JP2010230990A - Toner for electrostatic latent image development, electrostatic latent image developer, toner cartridge, process cartridge, and image forming apparatus - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a toner for electrostatic latent image development hardly causing a curl of a fixed image, an electrostatic latent image developer using the toner, a toner cartridge, a process cartridge, and an image forming apparatus. <P>SOLUTION: The toner for an electrostatic latent image development comprises a binder resin, a mold release agent, and silica particles. When an endothermic peak Tm in a temperature rising process and an exothermic peak Tc in the temperature lowering process of the mold release agent are measured by the ASTM method using a differential scanning calorimeter (DSC), a difference between the endothermic peak Tm and the exothermic peak Tc is 30-50°C. In the binder resin, 20-100 mass% of the whole binder resin is a resin wherein a ratio of the structural unit derived from an aliphatic monomer is 90-100 mol% among the structural units constituting the resin. A content of the silica particles for 100 pts.mass of the binder resin is 2-20 pts.mass. The electrostatic latent image developer using the above toner, a toner cartridge, a process cartridge, and an image forming apparatus are also provided. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

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

  A method of visualizing image information through an electrostatic latent image by electrophotography or the like is currently used in various fields. In electrophotography, image information is formed as an electrostatic latent image on the surface of a latent image carrier (photoreceptor) by charging and exposure processes, and the toner image is developed on the surface of the photoreceptor using a developer containing toner. The toner image is visualized as an image through a transfer process for transferring the toner image to a recording medium (transfer object) and a fixing process for fixing the toner image on the surface of the recording medium.

In recent years, color image formation by color electrophotography, which has been remarkably popular, generally uses four color toners, including three subtractive primary colors, yellow, magenta, and cyan, and black toner. It is a reproduction.
In general color electrophotography, first, an original (image information) is color-separated into yellow, magenta, cyan, and black, and an electrostatic latent image is formed on the surface of the photoreceptor for each color. At this time, the electrostatic latent image formed for each color is developed using a developer containing toner of each color to form a toner image, and the toner image is transferred to the surface of the recording medium through a transfer process. A series of steps from the formation of the electrostatic latent image to the transfer of the toner image onto the surface of the recording medium are sequentially performed for each color, and the toner images of the respective colors are superimposed and transferred onto the surface of the recording medium. The color toner image obtained by transferring the color toner images onto the surface of the recording medium in this manner is fixed as a color image through a fixing step.

  In these color image formations, in addition to conventional Y (yellow), M (magenta) C (cyan), and BK (black), a transparent toner is used to correct the gloss difference in the image plane, Attempts have been made to control the gloss on the transfer paper surface and to correct the image density and the toner adhesion amount.

Polyester resin is used as the binder resin in the toner, and the aromatic component as the acid-derived component is 90 mol% or more based on the total acid-derived component, and the linear aliphatic diol as the alcohol-derived component is derived from the entire alcohol. When the polyester resin containing in the range of 85 to 98 mol% with respect to the constituent components contains 70% by mass or more of the total binder resin component as a binder resin, and a film having a thickness of 20 μm is obtained with the polyester resin, The luminous reflectance Y of the film is 1.5% or less, and the polyester resin is a bisphenol S or bisphenol S alkylene oxide adduct in a range of 2 to 15 mol% with respect to all alcohol-derived components. An electrophotographic transparent toner containing the same is disclosed (for example, see Patent Document 1).
JP 2005-99122 A

  The present invention relates to a toner for developing an electrostatic latent image which is less likely to bend (hereinafter sometimes referred to as curling) of a fixed image after fixing, and an electrostatic latent image developer, toner cartridge, process cartridge and image using the same An object is to provide a forming apparatus.

  That is, the invention according to claim 1 includes a binder resin, a release agent, and silica particles, and an endothermic peak Tm and a temperature lowering process of the release agent in the temperature rising process by the ASTM method using a differential scanning calorimeter (DSC). The difference between Tm and Tc when measuring the exothermic peak Tc of the mold release agent at 30 ° C. or more and 30 ° C. or less is the structural unit derived from the aliphatic monomer among the structural units constituting the resin. The resin having a ratio of 90 mol% or more and 100 mol% or less occupies 20 mass% or more and 100 mass% or less of the entire binder resin, and the silica particles are 2 mass parts or more with respect to 100 mass parts of the binder resin. It is an electrostatic latent image developing toner contained in an amount of 20 parts by mass or less.

  In the invention according to claim 2, the polyester resin in which 5 mol% or more and 50 mol% or less of the acid-derived structural unit constituting the resin is derived from dodecenyl succinic acid is 10 mass% or more and 90 mass% or less of the whole binder resin. The toner for developing an electrostatic latent image according to claim 1.

  The invention according to claim 3 is the electrostatic latent image developing toner according to claim 1 or 2, wherein Al is contained in the release agent domain of the toner.

  The invention according to claim 4 is the electrostatic latent image developing according to claim 3, wherein the content of Al in the release agent domain by X-ray fluorescence analysis is 0.005 atom% or more and 0.1 atom% or less. Toner.

  A fifth aspect of the present invention is an electrostatic latent image developer including at least the electrostatic latent image developing toner according to any one of the first to fourth aspects.

  The invention according to claim 6 is detachably attached to the image forming apparatus, and contains toner to be supplied to the developing means provided in the image forming apparatus. A toner cartridge which is the electrostatic latent image developing toner according to any one of the items.

  According to a seventh aspect of the present invention, there is provided a process cartridge including at least a developer holder and containing the electrostatic latent image developer according to the fifth aspect.

  According to an eighth aspect of the present invention, there is provided a latent image holding member, and developing means for developing the electrostatic latent image formed on the latent image holding member as a toner image with the electrostatic latent image developer according to claim 5, An image forming apparatus comprising: a transfer unit that transfers a toner image formed on the latent image holding member to a transfer target; and a fixing unit that fixes the toner image transferred to the transfer target.

  According to the first aspect of the present invention, there is provided an electrostatic latent image developing toner that hardly causes curling of a fixed image after fixing.

  According to the invention of claim 2, curling of the fixed image is further suppressed.

  According to the invention of claim 3, curling of the fixed image is further suppressed.

  According to the invention of claim 4, curling of the fixed image is further suppressed.

  According to the fifth aspect of the present invention, there is provided an electrostatic latent image developer that hardly causes curling of a fixed image.

  According to the sixth aspect of the present invention, there is provided a toner cartridge that facilitates the supply of electrostatic latent image developing toner that is less likely to curl a fixed image.

  According to the seventh aspect of the present invention, it is possible to facilitate the handling of the electrostatic latent image developer that hardly causes the fixed image to be curled, and to improve the adaptability to the image forming apparatus having various configurations.

  According to the eighth aspect of the present invention, there is provided an image forming apparatus that forms an image in which a fixed image is hardly curled.

  Hereinafter, embodiments of an electrostatic latent image developing toner, an electrostatic latent image 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 latent image development>
The electrostatic latent image developing toner according to the present embodiment (hereinafter sometimes simply referred to as “toner”) includes a binder resin, a release agent, and silica particles, and is measured by a differential scanning calorimeter (DSC). When the endothermic peak Tm of the release agent in the temperature rising process and the exothermic peak Tc of the release agent in the temperature lowering process are measured by the ASTM method, the difference between Tm and Tc is 30 ° C. or more and 50 ° C. or less, A resin (hereinafter sometimes referred to as a specific binder resin) in which the proportion of structural units derived from an aliphatic monomer in the structural units constituting the resin is 90 mol% or more and 100 mol% or less. The toner occupies 20% by mass or more and 100% by mass or less of the entire resin, and the silica particles are contained in an amount of 2 parts by mass or more and 20 parts by mass or less based on 100 parts by mass of the binder resin.

  When the difference between Tm and Tc is less than 30 ° C., the crystallinity of the release agent is high (it is easy to crystallize as the release agent is cooled). Further, when the temperature is 30 ° C. or higher, it indicates that the crystallinity at the time of cooling is poor (it is difficult to crystallize even if the mold release agent is cooled), and this indicates that there is some crystallization inhibiting factor.

  When the release agent is crystallized, the resin constituting the fixed image contracts, and a phenomenon that the edge of the image bends in the image center direction with the image surface inside (forward curl phenomenon) occurs. When the curl phenomenon occurs, it may be inconvenient when images are continuously formed, for example, it becomes difficult to stack the image-fixed transfer materials. Further, if curling occurs during the image forming process, it may cause paper clogging, which is not preferable. The curling of the fixed image is particularly noticeable in the case of a transparent image formed with a transparent toner containing no color pigment.

  In the toner according to the exemplary embodiment, the difference between Tm and Tc is 30 ° C. or more and 50 ° C. or less, so that the crystal growth of the release agent contained in the toner is suppressed, and the fixed image derived from the crystal growth of the release agent. The contraction of the is suppressed.

  If the difference between Tm and Tc is less than 30 ° C., the shrinkage of the fixed image may not be suppressed. On the other hand, if the difference between Tm and Tc is larger than 50 ° C., the crystallization speed of the release agent is extremely slow, and problems such as image cracking are likely to occur immediately after fixing.

  In addition, Tm and Tc based on ASTM method (D3418-8) by a differential scanning calorimeter (DSC) are obtained by the following method. 1) Put 10 mg of sample in an aluminum cell and cover it (this is called a sample cell). For comparison, 10 mg of alumina is similarly put in an aluminum cell of the same type and covered (this is called a comparison cell). 2) Each of the sample cell and the comparison cell is set in a measuring device, heated from 30 ° C. to 200 ° C. at a temperature rising rate of 10 ° C./min in a nitrogen atmosphere, and left at 200 ° C. for 10 minutes. 3) After standing, the temperature is lowered to −30 ° C. at a temperature decreasing rate of −10 ° C./min using liquid nitrogen and left at −30 ° C. for 10 minutes. 4) After standing, the temperature is raised from −30 ° C. to 200 ° C. at a temperature raising rate of 20 ° C./min. During the operation of 4), an endothermic / exothermic curve is obtained. Tm and Tc are determined from the obtained endothermic / exothermic curve. As a measuring device, a differential scanning calorimeter DSC-7 manufactured by Perkin Elmer was used.

In the obtained endothermic / exothermic curve, whether or not Tm and Tc are derived from the release agent contained in the toner is determined as follows.
For Tm, the peak top temperature indicated by the endothermic curve generated near the melting temperature of the release agent was determined as the Tm of the release agent.
Regarding Tc, the peak top temperature indicated by the exothermic curve generated near the melting temperature of the release agent was determined as Tc of the release agent.

  In this embodiment, there is no particular limitation on the method of setting the difference between Tm and Tc to 30 ° C. or more and 50 ° C. or less. For example, a method of including a metal element such as Al in the release agent domain, a release agent, a dispersion There is a method of simultaneously dispersing an aggregating agent containing Al when mixing an agent and ion-exchanged water and dispersing at high pressure / high temperature.

Although the toner according to the exemplary embodiment includes a binder resin, the specific binder resin occupies 20% by mass to 100% by mass of the entire binder resin. The ratio of the structural unit derived from the aliphatic monomer in the specific binder resin is preferably 95 mol% or more and 97 mol% or less. If the proportion of the structural unit derived from the aliphatic monomer is less than 90 mol%, the binder resin may shrink during image fixing.
In the present embodiment, the aliphatic monomer refers to a monomer containing a chain aliphatic hydrocarbon and a cyclic aliphatic hydrocarbon in the monomer. A hydrocarbon containing a double bond such as a benzene ring may be contained in the aliphatic monomer.
If the specific binder resin is less than 20% by mass of the total binder resin, the binder resin may shrink during image fixing. The proportion of the specific binder resin in the entire binder resin is preferably 80% by mass or more and 100% by mass or less, more preferably 85% by mass or more and 100% by mass or less, and particularly preferably 90% by mass or more and 100% by mass or less.

  The toner according to the exemplary embodiment includes 2 parts by mass or more and 20 parts by mass or less of silica particles with respect to 100 parts by mass of the binder resin. When the content of the silica particles is less than 2 parts by mass, the effect of inhibiting the crystal growth of the release agent may not be exhibited. On the other hand, if the amount exceeds 20 parts by mass, the charging characteristics of the toner may be affected, and the transfer efficiency may not be maintained. The content of silica particles is preferably 5 parts by mass or more and 15 parts by mass or less with respect to 100 parts by mass of the binder resin.

In the present embodiment, a metal element such as Al may be contained in the release agent domain of the toner. Metal elements such as Al have a function as a crystal inhibitor for the release agent. Furthermore, a metal element such as Al is ionically bonded to the binder resin of the toner and has an effect of inhibiting the crystal growth of the release agent. As a result, the difference between Tm and Tc is set to 30 ° C. or more and 50 ° C. or less. Thereby, the occurrence of curling of the fixed image is further effectively prevented.
The metal element contained in the release agent domain is preferably Al since it has a high valence and is effective in suppressing crystallization of the release agent due to ionic bonds.
A method of including a metal element such as Al in the release agent domain will be described later.

