile, 2,2′-azobis (4-methoxy-2,4- Dimethylvaleronitrile), 2,2′-azobis (2,4-dimethylvaleronitrile), 2,2′-azobis (2-methylbutyronitrile), dimethyl-2,2′-azobisisobutyrate, 1 , 1′-azobis (1-cyclohexanecarbonitrile), 2- (carbamoylazo) -isobutyronitrile, 2,2′-azobis (2,4,4-trimethylpentane), 2-phenylazo-2 ′ , 4′-dimethyl-4′-methoxyvaleronitrile, 2,2′-azobis (2-methylpropane), methyl ethyl ketone peroxide, acetylacetone peroxide, Ketone peroxides such as rohexanone peroxide, 2,2-bis (tert-butylperoxy) butane, tert-butyl hydroperoxide, cumene hydroperoxide, 1,1,3,3-tetramethylbutyl Hydroperoxide, di-tert-butyl peroxide, tert-butylcumyl peroxide, dicumyl peroxide, α- (tert-butylperoxy) isopropylbenzene, isobutyl peroxide, octanoyl peroxide, decanoyl peroxide , Lauroyl peroxide, 3,5,5-trimethylhexanoyl peroxide, benzoyl peroxide, m-tolyl peroxide, di-isopropylperoxydicarbonate, di-2-ethylhexylpero Xidicarbonate, di-n-propyl peroxydicarbonate, di-2-ethoxyethyl peroxycarbonate, di-ethoxyisopropyl peroxydicarbonate, di (3-methyl-3-methoxybutyl) peroxycarbonate, acetylcyclo Hexylsulfonyl peroxide, tert-butyl peroxyacetate, tert-butyl peroxyisobutyrate, tert-butyl peroxy-2-ethylhexarate, tert-butyl peroxylaurate, tert-butyl-oxybenzoate, tert-butylperoxyisopropyl carbonate, di-tert-butylperoxyisophthalate, tert-butylperoxyallyl carbonate, isoamylperoxy-2-ethylhexanoate, di- tert- butylperoxy to hexa hydro terephthalate, tert- butylperoxy azelate, and the like.

  In the case where the binder resin is a styrene-acrylic resin, the molecular weight distribution by GPC soluble in the resin component tetrahydrofuran (THF) is at least one in the region of molecular weight 3,000 to 50,000 (in terms of number average molecular weight). A resin having a peak and having at least one peak in a region having a molecular weight of 100,000 or more is preferable in terms of fixing property, offset property, and storage property. Further, as the THF soluble component, a binder resin in which a component having a molecular weight distribution of 100,000 or less is 50 to 90% is preferable, and a binder resin having a main peak in a region having a molecular weight of 5,000 to 30,000. Is more preferable, and a binder resin having a main peak in the region of 5,000 to 20,000 is most preferable.

  The acid value when the binder resin is a vinyl polymer such as styrene-acrylic resin is preferably 0.1 mgKOH / g to 100 mgKOH / g, and preferably 0.1 mgKOH / g to 70 mgKOH / g. More preferably, it is most preferably 0.1 mgKOH / g to 50 mgKOH / g.

  The following are mentioned as a monomer which comprises a polyester-type polymer. Examples of the divalent alcohol component include ethylene glycol, propylene glycol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, diethylene glycol, triethylene glycol, 1,5-pentanediol, 1,6-hexanediol, neopentyl glycol, 2-ethyl-1,3-hexanediol, hydrogenated bisphenol A, or diol obtained by polymerizing cyclic ethers such as ethylene oxide and propylene oxide to bisphenol A, etc. Is mentioned.

  In order to crosslink the polyester resin, it is preferable to use a trivalent or higher alcohol together. Examples of the trihydric or higher polyhydric alcohol include sorbitol, 1,2,3,6-hexanetetrol, 1,4-sorbitan, pentaerythritol, such as dipentaerythritol, tripentaerythritol, 1,2,4- Butanetriol, 1,2,5-pentatriol, glycerol, 2-methylpropanetriol, 2-methyl-1,2,4-butanetriol, trimethylolethane, trimethylolpropane, 1,3,5-trihydroxybenzene , Etc.

