JP2009069535A - Electrostatic charge developing toner and manufacturing method therefor, electrostatic charge developing developer, toner cartridge, process cartridge, and image forming device - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an electrostatic charge developing toner capable of enhancing maintainability of thin line reproducibility under a high-temperature and high-humidity condition; a method for manufacturing the toner; an electrostatic charge developing developer; a toner cartridge; a process cartridge; and an image forming device. <P>SOLUTION: In the electrostatic charge developing toner, at least a binder resin is contained, an additive treated with a coupling agent is added, a shape coefficient is 110-140, and a variation of a repose angle of the toner is 0° to 3° before and after treated by a specified process. the electrostatic charge developing developer, the toner cartridge, the process cartridge and the image forming device are also provided. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to an electrostatic charge developing toner and a method for producing the same, an electrostatic charge developing developer, a toner cartridge, a process cartridge, and an image forming apparatus.

  A method of visualizing image information through an electrostatic latent image, such as electrophotography, is currently widely used in various fields. In the electrophotographic method, an electrostatic latent image on the surface of an electrophotographic photoreceptor (image carrier, hereinafter sometimes referred to simply as “photoreceptor”) is subjected to an electrostatic charge developing toner (hereinafter referred to as “electrostatic charge developing toner”). The electrostatic latent image is visualized through a transfer process, a fixing process, and the like.

Under such circumstances, a combination of a toner having a slightly higher angle of repose than conventional toners and a magnetic material-dispersed resin carrier characterized by unevenness on the surface makes it possible to reduce the angle of repose even at low repose and high-speed idling. A two-component developer with little increase has been proposed (see, for example, Patent Document 1).
JP 2005-181657 A

  An object of the present invention is to provide an electrostatic charge developing toner capable of improving the reproducibility of fine line reproducibility under high temperature and high humidity, a manufacturing method thereof, an electrostatic charge developing developer, a toner cartridge, a process cartridge, and an image forming apparatus. Is to provide.

The above-mentioned subject is achieved by the following present invention. That is,
In the invention according to claim 1 of the present invention, an external additive containing at least a binder resin and treated with a coupling agent is externally added, the shape factor is 110 to 140, and the following (1) to (3 The toner for electrostatic charge development is characterized in that the amount of change in the angle of repose of the toner before and after being processed in the step (1) is from 0 to 3 degrees.
(1) To 100 parts by mass of the toner, 0.2 part of a 10% by mass nitric acid aqueous solution is added and stirred at 100 rpm for 1 hour.
(2) The toner after stirring in (1) is dried under reduced pressure for 12 hours at 25 ° C.
(3) The toner after drying under reduced pressure in (2) is allowed to stand for 12 hours at a temperature of 30 ° C.-85% RH.

  According to the second aspect of the present invention, at least one of an alkali metal and an alkaline earth metal is contained in the toner surface, and a mass ratio of a total amount of the alkali metal and the alkaline earth metal to the binder resin on the toner surface. 2. The electrostatic charge developing toner according to claim 1, wherein the toner is 10 ppm or more and 500 ppm or less.

  The invention according to claim 3 of the present invention includes a step of forming aggregated particles to prepare an aggregated particle dispersion in a dispersion containing at least a resin particle dispersion in which binder resin particles are dispersed in a dispersion medium; A step of fusing the aggregated particles by heating the aggregated particle dispersion, wherein the amount of total nitrogen detected by the fluorescent X-ray method when the solid content concentration of the resin particle dispersion is 20% by mass is 10 mg N / L or more 3. The method for producing an electrostatic charge developing toner according to claim 1, wherein the toner is 500 mg N / L or less.

The invention according to claim 4 of the present invention includes a step of forming aggregated particles to prepare an aggregated particle dispersion in a dispersion containing at least a resin particle dispersion in which binder resin particles are dispersed in a dispersion medium; Heating the aggregated particle dispersion to fuse the aggregated particles,
After the resin particle dispersion has dispersed the binder resin particles, the pressure is controlled in the range of 60 Pa to 1 kPa and the saturated vapor pressure of the dispersion medium within a range of ± 3 kPa, and the temperature is adjusted to the binder resin. The electrostatic charge according to claim 1 or 2, wherein the electrostatic charge is a liquid obtained by controlling the glass transition temperature or melting point within a range of ± 20 ° C and further performing distillation under reduced pressure while satisfying the following conditions: This is a method for producing a developing toner.
0 ≦ | d ² p / dt ² (kPa / min ² ) | ≦ 20
Here, p represents pressure (kPa), and t represents time (min).

  The invention according to claim 5 of the present invention is a developer for electrostatic charge development, comprising a toner, wherein the toner is the toner for electrostatic charge development according to claim 1 or claim 2.

  According to a sixth aspect of the present invention, there is provided a toner cartridge comprising at least a toner, wherein the toner is the electrostatic charge developing toner according to the first or second aspect.

  According to a seventh aspect of the present invention, there is provided a process cartridge comprising at least a developer holder and containing the developer for electrostatic charge development according to the fifth aspect.

  According to an eighth aspect of the present invention, an image carrier, a charging means for charging the surface of the image carrier, and an electrostatic image formed on the charged image carrier are developed as a toner image with a developer. Developing means, transfer means for transferring the toner image formed on the image carrier onto the transfer target, and fixing means for fixing the toner image transferred onto the transfer target, An image forming apparatus, wherein the developer is the developer for electrostatic charge development according to claim 5.

  The invention according to claim 9 of the present invention is the image forming apparatus according to claim 8, wherein a charging voltage of the charging unit is 300 V or more and 800 V or less.

According to the first aspect of the present invention, a toner that improves the maintainability of fine line reproducibility under high temperature and high humidity can be obtained.
According to the invention of claim 2 of the present invention, it is possible to obtain a toner that further improves the maintainability of fine line reproducibility under high temperature and high humidity.

According to the third aspect of the present invention, it is possible to produce a toner that improves the maintainability of fine line reproducibility under high temperature and high humidity.
According to the invention of claim 4 of the present invention, it is possible to produce a toner that further improves the maintainability of fine line reproducibility under high temperature and high humidity.

According to the invention of claim 5 of the present invention, it is possible to obtain a developer for electrostatic charge development that improves the maintainability of fine line reproducibility under high temperature and high humidity.
According to the sixth aspect of the present invention, it is possible to obtain a toner cartridge that further improves the maintainability of fine line reproducibility under high temperature and high humidity.

According to the seventh aspect of the present invention, it is possible to obtain a process cartridge that improves the maintainability of fine line reproducibility under high temperature and high humidity.
According to the invention of claim 8 of the present invention, it is possible to obtain an image forming apparatus that further improves the maintainability of fine line reproducibility under high temperature and high humidity.
According to the ninth aspect of the present invention, it is possible to obtain an image forming apparatus that further improves the maintainability of fine line reproducibility under high temperature and high humidity.

Hereinafter, the present invention will be described in detail.
<Toner for electrostatic charge development>
The electrostatic charge developing toner of the present invention (hereinafter sometimes referred to as “the toner of the present invention”) contains at least a binder resin, and an external additive treated with a coupling agent is externally added to form a shape factor. 110 to 140, and the amount of change in the angle of repose of the toner before and after processing in the following steps (1) to (3) (hereinafter sometimes referred to as “stress processing according to the present invention”) is 0 degree. It is characterized by being 3 degrees or less.
(1) To 100 parts by mass of the toner, 0.2 part of a 10% by mass nitric acid aqueous solution is added and stirred at 100 rpm for 1 hour.
(2) The toner after stirring in (1) is dried under reduced pressure for 12 hours at 25 ° C.
(3) The toner after drying under reduced pressure in (2) is allowed to stand for 12 hours at a temperature of 30 ° C.-85% RH.

  When the external additive is treated with the coupling agent, an organic substituent is chemically bonded to the surface of the external additive, and it is possible to add a characteristic that the surface of the inorganic material does not originally have. This is because the alkoxysilyl group of the coupling agent is hydrolyzed with water or moisture to form a silanol group, and a substituent is introduced onto the surface by dehydration of the silanol group and the OH group on the surface of the external additive. By utilizing this, it becomes possible to add a function such as hydrophobization of the external additive.

