JP6020230B2 - Toner for developing electrostatic image, developer for developing electrostatic image, toner cartridge, process cartridge, and image forming apparatus - Google Patents

Description

  The present invention relates to an electrostatic image developing toner, an electrostatic image developing developer, a toner cartridge, a process cartridge, and an image forming apparatus.

  In recent years, image forming apparatuses such as printers and copiers have been widely used, and technologies relating to various elements constituting the image forming apparatus have also been widely used. Among image forming apparatuses that employ an electrophotographic system, a photosensitive member (image holding member) is charged by using a charging device, and an electrostatic charge having a potential different from the surrounding potential on the charged photosensitive member. In many cases, a pattern to be printed is formed by forming an image. The electrostatic image formed in this way is developed with toner, and finally transferred onto a transfer material such as recording paper. Is done.

  Here, in order to provide a method for producing a negatively charged toner mainly comprising a polyester resin having a uniform surface charge state, a method for producing a negatively charged toner mainly comprising a polyester resin, wherein the mother particles are obtained by emulsification of the polyester resin. A positively charged compound holding step for holding a positively charged compound on the surface of the mother particle, and the mother particle holding the positively charged compound and the negative charge control resin particle are brought into contact with each other to form the mother particle. And a toner base particle preparation step for fixing the negative charge control resin particles to the surface of the toner. A method for producing a negatively charged toner is disclosed (for example, see Patent Document 1).

  In addition, in order to provide a liquid developer having excellent positive charge characteristics and excellent long-term dispersion stability of toner particles, toner base particles composed of an insulating liquid and a material containing a rosin resin are used as polyalkyleneimine. And a liquid developer characterized by containing toner particles whose surface has been modified (see, for example, Patent Document 2).

  In addition, in order to provide a liquid developer excellent in positive charging characteristics, in an insulating liquid, resin fine particles composed of a resin material containing a polyester resin and a rosin resin, and a polyalkyleneimine dissolved in water A chemical modification step for obtaining a dispersion in which toner particles whose surfaces are chemically modified with polyalkyleneimine are dispersed in an insulating liquid, and a heating step for heating the dispersion while stirring. A method for producing a liquid developer is disclosed (see, for example, Patent Document 3).

JP 2009-244494 A JP 2010-025971 A JP 2011-221100 A

  An object of the present invention is to provide a toner for developing an electrostatic charge image in which unevenness in image density is suppressed.

Specific means for achieving the above object are as follows.
That is, the invention according to claim 1
Polyalkyleneimine adheres to the toner surface,
The nitrogen content derived from the adhesion amount of the polyalkyleneimine adhering to the toner surface is 0.015 mass% or more and 0.06 mass% or less,
Der alkaline earth metal content is 1.0 × ¹⁰ -10 mol / g or more 0.90 × ¹⁰ -6 mol / g or less, which is detected by the ion chromatography is,
As the binder resin, a toner for developing electrostatic images you containing amorphous polyester resin.

The invention according to claim 2
The electrostatic image developing toner according to claim 1, wherein the alkaline earth metal is calcium.
The invention according to claim 3
As a colorant, a toner for electrostatic image development according to claim 1 or claim 2 containing carbon black.

The invention according to claim 4
An electrostatic charge image developing developer comprising the electrostatic charge image developing toner according to claim 1 .

The invention according to claim 5
The toner cartridge according to any one of claims 1 to 3 , wherein the toner contains at least toner, and the toner is an electrostatic charge image developing toner according to any one of claims 1 to 3 .

The invention according to claim 6
A process cartridge comprising at least a developer holder and containing the developer for developing an electrostatic image according to claim 4 .

The invention according to claim 7 provides:
A photoreceptor,
Charging means for charging the photoreceptor;
An electrostatic charge image forming means for forming an electrostatic charge image on the surface of the charged photoreceptor;
Developing means for developing the electrostatic image formed on the surface of the photoreceptor as a toner image with the developer for developing an electrostatic image according to claim 4 ;
Transfer means for transferring the toner image onto a transfer target;
Fixing means for fixing the toner image transferred onto the transfer target;
An image forming apparatus having

According to the invention which concerns on Claim 1, nitrogen content is outside the range of 0.015 mass% or more and 0.06 mass% or less, or the amount of alkaline-earth metals detected by ion chromatography is 1. An electrostatic charge image developing toner in which unevenness of image density is suppressed is provided as compared with a case where it is out of the range of 0 × 10 ⁻¹⁰ mol / g or more and 0.90 × 10 ⁻⁶ mol / g or less.

According to the invention of claim 2, alkaline earth metal as compared with the case not calcium, toner for developing electrostatic images that are suppressed in image density unevenness is provided.

According to the invention of claim 4 , the nitrogen content is outside the range of 0.015 mass% or more and 0.06 mass% or less, or the alkaline earth metal content detected by ion chromatography is 1. A developer for developing an electrostatic charge image in which unevenness of image density is suppressed is provided as compared with a case where it is out of the range of 0 × 10 ⁻¹⁰ mol / g or more and 0.90 × 10 ⁻⁶ mol / g or less.

According to the invention which concerns on Claim 5 , nitrogen content is outside the range of 0.015 mass% or more and 0.06 mass% or less, or the amount of alkaline-earth metals detected by ion chromatography is 1. Compared to the case where it is out of the range of 0 × 10 ⁻¹⁰ mol / g or more and 0.90 × 10 ⁻⁶ mol / g or less, the toner cartridge containing the electrostatic charge image developing toner in which the image density unevenness is suppressed is Provided.

According to the invention of claim 6 , the nitrogen content is outside the range of 0.015 mass% or more and 0.06 mass% or less, or the alkaline earth metal content detected by ion chromatography is 1. Handling of a developer containing a toner for developing an electrostatic charge image in which unevenness of image density is suppressed as compared with a case where it is out of the range of 0 × 10 ⁻¹⁰ mol / g or more and 0.90 × 10 ⁻⁶ mol / g or less. And adaptability to image forming apparatuses having various configurations can be improved.

According to the invention of claim 7 , the nitrogen content is outside the range of 0.015 mass% or more and 0.06 mass% or less, or the alkaline earth metal content detected by ion chromatography is 1. Compared with the case where the density is outside the range of 0 × 10 ⁻¹⁰ mol / g or more and 0.90 × 10 ⁻⁶ mol / g or less, a developer containing toner for developing an electrostatic charge image in which image density unevenness is suppressed is used An image forming apparatus is provided.

1 is a schematic configuration diagram illustrating an example of an image forming apparatus according to an exemplary embodiment. It is a schematic block diagram which shows an example of the process cartridge of this embodiment.

  Hereinafter, embodiments of an electrostatic image developing toner, an electrostatic image developing developer, a toner cartridge, a process cartridge, and an image forming apparatus according to the present invention will be described in detail.

<Toner for electrostatic image development>
The toner for developing an electrostatic charge image of the present embodiment (hereinafter sometimes referred to as the toner of the present embodiment) has a nitrogen content of 0.015% by mass or more and 0.06% by mass or less by ion chromatography. A toner whose detected amount of alkaline earth metal is 1.0 × 10 ⁻¹⁰ mol / g or more and 0.90 × 10 ⁻⁶ mol / g or less.

The nitrogen content is derived from the adhesion amount of the nitrogen-containing water-soluble substance adhering to the toner surface.
For example, a polyalkyleneimine, which is a kind of nitrogen-containing water-soluble substance, has a positive chargeability, and a toner having a polyalkyleneimine attached to the surface tends to have a positive chargeability. However, polyalkylenimine has a hygroscopic property because it has a large amount of polar groups (primary, secondary, or tertiary amine) in the molecular skeleton. Therefore, the toner with polyalkyleneimine adhering to the surface deteriorates the powder flowability not only in high temperature and high humidity environment but also in medium or low humidity environment due to the hygroscopic property of polyalkyleneimine, resulting in uneven toner supply. Image density unevenness may occur.
In this embodiment, the high temperature environment refers to an environment of 28 ° C. or higher, the high humidity environment refers to an environment of 80% RH, the medium humidity environment refers to an environment of 50% RH, and the low humidity environment refers to 15 % RH environment.

The present inventors have, when the nitrogen content in the toner is less than 0.06 mass% to 0.015 mass%, the alkaline earth metal content which are detected by ion chromatography 1.0 × 10 ^- By adjusting the adhesion amount of the nitrogen-containing water-soluble substance (especially polyalkyleneimine) and the alkaline earth metal amount so as to be ¹⁰ mol / g or more and 0.90 × 10 ⁻⁶ mol / g or less, image density is adjusted. It was found that unevenness is suppressed.
The reason why the image density unevenness is suppressed by setting the nitrogen content contained in the toner and the alkaline earth metal amount detected by ion chromatography within the above range is not clear, but is presumed as follows. .
For example, when a toner obtained by treating polyalkyleneimine on the toner surface is further treated with an alkaline earth metal, the alkaline earth metal penetrates into the network skeleton of the polyalkyleneimine and is relatively negative with respect to the amino group. It is presumed that the alkaline earth metal is adsorbed on the charged portion, whereby the polarity of the polyalkyleneimine is lowered and the hydrophobicity is increased. It is presumed that the increase in hydrophobicity of polyalkyleneimine reduces the hygroscopicity of the toner and improves the powder fluidity, thereby preventing the occurrence of uneven image density due to uneven supply of toner. .

In the present embodiment, the nitrogen content is in the range of 0.015% by mass to 0.06% by mass, preferably 0.02% by mass to 0.04% by mass.
When the nitrogen content is less than 0.015% by mass, the positive chargeability may not be ensured. On the other hand, if the nitrogen content exceeds 0.06% by mass, the hygroscopicity is excessively increased, which may cause a problem of charge reduction.

