JP2016170345A - Toner, toner storage unit, and image forming apparatus - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a toner that has excellent fixability (low-temperature fixability and hot offset resistance), has sufficient stress resistance, and prevents cracks and chipping even when used in a one-component developing method.SOLUTION: There is provided a toner including at least a binder resin and a charge control agent, the toner including 10-40% of a THF insoluble, having a main peak between 12000 and 18000 in a molecular weight distribution obtained by GPC (gel permeation chromatography) from a THF soluble, and a molecular weight of a half band width of the main peak of 20000-50000, and containing a component having a molecular weight of 2000 or less in an amount of 10-20 wt.% and a component having a molecular weight of 100000 or more in an amount of 8 wt.% or less, where the charge control agent includes an azo iron compound.SELECTED DRAWING: Figure 1

Description

  The present invention relates to a toner, a toner storage unit, and an image forming apparatus.

  In recent years, printers of a single component development type tend to require further downsizing and longer life, and in addition to these, low-temperature fixing is being promoted. Accordingly, there is an urgent need to improve the stress resistance of the toner and ensure excellent fixing properties.

  In Patent Document 1, in a toner containing at least a binder resin, a colorant, and a release agent, the molecular weight by GPC (gel permeation chromatography) determined by the THF soluble content of the toner (mainly the binder resin). What is claimed is: 1. An electrostatic charge developing toner comprising: a distribution having a main peak between 1000 and 10000; a half width of the distribution having a molecular weight of 15,000 or less; and containing 5 to 40% of a chloroform-insoluble component. It is disclosed. As a result, it is possible to provide a toner that achieves low-temperature fixing that can be fixed at a low temperature, and furthermore, it is possible to provide a toner for image formation with good hot offset resistance and heat storage stability. Yes.

However, in Patent Document 1, the stress resistance of the toner is not sufficient, and the problem of occurrence of toner cracks cannot be solved when the toner is used in a one-component development system.
As described above, even if the conventional toner has excellent fixability (low-temperature fixability and hot offset resistance), the stress resistance is not sufficient, and particularly in the one-component development system in which the toner is easily stressed, There was a problem that toner cracks occurred and quality problems (blade sticking, photoconductor filming, etc.) due to toner cracks were likely to occur.

  Then, this invention makes it a subject to solve the said problem and to achieve the following objectives. That is, the present invention has excellent fixability (low temperature fixability and hot offset resistance), has sufficient stress resistance, and cracks occur even when used in a one-component development system. An object is to provide a toner that does not.

  In order to solve the above-mentioned problems, the present invention provides a toner containing at least a binder resin and a charge control agent, wherein the toner contains 10 to 40% of a THF-insoluble content, and the GPC determined by the THF-soluble content. In the molecular weight distribution by (gel permeation chromatography), it has a main peak between 12000 and 18000, the half-value width of the main peak is 20000 to 50000, and the component having a molecular weight of 2000 or less is 10% by weight. The component having a molecular weight of 100,000 or more and 8% by weight or less is -20% by weight, and the charge control agent contains an azo iron compound.

  According to the present invention, it has excellent fixability (low temperature fixability and hot offset resistance), has sufficient stress resistance, and cracks are generated even when used in a one-component development system. Toner can be provided.

FIG. 6 is a schematic diagram illustrating an example of a molecular weight distribution of toner. It is a schematic diagram which shows an example of the process cartridge which concerns on this invention. 1 is a schematic diagram illustrating an example of an image forming apparatus according to the present invention. It is a schematic diagram which shows the other example of the image forming apparatus which concerns on this invention. It is a schematic diagram which shows the other example of the image forming apparatus which concerns on this invention. It is a schematic diagram which shows the other example of the image forming apparatus which concerns on this invention.

  Hereinafter, a toner, a toner storage unit, and an image forming apparatus according to the present invention will be described with reference to the drawings. The present invention is not limited to the embodiments described below, and other embodiments, additions, modifications, deletions, and the like can be changed within a range that can be conceived by those skilled in the art, and any aspect is possible. As long as the functions and effects of the present invention are exhibited, the scope of the present invention is included.

  The present invention relates to a toner containing at least a binder resin and a charge control agent, and the toner contains 10 to 40% of a THF-insoluble content, and is determined by GPC (gel permeation chromatography) obtained from the THF-soluble content. In the molecular weight distribution, it has a main peak between 12000 and 18000, the half-value width of the main peak is 20000 to 50000, the component having a molecular weight of 2000 or less is 10 wt% to 20 wt%, and The component having a molecular weight of 100,000 or more is 8% by weight or less, and the charge control agent contains an azo iron compound.

  According to the present invention, while having excellent fixability (low-temperature fixability and hot offset resistance), it has sufficient stress resistance, even when used in a one-component development system (one-component development). It is possible to provide a toner that does not cause cracks (even if it is a toner for use).

  In the present invention, the present inventors sharpen the main peak in the molecular weight distribution of the toner, specify the peak molecular weight, and add an azo iron compound, which is extremely effective in improving the resistance to cracking of the toner. The new technical idea of being confirmed.

  As a result of repeated research, the value of the molecular weight distribution by GPC determined by the THF soluble content of the resin constituting the toner has a main peak between 12000 and 18000, and the half width of the main peak has a molecular weight of 20000 to 50000. In addition, it is important to add an azo iron compound to be present in the surface layer portion. As a result, it was found that particularly excellent resistance to cracking and cracking can be realized as compared with the prior art, and the present invention has been achieved. Details will be described below.

(toner)
The toner of the present invention contains 10 to 40% of THF insoluble matter. It is important to make the absolute amount of the THF-insoluble part of the toner smaller than the absolute amount of the THF-soluble part, that is, 10 to 40%. As a result, low-temperature fixability and hot offset resistance can be improved. If it is less than 10%, the fixing property is deteriorated and the toner is cracked, and if it is more than 40%, the low-temperature fixing property is deteriorated.

  The method for obtaining the THF-insoluble matter is not particularly limited, but can be obtained, for example, as follows. About 50 mg of toner is weighed, and 10 g of THF is added and sufficiently dissolved therein. After the solution is separated by centrifugation, the supernatant is dried and the solid content concentration of the supernatant is calculated. The difference between the toner solution prepared first and the supernatant is defined as THF-insoluble matter.

