JP2009186726A - Toner for developing electrostatic charge image, developer for developing electrostatic charge image, non-magnetic single component developer, image forming method, method of manufacturing toner for developing electrostatic charge image, and image forming device - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To improve the durability of a cleaning blade, and to prevent contamination inside a nonmagnetic single component developing device over a long period, when using toner for developing an electrostatic charge image as a non-magnetic single component developer. <P>SOLUTION: This toner for developing the electrostatic charge image contains a noncrystalline polyester resin, a crystalline polyester resin, and a coloring agent, and has phenol ester structure on a toner particle surface, and a phenol ester amount MPh [mol/g-TN] existing on a surface of 1 g toner satisfies the following expression: (1) 8.9×10<SP>-5</SP>≤MPh≤7.1×10<SP>-4</SP>, wherein TN represents the toner. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to an electrostatic charge developing toner (hereinafter also referred to as electrophotographic toner), an electrostatic charge developing developer, a non-magnetic one-component developer, an image forming method, a method for producing an electrostatic charge developing toner, and an image forming apparatus. .

  In electrophotography, an electrostatic charge image is formed on a photoreceptor by charging and exposure processes, an electrostatic latent image is developed with a developer containing toner to form a toner image, and the toner image is transferred to a recording medium. Fix and form an image. The developer used here includes a two-component developer comprising a toner and a carrier, and a one-component developer using a magnetic toner or a non-magnetic toner alone. In the production of toner, a so-called kneading and pulverizing method is generally used in which a thermoplastic resin is melt-kneaded together with a release agent such as a pigment, a charge control agent, and a wax, cooled, finely pulverized, and further classified. Yes.

  In the toner prepared by the usual kneading and pulverizing method, the shape of the toner particles is indeterminate, and the surface structure of the toner particles slightly changes depending on the pulverization properties of the materials used and the conditions of the pulverization process. It is difficult to intentionally control the shape and surface structure.

  On the other hand, in recent years, a toner manufacturing method using a wet manufacturing method has been proposed as a means capable of intentionally controlling the shape and surface structure of the toner. Examples of the wet production method include a wet spheronization method capable of controlling the shape, a suspension granulation method capable of controlling the surface composition, a suspension polymerization method capable of controlling the internal composition, and an agglomeration and coalescence method.

  On the other hand, as the demand for energy saving increases, in order to save power in the fixing process occupying a certain amount of power in the copying machine and expand the fixing area, the toner fixing temperature is lowered. It is necessary to make it. Lowering the toner fixing temperature not only saves power and expands the fixing area, but also reduces the waiting time until the fixing temperature on the surface of the fixing roll at the time of power input to the copying machine, so-called warm-up time. This makes it possible to shorten the time and extend the life of the fixing roll.

  By the way, lowering the fixing temperature of the toner leads to a decrease in the glass transition temperature of the toner, and there is a problem that the storage stability of the toner deteriorates. It was difficult to plan. In order to achieve both low-temperature fixing and toner storage stability, it is necessary to have a so-called sharp melt property in which the toner viscosity rapidly decreases in a high temperature region while maintaining the glass transition temperature of the toner at a higher temperature. Become.

  However, since the resin used for the toner usually has a variation range in the glass transition temperature, the molecular weight, and the like, it is necessary to extremely align the resin composition and the molecular weight in order to obtain sharp melt properties. In order to obtain such a resin, it becomes necessary to adjust the molecular weight of the resin by using a special production method or by treating the resin with a chromatograph or the like, so that the production cost of the resin becomes very high, and In this case, unnecessary resin is by-produced, which is not preferable from the viewpoint of environmental protection.

  As a method for lowering the toner fixing temperature, it has been proposed to use a crystalline resin as the binder resin (see, for example, Patent Documents 1 to 19).

  Although these methods can lower the fixing temperature, since the change in the resin viscosity with respect to the temperature change is large, a sufficient viscosity cannot be obtained at the time of preparation of the toner, for example, during kneading. As a result, the dispersibility of the toner is not stable, and a toner with uneven coloring and fixing properties is likely to be produced. Further, when the toner is produced using the kneading and pulverizing method, it becomes difficult to pulverize the kneaded product, which causes a problem that it is difficult to obtain a toner having a small particle diameter. In order to solve this problem, for example, there is a method of adding an auxiliary agent such as a thickener and a grinding auxiliary agent. However, these auxiliary agents are dispersed in the resin to break the crystallinity of the binder resin. Therefore, it is not preferable.

  From such a point of view, a toner particle production technique by the above-described wet manufacturing method that does not require excessive temperature and kneading energy has been actively studied.

  However, achieving the melt-melt property by means such as the molecular weight of the binder resin, the molecular weight distribution, the melt viscosity, and the inclusion of the crystalline resin results in a decrease in the resin strength, resulting in a decrease in the toner strength. In some cases, the image strength may be lowered, and it is not easy to achieve a plurality of characteristics.

  In addition, the addition of the crystalline resin may reduce the encapsulation stability such as particle size, particle shape control, etc. It affects other than the quality of toner.

  On the other hand, in recent years, from the viewpoint of waste tonerless, an image forming method using a cleaner-less, toner recycling method has been proposed. In particular, toner used in an image forming method using a toner recycling method has a particle strength, Particle size and shape uniformity are required. However, these characteristics often hinder the attempt to achieve the sharp melt property.

  Further, in recent years, long-life xerography has been desired in consideration of environmental load. In particular, in order to achieve a longer life, a photoreceptor using a material having a high hardness such as a-Si, a photoreceptor having a protective layer having a three-dimensional cross-linked structure on the outermost surface, and the like have been used. It's getting on. Since the surface of these photoreceptors is generally difficult to clean, when a cleaning blade is used as a cleaning means, it is necessary to apply a large pressure to the contact portion between the cleaning blade and the photoreceptor, and the cleaning blade is extremely deteriorated. It has become an important issue.

  The one-component toner developing method using the one-component developer is classified into a magnetic one-component developing method using magnetic toner and a non-magnetic one-component developing method using non-magnetic toner. The magnetic one-component development system uses a developer carrier provided with a magnetic field generating means such as a magnet inside, holds magnetic toner containing a magnetic material such as magnetite inside, and develops it with a thin layer by a layer regulating member. In recent years, many printers have been put to practical use. On the other hand, in the non-magnetic one-component development method, since the toner does not have a magnetic force, the toner supply roll or the like is pressed against the developer carrying member to supply the toner to the developer carrying member and held by the electrostatic force. Developed with a thin layer by a layer regulating member, it has the advantage of being able to cope with colorization because it does not contain a colored magnetic material, and because it does not use a magnet for the developer carrier, it is lighter and less expensive In recent years, it has begun to be put into practical use in small full-color printers and the like.

  However, in the one-component development system, there are still many problems to be improved. In the two-component development system, a carrier is used as a means for charging and transporting the toner, and the toner and the carrier are sufficiently stirred and mixed inside the developing device, and then transported to the developer carrying member for development. Even in use, it is possible to maintain stable charging and conveyance, and it is easy to cope with a high-speed developing device. Compared to this, in the one-component development method, there is no stable charging / conveying means like a carrier, so that charging / conveying defects are likely to occur due to long-term use or high speed. That is, in the one-component development method, after the toner is transported onto the developer carrying member, the toner is thinned and developed by the layer regulating member, and the charging member such as the toner and the developer carrying member or the layer regulating member is developed. The contact / friction charging opportunity with the toner is very short, so that the amount of low-charged or reverse-polarized toner tends to increase as compared with the two-component development method using a carrier. For this reason, the toner is required to have a quicker charging speed and an appropriate charge amount.

  In order to satisfy this requirement, it is preferable to increase the contact pressure of the layer regulating member to the developer carrier. However, in the development under high pressure contact, the contact area of the layer regulating member becomes large, and accordingly The charging time of the toner can be kept long, so that stable charging can be imparted to the toner, and a stable layer can be formed.

  However, in this case, since the contact area between the toner and the layer regulating member is wide, it is difficult to stably charge and form a layer with the sharp melt toner because the toner is fused and fixed to the layer regulating member. As a result, unevenness in the charge distribution of the toner occurs, and as a result, contamination in the apparatus due to the cloud of the low-charge toner becomes a problem.

JP 62-129867 A JP-A-62-170971 JP 62-170972 A JP 62-205365 A JP-A-62-276565 JP-A-62-276666 JP-A-63-038949 Japanese Unexamined Patent Publication No. 63-038950 Japanese Patent Laid-Open No. 63-038951 JP-A-63-038952 JP-A-63-038953 JP-A-63-038954 Japanese Unexamined Patent Publication No. 63-038955 JP 63-038956 A JP 05-001217 A Japanese Patent Laid-Open No. 06-148936 Japanese Patent Laid-Open No. 06-194874 JP 05-005056 A Japanese Patent Laid-Open No. 05-112715

  The main object of the present invention is to provide an electrostatic charge developing toner which improves the durability of the cleaning blade while realizing low-temperature fixing, and prevents in-machine contamination of the non-magnetic one-component developing device over a long period of time. An object of the present invention is to provide an electrostatic charge developing developer, a non-magnetic one-component developer, an image forming method, a method for producing an electrostatic charge developing toner, and an image forming apparatus.

  The present invention is as follows.

  (1) An electrostatic charge developing toner containing an amorphous polyester resin, a crystalline polyester resin, and a colorant and having a phenol ester structure on the surface of toner particles.

(2) In the electrostatic charge developing toner described in (1) above, the range of the amount of phenol ester MPh [mol / g-TN] (where TN is the toner) present on the surface of the toner 1 g is
8.9 × 10 ⁻⁵ ≦ MPh ≦ 7.1 × 10 ⁻⁴ Formula (1)
An electrostatic charge developing toner satisfying the above requirement.

  (3) An electrostatic charge image developing developer containing the electrostatic charge developing toner according to (1) or (2) and a carrier.

  (4) A latent image forming step for forming an electrostatic latent image on the surface of the latent image carrier, and developing the electrostatic latent image formed on the surface of the latent image carrier with the developer described in (3) above. A developing step for forming a toner image, a transferring step for transferring the toner image formed on the surface of the latent image carrier to the surface of the transfer target, and a fixing step for thermally fixing the toner image transferred on the surface of the transfer target And an image forming method having a cleaning step of cleaning the surface of the latent image carrier, and the cleaning step is an image forming method using a cleaning blade.

(5) Amount of phenol ester MPh [mol / g-TN], which contains an amorphous polyester resin, a crystalline polyester resin, and a colorant, has a phenol ester structure on the surface of toner particles, and exists on the surface of 1 g of toner. (Where TN is toner)
^{1.4 × 10 -4 ≦ MPh ≦ 6.6} × 10 -4 ····· formula (2)
A non-magnetic one-component developer containing the electrostatic charge developing toner.

  (6) A toner supply member that supplies the non-magnetic one-component developer described in (5) above to the developer carrying member and a layer regulating member that press-contacts the developer carrying member. Image forming method for use in one-component developing device for supplying non-magnetic one-component developer from member to developer carrying member and performing development using charged toner layer formed on developer carrying member by press-contacting layer regulating member In this image forming method, the rotational torque of the developer carrying member is in the range of 1.0 kgfcm to 2.5 kgfcm.

  (7) A non-crystalline polyester resin fine particle, a resin fine particle dispersion in which crystalline polyester resin fine particles are dispersed and mixed, and a colorant fine particle dispersion in which colorant fine particles are dispersed are mixed. An aggregation step of forming aggregated particles, a step of adjusting the pH in the aggregate system to stop the aggregation growth, a step of heating the aggregated particles to a temperature equal to or higher than the glass transition temperature of the resin fine particles, and fusing and coalescing. The step of washing the obtained base toner with at least water, the step of drying the washed base toner, and the dried base toner and phenyl acetate are mixed, and the glass transition temperature of the base toner is −2 ° C. or higher. And a step of gradually reducing the pressure while heating at a temperature of −5 ° C. or lower, and adding a phenol ester structure to the surface of the base toner. It is a manufacturing method.

  (8) A latent image forming unit that forms a latent image on the latent image carrier, a developing unit that develops the latent image using a developer for developing an electrostatic charge, and the developed toner image via an intermediate transfer member. Alternatively, the image forming apparatus includes: a transfer unit that transfers the toner image on the transfer body without being interposed; and a fixing unit that adds and fixes the toner image on the transfer body. An image forming apparatus which is the developer for electrostatic charge development described in 3) or the non-magnetic one-component developer described in (5).

  According to the present invention, by maintaining the sharp melt property inside the toner and increasing the hardness near the surface of the toner, the durability of the cleaning blade is improved while achieving low-temperature fixing as compared with the conventional electrostatic charge developing toner. In addition, when the electrostatic charge developing toner is used as a non-magnetic one-component developer, the in-machine contamination of the non-magnetic one-component developing device can be prevented over a long period of time.

<Toner for electrostatic charge development>
The electrostatic charge developing toner of the present embodiment (hereinafter sometimes abbreviated as “toner”) contains an amorphous polyester resin, a crystalline polyester resin, and a colorant, and has a phenol ester structure on the surface of the toner particles. It is characterized by.

The toner according to the present exemplary embodiment has a phenol ester structure on the toner surface, and thus has a higher toner hardness than a toner without a phenol ester structure without sacrificing low-temperature fixability. In the state of an externally added toner in which fine particles described later are externally added to the toner, even when stress is applied for a long period of time, the external additive is not embedded and movement of the external additive on the toner surface is not hindered. Sex can be maintained for a long time. As a result, the cleaning blade pressure contact pressure can be reduced from the conventional range (20 g / m ² or 40 g / m ² ) by using the developer containing the toner of the present invention in an image forming method using a cleaning blade as a cleaning means. In addition, the cleaning blade tip wear can be suppressed, and the life of the cleaning blade can be extended.

  In the toner of the present embodiment, the cause of the increase in the toner hardness due to the phenol ester structure on the toner surface has not been clearly clarified, but the toner surface probably has a higher degree of freedom of deformation than the linear structure. It is presumed that the toner hardness is increased by having a benzene ring having a small planar structure.

The range of the phenol ester amount MPh [mol / g-TN] (where TN is the toner) present on the toner surface of the present embodiment is:
[Equation 1]
8.9 × 10 ⁻⁵ ≦ MPh ≦ 7.1 × 10 ⁻⁴ Formula (1)
It is preferable that
[Equation 2]
1.8 × 10 ⁻⁴ ≦ MPh ≦ 5.3 × 10 ⁻⁴ Formula (1 ′)
It is more preferable that

If the MPh is less than 8.9 × 10 ⁻⁵ (mol / g-TN), the external additive is likely to be embedded in the toner surface, and the durability of the cleaning blade cannot be improved. When the amount is more than 1 × 10 ⁻⁴ (mol / g-TN), the toner hardness becomes too high, so that the difference between the hardness of the cleaning blade and the toner becomes large, and as a result, the cleaning blade tip wear is likely to occur. Thus, the above-described effect of improving the durability of the cleaning blade may not be exhibited.

  In the toner of the present embodiment, the volume average particle diameter D50v of the toner particles is preferably 3 to 8 μm, and more preferably 4 to 7 μm. When the volume average particle diameter D50v of the toner particles is less than 3 μm, the chargeability becomes insufficient and the developability may be deteriorated, and when it exceeds 8 μm, the resolution of the image may be deteriorated.

  Here, in the present embodiment, the volume average particle diameter D50v is measured using, for example, Multisizer II (manufactured by Beckman-Coulter) and the electrolyte using ISOTON-II (manufactured by Beckman-Coulter). Can do. In the measurement, 0.5 to 50 mg of a measurement sample is added to 2 ml of a 5% aqueous solution of a surfactant, preferably sodium alkylbenzenesulfonate as a dispersant. This is added to 100-150 ml of electrolyte.

  The electrolytic solution in which the sample is suspended is dispersed for about 1 minute with an ultrasonic disperser, and the particle size distribution of particles having a particle diameter in the range of 2 to 50 μm is obtained using the Multisizer II type with an aperture diameter of 100 μm. taking measurement. The number of particles to be sampled is 50,000.

  For the particle size range (channel) divided on the basis of the particle size distribution measured in this way, the cumulative distribution is drawn from the smaller diameter side for each volume and number, and the particle size that becomes 50% cumulative is the cumulative volume average particle size. It is defined as a diameter D50v.

  Further, the average circularity of the toner particles in the toner of the present embodiment is preferably in the range of 0.940 to 0.980, and more preferably in the range of 0.950 to 0.970. When the average circularity is less than 0.940, the shape becomes more irregular and the transferability, durability, fluidity, and the like may decrease. On the other hand, when the average circularity exceeds 0.980, the ratio of spherical particles increases and the cleaning property may deteriorate.

  The average circularity of the toner can be measured by a flow type particle image analyzer FPIA-2000 (manufactured by Toa Medical Electronics Co., Ltd.). As a specific measurement method, a surfactant, preferably an alkylbenzene sulfonate, is added in an amount of 0.1 to 0.5 ml as a dispersant in 100 to 150 ml of water from which impure solids have been removed in advance. Add about 1-0.5g. The suspension in which the measurement sample is dispersed is subjected to dispersion treatment for about 1 to 3 minutes using an ultrasonic wave disperser, and the average circularity of the toner is measured by the above apparatus with the dispersion concentration being 3000 to 10000 / μl.

  Hereinafter, components constituting the toner of the exemplary embodiment will be described in detail.

  As described above, the components constituting the toner of the present embodiment include amorphous polyesters, crystalline polyesters, and colorants, but include other components such as a release agent as necessary. May be.

<Binder resin>
In the electrostatic charge developing toner of the present embodiment, a crystalline polyester and an amorphous polyester are used in combination as a binder resin from the viewpoint of low-temperature fixability and toner strength. In the present invention, “crystalline polyester” refers to those having a clear endothermic peak, not a stepwise endothermic change in differential scanning calorimetry (DSC), but at least a weight average molecular weight (Mw). It means a crystalline polyester exceeding 5000, and usually means a crystalline polyester having a weight average molecular weight (Mw) of 10,000 or more.

[Crystalline polyester]
As the crystalline polyester used in the binder resin of the present embodiment, a known crystalline polyester can be used.

  Since the crystalline polyester has a melting point, the viscosity is greatly reduced at a specific temperature, and when the toner is heated at the time of fixing, the temperature difference between the crystalline polyester molecule starting the thermal activity and the fixable region is increased. Since it can be made small, further excellent low-temperature fixability can be provided. The preferred content of the crystalline polyester in the toner particles is in the range of 1 to 10% by mass, more preferably in the range of 2 to 8% by mass.

  The range of the glass transition temperature (Tg) of the crystalline polyester resin is preferably 45 ° C to 110 ° C, more preferably 50 ° C to 100 ° C, and further preferably 55 ° C to 90 ° C. If the glass transition temperature (Tg) is lower than 45 ° C., it may be difficult to store the toner, whereas if it is higher than 110 ° C., the effect of low-temperature fixability may not be enjoyed. The glass transition temperature (Tg) of the crystalline polyester was determined by a method based on ASTM D3418-8.