  The nitrogen content in the toner was measured by the modified Dumas method. The improved Dumas method was carried out under the conditions of a reduction furnace temperature of 600 ° C., a reaction furnace temperature of 830 ° C., a helium flow rate of 80 ml / min, and an oxygen flow rate of 450 ml / min using SUMIGRAPH NC22F, manufactured by Sumika Chemical Analysis Co., Ltd.

In the present embodiment, the amount of alkaline earth metal detected by ion chromatography is in the range of 1.0 × 10 ⁻¹⁰ mol / g or more and 0.90 × 10 ⁻⁶ mol / g or less. It is desirable that they are 00 * 10 < ^-9 > mol / g or more and 0.50 * 10 < ^-6 > mol / g or less.

  Measurement of the amount of alkaline earth metal by ion chromatography was carried out as follows. First, 0.5 g of toner and 5 g of a 10% by weight sodium dodecylbenzenesulfonate solution are weighed and stirred with respect to 100 g of ultrapure water. Dispersion is carried out for 20 minutes with an ultrasonic disperser controlled at 30 ° C. The obtained dispersion was filtered through a syringe with a filter and measured with a calibration curve sample having a known concentration.

Hereinafter, various materials constituting the toner of the exemplary embodiment will be described.
The toner of the exemplary embodiment includes toner particles containing at least a binder resin and an external additive, and may include other components as necessary.

(Binder resin)
The toner particles of the present embodiment include a binder resin. The type of the binder resin is not particularly limited, and a known crystalline resin or amorphous resin may be used. A crystalline resin and an amorphous resin may be used in combination.

-Crystalline resin-
Examples of the crystalline resin include crystalline polyester resins, polyalkylene resins, and long-chain alkyl (meth) acrylate resins. However, a sharp change in viscosity due to heating appears more, and mechanical strength and low-temperature fixability From the viewpoint of achieving both, it is desirable to use a crystalline polyester resin.

  Here, “crystallinity” in the crystalline resin means that in differential scanning calorimetry (DSC), it has a clear endothermic peak rather than a stepwise endothermic amount change. It means that the half width of the endothermic peak when measured at a speed of 10 (° C./min) is within 10 (° C.). On the other hand, a resin having a half width exceeding 10 ° C. or a resin having no clear endothermic peak means an amorphous resin (amorphous polymer).

  In addition, as the polymerizable monomer component constituting the crystalline resin, a polymerizable monomer having a linear aliphatic component rather than a polymerizable monomer having an aromatic component in order to easily form a crystal structure. The body is desirable. Furthermore, in order not to impair the crystallinity, it is desirable that the constituent component derived from the polymerizable monomer is 30 mol% or more for each single species in the polymer. In particular, when two or more kinds of polymerizable monomers are essential in a polyester resin or the like, it is desirable that each essential constituent polymerizable monomer type has the same configuration.

Hereinafter, the crystalline polyester resin will be mainly described as a representative of the crystalline resin.
The melting temperature of the crystalline polyester resin used in the present embodiment is preferably in the range of 50 ° C. or higher and 100 ° C. or lower, more preferably in the range of 55 ° C. or higher and 90 ° C. or lower, from the storage and low temperature fixability. It is further desirable that the temperature be in the range of 60 ° C or higher and 85 ° C or lower. When the melting temperature is lower than 50 ° C., toner storage properties such as blocking of stored toner and storage properties of fixed images after fixing may become difficult. Further, when the melting temperature exceeds 100 ° C., sufficient low-temperature fixability may not be obtained.
The melting temperature of the crystalline polyester resin was determined as the peak temperature of the endothermic peak obtained by the differential scanning calorimetry (DSC).

  In the present embodiment, the “crystalline polyester resin” includes not only a polymer having a 100% polyester structure as a constituent component but also a polymer (copolymer) obtained by polymerizing a component constituting a polyester and other components. means. However, in the latter case, the component other than the polyester constituting the polymer (copolymer) is 50% by mass or less.

  The crystalline polyester resin used for the toner particles of the present embodiment is synthesized from, for example, a polyvalent carboxylic acid component and a polyhydric alcohol component. In the present embodiment, a commercially available product may be used as the crystalline polyester resin, or a synthesized product may be used.

  Examples of the polyvalent carboxylic acid component include oxalic acid, succinic acid, glutaric acid, adipic acid, peric acid, azelaic acid, sebacic acid, 1,9-nonanedicarboxylic acid, 1,10-decanedicarboxylic acid, 1,12 -Aliphatic dicarboxylic acids such as dodecanedicarboxylic acid, 1,14-tetradecanedicarboxylic acid, 1,18-octadecanedicarboxylic acid; phthalic acid, isophthalic acid, terephthalic acid, naphthalene-2,6-dicarboxylic acid, malonic acid, mesaconic acid Aromatic dicarboxylic acids such as dibasic acids such as, and the like, and anhydrides and lower alkyl esters thereof are also included, but not limited thereto.

  Examples of the trivalent or higher carboxylic acid include specific aromatic carboxylic acids such as 1,2,3-benzenetricarboxylic acid, 1,2,4-benzenetricarboxylic acid, 1,2,4-naphthalenetricarboxylic acid, and the like. These anhydrides and their lower alkyl esters are exemplified. These may be used individually by 1 type and may use 2 or more types together.

  Moreover, as an acid component, the dicarboxylic acid component which has a sulfonic acid group other than the said aliphatic dicarboxylic acid and aromatic dicarboxylic acid may be contained.

  As the polyhydric alcohol component, an aliphatic diol is preferable, and a linear aliphatic diol having a main chain portion having 7 to 20 carbon atoms is more desirable. When the aliphatic diol is branched, the crystallinity of the polyester resin is lowered and the melting temperature may be lowered. Further, when the main chain portion has less than 7 carbon atoms, when the polycondensation with the aromatic dicarboxylic acid is performed, the melting temperature becomes high and low temperature fixing may be difficult. On the other hand, when the number of carbons in the main chain portion exceeds 20, it is difficult to obtain practical materials. The number of carbon atoms in the main chain portion is more preferably 14 or less.

  Specific examples of the aliphatic diol suitably used for the synthesis of the crystalline polyester used in the toner particles of the present embodiment include 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, Examples thereof include, but are not limited to, 12-dodecanediol, 1,13-tridecanediol, 1,14-tetradecanediol, 1,18-octadecanediol, 1,14-eicosandecanediol, and the like. Among these, considering availability, 1,8-octanediol, 1,9-nonanediol, and 1,10-decanediol are desirable.

  Examples of the trivalent or higher alcohol include glycerin, trimethylolethane, trimethylolpropane, pentaerythritol and the like. These may be used individually by 1 type and may use 2 or more types together.

  Among the polyhydric alcohol components, the content of the aliphatic diol is preferably 80 mol% or more, and more preferably 90 mol% or more. When the content of the aliphatic diol is less than 80 mol%, the crystallinity of the polyester resin is lowered and the melting temperature is lowered, so that toner blocking resistance, image storage stability, and low-temperature fixability may be deteriorated. .

  If necessary, a polycarboxylic acid or a polyhydric alcohol may be added at the final stage of the synthesis for the purpose of adjusting the acid value or the hydroxyl value. Examples of polycarboxylic acids include aromatic carboxylic acids such as terephthalic acid, isophthalic acid, phthalic anhydride, trimellitic anhydride, pyromellitic acid, naphthalenedicarboxylic acid; maleic anhydride, fumaric acid, succinic acid, alkenyl Aliphatic carboxylic acids such as succinic anhydride and adipic acid; alicyclic carboxylic acids such as cyclohexanedicarboxylic acid; 1,2,4-benzenetricarboxylic acid, 1,2,5-benzenetricarboxylic acid, 1,2,4- Examples thereof include aromatic carboxylic acids having at least three carboxyl groups in one molecule such as naphthalene tricarboxylic acid.

  Examples of polyhydric alcohols include aliphatic diols such as ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, butanediol, hexanediol, neopentyl glycol, glycerin; cyclohexanediol, cyclohexanedimethanol, hydrogenated bisphenol A, etc. And aromatic diols such as bisphenol A ethylene oxide adduct and bisphenol A propylene oxide adduct.

The production of the crystalline polyester resin can be carried out at a polymerization temperature of 180 ° C. or higher and 230 ° C. or lower. If necessary, the reaction system is reduced in pressure and reacted while removing water and alcohol generated during condensation. .
When the polymerizable 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 there is a polymerizable monomer having poor compatibility in the copolymerization reaction, the polymerizable monomer having poor compatibility and the polymerizable monomer and the acid or alcohol to be polycondensed are condensed in advance. And then polycondensation with the main component.

  The acid value of the crystalline polyester resin used in the present embodiment (the number of mg of KOH required to neutralize 1 g of resin) is preferably in the range of 3.0 mgKOH / g to 30.0 mgKOH / g, It is more preferably in the range of 6.0 mgKOH / g or more and 25.0 mgKOH / g or less, and further preferably in the range of 8.0 mgKOH / g or more and 20.0 mgKOH / g or less. In the present embodiment, the acid value is measured according to JIS K-0070-1992.

  When the acid value is lower than 3.0 mgKOH / g, the dispersibility in water is lowered, and thus it may be very difficult to produce emulsified particles by a wet process. Further, since stability as emulsified particles during aggregation is significantly reduced, it may be difficult to produce an efficient toner. On the other hand, when the acid value exceeds 30.0 mgKOH / g, the hygroscopicity as a toner increases and the toner may be easily affected by the environment.

