JP5983328B2 - 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.

  An electrostatic charge image developing toner comprising a crystalline resin, a colorant and a terphenyl compound in order to provide an electrostatic charge image developing toner having not only good low-temperature fixing properties but also excellent strength. It is disclosed (for example, see Patent Document 1).

JP 2006-330278 A

  An object of the present invention is to provide a toner for developing an electrostatic image having excellent low-temperature fixability.

Specific means for achieving the above object are as follows.
That is, the invention according to claim 1
Amorphous polyester resin, compound represented by the following formula (B), compound represented by the following formula (D), compound represented by the following formula (E), compound represented by the following formula (F) And at least one selected from the group consisting of compounds represented by the following formula (G): 1% by mass or more and 20% by mass or less .

The invention according to claim 2
2. The toner for developing an electrostatic charge image according to claim 1, further comprising a crystalline resin.

The invention according to claim 3
An electrostatic charge image developing developer comprising the electrostatic charge image developing toner according to claim 1.

The invention according to claim 4
The toner cartridge according to claim 1, wherein the toner contains at least toner and the toner is an electrostatic charge image developing toner according to claim 1.

The invention according to claim 5
A process cartridge comprising at least a developer holder and containing the developer for developing an electrostatic charge image according to claim 3.

The invention according to claim 6
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 charge image formed on the surface of the photoreceptor as a toner image with the developer for developing an electrostatic charge image according to claim 3;
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 first aspect of the present invention, there is provided an electrostatic image developing toner that is excellent in low-temperature fixability as compared with a case where the content of the specific compound is outside the range of 1% by mass or more and 20% by mass or less. The

  According to the second aspect of the present invention, there is provided a toner for developing an electrostatic charge image that hardly causes crushing of toner even when a crystalline resin is contained.

  The invention according to claim 3 provides a developer for developing an electrostatic charge image that is excellent in low-temperature fixability as compared with a case where the content of the specific compound is outside the range of 1% by mass or more and 20% by mass or less. Is done.

  According to the fourth aspect of the invention, the toner for developing an electrostatic charge image, which is excellent in low-temperature fixability as compared with the case where the content of the specific compound is outside the range of 1% by mass or more and 20% by mass or less, is accommodated. A toner cartridge is provided.

  According to the invention of claim 5, the handling of the developer for developing an electrostatic charge image having excellent low-temperature fixability as compared with the case where the content of the specific compound is outside the range of 1% by mass or more and 20% by mass or less. And adaptability to image forming apparatuses having various configurations can be improved.

  According to the sixth aspect of the present invention, the developer for developing an electrostatic charge image having excellent low-temperature fixability is used as compared with the case where the content of the specific compound is outside the range of 1% by mass or more and 20% by mass or less. 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 electrostatic image developing toner of the present embodiment (hereinafter sometimes referred to as the toner of the present embodiment) includes an amorphous polyester resin, a compound satisfying the following condition (1) and the following condition (2), the following formula 1% by mass or more and 20% by mass or less of at least one selected from the group consisting of the compound represented by (F) and the compound represented by the following formula (G) (hereinafter sometimes referred to as a specific compound). , Containing.

Condition (1) The following structural formula (X) is included as a partial structure.

In Structural Formula (X), R _A and R _B each independently represent a methyl group or a t-butyl group.

Condition (2) Of the carbon atoms contained in the molecule, the ratio (A / B) of the number A of carbon atoms constituting the aromatic ring to the number B of carbon atoms not constituting the aromatic ring is 0.2 or more. 5 or less.

Conventionally, additives such as a plasticizer and an anti-plasticizer have been added to the toner for the purpose of improving the low-temperature fixability of the toner.
A plasticizer such as phthalate ester contains an aromatic ring and an aliphatic group in the molecule, and it is assumed that the glass transition temperature of the toner is lowered by the spreading of the aliphatic group between the binder resins contained in the toner. ing. The effect of lowering the glass transition temperature of the toner is presumed to be due to an aliphatic group (alkyl group) contained in the plasticizer molecule. Low temperature fixability of the toner is realized by lowering the glass transition temperature of the toner. Moreover, the plasticizer containing an aliphatic group has a phase separation property due to the aliphatic group. However, when the glass transition temperature of the toner is lowered by the plasticizer, the heat storage property of the toner may be hindered. Further, the plasticizer may ooze out from the fixed image of the toner over time due to the phase separation of the plasticizer. Many plasticizers are liquid, and if the plasticizer oozes out from a fixed image of toner, various problems may occur.
Antiplasticizers such as terphenyl contain a plurality of aromatic rings in the molecule, and the aromatic rings fill the free volume of the binder resin contained in the toner, thereby reducing the melting temperature without lowering the glass transition temperature of the toner. Presumed to decrease. Low temperature fixability of the toner is realized by lowering the melting temperature of the toner. However, since the antiplasticizer contains a plurality of aromatic rings in the molecule, it is highly compatible with the binder resin (particularly, the binder resin containing an aromatic ring in the molecule), and the antiplasticizer is used when fixing a toner image. However, since it is difficult to separate the phase from the binder resin, the heat storage property of the toner may be hindered.

  As a result of intensive studies, the inventor causes the above problem by using a compound (specific compound) having both an aliphatic group presumed to contribute to phase separation and an aromatic ring presumed to contribute to compatibility. It has been found that low-temperature fixability of the toner can be realized without any problems.

The specific compound is required to contain an aromatic ring presumed to contribute to compatibility as an essential component in the specific compound. On the other hand, among the carbon atoms contained in the molecule, the ratio (A / B) of the number A of carbon atoms constituting the aromatic ring to the number B of carbon atoms not constituting the aromatic ring is 0.2 or more and 1.5 In the requirement “below”, “carbon atom not constituting an aromatic ring” is mainly derived from an aliphatic group presumed to contribute to phase separation. Further, by defining the ratio (A / B) of the number A of carbon atoms and the number B of carbon atoms, the ratio of aliphatic groups and aromatic rings contained in a specific compound is defined.
In the present embodiment, the “carbon atom that does not constitute an aromatic ring” refers to a carbon atom contained in a monovalent or divalent group composed of an alkyl group, an alkenyl group, an alkynyl group, and other carbon atoms and a hydrogen atom. This means that a carbon atom in a group containing a carbon atom such as a carboxyl group, a carbonyl group, an ester group or a cyano group and an atom other than a hydrogen atom is not included in the “carbon atom that does not constitute an aromatic ring”.

The specific compound contains one or more phenyl rings and an aliphatic group such as a methyl group, a t-butyl group, or a long-chain alkyl group in the molecular structure. The specific compound contains an aromatic ring, which is presumed to contribute to compatibility, as an essential component in the specific compound, and an aliphatic ring such as a methyl group, a t-butyl group, or a long-chain alkyl group in the aromatic ring. By containing the group, steric hindrance is easily generated in the aromatic ring, and compatibility is less likely to occur.
The specific compound has a structure in which one or more phenolic hydroxyl groups are contained in the molecule and two aliphatic groups exist in the ortho position with respect to the phenolic hydroxyl group. The phenolic hydroxyl group is technically common to specific compounds in that it is sterically hindered by the two aliphatic groups.

  In the present embodiment, “low temperature fixing” refers to fixing at a temperature of 155 ° C. or lower.

  Hereinafter, each component constituting the toner of the exemplary embodiment will be described.

-Binder resin-
In this embodiment, an amorphous polyester resin is used as the binder resin. Moreover, crystalline resins, such as crystalline polyester resin, may be used together as needed.