  However, it is hydrolyzed by a metal element having high water absorption such as Na on the toner surface, and the substituent on the surface returns to the bond between the silanol group and the OH group on the inorganic material surface. Sex was getting worse. This is because a metal ion is likely to adhere to the surface of a toner produced by a chemical manufacturing method, and the metal ion is present in a state close to a complex due to a highly polar functional group such as a carboxyl group or an ester group. Usually, such metal ions are thought to be removable by washing, but the state close to the complex varies to some extent, and some stable ones are metals such as alkali metals that have a high tendency to ionize. Even if it is an ion, it is considered to be in a state close to a complex and difficult to dissociate. In particular, the closer the shape of the toner is to a sphere, the smaller the surface area, and the more stable metal ions increase. This is ionized by a developing device, more specifically, nitrogen oxides generated in the charging step under high humidity conditions, and this decomposes the functional group subjected to the coupling treatment on the surface of the external additive.

  Therefore, in the present invention, metal elements that cause this hydrolysis are suppressed. Specifically, hydrolysis of the surface of the external additive was suppressed by removing metal ions in a state close to the part of the stable complex. That is, before the addition of the external additive, before the introduction of metal ions having high water absorption, this part of the stable complex state is converted to ammonium ions by the treatment with ammonium. In this way, even if the treatment is performed with metal ions by washing or the like, the problem of deterioration of the fluidity and jetting property of the toner is suppressed. As a result, the maintainability of fine line reproducibility under high temperature and high humidity can be improved.

  As described above, when the amount of the metal element that causes hydrolysis is suppressed, even if the shape factor is 110 to 140, the amount of change in the angle of repose of the toner before and after the stress treatment according to the present invention is 0 degree. This is 3 degrees or less. The addition of 0.2 part of a 10% by mass nitric acid aqueous solution to 100 parts by mass of the toner forcibly affects the influence of nitrogen oxides and the like generated in the charging process as described above. It is for promoting.

Here, the angle of repose confirms that the amount of the metal element causing the hydrolysis is suppressed for the following reason.
The evaluation of jetability index includes repose angle, compression angle (relaxed bulk density, compacted bulk density), spatula angle, and uniformity, but the compressibility etc. can be tapped during measurement of compacted bulk density. This is a measurement method in which the toner state changes before and after the stress such as the idling of the developing device is not observed, and no significant difference is observed between the present invention and other inventions. Although the spatula angle is the same as the angle of repose, there is no significant difference between the present invention and other inventions because of the large error. The uniformity is effective when there is a change in particle size distribution, but no significant difference was observed because it is not a change in fluidity due to a change in particle size. On the other hand, the angle of repose does not apply stress to the particles themselves, and therefore has a preferable sensitivity to changes in the characteristics of the external additive.

As described above, the toner of the present invention is characterized in that the amount of change in the angle of repose of the toner before and after the stress treatment according to the present invention is 0 degree or more and 3 degrees or less, and is 0 degree or more and 2 degrees or less. It is preferable that it is 0 degree or more and 1 degree or less. When the amount of change in the angle of repose exceeds 3 degrees, the amount of the metal element that causes hydrolysis is not suppressed, and the effect of improving the reproducibility of the fine line under high temperature and high humidity cannot be obtained. A method for controlling the angle of repose change from 0 degrees to 3 degrees will be described later.
In addition, the angle of repose is measured using a repose angle measuring instrument (manufactured by Tsutsui Chemical Co., Ltd.) in a cylindrical sample container having a rotation speed of 2.0 rpm and 500 ml. The test was carried out using a sample left for 24 hours in an environmental chamber. The repose angle measuring device was also left for 24 hours under the same temperature and humidity conditions.

In the toner of the present invention, at least one of an alkali metal and an alkaline earth metal is contained in the toner surface, and the mass ratio of the total amount of the alkali metal and the alkaline earth metal to the binder resin on the toner surface is 10 ppm. It is preferably 500 ppm or less, more preferably 10 ppm or more and 200 ppm or less, still more preferably 10 ppm or more and 100 ppm or less.
Here, the amount of alkali metal and alkaline earth metal relative to the binder resin on the toner surface is calculated by using X-ray photoelectron spectroscopy to calculate the ratio of the amount of alkali metal and alkaline earth metal to the total amount of carbon. Measured. In addition to carbon, hydrogen, oxygen, or the like is usually used as a constituent component of the resin. However, since carbon is overwhelmingly large, the measured value may be a value relative to the amount of carbon.

Examples of the alkali metal include lithium, sodium, and potassium, and sodium and potassium are more likely to be present.
Examples of the alkaline earth metal include beryllium, magnesium, calcium, strontium, and barium, and more calcium and barium are likely to be present.

The binder resin is preferably a polyester resin in that the toner of the present invention can exhibit the effect of improving the reproducibility of fine line reproducibility under high temperature and high humidity.
Hereinafter, the configuration of the toner of the present invention when the binder resin is a polyester resin will be described.

(Polyester resin)
The polyester resin used in the present invention is synthesized from a polyvalent carboxylic acid component and a polyhydric alcohol component. In addition, a commercial item may be used as said polyester resin, and what was synthesize | combined suitably may be used.
Examples of the polyvalent carboxylic acid component include oxalic acid, fumaric acid, succinic acid, glutaric acid, adipic acid, peric acid, azelaic acid, sebacic acid, 1,9-nonanedicarboxylic acid, and 1,10-decanedicarboxylic acid. 1,12-dodecanedicarboxylic acid, 1,14-tetradecanedicarboxylic acid, 1,18-octadecanedicarboxylic acid and other aliphatic dicarboxylic acids; cyclohexanedicarboxylic acid and other alicyclic carboxylic acids; phthalic acid, isophthalic acid, terephthalic acid Aromatic dicarboxylic acids such as dibasic acids such as naphthalene-2,6-dicarboxylic acid, malonic acid, and mesaconic acid; and phthalic anhydride, trimellitic anhydride, maleic anhydride, alkenyl succinic anhydride These anhydrides and their lower alkyl esters are also included. No.
Examples of trivalent or higher carboxylic acids include 1,2,4-benzenetricarboxylic acid, 1,2,5-benzenetricarboxylic acid, 1,2,4-naphthalenetricarboxylic acid, and the like, and anhydrides thereof. And lower alkyl esters. 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 above-mentioned aliphatic dicarboxylic acid and aromatic dicarboxylic acid may be contained. Examples of the dicarboxylic acid having a sulfone group include, but are not limited to, 2-sulfoterephthalic acid sodium salt, 5-sulfoisophthalic acid sodium salt, and sulfosuccinic acid sodium salt. Moreover, these lower alkyl esters, acid anhydrides, etc. are also mentioned.
The divalent or higher carboxylic acid component having a sulfonic acid group is desirably contained in the range of 0 to 20 mol%, more preferably 0 to 10 mol%, based on all carboxylic acid components constituting the polyester. Range. When the content is more than 20 mol%, for example, not only the crystallinity of the crystalline polyester resin is lowered, but also the process of coalescence after aggregation is adversely affected during granulation, making it difficult to adjust the toner diameter. There may be a problem that it becomes.

  As the polyhydric alcohol component, an aliphatic diol is desirable, and a linear aliphatic diol having 6 to 20 carbon atoms in the main chain portion is more preferable. When the aliphatic diol is branched, for example, the crystallinity of the crystalline polyester resin is lowered and the melting point is lowered, so that toner blocking resistance, image storage stability, and low-temperature fixability are deteriorated. There is. Further, if the number of carbon atoms is less than 6, when the polycondensation with an aromatic dicarboxylic acid is performed, the melting point becomes high and fixing at a low temperature may be difficult. On the other hand, if it exceeds 20, it is difficult to obtain practical materials. There is a case. The carbon number is more preferably 14 or less.