  Further, the number average molecular weight (Mn) of the crystalline polyester is preferably 2000 or more, and more preferably 4000 or more. If the number average molecular weight (Mn) is less than 2000, the toner may permeate into the surface of a recording medium such as paper at the time of fixing to cause uneven fixing, or the bending strength of the fixed image may be reduced.

  The crystalline polyester is synthesized from an acid (dicarboxylic acid) component and an alcohol (diol) component. Hereinafter, the acid (dicarboxylic acid) component and the alcohol (diol) component will be described in more detail. In the present invention, a copolymer obtained by copolymerizing other components at a ratio of 50% by mass or less with respect to the main chain of the crystalline polyester is also referred to as a crystalline polyester.

  The acid (dicarboxylic acid) component is preferably an aliphatic dicarboxylic acid, and particularly preferably a linear dicarboxylic acid. For example, succinic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelic acid, sebacic acid, 1,9-nonanedicarboxylic acid, 1,10-decanedicarboxylic acid, 1,10-undecanedicarboxylic acid Acid, 1,12-dodecanedicarboxylic acid, 1,13-tridecanedicarboxylic acid, 1,14-tetradecanedicarboxylic acid, 1,16-hexadecanedicarboxylic acid, 1,18-octadecanedicarboxylic acid, etc., or lower alkyl esters thereof An acid anhydride is mentioned, However, It is not limited to these.

  The acid (dicarboxylic acid) component may include components such as a dicarboxylic acid component having a double bond and a dicarboxylic acid component having a sulfonic acid group in addition to the aliphatic dicarboxylic acid component described above. The dicarboxylic acid component having a double bond includes a component derived from a lower alkyl ester or acid anhydride of a dicarboxylic acid having a double bond, in addition to a component derived from a dicarboxylic acid having a double bond. Is also included. The dicarboxylic acid component having a sulfonic acid group includes a component derived from a dicarboxylic acid having a sulfonic acid group, a lower alkyl ester of a dicarboxylic acid having a sulfonic acid group, or an acid anhydride. Is also included.

  The dicarboxylic acid having a double bond can be suitably used to prevent hot offset at the time of fixing because the entire resin can be crosslinked using the double bond. Examples of such dicarboxylic acids include, but are not limited to, fumaric acid, maleic acid, 3-hexenedioic acid, and 3-octenedioic acid. Moreover, these lower alkyl esters, acid anhydrides, etc. are also mentioned. Among these, fumaric acid, maleic acid and the like are preferable in terms of cost.

  The dicarboxylic acid having a sulfonic acid group is effective in that it can favorably disperse a coloring material such as a pigment. Further, if a sulfonic acid group is present when the entire resin is emulsified or suspended in water to produce fine particles, it can be emulsified or suspended without using a surfactant, as will be described later. Examples of the dicarboxylic acid having a sulfonic acid group include, but are not limited to, 2-sulfoterephthalic acid sodium salt, 5-sulfoisophthalic acid sodium salt, and sulfosuccinic acid sodium salt. Moreover, these lower alkyl esters, acid anhydrides, etc. are also mentioned. Among these, 5-sulfoisophthalic acid sodium salt and the like are preferable in terms of cost.

  As the content of the acid (carboxylic acid component) of the acid (dicarboxylic acid) component other than these aliphatic dicarboxylic acid components (dicarboxylic acid component having a double bond and / or dicarboxylic acid component having a sulfonic acid group), 1 component mol% or more and 20 component mol% or less are preferable, and 2 component mol% or more and 10 component mol% or less are more preferable.

  When the content is less than 1 component mol%, the dispersibility of the pigment in the toner may not be good. Further, when a toner is produced using an aggregation / unification method, the emulsion particle size in the dispersion becomes large, and it may be difficult to adjust the toner diameter by aggregation.

  On the other hand, when it exceeds 20 component mol%, the crystallinity of the crystalline polyester resin is lowered, the melting point is lowered, and the storage stability of the toner may be deteriorated. In addition, when a toner is produced using an agglomeration method, the emulsion particle size in the dispersion may be too small to dissolve in water, and latex may not occur. In the present invention, “constituent mol%” refers to a percentage when each constituent component [acid (carboxylic acid) component, alcohol (diol) component] in the polyester resin is 1 unit (mol).

  On the other hand, the alcohol (diol) component is preferably an aliphatic diol, such as ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1 , 7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,11-undecanediol, 1,12-dodecanediol, 1,13-tridecanediol, , 14-tetradecanediol, 1,18-octadecanediol, 1,20-eicosanediol and the like, but are not limited thereto.

  The alcohol (diol) component preferably has an aliphatic diol component content of 80 constituent mol% or more, and includes other components as necessary. As the alcohol (diol) component, the content of the aliphatic diol component is more preferably 90 constituent mol% or more.

  When the content is less than 80 mol%, the crystallinity of the polyester resin is lowered and the melting point is lowered, so that toner blocking resistance, toner storage stability and low-temperature fixability may be deteriorated.

  On the other hand, examples of other components included as necessary include diol components having a double bond and diol components having a sulfonic acid group.

  Examples of the diol having a double bond include 2-butene-1,4-diol, 3-butene-1,6-diol, 4-butene-1,8-diol and the like. On the other hand, as the diol having a sulfonic acid group, 1,4-dihydroxy-2-sulfonic acid benzene sodium salt, 1,3-dihydroxymethyl-5-sulfonic acid benzene sodium salt, 2-sulfo-1,4-butane Examples include diol sodium salt.

  When adding an alcohol (diol) component other than these linear aliphatic diol components, the content of (diol component having a double bond and / or diol component having a sulfonic acid group) in the alcohol (diol) component The amount is preferably from 1 to 20 mol%, more preferably from 2 to 10 mol%. When the content is less than 1 constituent mol%, pigment dispersion may be poor, the emulsified particle diameter may be large, and adjustment of the toner diameter by aggregation may be difficult. On the other hand, when it exceeds 20 mol%, the crystallinity of the polyester resin is lowered, the melting point is lowered, the storage stability of the toner is deteriorated, or the emulsion particle size is too small to be dissolved in water, and no latex is produced. There is a case.

  The method for producing the crystalline polyester resin is not particularly limited and can be produced by a general polyester polymerization method in which a carboxylic acid component and an alcohol component are reacted. Examples thereof include direct polycondensation and transesterification. Produced separately depending on the type of monomer. The molar ratio (acid component / alcohol component) when the acid component reacts with the alcohol component varies depending on the reaction conditions and the like, and cannot be generally stated, but is usually about 1/1.

  The crystalline polyester can be produced at a polymerization temperature of 180 to 230 ° C., and the reaction system is reduced in pressure as necessary, and the reaction is carried out while removing water and alcohol generated during condensation. When the monomer is not dissolved or compatible at the reaction temperature, a solvent having a high boiling point may be added as a solubilizer and dissolved. In the polycondensation reaction, the dissolution auxiliary solvent is distilled off. If a monomer with poor compatibility is present in the copolymerization reaction, the monomer with poor compatibility and the monomer and the carboxylic acid component or alcohol component to be polycondensed are condensed in advance and then polycondensed together with the main component. Good.

  Catalysts usable in the production of the crystalline polyester include alkali metal compounds such as sodium and lithium; alkaline earth metal compounds such as magnesium and calcium; metals such as zinc, manganese, antimony, titanium, tin, zirconium, and germanium Compound: Phosphorous acid compound, phosphoric acid compound, amine compound and the like are mentioned, and specifically, the following compounds are mentioned.

  For example, sodium acetate, sodium carbonate, lithium acetate, calcium acetate, zinc stearate, zinc naphthenate, zinc chloride, manganese acetate, manganese naphthenate, titanium tetraethoxide, titanium tetrapropoxide, titanium tetraisopropoxide, titanium tetra Butoxide, antimony trioxide, triphenylantimony, tributylantimony, tin formate, tin oxalate, tetraphenyltin, dibutyltin dichloride, dibutyltin oxide, diphenyltin oxide, zirconium tetrabutoxide, zirconium naphthenate, zirconyl carbonate, zirconyl acetate, zirconyl stearate , Zirconyl octylate, germanium oxide, triphenyl phosphite, tris (2,4-di-t-butylphenyl) phosphite Ethyltriphenylphosphonium bromide, triethylamine, compounds such as triphenyl amine.

  In addition to the above polymerizable monomers, compounds having shorter chain alkyl groups, alkenyl groups, aromatic rings and the like can also be used for the purpose of adjusting the melting point, molecular weight and the like of the crystalline polyester.

  Specific examples include dicarboxylic acids, alkyl dicarboxylic acids such as succinic acid, malonic acid, and oxalic acid, and phthalic acid, isophthalic acid, terephthalic acid, homophthalic acid, 4,4′-dibenzoic acid, 2,6- Examples include aromatic dicarboxylic acids such as naphthalenedicarboxylic acid and 1,4-naphthalenedicarboxylic acid, and nitrogen-containing aromatic dicarboxylic acids such as dipicolinic acid, dinicotinic acid, quinolinic acid, and 2,3-pyrazinedicarboxylic acid. Short chain alkyl diols such as succinic acid, malonic acid, acetone dicarboxylic acid and diglycolic acid. These polymerizable monomers may be used individually by 1 type, and may use 2 or more types together.

  In addition, a monofunctional monomer may be introduced into the crystalline polyester for the purpose of blocking the polar group at the end of the crystalline polyester and improving the environmental stability of toner charging characteristics.

  Monofunctional monomers include benzoic acid, chlorobenzoic acid, bromobenzoic acid, sulfobenzoic acid monoammonium salt, sulfobenzoic acid monosodium salt, cyclohexylaminocarbonylbenzoic acid, n-dodecylaminocarbonylbenzoic acid, tertiary butyl. Benzoic acid, naphthoic acid, 4-methylbenzoic acid, 3-methylbenzoic acid, salicylic acid, thiosalicylic acid, phenylacetic acid, acetic acid, propionic acid, butyric acid, isobutyric acid, octanecarboxylic acid, lauric acid, stearyl acid, and lower Monocarboxylic acids such as alkyl esters; or monoalcohols such as aliphatic alcohols, aromatic alcohols, and alicyclic alcohols can be used.

[Amorphous polyester]
As the amorphous polyester used in the toner of the present embodiment, a known amorphous polyester can be used.

  The range of the glass transition temperature (Tg) of the amorphous polyester is preferably 50 ° C. or higher and 80 ° C. or lower, more preferably 55 ° C. or higher and 65 ° C. or lower. If the glass transition temperature (Tg) is lower than 50 ° C., it may be difficult to store the toner. If the glass transition temperature (Tg) is higher than 80 ° C., the effect of low-temperature fixability may not be obtained.

  The weight average molecular weight (Mw) of the amorphous polyester is preferably in the range of 8000 to 30000, but the weight average molecular weight (Mw) is in the range of 8000 to 16000 from the viewpoint of low temperature fixability and mechanical strength. It is more preferable that The third component may be copolymerized from the viewpoints of low-temperature fixability and mixing properties.

  The resin acid value (AV) of the amorphous polyester is preferably in the range of 5 mgKOH / g to 50 mgKOH / g, and more preferably in the range of 12 mgKOH / g to 38 mgKOH / g. By setting the resin acid value (AV) within the above range, the surface acid value of the base toner (that is, the toner before adding the phenol ester structure to the surface) is controlled, and the amount of phenol ester added to the toner surface is preferable. It can be a range. The resin acid value was measured according to JIS K0070.

  The method for producing the amorphous polyester is not particularly limited, as with the method for producing the crystalline polyester described above, and can be produced by a general polyester polymerization method.

  As the acid (dicarboxylic acid) component used for the synthesis of the amorphous polyester, various dicarboxylic acids mentioned for the crystalline polyester can be used similarly. As the alcohol (diol) component, various diols used for the synthesis of the amorphous polyester resin can be used. In addition to the aliphatic diols mentioned for the crystalline polyester, bisphenol A and bisphenol A ethylene oxide adducts are used. Bisphenol A propylene oxide adduct, hydrogenated bisphenol A, bisphenol S, bisphenol S ethylene oxide adduct, bisphenol S propylene oxide adduct, etc. can be used, but from the viewpoint of toner productivity, heat resistance and transparency, It is particularly preferable to use bisphenol S derivatives such as bisphenol S, bisphenol S ethylene oxide adduct, and bisphenol S propylene oxide adduct. Moreover, both an acid (dicarboxylic acid) component and an alcohol component may contain a plurality of components. In particular, bisphenol S has an effect of improving heat resistance.

  Similarly to the crystalline polyester described above, a compound having a shorter chain alkyl group, alkenyl group, aromatic ring, etc. can be used for the purpose of adjusting the melting point and molecular weight of the amorphous polyester. The various dicarboxylic acids and diols mentioned in the above can be used.

  Similarly to the above-mentioned crystalline polyester, when a monofunctional monomer is introduced into the amorphous polyester for the purpose of blocking the polar group at the end of the amorphous polyester and improving the environmental stability of the toner charging characteristics. There is. As the monofunctional monomer, various compounds mentioned for the crystalline polyester can be used.

<Release agent>
The toner of this embodiment may contain a release agent. The release agent used is not particularly limited as long as it is a known release agent. For example, natural waxes such as carnauba wax, rice wax, and candelilla wax, low molecular weight polypropylene, low molecular weight polyethylene, sasol wax, Examples include, but are not limited to, synthesis of microcrystalline wax, Fischer-Tropsch wax, paraffin wax, montan wax, and the like, or ester-based waxes such as mineral / petroleum wax, fatty acid ester, and montanic acid ester. Moreover, these mold release agents may be used individually by 1 type, and may be used together 2 or more types.

  The melting point of the release agent is preferably 50 ° C. or higher, more preferably 60 ° C. or higher, from the viewpoint of storage stability. Moreover, it is preferable that it is 110 degrees C or less from a viewpoint of offset resistance, and it is more preferable that it is 100 degrees C or less.

  The content of the release agent is preferably in the range of 3 parts by mass to 20 parts by mass, and preferably in the range of 5 parts by mass to 18 parts by mass with respect to 100 parts by mass of the binder resin. More preferred. If the content of the release agent is less than 3 parts by mass, the effect of adding the release agent is not obtained, and hot offset at a high temperature may be caused. On the other hand, when the amount exceeds 20 parts by mass, the charging property is adversely affected, and the mechanical strength of the toner is reduced. Therefore, the toner is easily destroyed by stress in the developing machine, and may cause carrier contamination.

<Colorant>
Known colorants can be used as the colorant used in the toner of the exemplary embodiment. For example, examples of the black pigment include carbon black, copper oxide, manganese dioxide, aniline black, activated carbon, nonmagnetic ferrite, and magnetite.

  Examples of yellow pigments include yellow lead, zinc yellow, yellow iron oxide, cadmium yellow, chrome yellow, hansa yellow, hansa yellow 10G, benzidine yellow G, benzidine yellow GR, selenium yellow, quinoline yellow, and permanent yellow NCG. Can be given.

  Examples of the orange pigment include red yellow lead, molybdenum orange, permanent orange GTR, pyrazolone orange, vulcan orange, benzidine orange G, indanthrene brilliant orange RK, indanthrene brilliant orange GK and the like.

  Red pigments include Bengala, cadmium red, red lead, mercury sulfide, watch young red, permanent red 4R, risor red, brilliantamine 3B, brilliantamine 6B, dapon oil red, pyrazolone red, rhodamine B rake, lake red C Rose Bengal, Eoxin Red, Alizarin Lake and the like.

  Blue pigments include bitumen, cobalt blue, alkali blue rake, Victoria blue rake, fast sky blue, induslen blue BC, aniline blue, ultramarine blue, calco oil blue, methylene blue chloride, phthalocyanine blue, phthalocyanine green, malachite green oxare. For example, a rater.

  Examples of purple pigments include manganese purple, fast violet B, and methyl violet lake.

  Examples of the green pigment include chromium oxide, chromium green, pigment green, malachite green lake, final yellow green G, and the like.

  Examples of white pigments include zinc white, titanium oxide, antimony white, and zinc sulfide.

  Examples of extender pigments include barite powder, barium carbonate, clay, silica, white carbon, talc, and alumina white.

  Examples of the dye include various dyes such as basic, acidic, dispersed, and direct dyes, such as nigrosine. Furthermore, these can be used alone or in combination and further in a solid solution state.

  These colorants are dispersed by a known method, and for example, a rotary shear type homogenizer, a media type dispersing machine such as a ball mill, a sand mill, or an attritor, a high-pressure opposed collision type dispersing machine, or the like is preferably used.

  Further, these colorants are dispersed in an aqueous system by the homogenizer using a polar surfactant.

  The colorant of the present embodiment is selected from the viewpoints of hue angle, saturation, brightness, weather resistance, and dispersibility in the toner. The colorant is added in an amount of 1 to 20 parts by weight with respect to 100 parts by weight of the resin.

  When a magnetic material is used for the black colorant, it is added in an amount of 30 to 100 parts by weight, unlike other colorants.

  Further, when the toner is used as magnetism, magnetic powder may be contained. As such magnetic powder, a substance magnetized in a magnetic field is used, and it is a ferromagnetic powder such as iron, cobalt, or nickel, or a compound such as ferrite or magnetite.

  In particular, in this embodiment, in order to obtain toner in the aqueous layer, it is necessary to pay attention to the water layer's ability to migrate, dissolve, and oxidize, and surface modification, such as hydrophobization treatment, is preferably performed. It is preferable to keep it.

<Other ingredients-various additives>
The other components used in the toner in the exemplary embodiment are not particularly limited and can be appropriately selected depending on the purpose. Examples thereof include various known additives such as inorganic fine particles and a charge control agent.

  As the inorganic fine particles, known inorganic fine particles such as silica fine particles, titanium oxide fine particles, alumina fine particles, cerium oxide fine particles, or those obtained by hydrophobizing the surface thereof can be used alone or in combination of two or more kinds. From the viewpoint of not impairing the color developability, silica fine particles having a refractive index smaller than that of the binder resin are preferably used. Further, the silica fine particles may be subjected to various surface treatments, and for example, those subjected to surface treatment with a silane coupling agent, a titanium coupling agent, silicone oil or the like are preferably used.

  The addition amount of these inorganic fine particles is preferably in the range of 0.5% by weight to 20% by weight and more preferably in the range of 1% by weight to 15% by weight of the total toner mass.

  Known external additives such as inorganic fine particles and organic fine particles can be added to the toner in the present exemplary embodiment as necessary.

  Examples of the inorganic fine particles include silica, alumina, titanium oxide, barium titanate, magnesium titanate, calcium titanate, strontium titanate, zinc oxide, silica sand, clay, mica, wollastonite, diatomaceous earth, cerium chloride, Examples include Bengala, chromium oxide, cerium oxide, antimony trioxide, magnesium oxide, zirconium oxide, silicon carbide, and silicon nitride. Among them, silica fine particles and titanium oxide fine particles are preferable, and hydrophobized fine particles are particularly preferable.