(Crystalline resin)
Examples of the crystalline resin used in the present embodiment include a crystalline polyester resin, a polyalkylene resin, and a long chain alkyl (meth) acrylate resin. Among these, a crystalline polyester resin that is advantageous for low-temperature fixability of the toner when used in combination with an amorphous polyester resin is desirable.
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 exceeds 50 ° C., toner storage properties such as blocking of the stored toner and storage properties of the fixed image after fixing are not difficult. Further, if the melting temperature is 100 ° C. or less, sufficient low-temperature fixability can be obtained.

  “Crystalline polyester resin” according to the present embodiment refers to a distinct endothermic peak, not a stepwise endothermic amount change in differential scanning calorimetry (hereinafter sometimes abbreviated as “DSC”). The thing which has. The crystalline polyester resin is a polymer obtained by copolymerizing other components with respect to the main chain. When the other components are 50% by mass or less, the copolymer is also called crystalline polyester.

  The melting temperature of the crystalline polyester resin was determined as the peak temperature of the endothermic peak obtained by 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 in the toner of this 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. If the aliphatic diol is a linear type, the crystallinity of the polyester resin is improved and the melting temperature may be increased. Further, when the main chain portion has 7 or more carbon atoms, when polycondensation with an aromatic dicarboxylic acid is performed, the melting temperature is lowered and low-temperature fixing is facilitated. On the other hand, when the main chain portion has 20 or less carbon atoms, it is easy 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 of the exemplary 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, 1,12 -Dodecanediol, 1,13-tridecanediol, 1,14-tetradecanediol, 1,18-octadecanediol, 1,14-eicosandecanediol and the like are exemplified, but not limited thereto. 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. If the content of the aliphatic diol is 80 mol% or more, the crystallinity of the polyester resin is improved and the melting temperature is increased, so that the toner blocking resistance and the image storage stability are improved.

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 higher than 3.0 mgKOH / g, the dispersibility in water is improved, and thus the emulsified particles can be easily produced by the wet process. Further, since the stability as emulsified particles during aggregation is improved, efficient toner production is facilitated. On the other hand, if the acid value is 30.0 mgKOH / g or less, the hygroscopicity as a toner does not increase, and it becomes difficult to be affected by the environment as a toner.

  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 6,000 or more, the toner does not soak into the surface of a recording medium such as paper at the time of fixing to cause uneven fixing, and the strength against bending resistance of the fixed image does not decrease. In addition, when the weight average molecular weight (Mw) is 35,000 or less, the viscosity at the time of melting does not become excessively high, so that the temperature for reaching a viscosity suitable for fixing does not increase, and as a result, low temperature fixability is achieved. can get.

  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 is calculated from the measurement result using a molecular weight calibration curve prepared with a monodisperse polystyrene standard sample.

  The content of the crystalline resin in the toner 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 to 30%. It is the range below the mass%.

  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.

  When a crystalline resin is used as a toner constituent material, the strength of the toner may decrease due to the softness of the crystalline resin, and the toner may be crushed. However, by including a specific compound in the toner, a reduction in toner strength due to the crystalline resin is prevented. For this reason, the toner of the present exemplary embodiment prevents the toner from collapsing while enjoying the effects such as low-temperature fixability obtained by using the crystalline resin.

(Amorphous polyester resin)
The “amorphous polyester resin” according to the present embodiment is a resin in which a stepwise endothermic change is recognized instead of a clear endothermic peak in differential scanning calorimetry (DSC).

  In the present embodiment, the compatibility with the crystalline polyester resin is improved by using the amorphous polyester resin. Accordingly, the amorphous polyester resin is also used as the viscosity of the crystalline polyester resin is decreased at the melting temperature. Since the viscosity is lowered and the sharp melt property (sensitive melting property) as a toner is obtained, 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.

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.
The low-temperature fixability obtained by using a specific compound is more effectively expressed by including an aromatic ring in the amorphous polyester resin which is a binder resin. Therefore, by introducing an aromatic ring into the amorphous polyester resin using an aromatic diol as the polyhydric alcohol, the low-temperature fixability of the toner of this embodiment is further improved.

  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 80 ° C. When Tg is 50 ° C. or higher, the storage stability of the toner and the storage stability of the fixed image are improved. On the other hand, if it is 80 ° C. or lower, fixing is performed at a lower temperature than in the prior art.
The Tg of the amorphous polyester resin is more preferably 50 ° 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 differential scanning calorimetry (DSC).

  The content of the amorphous resin in the toner is desirably in the range of 40% by mass to 95% by mass, more desirably in the range of 50% by mass to 90% by mass, and further desirably 60% by mass or more. It is the range of 85 mass% or less.

  In addition, you may perform manufacture of the said amorphous polyester resin according to the case of the said crystalline polyester resin.

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, control of the low-temperature fixability of the toner becomes easy, and furthermore, high-temperature offset resistance can be 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 the present embodiment, a known resin material such as a styrene / acrylic resin, an epoxy resin, a polyurethane resin, a polyamide resin, a cellulose resin, a polyether resin, or a polyolefin resin may be used in combination as the amorphous resin.

-Specific compounds-
Among the specific compounds, the molecular weight of the compound satisfying the conditions (1) and (2) is preferably 1500 or less, and more preferably 1000 or less.

Among the specific compounds, in the compound satisfying the condition (1) and the condition (2), the number A of carbon atoms constituting the aromatic ring and the carbon atoms not constituting the aromatic ring among the carbon atoms contained in the molecule The ratio (A / B) to the number B is 0.2 or more and 1.5 or less, preferably 0.3 or more and 1.2 or less, more preferably 0.5 or more and 1.0 or less.
The content of the specific compound in the toner of the exemplary embodiment is 1% by mass to 20% by mass, preferably 1% by mass to 15% by mass, and more preferably 1% by mass to 10% by mass.
If the content of the specific compound in the toner is less than 1% by mass, sufficient low-temperature fixability may not be obtained. On the other hand, if the content of the specific compound in the toner exceeds 20% by mass, the specific compound cannot be contained in the toner, and various characteristics may be deteriorated.
In the present embodiment, two or more specific compounds may be used in combination. When two or more kinds of specific compounds are contained in the toner according to the exemplary embodiment, the total content of the specific compounds is set to 1% by mass to 20% by mass, and 1% by mass to 15% by mass. The following is desirable, and 1 mass% or more and 10 mass% or less are still more desirable.

  Specific examples of the specific compound used in the present embodiment will be disclosed below including the compound represented by the formula (F) and the compound represented by the following formula (G). It is not limited to the following specific examples.

  In the above specific compounds, (A) is IRGANOX-1010, (B) is IRGANOX-1035, (C) is IRGANOX-1076, (D) is IRGANOX-1098, (E) is IRGANOX- As 1135, (F) is marketed as IRGANOX-1330, (G) as IRGANOX-1726, and (H) as IRGANOX-245.

-Colorant-
The toner of this embodiment may contain a colorant.
The colorant used in this embodiment may be a dye or a pigment, but a pigment is desirable from the viewpoint of light resistance and water resistance.
Desirable colorants include carbon black, aniline black, aniline blue, calcoil blue, chrome yellow, ultramarine blue, dupont oil red, quinoline yellow, methylene blue chloride, phthalocyanine blue, malachite green oxalate, lamp black, rose bengal Quinacridone, benzicine yellow, C.I. I. Pigment red 48: 1, C.I. I. Pigment red 57: 1, C.I. I. Pigment red 122, C.I. I. Pigment red 185, C.I. I. Pigment red 238, C.I. I. Pigment yellow 12, C.I. I. Pigment yellow 17, C.I. I. Pigment yellow 180, C.I. I. Pigment yellow 97, C.I. I. Pigment yellow 74, C.I. I. Pigment blue 15: 1, C.I. I. A known pigment such as CI Pigment Blue 15: 3 is used.