  The crystalline polyester resin preferably has a weight average molecular weight (Mw) of 6,000 or more and 35,000 or less. When the molecular weight (Mw) is less than 6,000, the toner may permeate the surface of a recording medium such as paper at the time of fixing to cause fixing unevenness, or the strength of the fixed image against bending resistance may be reduced. On the other hand, when the weight average molecular weight (Mw) exceeds 35,000, the viscosity at the time of melting becomes too high, and the temperature for reaching a viscosity suitable for fixing may be increased, resulting in the deterioration of the low-temperature fixability. There is a case.

  The weight average molecular weight is measured by gel permeation chromatography (GPC). The molecular weight measurement by GPC was performed with a THF solvent using a Tosoh column / TSKgel Super HM-M (15 cm) using a Tosoh GPC / HLC-8120 as a measuring device. The weight average molecular weight and the number average molecular weight are calculated using a molecular weight calibration curve prepared from a monodisperse polystyrene standard sample from this measurement result.

  The content of the crystalline resin in the toner particles is preferably in the range of 3% by mass to 40% by mass, more preferably in the range of 4% by mass to 35% by mass, and further preferably in the range of 5% by mass or more. The range is 30% by mass or less.

  The crystalline resin containing the above crystalline polyester resin is mainly composed of a crystalline polyester resin synthesized from an aliphatic polymerizable monomer (hereinafter sometimes referred to as “crystalline aliphatic polyester resin”). 50 mass% or more) is desirable. Furthermore, in this case, the constituent ratio of the aliphatic polymerizable monomer constituting the crystalline aliphatic polyester resin is preferably 60 mol% or more, and more preferably 90 mol% or more. As the aliphatic polymerizable monomer, the above-mentioned aliphatic diols and dicarboxylic acids are preferably used.

(Amorphous resin)
As the amorphous resin in the present embodiment, known resin materials such as styrene / acrylic resin, epoxy resin, polyester resin, polyurethane resin, polyamide resin, cellulose resin, polyether resin, polyolefin resin may be used. Amorphous polyester resins are particularly desirable.

  By using an amorphous polyester resin, the compatibility with the crystalline polyester resin is improved, so that the amorphous polyester resin is also reduced in viscosity as the melting temperature of the crystalline polyester resin is lowered, and as a toner Therefore, it is advantageous for low temperature fixability. In addition, since the wettability with the crystalline polyester resin is good, the dispersibility of the crystalline polyester resin inside the toner is improved, and the exposure of the crystalline polyester resin to the toner surface is suppressed. Is suppressed. For this reason, it is also desirable from the viewpoint of improving the strength of the toner and the strength of the fixed image.

Hereinafter, the amorphous resin in the present embodiment will be described by focusing on the amorphous polyester resin.
The amorphous polyester resin desirably used in the present embodiment is obtained, for example, by condensation polymerization of polyvalent carboxylic acids and polyhydric alcohols.
Examples of polycarboxylic acids include aromatic carboxylic acids such as terephthalic acid, isophthalic acid, phthalic anhydride, trimellitic anhydride, pyromellitic acid, naphthalenedicarboxylic acid; maleic anhydride, fumaric acid, succinic acid, alkenyl Aliphatic carboxylic acids such as succinic anhydride and adipic acid; alicyclic carboxylic acids such as cyclohexanedicarboxylic acid, and the like. These polyvalent carboxylic acids may be used alone or in combination. Among these polyvalent carboxylic acids, it is desirable to use an aromatic carboxylic acid, and it is desirable to have a crosslinked structure or a branched structure in order to ensure good fixability. It is desirable to use an acid (such as trimellitic acid or its acid anhydride) in combination.

  Examples of the polyhydric alcohol in the amorphous polyester resin include aliphatic diols such as ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, butanediol, hexanediol, neopentylglycol, glycerin, etc .; cyclohexanediol, cyclohexane Examples thereof include alicyclic diols such as dimethanol and hydrogenated bisphenol A; aromatic diols such as an ethylene oxide adduct of bisphenol A and a propylene oxide adduct of bisphenol A. One or more of these polyhydric alcohols may be used. Among these polyhydric alcohols, aromatic diols and alicyclic diols are preferred, and among these, aromatic diols are more desirable. In order to secure better fixing properties, it is desirable to have a cross-linked structure or a branched structure. For this purpose, a trihydric or higher polyhydric alcohol (glycerin, trimethylolpropane, pentaerythritol) may be used in combination with the diol. Good.

  In this embodiment, it is desirable to contain alkenyl succinic acid or its anhydride as a constituent component of the amorphous polyester resin. By using an amorphous polyester resin containing alkenyl succinic acid or an anhydride thereof as a constituent component, compatibility with the crystalline resin is improved and good low-temperature fixability is obtained. Examples of alkenyl succinic acid include dodecenyl succinic acid and octyl succinic acid.

The glass transition temperature (Tg) of the amorphous polyester resin is desirably in the range of 50 ° C to 75 ° C. If Tg is lower than 50 ° C., problems may occur in terms of toner storage stability and fixed image storage stability. On the other hand, if it is higher than 75 ° C., it may not be possible to fix at a lower temperature than in the past.
The Tg of the amorphous polyester resin is more preferably 55 ° C. or higher and 65 ° C. or lower.
The glass transition temperature of the amorphous polyester resin was determined as the peak temperature of the endothermic peak obtained by the differential scanning calorimetry (DSC).

  The content of the amorphous resin in the toner particles is preferably in the range of 40% by mass to 95% by mass, more preferably in the range of 50% by mass to 90% by mass, and still more preferably 60% by mass. It is the range below 85 mass%.

The weight average molecular weight (Mw) of the amorphous polyester resin is desirably 30,000 or more and 80,000 or less. When the molecular weight (Mw) is 30,000 or more and 80,000 or less, the shape of the toner is controlled, and the potato shape is realized. Furthermore, high temperature offset resistance is obtained.
The weight average molecular weight (Mw) of the amorphous polyester resin is more preferably from 35,000 to 80,000, particularly preferably from 40,000 to 80,000.

In addition, you may perform manufacture of the said amorphous polyester resin according to the case of the said crystalline polyester resin.
As described above, the crystalline resin and the amorphous resin in the present embodiment have been described using the crystalline polyester resin and the amorphous polyester resin. However, the contents other than the production of the polyester resin are the other crystalline properties in the present embodiment. You may apply about resin and an amorphous resin.

  In this embodiment, it is desirable that the binder resin includes a crystalline polyester resin and an amorphous polyester resin having a glass transition temperature of 55 ° C. or higher and 65 ° C. or lower.

(Coloring agent)
The toner particles of this embodiment may contain a colorant. As a colorant used in this embodiment, carbon black is desirable.

  The content of the colorant in the toner particles of the present embodiment is desirably in the range of 1 part by mass to 30 parts by mass with respect to 100 parts by mass of the binder resin.

(Other additives)
In addition to the components described above, various components such as a release agent, an internal additive, a charge control agent, and organic particles may be added to the toner particles of the present embodiment as necessary.
Examples of the internal additive include metals such as ferrite, magnetite, reduced iron, cobalt, nickel, and manganese, alloys, and magnetic materials such as compounds containing these metals.

  Examples of the release agent include paraffin wax such as low molecular weight polypropylene and low molecular weight polyethylene; silicone resin; rosins; rice wax; carnauba wax; The melting temperature of these release agents is preferably 50 ° C. or higher and 100 ° C. or lower, and more preferably 60 ° C. or higher and 95 ° C. or lower. The content of the release agent in the toner is desirably 0.5% by mass or more and 15% by mass or less, and more desirably 1.0% by mass or more and 12% by mass or less. If the content of the release agent is less than 0.5% by mass, there is a risk of peeling failure particularly in oilless fixing. When the content of the release agent is more than 15% by mass, the fluidity of the toner is deteriorated and the image quality and the reliability of image formation may be deteriorated.

  Known charge control agents may be used, but azo metal complex compounds, metal complex compounds of salicylic acid, and resin type charge control agents containing polar groups may be used.

Examples of the nitrogen-containing water-soluble substance used in the present embodiment include polyalkyleneimine. Specific examples of the polyalkyleneimine used in the present embodiment include polyethyleneimine, polypropyleneimine, polybutyleneimine, and polyisopropyleneimine. Among these, polyethyleneimine is desirable because of its high nitrogen-containing density.
Further, by using a combination of an amorphous polyester resin as a binder resin and a polyalkyleneimine as a nitrogen-containing water-soluble substance, the carboxyl group of the amorphous polyester resin and the amino group of the polyalkyleneimine can be obtained. It is presumed that the polyalkyleneimine adheres firmly to the toner particle surface by forming a covalent bond (amide bond) through a chemical reaction (acid-base reaction).

  The molecular weight of the polyalkyleneimine used in this embodiment is preferably from 5,000 to 100,000, and more preferably from 10,000 to 90,000.

  Examples of the alkaline earth metal used in the present embodiment include calcium, strontium, barium and the like. Among these, calcium is desirable from the viewpoint of availability and safety. By using calcium as the alkaline earth metal, image density unevenness is further suppressed.

(Toner characteristics)
The toner of the present exemplary embodiment is preferably spherical with a shape factor SF1 in the range of 115 to 140.
As for the shape of the toner, the spherical toner is advantageous in terms of developability and transferability, but may be inferior to the indeterminate shape in terms of cleaning properties. When the toner has a shape in the above range, the transfer efficiency and image density are improved, high-quality image formation is performed, and the cleaning property of the surface of the photoreceptor is enhanced.
The shape factor SF1 is more preferably in the range of 120 to 138.