Whether or not a metal element such as Al is contained in the release agent domain is confirmed by the following method.
The toner is embedded in an epoxy resin and cut with a diamond knife to prepare a sample having a thickness of several microns. Observation with a field emission scanning electron microscope (FE-SEM) is performed to confirm the release agent portion of the cross section of the toner, and the portion can be confirmed from the detected element with SEM-XMA (X-ray microanalyzer).

The content of Al in the release agent domain by fluorescent X-ray analysis is preferably 0.005 atom% or more and 0.1 atom% or less, more preferably 0.04 atom% or more and 0.07 atom% or less, and 0.05 atom% or more. 0.06 atom% or less is particularly preferable.
If the Al content is less than 0.005 atom%, the crystal growth of the release agent may not be suppressed. On the other hand, when the amount is more than 0.1 atom%, it is possible to suppress the crystal growth of the release agent, but in order to suppress melting of the release agent, the peelability between the transfer target and the fixing member is poor. There is. In particular, during low-temperature fixing or under conditions where the process speed is 225 mm / s or more, the peelability deteriorates, which is not preferable as a toner. When the Al content in the release agent domain is in the above range, the occurrence of curling of the fixed image is further effectively prevented.

  In the present embodiment, the low temperature fixing means that the toner is heated and fixed at about 120 ° C. or less.

Hereinafter, each component constituting the toner according to the exemplary embodiment will be described.
The toner according to the exemplary embodiment includes a binder resin, a release agent, silica particles, and other additives as necessary.

(Binder resin)
The toner according to the exemplary embodiment includes a binder resin.
In the present embodiment, the resin in which the proportion of the structural unit derived from the aliphatic monomer among the structural units constituting the resin is 90% by mole or more and 100% by mole or less is 20% by weight or more and 100% by weight of the total binder resin. If it is set as the structure which occupies the mass% or less, the kind of binder resin will not be specifically limited, The thermoplastic resin which consists of various natural or synthetic polymer substances can be used. For example, copolymer of styrene and acrylic acid or methacrylic acid, polyester resin, polyvinyl chloride resin, phenol resin, acrylic resin, methacrylic resin, polyvinyl acetate, silicone resin, polyurethane resin, polyamide resin, furan resin, epoxy resin Xylene resin, polyvinyl butyral resin, terpene resin, coumarone indene resin, polyether polyol resin and the like are used alone or in combination. Among these binder resins, it is preferable to contain a polyester resin in terms of fixing with low energy.

  In the present embodiment, the polyester resin in which 5 mol% or more and 50 mol% or less of the structural unit derived from the acid constituting the resin is derived from dodecenyl succinic acid (hereinafter sometimes referred to as a polyester resin containing DSA) is described above. It is preferable that the binder resin occupy 20% by mass or more and 100% by mass or less. In the polyester resin containing DSA, 20 mol% or more and 30 mol% or less is more preferably a structural unit derived from dodecenyl succinic acid. The polyester resin in which 5 mol% or more of the acid-derived structural unit is derived from dodecenyl succinic acid has a higher glass transition temperature than the case where the structural unit derived from dodecenyl succinic acid is not included, so that the shrinkage of the resin constituting the fixed image is suppressed. Is done. Moreover, the polyester resin in which 50 mol% or less of the structural unit derived from the acid is derived from dodecenyl succinic acid is not conspicuous in yellow coloring of the resin, and is excellent in transparency.

The polyester resin containing DSA preferably occupies 80% by mass or more and 100% by mass or less, and more preferably 90% by mass or more and 95% by mass or less of the entire binder resin.
In addition, as a polyester resin, a crystalline polyester resin and an amorphous polyester resin can also be used together. In this case, the non-crystalline polyester resin may be a polyester resin containing DSA.

-Crystalline polyester resin-
In the present embodiment, it is desirable to use a crystalline polyester resin from the viewpoint of more rapid changes in viscosity due to heating, and from the viewpoint of achieving both mechanical strength and low-temperature fixability.

  Here, “crystallinity” in the crystalline polyester resin means that it has a clear endothermic peak, not a stepwise endothermic amount change in differential scanning calorimetry (DSC). It means that the half-value width of the endothermic peak when measured at a temperature rate of 10 (° C./min) is within 10 (° C.). On the other hand, a resin whose half width exceeds 10 ° C. or a resin in which no clear endothermic peak is observed means an amorphous polyester resin (amorphous polymer).

  In addition, the polymerizable monomer component constituting the crystalline polyester resin includes a polymerizable monomer component having a linear aliphatic component rather than a polymerizable monomer having an aromatic component in order to easily form a crystal structure. A mass is desirable. Furthermore, in order not to impair the crystallinity, it is preferable that the structural units derived from the polymerizable monomer are 30% by mole or more as a single species in the polymer.

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

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

  The crystalline polyester resin used 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 dodecenyl succinic acid, 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.
Furthermore, in addition to the aliphatic dicarboxylic acid and aromatic dicarboxylic acid, a dicarboxylic acid component having a double bond may be contained.

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

  Specific examples of the aliphatic diol suitably used for the synthesis of the crystalline polyester used in the toner 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. When the content of the aliphatic diol is less than 80 mol%, the crystallinity of the polyester resin is lowered and the melting temperature is lowered, so that toner blocking resistance, image storage stability, and low-temperature fixability may be deteriorated. .

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

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

The production of the crystalline polyester resin can be carried out at a polymerization temperature of 180 ° C. or higher and 230 ° C. or lower. If necessary, the reaction system is reduced in pressure and reacted while removing water and alcohol generated during condensation. .
When the polymerizable monomer is not dissolved or compatible at the reaction temperature, a solvent having a high boiling point may be added as a solubilizer and dissolved. In this case, the polycondensation reaction is performed while distilling off the solubilizing solvent. 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.

  Catalysts usable in the production of the polyester resin include alkali metal compounds such as sodium and lithium; alkaline earth metal compounds such as magnesium and calcium; zinc, manganese, antimony, titanium, tin, zirconium, germanium and the like Metal compounds; phosphorous acid compounds; phosphoric acid compounds; and amine compounds.

  Specifically, sodium acetate, sodium carbonate, lithium acetate, lithium carbonate, calcium acetate, calcium stearate, magnesium acetate, zinc acetate, zinc stearate, zinc naphthenate, zinc chloride, manganese acetate, manganese naphthenate, titanium tetraethoxy , Titanium tetrapropoxide, titanium tetraisopropoxide, titanium tetrabutoxide, antimony trioxide, triphenylantimony, tributylantimony, tin formate, tin oxalate, tetraphenyltin, dibutyltin dichloride, dibutyltin oxide, diphenyltin oxide, zirconium tetra Butoxide, Zirconium naphthenate, Zirconyl carbonate, Zirconyl acetate, Zirconyl stearate, Zirconyl octylate, Germanium oxide, Trif Alkenyl phosphite, tris (2,4-di -t- butyl-phenyl) phosphite, ethyltriphenylphosphonium bromide, triethylamine, compounds such as triphenyl amine.

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

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

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

  The weight average molecular weight can be 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 polyester resin 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% by mass. The range is as follows.

(Non-crystalline polyester resin)
In this embodiment, the use of an amorphous polyester resin as a binder resin improves compatibility with the crystalline polyester resin. The low-viscosity polyester resin also has a low viscosity, and a sharp melt property (sensitive melting property) as a toner can be obtained, which 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 toner and the strength of fixed images.

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 polyvalent carboxylic acids include aromatic carboxylic acids such as terephthalic acid, isophthalic acid, phthalic anhydride, trimellitic anhydride, pyromellitic acid, naphthalene dicarboxylic acid; maleic anhydride, fumaric acid, succinic acid, alkenyl Aliphatic carboxylic acids such as succinic anhydride, adipic acid, and dodecenyl succinic acid; and alicyclic carboxylic acids such as cyclohexanedicarboxylic acid. These polyvalent carboxylic acids can be used alone or in combination. Among these polyvalent carboxylic acids, it is desirable to use aromatic carboxylic acids. In order to secure good fixability, it is desirable to use a trivalent or higher carboxylic acid (trimellitic acid or acid anhydride thereof) together with a dicarboxylic acid in order to form a crosslinked structure or a branched structure.

  Examples of the polyhydric alcohol in the non-crystalline 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 can be used. Among these polyhydric alcohols, aromatic diols and alicyclic diols are preferred, and among these, aromatic diols are more desirable. In order to secure better fixability, a trihydric or higher polyhydric alcohol (glycerin, trimethylolpropane, pentaerythritol) may be used in combination with the diol in order to form a crosslinked structure or a branched structure.

The glass transition temperature (Tg) of the non-crystalline polyester resin is preferably in the range of 50 ° C to 80 ° C. If Tg is lower than 50 ° C., problems may occur in terms of toner storage stability and fixed image storage stability. On the other hand, if the temperature is higher than 80 ° C., it may not be possible to fix at a lower temperature than in the past.
The Tg of the amorphous polyester resin is more preferably 50 ° C. or higher and 65 ° C. or lower.
The glass transition temperature of the non-crystalline polyester resin was determined as the peak temperature of the endothermic peak obtained by the differential scanning calorimetry (DSC).

  The content of the amorphous polyester resin is preferably in the range of 40% by mass to 95% by mass, more preferably in the range of 50% by mass to 90% by mass, and still more preferably in the range of 60% by mass to 85% by mass. % Or less.

In addition, manufacture of the said amorphous polyester resin can be performed according to the case of the said crystalline polyester resin.
As described above, the crystalline resin and the non-crystalline resin in the present embodiment have been described using the crystalline polyester resin and the non-crystalline polyester resin. However, the contents other than the production of the polyester resin described above are other crystallinity in the present embodiment. This also applies to resins and non-crystalline resins.

(Release agent)
The toner according to the exemplary embodiment includes a release agent. Examples of the release agent include paraffin wax such as low molecular weight polypropylene and low molecular weight polyethylene; silicone resin; rosins; rice wax; carnauba wax; ester wax, montan wax, olefin wax and the like. Among these, paraffin wax, ester wax, olefin wax and the like are preferable, and paraffin wax, ester wax and the like are more preferable. The melting temperature of the release agent used in this embodiment is preferably 60 ° C. or higher and 105 ° C. or lower, and more preferably 75 ° 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.

(Silica particles)
The toner according to the exemplary embodiment includes 2 to 20 parts by mass of silica particles with respect to 100 parts by mass of the binder resin.
Examples of the silica particles used in the present embodiment include gas phase method silica, colloidal silica, metal alkoxide hydrolyzed silica, coprecipitation method silica, inorganic salt hydrolysis method silica, spray drying method silica, plasma method silica, laser method silica, and the like. Is mentioned.
The volume average particle diameter of the silica particles used in the present embodiment is preferably 20 nm to 1000 nm, more preferably 30 nm to 700 nm, and particularly preferably 50 nm to 500 nm.
The volume average particle size of the silica particles is a value obtained by measuring the particle size of 10000 arbitrary particles (magnification: 100000 times) using a scanning electron microscope apparatus (JSM-840F) manufactured by JEOL and measuring the number average. .
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.

The toner according to this embodiment may be a color toner such as cyan toner, magenta toner, yellow toner, or black toner, or may be a transparent toner.
In the present embodiment, the transparent toner is a toner used for a transparent toner image, and specifically, a toner having a content of a colorant such as a dye or a pigment of 0.01% by mass or less.

When the toner according to this embodiment is a colored toner, the toner according to this embodiment includes a colorant.
The colorant used in the colored toner may be a dye or a pigment, but is preferably a pigment 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 can be used.

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

  Since the transparent toner does not contain a colorant, the crystal growth of the release agent is hardly suppressed, and the fixed image is likely to curl. By configuring the transparent toner as the toner according to this embodiment, curling of the fixed image is effectively suppressed.

(Other additives)
In addition to the components described above, various components such as an internal additive, a charge control agent, inorganic powder (inorganic particles) other than silica particles, and organic particles are added to the toner according to the exemplary embodiment as necessary. be able to.
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, it is possible to adjust the image glossiness and the penetration into the paper. As the inorganic particles, for example, known inorganic particles such as titanium oxide particles, alumina particles, cerium oxide particles, or those obtained by hydrophobizing the surface thereof can be used alone or in combination of two or more.

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

  The volume average particle diameter can be measured using a Coulter Multisizer II (manufactured by Coulter) with an aperture diameter of 50 μm. In this case, the measurement was performed after the toner was dispersed in an electrolyte aqueous solution (Isoton aqueous solution) and dispersed with ultrasonic waves for 30 seconds.