  In the present invention, examples of the diol suitably used for the synthesis of the polyester resin include, for example, ethylene glycol, diethylene glycol, triethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, , 6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,11-undecanediol, 1,12-dodecanediol, 1, Alicyclic diols such as 13-tridecanediol, 1,14-tetradecanediol, 1,18-octadecanediol, 1,14-eicosandecanediol, neopentyl glycol, cyclohexanediol, cyclohexanedimethanol, hydrogenated bisphenol A, etc. Class: Bisuf Ethylene oxide adducts of Nord A, aromatic diols such as propylene oxide adduct of bisphenol A; but like, but is not limited thereto.

Examples of trihydric or higher alcohols include glycerin, trimethylolethane, trimethylolpropane, and pentaerythritol. These may be used individually by 1 type and may use 2 or more types together.
If necessary, monovalent acids such as acetic acid and benzoic acid, and monovalent alcohols such as cyclohexanol benzyl alcohol can also be used for the purpose of adjusting the acid value and the hydroxyl value.

  A polyester resin obtained by polycondensation of a polyvalent carboxylic acid and a polyhydric alcohol is further added with a monocarboxylic acid and / or monoalcohol to esterify the hydroxyl group and / or carboxyl group at the polymerization terminal, thereby producing a polyester. The acid value of the resin may be adjusted.

  Examples of the monocarboxylic acid include acetic acid, acetic anhydride, benzoic acid, trichloroacetic acid, trifluoroacetic acid, and propionic anhydride. Examples of the monoalcohol include methanol, ethanol, propanol, octanol, 2-ethylhexanol, trifluoroethanol, trichloroethanol, hexafluoroisopropanol, and phenol.

The production method of the polyester resin is not particularly limited, and can be produced by a general polyester polymerization method in which an acid component and an alcohol component are reacted. Examples thereof include direct polycondensation and transesterification. Depending on the type, it will be manufactured separately.
The production of the polyester resin can be carried out at a polymerization temperature of 150 to 250 ° C., and the reaction system is reacted under reduced pressure as necessary to remove water and alcohol generated during condensation. When the monomer is not dissolved or compatible at the reaction temperature, a solvent having a high boiling point may be added as a solubilizer and dissolved. In the polycondensation reaction, the dissolution auxiliary solvent is distilled off. When a monomer having poor compatibility exists in the copolymerization reaction, the monomer having poor compatibility and the monomer and the acid or alcohol to be polycondensed are condensed in advance and then polycondensed together with the main component.

Catalysts that can be used 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; metals such as zinc, manganese, antimony, titanium, tin, zirconium, germanium, and aluminum Compounds: Phosphorous acid compounds, phosphoric acid compounds, amine compounds, and the like, and specific examples include the following compounds.
Specifically, for example, 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 Tetraethoxide, titanium tetrapropoxide, titanium tetraisoproxide, titanium tetrabutoxide, antimony trioxide, triphenylantimony, tributylantimony, tin formate, tin oxalate, tetraphenyltin, dibutyltin dichloride, dibutyltin dilaurate, dibutyltin oxide, Diphenyltin oxide, zirconium tetrabutoxide, zirconium naphthenate, zirconyl carbonate, zirconyl acetate, zirconyl stearate, zirconyl octylate Le, germanium oxide, aluminum, triphenyl phosphite, tris (2, 4-t-butylphenyl) phosphite, ethyltriphenylphosphonium bromide, triethylamine, compounds such as triphenyl amine. From the viewpoint of reactivity, antimony, tin, and titanium are desirable. From the viewpoint of environmental impact and safety, titanium is more desirable. The amount of such a catalyst added is preferably in the range of 0.01 to 1.00% by mass with respect to the total amount of raw materials.

The glass transition point and melting point of the polyester resin are preferably in the range of 50 to 100 ° C, more preferably in the range of 60 to 80 ° C. When the melting point is lower than 50 ° C., the storage stability of the toner and the storage stability of the toner image after fixing may become a problem. On the other hand, when the temperature is higher than 100 ° C., sufficient low-temperature fixing may not be obtained as compared with conventional toners.
In addition, the glass transition point and melting | fusing point of the said polyester resin were calculated | required as the peak temperature of the endothermic peak obtained by the said differential scanning calorimetry (DSC).

  The molecular weight of the polyester resin can be adjusted depending on the reaction time and the molar ratio of the monomers. Although the reaction time varies depending on the type of catalyst and monomer, the molecular weight is small when the reaction time is short, and it is large when the reaction time is long. A high molecular weight product can be obtained by adjusting the molar ratio of the monomer so that the ratio of alcohol to carboxylic acid in the monomer is 1: 1.

  The weight average molecular weight (Mw) immediately after synthesis of the polyester resin is preferably in the range of 3000 to 100,000, and more preferably in the range of 10,000 to 50,000. If the molecular weight (Mw) is less than 3000, it is effective for low-temperature fixability, but the resin strength is reduced, so that the image strength fixed on the paper is reduced, or offset occurs during fixing. When the weight average molecular weight (Mw) exceeds 100,000, hot offset resistance can be sufficiently imparted, but fixability at low temperatures may be deteriorated.

A method for obtaining a polyester resin having a small amount of methanol-soluble components as described above is not particularly limited. For example, the polyester resin can be obtained by dissolving the resin in THF and performing reprecipitation purification.
Specifically, first, a crystalline polyester resin is dissolved in THF at a concentration of about 5 to 50% by mass, and this is dropped into stirred methanol having a mass 2 to 10 times that of the solution. . In this case, the dropping time and the stirring time vary depending on the amount of the solution. For example, when the amount of the solution is 100 g, it is desirable that the dropping time is about 5 minutes and the stirring time is about 30 minutes.

  In the purified polyester resin, the amount of the component dissolved in methanol is in the desired range. In this case, the weight average molecular weight (Mw) of the purified polyester resin is preferably in the range of 3000 to 80000. More desirably, it is in the range of 12000 to 60000. Further, the molecular weight distribution (Mw / Mn), which is the ratio with the number average molecular weight (Mn), is preferably in the range of 2 to 10, and more preferably in the range of 2.5 to 8.

  Moreover, it is desirable that the DSC peak temperature of the purified crystalline polyester resin is in the range of 70 to 90 ° C.

  The weight average molecular weight and molecular weight distribution 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.

(Release agent)
The release agent used in the present invention is not particularly limited as long as it is a known release agent. For example, natural wax such as carnauba wax, rice wax, candelilla wax; synthetic or mineral / petroleum system such as low molecular weight polypropylene, low molecular weight polyethylene, sazol wax, microcrystalline wax, Fischer-Tropsch wax, paraffin wax, montan wax Examples thereof include, but are not limited to, waxes; higher fatty acids such as stearic acid and palmitic acid; ester waxes; Moreover, these mold release agents may be used individually by 1 type, and may be used together 2 or more types.
Among these, use of one or more selected from paraffin wax, carnauba wax and its modified wax, and ester wax is preferable from the viewpoint of exudation of the release agent to the toner surface at the time of melting.

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

  The content of the release agent is preferably in the range of 2 to 30 parts by mass and more preferably in the range of 5 to 20 parts by mass with respect to 100 parts by mass of the binder resin. When the content of the release agent is less than 2 parts by mass, there is no effect of adding the release agent, and hot offset at a high temperature may be caused. On the other hand, when the amount is more than 30 parts by mass, the charging property is deteriorated and the strength of the toner is reduced, so that the toner is easily destroyed and may cause carrier contamination.