  Inorganic fine particles are generally used for the purpose of improving fluidity. The primary particle diameter of the inorganic fine particles is preferably in the range of 1 nm to 200 nm, and the addition amount is in the range of 0.01 parts by weight to 20 parts by weight with respect to 100 parts by weight of the toner. It is preferable.

  Organic fine particles are generally used for the purpose of improving cleaning properties and transfer properties, and specific examples include polystyrene, polymethyl methacrylate, polyvinylidene fluoride, and the like.

<Toner production method>
The toner of the present embodiment can be produced by an aggregation / unification method.

  The agglomeration / unification method of the present embodiment includes, for example, amorphous polyester resin fine particles, resin fine particle dispersion in which crystalline polyester resin fine particles are dispersed and mixed, and colorant fine particle dispersion in which colorant fine particles are dispersed. Mixing with the release agent fine particle dispersion liquid in which the mold agent fine particles are dispersed, the resin fine particles, the colorant fine particles and the release agent fine particles are formed to form an agglomeration step, and the pH in the aggregation system is adjusted. A step of stopping the agglomeration, a step of heating and fusing the agglomerated particles to a temperature higher than the glass transition temperature of the resin fine particles, a step of washing the obtained base toner with at least water, and washing The step of drying the base toner and the dried base toner and phenyl acetate are mixed and removed while heating at a temperature of −2 ° C. or higher and −5 ° C. or lower with respect to the base toner glass transition temperature. It is a manufacturing method and a step of reducing the pressure. In addition, the aggregation / unification method may have a shell forming step of adding other resin fine particles to adhere to the surface of the aggregated particles after the aggregation step, if necessary.

  Hereinafter, each process in an example of the aggregation / unification method mentioned above is demonstrated in detail. The toner manufacturing method in the present embodiment is not limited to this.

[Aggregation process]
In the aggregation step, first, a resin fine particle dispersion, a colorant fine particle dispersion, and a release agent fine particle dispersion are prepared.

  For the resin fine particle dispersion, a known phase inversion emulsification method is used, or a method in which the resin fine particle dispersion is heated to a temperature higher than the glass transition temperature of the resin and emulsified by a mechanical shearing force is used. At this time, an ionic surfactant may be added.

  The colorant fine particle dispersion is prepared by dispersing colorant fine particles of a desired color such as blue, red, and yellow in a solvent using an ionic surfactant.

  In addition, the release agent fine particle dispersion is obtained by dispersing the release agent together with a polymer electrolyte (for example, an ionic surfactant, a polymer acid, or a polymer base) in water and heating it above the melting point of the release agent. At the same time, the fine particles are adjusted by a homogenizer or a pressure discharge type disperser that can be subjected to strong shearing.

  Next, the resin fine particle dispersion, the colorant fine particle dispersion, and the release agent fine particle dispersion are mixed, and the resin fine particles, the color fine agent particles, and the release agent fine particles are hetero-agglomerated to obtain a diameter that is approximately close to the desired toner diameter. Aggregated particles having a core (core aggregated particles) are formed.

[Shell formation process]
In the shell forming step, the surface of the core aggregated particles is formed by attaching resin fine particles to the surface of the core aggregated particles using a resin fine particle dispersion containing resin fine particles to form a coating layer (shell layer) having a desired thickness. Aggregated particles having a core / shell structure in which a shell layer is formed (core / shell aggregated particles) are obtained.

  In addition, the aggregation process and the shell formation process may be repeatedly performed in a plurality of stages.

  Here, the volume average particle size of the resin fine particles, colorant fine particles, and release agent fine particles used in the aggregation step and the shell formation step is to facilitate adjustment of the toner diameter and the particle size distribution to desired values. It is preferable that it is 1 micrometer or less, and it is more preferable that it exists in the range of 100-300 nm.

  The volume average particle size is measured using a laser diffraction type laser diffraction type particle size distribution measuring device (LA-700: manufactured by Horiba, Ltd.). As a measurement method, a sample in a dispersion is adjusted to have a solid content of about 2 g, and ion exchange water is added thereto to make about 40 ml. This is put into the cell until an appropriate concentration is reached, waits for about 2 minutes, and is measured when the concentration in the cell becomes almost stable. The obtained volume average particle diameter for each channel is accumulated from the smaller volume average particle diameter, and the place where the accumulation reaches 50% is defined as the volume average particle diameter.

[Stop process]
In the stopping step, the aggregation growth of particles is stopped by adjusting the pH in the aggregation system. Specifically, the growth of the particles is stopped by adjusting the pH in the aggregation system to 6-9.

[Fusion / unification process]
In the fusion and coalescence process, first, the glass transition temperature of the resin fine particles contained in the aggregated particles in the solution containing the aggregated particles obtained through the aggregation process and the shell formation process performed as necessary. The base toner is obtained by heating to the above temperature and fusing and uniting.

[Washing process]
In the washing step, the base toner particle dispersion obtained in the fusion / unification step is at least subjected to substitution washing with ion-exchanged water to perform solid-liquid separation. Although there is no restriction | limiting in particular in a solid-liquid separation method, From the point of productivity, suction filtration, pressure filtration, etc. are used preferably.

[Drying process]
In the drying process, the solid-liquid separated wet cake is dried to obtain base toner particles. Although there is no restriction | limiting in particular in a drying method, From the point of productivity, freeze drying, flash jet drying, fluidized drying, vibration type fluidized drying, etc. are used preferably.

[Phenol esterification process]
In the phenol esterification step, the base toner particles obtained in the drying step are mixed with phenyl acetate, and the pressure is gradually reduced while heating at a temperature of −2 ° C. or lower and −5 ° C. or higher with respect to the glass transition temperature of the base toner. Acetic acid is removed from the system as a desorbed product, and a phenol ester structure is added to the toner surface by polycondensation of carboxyl groups on the toner surface and phenyl acetate. For the polycondensation of the carboxyl group on the toner surface and phenyl acetate, a catalyst used for esterification and transesterification can be used. Although there is no restriction | limiting in the kind of catalyst, For example, lithium acetate, sodium acetate, magnesium acetate, potassium acetate etc. are used. Here, the boiling point of phenyl acetate is about 85 ° C., and the boiling point of acetic acid, which is a desorption product from the polycondensation reaction, is about 25 ° C. Therefore, for example, acetic acid is preferentially used under a reduced pressure of about 25 Torr. It can be distilled out of the reaction system. This promotes the equilibrium during the polycondensation reaction to the esterification and transesterification side. In addition to the above-mentioned phenyl acetate, for example, it is also possible to use, for example, phenyl propionate. That is, a phenol ester satisfying the relationship of “boiling point of phenol ester to be reacted> boiling point of polycondensation reaction leaving product” can be used for the reaction.

[Other processes]
After completion of aggregation, fusion, coalescence, and metal addition, a desired toner is obtained through an arbitrary washing step, solid-liquid separation step, and drying step. In the washing step, it is preferable to sufficiently perform substitution washing with ion-exchanged water from the viewpoint of chargeability. The solid-liquid separation step is not particularly limited, but suction filtration, pressure filtration, and the like are preferably used from the viewpoint of productivity. Furthermore, the drying process is not particularly limited, but from the viewpoint of productivity, freeze drying, flash jet drying, fluidized drying, vibration fluidized drying and the like are preferably used.

<Developer for electrostatic charge development>
The developer for developing an electrostatic charge of the present embodiment is not particularly limited except that it contains the toner for developing an electrostatic latent image of the present embodiment described above, and can have an appropriate component composition depending on the purpose. . The electrostatic image developer of the present embodiment becomes a one-component electrostatic image developer (hereinafter also referred to as “one-component developer”) when the electrostatic charge developing toner is used alone, and is combined with a carrier. If used, a two-component electrostatic image developer (hereinafter also referred to as “two-component developer”) is obtained.

  Hereinafter, the developer for electrostatic charge development according to the present embodiment (hereinafter may be abbreviated as “developer”) will be described.

-Two-component developer-
There is no restriction | limiting in particular as a carrier, A well-known carrier can be used. Examples of the carrier include a resin-coated carrier having a resin coating layer in which a core resin surface is coated with a coating resin. The carrier may be a resin-dispersed carrier in which a conductive material or the like is dispersed in a matrix resin.

  Coating resins and matrix resins used for carriers include polyethylene, polypropylene, polystyrene, polyvinyl acetate, polyvinyl alcohol, polyvinyl butyral, polyvinyl chloride, polyvinyl ether, polyvinyl ketone, vinyl chloride-vinyl acetate copolymer, styrene-acrylic. Examples thereof include, but are not limited to, acid copolymers, straight silicone resins composed of organosiloxane bonds or modified products thereof, fluororesins, polyesters, polycarbonates, phenol resins, epoxy resins and the like.

  Examples of the conductive material include metals (for example, gold, silver, copper, etc.), carbon black, titanium oxide, zinc oxide, barium sulfide, aluminum borate, potassium titanate, tin oxide, carbon black, and the like. However, it is not limited to these.

  In addition, examples of the carrier core material include magnetic metals (for example, iron, nickel, cobalt, etc.), magnetic oxides (for example, ferrite, magnetite, etc.), glass beads, etc., because the carrier is used for the magnetic brush method. In this case, the core material of the carrier is preferably a magnetic material. The volume average particle size of the core material of the carrier is preferably in the range of 10 μm to 500 μm, and more preferably in the range of 30 μm to 100 μm.

  In order to coat the surface of the carrier core with a resin, a method of coating with a coating layer forming solution in which a coating resin and, if necessary, various additives are dissolved in an appropriate solvent may be mentioned. The solvent is not particularly limited, and may be appropriately selected in consideration of the coating resin to be used, application suitability, and the like.

  Specific resin coating methods include (1) a dipping method in which a carrier core material is immersed in a coating layer forming solution, (2) a spray method in which the coating layer forming solution is sprayed on the surface of the carrier core material, 3) Fluidized bed method in which the coating layer forming solution is sprayed in a state where the carrier core material is floated by flowing air. (4) The carrier core material and the coating layer forming solution are mixed in a kneader coater, and the solvent is added. The kneader coater method to remove is mentioned.

  In the developer containing a carrier, the above-mentioned mixing ratio (weight ratio) of the toner and the carrier is preferably in the range of toner: carrier = 1: 100 to 30: 100, and in the range of 3: 100 to 20: 100. Is more preferable.

-Non-magnetic one-component developer-
The electrostatic charge developing toner (hereinafter sometimes abbreviated as “toner”) used in the non-magnetic one-component developer of the present embodiment contains an amorphous polyester resin, a crystalline polyester resin, and a colorant, and has toner particle surfaces. Contains a toner having a phenol ester structure.

  The toner contained in the non-magnetic one-component developer has a phenol ester structure on the toner surface, and thus has a higher toner hardness than a toner not having a phenol ester structure without sacrificing low-temperature fixability. In the state of the externally added toner to which the above-mentioned fine particles are externally added, the external additive is not embedded even when stress is applied for a long time, and the movement of the external additive on the toner surface is not hindered. Good fluidity suitable for development can be maintained for a long time, and in the image forming method of the present embodiment described later, uniform layer formation and charging can be performed, and in-machine contamination due to cloud generation due to low-charged toner can be suppressed. I can do it.

  In the toner used in the non-magnetic one-component developer of the present embodiment, as described above, the cause of the increase in the toner hardness due to the phenol ester structure on the toner surface has not been clearly clarified. It is presumed that the toner hardness is increased by having a benzene ring having a planar structure with a lower degree of freedom of deformation than the linear structure on the surface.

The range of the amount of phenol ester MPh [mol / g-TN] (where TN is the toner) present on the toner surface contained in the non-magnetic one-component developer is:
[Equation 3]
1.4 × 10 ⁻⁴ ≦ MPh ≦ 6.6 × 10 ⁻⁴ Formula (2)
It is preferable that
[Equation 4]
^{1.8 × 10 -4 ≦ MPh ≦ 5.5} × 10 -4 ····· formula (2 ')
It is more preferable that

If the MPh is less than 1.4 × 10 ⁻⁴ (mol / g-TN), the external additive is embedded in the toner surface, resulting in a decrease in fluidity and a toner on a layer regulating member described later. Fixing and fusing occur, the toner layer thickness formed on the developer carrier becomes non-uniform, uneven toner charging occurs, clouding of low-charge toner cannot be suppressed, and internal contamination occurs. End up. On the other hand, if the MPh is more than 6.6 × 10 ⁻⁴ (mol / g-TN), the toner hardness becomes too high, so that the coat layer of the layer regulating member is worn, and the developer is carried on the developer carrier. The thickness of the toner layer to be formed becomes non-uniform. As a result, toner charging becomes uneven, and clouding of the low-charge side toner cannot be suppressed, resulting in in-machine contamination.

  The toner used in the above-described non-magnetic one-component developer is the same as the above-described electrostatic charge image toner except for the amount of phenol ester present on the toner surface, and is manufactured by the above-described toner manufacturing method. The

<Image Forming Apparatus and Image Forming Method>
Next, an example of the image forming apparatus and the image forming method of the present embodiment will be described.

-Image forming apparatus and image forming method using two-component developer-
FIG. 1 is a schematic diagram illustrating a configuration example of an image forming apparatus for forming an image by the image forming method of the present embodiment. In the illustrated image forming apparatus 200, four electrophotographic photosensitive members 401 a to 401 d are disposed in parallel in the housing 400 along the intermediate transfer belt 409. The electrophotographic photoreceptors 401a to 401d form, for example, images in which the electrophotographic photoreceptor 401a is yellow, the electrophotographic photoreceptor 401b is magenta, the electrophotographic photoreceptor 401c is cyan, and the electrophotographic photoreceptor 401d is black. Is possible.

  Each of the electrophotographic photosensitive members 401a to 401d can be rotated in a predetermined direction (counterclockwise on the paper surface), and the charging rolls 402a to 402d, the developing devices 404a to 404d, and the primary transfer roll 410a along the rotation direction. To 410d and cleaning blades 415a to 415d are arranged. Each of the developing devices 404a to 404d can be supplied with toner of four colors of black, yellow, magenta and cyan accommodated in the toner cartridges 405a to 405d, and the primary transfer rolls 410a to 410d are respectively intermediate transfer belts. 409 is in contact with the electrophotographic photoreceptors 401a to 401d.

  Further, an exposure device 403 is disposed at a predetermined position in the housing 400, and it becomes possible to irradiate the surfaces of the charged electrophotographic photoreceptors 401a to 401d with a light beam emitted from the exposure device 403. ing. Accordingly, charging, exposure, development, primary transfer, and cleaning are sequentially performed in the rotation process of the electrophotographic photosensitive members 401a to 401d, and the toner images of the respective colors are transferred onto the intermediate transfer belt 409 in an overlapping manner.

  Here, the charging rolls 402a to 402d contact the surface of the electrophotographic photoreceptors 401a to 401d with a conductive member (charging roll), and apply a voltage uniformly to the photoreceptor to charge the photoreceptor surface to a predetermined potential. (Charging process). In addition to the charging roll shown in this embodiment, charging by a contact charging method may be performed using a charging brush, a charging film, a charging tube, or the like. Moreover, you may charge by the non-contact system using a corotron or a scorotron.

  As the exposure apparatus 403, an optical system apparatus or the like that can expose a light source such as a semiconductor laser, an LED (light emitting diode), a liquid crystal shutter, or the like on the surfaces of the electrophotographic photosensitive members 401a to 401d can be used. Among these, when an exposure apparatus capable of exposing non-interference light is used, interference fringes between the electroconductive substrates of the electrophotographic photoreceptors 401a to 401d and the photosensitive layer can be prevented.

  As the developing devices 404a to 404d, a general developing device that develops the two-component electrostatic image developer in contact or non-contact with the developer can be used (developing step). Such a developing device is not particularly limited as long as a two-component electrostatic image developing developer is used, and a known one can be appropriately selected according to the purpose. In the primary transfer process, a primary transfer bias having a polarity opposite to that of the toner carried on the image carrier is applied to the primary transfer rolls 410a to 410d, so that each color toner is transferred from the image carrier to the intermediate transfer belt 409. The primary transfer is performed sequentially.

  The cleaning blades 415a to 415d are for removing residual toner adhering to the surface of the electrophotographic photosensitive member after the transfer process, and the electrophotographic photosensitive member cleaned by this cleaning process is repeatedly used in the above-described image forming process. Is done. Examples of the material for the cleaning blade include urethane rubber, neoprene rubber, and silicone rubber.

  The intermediate transfer belt 409 is supported with a predetermined tension by a drive roll 406, a backup roll 408, and a tension roll 407, and can rotate without causing deflection due to the rotation of these rolls. Further, the secondary transfer roll 413 is disposed so as to contact the backup roll 408 via the intermediate transfer belt 409.

  By applying a secondary transfer bias having a reverse polarity to the toner on the intermediate transfer member to the secondary transfer roll 413, the toner is secondarily transferred from the intermediate transfer belt to the recording medium. The intermediate transfer belt 409 that has passed between the backup roll 408 and the secondary transfer roll 413 is cleaned by, for example, a cleaning blade 416 disposed near the drive roll 406 or a static eliminator (not shown). It is repeatedly used for the next image forming process. A tray (transfer medium tray) 411 is provided at a predetermined position in the housing 400, and the transfer medium 500 such as paper in the tray 411 is transferred to the intermediate transfer belt 409 and the secondary transfer roll by the transfer roll 412. Then, the paper is sequentially transferred between the two fixing rolls 414 that are in contact with each other and the two fixing rolls 414 that are in contact with each other.

  The image forming method of the present embodiment includes a latent image forming step of forming an electrostatic latent image on the surface of the latent image carrier, and the electrostatic latent image formed on the surface of the latent image carrier using the above two-component developer. A developing step for developing and forming a toner image, a transferring step for transferring the toner image formed on the surface of the latent image carrier to the surface of the transfer target, and a heat fixing of the toner image transferred to the surface of the transfer target An image forming method including a fixing step of cleaning and a cleaning step of cleaning the surface of the latent image carrier, and the cleaning step is an image forming method using a cleaning blade.

  The latent image forming step is a step of forming an electrostatic latent image by uniformly charging the surface of the latent image carrier with a charging means and then exposing the latent image carrier with a laser optical system or an LED array. is there. Examples of the charging means include a non-contact charger such as corotron and scorotron, and a contact method in which a latent image carrier surface is charged by applying a voltage to a conductive member in contact with the latent image carrier surface. Any type of charger may be used. However, a contact charging type charger is preferable from the viewpoint that the amount of ozone generated is small, environmentally friendly, and excellent printing durability. In the contact charging type charger, the shape of the conductive member may be any of a brush shape, a blade shape, a pin electrode shape, a roller shape, and the like, but a roller-like member is preferable. The image forming method of the present invention is not subject to any particular limitation in the latent image forming process.

  The development step refers to bringing a developer carrier having a developer layer containing at least toner on the surface thereof into contact with or in proximity to the electrostatic latent image on the surface of the latent image carrier. In this step, particles are adhered to form a toner image (development image) on the surface of the latent image carrier. The development method can be performed using a known method, but examples of the development method using a two-component developer include a cascade method and a magnetic brush method. The image forming method of the present invention is not particularly limited with respect to the developing method.