Furthermore, the toner according to the present exemplary embodiment is preferably spherical 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 can be 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.

  In this embodiment, toner melted at 180 ° C. is poured into a mold (12 cm (X) × 1 cm (Y) × 1 cm (Z) rectangular parallelepiped) and left in a thermostatic chamber at 25 ° C. for 24 hours. When the length in the X direction of the obtained dimension measurement model is Q (cm), the molding shrinkage ratio Z (Q (cm) / 12 (cm)) obtained from the ratio to the dimension of the mold is It is preferably 0.5 or more and 1.0 or less, and more preferably 0.7 or more and 0.8 or less. If Z is 1.0 or less, image curling due to shrinkage of the fixed image is unlikely to occur. If it is 0.5 or more, the fixed image does not shrink, and the fixed image hardly permeates the paper.

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

  The emulsification aggregation method according to the present embodiment includes an emulsification process in which a raw material constituting a toner is emulsified to form resin particles (emulsion particles) of a binder resin such as a crystalline resin or an amorphous resin, and the aggregation of the resin particles. It has the aggregation process which forms an aggregate, and the fusion process which fuses an aggregate.

(Emulsification process)
For example, the crystalline resin dispersion can be produced by applying a shearing force to a solution obtained by mixing an aqueous medium and a crystalline resin with a disperser. At that time, particles can be formed by heating to lower the viscosity of the resin component. In addition, a dispersant may be used for stabilizing the dispersed resin particles. Furthermore, if the crystalline resin is oily and dissolves in a solvent having a relatively low solubility in water, the resin is dissolved in those solvents and dispersed in water together with a dispersant and a polymer electrolyte, and then heated or heated. A crystalline resin dispersion can be prepared by evaporating the solvent under reduced pressure. In the case of an amorphous resin, a dispersion of amorphous resin particles can be prepared according to the above.

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

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

  In preparing the release agent dispersion, the release agent is dispersed in water together with an ionic surfactant, a polymer electrolyte such as a polymer acid or a polymer base, and then heated to a temperature equal to or higher than the melting temperature of the release agent. Dispersion treatment is performed using a homogenizer or a pressure discharge type disperser capable of applying a strong shearing force while heating. By undergoing such treatment, a release agent dispersion can be obtained. During the dispersion treatment, an inorganic compound such as polyaluminum chloride can be added to the dispersion to allow the release agent to contain a metal element such as Al. Preferred inorganic compounds include, for example, polyaluminum chloride, aluminum sulfate, polyaluminum chloride (BAC), polyaluminum hydroxide, aluminum chloride and the like. Of these, polyaluminum chloride and aluminum sulfate are preferred. The release agent dispersion liquid is used in an emulsion aggregation method, but the release agent dispersion liquid can also be used when a toner is produced by a suspension polymerization method.

By the dispersion treatment, a release agent dispersion liquid containing release agent particles having a volume average particle diameter of 1 μm or less can be obtained. A more preferable volume average particle diameter of the release agent particles is 100 nm or more and 500 nm or less.
When the volume average particle diameter is less than 100 nm, although it depends on the properties of the binder resin used, it is generally difficult for the release agent component to be taken into the toner. On the other hand, if it exceeds 500 nm, the dispersion state of the release agent in the toner may be insufficient.

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

(Aggregation process)
In the agglomeration step, a dispersion of crystalline resin particles, a dispersion of amorphous resin particles, a release agent dispersion, a colorant dispersion used as necessary, and the like are mixed to form a mixed solution. The particles are aggregated by heating at a temperature lower than the glass transition temperature of the conductive resin particles to form aggregated particles. Aggregated particles are formed by acidifying the pH of the mixed solution with stirring. As pH, the range of 2-7 is desirable, The range of 2.2-6 is more desirable, The range of 2.4-5 is further more desirable. At this time, it is also effective to use a flocculant.
In the aggregation step, the release agent dispersion may be added and mixed at once with various dispersions such as a resin dispersion, or may be added in multiple portions.

  As the aggregating agent, a surfactant having a polarity opposite to that of the surfactant used for the dispersant, an inorganic metal salt, and a metal complex having a valence of 2 or more can be preferably used. In particular, the use of a metal complex is particularly desirable because the amount of the surfactant used can be reduced and the charging characteristics are improved.

Examples of the inorganic metal salt include metal salts such as calcium chloride, calcium nitrate, barium chloride, magnesium chloride, zinc chloride, aluminum chloride, and aluminum sulfate, and polyaluminum chloride, polyaluminum hydroxide, and calcium polysulfide. Examples thereof include inorganic metal salt polymers. Of these, aluminum salts and polymers thereof are particularly preferred. In order to obtain a sharper particle size distribution, the valence of the inorganic metal salt is bivalent than monovalent, trivalent than bivalent, trivalent than trivalent, and tetravalent than trivalent. The inorganic metal salt polymer is more suitable.
In the present embodiment, it is preferable to use a polymer of a tetravalent inorganic metal salt containing aluminum in order to obtain a sharp particle size distribution.

  Further, by adding non-crystalline resin particles when the agglomerated particles have a desired particle size (coating step), a toner having a structure in which the surface of the core agglomerated particles is coated with the non-crystalline resin is prepared. Also good. In this case, the crystalline resin is difficult to be exposed on the toner surface, which is desirable from the viewpoint of chargeability and developability. In the case of additional addition, a flocculant may be added or pH adjustment may be performed before additional addition.

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

Cool after fusion to obtain fused particles. Further, in the cooling step, crystallization may be promoted by so-called gradual cooling in which the cooling rate is reduced in the vicinity of the melting temperature of the crystalline resin (melting temperature ± 10 ° C.).
The fused particles obtained by fusing can be converted into toner particles through a solid-liquid separation process such as filtration, and a washing process and a drying process as necessary.

-External additive-
To the obtained toner particles, inorganic oxides typified by silica, titania and aluminum oxide can be added and adhered for the purpose of charge adjustment, fluidity provision, charge exchangeability and the like. These can be performed by, for example, a V-type blender, a Henschel mixer, a Redige mixer, or the like, and can be attached in stages.

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

The inorganic particles are generally used for the purpose of improving toner fluidity. Among the inorganic particles, by using TiO (OH) ₂ metatitanate, it has excellent transparency, good chargeability, environmental stability, fluidity, caking resistance, stable negative chargeability, and stable image quality maintainability. Is obtained. In addition, the hydrophobized compound of metatitanic acid has an electric resistance of 10 ¹⁰ Ω · cm or more, and can obtain high transferability without generating reversely charged toner even when the transfer electric field is increased. This is preferable because it is possible. The volume average particle diameter of the external additive for the purpose of imparting fluidity is preferably in the range of 1 nm to 40 nm in terms of the primary particle diameter, and more preferably in the range of 5 nm to 20 nm. The volume average particle diameter of the external additive for the purpose of improving transferability is preferably from 50 nm to 500 nm. These external additive particles are preferably subjected to surface modification such as hydrophobization in order to stabilize the chargeability and developability.

  A conventionally known method can be used as the surface modification means. Specific examples include coupling treatments such as silane, titanate, and aluminate. The coupling agent used for the coupling treatment is not particularly limited. For example, methyltrimethoxysilane, phenyltrimethoxysilane, methylphenyldimethoxysilane, diphenyldimethoxysilane, vinyltrimethoxysilane, γ-aminopropyltrimethoxysilane , Γ-chloropropyltrimethoxysilane, γ-bromopropyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-ureidopropyltrimethoxysilane, fluoroalkyltrimethoxysilane, hexa Silane coupling agents such as methyldisilazane; titanate coupling agents; aluminate coupling agents;

  Furthermore, various additives may be added as necessary. Examples of these additives include other fluidizing agents, cleaning aids such as polystyrene particles, polymethyl methacrylate particles, and polyvinylidene fluoride particles, and zinc stearyl. Examples thereof include abrasives for the purpose of removing adhering substances such as amide and strontium titanate.

The amount of the external additive added is preferably in the range of 0.1 to 5 parts by mass, more preferably in the range of 0.3 to 2 parts by mass with respect to 100 parts by mass of the toner particles. If the addition amount is less than 0.1 parts by mass, the fluidity of the toner may be deteriorated, and there are problems such as deterioration of chargeability and charge exchange property, which is not good. On the other hand, when the added amount is more than 5 parts by mass, an excessive covering state is caused, and the excessive inorganic oxide may be transferred to the contact member to cause a secondary failure.
Further, if necessary, coarse particles of toner may be removed after external addition using an ultrasonic sieving machine, a vibration sieving machine, a wind sieving machine, or the like.

  In addition to the external additives described above, it is possible to add other components (particles) such as a charge control agent, organic particles, a lubricant, and an abrasive.

  The charge control agent is not particularly limited, but a colorless or light-colored agent can be preferably used. For example, quaternary ammonium salt compounds, nigrosine compounds, complexes of aluminum, iron, chromium, and triphenylmethane pigments can be used.

Examples of the organic particles include particles usually used as an external additive on the toner surface, such as vinyl resins, polyester resins, and silicone resins. These inorganic particles and organic particles can be used as fluidity aids, cleaning aids, and the like.
Examples of the lubricant include fatty acid amides such as ethylene bis stearic acid amide and oleic acid amide, and fatty acid metal salts such as zinc stearate and calcium stearate.
As an abrasive | polishing agent, the above-mentioned silica, alumina, cerium oxide etc. are mentioned, for example.

<Electrostatic latent image developer>
The electrostatic latent image developer according to this embodiment includes at least the toner according to this embodiment.
The toner according to the exemplary embodiment is used as it is as a one-component developer or as a two-component developer. When used as a two-component developer, it is used by mixing with a carrier.

  There is no restriction | limiting in particular as a carrier which can be used for a two-component developer, A well-known carrier can be 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 containing organosiloxane bonds or modified products thereof, fluororesins, polyesters, polycarbonates, phenol resins, epoxy resins, etc., but are not limited thereto. Absent.

  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, tin oxide, and carbon black. It is not limited.

  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 desirable. The volume average particle diameter of the carrier core material is generally in the range of 10 to 500 μm, and preferably in the range of 30 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 a coating layer forming solution prepared by dissolving the coating resin and, if necessary, various additives in an appropriate solvent. The solvent is not particularly limited, and may be selected in consideration of the coating resin to be used, coating suitability, and the like.

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

  The mixing ratio (mass ratio) of the toner according to the exemplary embodiment and the carrier in the two-component developer is preferably in the range of toner: carrier = 1: 100 to 30: 100, and 3: 100 to 20: 100. A range of degree is more desirable.

<Toner cartridge, process cartridge, and image forming apparatus>
The image forming apparatus according to the present embodiment includes a latent image holding member, and a developing unit that develops the electrostatic latent image formed on the latent image holding member as a toner image with the electrostatic latent image developer according to the present embodiment. A transfer unit that transfers the toner image formed on the latent image holding member to the transfer target; and a fixing unit that fixes the toner image transferred to the transfer target. You may have other means, such as the cleaning means which cleans the transfer residual component of a holding body.
The image forming apparatus according to the present embodiment includes, for example, a color image forming apparatus that repeatedly performs primary transfer of a toner image held on a latent image holding body such as a photosensitive drum to an intermediate transfer body, and a developing device for each color. It may be a tandem color image forming apparatus in which a plurality of latent image holders provided are arranged in series on an intermediate transfer member.

  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 main body of the image forming apparatus. As the process cartridge, the process cartridge according to the present embodiment that includes at least a developer holder and accommodates the electrostatic latent image developer according to the present embodiment is preferably used.

The image forming apparatus according to the present embodiment will be described below with reference to the drawings.
FIG. 1 is a schematic configuration diagram illustrating an example of an image forming apparatus according to the present embodiment. The image forming apparatus according to the present embodiment has a tandem configuration in which a plurality of photosensitive members as latent image holding members, that is, a plurality of image forming units (image forming units) are provided.

As shown in FIG. 1, the image forming apparatus according to this embodiment forms a transparent image with four image forming units 50Y, 50M, 50C, and 50K that respectively form yellow, magenta, cyan, and black images. Image forming units 50T to be arranged are arranged in parallel (tandem) at intervals.
Here, each of the image forming units 50Y, 50M, 50C, 50K, and 50T has the same configuration except for the color of the toner in the stored developer. The unit 50Y will be described as a representative. Note that the same reference numerals with magenta (M), cyan (C), black (K), and transparency (T) are attached to the same parts as the image forming unit 50Y in place of yellow (Y). Description of the image forming units 50M, 50C, 50K, and 50T is omitted.
In the image forming apparatus according to this embodiment, the toner according to this embodiment is used as at least one selected from the group consisting of yellow toner, magenta toner, cyan toner, black toner, and transparent toner.