  A schematic diagram of an example of the molecular weight distribution obtained by GPC measurement of the THF soluble content of the toner is shown in FIG. The horizontal axis in FIG. 1 is the molecular weight, and the vertical axis is the peak intensity. (A) shown in FIG. 1 shows a low molecular weight region, and low temperature fixability is secured by the components of the low molecular weight region. Further, FIG. 1B shows that a main peak exists between the molecular weights 12000 and 18000, and the toughness of the toner is ensured by controlling the molecular weight and the half-value width of the peak. FIG. 1C shows a high molecular weight region, and the influence on the fixing lower limit can be suppressed by reducing the components of the high molecular weight region.

The peak value of the molecular weight distribution by GPC and the half-width molecular weight of the distribution are important for ensuring cracking and chipping properties, and it is necessary to obtain cracking resistance by controlling these to the desired values. The skeleton part of the molecular weight distribution is defined (see FIG. 1B).
In this invention, the value of the molecular weight distribution by GPC calculated | required by THF soluble content has a main peak between 12000-18000, and the half value width of this main peak is molecular weight 20000-50000. In the present invention, the main peak means a peak having the highest intensity among the measurement results.

  Thus, by adjusting the value of the main peak in the molecular weight distribution and the half-width molecular weight of the main peak, it is possible to suppress cracking of the toner. When the value of the main peak is less than 12000, cracking of the toner occurs, and when it is greater than 18000, the low-temperature fixability deteriorates. Further, when the half width of the main peak is less than 20000, the background of the photoreceptor is soiled, and when it is larger than 50000, the low temperature fixability is deteriorated.

In addition, it is considered that the toughness of the binder resin improves as the length of the main chain of the binder resin in the toner increases, because the toughness of the resin increases as the length of the main chain of the resin increases. By setting the main peak value within the desired range, the toughness of the resin can be improved and cracking of the toner can be suppressed. Moreover, the dispersion | distribution of molecular weight distribution shows presence of a low molecular weight component, and the low molecular weight component which leads to the fall of toughness of resin can be suppressed by making a half value width into the expected range.
In the present invention, the value of the main peak in the molecular weight distribution is preferably 15000 to 18000, and the half width of the main peak is preferably 35000 to 50000.

  Furthermore, in the present invention, it is important to control the proportion of the low molecular weight region and the proportion of the high molecular weight region of the molecular weight distribution by GPC for ensuring low temperature fixability (see FIGS. 1A and 1C). . That is, in the present invention, the component having a molecular weight of 2000 or less is 10% by weight to 20% by weight and the component having a molecular weight of 100,000 or more is 8% by weight or less in the molecular weight distribution by GPC determined by the THF soluble content of the toner. It is important that By satisfying this, excellent low-temperature fixability can be realized.

  This is mainly because the low molecular weight component of the resin contributes to the lower limit of fixing. By securing the fixing property by the content of the gel component (THF insoluble component) for ensuring hot offset resistance, It is possible to ensure the fixing property without impairing the stress property.

  In the present invention, it is important that the charge control agent contains an azo iron compound. Stress resistance can be improved by adding a relatively hard azo iron compound among charge control agents (hereinafter sometimes referred to as CCA) and making it exist in the surface layer portion.

GPC measurement can be performed as follows.
・ Apparatus: GPC-150C (manufactured by Waters)
Column: KF801-807 (manufactured by Shodex)
・ Temperature: 40 ℃
・ Solvent: THF (tetrahydrofuran)
Flow rate: 1.0 mL / min Sample: Inject 0.1 mL of a sample with a concentration of 0.05-0.6%.
The number average molecular weight and weight average molecular weight of the resin are calculated from the molecular weight distribution measured under the above conditions using a molecular weight calibration curve prepared with a monodisperse polystyrene standard sample.

  As standard polystyrene samples for preparing a calibration curve, Showdex STANDARD Std. No S-7300, S-210, S-390, S-875, S-1980, S-10.9, S-629, manufactured by Showa Denko KK S-3.0, S-0.580, and toluene are used. An RI (refractive index) detector is used as the detector.

<Toner component>
The toner of the present invention includes other components as needed, and further adds external additives as necessary to a toner base containing at least a binder resin and a charge control agent.

<< Binder resin >>
Examples of the binder resin used in the present invention include a polyester resin, and the polyester resin is usually obtained by condensation polymerization of alcohol and carboxylic acid.
Examples of the alcohol include glycols such as ethylene glycol, diethylene glycol, triethylene glycol and propylene glycol, etherified bisphenols such as 1.4-bis (hydroxymethyl) cyclohexane and bisphenol A, and other dihydric alcohols. Mention may be made of monomers and trihydric or higher polyhydric alcohol monomers.
Examples of the carboxylic acid include divalent organic acid monomers such as maleic acid, fumaric acid, phthalic acid, isophthalic acid, terephthalic acid, succinic acid, and malonic acid, 1,2,4-benzenetricarboxylic acid, 1 , 2,5-benzenetricarboxylic acid, 1,2,4-cyclohexanetricarboxylic acid, 1,2,4-naphthalenetricarboxylic acid, 1,2,5-hexanetricarboxylic acid, 1,3-dicarboxyl-2-methylenecarboxy Mention may be made of trivalent or higher polyvalent carboxylic acid monomers such as propane and 1,2,7,8-octanetetracarboxylic acid.

  Here, as the polyester resin, those having a glass transition temperature Tg of 55 ° C. or higher, and more preferably 60 ° C. or higher are preferable from the viewpoint of heat storage stability.

As described above, it is most suitable to use a polyester resin as the resin component in the toner, but other resins can be used in combination as long as the performance of the toner is not impaired. Examples of usable resins other than the polyester resin include the following.
Polystyrene, chloropolystyrene, poly α-methylstyrene, styrene / chlorostyrene copolymer, styrene / propylene copolymer, styrene / butadiene copolymer, styrene / vinyl chloride copolymer, styrene / vinyl acetate copolymer, styrene / Maleic acid copolymer, styrene / acrylic acid ester copolymer (styrene / methyl acrylate copolymer, styrene / ethyl acrylate copolymer, styrene / butyl acrylate copolymer, styrene / octyl acrylate copolymer) Styrene / phenyl acrylate copolymer), styrene / methacrylic acid ester copolymer (styrene / methyl methacrylate copolymer, styrene / ethyl methacrylate copolymer, styrene / butyl methacrylate copolymer, styrene) / Phenyl methacrylate copolymer, etc.) Styrene resins (homopolymers or copolymers containing styrene or styrene-substituted products) such as styrene / α-chloromethyl acrylate copolymer, styrene / acrylonitrile / acrylate ester copolymer, vinyl chloride resin, styrene / Vinyl acetate copolymer, rosin-modified maleic acid resin, phenol resin, epoxy resin, polyethylene resin, polypropylene resin, ionomer resin, polyurethane resin, silicone resin, ketone resin, ethylene / ethyl acrylate copolymer, xylene resin, polyvinyl butyral resin Petroleum resin, hydrogenated petroleum resin, etc.