  Examples of the acid component that forms the polyester polymer include benzene dicarboxylic acids such as phthalic acid, isophthalic acid, and terephthalic acid or anhydrides thereof, alkyldicarboxylic acids such as succinic acid, adipic acid, sebacic acid, and azelaic acid, or Unsaturated dibasic acids such as anhydride, maleic acid, citraconic acid, itaconic acid, alkenyl succinic acid, fumaric acid, mesaconic acid, maleic anhydride, citraconic anhydride, itaconic anhydride, alkenyl succinic anhydride And unsaturated dibasic acid anhydrides. Examples of the trivalent or higher polyvalent carboxylic acid component include trimet acid, pyromet acid, 1,2,4-benzenetricarboxylic acid, 1,2,5-benzenetricarboxylic acid, 2,5,7-naphthalenetricarboxylic acid, 1,2,4-naphthalenetricarboxylic acid, 1,2,4-butanetricarboxylic acid, 1,2,5-hexanetricarboxylic acid, 1,3-dicarboxy-2-methyl-2-methylenecarboxypropane, tetra (methylene Carboxy) methane, 1,2,7,8-octanetetracarboxylic acid, empol trimer acid, or anhydrides thereof, partial lower alkyl esters, and the like.

When the binder resin is a polyester-based resin, the toner has fixability and offset resistance because the molecular weight distribution of the THF soluble component of the resin component has at least one peak in the molecular weight region of 3,000 to 50,000. In addition, as a THF soluble component, a binder resin in which a component having a molecular weight of 100,000 or less is 60 to 100% is preferable, and at least one peak exists in a region having a molecular weight of 5,000 to 20,000. A binder resin is more preferable.
When the binder resin is a polyester resin, the acid value is preferably 0.1 mgKOH / g to 100 mgKOH / g, more preferably 0.1 mgKOH / g to 70 mgKOH / g, and 0.1 mgKOH / g. Most preferably, it is g-50 mgKOH / g.
In the present invention, the molecular weight distribution of the binder resin is measured by gel permeation chromatography (GPC) using THF as a solvent.

  As the binder resin that can be used in the toner of the present invention, a resin containing a monomer component capable of reacting with both of these resin components in at least one of the vinyl polymer component and the polyester resin component can also be used. . Examples of monomers that can react with the vinyl polymer among the monomers constituting the polyester resin component include unsaturated dicarboxylic acids such as phthalic acid, maleic acid, citraconic acid, and itaconic acid, or anhydrides thereof. Examples of the monomer constituting the vinyl polymer component include those having a carboxyl group or a hydroxy group, and acrylic acid or methacrylic acid esters.

  Moreover, when using together a polyester polymer, a vinyl polymer, and another binder resin, what has 60 mass% or more of resin whose acid value of the whole binder resin has 0.1-50 mgKOH / g is preferable.

In the present invention, the acid value of the binder resin component of the toner composition is determined by the following method, and the basic operation conforms to JIS K-0070.
(1) The sample is used by removing additives other than the binder resin (polymer component) in advance, or the acid value and content of components other than the binder resin and the crosslinked binder resin are obtained in advance. . The sample pulverized product 0.5 to 2.0 g is precisely weighed, and the weight of the polymer component is defined as Wg. For example, when measuring the acid value of the binder resin from the toner, the acid value and content of the colorant or magnetic material are separately measured, and the acid value of the binder resin is obtained by calculation.
(2) A sample is put into a 300 (ml) beaker, and a mixed solution 150 (ml) of toluene / ethanol (volume ratio 4/1) is added and dissolved.
(3) Titrate with a potentiometric titrator using an ethanol solution of 0.1 mol / l KOH.
(4) The amount of KOH solution used at this time is set to S (ml), and a blank is measured at the same time. The amount of KOH solution used at this time is set to B (ml), and the following calculation formula (a) is used. However, f is a factor of KOH.
Acid value (mgKOH / g) = [(SB) × f × 5.61] / W (a)

  The toner binder resin and the composition containing the binder resin preferably have a glass transition temperature (Tg) of 35 to 80 ° C., more preferably 40 to 75 ° C., from the viewpoint of toner storage stability. If the Tg is lower than 35 ° C., the toner is likely to deteriorate in a high temperature atmosphere, and offset may easily occur during fixing. On the other hand, when Tg exceeds 80 ° C., fixability may be deteriorated.