Here, the shape factor SF1 is obtained by the following equation (1).
SF1 = (ML ² / A) × (π / 4) × 100 (1)
In the above formula (1), ML represents the absolute maximum length of the toner particles, and A represents the projected area of the toner particles.

  SF1 is quantified mainly by analyzing a microscope image or a scanning electron microscope (SEM) image using an image analyzer, and is calculated as follows, for example. That is, an optical microscope image of particles scattered on the surface of the slide glass is taken into a Luzex image analyzer through a video camera, and the maximum length and projected area of 100 particles are obtained, calculated by the above equation (1), and the average value is calculated. It is obtained by seeking.

  The volume average particle size of the toner according to the exemplary embodiment is preferably in the range of 4 μm to 9 μm, more preferably in the range of 4.5 μm to 8.5 μm, and still more preferably in the range of 5 μm to 8 μm. . When the volume average particle diameter is less than 4 μm, the toner fluidity is lowered, and the chargeability of each particle tends to be lowered. Further, since the charge distribution is widened, fogging on the background, toner spillage from the developing device, and the like are likely to occur. On the other hand, if it is smaller than 4 μm, the cleaning property may be extremely difficult. If the volume average particle diameter is larger than 9 μm, the resolution decreases, so that sufficient image quality cannot be obtained, and it may be difficult to satisfy recent high image quality requirements.

  The volume average particle size is measured using a Coulter Multisizer (manufactured by Coulter Inc.) with an aperture diameter of 50 μm. In this case, the measurement is performed after the toner is dispersed in an electrolyte aqueous solution (isoton aqueous solution) and dispersed by ultrasonic waves for 30 seconds or more.

<Toner production method>
The method for producing the toner of the exemplary embodiment is not particularly limited, and the toner is manufactured by a known dry method such as a kneading / pulverizing method or a wet method such as an emulsion aggregation method or a suspension polymerization method. Among these methods, an emulsion aggregation method that can easily produce a toner having a core-shell structure is desirable. Hereinafter, a method for producing a toner by the emulsion aggregation method will be described in detail.

  In the emulsification aggregation method of the present embodiment, an emulsification step of emulsifying raw materials constituting the toner to form resin particles (emulsion particles), an aggregation step of forming aggregates of the resin particles, and a fusion step of fusing the aggregates You may have.

(Emulsification process)
For example, the resin particle dispersion may be produced by applying a shearing force to a solution obtained by mixing an aqueous medium and a binder resin with a disperser. At that time, particles may be formed by heating to lower the viscosity of the resin component. A dispersant may be used for stabilizing the dispersed resin particles. Furthermore, if the resin is oily and dissolves in a solvent with a relatively low solubility in water, the resin is dissolved in those solvents and dispersed in water together with a dispersant and a polymer electrolyte, and then heated or decompressed. By evaporating the solvent, a resin particle dispersion is produced.

Examples of the aqueous medium include water such as distilled water and ion-exchanged water; alcohols; and the like. Water is preferable.
Examples of the dispersant used in the emulsification step include water-soluble polymers such as polyvinyl alcohol, methyl cellulose, ethyl cellulose, hydroxyethyl cellulose, carboxymethyl cellulose, sodium polyacrylate, and sodium polymethacrylate; sodium dodecylbenzenesulfonate, Anionic surfactants such as sodium octadecyl sulfate, sodium oleate, sodium laurate, potassium stearate, cationic surfactants such as laurylamine acetate, stearylamine acetate, lauryltrimethylammonium chloride, amphoteric such as lauryldimethylamine oxide Ionic surfactant, polyoxyethylene alkyl ether, polyoxyethylene alkyl phenyl ether, polyoxyethylene Surfactants such as nonionic surfactants such as alkyl amines; and the like are; tricalcium phosphate, aluminum hydroxide, calcium sulfate, calcium carbonate, inorganic salts such as barium carbonate.

  Examples of the disperser used for preparing the emulsion include a homogenizer, a homomixer, a pressure kneader, an extruder, and a media disperser. As the size of the resin particles, the average particle diameter (volume average particle diameter) is desirably 1.0 μm or less, more desirably 60 nm or more and 300 nm or less, and further desirably 150 nm or more and 250 nm or less. . If it is less than 60 nm, the resin particles become stable particles in the dispersion, and thus aggregation of the resin particles may be difficult. On the other hand, if it exceeds 1.0 μm, the cohesiveness of the resin particles is improved and it becomes easy to prepare toner particles, but the particle size distribution of the toner may be widened.

  In preparing the release agent dispersion, the release agent is dispersed in water together with an ionic surfactant, a polymer electrolyte such as a polymer acid or a polymer base, and then heated to a temperature equal to or higher than the melting temperature of the release agent. Dispersion treatment is performed using a homogenizer or a pressure discharge type disperser to which a strong shearing force is applied while heating. Through the above treatment, a release agent dispersion is obtained. During the dispersion treatment, an inorganic compound such as polyaluminum chloride may be added to the dispersion. Examples of desirable inorganic compounds include polyaluminum chloride, aluminum sulfate, highly basic polyaluminum chloride (BAC), polyaluminum hydroxide, and aluminum chloride. Among these, polyaluminum chloride and aluminum sulfate are desirable. The release agent dispersion is used in the emulsion aggregation method, but the release agent dispersion may also be used when the toner is produced by suspension polymerization.

By the dispersion treatment, a release agent dispersion liquid containing release agent particles having a volume average particle diameter of 1 μm or less is obtained. In addition, the more preferable volume average particle diameter of the release agent particles is 100 nm or more and 500 nm or less.
When the volume average particle diameter is less than 100 nm, the properties of the binder resin used are affected, but generally the release agent component is hardly taken into the toner. On the other hand, if it exceeds 500 nm, the dispersion state of the release agent in the toner may be insufficient.

  For the preparation of the colorant dispersion, a known dispersion method can be used. For example, a general dispersion means such as a rotary shear type homogenizer, a ball mill having a medium, a sand mill, a dyno mill, or an optimizer can be employed. Is not to be done. The colorant is dispersed in water together with a polymer electrolyte such as an ionic surfactant, a polymer acid, or a polymer base. The volume average particle diameter of the dispersed colorant particles may be 1 μm or less, but if it is in the range of 80 nm or more and 500 nm or less, the dispersion of the colorant in the toner is preferable without impairing the cohesiveness.

(Aggregation process)
In the agglomeration step, a dispersion of resin particles, a colorant dispersion, a release agent dispersion, etc. are mixed to form a mixed solution, which is heated to agglomerate at a temperature lower than the glass transition temperature of the resin particles. Form. Aggregated particles are often formed by making the pH of the mixed solution acidic under stirring. The pH is preferably in the range of 2 to 7, and in this case, it is also effective to use a flocculant.
In the aggregation step, the release agent dispersion may be added and mixed at once with various dispersions such as a resin particle dispersion, or may be added in multiple portions.

  As the aggregating agent, a surfactant having a polarity opposite to that of the surfactant used for the dispersant, an inorganic metal salt, and a divalent or higher-valent metal complex are preferably used. In particular, the use of a metal complex is particularly desirable because the amount of the surfactant used can be reduced and the charging characteristics are improved.

As the inorganic metal salt, an aluminum salt and a polymer thereof are particularly suitable. In order to obtain a narrower particle size distribution, the valence of the inorganic metal salt is bivalent than monovalent, trivalent than bivalent, trivalent than trivalent, and tetravalent than trivalent. Inorganic metal salt polymers are more suitable.
In this embodiment, it is desirable to use a polymer of a tetravalent inorganic metal salt containing aluminum in order to obtain a narrow particle size distribution.

  Further, a toner having a structure in which the surface of the core aggregated particles is coated with a resin may be prepared by additionally adding a resin particle dispersion when the aggregated particles have a desired particle size (coating step). In this case, the release agent and the colorant are not easily exposed on the toner surface, which is desirable from the viewpoint of chargeability and developability. In the case of additional addition, a flocculant may be added or pH adjustment may be performed before additional addition.

(Fusion process)
In the fusion step, the agglomeration is stopped by raising the pH of the suspension of aggregated particles to a range of 3 to 9 under stirring conditions in accordance with the aggregation step, and the glass transition temperature of the resin is higher than the glass transition temperature. The aggregated particles are fused by heating at a temperature. Moreover, when it coat | covers with the said resin, this resin is also united and a core aggregated particle is coat | covered. The heating time may be performed to the extent that fusion is performed, and may be performed for about 0.5 hour to 10 hours.

Cool after fusion to obtain fused particles. Further, in the cooling step, crystallization may be promoted by reducing the cooling rate in the vicinity of the glass transition temperature (range of glass transition temperature ± 10 ° C.) of the resin, so-called slow cooling.
The fused particles obtained by fusing are made into toner particles through a solid-liquid separation process such as filtration and, if necessary, a washing process and a drying process.

In order to adjust the nitrogen content in the toner to 0.015 mass% or more and 0.06 mass% or less, a nitrogen-containing water-soluble substance such as polyalkyleneimine is attached to the surface of the toner particles obtained as described above. It is desirable to make it.
In order for the amount of alkaline earth metal detected from the toner of this embodiment by ion chromatography to be from 1.0 × 10 ⁻¹⁰ mol / g to 0.90 × 10 ⁻⁶ mol / g, It is desirable to attach an alkaline earth metal to the surface of the toner particles thus obtained.
The order of attaching the nitrogen-containing water-soluble substance such as polyalkyleneimine and the alkaline earth metal to the toner particle surface is not particularly limited, but the nitrogen-containing water-soluble substance such as polyalkyleneimine may be attached first. It is desirable from the viewpoint of the deposition efficiency of the polyalkyleneimine.