  The yellow image forming unit 50Y includes a photoconductor 11Y as a latent image holding member, and this photoconductor 11Y is rotationally driven at a predetermined process speed by a driving unit (not shown) along the direction of an arrow A shown in the drawing. It has come to be. As the photoreceptor 11Y, for example, an organic photoreceptor having sensitivity in the infrared region is used.

  A charging roll (charging means) 18Y is provided above the photoconductor 11Y. A predetermined voltage is applied to the charging roll 18Y by a power source (not shown), and the surface of the photoconductor 11Y is predetermined. Charged to a certain potential.

  Around the photoreceptor 11Y, an exposure device (electrostatic latent image forming unit) 19Y that exposes the surface of the photoreceptor 11Y to form an electrostatic latent image on the downstream side in the rotation direction of the photoreceptor 11Y with respect to the charging roll 18Y. Is arranged. Here, as the exposure device 19Y, an LED array that can be miniaturized is used because of space, but the present invention is not limited to this, and an electrostatic latent image forming unit using another laser beam or the like is used. Of course there is no problem.

  Further, a developing device (developing unit) 20Y including a developer holding body that holds a yellow developer is disposed around the photoconductor 11Y on the downstream side in the rotation direction of the photoconductor 11Y with respect to the exposure device 19Y. The electrostatic latent image formed on the surface of the photoreceptor 11Y is visualized with yellow toner, and a toner image is formed on the surface of the photoreceptor 11Y.

  Below the photoconductor 11Y, an intermediate transfer belt (primary transfer means) 33 for primary transfer of a toner image formed on the surface of the photoconductor 11Y extends below the five photoconductors 11T, 11Y, 11M, 11C, and 11K. Are arranged as follows. The intermediate transfer belt 33 is pressed against the surface of the photoreceptor 11Y by the primary transfer roll 17Y. Further, the intermediate transfer belt 33 is stretched by three rolls of a drive roll 12, a support roll 13, and a bias roll 14, and is rotated in the direction of arrow B at a moving speed equal to the process speed of the photoconductor 11Y. It has become. On the surface of the intermediate transfer belt 33, the transparent toner image is primarily transferred prior to the yellow toner image primarily transferred as described above, and then the yellow toner image is primarily transferred, and each of the colors magenta, cyan, and black is further transferred. The toner images are sequentially primary-transferred and stacked.

  Further, around the photoreceptor 11Y, the toner remaining on the surface of the photoreceptor 11Y and the retransferred toner are cleaned downstream of the primary transfer roll 17Y in the rotation direction (arrow A direction) of the photoreceptor 11Y. A cleaning device 15Y is arranged. The cleaning blade in the cleaning device 15Y is attached so as to be in pressure contact with the surface of the photoreceptor 11Y in the counter direction.

  A secondary transfer roll (secondary transfer unit) 34 is pressed against the bias roll 14 that stretches the intermediate transfer belt 33 via the intermediate transfer belt 33. The toner image that is primarily transferred and laminated on the surface of the intermediate transfer belt 33 is applied to the surface of the recording paper (transfer object) P fed from a paper cassette (not shown) at the pressure contact portion between the bias roll 14 and the secondary transfer roll 34. , Electrostatically transferred. At this time, the toner image transferred and laminated on the intermediate transfer belt 33 has the transparent toner image at the bottom (position in contact with the intermediate transfer belt 33). The transparent toner image is at the top.

  Also, downstream of the secondary transfer roll 34, a fixing device (fixing means) for fixing the toner image transferred on the recording paper P onto the surface of the recording paper P by heat and pressure to form a permanent image. 35 is arranged.

  As the fixing device used in this embodiment, for example, a low surface energy material typified by a fluororesin component or a silicone resin is used on the surface, a fixing belt having a belt shape, and a fluororesin component or the like on the surface. Using a low surface energy material typified by a silicone resin, a cylindrical fixing roll can be mentioned.

  Next, the operation of each of the image forming units 50T, 50Y, 50M, 50C, and 50K that forms images of each color of transparent, yellow, magenta, cyan, and black will be described. Since the operations of the image forming units 50T, 50Y, 50M, 50C, and 50K are the same, the operation of the yellow image forming unit 50Y will be described as a representative example.

  In the yellow developing unit 50Y, the photoreceptor 11Y rotates in the direction of arrow A at a predetermined process speed. The surface of the photoconductor 11Y is negatively charged to a predetermined potential by the charging roll 18Y. Thereafter, the surface of the photoreceptor 11Y is exposed by the exposure device 19Y, and an electrostatic latent image corresponding to the image information is formed. Subsequently, the negatively charged toner is reversely developed by the developing device 20Y, and the electrostatic latent image formed on the surface of the photoconductor 11Y is visualized on the surface of the photoconductor 11Y to form a toner image. Thereafter, the toner image on the surface of the photoreceptor 11Y is primarily transferred onto the surface of the intermediate transfer belt 33 by the primary transfer roll 17Y. After the primary transfer, transfer residual components such as toner remaining on the surface of the photoreceptor 11Y are scraped off and cleaned by the cleaning blade of the cleaning device 15Y to prepare for the next image forming process.

  The above operations are performed by the image forming units 50T, 50Y, 50M, 50C, and 50K, and the toner images visualized on the surfaces of the photoreceptors 11T, 11Y, 11M, 11C, and 11K are successively transferred to the intermediate transfer belt. 33 is transferred onto the surface. In the color mode, each color toner image is transferred in the order of transparent, yellow, magenta, cyan, and black. In the two-color and three-color modes, only the toner image of the required color is used in this order. Or, multiple transfer is performed. Thereafter, the toner image that has been single-transferred or multiple-transferred onto the surface of the intermediate transfer belt 33 is secondarily transferred onto the surface of the recording paper P conveyed from a paper cassette (not shown) by the secondary transfer roll 34, and then the fixing device 35. It is fixed by heating and pressurizing. The toner remaining on the surface of the intermediate transfer belt 33 after the secondary transfer is cleaned by the belt cleaner 16 constituted by a cleaning blade for the intermediate transfer belt 33.

  In FIG. 1, in a yellow image forming unit 50Y, a developing device 20Y including a developer holding body for holding a yellow electrostatic latent image developer, a photoconductor 11Y, a charging roll 18Y, and a cleaning device 15Y are integrated. The process cartridge is detachable from the image forming apparatus main body. The image forming units 50T, 50K, 50C, and 50M are also configured as process cartridges in the same manner as the image forming unit 50Y.

  Next, the toner cartridge according to this embodiment will be described. The toner cartridge according to the present embodiment is detachably attached to the image forming apparatus, and stores toner to be supplied to a developing unit provided in the image forming apparatus. Note that the toner cartridge according to the present embodiment only needs to contain at least toner, and may contain developer, for example, depending on the mechanism of the image forming apparatus.

  Therefore, in the image forming apparatus having a configuration in which the toner cartridge can be attached and detached, the toner according to the present embodiment can be easily supplied to the developing device by using the toner cartridge that stores the toner according to the present embodiment. Can do.

  The image forming apparatus shown in FIG. 1 is an image forming apparatus having a configuration in which the toner cartridges 40Y, 40M, 40C, 40K, and 40T can be attached and detached. The developing devices 20Y, 20M, 20C, 20K, and 20T are respectively Are connected to a toner cartridge corresponding to the developing device (color) by a toner supply pipe (not shown). Further, when the amount of toner stored in the toner cartridge is low, the toner cartridge can be replaced.

  Hereinafter, although this embodiment is described further in detail based on an Example, this embodiment is not limited to the following Example. “Part” means “part by mass” unless otherwise specified.

-Synthesis of crystalline polyester resin (1)-
Decane dicarboxylic acid: 100 mol%
Nonanediol: 100 mol%
・ Dibutyltin oxide (catalyst): 0.25% by mass
After putting the above components into a heat-dried three-necked flask, the air in the container was brought into an inert atmosphere with nitrogen gas by depressurization, and the mixture was stirred and refluxed at 180 ° C. for 5 hours with mechanical stirring.
Then, it heated up gradually to 230 degreeC under pressure reduction, stirred for 2 hours, and air-cooled when it became a viscous state, the reaction was stopped, and the crystalline polyester resin (1) was synthesize | combined.
As a result of molecular weight measurement (polystyrene conversion) by gel permeation chromatography, the crystalline polyester resin (1) obtained had a weight average molecular weight (Mw) of 24,000 and a number average molecular weight (Mn) of 7,600. The acid value was 10.5 mgKOH / g.
Further, when the melting temperature (Tm) of the crystalline polyester resin (1) was measured by a differential scanning calorimeter (DSC) by the above-described measuring method, a clear endothermic peak was shown, and the endothermic peak temperature was 72. It was 3 ° C.

-Preparation of crystalline polyester resin dispersion (1)-
-Crystalline polyester resin (1): 100 parts-Methyl ethyl ketone: 60 parts Charge the above amount of methyl ethyl ketone into a separable flask, then gradually add the resin, stir with a three-one motor, and dissolve completely. An oil phase was obtained. The separable flask containing the oil phase was set to 65 ° C. with a water bath, and a 10% aqueous ammonia solution was gradually added dropwise to the stirred oil phase with a dropper so that the total amount became 5 parts. Next, 230 parts of ion-exchanged water was gradually added dropwise at a rate of 10 ml / min to effect phase inversion emulsification, and the solvent was removed while reducing the pressure with an evaporator to obtain a crystalline polyester resin dispersion (1). The volume average particle diameter of the resin particles was 145 nm. The solid content of the resin particles was adjusted to 20% by mass with ion exchange water.

-Synthesis of Amorphous Polyester Resin (1)-
-Bisphenol A ethylene oxide (EO) 2 mol adduct: 10 mol%
-Bisphenol A propylene oxide (PO) 1 mol adduct: 90 mol%
・ Terephthalic acid: 10 mol%
・ Fumaric acid: 40 mol%
-Dodecenyl succinic acid (DSA): 25 mol%
Charge the above components into a flask equipped with a stirrer, nitrogen inlet tube, temperature sensor, and rectification tower, and take 1 hour to raise the temperature to 190 ° C. Confirm that the reaction system is uniformly stirred. After that, 0.9% by mass of tin distearate was added. Furthermore, while distilling off the generated water, the temperature was raised to 240 ° C. over 6 hours from the same temperature, and the dehydration condensation reaction was continued at 240 ° C. for another 3 hours. The glass transition temperature was 60 ° C., and the acid value was 13.6 mgKOH. A non-crystalline polyester resin (1) having a weight average molecular weight of 16,000 and a number average molecular weight of 6,000 was obtained.

-Preparation of non-crystalline polyester resin dispersion (1)-
-Amorphous polyester resin (1): 100 parts-Methyl ethyl ketone: 60 parts Charge the above amount of methyl ethyl ketone into a separable flask, then gradually add the resin, and stir with a three-one motor to completely dissolve. The oil phase was obtained. The separable flask containing the oil phase was set to 40 ° C. with a water bath, and a 10% aqueous ammonia solution was gradually added dropwise to the stirred oil phase with a dropper so that the total amount became 3.5 parts. Next, 230 parts of ion-exchanged water was gradually added dropwise at a rate of 10 ml / min for phase inversion emulsification, and solvent removal was performed while reducing the pressure with an evaporator to obtain an amorphous polyester resin dispersion (1). The volume average particle diameter of the resin particles was 175 nm. The solid content of the resin particles was adjusted to 20% by mass with ion exchange water.

-Synthesis of amorphous polyester resin (2)-
-Bisphenol A ethylene oxide 2 mol adduct: 10 mol%
-Bisphenol A propylene oxide 1 mol adduct: 90 mol%
・ Fumaric acid: 40 mol%
-Dodecenyl succinic acid: 45 mol%
The glass transition temperature is 57 ° C., the acid value is 13.3 mgKOH / g, the weight average molecular weight is 15,000, and the number average molecular weight is 5800 in the same manner as the synthesis of the amorphous polyester resin (1) except that the above components are used. An amorphous polyester resin (2) was obtained.

-Preparation of non-crystalline polyester resin dispersion (2)-
-Amorphous polyester resin (2): 100 parts-Methyl ethyl ketone: 60 parts Charge the above amount of methyl ethyl ketone into a separable flask, then gradually add the resin, and stir with a three-one motor to completely dissolve. The oil phase was obtained. The separable flask containing the oil phase was set to 40 ° C. with a water bath, and a 10% aqueous ammonia solution was gradually added dropwise to the stirred oil phase with a dropper so that the total amount became 3.5 parts. Next, 230 parts of ion-exchanged water was gradually added dropwise at a rate of 10 ml / min for phase inversion emulsification, and solvent removal was performed while reducing the pressure with an evaporator to obtain an amorphous polyester resin dispersion (2). The volume average particle diameter of the resin particles was 175 nm. The solid content of the resin particles was adjusted to 20% by mass with ion exchange water.