(Coloring agent)
The colorant is not particularly limited and may be appropriately selected from commonly used resins. For example, carbon black, nigrosine dye, iron black, naphthol yellow S, Hansa yellow (10G, 5G, G), cadmium yellow, yellow iron oxide, ocher, yellow lead, titanium yellow, polyazo yellow, oil yellow, Hansa yellow (GR, A, RN, R), pigment yellow L, benzidine yellow (G, GR), permanent Yellow (NCG), Vulcan Fast Yellow (5G, R), Tartrazine Lake, Quinoline Yellow Lake, Anthrazan Yellow BGL, Isoindolinone Yellow, Bengala, Lead Red, Lead Zhu, Cadmium Red, Cadmium Mercury Red, Antimon Zhu, Permanent Red 4R, Para Red, Fu Issey Red, Parachlor Ortho Nitroaniline Red, Resol Fast Scarlet G, Brilliant Fast Scarlet, Brilliant Carmin Min BS, Permanent Red (F2R, F4R, FRL, FRLL, F4RH), Fast Scarlet VD, Belkan Fast Rubin B, Brilliant Scarlet G, Risor Rubin GX, Permanent Red F5R, Brilliant Carmine 6B, Pigment Scarlet 3B, Bordeaux 5B, Toluidine Maroon, Permanent Bordeaux F2K, Helio Bordeaux BL, Bordeaux 10B, Bon Maroon Light, Bon Maroon Medium, Eosin Lake, Rhodamine Lake B, Rhodamine Lake Y, Alizarin Lake, Thioindigo Red B, Thioindigo Maroon, Oil Red, Nacridone Red, Pyrazolone Red, Polyazo Red, Chrome Vermilion, Benzidine Orange, Perinone Orange, Oil Orange, Cobalt Blue, Cerulean Blue, Alkaline Blue Lake, Peacock Blue Lake, Victoria Blue Lake, Metal Free Phthalocyanine Blue, Phthalocyanine Blue, Fast Sky Blue, Indanthrene Blue (RS, BC), Indigo, Ultramarine Blue, Bitumen, Anthraquinone Blue, Fast Violet B, Methyl Violet Lake, Cobalt Purple, Manganese Purple, Dioxane Violet, Anthraquinone Violet, Chrome Green, Zinc Green, Chrome Oxide , Pyridian, emerald green, pigment green B, naphthol green B, green gold, acid green , Malachite green lake, phthalocyanine green, anthraquinone green, titanium oxide, zinc white, litbon and mixtures thereof.
The content of the colorant is preferably 1 to 15% by mass and more preferably 3 to 10% by mass with respect to the toner.

  The colorant used in the present invention can also be used as a master batch combined with a resin. As the binder resin kneaded with the master batch, in addition to the modified and unmodified polyester resins mentioned above, for example, styrene such as polystyrene, poly p-chlorostyrene, polyvinyltoluene, and its substituted polymers; styrene- p-chlorostyrene copolymer, styrene-propylene 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-α-chloromethacrylate Methyl acid copolymer, styrene-acrylic Nitrile copolymer, styrene-vinyl methyl ketone copolymer, styrene-butadiene copolymer, styrene-isoprene copolymer, styrene-acrylonitrile-indene copolymer, styrene-maleic acid copolymer, styrene-maleic acid ester Styrene copolymers such as copolymers; polymethyl methacrylate, polybutyl methacrylate, polyvinyl chloride, polyvinyl acetate, polyethylene, polypropylene, polyester, epoxy resin, epoxy polyol resin, polyurethane, polyamide, polyvinyl butyral, polyacrylic acid Examples thereof include resins, rosins, modified rosins, terpene resins, aliphatic or alicyclic hydrocarbon resins, aromatic petroleum resins, chlorinated paraffins, and paraffin waxes. These may be used individually by 1 type, and 2 or more types may be mixed and used for them.

The master batch can be obtained by mixing and kneading a resin for a master batch and a colorant under a high shearing force. At this time, an organic solvent can be used in order to enhance the interaction between the colorant and the resin. There is also a method for removing water and organic solvent components by mixing and kneading an aqueous paste containing water, which is a so-called flushing method, together with a resin and an organic solvent, and transferring the colorant to the resin side. Since the wet cake can be used as it is, it does not need to be dried and is preferably used. For mixing and kneading, a high shearing dispersion device such as a three-roll mill is preferably used.

  As the usage-amount of the said masterbatch, 0.1-20 mass parts is preferable with respect to 100 mass parts of binder resin. The resin for the masterbatch preferably has an acid value of 30 mgKOH / g or less, an amine value of 1 to 100, and a colorant dispersed therein. The acid value is 20 mgKOH / g or less and the amine value is 10 It is more preferable that the colorant is dispersed and used at ˜50. When the acid value exceeds 30 mgKOH / g, the chargeability under high humidity may be lowered, and the pigment dispersibility may be insufficient. Also, when the amine value is less than 1 and when the amine value exceeds 100, the pigment dispersibility may be insufficient. The acid value can be measured by the method described in JIS K0070, and the amine value can be measured by the method described in JIS K7237.