  For example, the toner particles obtained through the solid-liquid separation step are redispersed in an aqueous medium, and a nitrogen-containing water-soluble substance is added to the surface of the toner particles by adding a nitrogen-containing water-soluble substance to the dispersion in which the toner particles are dispersed. Adhere to. The toner particles may be redispersed in an aqueous solution containing a nitrogen-containing water-soluble substance. Examples of the aqueous medium used for redispersion include water such as distilled water and ion exchange water; alcohols and the like, and water is preferable.

  Next, by adding an alkaline earth metal compound to the dispersion in which the toner particles are dispersed, the alkaline earth metal adheres to the surface of the toner particles to which the nitrogen-containing water-soluble substance is adhered. Examples of alkaline earth metal compounds include chlorides and hydroxides. Among these, calcium chloride is desirable.

To the obtained toner particles, inorganic oxides such as silica, titania, and aluminum oxide are added and adhered as external additives for the purpose of charge adjustment, fluidity provision, charge exchangeability and the like. These can be performed by, for example, a V-type blender, a Henschel mixer, a Redige mixer, or the like, and may be attached in stages. The addition amount of the external additive is preferably in the range of 0.1 to 5 parts by mass, more preferably in the range of 0.3 to 2 parts by mass with respect to 100 parts by mass of the toner particles.
Further, if necessary, coarse particles of toner may be removed after external addition using an ultrasonic sieving machine, a vibration sieving machine, a wind sieving machine, or the like.

  In addition to the external additives described above, other components (particles) such as a charge control agent, organic particles, a lubricant, and an abrasive may be added.

<Developer for developing electrostatic image>
The developer for developing an electrostatic image of the present embodiment (hereinafter sometimes referred to as the developer of the present embodiment) is a one-component developer including the toner of the present embodiment, or a carrier and the toner of the present embodiment. Any of two-component developers containing When used as a two-component developer, it is used by mixing with a carrier. Hereinafter, the case where it is a two-component developer will be described.

  The carrier that can be used in the two-component developer is not particularly limited, and a known carrier is used. Examples thereof include magnetic metals such as iron oxide, nickel and cobalt, magnetic oxides such as ferrite and magnetite, resin-coated carriers having a resin coating layer on the surface of the core material, and magnetic dispersion carriers. Further, a resin-dispersed carrier in which a conductive material or the like is dispersed in a matrix resin may be used.

  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 include acid copolymers, straight silicone resins composed of organosiloxane bonds or modified products thereof, fluororesins, polyesters, polycarbonates, phenol resins, epoxy resins, (meth) acrylic resins, dialkylaminoalkyl (meth) acrylic resins, etc. However, it is not limited to these. In order to obtain a positive charge, it is desirable to use a silicone resin.

  Examples of the conductive material include metals such as gold, silver, and copper, carbon black, titanium oxide, zinc oxide, barium sulfate, aluminum borate, potassium titanate, and tin oxide. However, the conductive material is not limited thereto. Absent.

  Examples of the core material of the carrier include magnetic metals such as iron, nickel, and cobalt, magnetic oxides such as ferrite and magnetite, and glass beads. However, in order to use the carrier for the magnetic brush method, it is a magnetic material. It is preferable. The volume average particle size of the core material of the carrier is generally in the range of 10 μm to 500 μm, and preferably in the range of 30 μm to 100 μm.

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

  Specific resin coating methods include an immersion method in which the carrier core material is immersed in the coating layer forming solution, a spray method in which the coating layer forming solution is sprayed onto the surface of the carrier core material, and the carrier core material is fluidized air. A fluidized bed method in which the coating layer forming solution is sprayed in a state of being suspended by the above, a kneader coater method in which the carrier core material and the coating layer forming solution are mixed in a kneader coater, and the solvent is removed.

  The mixing ratio (mass ratio) of the toner of this embodiment and the carrier in the two-component developer is preferably in the range of toner: carrier = 1: 100 or more and 30: 100 or less, and 3: 100 or more and 20 or more. : More preferably in the range of about 100 or less.

<Image forming apparatus>
Next, the image forming apparatus of this embodiment using the toner of this embodiment will be described.
The image forming apparatus according to the present embodiment includes a photosensitive member, a charging unit that charges the photosensitive member, an electrostatic charge image forming unit that forms an electrostatic charge image on the charged surface of the photosensitive member, and a surface of the photosensitive member. A developing unit that develops the formed electrostatic image as a toner image with the developer of the present embodiment, a transfer unit that transfers the toner image onto the transfer target, and a toner image that is transferred onto the transfer target. And fixing means for fixing.

In this image forming apparatus, for example, the part including the developing unit may have a cartridge structure (process cartridge) that can be attached to and detached from the image forming apparatus main body. As the process cartridge, a developer holding body is used. The process cartridge of this embodiment that is provided at least and contains the developer of this embodiment is preferably used.
Hereinafter, although an example of the image forming apparatus of this embodiment is shown, it is not necessarily limited to this. The main parts shown in the figure will be described, and the description of the other parts will be omitted.

  FIG. 1 is a schematic configuration diagram showing a four-tandem color image forming apparatus. The image forming apparatus shown in FIG. 1 is a first to first electrophotographic method that outputs yellow (Y), magenta (M), cyan (C), and black (K) images based on color-separated image data. Fourth image forming units 10Y, 10M, 10C, and 10K (image forming means) are provided. These image forming units (hereinafter sometimes simply referred to as “units”) 10Y, 10M, 10C, and 10K are arranged in parallel at a predetermined distance from each other in the horizontal direction. The units 10Y, 10M, 10C, and 10K may be process cartridges that are detachable from the main body of the image forming apparatus.

Above each of the units 10Y, 10M, 10C, and 10K, an intermediate transfer belt 20 as an intermediate transfer member is extended through each unit. The intermediate transfer belt 20 is provided by being wound around a driving roller 22 and a support roller 24 that are in contact with the inner surface of the intermediate transfer belt 20 that are spaced apart from each other from the left to the right in the drawing. The vehicle travels in the direction toward the unit 10K. A force is applied to the support roller 24 in a direction away from the drive roller 22 by a spring or the like (not shown), and tension is applied to the intermediate transfer belt 20 wound around the both. Further, an intermediate transfer member cleaning device 30 is provided on the side of the image carrier of the intermediate transfer belt 20 so as to face the driving roller 22.
Further, each of the developing devices (developing means) 4Y, 4M, 4C, and 4K of the units 10Y, 10M, 10C, and 10K has yellow, magenta, cyan, and black contained in the toner cartridges 8Y, 8M, 8C, and 8K. The four colors of toner are supplied.

  Since the first to fourth units 10Y, 10M, 10C, and 10K described above have the same configuration, here, the first image that forms the yellow image disposed on the upstream side in the intermediate transfer belt traveling direction is formed. The unit 10Y will be described as a representative. Note that the second to fourth components are denoted by reference numerals with magenta (M), cyan (C), and black (K) instead of yellow (Y) in the same parts as the first unit 10Y. Description of the units 10M, 10C, and 10K will be omitted.

The first unit 10Y includes a photoreceptor 1Y that functions as an image holding member. Around the photosensitive member 1Y, a charging roller 2Y for charging the surface of the photosensitive member 1Y to a predetermined potential, and the charged surface is exposed by a laser beam 3Y based on the color-separated image signal to form an electrostatic charge image. An exposure device (electrostatic image forming means) 3 for forming, a developing device (developing means) 4Y for supplying the charged toner to the electrostatic image and developing the electrostatic image, and transferring the developed toner image onto the intermediate transfer belt 20 A primary transfer roller 5Y (primary transfer unit) that performs the transfer and a photoconductor cleaning device (cleaning unit) 6Y that removes toner remaining on the surface of the photoconductor 1Y after the primary transfer are sequentially arranged.
The primary transfer roller 5Y is disposed inside the intermediate transfer belt 20, and is provided at a position facing the photoreceptor 1Y. Further, a bias power source (not shown) for applying a primary transfer bias is connected to each of the primary transfer rollers 5Y, 5M, 5C, and 5K. Each bias power source varies the transfer bias applied to each primary transfer roller under the control of a control unit (not shown).

Hereinafter, an operation of forming a yellow image in the first unit 10Y will be described. First, prior to the operation, the surface of the photoreceptor 1Y is charged by the charging roller 2Y.
The photoreceptor 1Y is formed by laminating a photosensitive layer on a conductive substrate (volume resistivity at 20 ° C .: 1 × 10 ⁻⁶ Ωcm or less). This photosensitive layer usually has a high resistance (a resistance equivalent to that of a general resin), but has a property that the specific resistance of the portion irradiated with the laser beam changes when irradiated with the laser beam 3Y. Therefore, a laser beam 3Y is output to the surface of the charged photoreceptor 1Y via the exposure device 3 in accordance with yellow image data sent from a control unit (not shown). The laser beam 3Y is applied to the photosensitive layer on the surface of the photoreceptor 1Y, whereby an electrostatic charge image of a yellow print pattern is formed on the surface of the photoreceptor 1Y.