-Synthesis of amorphous polyester resin (3)-
-Bisphenol A ethylene oxide 2 mol adduct: 10 mol%
-Bisphenol A propylene oxide 1 mol adduct: 90 mol%
・ Terephthalic acid: 18 mol%
・ Fumaric acid: 40 mol%
-Dodecenyl succinic acid: 4 mol%
The glass transition temperature is 59 ° C., the acid value is 13.4 mgKOH / g, the weight average molecular weight is 17,000, and the number average molecular weight is 6 in the same manner as in the synthesis of the amorphous polyester resin (1) except that the above components are used. 300 amorphous polyester resin (3).

-Preparation of non-crystalline polyester resin dispersion (3)-
-Amorphous polyester resin (3): 100 parts-Methyl ethyl ketone: 60 parts Charge the above amount of methyl ethyl ketone into a separable flask, then gradually add the resin, and stir with a three-one motor to completely dissolve. The oil phase was obtained. The separable flask containing the oil phase was set to 40 ° C. with a water bath, and a 10% aqueous ammonia solution was gradually added dropwise to the stirred oil phase with a dropper so that the total amount became 3.5 parts. Next, 230 parts of ion-exchanged water was gradually added dropwise at a rate of 10 ml / min to effect phase inversion emulsification, and the solvent was removed while reducing the pressure with an evaporator to obtain an amorphous polyester resin dispersion (3). The volume average particle diameter of the resin particles was 175 nm. The solid content of the resin particles was adjusted to 20% by mass with ion exchange water.

-Synthesis of amorphous polyester resin (4)-
-Bisphenol A ethylene oxide 2 mol adduct: 10 mol%
-Bisphenol A propylene oxide 1 mol adduct: 90 mol%
・ Terephthalic acid: 10 mol%
・ Fumaric acid: 40 mol%
The glass transition temperature was 61 ° C., the acid value was 13.1 mg KOH / g, the weight average molecular weight was 17,000, the number average molecular weight was 5 except that the above components were used. , 500 amorphous polyester resin (4) was obtained.

-Preparation of non-crystalline polyester resin dispersion (4)-
-Amorphous polyester resin (4): 100 parts-Methyl ethyl ketone: 60 parts Charge the above amount of methyl ethyl ketone into a separable flask, then gradually add the resin, stir with a three-one motor, and dissolve completely. The oil phase was obtained. The separable flask containing the oil phase was set to 40 ° C. with a water bath, and a 10% aqueous ammonia solution was gradually added dropwise to the stirred oil phase with a dropper so that the total amount became 3.5 parts. Next, 230 parts of ion-exchanged water was gradually added dropwise at a rate of 10 ml / min to effect phase inversion emulsification, and the solvent was removed while reducing the pressure with an evaporator to obtain an amorphous polyester resin dispersion (4). The volume average particle diameter of the resin particles was 175 nm. The solid content of the resin particles was adjusted to 20% by mass with ion exchange water.

-Synthesis of amorphous polyester resin (5)-
-Bisphenol A ethylene oxide 2 mol adduct: 10 mol%
-Bisphenol A propylene oxide 1 mol adduct: 90 mol%
・ Terephthalic acid: 10 mol%
・ Fumaric acid: 40 mol%
Dodecenyl succinic acid: 60 mol%
The glass transition temperature is 62 ° C., the acid value is 13.9 mgKOH / g, the weight average molecular weight is 16,000, the number average molecular weight is 6 except that the above components are used. 1,000 amorphous polyester resin (5) was obtained.

-Preparation of non-crystalline polyester resin dispersion (5)-
-Amorphous polyester resin (5): 100 parts-Methyl ethyl ketone: 60 parts Add the above amount of methyl ethyl ketone to a separable flask, then gradually add the resin, and stir with a three-one motor to completely dissolve. The oil phase was obtained. The separable flask containing the oil phase was set to 40 ° C. with a water bath, and 10% ammonia aqueous solution was gradually added dropwise to the stirred oil phase with a dropper so that the total amount was 3.5 parts. Then, 230 parts of ion-exchanged water was gradually added dropwise at a rate of 10 ml / min to carry out phase inversion emulsification, and the solvent was removed while reducing the pressure with an evaporator to obtain an amorphous polyester resin dispersion (5). The volume average particle diameter of the resin particles was 175 nm. The solid content of the resin particles was adjusted to 20% by mass with ion exchange water.

-Synthesis of Amorphous Polyester Resin (6)-
-Bisphenol A ethylene oxide 2 mol adduct: 50 mol%
-Bisphenol A propylene oxide 1 mol adduct: 50 mol%
・ Terephthalic acid: 16 mol%
-Dodecenyl succinic acid: 20 mol%
A glass transition temperature of 59 ° C., an acid value of 13.2 mgKOH / g, a weight average molecular weight of 19,000, and a number average molecular weight of 6 are the same as in the synthesis of the amorphous polyester resin (1) except that the above components are used. 300 amorphous polyester resin (6).

-Preparation of Amorphous Polyester Resin Dispersion (6)-
-Amorphous polyester resin (6): 100 parts-Methyl ethyl ketone: 60 parts Charge the above amount of methyl ethyl ketone into a separable flask, then gradually add the resin, and stir with a three-one motor to completely dissolve. The oil phase was obtained. The separable flask containing the oil phase was set to 40 ° C. with a water bath, and a 10% aqueous ammonia solution was gradually added dropwise to the stirred oil phase with a dropper so that the total amount became 3.5 parts. Next, 230 parts of ion-exchanged water was gradually added dropwise at a rate of 10 ml / min to effect phase inversion emulsification, and the solvent was removed while reducing the pressure with an evaporator to obtain an amorphous polyester resin dispersion (6). The volume average particle diameter of the resin particles was 175 nm. The solid content of the resin particles was adjusted to 20% by mass with ion exchange water.

-Synthesis of Amorphous Polyester Resin (7)-
-Bisphenol A ethylene oxide 2 mol adduct: 50 mol%
-Bisphenol A propylene oxide 1 mol adduct: 50 mol%
Dodecenyl succinic acid: 35 mol%
The glass transition temperature is 60 ° C., the acid value is 13.9 mgKOH / g, the weight average molecular weight is 19,000, and the number average molecular weight is 7 in the same manner as in the synthesis of the amorphous polyester resin (1) except that the above components are used. 1,000 amorphous polyester resin (7) was obtained.

-Preparation of non-crystalline polyester resin dispersion (7)-
-Amorphous polyester resin (7): 100 parts-Methyl ethyl ketone: 60 parts Charge the above amount of methyl ethyl ketone into a separable flask, then gradually add the resin, and stir with a three-one motor to dissolve completely. The oil phase was obtained. The separable flask containing the oil phase was set to 40 ° C. with a water bath, and a 10% aqueous ammonia solution was gradually added dropwise to the stirred oil phase with a dropper so that the total amount became 3.5 parts. Next, 230 parts of ion-exchanged water was gradually added dropwise at a rate of 10 ml / min to cause phase inversion emulsification, and the solvent was removed while reducing the pressure with an evaporator to obtain an amorphous polyester resin dispersion (7). The volume average particle diameter of the resin particles was 175 nm. The solid content of the resin particles was adjusted to 20% by mass with ion exchange water.

-Synthesis of amorphous polyester resin (8)-
-Bisphenol A ethylene oxide 2 mol adduct: 50 mol%
-Bisphenol A propylene oxide 1 mol adduct: 50 mol%
・ Terephthalic acid: 38 mol%
-Dodecenyl succinic acid: 3 mol%
The glass transition temperature is 60 ° C., the acid value is 13.5 mg KOH / g, the weight average molecular weight is 15,000, and the number average molecular weight is 6 in the same manner as in the synthesis of the amorphous polyester resin (1) except that the above components are used. 1,000 amorphous polyester resin (8) was obtained.

-Preparation of non-crystalline polyester resin dispersion (8)-
-Amorphous polyester resin (8): 100 parts-Methyl ethyl ketone: 60 parts Charge the above amount of methyl ethyl ketone into a separable flask, then gradually add the resin, and stir with a three-one motor to completely dissolve. The oil phase was obtained. The separable flask containing the oil phase was set to 40 ° C. with a water bath, and a 10% aqueous ammonia solution was gradually added dropwise to the stirred oil phase with a dropper so that the total amount became 3.5 parts. Next, 230 parts of ion-exchanged water was gradually added dropwise at a rate of 10 ml / min for phase inversion emulsification, and the solvent was removed while reducing the pressure with an evaporator to obtain an amorphous polyester resin dispersion (8). The volume average particle diameter of the resin particles was 175 nm. The solid content of the resin particles was adjusted to 20% by mass with ion exchange water.

-Synthesis of non-crystalline polyester resin (9)-
-Bisphenol A ethylene oxide 2 mol adduct: 50 mol%
-Bisphenol A propylene oxide 1 mol adduct: 50 mol%
・ Terephthalic acid: 15 mol%
A glass transition temperature of 67 ° C., an acid value of 11.8 mgKOH / g, a weight average molecular weight of 21,000, and a number average molecular weight of 9 are the same as in the synthesis of the amorphous polyester resin (1) except that the above components are used. 1,000 amorphous polyester resin (9) was obtained.

-Preparation of non-crystalline polyester resin dispersion (9)-
-Amorphous polyester resin (9): 100 parts-Methyl ethyl ketone: 60 parts Charge the above amount of methyl ethyl ketone into a separable flask, then gradually add the resin, and stir with a three-one motor to completely dissolve. The oil phase was obtained. The separable flask containing the oil phase was set to 40 ° C. with a water bath, and a 10% aqueous ammonia solution was gradually added dropwise to the stirred oil phase with a dropper so that the total amount became 3.5 parts. Next, 230 parts of ion-exchanged water was gradually added dropwise at a rate of 10 ml / min to effect phase inversion emulsification, and the solvent was removed while reducing the pressure with an evaporator to obtain an amorphous polyester resin dispersion (9). The volume average particle diameter of the resin particles was 175 nm. The solid content of the resin particles was adjusted to 20% by mass with ion exchange water.

-Synthesis of Amorphous Polyester Resin (10)-
-Bisphenol A ethylene oxide 2 mol adduct: 50 mol%
-Bisphenol A propylene oxide 1 mol adduct: 50 mol%
Dodecenyl succinic acid: 60 mol%
The glass transition temperature is 62 ° C., the acid value is 15.0 mgKOH / g, the weight average molecular weight is 21,000, and the number average molecular weight is 7 in the same manner as in the synthesis of the amorphous polyester resin (1) except that the above components are used. 1,000 amorphous polyester resin (10) was obtained.

-Preparation of non-crystalline polyester resin dispersion (10)-
-Amorphous polyester resin (10): 100 parts-Methyl ethyl ketone: 60 parts Charge the above amount of methyl ethyl ketone into a separable flask, then gradually add the resin, and stir with a three-one motor to completely dissolve. The oil phase was obtained. The separable flask containing the oil phase was set to 40 ° C. with a water bath, and a 10% aqueous ammonia solution was gradually added dropwise to the stirred oil phase with a dropper so that the total amount became 3.5 parts. Next, 230 parts of ion-exchanged water was gradually added dropwise at a rate of 10 ml / min for phase inversion emulsification, and solvent removal was performed while reducing the pressure with an evaporator to obtain an amorphous polyester resin dispersion (10). The volume average particle diameter of the resin particles was 175 nm. The solid content of the resin particles was adjusted to 20% by mass with ion exchange water.

  Table 1 shows the amount of each monomer used in the synthesis of the polyester resin, the proportion of structural units derived from aliphatic monomers among the structural units constituting the polyester resin, and the acid derived from the acid constituting the polyester resin. The ratio of the structural unit derived from dodecenyl succinic acid (DSA) in the structural unit is shown.

-Preparation of release agent dispersion 1-
・ Paraffin wax (melting temperature: 75 ° C., trade name HNP9, manufactured by Nippon Seiki Co., Ltd.): 50 parts ・ Ionic surfactant Neogen RK (Daiichi Kogyo Seiyaku Co., Ltd.): 1.0 part ・ Ion exchange Water: 200 parts ・ Aluminum polysulfate (Asada Chemical: Powder): 5 parts The above is heated to 95 ° C., dispersed with IKA Ultra Turrax T50, and heated to 110 ° C. with a pressure discharge type gorin homogenizer. Dispersion treatment was performed for 5 hours to obtain a release agent dispersion liquid 1 having a center diameter of 200 nm and a solid content of 20% by mass.