The method for producing these resins is not particularly limited, and any of bulk polymerization, solution polymerization, emulsion polymerization, and suspension polymerization can be used.
Further, the glass transition temperature Tg of the resin is preferably 55 ° C. or higher, more preferably 60 ° C. or higher, from the viewpoint of heat storage, similarly to the polyester resin.

<< Releasing agent >>
In the present invention, all known release agents for use in the toner can be used, and in particular, de-free fatty acid type carnauba wax, montan wax and oxidized rice wax can be used alone or in combination.

The carnauba wax is preferably a microcrystalline wax, preferably having an acid value of 5 or less and a particle size of 1 μm or less when dispersed in a toner binder.
The montan wax generally refers to a montan wax refined from minerals, and like a carnauba wax, it is microcrystalline and preferably has an acid value of 5 to 14.
The oxidized rice wax is obtained by air-oxidizing rice bran wax, and the acid value is preferably 10-30.
As other mold release agents, any conventionally known mold release agents such as solid silicone varnish, higher fatty acid higher alcohol, montan ester wax, and low molecular weight polypropylene wax can be mixed and used.
The amount of these release agents used is 1 to 20 parts by weight, preferably 2 to 10 parts by weight, based on the binder resin in the toner.

<< Charge Control Agent >>
As the charge control agent used in the toner of the present invention, any conventionally known charge control agent such as nigrosine dye, metal complex dye, quaternary ammonium salt, salicylic acid metal complex can be used alone or in combination. It is essential to use compounds. By using an azo iron compound, the stress resistance of the toner can be improved.

In the present invention, the metal complex is preferably a trivalent or higher-valent metal capable of taking a six-coordinate configuration, and among them, a non-toxic Fe is preferably used as the central metal.
Examples of the azo iron compound in the present invention include compounds represented by the following structural formula (1) and the following structural formula (2).

In the structural formula (1), A ⁺ represents an ammonium ion.

前記構造式（２）中、Ｊ^＋は、Ｈ、アルカリ金属、アンモニウム又はアルキルアンモニウムを表す。

In the structural formula (2), J ⁺ represents H, an alkali metal, ammonium, or alkylammonium.

Two or more of those shown above may be mixed.
Among these, it is preferable to use a compound represented by the structural formula (1) that has an appropriate chargeability and has a high effect of improving background stains.

Although it does not restrict | limit especially as a commercial item of the compound represented by the said Structural formula (1), For example, T-77 by Hodogaya Chemical Co., Ltd. is mentioned.
Although it does not restrict | limit especially as a commercial item of the compound represented by said Structural formula (2), For example, T-159 by Hodogaya Chemical Co., Ltd. is mentioned.

  The content of the azo iron compound is preferably 0.5 to 3.0 parts by weight with respect to 100 parts by weight of the binder resin in the toner.

Another charge control agent includes, for example, zirconium salicylate. Although it does not restrict | limit especially as a commercial item of zirconium salicylate, it can obtain from Hodogaya Chemical Co., Ltd.
The other charge control agent is 0.1 to 5 parts by weight, preferably 1 to 3 parts by weight with respect to the binder resin in the toner.

<< Colorant >>
Examples of the colorant used in the toner of the present invention include carbon black, lamp black, iron black, aniline blue, phthalocyanine blue, phthalocyanine green, Hansa Yellow G, rhodamine 6C lake, calco oil blue, chrome yellow, quinacridone, benzidine yellow, Any conventionally known dyes and pigments such as rose bengal and triallylmethane dyes can be used alone or as a mixture, and can be used as a black toner or a full color toner.
The amount of these colorants to be used is usually 1 to 30% by weight, preferably 3 to 20% by weight, based on the toner resin component.

<< Other >>
The toner of the present invention can be blended with a fluidity improver and the like as required.
As the fluidity improver, any conventionally known fluidity improver such as silicon oxide, titanium oxide, silicon carbide, aluminum oxide, and barium titanate can be used alone or in combination. The amount of these fluidity improvers used is 0.1 to 5 parts by weight, preferably 0.5 to 2 parts by weight, based on 100 parts by weight of the toner.

(Toner storage unit)
The toner storage unit in the present invention refers to a unit in which toner is stored in a unit having a function of storing toner. Here, examples of the toner storage unit include a toner storage container, a developing device, and a process cartridge.
The toner container is a container that contains toner.
The developing device is a unit having a means for containing and developing toner.
The process cartridge is a cartridge in which at least the image carrier and the developing unit are integrated, accommodates toner, and is detachable from the image forming apparatus. The process cartridge may further include at least one selected from charging means, exposure means, and cleaning means.

  Next, an embodiment of the process cartridge is shown in FIG. As shown in FIG. 2, the process cartridge according to this embodiment includes a latent image carrier 101, includes a charging device 102, a developing device 104, and a cleaning unit 107, and further includes other means as necessary. In FIG. 2, reference numeral 103 denotes exposure from the exposure apparatus, and reference numeral 105 denotes recording paper.

As the latent image carrier 101, the same one as an image forming apparatus described later can be used. An arbitrary charging member is used for the charging device 102.
In the image forming process using the process cartridge shown in FIG. 2, the latent image carrier 101 is exposed on the surface thereof by rotating in the direction of the arrow, charging by the charging device 102, and exposure 103 by the exposure means (not shown). An electrostatic latent image corresponding to is formed.
The electrostatic latent image is developed with toner by the developing device 104, and the toner development is transferred to the recording paper 105 by the transfer roller 108 and printed out. Next, the surface of the latent image carrier after the image transfer is cleaned by the cleaning unit 107 and further neutralized by a neutralizing unit (not shown), and the above operation is repeated again.