  The dispersant is preferably highly compatible with the binder resin in terms of pigment dispersibility. Specific examples of commercially available products include “Ajisper PB821” and “Azisper PB822” (manufactured by Ajinomoto Fine Techno Co., Ltd.). , “Disperbyk-2001” (manufactured by Big Chemie), “EFKA-4010” (manufactured by EFKA), and the like. The dispersant is preferably blended in the toner at a ratio of 0.1 to 10% by mass with respect to the colorant. When the blending ratio is less than 0.1% by mass, the pigment dispersibility may be insufficient, and when it is more than 10% by mass, the chargeability under high humidity may be deteriorated.

The weight average molecular weight of the dispersant is the maximum molecular weight of the main peak in terms of styrene mass in gel permeation chromatography, preferably 500 to 100,000, and from the viewpoint of pigment dispersibility, 3,000 to 100 1,000 is more preferred. In particular, 5,000 to 50,000 are preferable, and 5,000 to 30,000 are most preferable. When the molecular weight is less than 500, the polarity increases and the dispersibility of the colorant may decrease. When the molecular weight exceeds 100,000, the affinity with the solvent increases and the dispersibility of the colorant decreases. There are things to do.
The addition amount of the dispersant is preferably 1 to 50 parts by mass, and more preferably 5 to 30 parts by mass with respect to 100 parts by mass of the colorant. If it is less than 1 part by mass, the dispersibility may be lowered, and if it exceeds 50 parts by mass, the chargeability may be lowered.

(Release agent)
In the present invention, waxes are contained as a release agent for the purpose of preventing offset during fixing.
The waxes are not particularly limited, and those that are usually used as a release agent for toner can be appropriately selected and used. For example, low molecular weight polyethylene, low molecular weight polypropylene, polyolefin wax, microcrystalline wax, Aliphatic hydrocarbon waxes such as paraffin wax and sazol wax, oxides of aliphatic hydrocarbon waxes such as oxidized polyethylene wax or block copolymers thereof, candelilla wax, carnauba wax, wood wax, jojoba wax, etc. Plant waxes, animal waxes such as beeswax, lanolin and spermaceti, mineral waxes such as ozokerite, ceresin and petrolatum, and waxes based on fatty acid esters such as montanate ester wax and castor wax. Deoxidized carnauba wax and other fatty acid esters that have been partially or wholly deoxidized are included.

  Examples of the waxes further include saturated linear fatty acids such as palmitic acid, stearic acid, montanic acid, and linear alkyl carboxylic acids having a linear alkyl group, prandidic acid, eleostearic acid, and valinaline. Unsaturated fatty acids such as acids, stearyl alcohol, eicosyl alcohol, behenyl alcohol, carnaupyl alcohol, seryl alcohol, mesyl alcohol, saturated alcohols such as long-chain alkyl alcohols, polyhydric alcohols such as sorbitol, linoleic acid amides, olefins Fatty acid amides such as acid amides, lauric acid amides, methylene biscapric acid amides, ethylene bis lauric acid amides, saturated fatty acid bisamides such as hexamethylene bis stearic acid amides, ethylene bis oleic acid amides, hexamethylene vinyl Unsaturated fatty acid amides such as oleic acid amide, N, N′-dioleyl adipic acid amide, N, N′-dioleyl sepasic acid amide, m-xylene bisstearic acid amide, N, N-distearyl isophthalic acid Grafted onto aromatic bisamides such as amides, fatty acid metal salts such as calcium stearate, calcium laurate, zinc stearate and magnesium stearate, and aliphatic hydrocarbon waxes using vinyl monomers such as styrene and acrylic acid. Examples thereof include waxes, partial ester compounds of polyhydric alcohols such as behenic acid monoglycerides, and methyl ester compounds having a hydroxyl group obtained by hydrogenating vegetable oils and fats.

  More preferred examples include polyolefins obtained by radical polymerization of olefins under high pressure, polyolefins obtained by purifying low molecular weight by-products obtained during polymerization of high molecular weight polyolefins, and polymerization using a catalyst such as a Ziegler catalyst or a metallocene catalyst under low pressure. Polyolefin, polyolefin polymerized using radiation, electromagnetic waves or light, low molecular weight polyolefin obtained by thermal decomposition of high molecular weight polyolefin, paraffin wax, microcrystalline wax, Fischer-Tropsch wax, Jintole method, hydrocol method, age method, etc. Hydrocarbon wax synthesized by the above, synthetic wax using a compound having one carbon atom as a monomer, hydrocarbon wax having a functional group such as a hydroxyl group or a carboxyl group, hydrocarbon wax and hydrocarbon having a functional group Mixture of system wax, styrene these waxes as a matrix, maleic acid ester, acrylate, methacrylate, graft-modified wax with such vinyl monomers of maleic acid.