-Preparation of release agent dispersion 2-
・ Paraffin wax (melting temperature: 75 ° C., trade name HNP9, manufactured by Nippon Seiki Co., Ltd.): 50 parts ・ Ionic surfactant Neogen RK (Daiichi Kogyo Seiyaku Co., Ltd.): 1.0 part ・ Ion exchange Water: 200 parts Polyaluminum sulfate (Asada Chemical: Powder): 10 parts The above is heated to 95 ° C, dispersed with IKA Ultra Turrax T50, and then heated to 120 ° C with a pressure discharge type gorin homogenizer. Then, a dispersion treatment was performed for 7 hours to obtain a release agent dispersion 2 having a center diameter of 200 nm and a solid content of 20% by mass.

-Preparation of release agent dispersion 3-
・ Paraffin wax (melting temperature: 75 ° C., trade name HNP9, manufactured by Nippon Seiki Co., Ltd.): 50 parts ・ Ionic surfactant Neogen RK (Daiichi Kogyo Seiyaku Co., Ltd.): 1.0 part ・ Ion exchange Water: 200 parts Polyaluminum sulfate (Asada Chemical: Powder): 0.5 parts The above is heated to 95 ° C, dispersed with IKA Ultra Turrax T50, and then heated to 110 ° C with a pressure discharge type gorin homogenizer. The dispersion treatment was carried out for 4 hours with heating to obtain a release agent dispersion 3 having a center diameter of 200 nm and a solid content of 20% by mass.

-Preparation of release agent dispersion 4-
・ Paraffin wax (melting temperature: 75 ° C., trade name HNP9, manufactured by Nippon Seiki Co., Ltd.): 50 parts ・ Ionic surfactant Neogen RK (Daiichi Kogyo Seiyaku Co., Ltd.): 1.0 part ・ Ion exchange Water: 200 parts Polyaluminum sulfate (Asada Chemical: Powder): 30 parts The above is heated to 95 ° C, dispersed with IKA Ultra Turrax T50, and then heated to 130 ° C with a pressure discharge type gorin homogenizer. Then, a dispersion treatment was performed for 9 hours to obtain a release agent dispersion 4 having a center diameter of 200 nm and a solid content of 20% by mass.

-Preparation of release agent dispersion 5-
・ Paraffin wax (melting temperature: 75 ° C., trade name HNP9, manufactured by Nippon Seiki Co., Ltd.): 50 parts ・ Ionic surfactant Neogen RK (Daiichi Kogyo Seiyaku Co., Ltd.): 1.0 part ・ Ion exchange Water: 200 parts or more Heated to 95 ° C., dispersed with IKA Ultra Tarrax T50, heated to 110 ° C. with a pressure discharge type gorin homogenizer, dispersed for 3 hours, center diameter 200 nm, solid content Obtained 20% by mass of the release agent dispersion 5.

(Measurement method of content of metal element contained in mold release agent)
The release agent dispersion was frozen with liquid nitrogen, and then water was removed using a vacuum dryer to form a powder.
After pre-processing to compress 6g of powdered release agent under pressure for 10 tons for 1 minute with a pressure molder, use fluorescent X-rays (XRF-1500) from Shimadzu Corporation Then, the composition ratio (%) of the metal elements in all the elements was measured by the all element analysis method, and the Al content in the release agent was determined.
The measurement conditions were a tube voltage of 40 KV and a tube current of 90 mA.

  Table 2 summarizes the composition, dispersion method and conditions, and Al content (atom%) of each release agent dispersion.

[Example 1]
-Production of Toner 1-
-Crystalline polyester resin dispersion (1): 100 parts-Amorphous polyester resin dispersion (1): 300 parts-Amorphous polyester resin dispersion (6): 300 parts-Release agent dispersion (1) : 50 parts colloidal silica (trade name Snowtex PS): 18 parts The above was added to a round stainless steel flask, and 2.0 parts of the ionic surfactant Neogen RK was added, followed by stirring and mixing / dispersing. Subsequently, 1N nitric acid aqueous solution was dropped to pH 3.5, and then 0.40 part of polyaluminum chloride was added thereto, and the dispersion operation was continued with an ultra turrax. The flask was heated to 48 ° C. with stirring in an oil bath for heating. After holding at 48 ° C. for 40 minutes, a mixed solution of 100 parts of the amorphous polyester resin dispersion (1) and 100 parts of the amorphous polyester resin dispersion (6) was slowly added thereto.
Thereafter, 1N aqueous sodium hydroxide solution was added to bring the pH of the system to 7.0, and then the stainless steel flask was sealed and gradually heated to 90 ° C. while continuing stirring using a magnetic seal. Hold at 3 ° C. for 3 hours.
After completion of the reaction, the mixture was cooled, filtered, thoroughly washed with ion exchange water, and then subjected to solid-liquid separation by Nutsche suction filtration. This was further redispersed in 1 L of ion exchange water at 40 ° C., and stirred and washed at 300 rpm for 15 minutes.
This was repeated five more times, and when the pH of the filtrate became 7.5 and the electric conductivity was 7.0 μS / cm, solid-liquid separation was performed using No5A filter paper by Nutsche suction filtration. Next, vacuum drying was continued for 12 hours to obtain toner 1.
When the particle size at this time was measured by Coulter Multisizer II, the volume average particle size D50v was 5.9 μm, and the particle size distribution coefficient GSDv was 1.25. Moreover, the shape factor SF1 of the particle | grains calculated | required from the shape observation by Luzex was 136, and it was a potato form.
The particle size distribution coefficient GSDv is obtained by the equation “GSDv = (D84v / D16v) ^1/2 ”. Here, D84v is a particle diameter value that is 84% cumulative from the small diameter side in the volume distribution of the particle diameter, and D16v is a particle diameter value that is cumulative 16% from the small diameter side in the volume distribution of the particle diameter. D50v is a particle diameter value that is 50% cumulative from the small diameter side in the volume distribution of the particle diameter.
D16v, D50v, and D84v were performed using a Coulter Multisizer II (manufactured by Coulter, Inc.) with an aperture diameter of 50 μm. At this time, the measurement was performed after the sample was dispersed in an electrolyte aqueous solution (isoton aqueous solution) and dispersed by ultrasonic waves for 30 seconds.

<Creation of carrier>
Ferrite (trade name EFC-35B, manufactured by Powder Tech, weight average particle size: 35 μm): 100 parts Toluene: 13.5 parts Methyl methacrylate / perfluorooctyl methacrylate copolymer: 2.3 parts (polymerization ratio) 90:10, weight average molecular weight 49,000)
Carbon black (trade name: VXC72, manufactured by Cabot Corporation): 0.3 part Eposter S (melamine resin particles, manufactured by Nippon Shokubai Co., Ltd.): 0.3 part The above components except for ferrite are dispersed for 1 hour in a sand mill. A solution for forming a resin coating layer was prepared. Next, the resin coating layer forming solution and ferrite were put in a vacuum degassing kneader and stirred for 20 minutes while reducing the pressure at a temperature of 60 ° C. to form a resin coating layer on the ferrite to obtain a carrier. The volume resistance was 2 × 10 ¹¹ Ωcm.

<Preparation of electrostatic latent image developer>
The obtained carrier and toner 1 were mixed at a ratio of 100 parts: 8 parts by a 2 liter V blender to prepare an electrostatic latent image developer 1.

-Measurement of molding shrinkage ratio-
The obtained toner 1 was melted at 180 ° C., poured into a mold (a rectangular body of 12 cm (X) × 1 cm (Y) × 1 cm (Z)), and left in a constant temperature room at 25 ° C. for 24 hours. A dimension measurement model was created. The dimension Q in the X direction of the dimension measurement model was measured to determine the molding shrinkage ratio Z (Q (cm) / 12 (cm)). The results obtained are shown in Table 5.

-Judgment method of forward curl-
The electrostatic latent image developer 1 and toner 1 as a replenishing toner are charged into a modified Doccolor 500 (manufactured by Fuji Xerox Co., Ltd.) having a variable process speed, a process speed of 140 mm / sec; a fixing temperature of 140 ° C .; 5 g / m ² ; paper: Fuji Xerox J paper (basis weight 82 g / m ² ) A4 size (width 210 mm × height 297 mm); image part: width 205 mm × height 290 mm (solid image) An image was formed.
The 100th sheet of paper at this time is placed on a smooth board surface with the surface on which the solid image is formed facing upward, and the edge of the paper surface (the portion corresponding to 100 mm to 105 mm from the paper edge) is the paper edge (horizontal from the paper edge). The height of the portion corresponding to 1 mm to 5 mm) was measured with a caliper, and the curl condition was evaluated as follows based on the height of the image edge portion at this time. The allowable range was up to Δ. The evaluation results are shown in Table 3.
<Evaluation criteria>
0mm or more and less than 0.5mm ... ・ ◎ (not curled)
0.5mm or more and less than 2mm ・ ・ ・ ○ (almost not curled)
2 mm or more and less than 10 mm △△ (curled slightly)
10mm or more ・ ・ ・ ・ × (curled)

-Measuring method of transfer efficiency-
The electrostatic latent image developer 1 and toner 1 as a replenishing toner are charged into a modified Doccolor 500 (manufactured by Fuji Xerox Co., Ltd.) having a variable process speed. The process speed is 140 mm / sec; the fixing temperature is 140 ° C .; 5 g / m ² ; Paper: Fuji Xerox J paper (basis weight 82 g / m ² ) A4 size (width 210 × length 297 mm); image portion: width 205 mm × length 290 mm (solid image) An image was formed.
Then, the weight M1 before use of the toner hopper filled with the replenishing toner and the weight M2 after image formation of 1000 sheets are measured, and the toner consumption (mg / sheet) per A4 sheet is obtained by the following formula. It was.
Toner consumption (mg / sheet) = (M1-M2) / A4 number of copies (1000 sheets)
Further, the toner transfer efficiency (%) was obtained by the following equation from the amount of toner M3 collected by the copying machine cleaning device and the value of (M1-M2).
Transfer efficiency (%) = ((M1-M2) -M3) / (M1-M2) × 100
Based on the transfer efficiency at this time, evaluation was performed as follows. In addition, it was set as the tolerance | permissible_range to (triangle | delta). The evaluation results are shown in Table 3.
<Evaluation criteria>
97% or more ◎◎ (Good transfer efficiency)
95% or more and less than 97% ... ○ (good)
93% or more and less than 95% ... △ (Transfer is not good)
Less than 93% ・ ・ ・ × (Poor transfer efficiency)

-Evaluation of fixing temperature range-
Electrostatic latent image developer 1 and toner 1 as replenishment toner are filled in a modified Doccolor 500 (manufactured by Fuji Xerox) with a variable process speed, and the fixing temperature is 80 ° C. or higher under the condition that the process speed is fixed at 140 mm / sec. The fixing test was carried out by changing the temperature within a range of 180 ° C. or less.
The amount of applied toner was adjusted to 4.5 g / m ² . The toner has a good fixing temperature range in which a fixed solid image (25 mm × 25 mm) is fixed and then a fixed image portion is bent by applying a load of 1.0 kg to destroy the fixed image. The line width of the void was measured, and the lowest temperature that was 0.5 mm or less was defined as the lowest fixing temperature. Further, the lowest temperature at which the toner component migrates to the fixing member (hot offset) was set as the maximum fixing temperature, and the difference between the two temperatures was set as the fixing temperature range (MFT). MFT was evaluated based on the following criteria. The obtained results are shown in Table 3.
<Evaluation criteria>
◎: MFT is 65 ° C or higher ○: MFT is 60 ° C or higher and lower than 65 ° C Δ: MFT is 55 ° C or higher and lower than 60 ° C ×: MFT is lower than 55 ° C

[Example 2]
-Production of Toner 2-
Crystalline polyester resin dispersion (1): 100 parts Noncrystalline polyester resin dispersion (2): 300 parts Amorphous polyester resin dispersion (7): 300 parts Release agent dispersion (2) : 50 parts, colloidal silica (trade name Snowtex PS): 36 parts The above was added to a round stainless steel flask, and 2.0 parts of the ionic surfactant Neogen RK was added, followed by stirring and mixing / dispersing. Subsequently, 1N nitric acid aqueous solution was dropped to pH 3.5, and then 0.40 part of polyaluminum chloride was added thereto, and the dispersion operation was continued with an ultra turrax. The flask was heated to 48 ° C. with stirring in an oil bath for heating. After maintaining at 48 ° C. for 40 minutes, a mixed solution of 100 parts of the amorphous polyester resin dispersion (2) and 100 parts of the amorphous polyester resin dispersion (7) was slowly added thereto.
Thereafter, 1N aqueous sodium hydroxide solution was added to bring the pH of the system to 7.0, and then the stainless steel flask was sealed and gradually heated to 90 ° C. while continuing stirring using a magnetic seal. Hold at 3 ° C. for 3 hours.
After completion of the reaction, the mixture was cooled, filtered, thoroughly washed with ion exchange water, and then subjected to solid-liquid separation by Nutsche suction filtration. This was further redispersed in 1 L of ion exchange water at 40 ° C., and stirred and washed at 300 rpm for 15 minutes.
This was repeated five more times, and when the pH of the filtrate became 7.5 and the electric conductivity was 7.0 μS / cm, solid-liquid separation was performed using No5A filter paper by Nutsche suction filtration. Next, vacuum drying was continued for 12 hours to obtain toner 2.
When the particle diameter at this time was measured with a Coulter counter, the volume average particle diameter D50v was 5.9 μm, and the particle size distribution coefficient GSDv was 1.25. Moreover, the shape factor SF1 of the particle | grains calculated | required from the shape observation by Luzex was 136, and it was a potato form.
Evaluation was performed in the same manner as in Example 1 using the electrostatic latent image developer 2 obtained in the same manner as in Example 1 containing toner 2 and toner 2. The obtained results are shown in Table 3.