The electrostatic charge image is an image formed on the surface of the photoreceptor 1Y by charging, and the specific resistance of the irradiated portion of the photosensitive layer is lowered by the laser beam 3Y, and the charged charge on the surface of the photoreceptor 1Y flows. On the other hand, this is a so-called negative latent image formed by the charge remaining in the portion not irradiated with the laser beam 3Y.
The electrostatic charge image formed on the photoreceptor 1Y in this way is rotated to a predetermined development position as the photoreceptor 1Y travels. At this development position, the electrostatic charge image on the photoreceptor 1Y is visualized (developed image) by the developing device 4Y.

In the developing device 4Y, for example, an electrostatic charge image developer containing at least yellow toner and a carrier is accommodated. The yellow toner is triboelectrically charged by being stirred inside the developing device 4Y and is held on a developer roll (developer holder). As the surface of the photoreceptor 1Y passes through the developing device 4Y, yellow toner adheres electrostatically on the surface of the photoreceptor 1Y and is developed with the yellow toner.
From the viewpoint of development efficiency, image graininess, gradation reproducibility, and the like, a bias potential (development bias) in which an AC component is superimposed on a DC component may be applied to the developer holder.
The photoreceptor 1Y on which the yellow toner image is formed continues to run at a predetermined speed, and the toner image developed on the photoreceptor 1Y is conveyed to a predetermined primary transfer position.

When the yellow toner image on the photoreceptor 1Y is conveyed to the primary transfer position, a primary transfer bias is applied to the primary transfer roller 5Y, and electrostatic force directed from the photoreceptor 1Y to the primary transfer roller 5Y is applied to the toner image. As a result, the toner image on the photoreceptor 1 </ b> Y is transferred onto the intermediate transfer belt 20.
On the other hand, the toner remaining on the photoreceptor 1Y is removed and collected by the cleaning device 6Y.

Further, the primary transfer bias applied to the primary transfer rollers 5M, 5C, and 5K after the second unit 10M is also controlled according to the first unit.
Thus, the intermediate transfer belt 20 onto which the yellow toner image has been transferred by the first unit 10Y is sequentially conveyed through the second to fourth units 10M, 10C, and 10K, and the toner images of the respective colors are superimposed and transferred in a multiple manner. The

  The intermediate transfer belt 20 onto which the four color toner images have been transferred through the first to fourth units is arranged on the image transfer surface side of the intermediate transfer belt 20, the support roller 24 in contact with the inner surface of the intermediate transfer belt 20. The secondary transfer roller (secondary transfer means) 26 is connected to a secondary transfer portion. On the other hand, the recording paper (transfer object) P is fed at a predetermined timing to the gap where the secondary transfer roller 26 and the intermediate transfer belt 20 are pressed against each other via the supply mechanism, and the secondary transfer bias is supported. The toner image on the intermediate transfer belt 20 is transferred to the recording paper P by being applied to the roller 24. Note that the secondary transfer bias at this time is determined according to the resistance detected by a resistance detecting means (not shown) for detecting the resistance of the secondary transfer portion, and is voltage-controlled.

  Thereafter, the recording paper P is fed to the pressure contact portion (nip portion) of the pair of fixing rolls in the fixing device (roll-type fixing means) 28, the toner image is heated, and the color-superposed toner image is melted to record the recording paper. Fixed onto P.

  Examples of the transfer target to which the toner image is transferred include plain paper and OHP sheet used for electrophotographic copying machines, printers, and the like.

The recording paper P on which the color image has been fixed is carried out toward the discharge unit, and a series of color image forming operations is completed.
The image forming apparatus exemplified above is configured to transfer the toner image onto the recording paper P via the intermediate transfer belt 20, but the present invention is not limited to this configuration, and the toner image is directly transferred from the photoconductor. It may be a structure that is transferred to a recording sheet.

<Process cartridge, toner cartridge>
FIG. 2 is a schematic configuration diagram showing a preferred example embodiment of a process cartridge containing the developer according to the present embodiment. The process cartridge 200 combines the developing device 111 with the photosensitive member 107, the charging roller 108, the photosensitive member cleaning device 113, the opening 118 for exposure, and the opening 117 for static elimination exposure using the mounting rail 116. , And integrated. In FIG. 2, reference numeral 300 denotes a transfer target.
The process cartridge 200 is detachable from an image forming apparatus main body including a transfer device 112, a fixing device 115, and other components (not shown). It forms a forming apparatus.

  The process cartridge 200 shown in FIG. 2 includes a photosensitive member 107, a charging device 108, a developing device 111, a cleaning device 113, an opening 118 for exposure, and an opening 117 for static elimination exposure. The devices may be selectively combined. In the process cartridge of the present embodiment, in addition to the developing device 111, the photosensitive member 107, the charging device 108, the cleaning device (cleaning means) 113, the opening 118 for exposure, and the opening 117 for static elimination exposure. You may provide at least 1 sort (s) selected from the group comprised from these.

  Next, the toner cartridge of this embodiment will be described. The toner cartridge according to the exemplary embodiment is detachably mounted on the image forming apparatus, and at least the toner cartridge that stores toner to be supplied to the developing unit provided in the image forming apparatus is described above. The toner of this embodiment is used. It should be noted that at least the toner may be stored in the toner cartridge of the present embodiment, and for example, a developer may be stored depending on the mechanism of the image forming apparatus.

  Accordingly, in the image forming apparatus having a configuration in which the toner cartridge can be attached and detached, the toner of the present embodiment is easily supplied to the developing device by using the toner cartridge containing the toner of the present embodiment.

  The image forming apparatus shown in FIG. 1 is an image forming apparatus having a configuration in which the toner cartridges 8Y, 8M, 8C, and 8K can be attached and detached, and the developing devices 4Y, 4M, 4C, and 4K are respectively the developing devices ( And a toner supply pipe (not shown). Further, when the toner stored in the toner cartridge becomes low, the toner cartridge is replaced.

  As the toner cartridge, any known cartridge such as polystyrene, acrylic resin, polystyrene-acrylic copolymer, ABS resin, polycarbonate resin, polypropylene resin, polyethylene resin, polyester resin, acrylonitrile resin, or PET resin may be used. In view of strength, workability, stability, etc., more preferably, polystyrene, acrylic resin, polystyrene-acrylic copolymer, ABS resin, and polycarbonate resin are used. Moreover, you may use structural materials, such as a well-known metal material, paper, and a nonwoven fabric.

  The shape of the toner cartridge may be any shape such as a cylindrical shape, a columnar shape, a box shape, a bottle shape, a composite shape of these shapes, or other shapes. The selection is made from the viewpoint of the internal layout and replacement / mountability of the image forming apparatus and the supply of replenishing toner. The arrangement of the cartridges in the image forming apparatus is selected from the viewpoints of the internal layout of the image forming apparatus, such as vertical placement and horizontal placement, replacement / mountability, and supply capability of replenishment toner. Due to the high integration of the layout accompanying the downsizing of the image forming apparatus, the cartridge shape is suitable for the cylindrical shape, the columnar shape, or the combined shape of the cylindrical shape and the box shape. However, it is not limited to these.

  Hereinafter, although an Example and a comparative example are given and this embodiment is described in detail in detail, this embodiment is not limited to the following examples. In the following description, “part” represents “part by mass” and “%” represents “% by mass” unless otherwise specified.

[Example 1]
<Synthesis of amorphous polyester resin>
-Bisphenol A ethylene oxide 2.2 mol adduct: 40 mol%
-Bisphenol A propylene oxide 2.2 mol adduct: 60 mol%
・ Terephthalic acid: 47 mol%
・ Fumaric acid: 40 mol%
-Dodecenyl succinic anhydride: 15 mol%
-Trimellitic anhydride: 3 mol%

In a reaction vessel equipped with a stirrer, a thermometer, a condenser, and a nitrogen gas inlet tube, 0% of the above monomer components other than fumaric acid and trimellitic anhydride and tin dioctanoate with respect to 100 parts in total of the above monomer components. .25 parts were added. After reacting at 235 ° C. for 6 hours under a nitrogen gas stream, the temperature was lowered to 200 ° C., and the fumaric acid and trimellitic anhydride were added and reacted for 1 hour. The temperature was further raised to 220 ° C. over 4 hours, and polymerization was performed under a pressure of 10 kPa until a desired molecular weight was obtained, thereby obtaining a light yellow transparent amorphous polyester resin.
The obtained amorphous polyester resin has a glass transition temperature Tg by DSC of 59 ° C., a mass average molecular weight Mw by GPC of 25,000, a number average molecular weight Mn of 7,000, a softening temperature by a flow tester of 107 ° C., an acid The value AV was 13 mg KOH / g.

<Preparation of amorphous polyester resin dispersion>
While maintaining a jacketed 3 liter reaction tank (manufactured by Tokyo Rika Kikai Co., Ltd .: BJ-30N) equipped with a condenser, a thermometer, a water dropping device, and an anchor wing at 40 ° C. in a water circulation thermostat, the reaction tank Into this, a mixed solvent of 160 parts of ethyl acetate and 100 parts of isopropyl alcohol is added, and 300 parts of the above amorphous polyester resin is added thereto, stirred at 150 rpm using a three-one motor, and dissolved to obtain an oil phase. It was. To this stirred oil phase, 14 parts of a 10% aqueous ammonia solution was added dropwise for 5 minutes, mixed for 10 minutes, and 900 parts of ion-exchanged water was further added dropwise at a rate of 7 parts per minute to cause phase inversion. Thus, an emulsion was obtained.
Immediately, 800 parts of the obtained emulsion and 700 parts of ion-exchanged water were put into a 2-liter eggplant flask and set in an evaporator (Tokyo Rika Kikai Co., Ltd.) equipped with a vacuum control unit via a trap ball. While rotating the eggplant flask, the mixture was heated in a hot water bath at 60 ° C., and the solvent was removed by reducing the pressure to 7 kPa while paying attention to bumping. When the solvent recovery amount reached 1,100 parts, the pressure was returned to normal pressure, and the eggplant flask was cooled with water to obtain a dispersion. There was no solvent odor in the obtained dispersion. The volume average particle diameter D50 of the resin particles in this dispersion was 130 nm. In the following, the volume average particle diameter D50 is an average value of three measured values excluding a maximum value and a minimum value among five times measured with a microtrack.
Thereafter, ion exchange water was added to prepare a solid content concentration of 20%, and this was used as an amorphous polyester resin dispersion.