(Image forming method and image forming apparatus)
The image forming method used in the present invention includes an electrostatic latent image forming step (charging step and exposure step), a developing step, a transfer step, and a fixing step, and other types appropriately selected as necessary. The process includes, for example, a static elimination process, a cleaning process, a recycling process, a control process, and the like.
The image forming apparatus of the present invention includes an electrostatic latent image carrier, an electrostatic latent image forming unit (charging unit and exposure unit) that forms an electrostatic latent image on the electrostatic latent image carrier, and the electrostatic unit. Developing means for developing a latent image using a developer to form a visible image, transfer means for transferring the visible image onto a recording medium, and fixing for fixing the transferred image transferred onto the recording medium And at least means. Furthermore, other means appropriately selected as necessary, for example, a static elimination means, a cleaning means, a recycling means, a control means and the like are provided.

-Electrostatic latent image forming step and electrostatic latent image forming means-
The electrostatic latent image forming step is a step of forming an electrostatic latent image on the electrostatic latent image carrier.
The electrostatic latent image carrier (sometimes referred to as “electrophotographic photosensitive member” or “photosensitive member”) is not particularly limited in terms of material, shape, structure, size, etc. It can be selected appropriately. The shape is preferably a drum shape, and examples of the material include inorganic photoreceptors such as amorphous silicon and selenium, and organic photoreceptors (OPC) such as polysilane and phthalopolymethine. Among these, an organic photoreceptor (OPC) is preferable in that a higher definition image can be obtained.

The formation of the electrostatic latent image can be performed, for example, by uniformly charging the surface of the electrostatic latent image carrier and then performing imagewise exposure, and is performed by electrostatic latent image forming means. Can do.
The electrostatic latent image forming unit includes, for example, a charging unit (charger) that uniformly charges the surface of the electrostatic latent image carrier, and an exposure that exposes the surface of the electrostatic latent image carrier imagewise. Means (exposure unit).

The charging can be performed, for example, by applying a voltage to the surface of the electrostatic latent image carrier using the charger.
The charger is not particularly limited and may be appropriately selected depending on the purpose. For example, a known contact charging device including a conductive or semiconductive roll, brush, film, rubber blade, etc. And non-contact chargers utilizing corona discharge such as corotrons and corotrons.
The charger is preferably one that is arranged in contact or non-contact with the electrostatic latent image carrier and charges the surface of the electrostatic latent image carrier by applying a direct current and an alternating voltage.
Further, the charger is a charging roller disposed in a non-contact proximity to the electrostatic latent image carrier via a gap tape, and the electrostatic latent image is carried by applying a direct current and an alternating voltage to the charging roller. Those that charge the body surface are preferred.

The exposure can be performed, for example, by exposing the surface of the latent electrostatic image bearing member imagewise using the exposure device.
The exposure device is not particularly limited as long as it can expose the surface of the electrostatic latent image carrier charged by the charger so as to form an image to be formed, and is appropriately selected according to the purpose. For example, various exposure devices such as a copying optical system, a rod lens array system, a laser optical system, and a liquid crystal shutter optical system can be used.
In the present invention, a back light system in which imagewise exposure is performed from the back side of the electrostatic latent image carrier may be employed.

-Development process and development means-
The developing step is a step of developing the electrostatic latent image with the toner to form a visible image.
The visible image can be formed, for example, by developing the electrostatic latent image using the toner, and can be performed by the developing unit.
The developing unit preferably includes, for example, at least a developing unit that accommodates the toner and can apply the toner to the electrostatic latent image in a contact or non-contact manner, and includes a toner-containing container. Etc. are more preferable.

The developing device may be a monochromatic developing device or a multi-color developing device, and has, for example, an agitator that frictionally agitates and charges the toner and a rotatable magnet roller. A thing etc. are mentioned suitably.
In the developing device, for example, the toner and the carrier are mixed and agitated, and the toner is charged by friction at that time, and held on the surface of the rotating magnet roller in a raised state to form a magnetic brush. . Since the magnet roller is disposed in the vicinity of the electrostatic latent image carrier (photoconductor), a part of the toner constituting the magnetic brush formed on the surface of the magnet roller is electrically attracted. It moves to the surface of the electrostatic latent image carrier (photoconductor) by force. As a result, the electrostatic latent image is developed with the toner, and a visible image is formed with the toner on the surface of the electrostatic latent image carrier (photoconductor).

-Transfer process and transfer means-
The transfer step is a step of transferring the visible image onto a recording medium. After the primary transfer of the visible image onto the intermediate transfer member using an intermediate transfer member, the visible image is transferred onto the recording medium. A primary transfer step of forming a composite transfer image by transferring a visible image onto an intermediate transfer body using two or more colors, preferably full color toner as the toner, and a composite transfer image; A mode including a secondary transfer step of transferring the transfer image onto the recording medium is more preferable.
The transfer can be performed, for example, by charging the latent electrostatic image bearing member (photoconductor) of the visible image using a transfer charger, and can be performed by the transfer unit. The transfer means includes a primary transfer means for transferring a visible image onto an intermediate transfer member to form a composite transfer image, and a secondary transfer means for transferring the composite transfer image onto a recording medium. Embodiments are preferred.
The intermediate transfer member is not particularly limited and may be appropriately selected from known transfer members according to the purpose. For example, a transfer belt and the like are preferable.

The transfer means (the primary transfer means and the secondary transfer means) is a transfer for peeling and charging the visible image formed on the electrostatic latent image carrier (photoconductor) to the recording medium side. It is preferable to have at least a vessel. The number of the transfer means may be one, or two or more.
Examples of the transfer device include a corona transfer device using corona discharge, a transfer belt, a transfer roller, a pressure transfer roller, and an adhesive transfer device.
The recording medium is not particularly limited and can be appropriately selected from known recording media (recording paper).

-Fixing process and fixing means-
The fixing step is a step of fixing the visible image transferred to the recording medium using a fixing device, and may be performed each time the developer of each color is transferred to the recording medium, or the developer of each color. On the other hand, it may be carried out at the same time in a state where these are laminated.
There is no restriction | limiting in particular as said fixing device, Although it can select suitably according to the objective, A well-known heating-pressing means is suitable. Examples of the heating and pressing means include a combination of a heating roller and a pressing roller, a combination of a heating roller, a pressing roller, and an endless belt.
The fixing device includes a heating body including a heating element, a film in contact with the heating body, and a pressure member in pressure contact with the heating body through the film, and the film and the pressure member It is preferably a unit that heats and fixes a recording medium on which an unfixed image is formed. The heating in the heating and pressing means is usually preferably 80 ° C to 200 ° C.
In the present invention, for example, a known optical fixing device may be used together with or in place of the fixing step and the fixing unit depending on the purpose.