[Example 3]
-Manufacture of toner 3-
-Crystalline polyester resin dispersion (1): 200 parts-Amorphous polyester resin dispersion (3): 300 parts-Amorphous polyester resin dispersion (8): 300 parts-Release agent dispersion (3) : 50 parts, colloidal silica (trade name Snowtex PS): 3.6 parts Add the above to a round stainless steel flask, add 2.0 parts of the ionic surfactant Neogen RK, and mix and disperse with stirring. did. Subsequently, 1N nitric acid aqueous solution was dropped to pH 3.5, and then 0.40 part of polyaluminum chloride was added thereto, and the dispersion operation was continued with an ultra turrax. The flask was heated to 48 ° C. with stirring in an oil bath for heating. After maintaining at 48 ° C. for 40 minutes, a mixed solution of 100 parts of the amorphous polyester resin dispersion (3) and 100 parts of the amorphous polyester resin dispersion (8) was slowly added thereto.
Thereafter, 1N aqueous sodium hydroxide solution was added to bring the pH of the system to 7.0, and then the stainless steel flask was sealed and gradually heated to 90 ° C. while continuing stirring using a magnetic seal. Hold at 3 ° C. for 3 hours.
After completion of the reaction, the mixture was cooled, filtered, thoroughly washed with ion exchange water, and then subjected to solid-liquid separation by Nutsche suction filtration. This was further redispersed in 1 L of ion exchange water at 40 ° C., and stirred and washed at 300 rpm for 15 minutes.
This was repeated five more times, and when the pH of the filtrate became 7.5 and the electric conductivity was 7.0 μS / cm, solid-liquid separation was performed using No5A filter paper by Nutsche suction filtration. Then, vacuum drying was continued for 12 hours to obtain toner 3.
When the particle diameter at this time was measured with a Coulter counter, the volume average particle diameter D50v was 5.9 μm, and the particle size distribution coefficient GSDv was 1.25. Moreover, the shape factor SF1 of the particle | grains calculated | required from the shape observation by Luzex was 136, and it was a potato form.
Evaluation was performed in the same manner as in Example 1 using the electrostatic latent image developer 3 obtained in the same manner as in Example 1 containing toner 3 and toner 3. The obtained results are shown in Table 3.

[Comparative Example 1]
-Manufacture of toner 4-
-Crystalline polyester resin dispersion (1): 100 parts-Amorphous polyester resin dispersion (1): 300 parts-Amorphous polyester resin dispersion (6): 300 parts-Release agent dispersion (1) : 50 parts, colloidal silica (trade name Snowtex PS): 18 parts The above was added to a round stainless steel flask, and 2.0 parts of the ionic surfactant Neogen RK was added, followed by stirring and mixing / dispersing. Subsequently, 1N nitric acid aqueous solution was dropped to pH 3.5, and then 0.40 part of polyaluminum chloride was added thereto, and the dispersion operation was continued with an ultra turrax. The flask was heated to 48 ° C. with stirring in an oil bath for heating. After holding at 48 ° C. for 40 minutes, a mixed solution of 100 parts of the amorphous polyester resin dispersion (1) and 100 parts of the amorphous polyester resin dispersion (6) was slowly added thereto.
Thereafter, 1N aqueous sodium hydroxide solution was added to bring the pH of the system to 7.0, and then the stainless steel flask was sealed and gradually heated to 90 ° C. while continuing stirring using a magnetic seal. Hold at 3 ° C. for 3 hours.
After completion of the reaction, the mixture was cooled, filtered, thoroughly washed with ion exchange water, and then subjected to solid-liquid separation by Nutsche suction filtration. This was further redispersed in 1 L of ion exchange water at 40 ° C., and stirred and washed at 300 rpm for 15 minutes.
This was repeated five more times, and when the pH of the filtrate became 7.5 and the electric conductivity was 7.0 μS / cm, solid-liquid separation was performed using No5A filter paper by Nutsche suction filtration. Next, vacuum drying was continued for 12 hours to obtain toner 4.
When the particle diameter at this time was measured with a Coulter counter, the volume average particle diameter D50v was 5.9 μm, and the particle size distribution coefficient GSDv was 1.25. Moreover, the shape factor SF1 of the particle | grains calculated | required from the shape observation by Luzex was 136, and it was a potato form.
Evaluation was performed in the same manner as in Example 1 using the electrostatic latent image developer 4 obtained in the same manner as in Example 1 containing toner 4 and toner 4. The obtained results are shown in Table 3.

[Comparative Example 2]
-Production of Toner 5-
-Crystalline polyester resin dispersion (1): 100 parts-Amorphous polyester resin dispersion (1): 300 parts-Amorphous polyester resin dispersion (6): 300 parts-Release agent dispersion (1) : 50 parts, colloidal silica (trade name Snowtex PS): 18 parts The above was added to a round stainless steel flask, and 2.0 parts of the ionic surfactant Neogen RK was added, followed by stirring and mixing / dispersing. Subsequently, 1N nitric acid aqueous solution was dropped to pH 3.5, and then 0.40 part of polyaluminum chloride was added thereto, and the dispersion operation was continued with an ultra turrax. The flask was heated to 48 ° C. with stirring in an oil bath for heating. After holding at 48 ° C. for 40 minutes, a mixed solution of 100 parts of the amorphous polyester resin dispersion (1) and 100 parts of the amorphous polyester resin dispersion (6) was slowly added thereto.
Thereafter, 1N aqueous sodium hydroxide solution was added to bring the pH of the system to 7.0, and then the stainless steel flask was sealed and gradually heated to 90 ° C. while continuing stirring using a magnetic seal. Hold at 3 ° C. for 3 hours.
After completion of the reaction, the mixture was cooled, filtered, thoroughly washed with ion exchange water, and then subjected to solid-liquid separation by Nutsche suction filtration. This was further redispersed in 1 L of ion exchange water at 40 ° C., and stirred and washed at 300 rpm for 15 minutes.
This was repeated five more times, and when the pH of the filtrate became 7.5 and the electric conductivity was 7.0 μS / cm, solid-liquid separation was performed using No5A filter paper by Nutsche suction filtration. Next, vacuum drying was continued for 12 hours to obtain toner 5.
When the particle diameter at this time was measured with a Coulter counter, the volume average particle diameter D50v was 5.9 μm, and the particle size distribution coefficient GSDv was 1.25. Moreover, the shape factor SF1 of the particle | grains calculated | required from the shape observation by Luzex was 136, and it was a potato form.
Evaluation was conducted in the same manner as in Example 1 using the electrostatic latent image developer 5 obtained in the same manner as in Example 1 containing toner 5 and toner 5. The obtained results are shown in Table 3.

[Comparative Example 3]
-Manufacture of toner 6-
-Crystalline polyester resin dispersion (1): 100 parts-Amorphous polyester resin dispersion (1): 300 parts-Amorphous polyester resin dispersion (6): 300 parts-Release agent dispersion (1) : 50 parts The above was added to a round stainless steel flask, and 2.0 parts of the ionic surfactant Neogen RK was added, followed by stirring and mixing / dispersing. Subsequently, 1N nitric acid aqueous solution was dropped to pH 3.5, and then 0.40 part of polyaluminum chloride was added thereto, and the dispersion operation was continued with an ultra turrax. The flask was heated to 48 ° C. with stirring in an oil bath for heating. After holding at 48 ° C. for 40 minutes, a mixed solution of 100 parts of the amorphous polyester resin dispersion (1) and 100 parts of the amorphous polyester resin dispersion (6) was slowly added thereto.
Thereafter, 1N aqueous sodium hydroxide solution was added to bring the pH of the system to 7.0, and then the stainless steel flask was sealed and gradually heated to 90 ° C. while continuing stirring using a magnetic seal. Hold at 3 ° C. for 3 hours.
After completion of the reaction, the mixture was cooled, filtered, thoroughly washed with ion exchange water, and then subjected to solid-liquid separation by Nutsche suction filtration. This was further redispersed in 1 L of ion exchange water at 40 ° C., and stirred and washed at 300 rpm for 15 minutes.
This was repeated five more times, and when the pH of the filtrate became 7.5 and the electric conductivity was 7.0 μS / cm, solid-liquid separation was performed using No5A filter paper by Nutsche suction filtration. Next, vacuum drying was continued for 12 hours to obtain toner 6.
When the particle diameter at this time was measured with a Coulter counter, the volume average particle diameter D50v was 5.9 μm, and the particle size distribution coefficient GSDv was 1.25. Moreover, the shape factor SF1 of the particle | grains calculated | required from the shape observation by Luzex was 136, and it was a potato form.
Evaluation was performed in the same manner as in Example 1 using the electrostatic latent image developer 6 obtained in the same manner as in Example 1 containing toner 6 and toner 6. The obtained results are shown in Table 3.

[Comparative Example 4]
-Manufacture of toner 7-
-Crystalline polyester resin dispersion (1): 100 parts-Amorphous polyester resin dispersion (1): 300 parts-Amorphous polyester resin dispersion (6): 300 parts-Release agent dispersion (1) : 50 parts-colloidal silica (trade name Snowtex PS): 72 parts The above was added to a round stainless steel flask, and 2.0 parts of the ionic surfactant Neogen RK was added, followed by stirring and mixing / dispersing. Subsequently, 1N nitric acid aqueous solution was dropped to pH 3.5, and then 0.40 part of polyaluminum chloride was added thereto, and the dispersion operation was continued with an ultra turrax. The flask was heated to 48 ° C. with stirring in an oil bath for heating. After holding at 48 ° C. for 40 minutes, a mixed solution of 100 parts of the amorphous polyester resin dispersion (1) and 100 parts of the amorphous polyester resin dispersion (6) was slowly added thereto.
Thereafter, 1N aqueous sodium hydroxide solution was added to bring the pH of the system to 7.0, and then the stainless steel flask was sealed and gradually heated to 90 ° C. while continuing stirring using a magnetic seal. Hold at 3 ° C. for 3 hours.
After completion of the reaction, the mixture was cooled, filtered, thoroughly washed with ion exchange water, and then subjected to solid-liquid separation by Nutsche suction filtration. This was further redispersed in 1 L of ion exchange water at 40 ° C., and stirred and washed at 300 rpm for 15 minutes.
This was repeated five more times, and when the pH of the filtrate became 7.5 and the electric conductivity was 7.0 μS / cm, solid-liquid separation was performed using No5A filter paper by Nutsche suction filtration. Next, vacuum drying was continued for 12 hours to obtain toner 7.
When the particle diameter at this time was measured with a Coulter counter, the volume average particle diameter D50v was 5.9 μm, and the particle size distribution coefficient GSDv was 1.25. Moreover, the shape factor SF1 of the particle | grains calculated | required from the shape observation by Luzex was 136, and it was a potato form.
Evaluation was conducted in the same manner as in Example 1 using the electrostatic latent image developer 7 obtained in the same manner as in Example 1 containing toner 7 and toner 7. The obtained results are shown in Table 3.