  The content of the colorant in the toner of the exemplary 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 total resin content in the toner. It is also effective to use a surface-treated colorant or a pigment dispersant as necessary. By selecting the type of the colorant, yellow toner, magenta toner, cyan toner, black toner and the like can be obtained.

-Release agent-
The toner according to the exemplary embodiment may include a release agent.
Examples of the release agent used in the present embodiment 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.

-Other additives-
In addition to the above components, the toner of the exemplary embodiment may further contain various components such as an internal additive, a charge control agent, inorganic powder (inorganic particles), and organic particles 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.

  The inorganic particles are added for various purposes, but may be added for adjusting the viscoelasticity of the toner. By adjusting the viscoelasticity, image glossiness and penetration into paper are adjusted. As inorganic particles, known inorganic particles such as silica particles, titanium oxide particles, alumina particles, cerium oxide particles, or those obtained by hydrophobizing the surface thereof are used alone or in combination of two or more kinds. From the standpoint of not impairing transparency and transparency such as OHP permeability, silica particles having a refractive index smaller than that of the binder resin are preferably used. Further, the silica 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, a silicone oil or the like are preferably used.

-Toner characteristics-
The volume average particle diameter of the toner in 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 4 μm or more, the toner fluidity is improved and the chargeability of each particle is easily improved. Further, since the charge distribution does not widen, fogging on the background and toner spillage from the developing device are less likely to occur. Moreover, if it is 4 micrometers or more, cleaning property will not become difficult. If the volume average particle diameter is 9 μm or less, the resolution is improved, so that sufficient image quality can be obtained, and the recent demand for high image quality is satisfied.

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

Furthermore, it is preferable that the toner of the present exemplary embodiment has a spherical shape with a shape factor SF1 in the range of 110 to 140. When the shape is spherical in this range, transfer efficiency and image density are improved, and a high-quality image is formed.
The shape factor SF1 is more preferably in the range of 110 to 130.

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, and A represents the projected area of the toner.

  The 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.

<Manufacture of toner>
The toner manufacturing method of the present embodiment may use a kneading and pulverizing method or a wet granulation method that are generally used.

The kneading and pulverizing method is a method of preparing toner particles by kneading a kneaded product after kneading a toner forming material containing a binder resin and a specific compound to obtain a kneaded product.
More specifically, the kneading and pulverizing method is divided into a kneading process for kneading a toner forming material containing a binder resin and a specific compound, and a pulverizing process for pulverizing the kneaded product. You may have other processes, such as a cooling process which cools the kneaded material formed by the kneading process as needed.

As the wet granulation method, suspension polymerization method, emulsion polymerization method, emulsion polymerization aggregation method, soap-free emulsion polymerization method, non-aqueous dispersion polymerization method, in-situ polymerization method, interfacial polymerization method, emulsion dispersion granulation method, aggregation・ The unification law etc. are mentioned. Among these, wet granulation is preferable from the viewpoint of encapsulating the crystalline resin in the toner.
Suitable examples of the wet granulation method include known melt suspension methods, emulsion aggregation methods, and dissolution suspension methods. Hereinafter, the emulsion aggregation method will be described with reference to an example in which a crystalline polyester resin is used as the crystalline resin.

  The emulsion aggregation method includes a step of forming aggregated particles in a dispersion in which resin particles (hereinafter sometimes referred to as “emulsified liquid”) are dispersed to prepare an aggregated particle dispersion (aggregation step), and the aggregation This is a production method including a step of fusing the aggregated particles by heating the particle dispersion (fusion step). Further, before the agglomeration step, a particle dispersion in which particles are dispersed is added and mixed in the agglomerated particle dispersion between the step of dispersing the agglomerated particles (dispersion step) and the aggregation step and the fusion step. What provided the process (attachment process) of making particles adhere to the above-mentioned aggregation particles and forming adhesion particles may be provided. In the adhesion step, the particle dispersion is added to and mixed with the aggregated particle dispersion prepared in the aggregation step, and the particles are adhered to the aggregated particles to form adhered particles. Corresponds to particles newly added to the aggregated particles as viewed from the aggregated particles, and is sometimes referred to as “additional particles”.

  As the additional particles, in addition to the resin particles, release agent particles, colorant particles, or the like may be used alone or in combination. There is no restriction | limiting in particular as a method of adding and mixing the said particle dispersion liquid, For example, you may carry out gradually continuously, and may carry out in steps divided into several times. By providing the adhesion step, a pseudo shell structure is formed.

In the emulsion aggregation method, an amorphous polyester resin dispersion is used, and a crystalline polyester resin dispersion may be used together. It is more preferable to include an emulsification step of emulsifying the crystalline polyester resin dispersion and the amorphous polyester resin to form emulsified particles (droplets).
In the emulsification step, the non-crystalline polyester resin emulsified particles (droplets) are obtained by applying shear force to a solution obtained by mixing an aqueous medium, an amorphous polyester resin, and, if necessary, a specific compound. Preferably it is formed. In that case, the viscosity of a polymer liquid may be lowered | hung by heating to the temperature more than the glass transition temperature of an amorphous polyester resin, and an emulsified particle may be formed. Moreover, you may use a dispersing agent. Hereinafter, such a dispersion of emulsified particles may be referred to as an “amorphous polyester resin dispersion”.

  Examples of the emulsifier used when forming the emulsified particles include a homogenizer, a homomixer, a pressure kneader, an extruder, and a media disperser. The size of the emulsified particles (droplets) of the polyester resin is preferably 0.010 μm or more and 0.5 μm or less, and more preferably 0.05 μm or more and 0.3 μm or less in terms of the average particle size (volume average particle size). The volume average particle size of the resin particles was measured with a Doppler scattering type particle size distribution analyzer (manufactured by Nikkiso Co., Ltd., Microtrac UPA9340).

  In addition, if the melt viscosity of the resin at the time of emulsification is high, it does not decrease to the desired particle size, so by increasing the temperature using an emulsifier that pressurizes the pressure above atmospheric pressure, An amorphous polyester resin dispersion having a particle size is obtained.

  In the emulsification step, a solvent may be added to the resin in advance for the purpose of reducing the viscosity of the resin. The solvent to be used is not particularly limited as long as it dissolves the polyester resin, but ether solvents such as tetrahydrofuran (THF), ester solvents such as methyl acetate, ethyl acetate, and methyl ethyl ketone, ketone solvents, benzene, Benzene solvents such as toluene and xylene can be used, and it is preferable to use ester solvents and ketone solvents such as ethyl acetate and methyl ethyl ketone.

  Further, an alcohol solvent such as ethanol or isopropyl alcohol may be added directly to water or resin. Further, a salt such as sodium chloride or potassium chloride, ammonia or the like may be added. Of these, ammonia is preferably used.

  Further, a dispersant may be added. Examples of the dispersant include water-soluble polymers such as polyvinyl alcohol, methyl cellulose, carboxymethyl cellulose, and sodium polyacrylate; anionic surfactants such as sodium octadecyl sulfate, sodium oleate, sodium laurate, and potassium stearate; Cationic surfactants such as laurylamine acetate and lauryltrimethylammonium chloride; zwitterionic surfactants such as lauryldimethylamine oxide; nonions such as polyoxyethylene alkyl ether, polyoxyethylene alkylphenyl ether, and polyoxyethylene alkylamine Surfactants such as ionic surfactants; inorganic compounds such as tricalcium phosphate, aluminum hydroxide, calcium sulfate, calcium carbonate, and barium carbonate It is. Among these, anionic surfactants are preferably used.