-Other processes and other means-
The neutralization step is a step of performing neutralization by applying a neutralization bias to the electrostatic latent image carrier, and can be suitably performed by a neutralization unit.
The neutralization means is not particularly limited, and may be appropriately selected from known neutralizers as long as it can apply a neutralization bias to the electrostatic latent image carrier. Preferably mentioned.

The cleaning step is a step of removing the toner remaining on the electrostatic latent image carrier and can be suitably performed by a cleaning unit.
The cleaning means is not particularly limited, and may be appropriately selected from known cleaners as long as the toner remaining on the electrostatic latent image carrier can be removed. For example, a magnetic brush cleaner Suitable examples include electrostatic brush cleaners, magnetic roller cleaners, blade cleaners, brush cleaners, web cleaners, and the like.

The recycling step is a step of recycling the toner removed by the cleaning step to the developing unit, and can be suitably performed by the recycling unit. There is no restriction | limiting in particular as said recycling means, A well-known conveyance means etc. are mentioned.
The control step is a step of controlling each step, and each step can be suitably performed by a control means.
The control means is not particularly limited as long as the movement of each means can be controlled, and can be appropriately selected according to the purpose. Examples thereof include devices such as a sequencer and a computer.

  FIG. 3 shows a first example of the image forming apparatus of the present invention. The image forming apparatus 100 </ b> A includes a photosensitive drum 10, a charging roller 20, an exposure device, a developing device 40, an intermediate transfer belt 50, a cleaning device 60 having a cleaning blade, and a static elimination lamp 70.

  The intermediate transfer belt 50 is an endless belt stretched by three rollers 51 arranged on the inner side, and can move in the direction of the arrow in the figure. A part of the three rollers 51 also functions as a transfer bias roller that can apply a transfer bias (primary transfer bias) to the intermediate transfer belt 50. Further, a cleaning device 90 having a cleaning blade is disposed in the vicinity of the intermediate transfer belt 50. Further, a transfer roller 80 capable of applying a transfer bias (secondary transfer bias) for transferring the toner image to the transfer paper 95 is disposed opposite to the intermediate transfer belt 50. Further, around the intermediate transfer belt 50, a corona charging device 58 for applying a charge to the toner image transferred to the intermediate transfer belt 50 is connected to the photosensitive drum 10 with respect to the rotation direction of the intermediate transfer belt 50. It is disposed between the contact portion of the intermediate transfer belt 50 and the contact portion of the intermediate transfer belt 50 and the transfer paper 95.

  The developing device 40 includes a developing belt 41 and a black developing unit 45K, a yellow developing unit 45Y, a magenta developing unit 45M, and a cyan developing unit 45C provided around the developing belt 41. Each color developing unit 45 includes a developer container 42, a developer supply roller 43, and a developing roller (developer carrier) 44. The developing belt 41 is an endless belt stretched by a plurality of belt rollers, and can move in the direction of the arrow in the figure. Further, a part of the developing belt 41 is in contact with the photosensitive drum 10.

  Next, a method for forming an image using the image forming apparatus 100A will be described. First, the charging roller 20 is used to uniformly charge the surface of the photosensitive drum 10, and then the exposure light L is exposed to the photosensitive drum 10 using an exposure device (not shown) to form an electrostatic latent image. Form. Next, the electrostatic latent image formed on the photosensitive drum 10 is developed with the toner supplied from the developing device 40 to form a toner image. Further, after the toner image formed on the photosensitive drum 10 is transferred (primary transfer) onto the intermediate transfer belt 50 by the transfer bias applied from the roller 51, the transfer bias applied from the transfer roller 80 is used. Then, it is transferred (secondary transfer) onto the transfer paper 95. On the other hand, the photosensitive drum 10 on which the toner image is transferred to the intermediate transfer belt 50 is discharged by the discharging lamp 70 after the toner remaining on the surface is removed by the cleaning device 60.

  FIG. 4 shows a second example of the image forming apparatus used in the present invention. In the image forming apparatus 100B, the black developing unit 45K, the yellow developing unit 45Y, the magenta developing unit 45M, and the cyan developing unit 45C are arranged directly facing each other around the photosensitive drum 10 without providing the developing belt 41. Other than that, the configuration is the same as that of the image forming apparatus 100A.

  FIG. 5 shows a third example of the image forming apparatus used in the present invention. The image forming apparatus 100 </ b> C is a tandem type color image forming apparatus, and includes a copying apparatus main body 150, a paper feed table 200, a scanner 300, and an automatic document feeder (ADF) 400.

  The intermediate transfer belt 50 provided at the center of the copying apparatus main body 150 is an endless belt stretched around three rollers 14, 15 and 16, and can move in the direction of the arrow in the figure. In the vicinity of the roller 15, a cleaning device 17 having a cleaning blade for removing toner remaining on the intermediate transfer belt 50 on which the toner image has been transferred onto the recording paper is disposed. The image forming units 120Y, 120C, 120M, and 120K for yellow, cyan, magenta, and black are juxtaposed along the conveying direction while facing the intermediate transfer belt 50 stretched by the rollers 14 and 15.

  An exposure device 21 is disposed in the vicinity of the image forming unit 120. Further, the secondary transfer belt 24 is disposed on the side of the intermediate transfer belt 50 opposite to the side on which the image forming unit 120 is disposed. The secondary transfer belt 24 is an endless belt stretched around a pair of rollers 23, and the recording paper and the intermediate transfer belt 50 conveyed on the secondary transfer belt 24 are between the rollers 16 and 23. Can touch.

  Further, in the vicinity of the secondary transfer belt 24, a fixing device 25 is provided with a fixing belt 26 that is an endless belt stretched between a pair of rollers, and a pressure roller 27 that is arranged to be pressed against the fixing belt 26. Is arranged. A sheet reversing device 28 for reversing the recording paper when an image is formed on both sides of the recording paper is disposed in the vicinity of the secondary transfer belt 24 and the fixing device 25.