[Comparative Example 5]
-Production of Toner 8-
-Crystalline polyester resin dispersion (1): 100 parts-Amorphous polyester resin dispersion (4): 300 parts-Amorphous polyester resin dispersion (9): 300 parts-Release agent dispersion (1) : 50 parts, colloidal silica (trade name Snowtex PS): 18 parts The above was added to a round stainless steel flask, and 2.0 parts of the ionic surfactant Neogen RK was added, followed by stirring and mixing / dispersing. Subsequently, 1N nitric acid aqueous solution was dropped to pH 3.5, and then 0.40 part of polyaluminum chloride was added thereto, and the dispersion operation was continued with an ultra turrax. The flask was heated to 48 ° C. with stirring in an oil bath for heating. After maintaining at 48 ° C. for 40 minutes, a mixed solution of 100 parts of the amorphous polyester resin dispersion (4) and 100 parts of the amorphous polyester resin dispersion (9) was slowly added thereto.
Thereafter, 1N aqueous sodium hydroxide solution was added to bring the pH of the system to 7.0, and then the stainless steel flask was sealed and gradually heated to 90 ° C. while continuing stirring using a magnetic seal. Hold at 3 ° C. for 3 hours.
After completion of the reaction, the mixture was cooled, filtered, thoroughly washed with ion exchange water, and then subjected to solid-liquid separation by Nutsche suction filtration. This was further redispersed in 1 L of ion exchange water at 40 ° C., and stirred and washed at 300 rpm for 15 minutes.
This was repeated five more times, and when the pH of the filtrate became 7.5 and the electric conductivity was 7.0 μS / cm, solid-liquid separation was performed using No5A filter paper by Nutsche suction filtration. Then, vacuum drying was continued for 12 hours to obtain toner 8.
When the particle diameter at this time was measured with a Coulter counter, the volume average particle diameter D50v was 5.9 μm, and the particle size distribution coefficient GSDv was 1.25. Moreover, the shape factor SF1 of the particle | grains calculated | required from the shape observation by Luzex was 136, and it was a potato form.
Evaluation was conducted in the same manner as in Example 1 using the electrostatic latent image developer 8 obtained in the same manner as in Example 1 containing toner 8 and toner 8. The obtained results are shown in Table 3.

[Comparative Example 6]
-Manufacture of toner 9-
Non-crystalline polyester resin dispersion (5): 350 parts Non-crystalline polyester resin dispersion (10): 350 parts Release agent dispersion (1): 50 parts Colloidal silica (trade name Snowtex PS) : 18 parts The above was added to a round stainless steel flask, and 2.0 parts of the ionic surfactant Neogen RK was added, followed by stirring and mixing / dispersing. Subsequently, 1N nitric acid aqueous solution was dropped to pH 3.5, and then 0.40 part of polyaluminum chloride was added thereto, and the dispersion operation was continued with an ultra turrax. The flask was heated to 48 ° C. with stirring in an oil bath for heating. After maintaining at 48 ° C. for 40 minutes, a mixed solution of 100 parts of the amorphous polyester resin dispersion (5) and 100 parts of the amorphous polyester resin dispersion (10) was slowly added thereto.
Thereafter, 1N aqueous sodium hydroxide solution was added to bring the pH of the system to 7.0, and then the stainless steel flask was sealed and gradually heated to 90 ° C. while continuing stirring using a magnetic seal. Hold at 3 ° C. for 3 hours.
After completion of the reaction, the mixture was cooled, filtered, thoroughly washed with ion exchange water, and then subjected to solid-liquid separation by Nutsche suction filtration. This was further redispersed in 1 L of ion exchange water at 40 ° C., and stirred and washed at 300 rpm for 15 minutes.
This was repeated five more times, and when the pH of the filtrate became 7.5 and the electric conductivity was 7.0 μS / cm, solid-liquid separation was performed using No5A filter paper by Nutsche suction filtration. Next, vacuum drying was continued for 12 hours to obtain toner 9.
When the particle diameter at this time was measured with a Coulter counter, the volume average particle diameter D50v was 5.9 μm, and the particle size distribution coefficient GSDv was 1.25. Moreover, the shape factor SF1 of the particle | grains calculated | required from the shape observation by Luzex was 136, and it was a potato form.
Evaluation was performed in the same manner as in Example 1 using the electrostatic latent image developer 9 obtained in the same manner as in Example 1 containing toner 9 and toner 9. The obtained results are shown in Table 3.

[Comparative Example 7]
-Production of Toner 10-
-Crystalline polyester resin dispersion (1): 100 parts-Amorphous polyester resin dispersion (1): 300 parts-Amorphous polyester resin dispersion (6): 300 parts-Release agent dispersion (4) : 50 parts, colloidal silica (trade name Snowtex PS): 18 parts The above was added to a round stainless steel flask, and 2.0 parts of the ionic surfactant Neogen RK was added, followed by stirring and mixing / dispersing. Subsequently, 1N nitric acid aqueous solution was dropped to pH 3.5, and then 0.40 part of polyaluminum chloride was added thereto, and the dispersion operation was continued with an ultra turrax. The flask was heated to 48 ° C. with stirring in an oil bath for heating. After holding at 48 ° C. for 40 minutes, a mixed solution of 100 parts of the amorphous polyester resin dispersion (1) and 100 parts of the amorphous polyester resin dispersion (6) was slowly added thereto.
Thereafter, 1N aqueous sodium hydroxide solution was added to bring the pH of the system to 7.0, and then the stainless steel flask was sealed and gradually heated to 90 ° C. while continuing stirring using a magnetic seal. Hold at 3 ° C. for 3 hours.
After completion of the reaction, the mixture was cooled, filtered, thoroughly washed with ion exchange water, and then subjected to solid-liquid separation by Nutsche suction filtration. This was further redispersed in 1 L of ion exchange water at 40 ° C., and stirred and washed at 300 rpm for 15 minutes.
This was repeated five more times, and when the pH of the filtrate became 7.5 and the electric conductivity was 7.0 μS / cm, solid-liquid separation was performed using No5A filter paper by Nutsche suction filtration. Then, vacuum drying was continued for 12 hours to obtain toner 10.
When the particle diameter at this time was measured with a Coulter counter, the volume average particle diameter D50v was 5.9 μm, and the particle size distribution coefficient GSDv was 1.25. Moreover, the shape factor SF1 of the particle | grains calculated | required from the shape observation by Luzex was 136, and it was a potato form.
Evaluation was conducted in the same manner as in Example 1 using the electrostatic latent image developer 10 obtained in the same manner as in Example 1 containing toner 10 and toner 10. The obtained results are shown in Table 3.

[Comparative Example 8]
-Manufacture of toner 11-
Crystalline polyester resin dispersion (1): 100 parts Noncrystalline polyester resin dispersion (1): 300 parts Noncrystalline polyester resin dispersion (6): 300 parts Release agent dispersion (5) : 50 parts, colloidal silica (trade name Snowtex PS): 18 parts The above was added to a round stainless steel flask, and 2.0 parts of the ionic surfactant Neogen RK was added, followed by stirring and mixing / dispersing. Subsequently, 1N nitric acid aqueous solution was dropped to pH 3.5, and then 0.40 part of polyaluminum chloride was added thereto, and the dispersion operation was continued with an ultra turrax. The flask was heated to 48 ° C. with stirring in an oil bath for heating. After holding at 48 ° C. for 40 minutes, a mixed solution of 100 parts of the amorphous polyester resin dispersion (1) and 100 parts of the amorphous polyester resin dispersion (6) was slowly added thereto.
Thereafter, 1N aqueous sodium hydroxide solution was added to bring the pH of the system to 7.0, and then the stainless steel flask was sealed and gradually heated to 90 ° C. while continuing stirring using a magnetic seal. Hold at 3 ° C. for 3 hours.
After completion of the reaction, the mixture was cooled, filtered, thoroughly washed with ion exchange water, and then subjected to solid-liquid separation by Nutsche suction filtration. This was further redispersed in 1 L of ion exchange water at 40 ° C., and stirred and washed at 300 rpm for 15 minutes.
This was repeated five more times, and when the pH of the filtrate became 7.5 and the electric conductivity was 7.0 μS / cm, solid-liquid separation was performed using No5A filter paper by Nutsche suction filtration. Then, vacuum drying was continued for 12 hours to obtain toner 11.
When the particle diameter at this time was measured with a Coulter counter, the volume average particle diameter D50v was 5.9 μm, and the particle size distribution coefficient GSDv was 1.25. Moreover, the shape factor SF1 of the particle | grains calculated | required from the shape observation by Luzex was 136, and it was a potato form.
Evaluation was performed in the same manner as in Example 1 using the electrostatic latent image developer 11 obtained in the same manner as in Example 1 containing toner 11 and toner 11. The obtained results are shown in Table 3.

  The composition of the binder resin composition (two types of non-crystalline polyester resin and the crystalline polyester resin and the release agent) constituting each toner, and the structural unit derived from an aliphatic monomer among the structural units constituting the resin The proportion of the binder resin (specific binder resin) having a ratio of 90 mol% to 100 mol%, and 5 mol% to 50 mol% of the acid-derived structural units constituting the resin is derived from dodecenyl succinic acid Table 4 shows the ratio of polyester resin (polyester resin containing DSA).

  Also, the type of the binder resin composition used for each toner, the difference between Tm and Tc, the molding shrinkage ratio Z, the silica particle content (relative to 100 parts of the binder resin), and the Al in the release agent Table 5 shows the content.

Table 3 shows the following.
Example 1
All the requirements of this embodiment were satisfied, and good results were obtained for all the evaluation items (curl evaluation / transfer efficiency / fixing temperature range).
(Example 2)
Since Tm-Tc is higher than that of the first embodiment, the same effect as that of the first embodiment cannot be obtained in the fixing temperature range, but the other characteristics are the same as those of the first embodiment, which is a good result.
Example 3
Since Tm-Tc is lower than that of Example 1, curl evaluation and transfer efficiency are not as good as those of Example 1, but the other characteristics are the same as those of Example 1 and can be said to be good results.
Example 4
Fixing temperature range is slightly inferior.
(Example 5)
Compared with Examples 1 to 3, the Al content in the release agent is large, so the fixing temperature range is slightly inferior, but the curl characteristics are good.
(Comparative Example 1)
Since the Tm-Tc of DSC is lower than the requirement range of this embodiment (Tm-Tc = 25 ° C.), the curl evaluation is slightly worse. Also, the fixing temperature range is inferior.
(Comparative Example 2)
Although curling can be prevented by suppressing the crystal of the release agent, there is a problem because the fixing temperature range is inferior.
(Comparative Example 3)
Although the curl evaluation result is good, there is a problem because the fixing temperature range is inferior.
(Comparative Example 4)
There is a problem in that transfer efficiency is poor because silica particles are excessively contained.
(Comparative Example 5)
Since the polyester resin containing DSA is not included, there are problems in both the fixing temperature range and the curling characteristics.
(Comparative Example 6)
There is a problem in curl evaluation because Al is not contained in the release agent domain.

1 is a schematic configuration diagram illustrating an example of an image forming apparatus according to an exemplary embodiment.

DESCRIPTION OF SYMBOLS 11 Photoconductor 12 Drive roll 13 Support roll 14 Bias roll 15 Cleaning apparatus 16 Belt cleaner 17 Primary transfer roll 18 Charging roll 19 Exposure apparatus 20 Developing apparatus 34 Secondary transfer roll 35 Fixing device 40 Toner cartridge 50 Image forming unit P Recording paper

Claims (8)

A binder resin, a release agent, and silica particles;
When the endothermic peak Tm of the release agent in the temperature rising process and the exothermic peak Tc of the release agent in the temperature lowering process are measured by the ASTM method with a differential scanning calorimeter (DSC), the difference between Tm and Tc is 30. ℃ to 50 ℃,
The proportion of the structural unit derived from the aliphatic monomer in the structural units constituting the resin is 90% by mass or more and 100% by mol or less, accounting for 20% by mass or more and 100% by mass or less of the total binder resin,
A toner for developing an electrostatic latent image, wherein the silica particles are contained in an amount of 2 parts by mass to 20 parts by mass with respect to 100 parts by mass of the binder resin.   The polyester resin in which 5 mol% or more and 50 mol% or less of the structural unit derived from the acid constituting the resin is derived from dodecenyl succinic acid occupies 10 mass% or more and 90 mass% or less of the entire binder resin. Toner for electrostatic latent image development.   The electrostatic latent image developing toner according to claim 1, wherein Al is contained in a release agent domain of the toner.   The electrostatic latent image developing toner according to claim 3, wherein the content of Al in the release agent domain by fluorescent X-ray analysis is 0.005 atom% or more and 0.1 atom% or less.   An electrostatic latent image developer comprising at least the electrostatic latent image developing toner according to claim 1.   5. The toner according to claim 1, wherein the toner is detachably attached to the image forming apparatus and contains toner to be supplied to a developing unit provided in the image forming apparatus. The toner according to claim 1. A toner cartridge that is a toner for developing an electrostatic latent image.   A process cartridge comprising at least a developer holder and containing the electrostatic latent image developer according to claim 5.   A latent image holding member, a developing unit that develops the electrostatic latent image formed on the latent image holding member as a toner image with the electrostatic latent image developer according to claim 5, and a latent image holding member formed on the latent image holding member. An image forming apparatus comprising: a transfer unit that transfers the toner image to a transfer target; and a fixing unit that fixes the toner image transferred to the transfer target.

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