(Coloring agent)
The colorant used in the present invention is not particularly limited as long as it is a known colorant. For example, carbon black such as furnace black, channel black, acetylene black, thermal black; inorganic pigments such as Bengala, bitumen, titanium oxide; azo pigments such as fast yellow, disazo yellow, pyrazolone red, chelate red, brilliant carmine, para brown Phthalocyanine pigments such as copper phthalocyanine and metal-free phthalocyanine; condensed polycyclic pigments such as flavantron yellow, dibromoanthrone orange, perylene red, quinacridone red and dioxazine violet;

  More specifically, Chrome Yellow, Hansa Yellow, Benzidine Yellow, Slen Yellow, Quinoline Yellow, Permanent Orange GTR, Pyrarozone Orange, Vulcan Orange, Watch Young Red, Permanent Red, Dupont Oil Red, Resol Red, Rhodamine B Lake , Lake Red C, Rose Bengal, Aniline Blue, Ultramarine Blue, Calco Oil Blue, Methylene Blue Chloride, Phthalocyanine Blue, Phthalocyanine Green, Malachite Green Oxalate, C.I. I. Pigment red 48: 1, C.I. I. Pigment red 122, C.I. I. Pigment red 57: 1, C.I. I. Pigment yellow 12, C.I. I. Pigment yellow 97, C.I. I. Pigment yellow 17, C.I. I. Pigment yellow 180, C.I. I. Pigment yellow 74, C.I. I. Pigment blue 15: 1, C.I. I. Examples thereof include various pigments such as CI Pigment Blue 15: 3, and these can be used alone or in combination of two or more.

  The content of the colorant is preferably in the range of 1 to 30 parts by mass with respect to 100 parts by mass of the binder resin, but if necessary, a surface-treated colorant or a pigment dispersant is used. It is also effective to do. By appropriately selecting the type of the colorant, yellow toner, magenta toner, cyan toner, black toner and the like can be obtained.

(Other additives)
In the present invention, in addition to the above components, various components such as an internal additive, a charge control agent, inorganic powder (inorganic particles), and organic particles can be added as necessary.
As the internal additive, for example, metals such as ferrite, magnetite, reduced iron, cobalt, nickel, manganese, etc., magnetic materials such as alloys, compounds containing these metals, etc., or inorganic powders are mainly used as viscoelasticity of toner. All the additives that are added for the purpose of adjustment, such as silica, alumina, titania, calcium carbonate, magnesium carbonate, calcium phosphate, cerium oxide, etc., which are usually used as external additives on the toner surface as listed in detail below. Inorganic particles are exemplified. Examples of the charge control agent include quaternary ammonium salt compounds, nigrosine compounds, dyes composed of complexes of aluminum, iron, chromium, and triphenylmethane pigments.

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

The inorganic particles are generally used for the purpose of improving fluidity. The primary particle diameter of the inorganic particles is preferably 1 to 200 nm, and the addition amount is preferably 0.01 to 20 parts by mass with respect to 100 parts by mass of the toner.
The organic particles are generally used for the purpose of improving cleaning properties and transfer properties, and specifically include polystyrene, polymethyl methacrylate, polyvinylidene fluoride, and the like.

  In the toner of the present invention, an external additive treated with a coupling agent is externally added. Examples of the external additive in this case include the above external additives. The treatment with the coupling agent is not particularly limited, but for example, methyltrimethoxysilane, phenyltrimethoxysilane, methylphenyldimethoxysilane, diphenyldimethoxysilane, vinyltrimethoxysilane, γ-aminopropyltrimethoxysilane, γ -Chloropropyltrimethoxysilane, γ-bromopropyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-ureidopropyltrimethoxysilane, fluoroalkyltrimethoxysilane, hexamethyldi Silane coupling agents such as silazane; titanate coupling agents; aluminate coupling agents; These can be dispersed or dissolved in a solvent or the like, mixed with the above external additives, and the solvent can be removed to treat the surface.

A method for producing the toner of the present invention will be described.
As a method for producing the toner of the present invention, a step of forming aggregated particles to prepare an aggregated particle dispersion in a dispersion containing at least a resin particle dispersion in which binder resin particles are dispersed in a dispersion medium; Including a step of fusing the agglomerated particle dispersion to fuse the agglomerated particles, and the amount of total nitrogen detected by the fluorescent X-ray method when the solid content concentration of the resin particle dispersion is 20% by mass is 10 mgN / L or more and 500 mgN / L or less manufacturing method,
Forming agglomerated particles to prepare an agglomerated particle dispersion in a dispersion containing at least a resin particle dispersion in which binder resin particles are dispersed in a dispersion medium; and heating the agglomerated particle dispersion to agglomerate Including a step of fusing particles, and after the resin particle dispersion has dispersed the particles of the binder resin, the pressure is controlled in the range of 60 kPa to 1 kPa and within the range of ± 3 kPa of the saturated vapor pressure of the dispersion medium. The temperature is controlled within the range of ± 20 ° C. of the glass transition temperature or melting point of the binder resin, and the production method is characterized by being a liquid obtained by distillation under reduced pressure while satisfying the following conditions: Is mentioned.
0 ≦ | d ² p / dt ² (kPa / min ² ) | ≦ 20
Here, p represents pressure (kPa), and t represents time (min).
By these methods, the amount of alkali metal and alkaline earth metal with respect to the binder resin on the toner surface can be controlled, and the amount of change in the angle of repose can be controlled from 0 degree to 3 degrees.

Hereinafter, the method for producing the toner of the present invention will be described in detail.
The toner production method of the present invention forms aggregated particles in a dispersion (hereinafter sometimes referred to as an “emulsion”) containing at least a resin particle dispersion in which binder resin particles are dispersed in a dispersion medium. It is a manufacturing method including a step of preparing an aggregated particle dispersion (aggregation step) and a step of fusing the aggregated particles by heating the aggregated particle dispersion (fusion step). In addition, a step (adhesion step) of forming adhering particles by adding and mixing a particle dispersion in which particles are dispersed in the agglomerated particle dispersion and adhering the particles to the agglomerated particles between the aggregation step and the fusion step. It may be provided. In the adhesion step, the particle dispersion is added to and mixed with the aggregated particle dispersion prepared in the aggregation step, and the particles are adhered to the aggregated particles to form adhered particles. Corresponds to particles newly added to the aggregated particles as viewed from the aggregated particles, and is sometimes referred to as “additional particles”.

  As the additional particles, in addition to the resin particles, release agent particles, colorant particles and the like may be used singly or in combination. There is no restriction | limiting in particular as a method of adding and mixing the said particle dispersion liquid, For example, you may carry out gradually continuously, and may carry out in steps divided into several times. It is desirable to form a core-shell structure by the operation of adding such additional particles. The binder resin that is the main component of the write-once particles is a shell layer resin. If this method is used, the toner shape can be easily controlled by adjusting the temperature, the number of stirring, the pH and the like in the fusing step.

When an amorphous polyester resin or a crystalline polyester resin is used in the emulsion aggregation method, for example, an emulsification step of emulsifying the amorphous polyester resin to form emulsified particles (droplets) is preferably used.
In the emulsification step, for example, the emulsion particles (droplets) of the amorphous polyester resin are mixed with an aqueous medium and a mixed liquid (polymer liquid) containing a polyester resin and, if necessary, a colorant. It is formed by applying a shearing force. At that time, the viscosity of the polymer liquid can be lowered to form emulsified particles by heating to a temperature equal to or higher than the glass transition temperature of the amorphous polyester resin. Moreover, a dispersing agent can also be used for stabilization of emulsified particles and thickening of an aqueous medium. Hereinafter, such a dispersion of emulsified particles may be referred to as a “resin particle dispersion”.

  Examples of the emulsifier used when forming the emulsified particles include a homogenizer, a homomixer, a pressure kneader, an extruder, and a media disperser. The size of the emulsified particles (droplets) of the polyester resin is preferably in the range of 80 to 300 nm and more preferably in the range of 120 to 250 nm in terms of the average particle size (volume average particle size). If it is less than 80 nm, it is almost dissolved in water, making it difficult to produce particles. If it exceeds 300 nm, it may be difficult to obtain particles having a desired particle size of 3.0 to 7.5 μm. . The volume average particle size of the resin particles was measured with a Doppler scattering type particle size distribution analyzer (manufactured by Nikkiso Co., Ltd., Microtrac UPA9340).

  In the present invention, it is desirable to use a phase inversion emulsification method to emulsify the resin. In the phase inversion emulsification method, at least a polyester resin is dissolved in an organic solvent, a neutralizing agent and a dispersion stabilizer are added as necessary, and an aqueous solvent is dropped under stirring to obtain emulsified particles. In this method, the solvent in the resin dispersion is removed to obtain an emulsion. At this time, the order of adding the neutralizing agent and the dispersion stabilizer may be changed.