Next, a method for forming a full-color image using the image forming apparatus 100C will be described. First, a color document is set on the document table 130 of the automatic document feeder (ADF) 400, or the automatic document feeder 400 is opened and a color document is set on the contact glass 32 of the scanner 300 to automatically convey the document. The device 400 is closed.
When the start switch is pressed, when an original is set on the automatic document feeder 400, after the original is conveyed and moved onto the contact glass 32, on the other hand, when the original is set on the contact glass 32, Immediately, the scanner 300 is driven, and the first traveling body 33 including the light source and the second traveling body 34 including the mirror travel. At this time, the reflected light from the original surface of the light irradiated from the first traveling body 33 is reflected by the second traveling body 34 and then received by the reading sensor 36 via the imaging lens 35, whereby the original is received. It is read and image information of black, yellow, magenta and cyan is obtained.

The image information for each color is transmitted to the image forming unit 120 for each color, and a toner image for each color is formed. As shown in FIG. 6, each color image forming unit 120 includes a photosensitive drum 10, a charging roller 160 that uniformly charges the photosensitive drum 10, and image information of each color, respectively. An exposure device that exposes the exposure light L to form an electrostatic latent image of each color; a developing device 61 that develops the electrostatic latent image with a developer of each color to form a toner image of each color; A transfer roller 62 for transferring onto the transfer belt 50, a cleaning device 63 having a cleaning blade, and a static elimination lamp 64 are provided.
The toner images of the respective colors formed by the image forming units 120 of the respective colors are sequentially transferred (primary transfer) onto the intermediate transfer body 50 that is stretched and moved by the rollers 14, 15, and 16, and superimposed to form a composite toner image. It is formed.

  On the other hand, in the paper feed table 200, one of the paper feed rollers 142 is selectively rotated to feed recording paper from one of the paper feed cassettes 144 provided in multiple stages in the paper bank 143, and one sheet at a time by the separation roller 145. The paper is separated and sent to the paper feed path 146, transported by the transport roller 147, guided to the paper feed path 148 in the copying machine main body 150, and abutted against the registration roller 49 to stop. Alternatively, the paper feed roller is rotated to feed out the recording paper on the manual feed tray 54, separated one by one by the separation roller 52, guided to the manual paper feed path 53, and abutted against the registration roller 49 and stopped. The registration roller 49 is generally used while being grounded, but may be used in a state where a bias is applied in order to remove paper dust from the recording paper.

  Next, by rotating the registration roller 49 in synchronization with the composite toner image formed on the intermediate transfer belt 50, the recording paper is sent between the intermediate transfer belt 50 and the secondary transfer belt 24, and the composite toner image is sent. The toner image is transferred onto the recording paper (secondary transfer). The toner remaining on the intermediate transfer belt 50 to which the composite toner image has been transferred is removed by the cleaning device 17.

  The recording paper on which the composite toner image has been transferred is conveyed by the secondary transfer belt 24 and then the composite toner image is fixed by the fixing device 25. Next, the conveyance path of the recording paper is switched by the switching claw 55, and the recording paper is discharged onto the paper discharge tray 57 by the discharge roller 56. Alternatively, the recording path of the recording paper is switched by the switching claw 55, reversed by the sheet reversing device 28, an image is similarly formed on the back side, and then discharged onto the discharge tray 57 by the discharge roller 56. .

  EXAMPLES Hereinafter, although an Example demonstrates this invention in detail, this invention is not limited to the following Example. In the description in the examples, [%] indicates% by weight, and unless otherwise specified, when “part” is simply indicated, it indicates “part by weight”.

(Manufacture of polyester)
The compositions shown in Tables 1 and 2 were placed in a 1 L four-necked round bottom flask equipped with a thermometer, a stirrer, a condenser and a nitrogen gas inlet tube. The flask was set in a mantle heater, and nitrogen was added. Nitrogen gas was introduced from the gas introduction tube, and the temperature was raised in a state where the inside of the flask was maintained in an inert atmosphere. Subsequently, 0.05 g of dibutyltin oxide was added and reacted at a temperature of 200 ° C. to obtain each polyester shown in Tables 1 and 2.

<Measurement of physical properties>
The following measurements were performed for each obtained polyester.

-Molecular weight measurement (GPC)-
GPC (gel permeation chromatography) measurement was performed under the following conditions.
・ Apparatus: GPC-150C (manufactured by Waters)
Column: KF801-807 (manufactured by Shodex)
・ Temperature: 40 ℃
・ Solvent: THF (tetrahydrofuran)
Flow rate: 1.0 mL / min Sample: 0.1 mL of a sample having a concentration of 0.05 to 0.6% was injected.
The number average molecular weight and weight average molecular weight of the resin were calculated from the molecular weight distribution of the resin measured under the above conditions using a molecular weight calibration curve prepared with a monodisperse polystyrene standard sample.
As standard polystyrene samples for preparing a calibration curve, Showdex STANDARD Std. No S-7300, S-210, S-390, S-875, S-1980, S-10.9, S-629, manufactured by Showa Denko KK S-3.0, S-0.580, and toluene were used. An RI (refractive index) detector was used as the detector.

-THF insoluble matter-
About 50 mg of the binder resin was weighed, and 10 g of THF (tetrahydrofuran) was added and sufficiently dissolved therein. After centrifugation, the supernatant was dried and the solid content concentration of the supernatant was calculated. The difference between the toner solution prepared first and the supernatant was defined as THF-insoluble matter.

  Tables 1 and 2 show the prescription and physical properties of each polyester. In the table, the acid component and the alcohol component represent “parts by weight”, “Mw” represents the weight average molecular weight, and the THF-insoluble matter represents “%”.

Example 1
A mixture having the following composition was sufficiently stirred and mixed in a Henschel mixer, then melt-kneaded with a twin-screw extruder kneader (TEM-18SS, manufactured by Toshiba Machine Co., Ltd.), cooled to room temperature, and the resulting kneaded product was jet milled (IDS). -2, manufactured by Nippon New Matchk Co., Ltd.) and a rotor classifier (50 ATP, manufactured by Hosokawa Micron Corporation), a toner base having an average particle size of 8 μm was obtained.

-Composition-
Polyester resin A-1 50 parts Polyester resin B-1 50 parts Refined rice wax (endothermic start temperature 66.3 ° C. manufactured by Toa Kasei Co., Ltd.) 3 parts Carbon black (# 44, manufactured by Mitsubishi Chemical Corporation) 10 parts Azoiron compound (T -77, manufactured by Hodogaya Chemical Co., Ltd., referred to as [CCA1]) 1.8 parts

  The toner base thus obtained was mixed with 2 parts by weight of 12 nm HMDS treated hydrophobic silica (RX200: manufactured by Nippon Aerosil Co., Ltd.) to obtain [Toner 1]. The toner properties are shown in Table 3.