  Hereinafter, in the image forming method of the present embodiment, a photoconductor in the case of using a photoconductor as a latent image carrier will be described.

  In the photoreceptor used in the image forming method of the present embodiment, an organic photosensitive layer is formed on a conductive support. The organic photosensitive layer includes at least a charge generation layer formed by binding a charge generation material with a suitable resin as a binder (binder resin), and a charge transport layer in which the charge transport material is dispersed or dissolved in the binder resin. It is preferable that an undercoat layer, a protective layer, and the like are formed as necessary. Here, the “surface layer” means a layer formed on the outermost surface of the photoreceptor. For example, when the charge transport layer is provided on the outermost surface of the photoreceptor, the charge transport layer becomes the surface layer. When a protective layer is further provided, the protective layer becomes a surface layer.

-Conductive support:
Any conductive support may be used as long as it is conventionally used. For example, metals such as aluminum, nickel, chromium, stainless steel; plastic films provided with thin films such as aluminum, titanium, nickel, chromium, stainless steel, gold, vanadium, tin oxide, indium oxide, ITO; And paper coated with or impregnated with an agent, plastic film, and the like. Furthermore, if necessary, the surface of the conductive support can be subjected to various treatments within a range that does not affect the image quality. For example, surface anodization treatment, chemical treatment or coloring treatment, or irregular reflection treatment such as graining or liquid honing can be performed.

  An undercoat layer may be formed on the surface of the conductive support as desired.

  Undercoat layer is acetal resin such as polyvinyl butyral, polyvinyl alcohol resin, polyamide resin, cellulose resin, gelatin, polyurethane resin, polyester resin, methacrylic resin, acrylic resin, polyvinyl chloride resin, polyvinyl acetate resin, vinyl chloride-vinyl acetate -In addition to polymer resin compounds such as maleic anhydride resin, silicone resin, phenol-formaldehyde resin and melamine resin, there are organometallic compounds containing zirconium, titanium, aluminum, manganese, silicon atoms and the like. These compounds can be used alone or as a mixture or polycondensate of a plurality of compounds. The thickness of the undercoat layer is preferably 0.1 to 50 μm, and more preferably 0.2 to 30 μm.

-Charge generation layer:
The charge generation layer is formed on the conductive support (when the undercoat layer is formed, on the undercoat layer). As the charge generation material contained in the charge generation layer, phthalocyanine pigments such as metal-free phthalocyanine, chlorogallium phthalocyanine, hydroxygallium phthalocyanine, dichlorotin phthalocyanine, and titanyl phthalocyanine can be used. Chlorogallium phthalocyanine crystal having strong diffraction peaks at least at 7.4 °, 16.6 °, 25.5 ° and 28.3 ° of (2θ ± 0.2 °), Bragg angle (2θ ± 0.2 °) metal-free phthalocyanine crystal having strong diffraction peaks at 7.7 °, 9.3 °, 16.9 °, 17.5 °, 22.4 ° and 28.8 °, CuKα characteristic X Bragg angle to the line (2θ ± 0.2 °) at least 7.5 °, 9.9 °, 12.5 A hydroxygallium phthalocyanine crystal having strong diffraction peaks at 16.3 °, 18.6 °, 25.1 ° and 28.3 °, a Bragg angle (2θ ± 0.2 °) with respect to CuKα characteristic X-ray of at least 9. Titanyl phthalocyanine crystals having strong diffraction peaks at 6 °, 24.1 ° and 27.2 ° can be used.

  In addition, as the charge generation material, a quinone pigment, a perylene pigment, an indigo pigment, a bisbenzimidazole pigment, an anthrone pigment, a quinacridone pigment, and the like can be used. The above charge generation materials can be used alone or in admixture of two or more.

  Examples of the binder resin in the charge generation layer include the following. That is, polycarbonate resin such as bisphenol A type or bisphenol Z type, polyester resin, methacrylic resin, acrylic resin, polyvinyl chloride resin, polystyrene resin, polyvinyl acetate resin, styrene-butadiene copolymer resin, vinylidene chloride-acrylonitrile copolymer Examples thereof include a coalescing resin, vinyl chloride-vinyl acetate-maleic anhydride resin, silicone resin, phenol-formaldehyde resin, poly-N-vinylcarbazole and the like. These binder resins can be used alone or in combination of two or more. The compounding ratio (mass ratio) of the charge generating material and the binder resin is preferably in the range of 10: 1 to 1:10.

  As a solvent used for dispersion of the charge generating material, a solvent capable of dissolving the binder resin can be appropriately selected. As a method for dispersing the charge generating material in the resin, methods such as a roll mill, a ball mill, a vibrating ball mill, an attritor, a sand mill, a colloid mill, and a high pressure homogenizer can be used.

  Examples of the coating method include dip coating, push-up coating, spray coating, roll coater coating, and gravure coater coating. The thickness of the charge generation layer is generally set in the range of 0.01 to 5 μm, preferably 0.05 to 2.0 μm.

-Charge transport layer:
The charge transport layer is formed on the charge generation layer. When the charge transport layer is the surface layer of the photoreceptor, the charge transport layer contains fluorine-based resin particles. The content of the fluorine-based resin particles in the charge transport layer is required to be 0.1 to 40% by mass, and preferably 1 to 30% by mass, based on the total mass of the charge transport layer. When the content is less than 1% by mass, the modification effect due to the dispersion of the fluororesin particles is not sufficient, and when it exceeds 40% by mass, the light transmission property is lowered and the residual potential is increased by repeated use.

  Fluorine-based resin particles include tetrafluoroethylene resin, trifluorinated ethylene resin, hexafluoropropylene resin, vinyl fluoride resin, vinylidene fluoride resin, difluorodiethylene chloride resin and copolymers thereof. It is desirable to appropriately select one or two or more kinds from among them, and particularly preferred are tetrafluoroethylene resin and vinylidene fluoride resin.

  The primary particle size of the fluororesin particles is preferably 0.05 to 1 μm, more preferably 0.1 to 0.5 μm, as a volume average particle size. When the volume average particle size is less than 0.05 μm, aggregation at the time of dispersion tends to proceed, and when it exceeds 1 μm, image quality defects are likely to occur.

  The charge transport layer may contain inorganic particles. The content of the inorganic particles in the charge transport layer is suitably from 0.1 to 30% by weight, particularly preferably from 1 to 20% by weight, based on the total amount of the charge transport layer. If the content is less than 1% by mass, the modification effect due to the dispersion of inorganic particles is not sufficient. On the other hand, if the content exceeds 30% by mass, the residual potential increases due to repeated use.

  Examples of inorganic particles include alumina, silica, titanium oxide, zinc oxide, cerium oxide, zinc sulfide, magnesium oxide, copper sulfate, sodium carbonate, magnesium sulfate, potassium chloride, calcium chloride, sodium chloride, nickel sulfate, antimony, and dioxide. Manganese, chromium oxide, tin oxide, zirconium oxide, barium sulfate, aluminum sulfate, silicon carbide, titanium carbide, boron carbide, tungsten carbide, zirconium carbide and the like can be mentioned, and silica is preferably used. These may be used alone or in combination of two or more as required.

  The silica particles are preferably produced by chemical flame CVD, and as a specific example, produced by gas phase reaction of chlorosilane gas in a high-temperature flame of oxygen-hydrogen mixed gas or hydrocarbon-oxygen mixed gas. Is preferred.

  The inorganic particles are preferably those that have been hydrophobized with a hydrophobizing agent. As the hydrophobizing agent, for example, a siloxane compound, a silane coupling agent, a titanium coupling agent, a polymer fatty acid or a metal salt thereof is used.

  Examples of the siloxane compound include dihydroxypolysiloxane and octamethylcyclotetrasiloxane. Examples of the silane coupling agent include γ- (2-aminoethyl) aminopropyltrimethoxysilane, γ- (2-aminoethyl) aminopropylmethyldimethoxysilane, γ-methacryloxypropyltrimethoxysilane, N-β- (N -Vinylbenzylaminoethyl) γ-aminopropyltrimethoxysilane hydrochloride, hexamethyldisilazane, methyltrimethoxysilane, butyltrimethoxysilane, isobutyltrimethoxysilane, hexyltrimethoxysilane, octyltrimethoxysilane, decyltrimethoxysilane , Dodecyltrimethoxysilane, phenyltrimethoxysilane, o-methylphenyltrimethoxysilane, p-methylphenyltrimethoxysilane, and the like.

  The primary particle size of the inorganic particles is preferably 0.005 to 2.0 μm, and more preferably 0.01 to 1.0 μm, as the number average particle size. If it is less than 0.005 μm, sufficient mechanical strength on the surface of the photoreceptor cannot be obtained, and aggregation during dispersion tends to proceed. If it exceeds 2 μm, the surface roughness of the photoreceptor increases, the cleaning blade is worn and damaged, the cleaning characteristics are deteriorated, and image blurring tends to occur.

  Examples of the charge transport material include oxadiazole derivatives such as 2,5-bis (p-diethylaminophenyl) -1,3,4-oxadiazole; 1,3,5-triphenyl-pyrazolin, 1- [ Pyrazoline derivatives such as pyridyl- (2)]-3- (p-diethylaminostyryl) -5- (p-diethylaminostyryl) pyrazolin; triphenylamine, tri (p-methylphenyl) aminyl-4-amine, dibenzylaniline Aromatic tertiary amino compounds such as N, N′-bis (3-methylphenyl) -N, N′-diphenylbenzidine etc .; 3- (4′-dimethylaminophenyl) 1,2,4-triazine derivatives such as -5,6-di- (4'-methoxyphenyl) -1,2,4-triazine; Hydrazone derivatives such as zaldehyde-1,1-diphenylhydrazone; quinazoline derivatives such as 2-phenyl-4-styryl-quinazoline; benzofuran derivatives such as 6-hydroxy-2,3-di (p-methoxyphenyl) benzofuran; p Α-stilbene derivatives such as — (2,2-diphenylvinyl) -N, N-diphenylaniline; enamine derivatives; carbazole derivatives such as N-ethylcarbazole; hole transport such as poly-N-vinylcarbazole and its derivatives; Mention may be made of substances.

  In addition, quinone compounds such as chloranil and broanthraquinone; tetraanoquinodimethane compounds; fluorenone compounds such as 2,4,7-trinitrofluorenone and 2,4,5,7-tetranitro-9-fluorenone; xanthone An electron transport material such as a compound; a thiophene compound; and the like, and a polymer having a group composed of the above-described compound in the main chain or side chain can also be exemplified. These charge transport materials can be used alone or in combination of two or more.

  Examples of the binder resin include an acrylic resin, polyarylate, polyester resin, bisphenol A type or bisphenol Z type polycarbonate resin; polystyrene, acrylonitrile-styrene copolymer, acrylonitrile-butadiene copolymer, polyvinyl butyral, polyvinyl formal, and the like. Insulating resins such as polysulfone, polyacrylamide, polyamide, and chlorine rubber; organic photoconductive polymers such as polyvinyl carbazole, polyvinyl anthracene, and polyvinyl pyrene;

  The charge transport layer is a solution in which the charge transport material and the binder resin are dissolved in an appropriate solvent (when the charge transport layer is a surface layer, together with the aforementioned fluorine-based resin particles and, if necessary, inorganic particles). It can form by apply | coating and drying.

  Examples of the solvent used for forming the charge transport layer include aromatic hydrocarbon solvents such as toluene and chlorobenzene; aliphatic alcohol solvents such as methanol, ethanol and n-butanol; acetone, cyclohexanone and 2-butanone. Ketone solvents such as; halogenated aliphatic hydrocarbon solvents such as methylene chloride, chloroform and ethylene chloride; cyclic or linear ether solvents such as tetrahydrofuran, dioxane, ethylene glycol and diethyl ether; or a mixed solvent thereof Can be used.

  The blending ratio (mass ratio) of the charge transport material and the binder resin is preferably 10: 1 to 1: 5. As a method for dispersing the fluorine resin particles and further inorganic particles in the charge transport layer, it is possible to use a method such as a roll mill, a ball mill, a vibrating ball mill, an attritor, a sand mill, a high-pressure homogenizer, an ultrasonic disperser, a colloid mill. it can.

  Examples of dispersion of the coating liquid for forming the charge transport layer include dispersion of fluorine resin particles when inorganic particles or the charge transport layer is a surface layer in a solution of a binder resin or charge transport material dissolved in the above solvent. The method of doing is mentioned. It is also effective to add a small amount of a dispersion aid in order to improve the dispersion stability of the dispersion and to prevent aggregation during the formation of the coating film.

  Examples of the dispersion aid include fluorine-based surfactants, fluorine-based polymers, silicone-based polymers, and silicone oils. From the viewpoint of high sensitivity and reduction in residual potential during repeated use, 0.1 to 1% by mass. 0.0% by mass of a fluorine-based graft polymer is preferably used.

  Examples of the coating method include dip coating, push-up coating, spray coating, roll coater coating, and gravure coater coating. The film thickness of the charge transport layer is generally 5 to 60 μm, and preferably 10 to 50 μm. The above range is preferably selected from the viewpoint of surface abrasion resistance and charge retention performance. Furthermore, the surface roughness Rz when the charge transport layer is a surface layer is measured with, for example, a surface roughness meter (manufactured by Tokyo Seimitsu Co., Ltd., JIS-94 standard), and is in the range of 0.01 μm to 1.0 μm (preferably, 0.1 μm to 0.8 μm) is preferably selected from the viewpoints of maintaining transfer performance, cleaning performance, and both.

・ Surface layer:
Next, the surface layer (surface protective layer) will be described. A high-strength surface layer can also be provided in order to provide resistance to abrasion and scratches on the surface layer. As this high-strength surface layer, conductive fine particles dispersed in a binder resin, lubricating fine particles such as fluororesin and acrylic resin dispersed in an ordinary charge transport layer material, silicon and acrylic hard A coating agent can be used, but from the viewpoint of strength, electrical characteristics, image quality maintenance, etc., those having a crosslinked structure are preferred, and those containing a charge transporting material are more preferred. Various materials can be used for forming the crosslinked structure, but phenolic resins, urethane resins, siloxane resins, and the like are preferable in view of characteristics, and those made of siloxane resins are particularly preferable. The surface layer can be formed by a known method.

  In addition, since the resin layer having a charge transporting property and having a crosslinked structure has excellent mechanical strength and sufficient photoelectric characteristics, it can also be used as it is as a charge transport layer of a multilayer photoreceptor. In that case, a usual method such as a blade coating method, a Meyer bar coating method, a spray coating method, a dip coating method, a bead coating method, an air knife coating method, or a curtain coating method can be used. However, when a required film thickness cannot be obtained by a single application, the necessary film thickness can be obtained by applying a plurality of times. When performing multiple times of repeated application, the heat treatment may be performed every time of application, or after multiple times of repeated application.

  In the case of a single-layer type photosensitive layer, it is formed containing the charge generating material and a binder resin. As the binder resin, the same binder resins as those used for the charge generation layer and the charge transport layer can be used. The content of the charge generating material in the single-layer type photosensitive layer is about 10% to 85% by weight, preferably 20% to 50% by weight. A charge transport material or a polymer charge transport material may be added to the single-layer type photosensitive layer for the purpose of improving photoelectric characteristics. The addition amount is preferably 5 to 50% by weight. The solvent and coating method used for coating can be the same as described above. The film thickness is preferably about 5 μm to 50 μm, and more preferably 10 μm to 40 μm.

The hardness of the photosensitive member may be in the range of 15 mN / [mu] m ² of 35 mN / [mu] m ² dynamic hardness is preferred. The dynamic hardness can be measured with a Shimadzu dynamic hardness meter DUH-201.

  The transfer process is a process in which the toner image formed on the surface of the latent image carrier is directly transferred to the recording medium, or the image once transferred to the intermediate transfer body is transferred again to the recording medium to form a transfer image. is there.

  A corotron can be used as a transfer device for transferring the toner image from the latent image carrier to paper or the like. The corotron is effective as a means for uniformly charging the paper, but a high voltage of several kV must be applied and a high voltage power source is required in order to give a predetermined charge to the paper as a recording medium. Further, since ozone is generated by corona discharge, the rubber parts and the latent image carrier are deteriorated. Therefore, a conductive transfer roll made of an elastic material is pressed against the latent image carrier to transfer the toner image onto the paper. A contact transfer method is preferred. In the image forming method of the present invention, the transfer device is not particularly limited.

  The fixing step is a step of fixing the developed image (toner image) transferred to the surface of the recording medium with a fixing device. As the fixing device, an oilless heat fixing device using a heat roll is preferably used. The heat fixing device includes a fixing roller having a heater lamp for heating inside a cylindrical metal core, a so-called release layer formed on the outer peripheral surface by a heat resistant resin film layer or a heat resistant rubber film layer, and the fixing roller. The pressure roller or pressure belt is disposed in pressure contact with the roller and has a heat-resistant elastic body layer formed on the outer peripheral surface of the cylindrical metal core or the surface of the belt-like base material. The fixing process of the unfixed toner image is performed by inserting a recording material on which an unfixed toner image is formed between a fixing roller and a pressure roller or a pressure belt, and using a binder resin, an additive, and the like in the toner. Fix by heat melting. In the image forming method of the present invention, the fixing method is not particularly limited as long as it is oilless fixing.

  In the image forming method of the present embodiment, a cleaning blade is provided as means for cleaning the surface of the latent image carrier, and the cleaning blade is brought into direct contact with the surface of the latent image carrier and adhered to the surface of the latent image carrier. Remove toner, paper dust, dust, etc.

  As a material of the cleaning blade, urethane rubber, silicone rubber, fluorine rubber, chloroprene rubber, butadiene rubber, or the like can be used. Among them, it is preferable to use a polyurethane elastic body because of its excellent wear resistance.

  As the polyurethane elastic body, a polyurethane generally synthesized through an addition reaction between an isocyanate and a polyol and various hydrogen-containing compounds is used. As a polyol component, a polyether-based polyol such as polypropylene glycol or polytetramethylene glycol, Polyester polyols such as adipate polyols, polycaprolactam polyols, polycarbonate polyols are used, and polyisocyanate components include aromatics such as tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, polymethylene polyphenyl polyisocyanate, toluidine diisocyanate, etc. Group polyisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, xylylene diisocyanate, dicycle Manufactured by preparing a urethane prepolymer using an aliphatic polyisocyanate such as hexylmethane diisocyanate, adding a curing agent to the urethane prepolymer, pouring it into a predetermined mold, crosslinking and curing, and then aging at room temperature. ing. As the curing agent, a dihydric alcohol such as 1,4-butanediol and a trihydric or higher polyhydric alcohol such as trimethylolpropane or pentaerythritol are usually used in combination.

The physical property value of the cleaning blade is not particularly limited. For example, a cleaning blade having a hardness (JISA scale) of 40 to 60 and a Young's modulus of 90 kg / cm ² to 130 kg / cm ² can be used.