  As the usage-amount of the said dispersing agent, 0.01 to 20 mass parts is preferable with respect to 100 mass parts of said resin. However, since the dispersant may affect the chargeability, it is better not to add it when emulsifiability is ensured by the hydrophilicity of the polyester resin main chain, the acid value of the terminal, the amount of the hydroxyl value, and the like.

  In the emulsification step, the amorphous polyester resin is copolymerized with a dicarboxylic acid having a sulfonic acid group (that is, a suitable amount of a dicarboxylic acid-derived structural unit having a sulfonic acid group in the acid-derived structural unit). Included). The addition amount is preferably 10 mol% or less in the acid-derived structural unit, but when emulsification is ensured by the hydrophilicity of the polyester resin main chain, the acid value of the terminal, the hydroxyl value, etc., it is better not to add it. Good.

  Further, a phase inversion emulsification method may be used for forming the emulsified particles. In the phase inversion emulsification method, an amorphous polyester resin is dissolved in a solvent, a neutralizing agent and a dispersion stabilizer are added as necessary, and an aqueous medium is dropped under stirring to obtain emulsified particles. Thereafter, the solvent in the resin dispersion is removed to obtain an emulsion. At this time, the order of adding the neutralizing agent and the dispersion stabilizer may be changed. Moreover, when implementing the phase inversion emulsification method with respect to an amorphous polyester resin, you may add a specific compound in a solvent. Thereby, a specific compound is contained in the amorphous polyester resin.

  Examples of the solvent for dissolving the resin include formic acid esters, acetic acid esters, butyric acid esters, ketones, ethers, benzenes, and halogenated carbons. Specifically, esters such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, t-butyl such as formic acid, acetic acid, butyric acid, acetone, methyl ethyl ketone (MEK), methyl propyl ketone ( MPK), methyl ketones such as methyl isopropyl ketone (MIPK), methyl butyl ketone (MBK) and methyl isobutyl ketone (MIBK), ethers such as diethyl ether and diisopropyl ether, and heterocyclic substituents such as toluene, xylene and benzene , Carbon tetrachloride, methylene chloride, 1,2-dichloroethane, 1,1,2-trichloroethane, trichloroethylene, chloroform, monochlorobenzene, dichloroethylidene, etc. may be used alone or in combination of two or more. Good. Of these, acetic acid esters, methyl ketones and ethers which are low boiling solvents are usually preferably used, and acetone, methyl ethyl ketone, acetic acid, ethyl acetate and butyl acetate are particularly preferred. These solvents are preferably those having a relatively high volatility so as not to remain in the resin particles. The amount of these solvents used is preferably 20% by mass or more and 200% by mass or less, and more preferably 30% by mass or more and 100% by mass or less with respect to the resin amount.

As a method for removing the solvent from the emulsion, a method of volatilizing the solvent from the emulsion to 15 ° C. or more and 70 ° C. or less, and a method of combining this with reduced pressure are preferably used.
In the present embodiment, from the viewpoint of particle size distribution and particle size controllability, it is preferable to use a method of emulsifying by a phase inversion emulsification method and then removing the solvent by heating under reduced pressure. In addition, when used for toner, from the viewpoint of influence on the charging property, emulsification is carried out according to the hydrophilicity of the polyester resin main chain, the acid value of the terminal, the amount of hydroxyl value, etc. without using a dispersant or surfactant as much as possible. It is preferable to control the property.
The emulsification of the crystalline polyester may be performed by the same operation as in the case of the amorphous polyester resin. In the emulsification step, the crystalline polyester resin emulsified particles (droplets) are preferably formed by applying a shearing force to a solution obtained by mixing an aqueous medium and the crystalline polyester resin. At that time, after heating once to a temperature equal to or higher than the melting temperature of the crystalline polyester resin and dissolving, the emulsion is emulsified at a temperature 10 to 20 ° C. higher than the recrystallization temperature, thereby reducing the viscosity of the polymer liquid and It may be formed. Moreover, you may use a dispersing agent. Hereinafter, such a dispersion of emulsified particles may be referred to as a “crystalline polyester resin dispersion”.
Further, a phase inversion emulsification method may be applied to the dispersion of a specific compound. Thereby, the dispersion liquid of a specific compound is prepared.

  Examples of the dispersion method of the colorant and the release agent include general dispersions such as a high-pressure homogenizer, a rotary shearing homogenizer, an ultrasonic disperser, a high-pressure impact disperser, a ball mill having a medium, a sand mill, and a dyno mill. The method can be used and is not limited in any way.

  If necessary, an aqueous dispersion of a colorant may be prepared using a surfactant, or an organic solvent dispersion of a colorant may be prepared using a dispersant. Hereinafter, the dispersion of the colorant and the release agent may be referred to as “colorant dispersion” or “release agent dispersion”.

  The dispersant used for the colorant dispersion or the release agent dispersion is generally a surfactant. As the surfactant, a surfactant such as an anionic surfactant, a cationic surfactant, a zwitterionic surfactant, or a nonionic surfactant described as the dispersant used in the emulsification step should be used. Can do. The nonionic surfactant may be used in combination with the anionic surfactant or the cationic surfactant. Moreover, it is preferable that it is the same polarity as the dispersing agent used for other dispersion liquids, such as a mold release agent dispersion liquid.

In the agglomeration step, a dispersion of amorphous polyester resin particles, a dispersion of crystalline polyester resin particles, a colorant dispersion, a release agent dispersion, etc. are mixed to obtain a mixed solution. Aggregation is performed by heating at a temperature not higher than the glass transition temperature to form agglomerated particles including amorphous polyester resin particles, crystalline polyester resin particles, colorant particles, and release agent particles. 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 agglomerated particle forming step, the release agent dispersion may be added and mixed at the same time with various dispersions such as a resin particle dispersion, or may be added in multiple portions.
About a specific compound, a specific compound is added in an aggregated particle by using the amorphous polyester resin particle containing a specific compound, or using the dispersion liquid of a specific compound separately.

  In the aggregation step, it is preferable to use an aggregating agent in order to form aggregated particles. Examples of the flocculant used include a surfactant having a polarity opposite to that of the surfactant used in the dispersant, a general inorganic metal compound (inorganic metal salt), or a polymer thereof. The metal element constituting the inorganic metal salt has a divalent or higher charge belonging to the 2A, 3A, 4A, 5A, 6A, 7A, 8, 1B, 2B, 3B group in the periodic table (long periodic table). There is no limitation as long as it dissolves in the form of ions in the aggregation system of resin particles.

  Specific examples of inorganic metal salts that may be used include calcium chloride, calcium nitrate, barium chloride, magnesium chloride, zinc chloride, aluminum chloride, aluminum sulfate, and other metal salts, and polyaluminum chloride and polyhydroxide. Examples thereof include inorganic metal salt polymers such as aluminum and calcium polysulfide, among which aluminum salts and polymers thereof are preferred. In general, in order to obtain a sharper particle size distribution, even if the valence of the inorganic metal salt is divalent to monovalent, bivalent to trivalent or higher, and even to the same valence, the polymerization type inorganic metal salt weight Combined is more suitable.

  The amount of the flocculant added varies depending on the type and valence of the flocculant, but is preferably in the range of 0.05% by mass to 0.1% by mass. Not all of the aggregating agent remains in the toner due to outflow into an aqueous medium, formation of coarse powder, and the like during the toner forming process. In particular, when the amount of the solvent in the resin is large in the step of forming a toner, the solvent and the aggregating agent interact and easily flow out into the aqueous medium. Therefore, it is preferable to adjust according to the amount of the remaining solvent.