(Example 2)
[Toner 2] was obtained in the same manner as in Example 1 except that [Polyester resin B-1] was changed to [Polyester resin B-2] in Example 1.

(Example 3)
In Example 1, [Polyester Resin A-1] was changed to [Polyester Resin A-2], and [Polyester Resin B-1] was changed to [Polyester Resin B-3]. [Toner 3] was obtained.

Example 4
[Toner 4] was obtained in the same manner as in Example 1 except that [Polyester resin B-1] was changed to [Polyester resin B-4] in Example 1.

(Example 5)
[Toner] in the same manner as in Example 1 except that the type and addition amount of the binder resin are changed to 60 parts by weight of [Polyester resin A-2] and 40 parts by weight of [Polyester resin B-3]. 5] was obtained.

(Example 6)
[Toner] in the same manner as in Example 1 except that the type and amount of the binder resin were changed to 50 parts by weight of [Polyester resin A-3] and 50 parts by weight of [Polyester resin B-4]. 6] was obtained.

(Example 7)
[Toner] in the same manner as in Example 1 except that the type and amount of the binder resin were changed to 40 parts by weight of [Polyester resin A-3] and 60 parts by weight of [Polyester resin B-4]. 7] was obtained.

(Example 8)
[Toner] in the same manner as in Example 1 except that the type and addition amount of the binder resin were changed to 70 parts by weight of [Polyester resin A-2] and 30 parts by weight of [Polyester resin B-3]. 8] was obtained.

Example 9
[Toner 9] was obtained in the same manner as in Example 1 except that 1.8 parts by weight of [CCA1] was changed to 0.5 parts by weight of [CCA1] in Example 1.

(Example 10)
[Toner 10] was obtained in the same manner as in Example 1 except that 1.8 parts by weight of [CCA1] was changed to 3.0 parts by weight of [CCA1] in Example 1.

(Example 11)
[Toner 11] was obtained in the same manner as in Example 1 except that [CCA1] was changed to T-159 (referred to as [CCA2]) manufactured by Hodogaya Chemical Co., Ltd. in Example 1.

(Example 12)
[Toner 12] was obtained in the same manner as in Example 1 except that 1.8 parts by weight of [CCA1] in Example 1 was changed to 0.3 parts by weight of [CCA1].

(Example 13)
[Toner 13] was obtained in the same manner as in Example 1 except that 1.8 parts by weight of [CCA1] was changed to 4.0 parts by weight of [CCA1] in Example 1.

(Comparative Example 1)
[Comparative toner 1] was obtained in the same manner as in Example 1 except that [Polyester resin B-1] was changed to [Polyester resin B-5] in Example 1.

(Comparative Example 2)
In Example 1, except that the type and amount of the binder resin were changed to 35 parts by weight of [Polyester resin A-1] and 65 parts by weight of [Polyester resin B-2] [Comparison Toner 2] was obtained.

(Comparative Example 3)
In Example 1, except that the type and amount of the binder resin were changed to 65 parts by weight of [Polyester Resin A-2] and 35 parts by weight of [Polyester Resin B-3] [Comparison Toner 3] was obtained.

(Comparative Example 4)
In Example 1, except that the type and amount of the binder resin were changed to 35 parts by weight of [Polyester resin A-1] and 65 parts by weight of [Polyester resin B-4] [Comparison Toner 4] was obtained.

(Comparative Example 5)
In Example 1, except that the type and amount of the binder resin were changed to 50 parts by weight of [Polyester Resin A-2] and [Polyester Resin B-6] [Comparison Toner 5] was obtained.

(Comparative Example 6)
[Comparative toner 6] was obtained in the same manner as in Example 1 except that the type of binder resin in Example 1 was changed to [Polyester resin A-3] and [Polyester resin B-4].

(Comparative Example 7)
In Example 1, except that the type and amount of the binder resin were changed to 45 parts by weight of [Polyester resin A-4] and 55 parts by weight of [Polyester resin B-4] [Comparison Toner 7] was obtained.

(Comparative Example 8)
In Example 1, except that the type and amount of the binder resin were changed to 70 parts by weight of [Polyester resin A-2] and 30 parts by weight of [Polyester resin B-6] [Comparison Toner 8] was obtained.

(Comparative Example 9)
[Comparative toner 9] was obtained in the same manner as in Example 1 except that [CCA1] was changed to zirconium salicylate (referred to as [CCA3]) manufactured by Hodogaya Chemical Co., Ltd. in Example 1.

  Table 3 shows the physical properties of the toner thus obtained. In the table, the numerical values of the resins A and B represent “parts by weight”, the THF-insoluble matter represents “%”, and 2000 or less and 100,000 or more represent “% by weight”. The CCA addition amount (parts) represents the content (parts by weight) relative to 100 parts by weight of the binder resin.

(Measurement)
The following measurement was performed on the obtained toner.

<GPC measurement>
The obtained toner was subjected to GPC (gel permeation chromatography) measurement under the following conditions.
・ Apparatus: GPC-150C (manufactured by Waters)
Column: KF801-807 (manufactured by Shodex)
・ Temperature: 40 ℃
・ Solvent: THF (tetrahydrofuran)
Flow rate: 1.0 mL / min Sample: 0.1 mL of a sample having a concentration of 0.05 to 0.6% was injected.
The number average molecular weight and weight average molecular weight of the resin were calculated from the molecular weight distribution measured under the above conditions using a molecular weight calibration curve prepared with a monodisperse polystyrene standard sample.
As standard polystyrene samples for preparing a calibration curve, Showdex STANDARD Std. No S-7300, S-210, S-390, S-875, S-1980, S-10.9, S-629, manufactured by Showa Denko KK S-3.0, S-0.580, and toluene were used. An RI (refractive index) detector was used as the detector.

<THF insoluble matter>
About 50 mg of the toner was weighed, and 10 g of THF (tetrahydrofuran) was added and sufficiently dissolved therein. After centrifuging, the supernatant was dried and the solid content concentration of the supernatant was calculated. The difference between the toner solution prepared first and the supernatant was defined as THF-insoluble matter.

(Evaluation)
The toner obtained above was evaluated as follows.