  Examples of the organic solvent for dissolving the resin include formic acid esters, acetic acid esters, butyric acid esters, ketones, ethers, benzenes, and halogenated carbons. Specifically, esters such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, t-butyl such as formic acid, acetic acid and butyric acid; acetone, MEK (methyl ethyl ketone), MPK (methyl propyl) Ketones), methyl ketones such as MIPK (methyl isopropyl ketone), MBK (methyl butyl ketone), MIBK (methyl isobutyl ketone), etc .; ethers such as diethyl ether and diisopropyl ether; heterocyclic substituents such as toluene, xylene and benzene Use carbon halides such as carbon tetrachloride, methylene chloride, 1,2-dichloroethane, 1,1,2-trichloroethane, trichloroethylene, chloroform, monochlorobenzene, dichloroethylidene, etc., alone or in combination of two or more. Is possible That. Acetic acid esters, methyl ketones and ethers of low-boiling solvents (50 to 150 ° C.) are usually preferably used from the viewpoint of easy availability, ease of recovery during solvent removal, and environmental considerations, particularly acetone and methyl ethyl ketone. Those having partial solubility in water such as acetic acid, ethyl acetate, and butyl acetate are preferred. If the organic solvent remains in the resin particles, the surface of the heating member may be modified at the time of fixing. Therefore, it is desirable to use a relatively volatile organic solvent.

In the present invention, for example, an amorphous or crystalline polyester resin and the above organic solvent are mixed, heated to 20 to 90 ° C., dissolved, and then added with water or before emulsification. Is desirable. Thereby, the stability of emulsified particles can be maintained by neutralizing carboxylic acid groups on the surface of the polyester resin and increasing hydrophilicity. Examples of the base include aqueous ammonia and aqueous solutions of sodium hydroxide, potassium hydroxide, sodium carbonate, and the like.
It is also desirable to add a salt or acid. Thereby, the particle size of emulsified particles (resin particles) can be kept large to some extent. The amount of the base added is desirably in the range of 1 to 10% by mass with respect to the resin.

  Furthermore, it is desirable to add acids and salts before or after adding the bases or before emulsification. That is, when the resin is purified with methanol, low-molecular hydrophilic components in the resin are removed, making it difficult to control the particle size when preparing an emulsified dispersion of the resin. May get worse. In this case, it was found that an emulsified dispersion can be stably produced by adding an acid or salt to the system.

  Examples of the salt include salts such as sodium chloride and potassium chloride as they are, or an aqueous solution thereof or an organic solvent solution such as alcohol, or an aqueous ammonia solution. Examples of the acid include inorganic acids such as hydrochloric acid and nitric acid, organic acids such as acetic acid and citric acid, and monomers such as fumaric acid and maleic acid. These salts or acids are desirably soluble in water. The addition amount of the acid or salt is desirably in the range of 0.005 to 1% by mass with respect to the resin.

  As the aqueous solvent, ion-exchanged water is basically used, but a water-soluble organic solvent may be included so as not to destroy the oil droplets. Examples of water-soluble organic solvents include methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, t-butanol, 1-pentanol and other short carbon chain alcohols; ethylene glycol monomethyl ether, ethylene glycol Examples include ethylene glycol monoalkyl ethers such as monoethyl ether and ethylene glycol monobutyl ether; ethers, diols, THF, acetone and the like. The mixing ratio of these water-soluble organic solvents to ion-exchanged water is selected in the range of 1% to 50%, more preferably 1% to 30%, and used as an aqueous component. In addition, the water-soluble organic solvent may be added to the resin solution and used in addition to the ion-exchanged water to be added. In the case of adding a water-soluble organic solvent, the wettability between the resin and the resin dissolving solvent can be adjusted, and a function of reducing the liquid viscosity after the resin is dissolved can be expected.

  Moreover, you may add a dispersing agent to a resin solution and an aqueous component as needed so that the said emulsion may maintain a dispersed state stably. As the dispersant, a hydrophilic colloid is formed in an aqueous component, and in particular, cellulose derivatives such as hydroxymethyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose; polyvinyl alcohol, polyvinyl pyrrolidone, polyacrylamide, polyacrylate, Synthetic polymers such as polymethacrylates; dispersion stabilizers such as gelatin; gum arabic; agar; Solid fine powders such as silica, titanium oxide, alumina, tricalcium phosphate, calcium carbonate, calcium sulfate, and barium carbonate can also be used. These dispersion stabilizers are usually added so that the concentration in the aqueous component is 0 to 20% by mass, preferably 0 to 10% by mass.

A surfactant is also used as the dispersant. As examples of the surfactant, those according to those used in the colorant dispersion described later can be used. For example, in addition to natural surfactant components such as saponin, cationic surfactants such as alkylamine hydrochlorides / acetates, quaternary ammonium salts, glycerols, fatty acid soaps, sulfates, alkylnaphthalene sulfonates, sulfones Anionic surfactants such as acid salts, phosphoric acid, phosphate esters, sulfosuccinates and the like can be mentioned, and anionic surfactants and nonionic surfactants are preferably used. In order to adjust the pH of the emulsion, a neutralizing agent may be added. As the neutralizing agent, general acids such as nitric acid, hydrochloric acid, sodium hydroxide and ammonia, and alkalis can be used.
As a method for removing the organic solvent from the emulsion, a method in which the organic solvent is volatilized at room temperature (20 to 25 ° C.) or under heating, and a method in which this is combined with reduced pressure are preferably used.

  In the toner production method of the present invention, the amount of total nitrogen detected by the fluorescent X-ray method at a solid content concentration of 20% by mass of the resin particle dispersion is preferably 10 mgN / L or more and 500 mgN / L or less. More preferably, it is 10 mgN / L or more and 200 mgN / L or less, and further preferably 10 mgN / L or more and 50 mgN / L or less. There is no problem even if the total amount of nitrogen is less than 10 mgN / L, but it is not realistic due to problems such as measurement accuracy. Moreover, when it exceeds 500 mgN / L, the effect of this application is not acquired and the coupling agent of an external additive may become easy to be hydrolyzed.

The amount of the total nitrogen can be set to 10 mgN / L or more and 500 mgN / L or less by the following steps.
After dispersing the binder resin particles, the pressure is controlled in the range of 60 Pa to 1 kPa and ± 3 kPa of the saturated vapor pressure of the dispersion medium, and the temperature is equal to the glass transition temperature or melting point of the binder resin. Control within a range of ± 20 ° C., and further perform distillation under reduced pressure while satisfying the following conditions.
0 ≦ | d ² p / dt ² (kPa / min ² ) | ≦ 20
Here, p represents pressure (kPa), and t represents time (min).

The | d ² p / dt ² (kPa / min ² ) | is more preferably 0 or more and 10 or less, and further preferably 0 or more and 5 or less. If this value exceeds 20, it may be difficult to adjust the total nitrogen amount to 10 mgN / L or more and 500 mgN / L or less.

  On the other hand, as a dispersion method of the colorant and the release agent, for example, a general dispersion method such as a rotary shear type homogenizer, a ball mill having a medium, a sand mill, a dyno mill, or the like can be used. is not.

If necessary, an aqueous dispersion of these colorants can be prepared using a surfactant, or an organic solvent dispersion of these colorants can be prepared using a dispersant. Hereinafter, the dispersion of the colorant and the release agent may be referred to as “colorant dispersion” or “release agent dispersion”.
The dispersant used for the colorant dispersion or the release agent dispersion station is generally a surfactant. Examples of the surfactant include anionic surfactants such as sulfate ester, sulfonate, phosphate, and soap; cationic surfactants such as amine salt type and quaternary ammonium salt type; polyethylene glycol Suitable examples include nonionic surfactants such as polyphenols, alkylphenol ethylene oxide adducts, and polyhydric alcohols. Among these, an ionic surfactant is preferable, and an anionic surfactant and a cationic surfactant are more preferable. The nonionic surfactant is preferably used in combination with the anionic surfactant or the cationic surfactant. The said surfactant may be used individually by 1 type, and may use 2 or more types together. Moreover, it is preferable that it is the same polarity as the dispersing agent used for other dispersion liquids, such as a mold release agent dispersion liquid.