  In the fusion step, the agglomeration suspension is controlled to have a pH of 5 or more and 10 or less under stirring according to the aggregation step to stop the progress of aggregation, and the glass transition temperature (Tg) or higher of the resin. The aggregated particles are fused and united by heating at a temperature equal to or higher than the melting temperature of the crystalline resin (hereinafter, the glass transition temperature and the melting temperature are simply referred to as “Tg etc.”). It is preferable. Further, the heating time may be performed to the extent that desired coalescence is achieved, and may be performed for 0.2 hours or more and 10 hours or less. Thereafter, when the temperature is lowered to Tg or less of the resin to solidify the particles, the particle shape and surface properties change depending on the temperature lowering rate. The temperature is desirably lowered to a Tg or less of the resin at a rate of 0.5 ° C./min or more, more desirably at a rate of 1.0 ° C./min or more.

  Also, while heating at a temperature equal to or higher than the Tg of the resin, the particles are grown by adding a pH or a flocculant according to the aggregation process, and when the desired particle size is reached, 0.5 ° C. according to the case of the fusion process. It is preferable in terms of simplification of the process because the aggregation process and the fusion process may be performed at the same time if the particle growth is stopped at the same time as solidification by lowering the temperature to below the Tg of the resin at a rate of / min. It may be difficult to make the aforementioned core-shell structure.

  After completing the fusing step, the particles are washed and dried to obtain toner particles. In addition, it is preferable to perform substitution washing with ion-exchanged water, and the degree of washing is generally monitored by the electric conductivity of the filtrate, and finally the electric conductivity is set to 25 μS / cm or less. Is preferred. The washing may include a step of neutralizing ions with an acid or an alkali. The treatment with an acid preferably has a pH of 6.0 or less, and the treatment with an alkali preferably has a pH of 8.0 or more.

  The solid-liquid separation after washing is not particularly limited, but suction filtration, pressure filtration such as a filter press, etc. are preferably used from the viewpoint of productivity. Further, the drying method is not particularly limited, but from the viewpoint of productivity, freeze drying, flash jet drying, fluidized drying, vibration fluidized drying, etc. are preferably used, and the final toner moisture content is 1% by mass or less. More desirably, the film is dried to 0.7% by mass or less.

  The toner particles obtained as described above may be externally mixed with inorganic particles and / or organic particles as external additives as fluidity aids, cleaning aids, abrasives, and the like.

  As inorganic particles that may be externally added, for example, all particles used as external additives on the normal toner surface such as silica, alumina, titanium oxide, calcium carbonate, magnesium carbonate, tricalcium phosphate, cerium oxide, etc. Is mentioned. These inorganic particles preferably have a hydrophobic surface.

  Examples of organic particles that may be externally added include normal toner surfaces such as vinyl resins such as styrene polymers, (meth) acrylic polymers, and ethylene polymers, polyester resins, silicone resins, and fluorine resins. All the particles used as external additives are included.

  These external additives preferably have a primary particle size of 0.01 μm or more and 0.5 μm or less. Further, a lubricant may be added. Examples of the lubricant include fatty acid amides such as ethylene bisstearyl acid amide and oleic acid amide, fatty acid metal salts such as zinc stearate and calcium stearate, higher alcohols such as uniline, and the like. The primary particle size is preferably 0.5 μm or more and 8.0 μm or less.

  In addition, two or more kinds of inorganic particles are used among the inorganic particles, and one kind of the inorganic particles preferably has an average primary particle diameter of 30 nm or more and 200 nm or less, and an average 1 of 30 nm or more and 180 nm or less. More preferably, it has a secondary particle size.

Specifically, silica, alumina, and titanium oxide are preferable, and it is particularly preferable to add hydrophobized silica. In particular, it is preferable to use silica and titanium oxide in combination, or to use silica having different particle diameters in combination. It is also preferable to use organic particles having a particle size of 80 nm or more and 500 nm or less in combination. Examples of the hydrophobizing agent for hydrophobizing the external additive include known materials, such as silane coupling agents, titanate coupling agents, aluminate coupling agents, and zirconium coupling agents. Silicone oil etc. are mentioned. Examples of the hydrophobic treatment of the external additive include a polymer coating treatment.
The external additive is preferably adhered or fixed to the toner surface by applying a mechanical impact force with a V-type blender, a sample mill, a Henschel mixer or the like.

<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. Among these, dialkylaminoalkyl (meth) acrylic resins are preferable from the viewpoint of high charge amount and the like.

  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 (weight 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 to a potential of about −600V to −800V 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 agitated inside the developing device 4Y, and has a charge of the same polarity (negative polarity) as the charged charge on the photoreceptor 1Y, and a developer roll (developer holder). Is held on. As the surface of the photoreceptor 1Y passes through the developing device 4Y, the yellow toner is electrostatically attached to the latent image portion on the surface of the photoreceptor 1Y, and the latent image 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. Specifically, when the developer holder DC applied voltage Vdc is −300 to −700 V, the developer holder AC voltage peak width Vp-p may be in the range of 0.5 to 2.0 kV.
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. The transfer bias applied at this time is a (+) polarity opposite to the polarity (−) of the toner, and is controlled to about +10 μA by the control unit (not shown) in the first unit 10Y, for example.
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 on which the four color toner images are transferred in multiple ways through the first to fourth units is disposed on the intermediate transfer belt 20, the support roller 24 in contact with the inner surface of the intermediate transfer belt, and the image holding surface side 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. Applied to the roller 24. The transfer bias applied at this time is a (−) polarity that is the same polarity as the polarity (−) of the toner, and an electrostatic force from the intermediate transfer belt 20 toward the recording paper P is applied to the toner image, and the transfer bias is applied to the intermediate transfer belt 20. The toner image is transferred onto the recording paper P. 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, processability, 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 cartridge in the image forming apparatus is selected from the viewpoints of the internal layout of the image forming apparatus, replacement / mountability, and supply 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. Examples 1, 3, 8, 9, 11, and 16 are reference examples.

<Preparation of Amorphous Polyester Resin Particle Dispersion 1>
525 parts by mass of bisphenol A propylene oxide 2-mole adduct, 225 parts by mass of bisphenol A ethylene oxide 2-mole adduct, 380 parts by mass of terephthalic acid, 250 parts by mass of dodecenyl succinic acid and 6 parts by mass of dibutyltin oxide are placed in a heat-dried three-necked flask. After that, the air in the container is depressurized by a depressurization operation, and is further brought into an inert atmosphere with nitrogen gas, reacted at 230 ° C. and normal pressure (101.3 kPa) for 10 hours by mechanical stirring, and further at 1 at 8 kPa. Reacted for hours. After cooling to 210 ° C. and adding 75 parts by mass of trimellitic anhydride and reacting for 1 hour, the reaction was continued at 8 kPa until the softening temperature reached 120 ° C. to obtain an amorphous polyester resin.
Next, 332 parts by mass of an amorphous polyester resin, 18 parts by mass of IRGANOX-1010, 245 parts by mass of methyl ethyl ketone, 70 parts by mass of isopropyl alcohol, and 11.2 parts by mass of a 10% by mass aqueous ammonia solution After putting in a separable flask, mixing and dissolving, ion-exchanged water was added dropwise at a liquid feed speed of 8 g / min using a liquid feed pump while stirring at 40 ° C. with heating. After the liquid became cloudy, the liquid feeding speed was increased to 12 g / min for phase inversion, and dropping was stopped when the liquid feeding amount reached 1050 parts by mass. Thereafter, the solvent was removed under reduced pressure to obtain an amorphous polyester resin particle dispersion 1 containing a specific compound.