<Evaluation of dirt>
A modified Ricoh IPSiO SP C220, 13.5 g of the deteriorated toner produced in the blade fixing durability evaluation was put, and the exposed scotch tape was applied to the entire exposed surface of the photosensitive member that was stopped during the white paper printing. Was pasted and stored on a type 6000T paper made by Ricoh. On the tape, L * was measured by X-rite (manufactured by Videojet X-Rite). The evaluation criteria are as follows.
[Evaluation criteria]
◎: L * is 91 or more ○: L * is 89 or more and less than 91 △: L * is 85 or more and less than 89 ×: L * is less than 85

<Fixability evaluation>
-Low temperature fixability-
A modified Ricoh IPSiO SP C220 was used, and a toner was added. A 40 mm square unfixed solid image was printed on a Ricoh type 6000T eye paper with an adhesion amount of 10 g / m ² . .
Next, using a modified fixing unit of IPSiO SP 4510SF made by Ricoh, the system speed was set to 240 mm / sec, and the prepared unfixed solid image was passed through to fix the image. The fixing temperature was tested from 120 ° C. to 160 ° C. in increments of 2 ° C. and visually observed, and the temperature at which no toner image appeared on the white paper portion was defined as the lower limit fixing temperature. The evaluation criteria are as follows.
[Evaluation criteria]
: Fixing lower limit temperature is less than 130 ° C ○: Fixing lower limit temperature is 130 ° C or more and less than 140 ° C Δ: Fixing lower limit temperature is 140 ° C or more and less than 150 ° C

−High temperature releasability−
A modified Ricoh IPSiO SP C220 was used, and a toner was added. A 40 mm square unfixed solid image was printed on a Ricoh type 6000T eye paper with an adhesion amount of 10 g / m ² . .
Next, using a modified fixing unit of IPSiO SP 4510SF made by Ricoh, the system speed was set to 240 mm / sec, and the prepared unfixed solid image was passed through to fix the image. The fixing temperature was tested from 160 ° C. to 200 ° C. in increments of 2 ° C., and visually observed, and the temperature at which the toner image did not appear on the white paper portion was defined as the fixing upper limit temperature. The evaluation criteria are as follows.
[Evaluation criteria]
A: Maximum fixing temperature is 190 ° C. or higher. ○: Upper fixing temperature is 180 ° C. or higher and lower than 190 ° C. Δ: Upper fixing temperature is 170 ° C. or higher and lower than 180 ° C.

<Evaluation for cracking>
After putting 50 g of toner in a 250 ml plastic container, 120 g of φ10 mm alumina beads were added and stirred for 44 hours at 150 rpm in a ball mill to prepare a deteriorated toner for evaluation. Using a COULTER COUNTER Multisizer III, the particle diameters of the pre-deterioration toner and the post-deterioration toner were measured, and the increase in the small-diameter component smaller than 3 μm was measured. The evaluation criteria are as follows.
[Evaluation criteria]
◎: Increase is less than 4% ○: Increase is from 4% to less than 7% △: Increase is from 7% to less than 10% ×: Increase is 10% or more

  Table 4 shows the evaluation results of Examples and Comparative Examples.

10 Electrostatic latent image carrier (photosensitive drum)
10K Black electrostatic latent image carrier 10Y Yellow electrostatic latent image carrier 10M Magenta electrostatic latent image carrier 10C Cyan electrostatic latent image carrier 14 Support roller 15 Support roller 16 Support roller 17 Intermediate transfer cleaning device 18 Image forming means 20 Charging roller 21 Exposure device 22 Secondary transfer device 23 Roller 24 Secondary transfer belt 25 Fixing device 26 Fixing belt 27 Pressure roller 28 Sheet reversing device 32 Contact glass 33 First traveling body 34 Second traveling body 35 Imaging lens 36 Reading sensor 40 Developing device 41 Developing belt 42K Developer container 42Y Developer container 42M Developer container 42C Developer container 43K Developer supply roller 43Y Developer supply roller 43M Developer supply roller 43C Developer Supply roller 44K Developing roller 44Y Developing roller 44M Developing row 44C Development roller 45K Black development unit 45Y Yellow development unit 45M Magenta development unit 45C Cyan development unit 49 Registration roller 50 Intermediate transfer belt 51 Roller 52 Separation roller 53 Manual feed path 54 Manual feed tray 55 Switching claw 56 Discharge roller 57 Discharge tray 58 Corona Charging device 60 Cleaning device 61 Developing device 62 Transfer roller 63 Photoconductor cleaning device 64 Static discharge lamp 70 Static discharge lamp 80 Transfer roller 90 Cleaning device 95 Transfer paper 100A, 100B, 100C Image forming device 120 Image forming unit 130 Document base 142 Paper feed roller 143 Paper bank 144 Paper cassette 145 Separation roller 146 Paper feed path 147 Transport roller 148 Paper feed path 150 Copying device main body 160 Charging device 200 Paper feed tray Le 300 Scanner 400 automatic document feeder (ADF)

Japanese Patent No. 4118498

Claims (6)

A toner containing at least a binder resin and a charge control agent,
The toner contains 10 to 40% of a THF-insoluble content, has a main peak between 12000 and 18000 in a molecular weight distribution by GPC (gel permeation chromatography) determined by the THF-soluble content, and the toner The half width of the main peak is 20000 to 50000 in molecular weight, the component having a molecular weight of 2000 or less is 10% by weight to 20% by weight, and the component having a molecular weight of 100,000 or more is 8% by weight or less,
A toner wherein the charge control agent contains an azo iron compound. The toner according to claim 1, wherein the azo iron compound is represented by the following structural formula (1).

(In the structural formula (1), A ⁺ represents an ammonium ion.)   The toner according to claim 1, wherein the azo iron compound is contained in an amount of 0.5 to 3.0 parts by weight with respect to 100 parts by weight of the binder resin.   The toner according to claim 1, wherein the toner is a one-component developing toner.   A toner storage unit for storing the toner according to claim 1. An electrostatic latent image carrier;
An electrostatic latent image forming means for forming an electrostatic latent image on the electrostatic latent image carrier;
Developing means for developing the electrostatic latent image with a developer to form a visible image;
Transfer means for transferring the visible image onto a recording medium;
Fixing means for fixing the transferred image transferred onto the recording medium,
An image forming apparatus, wherein the developer is the toner according to claim 1.

Images