Of these waxes, carnauba wax, synthetic ester wax, and paraffin wax are particularly preferable from the viewpoint of preventing offset.
In addition, these waxes have a sharp molecular weight distribution using a press sweating method, a solvent method, a recrystallization method, a vacuum distillation method, a supercritical gas extraction method, or a solution liquid crystal deposition method, a low molecular weight solid fatty acid, a low A molecular weight solid alcohol, a low molecular weight solid compound, and other impurities are preferably used.
The melting point of the wax is preferably 60 to 140 ° C., and more preferably 60 to 120 ° C., in order to balance blocking resistance and offset resistance. If it is less than 60 degreeC, blocking resistance may fall, and if it exceeds 140 degreeC, an offset-proof effect may become difficult to express.

Further, by using two or more different types of waxes in combination, the plasticizing action and the releasing action which are the actions of the wax can be expressed simultaneously.
Examples of the types of wax having a plasticizing action include waxes having a low melting point, those having a branch on the molecular structure, and those having a polar group.
Examples of the wax having a releasing action include a wax having a high melting point, and the molecular structure includes a linear structure and a non-polar one having no functional group. Examples of use include a combination of two or more different waxes having a melting point difference of 10 ° C. to 100 ° C., a combination of polyolefin and graft-modified polyolefin, and the like.
When selecting two types of wax, in the case of a wax having the same structure, a wax having a relatively low melting point exhibits a plasticizing action, and a wax having a high melting point exhibits a releasing action. At this time, when the difference in melting point is 10 to 100 ° C., functional separation is effectively expressed. If it is less than 10 ° C., the function separation effect may be difficult to appear, and if it exceeds 100 ° C., the function may not be emphasized by interaction. At this time, the melting point of at least one wax is preferably 60 to 120 ° C., more preferably 60 to 100 ° C., because the function separation effect tends to be easily exhibited.

  As for the wax, those having a branched structure, those having a polar group such as a functional group, and those modified with a component different from the main component exhibit a plastic action, and those having a more linear structure or functional group Nonpolar or non-denatured straight materials that do not have a mold exhibit a releasing action. Preferred combinations include polyethylene homopolymers or copolymers based on ethylene and polyolefin homopolymers or copolymers based on olefins other than ethylene, combinations of polyolefins and graft modified polyolefins, alcohol waxes, fatty acid waxes or ester waxes. And hydrocarbon wax combinations, Fischer-Tropsch wax or polyolefin wax and paraffin wax or microcrystal wax combination, Fischer-Tropsch wax and polyolefin wax combination, paraffin wax and microcrystal wax combination, Carnauba Wax, Candelilla Wax, rice wax or montan wax and hydrocarbon wax The combination of the scan and the like.

  In any case, since it becomes easy to balance the toner storage stability and the fixability, there is a maximum peak peak temperature in the region of 60 to 110 ° C. in the endothermic peak observed in the DSC measurement of the toner. Preferably, it has a maximum peak in the region of 60 to 110 ° C.

The total content of the wax is preferably 0.2 to 20 parts by mass and more preferably 0.5 to 10 parts by mass with respect to 100 parts by mass of the binder resin.
In the present invention, the peak top temperature of the endothermic peak of the wax measured by DSC is defined as the melting point of the wax.
The wax or toner DSC measuring device is preferably measured with a highly accurate internal heat input compensation type differential scanning calorimeter. The measurement is performed according to ASTM D3418-82. The DSC curve used in the present invention is one that is measured when the temperature is raised at a temperature rate of 10 ° C./min after once raising and lowering the temperature and taking a previous history.

  Next, production of a developing roller according to an embodiment of the present invention will be described based on examples.

[Coating liquid for insulating support]
The following materials were mixed to obtain a coating solution for forming an insulating support.
Alkyd resin 30 parts by weight Melamine resin 20 parts by weight 2-butanone 60 parts by weight

[Surface layer coating solution]
The following materials were mixed to obtain a surface layer forming coating solution.
In a mixed solvent of 70 parts by weight of tetrahydrofuran and 20 parts by weight of cyclohexanone, 10 parts by weight of a polymer compound having a molecular weight of 50000 (Example 1) composed of the structural unit M-15, silicone oil (KF-50 (manufactured by Shin-Etsu Chemical Co., Ltd.)) 0.002 part by weight was dissolved to prepare a surface layer coating solution.