<Preparation of Amorphous Polyester Resin Particle Dispersion 2>
Amorphous polyester resin particle dispersion 2 was obtained in the same manner as in preparation of amorphous polyester resin particle dispersion 1, except that IRGANOX-1035 was used instead of IRGANOX-1010.

<Preparation of Amorphous Polyester Resin Particle Dispersion 3>
Amorphous polyester resin particle dispersion 3 was obtained by the same method except that IRGANOX-1076 was used instead of IRGANOX-1010 in preparation of amorphous polyester resin particle dispersion 1.

<Preparation of Amorphous Polyester Resin Particle Dispersion 4>
Amorphous polyester resin particle dispersion 4 was obtained by the same method except that IRGANOX-1098 was used instead of IRGANOX-1010 in the preparation of amorphous polyester resin particle dispersion 1.

<Preparation of Amorphous Polyester Resin Particle Dispersion 5>
Amorphous polyester resin particle dispersion 5 was obtained by the same method except that IRGANOX-1135 was used instead of IRGANOX-1010 in the preparation of amorphous polyester resin particle dispersion 1.

<Preparation of Amorphous Polyester Resin Particle Dispersion 6>
Amorphous polyester resin particle dispersion 6 was obtained in the same manner as in preparation of amorphous polyester resin particle dispersion 1, except that IRGANOX-1330 was used instead of IRGANOX-1010.

<Preparation of Amorphous Polyester Resin Particle Dispersion 7>
Amorphous polyester resin particle dispersion 7 was obtained by the same method except that IRGANOX-1726 was used instead of IRGANOX-1010 in preparation of amorphous polyester resin particle dispersion 1.

<Preparation of Amorphous Polyester Resin Particle Dispersion 8>
Amorphous polyester resin particle dispersion 8 was obtained by the same method except that IRGANOX-245 was used instead of IRGANOX-1010 in the preparation of amorphous polyester resin particle dispersion 1.

<Preparation of Amorphous Polyester Resin Particle Dispersion 9>
In producing the amorphous polyester resin particle dispersion 1, an amorphous polyester resin particle dispersion 9 was obtained in the same manner except that IRGANOX-1010 was not used.

<Preparation of Amorphous Polyester Resin Particle Dispersion 10>
Amorphous polyester resin particle dispersion 10 was obtained in the same manner as in preparation of amorphous polyester resin particle dispersion 1, except that terphenyl was used instead of IRGANOX-1010.

<Preparation of Amorphous Polyester Resin Particle Dispersion 11>
Amorphous polyester resin particle dispersion 11 was obtained by the same method except that IRGACURE-819 was used instead of IRGANOX-1010 in the preparation of amorphous polyester resin particle dispersion 1.

A heat-dried three-necked flask was charged with 250 parts by mass of 1,10-dodecanedioic acid, 150 parts by mass of 1,9-nonanediol (polyhydric alcohol) and 0.4 parts by mass of dibutyltin oxide as a catalyst, and then decompressed. Then, the air in the three-necked flask was replaced with nitrogen to create an inert atmosphere, and the reaction was allowed to proceed by stirring at 180 ° C. for 5 hours by mechanical stirring and refluxing. During the reaction, water generated in the reaction system was distilled off. Thereafter, the temperature was gradually raised to 230 ° C. under reduced pressure, and when the mixture was stirred for 3 hours to become a viscous state, the molecular weight was confirmed by GPC (gel permeation chromatography; converted to polystyrene), and the weight average molecular weight was 25,000. Then, the reaction was stopped to obtain a crystalline polyester resin.
Next, 350 parts by mass of this crystalline polyester resin, 210 parts by mass of methyl ethyl ketone, and 61.8 parts by mass of isopropyl alcohol were placed in a separable flask, and sufficiently mixed and dissolved at 40 ° C. Of 16.24 parts by mass was added dropwise. The heating temperature is lowered to 65 ° C., and ion-exchanged water is added dropwise with stirring using a liquid feed pump at a liquid feed speed of 8 g / min. After the liquid becomes cloudy, the liquid feed speed is increased to 12 g / min. When the amount reached 1400 parts by mass, the dropping of ion exchange water was stopped. Thereafter, the solvent was removed under reduced pressure to obtain a crystalline polyester resin particle dispersion.

Cyan pigment (manufactured by Dainichi Seika Co., Ltd., Pigment Blue 15: 3 (copper phthalocyanine)): 1000 parts by mass Anionic surfactant (Daiichi Kogyo Seiyaku Co., Ltd .: Neogen RK): 150 parts by mass Water: 9000 parts by mass The above components are mixed, dissolved, and dispersed for 1 hour using a high-pressure impact disperser Ultimateizer (manufactured by Sugino Machine, HJP30006) to disperse the colorant (cyan pigment). A colorant dispersion was prepared. The volume average particle size of the colorant (cyan pigment) in the colorant dispersion was 0.136 μm, and the colorant particle concentration was 25.1% by mass.

Ester wax WEP5 (manufactured by NOF Corporation): 500 parts by mass Anionic surfactant (Daiichi Kogyo Seiyaku Co., Ltd .: Neogen RK): 50 parts by mass Ion-exchanged water: 1700 parts by mass A mold release agent having a volume average particle size of 0.180 μm after being heated to ° C. and dispersed using a homogenizer (manufactured by IKA: Ultra Turrax T50) and then dispersed by a Manton Gorin high-pressure homogenizer (Gorin). A release agent dispersion liquid (release agent concentration: 31.1% by mass) was prepared.

[Example 1]
Amorphous polyester resin particle dispersion 1: 367 parts by weight Colorant dispersion: 62 parts by weight Anionic surfactant (20% aqueous solution of Dowfax2A1): 15 parts by weight Release agent dispersion: 77 parts by weight pH A non-crystalline polyester resin particle dispersion 1, an anionic surfactant and 250 parts by mass of ion-exchanged water among the above raw materials are placed in a polymerization kettle equipped with a meter, a stirring blade, and a thermometer, and stirred at 130 rpm for 115 minutes. However, the surfactant was blended with the amorphous polyester resin particle dispersion. A colorant dispersion and a release agent dispersion were added to and mixed with this, and then a 0.3 M nitric acid aqueous solution was added to the raw material mixture to adjust the pH to 4.8.
Subsequently, 13 parts by mass of a 10% by mass nitric acid aqueous solution of aluminum sulfate as a flocculant was dropped while applying a shearing force at 3000 rpm with an ultra turrax. Since the viscosity of the raw material mixture increased during the dropping of the flocculant, when the viscosity increased, the dropping speed was slowed so that the flocculant was not biased to one place. When the dropping of the flocculant was completed, the rotation speed was further increased to 5000 rpm, and the mixture was stirred for 5 minutes to sufficiently mix the flocculant and the raw material mixture.
Subsequently, the raw material mixture was stirred at 500 rpm while being heated to 25 ° C. with a mantle heater. After stirring for 10 minutes, it was confirmed that a primary particle size was formed using a Coulter Multisizer II (aperture diameter: 50 μm; manufactured by Coulter, Inc.), and then 43 ° C. at 0.1 ° C./min for growing aggregated particles. The temperature was raised to. Agglomerated particle growth was confirmed at any time using a Coulter Multisizer, and the agglomeration temperature and the number of rotations of stirring were changed depending on the agglomeration speed.
On the other hand, for agglomerated particles coating, 118 parts by mass of ion-exchanged water and 8.2 parts by mass of an anionic surfactant (20% aqueous solution of Dowfax2A1) are added to 171 parts by mass of the amorphous polyester resin particle dispersion 1. The mixture was mixed and previously adjusted to pH 3.8 to obtain a resin particle dispersion for coating. When the aggregated particles grew to 5.2 μm in the aggregation step, a coating resin particle dispersion prepared in advance was added and held for 20 minutes with stirring. Thereafter, in order to stop the growth of the coated aggregated particles, 1.5 parts by mass of EDTA was added, and then a 1M sodium hydroxide aqueous solution was added to control the pH of the raw material mixture to 7.6. Subsequently, in order to fuse the aggregated particles, the temperature was raised to 85 ° C. at a temperature raising rate of 1 ° C./min while adjusting the pH to 7.6. After reaching 85 ° C., the pH is adjusted to 7.6 or less in order to proceed with the fusion, and after confirming that the aggregated particles have fused with an optical microscope, ice water is used to stop the growth of the particle size. Was injected and quenched at a temperature lowering rate of 10 ° C./min.
Subsequently, the obtained particles were sieved once with a 15 μm mesh for the purpose of washing. Thereafter, approximately 10 times the amount of ion-exchanged water (30 ° C.) was added to the solid content, stirred for 20 minutes, and then once filtered. Further, the solid content remaining on the filter paper was dispersed in a slurry, washed with ion exchange water at 30 ° C. four times and dried to obtain toner particles having a volume average particle size of 5.8 μm.