<Preparation of release agent dispersion>
・ Hydrocarbon wax (Nippon Seiki Co., Ltd., trade name: FNP0080, melting temperature = 80 ° C.): 270 parts ・ Anionic surfactant (Daiichi Kogyo Seiyaku Co., Ltd., Neogen RK, active ingredient amount) : 60%): 13.5 parts (as active ingredient, 3.0% with respect to the release agent)
-Ion-exchanged water: 21.6 parts The above components were mixed, and the release agent was dissolved at a temperature of the internal solution of 120 ° C with a pressure discharge type homogenizer (Gorin homogenizer manufactured by Gorin), and then at a dispersion pressure of 5 MPa for 120 minutes. Subsequently, the dispersion treatment was carried out at 40 MPa for 360 minutes, followed by cooling to obtain a release agent dispersion. The volume average particle diameter D50 of the particles in this release agent dispersion is 225 nm. Thereafter, ion exchange water was added to adjust the solid content concentration to 20.0%.

<Preparation of black pigment dispersion>
Carbon black (Cabot, Regal 330): 250 parts Anionic surfactant (Daiichi Kogyo Seiyaku, Neogen SC): 33 parts (60% active ingredient, 8% based on colorant)
・ Ion-exchanged water: 750 parts Ion-exchanged water and 280 parts of ion-exchanged water in a stainless steel container whose liquid level is about 1/3 of the height of the container when all of the above components are added. After adding 33 parts of the agent and sufficiently dissolving the surfactant, all of the pigment was added, and the mixture was stirred using a stirrer until there was no wet pigment, and was sufficiently degassed. After defoaming, the remaining ion-exchanged water was added, and the mixture was dispersed for 10 minutes at 5000 revolutions using a homogenizer (manufactured by IKA, Ultra Tarrax T50). After defoaming, the mixture was dispersed again at 6000 rpm for 10 minutes using a homogenizer, and then defoamed by stirring for one day with a stirrer. Subsequently, the dispersion liquid was dispersed at a pressure of 240 MPa using a high-pressure impact disperser ultimateizer (manufactured by Sugino Machine Co., Ltd., HJP30006). The dispersion was equivalent to 25 passes in terms of the total charge and the processing capacity of the apparatus. The resulting dispersion was allowed to stand for 72 hours to remove precipitates, and ion exchange water was added to adjust the solid content concentration to 15%. The volume average particle diameter D50 of the particles in this black pigment dispersion was 135 nm.

<Synthesis of crystalline polyester resin>
1,10-dodecanedioic acid: 50 mol%
・ 1,9-nonanediol: 50 mol%
After the monomer component is put into a reaction vessel equipped with a stirrer, thermometer, condenser and nitrogen gas introduction tube, and the reaction vessel is replaced with dry nitrogen gas, titanium tetrabutoxide (reagent) is added to 100 parts of the monomer component. In contrast, 0.25 parts were added. After stirring and reacting at 170 ° C. for 3 hours under a nitrogen gas stream, the temperature was further raised to 210 ° C. over 1 hour, the pressure inside the reaction vessel was reduced to 3 kPa, and the stirring reaction was performed for 13 hours under reduced pressure to produce crystals. A functional polyester resin was obtained.
The obtained crystalline polyester resin had a melting temperature by DSC of 73.6 ° C., a mass average molecular weight Mw by GPC of 25,000, a number average molecular weight Mn of 10,500, and an acid value AV of 10.1 mgKOH / g. It was.

<Preparation of crystalline polyester resin dispersion>
A jacketed 3 liter reactor (Tokyo Rika Kikai Co., Ltd .: BJ-30N) equipped with a condenser, thermometer, water dripping device, anchor blade, 300 parts of the crystalline polyester resin and 160 parts of methyl ethyl ketone (solvent) And 100 parts of isopropyl alcohol (solvent) were added, and the resin was dissolved while stirring and mixing at 100 rpm while maintaining the temperature at 70 ° C. in a water circulating thermostat (dissolution preparation step).
Thereafter, the stirring speed was set to 150 rpm, the water circulating thermostat was set to 66 ° C., 17 parts of 10% ammonia water (reagent) was added over 10 minutes, and then 7 parts / ion of ion-exchanged water kept at 66 ° C. A total of 900 parts was dropped at a rate of minutes to invert the phase to obtain an emulsion.
Immediately, 800 parts of the obtained emulsion and 700 parts of ion-exchanged water were put into a 2-liter eggplant flask and set in an evaporator (Tokyo Rika Kikai Co., Ltd.) equipped with a vacuum control unit via a trap ball. While rotating the eggplant flask, the mixture was heated in a hot water bath at 60 ° C., and the solvent was removed by reducing the pressure to 7 kPa while paying attention to bumping. When the solvent recovery amount reached 1,100 parts, the pressure was returned to normal pressure, and the eggplant flask was cooled with water to obtain a dispersion. There was no solvent odor in the obtained dispersion. The volume average particle diameter D50 of the resin particles in this dispersion was 130 nm. Thereafter, ion exchange water was added to prepare a solid content concentration of 20%, and this was used as a crystalline polyester resin dispersion.

<Preparation of toner>
Amorphous polyester resin dispersion: 700 parts Black pigment dispersion: 133 parts Release agent dispersion: 100 parts Crystalline polyester resin dispersion: 50 parts Ion exchange water: 350 parts Anionic surface activity Agent (Dowfax 2A1 manufactured by Dow Chemical Company): 2.9 parts

The above components were put into a 3 liter reaction vessel equipped with a thermometer, pH meter, and stirrer, and at a temperature of 25 ° C., 1.0% nitric acid was added to adjust the pH to 3.0, and then a homogenizer (IKA Japan). 130 parts of the prepared aluminum sulfate aqueous solution was added and dispersed for 6 minutes while dispersing at 5,000 rpm with a product manufactured by: Ultratarax T50.
Thereafter, a stirrer and a mantle heater are installed in the reaction vessel, and the temperature increase rate is 0.2 ° C./min up to a temperature of 40 ° C. while adjusting the rotation speed of the stirrer so that the slurry is sufficiently stirred. After exceeding the temperature, the temperature was increased at a temperature increase rate of 0.05 ° C./min, and the particle size was measured every 10 minutes with Multisizer II (aperture diameter: 50 μm, manufactured by Coulter). When the volume average particle diameter reached 5.0 μm, the temperature was maintained, and 50 parts of an amorphous polyester resin dispersion was added over 5 minutes.
After maintaining for 30 minutes, the pH was adjusted to 9.0 with 1% aqueous sodium hydroxide solution. Thereafter, the temperature was raised to 90 ° C. at a rate of temperature rise of 1 ° C./min while maintaining the temperature at 98 ° C. while adjusting the pH to 9.0 at every 5 ° C. in the same manner. When the particle shape and surface properties were observed with an optical microscope and a scanning electron microscope (FE-SEM), coalescence of the particles was confirmed at 10.0 hours, and the container was cooled to 30 ° C. for 5 minutes with cooling water. And cooled.
The cooled slurry was passed through a nylon mesh having a mesh size of 15 μm to remove coarse powder, and the toner slurry that passed through the mesh was filtered under reduced pressure with an aspirator. The toner particles remaining on the filter paper were finely pulverized by hand, put into ion exchange water 10 times the amount of toner particles at a temperature of 30 ° C., and mixed with stirring for 30 minutes.

  A 10% aqueous solution of polyethyleneimine was added to the washed toner slurry so that polyethyleneimine was 0.1% with respect to the toner particle weight, and the mixture was stirred for 30 minutes. The slurry was filtered under reduced pressure with an aspirator, and the toner particles remaining on the filter paper were finely pulverized by hand and poured into ion exchange water at a temperature of 30 ° C. and 5 times the amount of toner particles, and mixed with stirring for 30 minutes. The toner particles remaining on the filter paper were again filtered under reduced pressure with an aspirator, and finely crushed by hand. The toner particles were poured into ion-exchanged water 10 times the amount of toner particles at a temperature of 30 ° C. to form a slurry. A 1% aqueous solution of calcium chloride was added so that the amount of calcium chloride was 0.5% with respect to the toner particle weight, and the mixture was further stirred and mixed for 30 minutes. Subsequently, it was filtered under reduced pressure with an aspirator, and the toner particles remaining on the filter paper were finely crushed by hand, poured into ion-exchanged water 10 times the amount of toner particles at a temperature of 30 ° C., stirred and mixed for 30 minutes, and then again with an aspirator. The filtrate was filtered under reduced pressure, and the electrical conductivity of the filtrate was measured. This operation was repeated until the electric conductivity of the filtrate reached 10 μS / cm or less, and the toner particles were washed. The obtained toner was vacuum-dried to obtain a dry toner.