  A surface layer coating solution was prepared using a polymer compound having a molecular weight of 37500 consisting of the structural unit M-1 instead of the polymer compound having a molecular weight of 50000 consisting of the structural unit M-15.

  A surface layer coating solution was prepared using a polymer compound having a molecular weight of 60000 consisting of the structural unit M-9 instead of the polymer compound having a molecular weight of 50000 consisting of the structural unit M-15.

  A surface layer coating solution was prepared using a polymer compound having a molecular weight of 30000 consisting of the structural unit M-14 instead of the polymer compound having a molecular weight of 50000 consisting of the structural unit M-15.

An insulating support (9a) was prepared by immersing a cylindrical aluminum tube having a diameter of 16 mm and a length of 230 mm in the above-mentioned coating solution for forming an insulating support and covering it with an insulating film having a thickness of 20 μm. A copper foil film having a thickness of 0.8 μm, which is a conductive metal foil film, was formed on the insulating support (9a) by vapor deposition. Further, a resist film having a thickness of 5 μm was applied on the copper foil film. A plurality of linear electrodes (9bA) and (9bB) having a width (d) = 100 μm and a length (L) = 200 mm are spaced apart (D) on the insulating support (9a) covered with the copper foil film and the resist film. ) = electrode pattern is separated by 200μm to (9b) is exposed by a laser writing apparatus, subsequent to the development of _Na 2 CO ₃ aqueous solution, etched by immersion in an aqueous FeCl ₃ solution, having an electrode pattern (9b) Electrodes (9bA) and (9bB) were formed.

Next, the coating solution for forming the surface layer is insulatively supported on the electrodes (9bA) and (9bB) provided on the insulative support (9a) on which the electrode having the predetermined electrode pattern 9b is thus formed. Coating was performed so that the electrode shafts (9bA1) and (9bB1) were exposed at both ends of the body (9a), and a surface layer (9c) covering these electrodes (9bA) and (9bB) was formed to a thickness of 10 μm. The developing roller (9) thus produced is incorporated into the developing device (4), and -400V and 0V are respectively applied to the terminals (13A) and (13B) attached to the opening (8a) of the developing device (4). An alternating current bias having an average potential of −200 V by having it at the peak was applied from an alternating current power source at a frequency of 5 KHz.
In this case, the AC bias of the odd-numbered electrode group (9bA) and the even-numbered electrode group (9bB) are in reverse phase.

  In addition, a method for manufacturing toner used in the examples is described below.

(Wax Dispersion Production Example-1)
In a container in which a stirring blade and a thermometer are set, 120 parts by mass of a polyester resin (weight average molecular weight 20,000) as a wax dispersion resin, 40 parts by mass of carnauba wax, 40 parts by mass of a graft polymer, and 800 parts by mass of ethyl acetate are charged. The mixture was heated to 85 ° C. and stirred for 20 minutes to dissolve the polyester resin, carnauba wax and graft polymer, and then rapidly cooled to precipitate carnauba wax fine particles. This dispersion was further finely dispersed by a strong shear stress using a bead disperser (Star Mill Lab Star LMZ06; manufactured by Ashizawa Finetech). The dispersion conditions are shown below. As a result, a wax dispersion 1 (W-1) having a dispersed particle diameter of 8% with respect to a nozzle having a weight average particle diameter of 0.8 μm and an opening diameter of 10 μm was obtained.
・ Beads: PSZ 0.3mmΦ
・ Bead filling amount: 80%
・ Crushing chamber rotation speed (peripheral speed): 2500 rpm (10 m / sec)
・ Liquid feeding speed: 300ml / min
・ Dispersion time: 1 hr

-Preparation of colorant dispersion-
First, a carbon black dispersion as a colorant was prepared.
Carbon black (Regal 400; manufactured by Cabot) 20 parts by mass and pigment dispersant 2 parts by mass were primarily dispersed in 78 parts by mass of ethyl acetate using a mixer having stirring blades. As the pigment dispersant, Ajisper PB821 (manufactured by Ajinomoto Fine Techno Co., Ltd.) was used. The obtained primary dispersion was finely dispersed by a strong shearing force using a dyno mill to prepare a secondary dispersion from which aggregates were completely removed. Furthermore, a liquid having a pore size of 0.45 μm (manufactured by PTFE) and passing through a submicron region was prepared.