  To 100 parts of the toner particles prepared above, 1.2 parts of hydrophobic titania powder (Tokuyama, 20 nm) was added and externally added with a stirring mixer to obtain toner 1.

  Toner having a volume average particle diameter of 35 μm coated with 1% of polymethyl methacrylate resin (Mw: 80000, manufactured by Soken Chemical Co., Ltd.) is weighed so that the toner concentration is 5%, and 5% by a ball mill. Developer 1 was prepared by stirring and mixing for a minute.

-Low temperature fixability evaluation (minimum fixing temperature)-
As an image forming apparatus, a color copying machine DocuCenter II-C3300 manufactured by Fuji Xerox Co., Ltd. modified so that the fixing temperature can be changed every 5 ° C. from 100 ° C. to 200 ° C. was used.
Using this modified machine, an image was formed under the conditions of a toner applied amount of 15.0 g / m ² and a process speed of 250 mm / s, and a fixed image was evaluated from the viewpoint of the minimum fixing temperature.
A good fixed image with no image defect due to mold release failure is folded using a constant load weight (0.5 kg), and the degree of image defect in the bent part is observed, and some peeling of the image is observed. The fixing temperature at which the level at which it is determined that there is no problem above is the minimum fixing temperature, and is used as an index for low-temperature fixing property.
Specifically, the allowable range of the minimum fixing temperature is 155 ° C. or lower, and preferably 145 ° C. or lower.
The obtained results are shown in Table 1.

-Thermal storage-
The thermal storage property (blocking resistance) of the toner was evaluated by the following method.
For heat storage, a powder tester (manufactured by Hosokawa Micron Co., Ltd.) was used, and sieves with openings of 53 μm, 45 μm, and 38 μm were arranged in series from the top, and 2 g of toner accurately weighed on the sieve with openings of 53 μm. The obtained toner was vibrated for 90 seconds with an amplitude of 1 mm, and the toner mass on each sieve after the vibration was measured.
Thermal storage property = [(toner mass on a sieve having an opening of 53 μm) × 0.5 + (toner mass on a sieve having an opening of 45 μm) × 0.3 + (toner mass on a sieve having an opening of 38 μm) × 0.1 ] × 100 / (toner mass used for measurement) (%).
The measurement was performed in an environment of 25 ° C. and 50% RH, and the heat storage property was judged as follows.
1: Less than 20% thermal storage index (no problem in actual use)
2: The index of heat storage property is 20% or more and less than 50% (there may be a problem in actual use)
3: Thermal storage stability index is 50% or more (apparently unacceptable in actual use)

[Example 2]
Toner 2 and developer 2 were produced in the same manner as in Example 1 except that amorphous polyester resin particle dispersion 2 was used instead of amorphous polyester resin particle dispersion 1.
Evaluation was carried out in the same manner as in Example 1 using the obtained toner 2 and developer 2. The evaluation results are shown in Table 1.

[Example 3]
Toner 3 and developer 3 were produced in the same manner as in Example 1 except that amorphous polyester resin particle dispersion 3 was used instead of amorphous polyester resin particle dispersion 1.
Evaluation was performed in the same manner as in Example 1 by using the obtained toner 3 and developer 3. The evaluation results are shown in Table 1.

[Example 4]
Toner 4 and developer 4 were produced in the same manner as in Example 1, except that amorphous polyester resin particle dispersion 4 was used instead of amorphous polyester resin particle dispersion 1.
The obtained toner 4 and developer 4 were used and evaluated in the same manner as in Example 1. The evaluation results are shown in Table 1.

[Example 5]
Toner 5 and developer 5 were produced in the same manner as in Example 1 except that amorphous polyester resin particle dispersion 5 was used instead of amorphous polyester resin particle dispersion 1.
Evaluation was performed in the same manner as in Example 1 by using the obtained toner 5 and developer 5. The evaluation results are shown in Table 1.

[Example 6]
A toner 6 and a developer 6 were produced in the same manner as in Example 1 except that the amorphous polyester resin particle dispersion 6 was used instead of the amorphous polyester resin particle dispersion 1.
Evaluation was performed in the same manner as in Example 1 by using the obtained toner 6 and developer 6. The evaluation results are shown in Table 1.

[Example 7]
Toner 7 and developer 7 were produced in the same manner as in Example 1 except that amorphous polyester resin particle dispersion 7 was used instead of amorphous polyester resin particle dispersion 1.
Evaluation was performed in the same manner as in Example 1 by using the obtained toner 7 and developer 7. The evaluation results are shown in Table 1.

[Example 8]
Toner 8 and developer 8 were produced in the same manner as in Example 1, except that amorphous polyester resin particle dispersion 8 was used instead of amorphous polyester resin particle dispersion 1.
Evaluation was performed in the same manner as in Example 1 by using the obtained toner 8 and developer 8. The evaluation results are shown in Table 1.