  The contact pressure of the cleaning blade / latent image carrier is preferably in the range of 8 g / cm to 25 g / cm.

  In the image forming method of the present embodiment, when a full-color image is produced, each of the plurality of latent image carriers has a developer carrier for each color, and the plurality of latent image carriers and the development are developed. Each color toner image for each step is sequentially laminated on the same surface of the recording medium by a series of steps consisting of a latent image forming step, a developing step, a transfer step, and a cleaning step by each agent carrier, and the full color layered An image forming method in which the toner image is thermally fixed in a fixing step is preferably used. By using the developer for developing an electrostatic image in the image forming method, stable development, transfer, and fixing performance can be obtained even in a tandem system suitable for, for example, miniaturization and color acceleration. .

  Examples of the recording material to which the toner image is transferred include plain paper, OHP sheet, and the like used in electrophotographic copying machines and printers. In order to further improve the smoothness of the image surface after fixing, the surface of the recording medium is preferably as smooth as possible. For example, coated paper in which the surface of plain paper is coated with a resin or the like, art paper for printing Etc. can be used suitably.

-Image forming apparatus and image forming method using non-magnetic one-component developer-
An example of a developer apparatus that develops using the above-described non-magnetic one-component developer will be described below with reference to FIG. In addition, by using the developing device 10 shown in FIG. 2 for each of the developing devices 404a to 404d in FIG. 1 described above, image formation can be similarly performed.

  As shown in FIG. 2, the developing device 10 is disposed so as to abut on an image carrier 26 that can be rotated in the direction of arrow A by a drive source (not shown), and the arrow moves along with the rotation of the image carrier (photosensitive member) 26. A developing roller 12 that can be driven to rotate in the B direction, a bias power source 14 connected to the developing roller 12, and a position downstream of the contact portion between the developing roller 12 and the image carrier 26 in the rotating direction of the developing roller 12. In addition, a toner scraping member 16 that is disposed so as to be in pressure contact with the developing roll 12 and is rotatable in the direction of arrow C so as to run against the rotation of the developing roll 12, and in the rotating direction of the developing roll 12, the developing roll 12 And a toner layer reference disposed so as to abut on the developing roll 12 at a position downstream of the pressure contact portion between the developing roller 12 and the toner scraping member 16 and upstream of a contact portion between the developing roll 12 and the image carrier 26. The member 18 is located on the side opposite to the side on which the image carrier 26 of the developing roll 12 is disposed, the housing 22 having an opening on the side on which the developing roll 12 is disposed, and the housing 22 is disposed in the housing 22. And an agitator 20.

  The toner layer regulating member 18 is once fixed to the opening of the housing 22 so as to close the opening of the housing 22. The side of the opening of the housing 22 opposite to the side on which the toner layer regulating member 18 is attached (upper side of the opening) (lower side of the opening) covers the lower side of the developing roll 12 and the toner scraping member 16. It is configured. Here, the toner (which is also a “non-magnetic one-component developer”) 24 is disposed so as to be deposited on the lower side of the casing 22, and the lower side of the developing roll 12 and the lower side of the opening of the casing 22. And the toner scraping member 16 is deposited so as to cover the space. The toner 24 is appropriately supplied from the inside of the housing 22 to the opening side of the housing 22 where the developing roll 12 is disposed by an agitator 20 provided in the housing 22.

  When developing, first, the toner 24 in the housing 22 is supplied from the agitator 20 to the surface of the developing roll 12 by the toner scraping member 16. Next, the toner 24 attached to the surface of the developing roll 12 is attached by the toner layer regulating member 18 so as to form a toner layer having a uniform thickness on the surface of the developing roll 12. Subsequently, it adheres to the surface of the developing roll 12 according to the potential difference between the surface of the image carrier 26 on which an electrostatic latent image (not shown) is formed and the developing roll 12 to which a bias voltage is applied by the bias power supply 14. The toner 24 is transferred to the developing roll 12 side, and the electrostatic latent image is developed. The toner 24 remaining on the surface of the developing roll 12 after the development is scraped off by the toner scraping member 16.

  Another image forming method of the present embodiment is an image forming method using the above-described nonmagnetic one-component developer, and the nonmagnetic one-component developer is used as a developer carrier (developing roll 12). A toner supply member for supplying toner thereon and a layer regulating member pressed against the developer carrier, and a non-magnetic one-component developer is supplied from the toner supply member to the developer carrier, and the layer regulating member is in pressure contact An image forming method for use in a one-component developing device that performs development using a charged toner layer formed on a developer carrying member, wherein a rotational torque of the developer carrying member is in a range of 1.0 kgfcm to 2.5 kgfcm. Image forming method.

  A conventionally known method can be applied to the latent image forming step (step of forming an electrostatic latent image on the electrostatic latent image holding member). In the latent image forming step, an electrostatic latent image is formed on a latent image holding member such as a photosensitive layer or a dielectric layer by electrophotography or electrostatic recording. As the photosensitive layer of the latent image carrier used in the present invention, known ones such as organic and amorphous silicon can be used. The latent image carrier is obtained by a known production method such as surface processing after extrusion molding of aluminum or an aluminum alloy, and may have a preferable shape such as a cylindrical shape or a belt shape depending on the apparatus.

  In the developing step (the step of visualizing the electrostatic latent image on the electrostatic latent image holding member), the toner is thinly layered on the rotating cylinder as the developer carrying member (developing roll) by the layer regulating member. Formed, transported to the developing nip, and placed between the developing roll and the latent image holding body by placing the developing roll and the latent image holding body holding the electrostatic latent image in contact with the developing unit or providing a certain gap. The electrostatic latent image is developed with toner while applying a bias to the toner. In the case of magnetic one-component development, a rotating cylindrical body having a magnet incorporated therein is used as a developer carrier, and toner having a magnetic body is conveyed and held by magnetic force. In the case of non-magnetic one-component development, a method may be employed in which a toner supply roll such as urethane sponge is pressed against the developer carrying member to supply toner onto the developer carrying member.

  As the developer carrying member (developing roll 12) used in the present embodiment, an elastic sleeve in which a conductive agent such as carbon is dispersed in silicone rubber, NBR, EPDM, or the like, or metal or ceramics such as aluminum or SUS is pulled out. In order to control the transportability and chargeability of the toner, it is possible to use a sleeve that has been subjected to surface treatment such as oxidation or metal plating, polishing, blasting, etc. on the substrate surface or coating with a resin / charge control agent.

  In the present embodiment, a blade obtained by coating a resin on a substrate such as SUS, an aluminum plate, or phosphor bronze can be used as the layer regulating member. Examples of the resin for coating include resins such as acrylic resin, phenol resin, and urethane resin. Moreover, you may use resin which mixed molybdenum disulfide, melamine, graphite, silicone acryl, etc. in those resin as coating resin. In addition, a thin plate or tape of acrylic resin, aluminum, Teflon, vinyl chloride, high-density polyethylene or the like may be used on a substrate such as SUS. A plate-like blade such as polyoxymethylene resin or acrylic resin can also be used.

  Further, the rotational torque of the developer carrier is in the range of 1.0 kgfcm to 2.5 kgfcm, and more preferably in the range of 1.3 kgfcm to 2.3 kgfcm.

  If the rotational torque of the developer carrier is less than 1.0 kgfcm, it is difficult to form a stable layer on the developer carrier, causing uneven toner charging, and it is impossible to suppress low-charge toner clouding. Inflight contamination will occur. On the other hand, if the rotational torque of the developer carrier is greater than 2.5 kgfcm, toner fusion to the layer regulating member occurs, and the thickness of the toner layer formed on the developer carrier becomes non-uniform, resulting in toner charging. As a result, unevenness of the toner is caused, and the cloud of the low-charge toner cannot be suppressed.

  The image forming method of the present embodiment may include a transfer process, a cleaning process, or a fixing process as necessary in addition to the latent image forming process and the developing process. In the transfer step in the present invention, a known method such as contact-type transfer in which a toner image is transferred by pressing a transfer roller, a transfer belt or the like to the latent image holding member, or non-contact type transfer using a corotron is used. In the cleaning process, the toner remaining on the latent image holding member without being transferred in the transfer process is removed by a cleaner. Examples of the cleaning means in the present invention include known means such as blade cleaning or roller cleaning. For blade cleaning, a blade made of elastic rubber such as silicone rubber or urethane rubber is used. The image forming method of the present invention can also be applied to a so-called cleaner-less system that does not include a cleaning step. In the fixing step, the toner image transferred to the transfer body is fixed by a fixing device. As the fixing means, a heat fixing method using a heat roll is preferable.

  EXAMPLES Hereinafter, although an Example demonstrates this invention, this invention is not limited. In the examples, unless otherwise specified, “part” represents “part by mass” and “%” represents “% by mass”.

<Measuring method of various characteristics>
First, methods for measuring physical properties of toners and the like used in Examples and Comparative Examples will be described.

(Toner particle size and particle size distribution measurement method)
To measure the toner particle size and particle size distribution in the present invention, Multisizer II type (manufactured by Beckman-Coulter) was used as a measuring device, and ISOTON-II (manufactured by Beckman-Coulter) was used as the electrolyte.

  As a measurement method, 0.5 to 50 mg of a measurement sample is added to 2 ml of a 5% aqueous solution of a surfactant, preferably sodium alkylbenzenesulfonate, as a dispersant. This was added to 100 to 150 ml of the electrolytic solution. The electrolytic solution in which the sample is suspended is subjected to a dispersion treatment with an ultrasonic disperser for about 1 minute, and the particle size distribution of 2 to 60 μm particles is measured using the Multisizer II type with an aperture diameter of 100 μm. Thus, the volume average particle diameter, GSDv, and GSDp were obtained. The number of particles to be measured was 50,000.

(Measurement method of weight average molecular weight and molecular weight distribution of resin)
In the present invention, the molecular weight and molecular weight distribution of the binder resin and the like are those obtained under the following conditions. GPC uses “HLC-8120GPC, SC-8020 (manufactured by Tosoh Corporation)”, and the column uses two “TSKgel, SuperHM-H (6.0 mm ID × 15 cm, manufactured by Tosoh Corporation)” THF (tetrahydrofuran) was used as an eluent. As experimental conditions, an experiment was performed using a sample concentration of 0.5%, a flow rate of 0.6 ml / min, a sample injection amount of 10 μl, a measurement temperature of 40 ° C., and an IR detector. The calibration curve is “polystylen standard sample TSK standard” manufactured by Tosoh Corporation: “A-500”, “F-1”, “F-10”, “F-80”, “F-380”, “A-2500”. ”,“ F-4 ”,“ F-40 ”,“ F-128 ”, and“ F-700 ”.

(Volume average particle diameter of resin fine particles, colorant particles, etc.)
Volume average particle diameters of resin fine particles, colorant particles, and the like were measured with a laser diffraction particle size distribution analyzer (LA-700, manufactured by Horiba, Ltd.).

[Resin acid value]
The resin acid value was measured as follows. About 1 g of resin is precisely weighed and dissolved in 80 ml of tetrahydrofuran. Phenolphthalein was added as an indicator, titrated with a 0.1N KOH ethanol solution, and the end point was when the color lasted for 30 seconds. From the amount of 0.1N KOH ethanol solution used, the acid value (contained in 1 g of resin) The number of mg of KOH necessary to neutralize free fatty acids was calculated according to JIS K0070: 92).

[Toner surface acid value]
As a dispersant, 10 g of a measurement sample (toner) is added to 100 ml of a 2% aqueous solution of a surfactant, preferably sodium alkylbenzenesulfonate, and a toner dispersion is prepared by performing a dispersion treatment with an ultrasonic disperser for about 3 minutes. Next, neutralization titration of the above-mentioned toner dispersion was performed using 0.3N aqueous sodium hydroxide solution, and 0. required for neutralization titration of 100 ml of an aqueous dispersant solution (2% sodium alkylbenzene sulfonate) without addition of toner. The amount of sodium hydroxide required to neutralize the acidic groups on the toner surface is calculated from the difference from the amount of 3N sodium hydroxide aqueous solution. The toner surface acid value [mg KOH / g] can be determined by replacing the amount of sodium hydroxide required for neutralizing 1 g of toner with an equimolar amount of potassium hydroxide.

(Measuring method of melting point and glass transition temperature of resin)
The melting point of the crystalline polyester resin and the glass transition temperature (Tg) of the amorphous polyester resin were measured using a differential scanning calorimeter (manufactured by Perkin Elmer: DSC-7) according to ASTM D3418-8. It calculated | required from the maximum peak. The temperature correction of the detection part of this apparatus (DSC-7) uses the melting point of indium and zinc, and the correction of heat quantity uses the heat of fusion of indium. As the sample, an aluminum pan was used, an empty pan was set as a control, and the measurement was performed at a heating rate of 10 ° C./min.

(Phenol ester amount on the toner surface)
The surface phenol ester content of the toner was measured by the following method. In the measurement, 1 g of a measurement sample (toner) is added to 1 liter of a 1% aqueous solution of a surfactant, preferably sodium alkylbenzene sulfonate as a dispersant, and subjected to a dispersion treatment with an ultrasonic disperser for about 3 minutes. Create

  To the above toner dispersion, 100 ml of 0.1N sodium hydroxide aqueous solution was added, heated to 60 ° C. and held at 60 ° C. for 8 hours, and then cooled to 20 ° C. or lower and solid-liquid separated. The obtained filtrate was analyzed according to “Solid Phase Extraction-Derivatization-Gas Chromatograph-Mass Spectrometry” described in Ministry of Health, Labor and Welfare Notification No. 261-Attached Table 29, and the result calculated as the amount of phenol was the amount of phenol ester. It was.

<Preparation of each dispersion>
[Preparation of Crystalline Polyester Resin Fine Particle Dispersion 1]
Into a heat-dried three-necked flask, 266 parts of 1,12-dodecanedicarboxylic acid and 169 parts of 1,10-decanediol and 0.035 part of tetrabutoxytitanate as a catalyst were placed, and then the air in the container was reduced by depressurization. The pressure was reduced, and the mixture was further inerted with nitrogen gas, and refluxed at 180 ° C. for 6 hours with mechanical stirring. Thereafter, the temperature was gradually raised to 220 ° C. by vacuum distillation and stirred for 2.5 hours. When the solution became viscous, the resin acid value was measured, and the resin acid value became 15.0 mgKOH / g. By the way, vacuum distillation was stopped and air-cooled to obtain a crystalline polyester resin 1.

  It was 13000 when the weight average molecular weight (Mw) of the obtained crystalline polyester resin 1 was measured by the above-mentioned method. Further, the melting point of the obtained crystalline polyester resin 1 was 73 ° C. when measured by a differential scanning calorimeter (DSC) by the above-described measuring method.

  Next, 180 parts of this crystalline polyester resin 1 and 585 parts of deionized water were placed in a stainless beaker, placed in a warm bath, and heated to 95 ° C. When the crystalline polyester resin 1 was melted, the mixture was stirred at 8000 rpm using a homogenizer (manufactured by IKA: Ultra Turrax T50), and at the same time, diluted ammonia water was added to adjust the pH to 7.0. Then, 20 parts of an aqueous solution obtained by diluting 0.8 part of an anionic surfactant (Daiichi Kogyo Seiyaku Co., Ltd .: Neogen R) is added dropwise to carry out emulsification and dispersion, and a crystalline polyester having a volume average particle size of 0.23 μm. Resin fine particle dispersion 1 [resin fine particle concentration: 12.4%] was prepared.

[Preparation of Amorphous Polyester Resin Fine Particle Dispersion 1]
In a heat-dried two-necked flask, 74 parts of dimethyl adipate, 192 parts of dimethyl terephthalate, 216 parts of bisphenol A ethylene oxide adduct, 38 parts of ethylene glycol, and 0.037 parts of tetrabutoxy titanate as a catalyst are placed in a container. Nitrogen gas was introduced and the temperature was raised while stirring in an inert atmosphere, followed by a copolycondensation reaction at 160 ° C. for about 7 hours, and then the temperature was raised to 220 ° C. while gradually reducing the pressure to 10 Torr and held for 4 hours. . Once the pressure was returned to normal pressure, 9 parts of trimellitic anhydride was added, and the pressure was gradually reduced again to 10 Torr and maintained for 1 hour to synthesize amorphous polyester resin 1.

  It was 60 degreeC when the glass transition temperature of the obtained amorphous polyester resin 1 was measured using the differential scanning calorific value system (DSC) with the above-mentioned measuring method. When the molecular weight of the obtained amorphous polyester resin 1 was measured by GPC by the above-mentioned measuring method, the weight average molecular weight (Mw) was 12000. Moreover, it was 25.0 mgKOH / g when the acid value of the obtained amorphous polyester resin 1 was measured.

  Next, 115 parts of this amorphous polyester resin 1, 180 parts of deionized water, and 5 parts of an anionic surfactant (Daiichi Kogyo Seiyaku Co., Ltd .: Neogen R) were mixed and heated to 120 ° C. Then, after sufficiently dispersing with a homogenizer (manufactured by IKA: Ultra Tarrax T50), the dispersion treatment is carried out for 1 hour with a pressure discharge type gorin homogenizer, whereby an amorphous polyester resin fine particle dispersion 1 (resin particle concentration: 40). % By weight) was adjusted.

[Preparation of Amorphous Polyester Resin Fine Particle Dispersion 2]
In a heat-dried two-necked flask, 71 parts of dimethyl adipate, 184 parts of dimethyl terephthalate, 206 parts of bisphenol A ethylene oxide adduct, 42 parts of biphenol, 27 parts of ethylene glycol and 0.036 parts of tetrabutoxy titanate as a catalyst Then, after introducing nitrogen gas into the container and keeping the temperature in an inert atmosphere, the temperature was raised and subjected to a copolycondensation reaction at 160 ° C. for about 10 hours, and then the temperature was raised to 220 ° C. while gradually reducing the pressure to 10 Torr and held for 8 hours. Thus, an amorphous polyester resin 2 was synthesized.

  It was 64 degreeC when the glass transition temperature of the obtained amorphous polyester resin 2 was measured using the differential scanning calorific value system (DSC) with the above-mentioned measuring method. When the molecular weight of the obtained amorphous polyester resin 2 was measured by GPC by the above-mentioned measuring method, the weight average molecular weight (Mw) was 15000. Moreover, when the acid value of the obtained amorphous polyester resin 2 was measured, it was 9.0 mgKOH / g.

  Next, 115 parts of this amorphous polyester resin 2, 180 parts of deionized water, and 5 parts of an anionic surfactant (Daiichi Kogyo Seiyaku Co., Ltd .: Neogen R) were mixed and heated to 120 ° C. Then, after sufficiently dispersing with a homogenizer (manufactured by IKA: Ultra Tarrax T50), the dispersion treatment is carried out for 1 hour with a pressure discharge type gorin homogenizer, whereby an amorphous polyester resin fine particle dispersion 2 (resin particle concentration: 40). % By weight) was adjusted.