-Preparation of toner composition liquid-
15 parts by mass of the carbon black dispersion, 100 parts by mass of a polyester resin ethyl acetate solution (weight average molecular weight 20,000, solid content 20%) similar to the wax dispersion resin, and 30 parts by mass of the wax dispersion (W-1) Then, 150 parts by mass of ethyl acetate was mixed using a mixer having stirring blades to prepare a toner composition liquid.

-Preparation of toner-
The obtained toner composition liquid was supplied to a ring-type vibrator head of a toner manufacturing apparatus described in JP-A-2008-276146 (not shown). In addition, the used thin film produced the discharge hole (nozzle) of a 10-micrometer-diameter diameter in the nickel plate with an outer diameter of 8.0 mm and thickness 20 micrometers by the process by an electroforming method. The discharge holes were provided only in a range of about 5 mmφ at the center of the thin film in a staggered pattern so that the distance between the discharge holes was 100 μm. As the piezoelectric body, lead zirconate titanate (PZT) was used by lamination, and the vibration frequency was set to 100 KHz.
After the dispersion was prepared, the droplets were discharged under the following toner production conditions, and then the droplets were dried and solidified to produce toner base particles.
[Toner preparation conditions]
Dry air flow rate: Dispersing nitrogen gas 2.0 L / min,
Dry nitrogen gas in the device 30.0 L / min Temperature in the device: 27 to 28 ° C
Dew point temperature: -20 ° C
Nozzle frequency: 98 kHz
The dried and solidified particles were collected by suction with a filter having 1 μm pores. Further, 2.0 mass% of hydrophobic silica (H2000, manufactured by Clariant Japan) was externally added to the particles using a Henschel mixer (manufactured by Mitsui Mining) to obtain a black toner.

  These developing devices and toner were incorporated into an imagio Neo C320 black station to output an image, and the toner flying state on the toner carrier after the output of 50,000 sheets of images and the presence or absence of abnormal images were compared.

(Comparative Examples 1-4)
For comparison, the same evaluation rollers as in Examples 1 to 4 were used as comparative examples, and the same evaluation as in Examples was performed using black toner for imgio MP C5000. The toner for imgio MP C5000 is a toner produced by a polymerization method.

(Comparative Example 5)
[Coating liquid for insulating support]
The following materials were mixed to obtain a coating solution for forming an insulating support.
Alkyd resin 30 parts by weight Melamine resin 20 parts by weight 2-butanone 60 parts by weight [surface layer coating solution]
The coating solution for insulating support was used as the coating solution for forming the surface layer.
As the toner, a toner in a gas phase droplet forming method was used.

(Comparative Example 6)
[Coating liquid for insulating support]
The following materials were mixed to obtain a coating solution for forming an insulating support.
Alkyd resin 30 parts by weight Melamine resin 20 parts by weight 2-butanone 60 parts by weight [surface layer coating solution]
Silicone resin (RSR213 (manufactured by Toray Dow Corning Silicone)) was spray coated.
As the toner, a toner in a gas phase droplet forming method was used.

(Comparative Example 7)
[Coating liquid for insulating support]
The following materials were mixed to obtain a coating solution for forming an insulating support.
Alkyd resin 30 parts by weight Melamine resin 20 parts by weight 2-butanone 60 parts by weight [surface layer coating solution]
The following materials were mixed to obtain a surface layer forming coating solution.
89 parts by weight of a polyester resin (Byron 20SS (Toyobo Co., Ltd.)) and 143 parts by weight of a melamine resin (Cymel 325 (Mitsui Cytec Co., Ltd.)) were dissolved in 238 parts by weight of methyl ethyl ketone to prepare a surface layer coating solution.
As the toner, a toner in a gas phase droplet forming method was used.

(Comparative Example 8)
The same development roller as in Comparative Example 5 was used, and the same evaluation as in Example was performed using black toner for imgio MP C5000. The toner for imgio MP C5000 is a toner produced by a polymerization method.

(Comparative Example 9)
The same developing roller as in Comparative Example 6 was used, and the same evaluation as in Example was performed using black toner for imgio MP C5000. The toner for imgio MP C5000 is a toner produced by a polymerization method.

(Comparative Example 10)
The same development roller as in Comparative Example 7 was used, and the same evaluation as in Example was performed using black toner for imgio MP C5000. The toner for imgio MP C5000 is a toner produced by a polymerization method.

The measurement results of each example and comparative example are shown in Table 1.
In the example, there was little abnormality in the flying of the toner, and no problem occurred in the output image. On the other hand, in the comparative example, an abnormality occurred in the toner flying, and an abnormality occurred in the output image.