Through the above-described steps, toner particles 1 were obtained. The obtained toner particles 1 had a nitrogen content of 0.04% by mass, and the amount of alkaline earth metal detected by ion chromatography was 1.00 × 10 ⁻⁸ mol / g. To 100 parts, 1.0 part of hydrophobic silica (manufactured by Nippon Aerosil Co., Ltd., RY200S) was added and mixed and blended at 13,000 rpm for 30 seconds using a sample mill. Thereafter, the mixture was sieved with a vibration sieve having an opening of 45 μm to obtain a black toner (toner 1).
The obtained black toner had a volume average particle diameter D50 of 6.0 μm.

<Creation of carrier>
Ferrite particles (volume average particle size: 35 μm): 100 parts Toluene: 14 parts Silicone resin (Toray Dow Corning Silicone, SR2411): 2.0 parts Carbon black (trade name: VXC-72, Cabot 0.12 part: volume resistivity: 100 Ωcm or less

  First, carbon black was diluted in toluene and added to a silicone resin and dispersed with a sand mill to prepare a coating layer forming solution. Next, this coating layer forming liquid and ferrite particles were put into a vacuum degassing type kneader and stirred at a temperature of 60 ° C. for 30 minutes, and then the pressure was reduced and toluene was distilled off to form a resin coating layer to obtain a carrier. .

<Production of developer>
A toner (36 parts) and a carrier (414 parts) were put in a 2 liter V blender, stirred for 20 minutes, and then sieved at 212 μm to prepare a developer.

-Image density unevenness-
The developer prepared as described above is set on a machine prepared by Fuji Xerox DocuCenterColor450CP so that it can be developed with positively charged toner, and high temperature and high humidity (28 ° C 85% RH), low temperature and low humidity (10 ° C 15% RH) ) After conditioning overnight in each environment, output 10,000 images with an image density of 2.5% in the same environment, then output an image with an image density of 80%, and use the X-rite 938 The image density at five locations was measured, and the average image density and standard deviation were calculated. The obtained results are shown in Table 1.
An image density of 1.40 or more was considered good, and a standard deviation of 0.3 or less was considered good.

[Example 2]
Toner particles 2 were obtained in the same procedure except that in the polyethyleneimine treatment of Example 1, a 10% aqueous solution of polyethyleneimine was changed to 0.05% of polyethyleneimine with respect to the toner particle weight.
The obtained toner particles 2 had a nitrogen content of 0.017%, and the amount of alkaline earth metal detected by ion chromatography was 1.13 × 10 ⁻⁸ mol / g.
Toner 2 and developer 2 were prepared and evaluated in the same manner as in Example 1 except that toner particle 2 was used instead of toner particle 1. The obtained results are shown in Table 1.

[Example 3]
Toner particles 3 were obtained in the same procedure except that in the polyethyleneimine treatment of Example 1, a 10% aqueous solution of polyethyleneimine was changed so that polyethyleneimine was 0.5% based on the toner particle weight.
The obtained toner particles 3 had a nitrogen content of 0.055%, and the amount of alkaline earth metal detected by ion chromatography was 0.98 × 10 ⁻⁸ mol / g.
A toner 3 and a developer 3 were prepared and evaluated in the same manner as in Example 1 except that the toner particles 3 were used instead of the toner particles 1. The obtained results are shown in Table 1.

[Example 4]
Toner particles 4 were obtained in the same procedure except that the calcium chloride treatment in Example 1 was changed so that the calcium chloride content was 0.001% with respect to the toner particle weight.
The obtained toner particles 4 had a nitrogen content of 0.041%, and the amount of alkaline earth metal detected by ion chromatography was 1.20 × 10 ⁻¹⁰ mol / g.
A toner 4 and a developer 4 were prepared and evaluated in the same manner as in Example 1 except that the toner particles 4 were used in place of the toner particles 1. The obtained results are shown in Table 1.

[Example 5]
Toner particles 5 were obtained in the same procedure except that in the calcium chloride treatment of Example 1, a 10% aqueous solution of calcium chloride was changed to 10% calcium chloride based on the toner particle weight.
The obtained toner particles 5 had a nitrogen content of 0.039%, and the amount of alkaline earth metal detected by ion chromatography was 0.86 × 10 ⁻⁶ mol / g.
Toner 5 and developer 5 were prepared and evaluated in the same manner as in Example 1 except that toner particle 5 was used instead of toner particle 1. The obtained results are shown in Table 1.

[Example 6]
Toner particles 6 were obtained in the same procedure except that calcium chloride was changed to barium chloride in the calcium chloride treatment of Example 1.
The resulting nitrogen content of the toner particles 6 is 0.042% alkaline earth metal amount detected by ion chromatography was 1.10 × ¹⁰ -8 mol / g.
A toner 6 and a developer 6 were prepared and evaluated in the same manner as in Example 1 except that the toner particles 6 were used instead of the toner particles 1. The obtained results are shown in Table 1.

[Comparative Example 1]
Toner particles 7 were obtained in the same procedure except that in the polyethyleneimine treatment of Example 1, a 10% aqueous solution of polyethyleneimine was changed to 0.005% of polyethyleneimine with respect to the toner particle weight.
The obtained toner particles 7 had a nitrogen content of 0.012% by mass, and the amount of alkaline earth metal detected by ion chromatography was 1.11 × 10 ⁻⁸ mol / g.
A toner 7 and a developer 7 were prepared and evaluated in the same manner as in Example 1 except that the toner particles 7 were used instead of the toner particles 1. The obtained results are shown in Table 1.

[Comparative Example 2]
Toner particles 8 were obtained in the same procedure except that in the polyethyleneimine treatment of Example 1, a 30% aqueous solution of polyethyleneimine was changed to 5.0% of polyethyleneimine with respect to the toner particle weight.
The obtained toner particles 8 had a nitrogen content of 0.190%, and the amount of alkaline earth metal detected by ion chromatography was 1.10 × 10 ⁻⁸ mol / g.
Toner 8 and developer 8 were prepared and evaluated in the same manner as in Example 1 except that toner particles 8 were used instead of toner particles 1. The obtained results are shown in Table 1.

[Comparative Example 3]
Toner particles 9 were obtained in the same procedure except that in the calcium chloride treatment of Example 1, a 1% aqueous solution of calcium chloride was changed to 0.0005% calcium chloride based on the toner particle weight.
The obtained toner particles 9 had a nitrogen content of 0.041%, and the amount of alkaline earth metal detected by ion chromatography was 0.90 × 10 ⁻¹⁰ mol / g.
A toner 9 and a developer 9 were prepared and evaluated in the same manner as in Example 1 except that the toner particles 9 were used in place of the toner particles 1. The obtained results are shown in Table 1.

[Comparative Example 4]
Toner particles 10 were obtained in the same procedure except that the calcium chloride treatment in Example 1 was changed so that the 1% aqueous solution of calcium chloride was 15.0% of calcium chloride with respect to the weight of the toner particles.
The obtained toner particles 10 had a nitrogen content of 0.043%, and the amount of alkaline earth metal detected by ion chromatography was 1.00 × 10 ⁻⁶ mol / g.
A toner 10 and a developer 10 were prepared and evaluated in the same manner as in Example 1 except that the toner particles 10 were used in place of the toner particles 1. The obtained results are shown in Table 1.
The nitrogen content and alkaline earth metal content of the toner particles in the above examples and comparative examples were the same as the nitrogen content and alkaline earth metal content of the toner.

1Y, 1M, 1C, 1K, 107 photoconductor (image carrier)
2Y, 2M, 2C, 2K, 108 Charging roller 3Y, 3M, 3C, 3K Laser beam 3, 110 Exposure device 4Y, 4M, 4C, 4K, 111 Developing device (developing means)
5Y, 5M, 5C, 5K Primary transfer rollers 6Y, 6M, 6C, 6K, 113 Photoconductor cleaning device (cleaning means)
8Y, 8M, 8C, 8K Toner cartridge 10Y, 10M, 10C, 10K Unit 20 Intermediate transfer belt 22 Drive roller 24 Support roller 26 Secondary transfer roller (transfer means)
28, 115 Fixing device (fixing means)
30 Intermediate transfer member cleaning device 112 Transfer device 116 Mounting rail 117 Opening 118 for static elimination exposure Opening 200 for exposure Process cartridge,
P, 300 Recording paper (transfer object)

Claims (7)

Polyalkyleneimine adheres to the toner surface,
The nitrogen content derived from the adhesion amount of the polyalkyleneimine adhering to the toner surface is 0.015 mass% or more and 0.06 mass% or less,
Der alkaline earth metal content is 1.0 × ¹⁰ -10 mol / g or more 0.90 × ¹⁰ -6 mol / g or less, which is detected by the ion chromatography is,
As the binder resin, the toner for developing electrostatic images you containing amorphous polyester resin. The electrostatic image developing toner according to claim 1, wherein the alkaline earth metal is calcium. As a colorant, an electrostatic charge image developing toner according to claim 1 or claim 2 containing carbon black. An electrostatic charge image developing developer comprising the electrostatic charge image developing toner according to claim 1 . 4. A toner cartridge that contains at least toner, and the toner is the electrostatic image developing toner according to claim 1 . A process cartridge comprising at least a developer holder and containing the developer for developing an electrostatic image according to claim 4 . A photoreceptor,
Charging means for charging the photoreceptor;
An electrostatic charge image forming means for forming an electrostatic charge image on the surface of the charged photoreceptor;
Developing means for developing the electrostatic image formed on the surface of the photoreceptor as a toner image with the developer for developing an electrostatic image according to claim 4 ;
Transfer means for transferring the toner image onto a transfer target;
Fixing means for fixing the toner image transferred onto the transfer target;
An image forming apparatus.

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