  Specific examples of the anionic surfactant include fatty acid soaps such as potassium laurate, sodium oleate and sodium castor oil; sulfates such as octyl sulfate, lauryl sulfate, lauryl ether sulfate and nonylphenyl ether sulfate; lauryl sulfonate , Dodecyl sulfonate, dodecyl benzene sulfonate, triisopropyl naphthalene sulfonate, dibutyl naphthalene sulfonate, etc. Sulfonates such as lauryl phosphate, isopropyl phosphate, Phosphoric acid esters such as alkenyl phenyl ether phosphates; dialkyl sodium sulfosuccinates of sodium dioctyl sulfosuccinate, sodium lauryl sulfosuccinate 2, polyoxyethylene sulfo sulfosuccinate salts such as succinic acid lauryl disodium and the like. Of these, alkylbenzene sulfonate compounds such as dodecylbenzene sulfonate and its branched products are preferred.

  Specific examples of the cationic surfactant include laurylamine hydrochloride, stearylamine hydrochloride, oleylamine acetate, stearylamine acetate, stearylaminopropylamine acetate, and other amine salts; lauryltrimethylammonium chloride, dilauryldimethylammonium Chloride, distearyl ammonium chloride, distearyl dimethyl ammonium chloride, lauryl dihydroxyethyl methyl ammonium chloride, oleyl bis polyoxyethylene methyl ammonium chloride, lauroyl aminopropyl dimethyl ethyl ammonium etosulphate, lauroyl aminopropyl dimethyl hydroxyethyl ammonium perchlorate, alkylbenzene dimethyl Ammonium chloride, alkylto Such as quaternary ammonium salts such as ammonium chloride.

  Specific examples of the nonionic surfactant include polyoxyethylene octyl ether, polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether and other alkyl ethers; Alkylphenyl ethers such as oxyethylene nonylphenyl ether; alkyl esters such as polyoxyethylene laurate, polyoxyethylene stearate, polyoxyethylene oleate; polyoxyethylene lauryl amino ether, polyoxyethylene stearyl amino ether, polyoxy Alkylamines such as ethylene oleyl amino ether, polyoxyethylene soybean amino ether, polyoxyethylene beef tallow amino ether; Alkyl amides such as xylethylene lauric acid amide, polyoxyethylene stearic acid amide, polyoxyethylene oleic acid amide; vegetable oil ethers such as polyoxyethylene castor oil ether, polyoxyethylene rapeseed oil ether; lauric acid diethanolamide, stearin Alkanolamides such as acid diethanolamide and oleic acid diethanolamide; sorbitan ester ethers such as polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan monooleate And the like.

  The addition amount of the dispersant used is desirably 2% by mass or more and 30% by mass or less, and more preferably 5% by mass or more and 20% by mass or less with respect to the colorant or the release agent. If the amount of the dispersant is too small, the particle size may not be reduced, or the storage stability of the dispersion may be reduced. On the other hand, when the amount is too large, the amount of the dispersant remaining in the toner increases, and the chargeability and powder fluidity of the toner may be reduced.

  The aqueous dispersion medium to be used is preferably one having few impurities such as metal ions such as distilled water and ion exchange water. In addition, alcohol or the like can be added for the purpose of defoaming or adjusting the surface tension. Moreover, polyvinyl alcohol, a cellulose polymer, etc. can also be added for viscosity adjustment.

  The means for preparing the dispersion of the various additives is not particularly limited, and examples thereof include a ball mill, a sand mill, and a dyno mill having a rotary shearing homogenizer and a media, as well as a colorant dispersion and a release agent. Examples of the dispersion apparatus known per se include an apparatus according to the one used for the preparation of the dispersion, and an optimum apparatus can be selected and used.

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

  Specific examples of 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. And inorganic metal salt polymers. Among these, an aluminum salt and a polymer thereof are particularly preferable. In general, in order to obtain a sharper particle size distribution, even if the valence of the inorganic metal salt is divalent to monovalent, bivalent to trivalent or higher, and even to the same valence, the polymerization type inorganic metal salt weight Combined is more suitable.

  The amount of the flocculant added varies depending on the type and valence of the flocculant, but is generally in the range of 0.05 to 0.1% by mass. The aggregating agent does not always remain in the toner due to outflow into the aqueous medium or formation of coarse powder during the toner forming process. In particular, when the amount of the solvent in the resin is large in the toner forming step, the solvent and the flocculant interact and easily flow out into the aqueous medium, so it is necessary to adjust the amount according to the amount of the remaining solvent.

  In the fusion step, the agglomeration suspension is brought to a pH of 5 to 10 under stirring according to the agglomeration step to stop the agglomeration, and the resin has a glass transition temperature (Tg) or higher. The aggregated particles are fused and united by heating at a temperature (or a temperature equal to or higher than the melting point of the crystalline resin). The heating time may be as long as desired coalescence is achieved, and may be performed for about 0.2 to 10 hours. Thereafter, when the temperature is lowered to Tg or less of the resin to solidify the particles, the particle shape and surface properties change depending on the temperature lowering rate. For example, when the temperature is lowered at a high speed, spheroidization and surface irregularities tend to decrease, and conversely, when the temperature is lowered slowly, the particle shape becomes irregular and irregularities are likely to occur on the particle surface. Therefore, it is preferable to lower the temperature to at most Tg of the resin at a rate of at least 0.5 ° C./min, more preferably at a rate of 1.0 ° C./min or more.

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

  After completing the fusing step, the particles are washed and dried to obtain toner particles. Considering the chargeability of the toner, it is preferable to perform substitution cleaning with ion-exchanged water, and the degree of cleaning is generally monitored by the conductivity of the filtrate, so that the conductivity finally becomes 25 μS / cm or less. It is preferable to make it. The washing may include a step of neutralizing ions with an acid or an alkali. The treatment with an acid preferably has a pH of 4.0 or less, and the treatment with an alkali preferably has a pH of 8.0 or more. The solid-liquid separation after washing is not particularly limited, but from the viewpoint of productivity, suction filtration, pressure filtration such as a filter press, and the like are preferably used. Further, the drying method is not particularly limited, but from the viewpoint of productivity, freeze drying, flash jet drying, fluidized drying, vibration fluidized drying, etc. are preferably used, and the final toner moisture content is 1% by mass or less. More preferably, drying is performed so that the content is 0.7% by mass or less.

  The toner particles obtained as described above can be externally mixed with inorganic particles and organic particles as fluidity aids, cleaning aids, abrasives, and the like. Examples of the inorganic particles include all particles usually used as external additives on the toner surface, such as silica, alumina, titanium oxide, calcium carbonate, magnesium carbonate, tricalcium phosphate, and cerium oxide. These inorganic particles preferably have a hydrophobic surface, and are used to control various toner characteristics such as chargeability, powder characteristics, and storage stability, and system suitability such as developability and transferability. It is done. As organic particles, for example, they are usually used as external additives on the surface of toner such as vinyl resins such as styrene polymers, (meth) acrylic polymers, and ethylene polymers, polyester resins, silicone resins, and fluorine resins. All particles.

These particles are added for the purpose of improving transferability, and the primary particle size is preferably 0.05 to 1.0 μm. Further, a lubricant can be added. Examples of the lubricant include fatty acid amides such as ethylene bisstearyl amide and oleic acid amide, and higher alcohols such as fatty acid metal salt unilin such as zinc stearate and calcium stearate. These are generally added for the purpose of improving the cleaning property, and those having a primary particle size of 0.150 μm are used.
The external additive is adhered or fixed to the toner surface by applying a mechanical impact force with a sample mill or a Henschel mixer.

(Toner characteristics)
The volume average particle size of the toner in the present invention is preferably in the range of 4 to 9 μm, more preferably in the range of 4.5 to 8.5 μm, and still more preferably in the range of 5 to 8 μm. When the volume average particle size is smaller than 4 μm, the toner fluidity is lowered, the chargeability of each particle is likely to be lowered, and the charge distribution is widened, so that fogging on the background and toner spillage from the developing device 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 size 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.