[Preparation of Amorphous Polyester Resin Fine Particle Dispersion 3]
In a heat-dried two-necked flask, 72 parts of dimethyl adipate, 188 parts of dimethyl terephthalate, 211 parts of bisphenol A ethylene oxide adduct, 37 parts of ethylene glycol and 0.036 parts of tetrabutoxy titanate as a catalyst are placed in a container. Nitrogen gas was introduced and the temperature was increased while stirring in an inert atmosphere, followed by a co-condensation polymerization reaction at 160 ° C. for about 5 hours, and then the temperature was increased to 220 ° C. while gradually reducing the pressure to 10 Torr and maintained for 3 hours. . The pressure was returned to normal pressure, 18 parts of trimellitic anhydride was added, and the pressure was gradually reduced again to 10 Torr and held for 1 hour to synthesize amorphous polyester resin 3.

  It was 56 degreeC when the glass transition temperature of the obtained amorphous polyester resin 3 was measured using the differential scanning calorific value system (DSC) with the above-mentioned measuring method. When the molecular weight of the obtained amorphous polyester resin 3 was measured by GPC by the above-mentioned measuring method, the weight average molecular weight (Mw) was 8000. Moreover, when the acid value of the obtained amorphous polyester resin 3 was measured, it was 44.0 mgKOH / g.

  Next, 115 parts of this amorphous polyester resin 3, 180 parts of deionized water, and 5 parts of an anionic surfactant (Daiichi Kogyo Seiyaku Co., Ltd .: Neogen R) were mixed and heated to 120 ° C. Then, after sufficiently dispersing with a homogenizer (manufactured by IKA: Ultra Tarrax T50), the dispersion treatment is performed for 3 hours with a pressure discharge type gorin homogenizer, whereby amorphous polyester resin fine particle dispersion 3 (resin particle concentration: 40). % By weight) was adjusted.

[Adjustment of colorant dispersion]
-Preparation of cyan colorant dispersion-
98 parts by weight of a cyan pigment (manufactured by Dainichi Seika Co., Ltd., Pigment Blue 15: 3 (copper phthalocyanine)), 15 parts by weight of an anionic surfactant (manufactured by Daiichi Kogyo Seiyaku Co., Ltd .: Neogen R), and 300 ion-exchanged water After mixing with parts by weight and dispersing for 10 minutes using a homogenizer (manufactured by IKA: Ultra Turrax T50), the colorant is dispersed by applying to a circulating ultrasonic disperser (RUS-600TCVP, manufactured by Nippon Seiki Seisakusho). A liquid was obtained.

  The volume average particle diameter of the colorant (cyan pigment) in the obtained colorant dispersion was measured using a laser diffraction particle size measuring instrument according to the measurement method described above, and the volume average particle diameter was 0.17 μm. It was. The solid content ratio of the colorant dispersion was 23% by weight.

-Preparation of yellow colorant dispersion-
99 parts by weight of a yellow pigment (PY74: manufactured by Dainichi Seika), 15 parts by weight of an anionic surfactant (manufactured by Daiichi Kogyo Seiyaku Co., Ltd .: Neogen R), and 300 parts by weight of ion-exchanged water are mixed together to produce a homogenizer (IKA). (Manufactured by Ultra Turrax T50) for 10 minutes, and then subjected to a circulating ultrasonic disperser (manufactured by Nippon Seiki Seisakusho, RUS-600TCVP) to obtain a yellow colorant dispersion.

  The volume average particle diameter of the colorant (yellow pigment) in the obtained yellow colorant dispersion was measured using a laser diffraction particle size measuring instrument according to the measurement method described above. The volume average particle diameter was 0.20 μm. there were. The solid content ratio of the yellow colorant dispersion was 24% by weight.

-Preparation of magenta colorant dispersion-
99 parts by weight of a magenta pigment (CI Pigment Red 122: manufactured by Clariant), 15 parts by weight of an anionic surfactant (manufactured by Daiichi Kogyo Seiyaku Co., Ltd .: Neogen R), and 300 parts by weight of ion-exchanged water are mixed, and the homogenizer is mixed. After being dispersed for 10 minutes using (IKA Corp .: ULTRA TALLAX T50), a magenta colorant dispersion was obtained by applying to a circulating ultrasonic disperser (manufactured by Nippon Seiki Seisakusho, RUS-600TCVP).

  When the volume average particle size of the colorant (magenta pigment) in the obtained magenta colorant dispersion was measured using a laser diffraction particle size measuring instrument by the above-described measurement method, the volume average particle size was 0.19 μm. there were. The solid content ratio of the magenta colorant dispersion was 24% by weight.

-Preparation of black colorant dispersion-
Carbon black Legal 330: 99 parts by weight (manufactured by Cabot), 15 parts by weight of an anionic surfactant (manufactured by Daiichi Kogyo Seiyaku Co., Ltd .: Neogen R), and 300 parts by weight of ion-exchanged water are mixed together, and a homogenizer (IKA Co. (Manufactured by Ultra Turrax T50) for 10 minutes, and then applied to a circulating ultrasonic disperser (manufactured by Nippon Seiki Seisakusho, RUS-600TCVP) to obtain a black colorant dispersion.

  When the volume average particle diameter of the colorant (carbon black) in the obtained black colorant dispersion was measured using a laser diffraction particle size measuring instrument according to the measurement method described above, the volume average particle diameter was 0.25 μm. there were. The solid content ratio of the black colorant dispersion was 24% by weight.

[Adjustment of release agent dispersion]
90 parts by weight of Fischer-Tropsch wax FNP92 (melting point 92 ° C .: manufactured by Nippon Seiki Co., Ltd.), 3.6 parts by weight of an anionic surfactant (manufactured by Daiichi Kogyo Co., Ltd .: Neogen R), and 360 parts by weight of ion-exchanged water The mixture was heated to 100 ° C. and sufficiently dispersed with a homogenizer (manufactured by IKA: Ultra Tarrax T50), and then dispersed with a pressure discharge type gorin homogenizer to obtain a release agent dispersion.

  When the volume average particle size of the release agent in the obtained release agent dispersion was measured using a laser diffraction particle size measuring instrument by the above-described measurement method, the volume average particle size was 0.23 μm. The solid content ratio of the release agent dispersion was 20% by weight.

<Manufacture of toner>
[Production of Toner 1]
(Manufacture of base toner 1)
104.4 parts of crystalline polyester resin fine particle dispersion 1, 336.1 parts of amorphous polyester resin fine particle dispersion 1, 45.4 parts of cyan colorant dispersion, and 115.3 parting agent dispersion 115.3. And 484 parts of deionized water were placed in a round stainless steel flask and thoroughly mixed and dispersed with an Ultra Turrax T50.

  Next, 0.37 parts of polyaluminum chloride was added thereto, and the dispersion operation was continued with an ultra turrax. Further, the flask was heated to 52 ° C. with stirring in an oil bath for heating. After maintaining at 52 ° C. for 3 hours, 175 parts of amorphous polyester resin fine particle dispersion 1 was gradually added thereto.

  Thereafter, the pH of the system was adjusted to 8.5 with a 0.5N aqueous sodium hydroxide solution, and then the stainless steel flask was sealed, heated to 90 ° C. while continuing stirring using a magnetic seal, and maintained for 3 hours.

  After completion of the reaction, the mixture was cooled, filtered, thoroughly washed with ion exchange water, and then subjected to solid-liquid separation by Nutsche suction filtration. This was further redispersed in 3 liters of ion exchanged water at 40 ° C., and stirred and washed at 300 rpm for 15 minutes.

  This was repeated five more times. When the pH of the filtrate was 6.88, the electric conductivity was 8.4 μS / cm, and the surface tension was 7.02 Nm, No. Solid-liquid separation was performed using 5A filter paper, and then vacuum drying was performed for 12 hours to obtain base toner 1.

  The toner surface acid value of the obtained base toner 1 was measured by the above-described method and found to be 20.0 mgKOH / g-TN. Further, the glass transition temperature of the base toner 1 was measured by the above-mentioned method and found to be 54.0 ° C.

(Phenol ester addition)
In a heat-dried two-necked flask, 200 parts of base toner 1, 400 parts of phenyl acetate, and 0.08 part of potassium acetate as a catalyst were placed, heated to 52 ° C. with stirring, and held for 8 hours. While maintaining the temperature at 52 ° C., the pressure was gradually reduced to 25.0 Torr and maintained for 7 hours to remove the acetic acid distilled out of the system.

  After completion of the reaction, the mixture was cooled and filtered to separate the toner and unreacted phenyl acetate, and the toner was sufficiently washed with ion exchange water, and then subjected to solid-liquid separation by Nutsche suction filtration. This was further redispersed in 3 liters of ion exchanged water at 40 ° C., and stirred and washed at 300 rpm for 15 minutes.

  This was repeated five more times, and when the pH of the filtrate was 7.01, the electric conductivity was 8.8 μS / cm, and the surface tension was 7.00 Nm, No. 3 was obtained by Nutsche suction filtration. Solid-liquid separation was performed using 5A filter paper, and then vacuum drying was performed for 12 hours to obtain toner 1.

The surface phenol ester content of the obtained toner 1 was measured by the method described above, and found to be 3.6 × 10 ⁻⁴ mol / g-TN. The volume average particle diameter of the toner 1 was measured by the above-described measuring method and found to be 5.8 μm. Further, the average circularity of the toner 1 was measured by the above-described measuring method and found to be 0.960.

[Production of Toner 1y, Base Toner 1m, Base Toner 1k]
Using the yellow colorant dispersion, the magenta colorant dispersion, and the black colorant dispersion instead of the cyan colorant dispersion, the base toner 1y, the base toner 1m, and the base toner 1k are manufactured in the same manner as described above. did. The toner surface acid values of the obtained base toner 1y, base toner 1m, and base toner 1k were measured by the method described above, and found to be 20.0 mgKOH / g-TN. Further, the glass transition temperatures of the base toner 1y, the base toner 1m, and the base toner 1k were measured by the above-described method, and found to be 54.0 ° C.

(Phenol ester addition)
The base toner 1y, base toner 1m, and base toner 1k were obtained in the same manner as described above except that the base toner 1y, the base toner 1m, and the base toner 1k were used instead of the base toner 1.

The surface phenol ester amounts of the obtained toner 1y, toner 1m, and toner 1k were measured by the method described above, and all were 3.6 × 10 ⁻⁴ mol / g-TN. The volume average particle diameters of Toner 1y, Toner 1m, and Toner 1k were measured by the measurement method described above, and were 5.8 μm, 0.585 μm, and 0.578 μm, respectively. Further, the average circularity of the toner 1y, the toner 1m, and the toner 1k was measured by the above-described measurement method, and was 0.960, 0.959, and 0.960, respectively.

[Production of Toner 2]
(Manufacture of base toner 2)
34.8 parts of crystalline polyester resin fine particle dispersion 1, 357.9 parts of amorphous polyester resin fine particle dispersion 2, 45.4 parts of cyan colorant dispersion, and 115.3 parting agent dispersion 115.3 And 532 parts of deionized water were placed in a round stainless steel flask, and thoroughly mixed and dispersed with an Ultra Turrax T50.

  Next, 0.37 parts of polyaluminum chloride was added thereto, and the dispersion operation was continued with an ultra turrax. Further, the flask was heated to 52 ° C. with stirring in an oil bath for heating. After maintaining at 52 ° C. for 4 hours, 175 parts of the amorphous polyester resin fine particle dispersion 2 was gradually added thereto.

  Thereafter, the pH of the system was adjusted to 8.5 with a 0.5N aqueous sodium hydroxide solution, and then the stainless steel flask was sealed, heated to 90 ° C. while continuing stirring using a magnetic seal, and maintained for 2 hours.

  After completion of the reaction, the mixture was cooled, filtered, thoroughly washed with ion exchange water, and then subjected to solid-liquid separation by Nutsche suction filtration. This was further redispersed in 3 liters of ion exchanged water at 40 ° C., and stirred and washed at 300 rpm for 15 minutes.

  This was repeated five more times, and when the pH of the filtrate was 6.90, the electric conductivity was 8.02 μS / cm, and the surface tension was 6.98 Nm, No. 3 was obtained by Nutsche suction filtration. Solid-liquid separation was performed using 5A filter paper, and then vacuum drying was performed for 12 hours to obtain base toner 2.

  The toner surface acid value of the obtained base toner 2 was measured by the above-described method and found to be 7.0 mgKOH / g-TN. Further, the glass transition temperature of the base toner 2 was measured by the above method and found to be 58.0 ° C.

(Phenol ester addition)
In a heat-dried two-necked flask, 200 parts of base toner 2, 400 parts of phenyl acetate and 0.08 part of potassium acetate as a catalyst were placed, heated to 56 ° C. with stirring and held for 8 hours. While maintaining the temperature at 56 ° C., the pressure was gradually reduced to 25 Torr and maintained for 7 hours to remove the acetic acid distilled out of the system.

  After completion of the reaction, the mixture was cooled and filtered to separate the toner and unreacted phenyl acetate, and the toner was sufficiently washed with ion exchange water, and then subjected to solid-liquid separation by Nutsche suction filtration. This was further redispersed in 3 liters of ion exchanged water at 40 ° C., and stirred and washed at 300 rpm for 15 minutes.

  This was repeated five more times, and when the pH of the filtrate was 7.00, the electric conductivity was 8.52 μS / cm, and the surface tension was 7.10 Nm, No. 3 was obtained by Nutsche suction filtration. Solid-liquid separation was performed using 5A filter paper, and then vacuum drying was performed for 12 hours to obtain toner 2.

The surface phenol ester content of the obtained toner 2 was measured by the above-described method and found to be 1.2 × 10 ⁻⁴ mol / g-TN. The volume average particle diameter of the toner 2 was measured by the above-described measuring method and found to be 7.2 μm. Further, the average circularity of the toner 2 was measured by the above-described measuring method and found to be 0.948.

[Production of Toner 3]
(Manufacture of base toner 3)
174.0 parts of crystalline polyester resin fine particle dispersion 1, 314.4 parts of amorphous polyester resin fine particle dispersion 3, 45.4 parts of cyan colorant dispersion, 115.3 parting agent dispersion 115.3 And 436 parts of deionized water were placed in a round stainless steel flask and thoroughly mixed and dispersed with an Ultra Turrax T50.

  Next, 0.37 parts of polyaluminum chloride was added thereto, and the dispersion operation was continued with an ultra turrax. Further, the flask was heated to 52 ° C. with stirring in an oil bath for heating. After maintaining at 52 ° C. for 2 hours, 175 parts of amorphous polyester resin fine particle dispersion 3 was gradually added thereto.

  Thereafter, the pH of the system was adjusted to 8.5 with a 0.5N aqueous sodium hydroxide solution, and then the stainless steel flask was sealed, heated to 90 ° C. while continuing stirring using a magnetic seal, and maintained for 4 hours.

  After completion of the reaction, the mixture was cooled, filtered, thoroughly washed with ion exchange water, and then subjected to solid-liquid separation by Nutsche suction filtration. This was further redispersed in 3 liters of ion exchanged water at 40 ° C., and stirred and washed at 300 rpm for 15 minutes.

  This was repeated 5 times, and when the pH of the filtrate was 6.95, the electric conductivity was 8.6 μS / cm, and the surface tension was 6.96 Nm, No. Solid-liquid separation was performed using 5A filter paper, and then vacuum drying was performed for 12 hours to obtain base toner 3.

  The toner surface acid value of the obtained base toner 3 was measured by the method described above, and found to be 35.0 mgKOH / g-TN. Further, the glass transition temperature of the base toner 3 was measured by the above-described method and found to be 50.0 ° C.

(Phenol ester addition)
In a heat-dried two-necked flask, 200 parts of base toner 3, 400 parts of phenyl acetate and 0.08 part of potassium acetate as a catalyst were placed, heated to 48 ° C. with stirring and held for 8 hours. While maintaining the temperature at 48 ° C., the pressure was gradually reduced to 25.0 Torr and maintained for 7 hours to remove the acetic acid distilled out of the system.

  After completion of the reaction, the mixture was cooled and filtered to separate the toner and unreacted phenyl acetate, and the toner was sufficiently washed with ion exchange water, and then subjected to solid-liquid separation by Nutsche suction filtration. This was further redispersed in 3 liters of ion exchanged water at 40 ° C., and stirred and washed at 300 rpm for 15 minutes.

  This was repeated five more times, and when the pH of the filtrate was 7.03, the electric conductivity was 8.92 μS / cm, and the surface tension was 7.10 Nm, No. 3 was obtained by Nutsche suction filtration. Solid-liquid separation was performed using 5A filter paper, and then vacuum drying was performed for 12 hours to obtain toner 3.

The surface phenol ester content of the obtained toner 3 was measured by the above-described method and found to be 6.2 × 10 ⁻⁴ mol / g-TN. The volume average particle diameter of the toner 3 was measured by the above-described measuring method and found to be 3.5 μm. In addition, the average circularity of the toner 3 was 0.975 as measured by the measurement method described above.

[Production of Toner 4]
(Manufacture of base toner 4)
104.4 parts of crystalline polyester resin fine particle dispersion 1, 336.1 parts of amorphous polyester resin fine particle dispersion 1, 45.4 parts of cyan colorant dispersion, and 115.3 parting agent dispersion 115.3. And 484 parts of deionized water were placed in a round stainless steel flask and thoroughly mixed and dispersed with an Ultra Turrax T50.

  Next, 0.37 parts of polyaluminum chloride was added thereto, and the dispersion operation was continued with an ultra turrax. Further, the flask was heated to 52 ° C. with stirring in an oil bath for heating. After maintaining at 52 ° C. for 3.5 hours, 175 parts of amorphous polyester resin fine particle dispersion 1 was gradually added thereto.

  Then, after adjusting the pH of the system to 8.5 with a 0.5N sodium hydroxide aqueous solution, the stainless steel flask was sealed, heated to 90 ° C. while continuing stirring using a magnetic seal, and maintained for 3.5 hours. did.

  After completion of the reaction, the mixture was cooled, filtered, thoroughly washed with ion exchange water, and then subjected to solid-liquid separation by Nutsche suction filtration. This was further redispersed in 3 liters of ion exchanged water at 40 ° C., and stirred and washed at 300 rpm for 15 minutes.

  This was repeated 5 times, and when the pH of the filtrate was 6.95, the electric conductivity was 8.6 μS / cm, and the surface tension was 6.96 Nm, No. Solid-liquid separation was performed using 5A filter paper, and then vacuum drying was performed for 12 hours to obtain base toner 4.

  The toner surface acid value of the obtained base toner 4 was measured by the method described above, and found to be 20.0 mgKOH / g-TN. Further, the glass transition temperature of the base toner 4 was measured by the above method and found to be 53 ° C.

(Phenol ester addition)
In a heat-dried two-necked flask, 200 parts of base toner 4, 400 parts of phenyl acetate and 0.08 part of potassium acetate as a catalyst were placed, heated to 48 ° C. with stirring and held for 8 hours. While maintaining the temperature at 48 ° C., the pressure was gradually reduced to 25.0 Torr and maintained for 7 hours to remove the acetic acid distilled out of the system.