[Example 9]
-Crystalline polyester resin particle dispersion: 57 parts by mass-Amorphous polyester resin particle dispersion 1: 310 parts by mass-Colorant dispersion: 62 parts by mass-Anionic surfactant (20% aqueous solution of Dowfax2A1): 15 parts by mass Part / release agent dispersion: 77 parts by mass In the above raw material, a crystalline polyester resin particle dispersion, an amorphous polyester resin particle dispersion 1, an anion in a polymerization kettle equipped with a pH meter, stirring blades, and thermometer. The surfactant was added to the polyester resin particle dispersion while stirring at 130 rpm for 115 minutes. A colorant dispersion and a release agent dispersion were added to and mixed with this, and then a 0.3 M nitric acid aqueous solution was added to the raw material mixture to adjust the pH to 4.8.
Subsequently, 13 parts by mass of a 10% by mass nitric acid aqueous solution of aluminum sulfate as a flocculant was dropped while applying a shearing force at 3000 rpm with an ultra turrax. Since the viscosity of the raw material mixture increased during the dropping of the flocculant, when the viscosity increased, the dropping speed was slowed so that the flocculant was not biased to one place. When the dropping of the flocculant was completed, the rotation speed was further increased to 5000 rpm, and the mixture was stirred for 5 minutes to sufficiently mix the flocculant and the raw material mixture.
Subsequently, the raw material mixture was stirred at 500 rpm while being heated to 25 ° C. with a mantle heater. After stirring for 10 minutes, it was confirmed that a primary particle size was formed using a Coulter Multisizer II (aperture diameter: 50 μm; manufactured by Coulter, Inc.), and then 43 ° C. at 0.1 ° C./min for growing aggregated particles. The temperature was raised to. Agglomerated particle growth was confirmed at any time using a Coulter Multisizer, and the agglomeration temperature and the number of rotations of stirring were changed depending on the agglomeration speed.
On the other hand, for agglomerated particles coating, 118 parts by mass of ion-exchanged water and 8.2 parts by mass of an anionic surfactant (20% aqueous solution of Dowfax2A1) are added to 171 parts by mass of the amorphous polyester resin particle dispersion 1. The mixture was mixed and previously adjusted to pH 3.8 to obtain a resin particle dispersion for coating. When the aggregated particles grew to 5.2 μm in the aggregation step, a coating resin particle dispersion prepared in advance was added and held for 20 minutes with stirring. Thereafter, in order to stop the growth of the coated aggregated particles, 1.5 parts by mass of EDTA was added, and then a 1M sodium hydroxide aqueous solution was added to control the pH of the raw material mixture to 7.6. Subsequently, in order to fuse the aggregated particles, the temperature was raised to 85 ° C. at a temperature raising rate of 1 ° C./min while adjusting the pH to 7.6. After reaching 85 ° C., the pH is adjusted to 7.6 or less in order to proceed with the fusion, and after confirming that the aggregated particles have fused with an optical microscope, ice water is used to stop the growth of the particle size. Was injected and quenched at a temperature lowering rate of 10 ° C./min.
Subsequently, the obtained particles were sieved once with a 15 μm mesh for the purpose of washing. Thereafter, approximately 10 times the amount of ion-exchanged water (30 ° C.) was added to the solid content, stirred for 20 minutes, and then once filtered. Further, the solid content remaining on the filter paper was dispersed in a slurry, washed with ion exchange water at 30 ° C. four times and dried to obtain toner particles having a volume average particle size of 5.8 μm.

To 100 parts of the toner particles prepared above, 1.2 parts of hydrophobic titania powder (Tokuyama, 20 nm) was added and externally added with a stirring mixer to obtain toner 9. Using the obtained toner 9, a developer 9 was obtained in the same manner as in Example 1.
Evaluation was performed in the same manner as in Example 1 by using the obtained toner 9 and developer 9. The evaluation results are shown in Table 1.

[Example 10]
A toner 10 and a developer 10 were produced in the same manner as in Example 9 except that the amorphous polyester resin particle dispersion 2 was used instead of the amorphous polyester resin particle dispersion 1.
Evaluation was carried out in the same manner as in Example 1 using the obtained toner 10 and developer 10. The evaluation results are shown in Table 1.

[Example 11]
In Example 9, a toner 11 and a developer 11 were produced in the same manner except that the amorphous polyester resin particle dispersion 3 was used instead of the amorphous polyester resin particle dispersion 1.
Evaluation was performed in the same manner as in Example 1 using the obtained toner 11 and developer 11. The evaluation results are shown in Table 1.

[Example 12]
A toner 12 and a developer 12 were produced in the same manner as in Example 9 except that the amorphous polyester resin particle dispersion 4 was used instead of the amorphous polyester resin particle dispersion 1.
Evaluation was performed in the same manner as in Example 1 using the obtained toner 12 and developer 12. The evaluation results are shown in Table 1.

[Example 13]
A toner 13 and a developer 13 were produced in the same manner as in Example 9 except that the amorphous polyester resin particle dispersion 5 was used instead of the amorphous polyester resin particle dispersion 1.
Evaluation was performed in the same manner as in Example 1 using the obtained toner 13 and developer 13. The evaluation results are shown in Table 1.

[Example 14]
A toner 14 and a developer 14 were produced in the same manner as in Example 9 except that the amorphous polyester resin particle dispersion 6 was used instead of the amorphous polyester resin particle dispersion 1.
Evaluation was performed in the same manner as in Example 1 using the obtained toner 14 and developer 14. The evaluation results are shown in Table 1.

[Example 15]
A toner 15 and a developer 15 were produced in the same manner as in Example 9 except that the amorphous polyester resin particle dispersion 7 was used instead of the amorphous polyester resin particle dispersion 1.
Evaluation was performed in the same manner as in Example 1 using the obtained toner 15 and developer 15. The evaluation results are shown in Table 1.

[Example 16]
In Example 9, a toner 16 and a developer 16 were produced in the same manner except that the amorphous polyester resin particle dispersion 8 was used instead of the amorphous polyester resin particle dispersion 1.
Evaluation was performed in the same manner as in Example 1 using the obtained toner 16 and developer 16. The evaluation results are shown in Table 1.

[Comparative Example 1]
Toner 17 and developer 17 were produced in the same manner as in Example 1 except that amorphous polyester resin particle dispersion 9 was used instead of amorphous polyester resin particle dispersion 1.
Evaluation was performed in the same manner as in Example 1 using the obtained toner 17 and developer 17. The evaluation results are shown in Table 1.

[Comparative Example 2]
A toner 18 and a developer 18 were produced in the same manner as in Example 1 except that the amorphous polyester resin particle dispersion 10 was used instead of the amorphous polyester resin particle dispersion 1.
Evaluation was performed in the same manner as in Example 1 by using the obtained toner 18 and developer 18. The evaluation results are shown in Table 1.

[Comparative Example 3]
A toner 19 and a developer 19 were produced in the same manner as in Example 1 except that the amorphous polyester resin particle dispersion 11 was used instead of the amorphous polyester resin particle dispersion 1.
Evaluation was performed in the same manner as in Example 1 by using the obtained toner 19 and developer 19. The evaluation results are shown in Table 1.

[Comparative Example 4]
An amorphous polyester resin particle dispersion was prepared in the same manner as in the amorphous polyester resin particle dispersion 1, except that IRGANOX-1010 was 101.3 parts by mass and the amorphous polyester resin was 248.7 parts by mass. Using this amorphous polyester resin particle dispersion, toner 20 and developer 20 were produced in the same manner as toner 1.
Evaluation was performed in the same manner as in Example 1 using the obtained toner 20 and developer 20. The evaluation results are shown in Table 1.

[Comparative Example 5]
A toner 21 and a developer 21 were produced in the same manner as in Example 9 except that the amorphous polyester resin particle dispersion 9 was used instead of the amorphous polyester resin particle dispersion 1.
The obtained toner 21 and developer 21 were used for evaluation in the same manner as in Example 1. The evaluation results are shown in Table 1.

1Y, 1M, 1C, 1K, 107 photoconductor (image carrier)
2Y, 2M, 2C, 2K, 108 Charging roller 3Y, 3M, 3C, 3K Laser beam 3 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 (6)

Amorphous polyester resin, compound represented by the following formula (B), compound represented by the following formula (D), compound represented by the following formula (E), compound represented by the following formula (F) And 1% by mass or more and 20% by mass or less of at least one selected from the group consisting of compounds represented by the following formula (G).




  The electrostatic image developing toner according to claim 1, further comprising a crystalline resin.   An electrostatic charge image developing developer comprising the electrostatic charge image developing toner according to claim 1.   A toner cartridge containing at least toner, wherein the toner is the electrostatic image developing toner according to claim 1.   A process cartridge comprising at least a developer holding member and containing the developer for developing an electrostatic image according to claim 3. 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 charge image formed on the surface of the photoreceptor as a toner image with the developer for developing an electrostatic charge image according to claim 3;
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.