In addition, the toner of the present invention draws a cumulative distribution from the small diameter side for each of the volume and number, and the particle size range (channel) obtained by dividing the particle size distribution measured by the following method. Is the volume average particle size calculated from (D84% / D16%) ^{1/2, where the} particle size at which volume D16% is defined and the particle size at which volume D50% is accumulated 84% is defined as volume D84%. The distribution index (GSDv) is preferably 1.15 to 1.30, and more preferably 1.15 to 1.25.

  The volume average particle diameter and the like can be measured using Multisizer II (manufactured by Beckman Coulter, Inc.) with an aperture diameter of 50 μm. At this time, the measurement was performed after the toner was dispersed in an electrolyte aqueous solution (isoton aqueous solution) (concentration: 10% by mass) and dispersed by ultrasonic waves for 30 seconds or more. As for the particle size distribution, the particle size range divided on the basis of the particle size distribution measured using Multisizer II (divided number: from 1.26 to 50.8 μm in 16 channels, 0.1 in log scale) Specifically, channel 1 is 1.26 μm or more and less than 1.59 μm, channel 2 is 1.59 μm or more and less than 2.00 μm, channel 3 is 2.00 μm or more and less than 2.52 μm. The log values of the lower limit value on the left side are (log1.26 =) 0.1, (log1.59 =) 0.2, (log2.00 =) 0.3, ..., 1.6 In other words, the cumulative distribution is subtracted from the small particle size side, and the particle size that becomes 16% is the volume D16v, the number D16p, and the particle size that is 50% is the volume. D50v (volume average grain ), Number D50p, volume particle size at a cumulative 84% D84v, was defined as the number D84p.

The toner of the present invention has a spherical shape with a shape factor (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 high-quality image formation can be performed.
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 particles, and A represents the projected area of the toner particles.

  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 toner particles dispersed on the surface of a slide glass is taken into a Luzex image analyzer through a video camera, the maximum length and projected area of 100 particles are obtained, calculated by the above equation (1), and the average value thereof Is obtained.

<Electrostatic image developer>
The developer for developing electrostatic charge of the present invention includes the toner for developing electrostatic charge of the present invention described above.
The electrostatic charge developing toner of the present invention is used as it is as a one-component developer or a two-component developer composed of a carrier, but a two-component developer excellent in charge maintenance and stability is desirable. Hereinafter, the embodiment of the two-component developer will be described.

  The carrier is preferably a carrier coated with a resin, and more preferably a carrier coated with a nitrogen-containing resin. Examples of the nitrogen-containing resin include acrylic resins including dimethylaminoethyl methacrylate, dimethylacrylamide, acrylonitrile and the like, amino resins including urea, urethane, melamine, guanamine, aniline, amide resins, and urethane resins. These copolymer resins may also be used. As the carrier coating resin, two or more of the nitrogen-containing resins may be used in combination. Moreover, you may use combining the said nitrogen containing resin and resin which does not contain nitrogen. The nitrogen-containing resin may be used in the form of particles and dispersed in a resin not containing nitrogen. In particular, urea resins, urethane resins, melamine resins, and amide resins have high negative chargeability and high resin hardness, so that a decrease in charge amount due to peeling of the coating resin can be effectively suppressed.

In general, the carrier needs to have an appropriate electric resistance value, and specifically, an electric resistance value of about 10 ⁹ to 10 ¹⁴ Ωcm is required. For example, when the electrical resistance value is as low as 10 ⁶ Ωcm as in the case of an iron powder carrier, the carrier adheres to the image portion of the photoreceptor due to charge injection from the sleeve, or the latent image charge escapes through the carrier, and the latent image In some cases, problems such as disturbance of the image or loss of images may occur. On the other hand, if an insulating resin (volume resistivity of 10 ¹⁴ Ωcm or more) is thickly coated, the electric resistance value becomes too high and carrier charges are less likely to leak, resulting in an edged image. On the other hand, there may be a problem of an edge effect that the image density in the central portion becomes very thin on a large image area. Therefore, it is desirable to disperse the conductive powder in the resin coating layer in order to adjust the resistance of the carrier.

  Specific examples of the conductive powder include metals such as gold, silver and copper; carbon black; semiconductive oxides such as titanium oxide and zinc oxide; titanium oxide, zinc oxide, barium sulfate, aluminum borate and potassium titanate. And the like, such as powder coated with tin oxide, carbon black, or metal. Among these, carbon black is preferable from the viewpoint of production stability, cost, and conductivity.

  Examples of the method for forming the resin coating layer on the surface of the carrier core material include an immersion method in which a powder of the carrier core material is immersed in the solution for forming the coating layer, and a solution for forming the coating layer on the surface of the carrier core material. Spraying method for spraying, fluidized bed method for spraying the solution for forming the coating layer in a state where the carrier core material is floated by flowing air, and a kneader for mixing the carrier core material and the coating layer forming solution in a kneader coater to remove the solvent. Examples of the coater method include a powder coating method in which a coating resin is formed into particles and mixed at a temperature equal to or higher than the melting point of the coating resin in a carrier core material and a kneader coater and then cooled to form a coating. The kneader coating method and the powder coating method are particularly preferably used. The average film thickness of the resin coating layer formed by the above method is usually in the range of 0.1 to 10 μm, more preferably 0.2 to 5 μm.

The core material (carrier core material) used for the carrier is not particularly limited, and examples thereof include magnetic metals such as iron, steel, nickel, and cobalt, or magnetic oxides such as ferrite and magnetite, glass beads, and the like. From the viewpoint of using the magnetic brush method, a magnetic carrier is desirable. As an average particle diameter of a carrier core material, generally 10-100 micrometers is preferable and 20-80 micrometers is more preferable.
The mixing ratio (mass ratio) of the toner and the carrier in the two-component developer is in the range of toner: carrier = 1: 100 to 30: 100, more preferably in the range of 3: 100 to 20: 100. desirable.

<Image forming apparatus>
Next, the image forming apparatus of the present invention using the electrostatic charge developing toner of the present invention will be described.
An image forming apparatus according to the present invention includes an image carrier, a charging unit that charges the surface of the image carrier, and a developing unit that develops an electrostatic image formed on the charged image carrier as a toner image using a developer. And a transfer unit that transfers the toner image formed on the image carrier onto the transfer body, and a fixing unit that fixes the toner image transferred onto the transfer body. The electrostatic image developer of the invention is used.

In this image forming apparatus, for example, the part including the developing unit may have a cartridge structure (process cartridge) that can be attached to and detached from the image forming apparatus main body. As the process cartridge, a developer holding body is used. The process cartridge of the present invention that contains at least the electrostatic image developer of the present invention is preferably used.
Hereinafter, an example of the image forming apparatus of the present invention will be described by way of an embodiment, but the present invention is not limited to this. In addition, the main part shown to a figure is demonstrated and the description is abbreviate | omitted about others.

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

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

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

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

Hereinafter, an operation of forming a yellow image in the first unit 10Y will be described. First, prior to the operation, the surface of the photoreceptor 1Y is charged to a potential of about −600V to −800V by the charging roller 2Y.
The photoreceptor 1Y is formed by laminating a photosensitive layer on a conductive substrate (volume resistivity at 20 ° C .: 1 × 10 ⁻⁶ Ωcm or less). This photosensitive layer usually has a high resistance (a resistance equivalent to that of a general resin), but has a property that the specific resistance of the portion irradiated with the laser beam changes when irradiated with the laser beam 3Y. Therefore, the photosensitive member 1Y is charged by the charging roller 2Y, and a laser beam 3Y is output to the surface of the charged photosensitive member 1Y via the exposure device 3 in accordance with yellow image data sent from a control unit (not shown). . The laser beam 3Y is applied to the photosensitive layer on the surface of the photoreceptor 1Y, whereby an electrostatic latent image of a yellow print pattern is formed on the surface of the photoreceptor 1Y.

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

  In the present invention, the charging voltage of the charging roller 2Y is preferably 300 V or more and 800 V or less, more preferably 300 V or more and 600 V or less, from the viewpoint of suppressing the generation amount of nitrogen oxides and the like.