  After completion of the reaction, the mixture was cooled and filtered to separate the toner and unreacted phenyl acetate, and the toner was sufficiently washed with ion exchange water, and then subjected to solid-liquid separation by Nutsche suction filtration. This was further redispersed in 3 liters of ion exchanged water at 40 ° C., and stirred and washed at 300 rpm for 15 minutes.

  This was repeated five more times, and when the pH of the filtrate was 7.03, the electric conductivity was 8.92 μS / cm, and the surface tension was 7.10 Nm, No. 3 was obtained by Nutsche suction filtration. Solid-liquid separation was performed using 5A filter paper, and then vacuum drying was performed for 12 hours to obtain toner 4.

The surface phenol ester content of the obtained toner 4 was measured by the method described above, and found to be 3.4 × 10 ⁻⁴ mol / g-TN. The volume average particle diameter of the toner 4 was measured by the above-described measuring method and found to be 6.3 μm. Further, the average circularity of the toner 4 was measured by the above-described measuring method and found to be 0.970.

[Production of Toner 5]
104.4 parts of crystalline polyester resin fine particle dispersion 1, 336.1 parts of amorphous polyester resin fine particle dispersion 1, 45.4 parts of cyan colorant dispersion, and 115.3 parting agent dispersion 115.3. And 484 parts of deionized water were placed in a round stainless steel flask and thoroughly mixed and dispersed with an Ultra Turrax T50.

  Next, 0.37 parts of polyaluminum chloride was added thereto, and the dispersion operation was continued with an ultra turrax. Further, the flask was heated to 52 ° C. with stirring in an oil bath for heating. After maintaining at 52 ° C. for 3 hours, 175 parts of amorphous polyester resin fine particle dispersion 1 was gradually added thereto.

  Then, after adjusting the pH of the system to 8.5 with a 0.5N sodium hydroxide aqueous solution, the stainless steel flask was sealed, heated to 90 ° C. while continuing stirring using a magnetic seal, and maintained for 3.5 hours. did.

  After completion of the reaction, the mixture was cooled, filtered, thoroughly washed with ion exchange water, and then subjected to solid-liquid separation by Nutsche suction filtration. This was further redispersed in 3 liters of ion exchanged water at 40 ° C., and stirred and washed at 300 rpm for 15 minutes.

  This was repeated five more times, and when the pH of the filtrate was 6.91, the electric conductivity was 8.21 μS / cm, and the surface tension was 6.97 Nm, No. 3 was obtained by Nutsche suction filtration. Solid-liquid separation was performed using 5A filter paper, and then vacuum drying was performed for 12 hours to obtain toner 5.

  The glass transition temperature of the obtained toner 5 was measured by the above-described method and found to be 53.0 ° C. When the surface phenol ester amount of the toner 5 was measured by the above-mentioned method, it was not detected. The volume average particle diameter of the toner 5 was measured by the above-described measuring method and found to be 5.82 μm. Further, the average circularity of the toner 5 was measured by the above-described measuring method and found to be 0.966.

<Manufacture of external toner>
To 50 g of the manufactured toner, 0.21 g of hydrophobic silica (Cabot, TS720) was added and blended in a sample mill to prepare an externally added toner.

<Adjustment of developer>
The externally added toner is weighed to a ferrite carrier having an average particle diameter of 50 μm coated with 1% methacrylate (manufactured by Soken Chemical Co., Ltd.) so that the toner concentration becomes 5%, and the developer is stirred and mixed for 5 minutes with a ball mill. Adjusted.

<Manufacture of cleaning blade 1>
A cleaning blade 1 made of a polyurethane elastic body having a hardness (JISA scale) of 45 and 120 kg / cm ² was prepared by a conventional method.

<Manufacture of photoreceptor 1>
The aluminum substrate on the cylinder was polished by a centerless polishing apparatus, and the surface roughness was set to Rz = 0.5 μm. As a cleaning process, this cylinder was degreased, etched with a 2 wt% sodium hydroxide solution for 1 minute, neutralized, and further washed with pure water. Next, as an anodizing treatment step, an anodized film (current density 1.0 A / dm ² ) was formed on the cylinder surface with a 10 wt% sulfuric acid solution. After washing with water, sealing was performed by dipping in a 1 wt% nickel acetate solution at 80 ° C. for 20 minutes. Furthermore, pure water washing | cleaning and the drying process were performed. In this way, a 6 μm anodic oxide film was formed on the surface of the aluminum cylinder.

  One part of titanyl phthalocyanine having a strong diffraction peak at a Bragg angle (2θ ± 0.2 °) of X-ray diffraction spectrum on this aluminum substrate of 27.2 ° is polyvinyl butyral (ESREC BM-S, Sekisui Chemical). After mixing with 1 part and 100 parts of n-butyl acetate and dispersing with glass beads for 1 hour in a paint shaker, the resulting coating solution was dip coated on the undercoat layer on the aluminum substrate, A charge generation layer having a film thickness of about 0.15 μm was formed by heating and drying at 100 ° C. for 10 minutes.

  A coating solution prepared by dissolving 2 parts of a benzidine compound represented by [Chemical Formula 1] and 2.5 parts of a polymer compound having a repeating unit represented by [Chemical Formula 2] (viscosity average molecular weight 39000) in 20 parts of chlorobenzene The charge generation layer was applied on the charge generation layer by dip coating, and heated at 110 ° C. for 40 minutes to form a charge transport layer having a thickness of 20 μm.

To the constituent materials shown below, 5 parts of methyl alcohol and 0.5 part of an ion exchange resin (Amberlyst 15E) were added and stirred at room temperature to carry out a protective group exchange reaction for 24 hours.
-Constituent material-
-Compound represented by [Chemical Formula 3] 2 parts-Methyltrimethoxysilane 2 parts-Tetramethoxysilane 0.5 parts-Colloidal silica 0.3 parts Then add n-butanol 10 parts, distilled water 0.3 parts And hydrolyzed for 15 minutes. 0.04 part of aluminum trisacetylacetonate and 0.1 part of 3,5-di-tert-butyl-4-hydroxytoluene are added to 2 parts of the filtrate obtained by filtering and separating the ion exchange resin from the hydrolyzed product. This coating solution is applied onto the charge transport layer by a ring-type dip coating method, air-dried at room temperature for 30 minutes, and then cured by heat treatment at 170 ° C. for 1 hour to form a surface layer having a thickness of about 3 μm. As a result, the photoreceptor 1 was manufactured.

When the hardness of the obtained photoreceptor 1 was measured, it was 34 mN / μm ² in terms of dynamic hardness.

<Evaluation method>
[Evaluation of low-temperature fixability]
The obtained developer was filled in a developing device of a modified machine of DocuPrint C2220 (hereinafter sometimes abbreviated as “DPC2220”) manufactured by Fuji Xerox Co., Ltd., from which the fixing device was removed, and an unfixed image was collected.

The image conditions were a solid image of 40 mm × 50 mm, the toner amount was 4.5 g / m ² , and the recording paper was mirror-coated platinum paper (basis weight: 127 gsm).

  Next, using the fixing device of the DPC2220 modified so that the fixing temperature can be changed, the fixing temperature is increased at intervals of 10 ° C. between 70 ° C. and 200 ° C., and the low temperature fixing property is evaluated. did.

  Low temperature fixability is achieved by bending the fixed image with a constant load weight, measuring the maximum image defect width at that portion, and setting the fixing temperature at which the maximum defect image width is 0.2 mm as the minimum fixing temperature. It was used as an index of sex.

[Evaluation of cleaning blade durability]
A long-term running test of 70,000 copies was carried out using a modified machine combining the cleaning blade 1 and the photoreceptor 1 with the Fuji Xerox Docu Center Color 500. At the stages of 30,000, 50,000, and 70,000 The cleaning blade was removed, and the blade wear amount (μm) was measured with an ultra-deep shape measuring microscope VK8500 (laser microscope), which was used as an index of durability.

[Cleanability evaluation]
In the above 70,000 sheet copy long-term running test, the output image was visually evaluated for cleanability according to the following criteria.
G5: No problem G4: Slight streaks appear on the image occasionally G3: Slight streaks appear on the image continuously G2: Clear streaks appear on the image continuously G1: Clear on the image Many streaks appear in succession

<Example 1>
The minimum fixing temperature measured by the above-described method using a developer prepared using toner 1 was 110 ° C. When the contact pressure between the cleaning blade 1 and the photosensitive member 1 was set to 15 g / cm and a long-term running test was performed, the abrasion amount of the cleaning blade at 70,000 sheets showed a good durability of 0.6 μm, The cleanability standard was also satisfactory with G5.

<Example 2>
The minimum fixing temperature measured by the above-described method using the developer prepared using the toner 2 was 115 ° C. When the contact pressure between the cleaning blade 1 and the photosensitive member 1 was set to 15 g / cm and a long-term running test was performed, the wear amount of the cleaning blade at 70,000 sheets showed a good durability of 1.2 μm, The cleaning standard was also within the allowable range for G4.

<Example 3>
The minimum fixing temperature measured by the above-described method using the developer prepared using the toner 3 was 105 ° C. When the contact pressure between the cleaning blade 1 and the photosensitive member 1 was set to 15 g / cm and a long-term running test was performed, the amount of wear of the cleaning blade at the stage of 70,000 sheets showed a good durability of 1.5 μm, The cleaning standard was also within the allowable range for G4.

<Example 4>
The minimum fixing temperature measured by the above-described method using the developer prepared using the toner 4 was 110 ° C. When the contact pressure between the cleaning blade 1 and the photosensitive member 1 was set to 10 g / cm and a long-term running test was performed, the abrasion amount of the cleaning blade at 70,000 sheets showed a good durability of 1.0 μm, The cleaning standard was also within the allowable range for G4.

<Comparative Example 1>
The minimum fixing temperature measured by the above-described method using the developer prepared using the toner 5 was 110 ° C. When the contact pressure between the cleaning blade 1 and the photosensitive member 1 was set to 30 g / cm and a long-term running test was performed, the amount of wear of the cleaning blade at the 50,000-sheet stage was 2.5 μm, within the allowable range, and the cleaning standard Was within the allowable range for G4, but at 70,000 sheets, the amount of wear of the cleaning blade deteriorated to 11.5 μm, resulting in insufficient durability, and the cleanability standard became G2, and clear streaks continued on the image. It was confirmed by.

<Comparative Example 2>
Using a developer adjusted with toner 5, the contact pressure between the cleaning blade 1 and the photosensitive member 1 was set to 15 g / cm and a long-term running test was performed. A large number of clear streaks were continuously observed on the image.

<Manufacture of toner>
[Production of Toner 6]
(Manufacture of base toner 6)
104.4 parts of crystalline polyester resin fine particle dispersion 1, 336.1 parts of amorphous polyester resin fine particle dispersion 1, 45.4 parts of cyan colorant dispersion, and 115.3 parting agent dispersion 115.3. Part and 484.5 parts of deionized water were placed in a round stainless steel flask and thoroughly mixed and dispersed with an Ultra Turrax T50.

  Next, 0.37 parts of polyaluminum chloride was added thereto, and the dispersion operation was continued with an ultra turrax. Further, the flask was heated to 52 ° C. with stirring in an oil bath for heating. After maintaining at 52 ° C. for 3 hours, 175.0 parts of the amorphous polyester resin fine particle dispersion 1 was gradually added thereto.

  Thereafter, the pH of the system was adjusted to 8.5 with a 0.5N aqueous sodium hydroxide solution, and then the stainless steel flask was sealed, heated to 90 ° C. while continuing stirring using a magnetic seal, and maintained for 3 hours.

  After completion of the reaction, the mixture was cooled, filtered, thoroughly washed with ion exchange water, and then subjected to solid-liquid separation by Nutsche suction filtration. This was further redispersed in 3 liters of ion exchanged water at 40 ° C., and stirred and washed at 300 rpm for 15 minutes.

  This was repeated five more times. When the pH of the filtrate was 6.88, the electric conductivity was 8.4 μS / cm, and the surface tension was 7.02 Nm, No. Solid-liquid separation was performed using 5A filter paper, and then vacuum drying was performed for 12 hours to obtain base toner 6.

  The toner surface acid value of the obtained base toner 6 was measured by the method described above and found to be 22.5 mgKOH / g-TN. Further, the glass transition temperature of the base toner 6 was measured by the above-described method and found to be 54.0 ° C.

(Phenol ester addition)
In a heat-dried two-necked flask, 200 parts of base toner 6, 400 parts of phenyl acetate and 0.08 part of potassium acetate as a catalyst were placed, heated to 52 ° C. with stirring and held for 8 hours. While maintaining the temperature at 52 ° C., the pressure was gradually reduced to 25.0 Torr and maintained for 7 hours to remove the acetic acid distilled out of the system.

  After completion of the reaction, the mixture was cooled and filtered to separate the toner and unreacted phenyl acetate, and the toner was sufficiently washed with ion exchange water, and then subjected to solid-liquid separation by Nutsche suction filtration. This was further redispersed in 3 liters of ion exchanged water at 40 ° C., and stirred and washed at 300 rpm for 15 minutes.

  This was repeated five more times, and when the pH of the filtrate was 7.01, the electric conductivity was 8.8 μS / cm, and the surface tension was 7.00 Nm, No. 3 was obtained by Nutsche suction filtration. Solid-liquid separation was performed using 5A filter paper, and then vacuum drying was performed for 12 hours to obtain toner 6.

The surface phenol ester amount of the obtained toner 6 was measured by the above-described method, and found to be 4.0 × 10 ⁻⁴ mol / g-TN. The volume average particle diameter of the toner 6 was measured by the above-described measuring method and found to be 5.8 μm. Further, the average circularity of the toner 6 was measured by the above-described measuring method and found to be 0.960.

[Production of Toner 7]
(Manufacture of base toner 7)
34.8 parts of crystalline polyester resin fine particle dispersion 1, 357.9 parts of amorphous polyester resin fine particle dispersion 2, 45.4 parts of cyan colorant dispersion, and 115.3 parting agent dispersion 115.3 And 532.4 parts of deionized water were placed in a round stainless steel flask, and thoroughly mixed and dispersed with an Ultra Turrax T50.

  Next, 0.37 parts of polyaluminum chloride was added thereto, and the dispersion operation was continued with an ultra turrax. Further, the flask was heated to 52 ° C. with stirring in an oil bath for heating. After maintaining at 52 ° C. for 4 hours, 175.0 parts of amorphous polyester resin fine particle dispersion 2 was gradually added thereto.

  Thereafter, the pH of the system was adjusted to 8.5 with a 0.5N aqueous sodium hydroxide solution, and then the stainless steel flask was sealed, heated to 90 ° C. while continuing stirring using a magnetic seal, and maintained for 2 hours.

  After completion of the reaction, the mixture was cooled, filtered, thoroughly washed with ion exchange water, and then subjected to solid-liquid separation by Nutsche suction filtration. This was further redispersed in 3 liters of ion exchanged water at 40 ° C., and stirred and washed at 300 rpm for 15 minutes.

  This was repeated five more times, and when the pH of the filtrate was 6.90, the electric conductivity was 8.02 μS / cm, and the surface tension was 6.98 Nm, No. 3 was obtained by Nutsche suction filtration. Solid-liquid separation was performed using 5A filter paper, and then vacuum drying was performed for 12 hours to obtain base toner 7.

  The toner surface acid value of the obtained base toner 7 was measured by the above-described method, and found to be 8.5 mgKOH / g-TN. Further, the glass transition temperature of the base toner 7 was measured by the above-described method, and found to be 58.0 ° C.

(Phenol ester addition)
In a heat-dried two-necked flask, 200 parts of base toner 7, 400 parts of phenyl acetate and 0.08 part of potassium acetate as a catalyst were placed, heated to 56 ° C. with stirring and held for 8 hours. While maintaining the temperature at 56 ° C., the pressure was gradually reduced to 25 Torr and maintained for 7 hours to remove the acetic acid distilled out of the system.

  After completion of the reaction, the mixture was cooled and filtered to separate the toner and unreacted phenyl acetate, and the toner was sufficiently washed with ion exchange water, and then subjected to solid-liquid separation by Nutsche suction filtration. This was further redispersed in 3 liters of ion exchanged water at 40 ° C., and stirred and washed at 300 rpm for 15 minutes.

  This was repeated five more times, and when the pH of the filtrate was 7.00, the electric conductivity was 8.52 μS / cm, and the surface tension was 7.10 Nm, No. 3 was obtained by Nutsche suction filtration. Solid-liquid separation was performed using 5A filter paper, and then vacuum drying was performed for 12 hours to obtain toner 7.

When the surface phenol ester content of the obtained toner 7 was measured by the above-described method, it was 1.5 × 10 ⁻⁴ mol / g-TN. The volume average particle diameter of the toner 7 was measured by the above-described measuring method and found to be 7.2 μm. Further, when the average circularity of the toner 7 was measured by the above-described measuring method, it was 0.948.

[Production of Toner 8]
(Manufacture of base toner 8)
174.0 parts of crystalline polyester resin fine particle dispersion 1, 314.4 parts of amorphous polyester resin fine particle dispersion 3, 45.4 parts of cyan colorant dispersion, 115.3 parting agent dispersion 115.3 And 436.7 parts of deionized water were placed in a round stainless steel flask and thoroughly mixed and dispersed with an Ultra Turrax T50.

  Next, 0.37 parts of polyaluminum chloride was added thereto, and the dispersion operation was continued with an ultra turrax. Further, the flask was heated to 52 ° C. with stirring in an oil bath for heating. After maintaining at 52 ° C. for 2 hours, 175.0 parts of amorphous polyester resin fine particle dispersion 3 was gradually added thereto.

  Thereafter, the pH of the system was adjusted to 8.5 with a 0.5N aqueous sodium hydroxide solution, and then the stainless steel flask was sealed, heated to 90 ° C. while continuing stirring using a magnetic seal, and maintained for 4 hours.

  After completion of the reaction, the mixture was cooled, filtered, thoroughly washed with ion exchange water, and then subjected to solid-liquid separation by Nutsche suction filtration. This was further redispersed in 3 liters of ion exchanged water at 40 ° C., and stirred and washed at 300 rpm for 15 minutes.

  This was repeated 5 times, and when the pH of the filtrate was 6.95, the electric conductivity was 8.6 μS / cm, and the surface tension was 6.96 Nm, No. Solid-liquid separation was performed using 5A filter paper, and then vacuum drying was performed for 12 hours to obtain base toner 8.

  The toner surface acid value of the obtained base toner 8 was measured by the above-mentioned method and found to be 35.5 mgKOH / g-TN. Further, the glass transition temperature of the base toner 8 was measured by the above method and found to be 50.0 ° C.

(Phenol ester addition)
In a heat-dried two-necked flask, 200 parts of base toner 8, 400 parts of phenyl acetate and 0.08 part of potassium acetate as a catalyst were placed, heated to 48 ° C. with stirring, and held for 8 hours. While maintaining the temperature at 48 ° C., the pressure was gradually reduced to 25.0 Torr and maintained for 7 hours to remove the acetic acid distilled out of the system.