DESCRIPTION OF SYMBOLS 1 Photoconductor 2 Charging roller 3 Exposure apparatus 4 Developing apparatus 5 Transfer roller 6 Cleaning apparatus 7 Fixing apparatus 7a Heating roller 7b Pressure roller 8 Container 8a Opening part 9 Developing roller 9a Support body 9b Electrode pattern 9bA Electrode 9bB Electrode 9c Surface layer 9d Rotating shaft 9bA1 End 9bB1 End 10 Circulating paddle 11 Toner regulating member 12 Toner supply port 13A Terminal 13B Terminal 14 Alternating voltage 9bA Electrode pattern 9bAa Electrode 9bB Electrode pattern 9bBb Electrode 91A Conductive support 93 Support 95 Insulating layer A Rotation direction B Transport direction C Rotational direction D Interval T Toner d Width 56 Two-component developer 57 Magnet sleeve 59 Alternating voltage 60 Container 61 Developer stirring device 62 Developer stirring device 63 Developer

JP-A-3-21967 JP 2004-198675 A JP 2007-133388 A JP 2008-070674 A

Claims (11)

In a hopping developing device that hops toner carried on a toner carrier by an electric field formed by a plurality of electrodes of the toner carrier and develops an electrostatic latent image on the surface of the photoreceptor facing the toner carrier. The toner is produced by forming a toner composition liquid in which a toner composition containing at least a resin, a colorant, and a release agent is dissolved or dispersed in a solvent into liquid droplets and then solidifying the liquid droplets. The solidified toner in the vapor phase, wherein the toner carrier is an insulating support, and an electrode arranged on the insulating support in the toner transport direction to generate the electric field; And a surface layer covering the electrode, the surface layer containing a polymer compound containing a structural unit represented by the following general formula (1).

(In the general formula ^(1), R 1, ^{R 2} represents a hydrogen atom, an alkyl group, an aryl group, a cyclic hydrocarbon residue having a carbon formed by ^{R 1} and ^{R 2 5~8, R 3, R} 4 Represents a hydrogen atom, a halogen atom, an alkyl group or an aryl group, and a and b are integers of 1 or 2, each representing the number of R ³ and R ⁴ substituted on the benzene ring, and a = 2 In this case, R ³ may be the same or different, and when b = 2, R ⁴ may be the same or different, wherein the alkyl group and aryl group may have a substituent. .)   The developing device according to claim 1, further comprising a toner charging unit that charges the toner in addition to the toner carrier.   The developing device according to claim 1, wherein the toner has a particle size distribution (weight average particle diameter / number average particle diameter) of 1.00 to 1.15.   4. The development according to claim 1, wherein the toner contains a release agent, and the content thereof is 0.2 to 20 parts by mass with respect to 100 parts by mass of the resin. apparatus.   The developing device according to claim 1, wherein the toner has a weight average particle diameter of 3 μm to 10 μm.   6. The electrode according to claim 1, wherein the electrode of the toner carrier is an insulating support and is arranged on the insulating support in a toner transport direction to generate an electric field. The developing device according to 1.   The developing device according to claim 1, wherein the toner carrying member is disposed in a non-contact state having a space and facing the photoconductor.   8. The developing device according to claim 1, wherein a plurality of opposing electrodes of the toner carrying member are arranged in a comb tooth.   8. A plurality of opposing electrodes of the toner carrying member, wherein one is a lower support and the other is a plurality of electrodes provided on the upper portion via an insulating layer. The developing device according to any one of the above.   An electrostatic latent image forming step of forming an electrostatic latent image on the image carrier, and toner carried on the toner carrier is hopped by an electric field formed by a plurality of electrodes of the toner carrier, and the toner In the image forming method including a hopping development process for developing an electrostatic latent image on the surface of the photoreceptor facing the carrier, the toner is a toner composition containing at least a resin, a colorant, and a release agent dissolved in a solvent. Is a droplet solidified toner in the gas phase produced by forming the dispersed toner composition liquid into droplets in the gas phase and then solidifying the droplets, and the toner carrier is an insulating support. And an electrode for generating the electric field and a surface layer covering the electrode, the surface layer being represented by the general formula (1). Containing polymerized compounds containing structural units Image forming method which is a shall.   Electrostatic latent image forming means for forming an electrostatic latent image on the image carrier, and toner carried on the toner carrier are hopped by an electric field formed by a plurality of electrodes of the toner carrier, and the toner An image forming apparatus including a hopping developing unit that develops an electrostatic latent image on the surface of the photosensitive member facing the carrier, wherein the hopping developing unit is the developing device according to any one of claims 1 to 9. Image forming apparatus.

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