  After completion of the reaction, the mixture was cooled and filtered to separate the toner and unreacted phenyl acetate, and the toner was sufficiently washed with ion exchange water, and then subjected to solid-liquid separation by Nutsche suction filtration. This was further redispersed in 3 liters of ion exchanged water at 40 ° C., and stirred and washed at 300 rpm for 15 minutes.

  This was repeated five more times, and when the pH of the filtrate was 7.03, the electric conductivity was 8.92 μS / cm, and the surface tension was 7.10 Nm, No. 3 was obtained by Nutsche suction filtration. Solid-liquid separation was performed using 5A filter paper, and then vacuum drying was performed for 12 hours to obtain toner 8.

When the surface phenol ester content of the obtained toner 8 was measured by the above-described method, it was 6.3 × 10 ⁻⁴ mol / g-TN. The volume average particle diameter of the toner 8 was measured by the above-described measuring method and found to be 3.5 μm. Further, the average circularity of the toner 8 was measured by the above-described measuring method and found to be 0.975.

[Preparation of Amorphous Polyester Resin Fine Particle Dispersion 4]
In a heat-dried two-necked flask, 71 parts of dimethyl adipate, 184 parts of dimethyl terephthalate, 206 parts of bisphenol A ethylene oxide adduct, 30 parts of hydroquinone, 27 parts of ethylene glycol, and 0.036 parts of tetrabutoxy titanate as a catalyst Then, after introducing nitrogen gas into the container and keeping the temperature in an inert atmosphere, the temperature was raised and subjected to a copolycondensation reaction at 160 ° C. for about 10 hours, and then the temperature was raised to 220 ° C. while gradually reducing the pressure to 10 Torr and held for 8 hours. Thus, an amorphous polyester resin 4 was synthesized.

  It was 66 degreeC when the glass transition temperature of the obtained amorphous polyester resin 4 was measured using the differential scanning calorific value system (DSC) with the above-mentioned measuring method. When the molecular weight of the obtained amorphous polyester resin 4 was measured by GPC by the above-mentioned measuring method, the weight average molecular weight (Mw) was 18000. Further, the acid value of the obtained amorphous polyester resin 4 was measured and found to be 7.2 mgKOH / g.

  Next, 115 parts of this amorphous polyester resin 4, 180 parts of deionized water, and 5 parts of an anionic surfactant (Daiichi Kogyo Seiyaku Co., Ltd .: Neogen R) were mixed and heated to 120 ° C. Then, after sufficiently dispersing with a homogenizer (manufactured by IKA: Ultra Turrax T50), the dispersion treatment is carried out for 1 hour with a pressure discharge type gorin homogenizer, whereby an amorphous polyester resin fine particle dispersion 4 (resin particle concentration: 40). % By weight) was adjusted.

[Preparation of Amorphous Polyester Resin Fine Particle Dispersion 5]
In a heat-dried two-necked flask, 71 parts of dimethyl adipate, 184 parts of dimethyl terephthalate, 206 parts of bisphenol A ethylene oxide adduct, 34 parts of ethylene glycol, 22 parts of trimellitic anhydride, 4 parts of hydroquinone, 0.036 parts of butoxy titanate was added, and nitrogen gas was introduced into the container and the temperature was raised while stirring in an inert atmosphere. Then, a copolycondensation reaction was performed at 160 ° C. for about 7 hours, and then gradually increased to 10 Torr. While depressurizing, the temperature was raised to 220 ° C. and held for 4 hours. Once the pressure was returned to normal pressure, 9 parts of trimellitic anhydride was added, and the pressure was gradually reduced again to 10 Torr and maintained for 1 hour to synthesize amorphous polyester resin 5.

  It was 54 degreeC when the glass transition temperature of the obtained amorphous polyester resin 5 was measured using the differential scanning calorific value system (DSC) with the above-mentioned measuring method. When the molecular weight of the obtained amorphous polyester resin 5 was measured by GPC by the above-mentioned measuring method, the weight average molecular weight (Mw) was 7000. Moreover, it was 47.5 mgKOH / g when the acid value of the obtained amorphous polyester resin 5 was measured.

  Next, 115 parts of this amorphous polyester resin 5, 180 parts of deionized water, and 5 parts of an anionic surfactant (Daiichi Kogyo Seiyaku Co., Ltd .: Neogen R) were mixed and heated to 120 ° C. Then, after sufficiently dispersing with a homogenizer (manufactured by IKA: Ultra Tarrax T50), the dispersion treatment is carried out for 1 hour with a pressure discharge type gorin homogenizer, whereby an amorphous polyester resin fine particle dispersion 5 (resin particle concentration: 40). % By weight) was adjusted.

[Production of Toner 9]
(Manufacture of base toner 9)
104.4 parts of crystalline polyester resin fine particle dispersion 1, 336.1 parts of amorphous polyester resin fine particle dispersion 4, 45.4 parts of cyan colorant dispersion, and 115.3 parting agent dispersion 115.3. Part and 484.5 parts of deionized water were placed in a round stainless steel flask and thoroughly mixed and dispersed with an Ultra Turrax T50.

  Next, 0.37 parts of polyaluminum chloride was added thereto, and the dispersion operation was continued with an ultra turrax. Further, the flask was heated to 52 ° C. with stirring in an oil bath for heating. After maintaining at 52 ° C. for 4 hours, 175.0 parts of the amorphous polyester resin fine particle dispersion 4 was gradually added thereto.

  Thereafter, the pH of the system was adjusted to 8.5 with a 0.5N aqueous sodium hydroxide solution, and then the stainless steel flask was sealed, heated to 90 ° C. while continuing stirring using a magnetic seal, and maintained for 2 hours.

  After completion of the reaction, the mixture was cooled, filtered, thoroughly washed with ion exchange water, and then subjected to solid-liquid separation by Nutsche suction filtration. This was further redispersed in 3 liters of ion exchanged water at 40 ° C., and stirred and washed at 300 rpm for 15 minutes.

  This was repeated 5 times, and when the pH of the filtrate was 6.95, the electric conductivity was 8.6 μS / cm, and the surface tension was 6.96 Nm, No. Solid-liquid separation was performed using 5A filter paper, and then vacuum drying was performed for 12 hours to obtain a base toner 9.

When the toner surface acid value of the obtained base toner 9 was measured by the above-mentioned method, 5.8 mgKOH / g-TN. Further, the glass transition temperature of the base toner 9 was measured by the above method and found to be 60.0 ° C.

(Phenol ester addition)
In a heat-dried two-necked flask, 200 parts of base toner 9, 400 parts of phenyl acetate and 0.08 part of potassium acetate as a catalyst were placed, heated to 58.0 ° C. with stirring, and held for 8 hours. While maintaining 58 ° C., the pressure was gradually reduced to 25.0 Torr and maintained for 7 hours to remove the acetic acid distilled out of the system.

  After completion of the reaction, the mixture was cooled and filtered to separate the toner and unreacted phenyl acetate, and the toner was sufficiently washed with ion exchange water, and then subjected to solid-liquid separation by Nutsche suction filtration. This was further redispersed in 3 liters of ion exchanged water at 40 ° C., and stirred and washed at 300 rpm for 15 minutes.

  This was repeated five more times, and when the pH of the filtrate was 7.03, the electric conductivity was 8.92 μS / cm, and the surface tension was 7.10 Nm, No. 3 was obtained by Nutsche suction filtration. Solid-liquid separation was performed using 5A filter paper, and then vacuum drying was performed for 12 hours to obtain toner 9.

The surface phenol ester content of the obtained toner 9 was measured by the method described above and found to be 1.0 × 10 ⁻⁴ mol / g-TN. The volume average particle diameter of the toner 9 was measured by the above-described measuring method and found to be 7.1 μm. Further, the average circularity of the toner 9 was measured by the above-described measuring method and found to be 0.947.

[Production of Toner 10]
(Manufacture of base toner 10)
104.4 parts of crystalline polyester resin fine particle dispersion 1, 336.1 parts of amorphous polyester resin fine particle dispersion 5, 45.4 parts of cyan colorant dispersion, and 115.3 parting agent dispersion 115.3. Part and 484.5 parts of deionized water were placed in a round stainless steel flask and thoroughly mixed and dispersed with an Ultra Turrax T50.

  Next, 0.37 parts of polyaluminum chloride was added thereto, and the dispersion operation was continued with an ultra turrax. Further, the flask was heated to 52 ° C. with stirring in an oil bath for heating. After maintaining at 52 ° C. for 2 hours, 175.0 parts of the amorphous polyester resin fine particle dispersion 4 was gradually added thereto.

  Thereafter, the pH of the system was adjusted to 8.5 with a 0.5N aqueous sodium hydroxide solution, and then the stainless steel flask was sealed, heated to 90 ° C. while continuing stirring using a magnetic seal, and maintained for 2 hours.

  After completion of the reaction, the mixture was cooled, filtered, thoroughly washed with ion exchange water, and then subjected to solid-liquid separation by Nutsche suction filtration. This was further redispersed in 3 liters of ion exchanged water at 40 ° C., and stirred and washed at 300 rpm for 15 minutes.

  This was repeated 5 times, and when the pH of the filtrate was 6.95, the electric conductivity was 8.6 μS / cm, and the surface tension was 6.96 Nm, No. Solid-liquid separation was performed using 5A filter paper, and then vacuum drying was performed for 12 hours to obtain a base toner 10.

When the toner surface acid value of the obtained base toner 10 was measured by the method described above, 38 mgKOH / g-TN. Further, the glass transition temperature of the base toner 10 was measured by the above-described method and found to be 48.0 ° C.

(Phenol ester addition)
In a heat-dried two-necked flask, 200 parts of base toner 10, 400 parts of phenyl acetate and 0.08 part of potassium acetate as a catalyst were placed, heated to 46.0 ° C. with stirring, and held for 8 hours. While maintaining 46.0 ° C., the pressure was gradually reduced to 25.0 Torr and maintained for 7 hours, and acetic acid distilled off was removed out of the system.

  After completion of the reaction, the mixture was cooled and filtered to separate the toner and unreacted phenyl acetate, and the toner was sufficiently washed with ion exchange water, and then subjected to solid-liquid separation by Nutsche suction filtration. This was further redispersed in 3 liters of ion exchanged water at 40 ° C., and stirred and washed at 300 rpm for 15 minutes.

  This was repeated five more times, and when the pH of the filtrate was 7.03, the electric conductivity was 8.92 μS / cm, and the surface tension was 7.10 Nm, No. 3 was obtained by Nutsche suction filtration. Solid-liquid separation was performed using 5A filter paper, and then vacuum drying was performed for 12 hours to obtain toner 10.

The surface phenol ester content of the obtained toner 10 was measured by the method described above, and found to be 6.8 × 10 ⁻⁴ mol / g-TN. The volume average particle diameter of the toner 10 was measured by the above-described measuring method and found to be 3.5 μm. Further, the average circularity of the toner 10 was 0.974 as measured by the measurement method described above.

<Production of externally added toner and non-magnetic one-component developer>
0.21 g of hydrophobic silica (manufactured by Cabot, TS720) was added to 50 g of the manufactured toner, and blended in a sample mill to produce a nonmagnetic one-component developer composed of an externally added toner.

<Evaluation method>
[Evaluation of low-temperature fixability]
The obtained developer was filled in a developing device of a modified machine of DocuPrint C2220 (hereinafter sometimes abbreviated as “DPC2220”) manufactured by Fuji Xerox Co., Ltd., from which the fixing device was removed, and an unfixed image was collected.

The image conditions were a solid image of 40 mm × 50 mm, the toner amount was 4.5 g / m ² , and the recording paper was mirror-coated platinum paper (basis weight: 127 gsm).

  Next, using the fixing device of the DPC2220 modified so that the fixing temperature can be changed, the fixing temperature is increased at intervals of 10 ° C. between 70 ° C. and 200 ° C., and the low temperature fixing property is evaluated. did.

  Low temperature fixability is achieved by bending the fixed image with a constant load weight, measuring the maximum image defect width at that portion, and setting the fixing temperature at which the maximum defect image width is 0.2 mm as the minimum fixing temperature. It was used as an index of sex.

[Evaluation of in-flight contamination]
After performing a long-term running test for 20,000 copies using a modified DPC2220 machine with a developing device shown in FIG. 2 made by Fuji Xerox, the machine was visually evaluated for contamination.
◎: No in-flight contamination ○: Although there is some in-flight contamination, there is no problem ×: In-flight contamination

<Example 5>
The minimum fixing temperature measured by the above-described method using a non-magnetic one-component developer using toner 6 was 110 ° C. The rotation torque of the developing roll as the developer carrying member is 1.7 kgfcm.
When a long-term running test was carried out with this setting, there was no in-flight contamination at the stage of 20,000 sheets.

<Example 6>
The minimum fixing temperature measured by the above-described method using a non-magnetic one-component developer using toner 7 was 115 ° C. The rotational torque of the developing roll as the developer carrying member is 2.3 kgfcm.
When a long-term running test was carried out with this setting, there was no in-flight contamination at the stage of 20,000 sheets.

<Example 7>
The minimum fixing temperature measured by the above-described method using a non-magnetic one-component developer using toner 8 was 105 ° C. The rotation torque of the developing roll as the developer carrying member is 1.1 kgfcm.
When a long-term running test was carried out with this setting, there was no in-flight contamination at the stage of 20,000 sheets.

<Example 8>
The minimum fixing temperature measured by the above-described method using a non-magnetic one-component developer using toner 8 was 104 ° C. The rotational torque of the developing roll as the developer carrying member is 2.3 kgfcm.
When a long-term running test was carried out with this setting, there was no in-flight contamination at the stage of 20,000 sheets.

<Example 9>
The minimum fixing temperature measured by the above-described method using a non-magnetic one-component developer using toner 7 was 115 ° C. The rotation torque of the developing roll as the developer carrying member is 1.1 kgfcm.
When a long-term running test was carried out, there was no in-flight contamination at the stage of 20,000 sheets.

<Comparative Example 3>
The minimum fixing temperature measured by the above-described method using a non-magnetic one-component developer using toner 5 was 110 ° C. The rotation torque of the developing roll as the developer carrying member is 1.7 kgfcm.
When a long-term running test was carried out, there was in-flight contamination at the stage of 20,000 sheets.

<Comparative example 4>
Using a non-magnetic one-component developer using toner 9, the minimum fixing temperature measured by the method described above was 110 ° C. The rotational torque of the developing roll as the developer carrying member is 0.7 kgfcm.
When a long-term running test was carried out, there was in-flight contamination at the stage of 20,000 sheets.

<Comparative Example 5>
Using a non-magnetic one-component developer using toner 9, the minimum fixing temperature measured by the method described above was 110 ° C. The rotational torque of the developing roll as the developer carrying member is 2.7 kgfcm.
When a long-term running test was carried out, there was in-flight contamination at the stage of 20,000 sheets.

  The electrostatic charge developing toner of the present invention is particularly useful for uses such as electrophotography and electrostatic recording.

1 is a schematic diagram illustrating a configuration example of an image forming apparatus used in the present embodiment. FIG. 2 is a schematic diagram illustrating a configuration example of a developing device using the nonmagnetic one-component developer according to the present embodiment.

Explanation of symbols

  200 Image forming apparatus, 400 housing, 401a to 401d electrophotographic photosensitive member, 402a to 402d charging roll, 403 exposure apparatus, 404a to 404d developing apparatus, 405a to 405d toner cartridge, 406 driving roll, 407 tension roll, 408 backup roll, 409 Intermediate transfer belt, 410a to 410d Primary transfer roll, 411 Tray (transfer medium tray), 412 Transfer roll, 413 Secondary transfer roll, 414 Fixing roll, 415a to 415d, 416 Cleaning blade, 500 Transfer medium.

Claims (8)

  An electrostatic charge developing toner comprising an amorphous polyester resin, a crystalline polyester resin, and a colorant, and having a phenol ester structure on a toner particle surface. The electrostatic charge developing toner according to claim 1,
The range of the phenol ester amount MPh [mol / g-TN] (where TN is the toner) existing on the surface of 1 g of toner is
8.9 × 10 ⁻⁵ ≦ MPh ≦ 7.1 × 10 ⁻⁴ Formula (1)
An electrostatic charge developing toner characterized by satisfying:   An electrostatic charge image developing developer comprising the electrostatic charge developing toner according to claim 1 and a carrier. A latent image forming step of forming an electrostatic latent image on the surface of the latent image carrier;
A developing step of developing the electrostatic latent image formed on the surface of the latent image carrier with the developer according to claim 3 to form a toner image;
A transfer step of transferring the toner image formed on the surface of the latent image carrier to the surface of the transfer target;
A fixing step of thermally fixing the toner image transferred to the surface of the transfer target;
An image forming method comprising a cleaning step of cleaning the surface of the latent image carrier,
An image forming method, wherein a cleaning blade is used in the cleaning step. It contains an amorphous polyester resin, a crystalline polyester resin, and a colorant, has a phenol ester structure on the surface of the toner particles, and the amount of phenol ester MPh [mol / g-TN] (here, , TN is toner)
^{1.4 × 10 -4 ≦ MPh ≦ 6.6} × 10 -4 ····· formula (2)
A non-magnetic one-component developer comprising: an electrostatic charge developing toner. A non-magnetic one-component developer according to claim 5, comprising: a toner supply member that supplies toner onto the developer carrying member; and a layer regulating member that is in pressure contact with the developer carrying member, from the toner supply member to the developer An image forming method used in a one-component developing device that supplies a non-magnetic one-component developer to a carrier and performs development using a charged toner layer formed on the developer carrier by a pressure-contacting layer regulating member.
An image forming method, wherein a rotational torque of the developer carrying member is in a range of 1.0 kgfcm to 2.5 kgfcm. A non-crystalline polyester resin fine particle, a resin fine particle dispersion in which crystalline polyester resin fine particles are dispersed and mixed, and a colorant fine particle dispersion in which colorant fine particles are dispersed are mixed to form aggregated particles of the resin fine particles and the adsorbent fine particles. An aggregation process to form;
Adjusting the pH in the agglomeration system to stop agglomeration growth;
Heating the aggregated particles to a temperature equal to or higher than the glass transition temperature of the resin fine particles, and fusing and coalescing;
Cleaning the obtained base toner with at least water;
Drying the washed base toner;
A step of mixing the dried base toner and phenyl acetate and gradually reducing the pressure while heating at a temperature of −2 ° C. to −5 ° C. with respect to the glass transition temperature of the base toner. A process for producing an electrostatic charge developing toner, comprising adding an ester structure. A latent image forming unit that forms a latent image on the latent image carrier, a developing unit that develops the latent image using a developer for developing an electrostatic charge, and the developed toner image via an intermediate transfer member or not. An image forming apparatus including: a transfer unit that transfers the toner image on the transfer member; and a fixing unit that adds and fixes the toner image on the transfer member.
The image forming apparatus according to claim 3, wherein the developer for developing an electrostatic charge is the developer for developing an electrostatic charge according to claim 3 or the non-magnetic one-component developer according to claim 5.

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