  In the developing device 4Y, for example, yellow toner having a volume average particle diameter of 7 μm containing at least a yellow colorant, a crystalline polyester resin, and an amorphous polyester resin is accommodated. The yellow toner is triboelectrically charged by being agitated inside the developing device 4Y, and has a charge of the same polarity (negative polarity) as the charged charge on the photoreceptor 1Y, and a developer roll (developer holder). Is held on. As the surface of the photoreceptor 1Y passes through the developing device 4Y, the yellow toner is electrostatically attached to the latent image portion on the surface of the photoreceptor 1Y, and the latent image is developed with the yellow toner. . The photoreceptor 1Y on which the yellow toner image is formed continues to run at a predetermined speed, and the toner image developed on the photoreceptor 1Y is conveyed to a predetermined primary transfer position.

When the yellow toner image on the photoreceptor 1Y is conveyed to the primary transfer, a predetermined primary transfer bias is applied to the primary transfer roller 5Y, and the electrostatic force directed from the photoreceptor 1Y to the primary transfer roller 5Y generates a toner image. The toner image on the photoreceptor 1 </ b> Y is transferred onto the intermediate transfer belt 20. The transfer bias applied at this time is a (+) polarity opposite to the polarity (−) of the toner, and is controlled to about +10 μA by the control unit (not shown) in the first unit 10Y, for example.
On the other hand, the toner remaining on the photoreceptor 1Y is removed and collected by the cleaning device 6Y.

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

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

Thereafter, the recording paper P is sent to a fixing device (fixing means) 28, where the toner image is heated, and the color-superposed toner image is melted and fixed on the recording paper P. The recording paper P on which the color image has been fixed is carried out toward the discharge unit, and a series of color image forming operations is completed.
The image forming apparatus exemplified above is configured to transfer the toner image onto the recording paper P via the intermediate transfer belt 20, but the present invention is not limited to this configuration, and the toner image is directly transferred from the photoconductor. It may be a structure that is transferred to a recording sheet.

<Process cartridge, toner cartridge>
FIG. 2 is a schematic configuration diagram showing an example of a process cartridge containing the electrostatic charge image developer of the present invention. In the process cartridge 200, a charging roller 108, a developing device 111, a photoconductor cleaning device (cleaning means) 113, an opening 118 for exposure, and an opening 117 for static elimination exposure are attached to a rail 116 together with the photoconductor 107. Are combined and integrated with each other.
The process cartridge 200 is detachable from an image forming apparatus main body including a transfer device 112, a fixing device 115, and other components (not shown). It forms a forming apparatus. Reference numeral 300 denotes a recording paper (transfer object).

  The process cartridge shown in FIG. 2 includes a charging device 108, a developing device 111, a cleaning device (cleaning means) 113, an opening 118 for exposure, and an opening 117 for static elimination exposure. Can be selectively combined. In the process cartridge of the present invention, in addition to the photosensitive member 107, from the charging device 108, the developing device 111, the cleaning device (cleaning means) 113, the opening 118 for exposure, and the opening 117 for static elimination exposure. It comprises at least one selected from the group consisting of.

  Next, the toner cartridge of the present invention will be described. The toner cartridge of the present invention is detachably attached to the image forming apparatus, and at least the toner cartridge for storing toner to be supplied to the developing means provided in the image forming apparatus, the toner described above. Toner. The toner cartridge in the present invention 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, by using the toner cartridge containing the toner, storability can be maintained even in a toner cartridge whose container is miniaturized, It is possible to achieve low-temperature fixing while maintaining high image quality.

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

  Hereinafter, the present invention will be described in more detail with reference to examples. However, the present invention is not limited to the following examples. In the following description, “part” means “part by mass” and “%” means “mass%” unless otherwise specified.

-Synthesis of polyester resin 1-
-Dimethyl terephthalate: 58 parts-Dimethyl isophthalate: 78 parts-Succinic anhydride: 30 parts-Bisphenol A-ethylene oxide 2 mol adduct: 158 parts-Ethylene glycol: 100 parts-Tetrabutoxy titanate: 0.07 parts The above components were charged into a heat-dried three-necked flask and heated at 170 to 220 ° C. for 180 minutes to conduct a transesterification reaction. Subsequently, as a result of continuing reaction for 60 minutes at 220 degreeC and the system pressure of 1-10 mmHg, the polyester resin 1 was obtained. The glass transition temperature of the polyester resin 1 was 53 ° C.

-Synthesis of polyester resin 2-
-Dimethyl naphthalenedicarboxylate: 114 parts-Dimethyl terephthalate: 99 parts-Bisphenol A-ethylene oxide 2-mol adduct: 221 parts-Ethylene glycol: 80 parts-Tetrabutoxy titanate: 0.07 parts 3 The mixture was charged into a neck flask and heated at 170 to 220 ° C. for 180 minutes to conduct a transesterification reaction. Subsequently, as a result of continuing reaction for 60 minutes at 220 degreeC and the system pressure of 1-10 mmHg, the polyester resin 2 was obtained. The glass transition temperature of the polyester resin 2 was 62 ° C.

<Preparation of each dispersion>
-Preparation of polyester resin dispersion A-
-Polyester resin 1: 100 parts-Ethyl acetate: 900 parts-20% anionic surfactant: 2 parts-Ammonium acetate: 10 parts The above ingredients are put into a closed container and emulsified with a homogenizer, and polyester resin dispersion a Got.

The obtained polyester resin dispersion a was transferred to a distillation flask and heated to 50 ° C.
-10 kPa / min from 101.3 to 80 kPa,
Up to 80-60 kPa -2 kPa / min,
-1 kPa / min from 60 to 40 kPa,
From 40 to 20 kPa -0.5 kPa / min
Distillation was carried out under the conditions described above, and after cooling, ion exchange water was added to obtain a polyester resin dispersion A having a solid content concentration of 20%. The amount of total nitrogen was 300 mgN / L.

-Preparation of polyester resin dispersion B-
・ Polyester resin 2: 100 parts ・ Ethyl acetate: 40 parts ・ 1-propanol: 15 parts The above ingredients are put into a sealed container, and 10% ammonia water is added so as to be equivalent to the resin acid value. Ion exchange water was added dropwise with emulsification and emulsification to obtain a polyester resin dispersion b.

After raising the obtained polyester resin dispersion b to 55 ° C. in a distillation flask,
-10 kPa / min from 101.3 to 50 kPa,
-3 kPa / min from 50 to 35 kPa,
Up to 35-20 kPa -2 kPa / min,
From 20 to 20 kPa, -1 kPa / min
Distillation was carried out under the conditions described above, and after cooling, ion exchange water was added to obtain a polyester resin dispersion B having a solid concentration of 20%. The amount of total nitrogen was 200 mgN / L.

-Preparation of polyester resin dispersion C-
After heating the polyester resin dispersion a to 55 ° C. in a distillation flask,
-50 kPa / min from 101.3 to 60 kPa,
-5 kPa / min from 60 to 35 kPa,
-35 kPa / min up to 35-20 kPa,
20min at 15kPa
Distillation was carried out under the conditions described above, and after cooling, ion-exchanged water was added to obtain a polyester resin dispersion C having a solid content concentration of 20%. The amount of total nitrogen was 900 mg N / L.

-Preparation of polyester resin dispersion D-
After heating the polyester resin dispersion b to 55 ° C. in a distillation flask,
-10 kPa / min from 101.3 to 80 kPa,
-10 kPa / min from 80 to 60 kPa,
-60 kPa / min from 60 to 40 kPa,
-40 kPa / min from 40 to 5 kPa,
60 min at 5 kPa
Distillation was carried out under the conditions, and after cooling, ion exchange water was added to obtain a polyester resin dispersion D having a solid content concentration of 20%. The amount of total nitrogen was 15 mg N / L.

-Preparation of polyester resin dispersion E-
In the preparation of the polyester resin dispersion C, the polyester resin dispersion E was prepared in the same manner as in the preparation of the polyester resin dispersion C, except that the amount of ammonium acetate in the polyester resin dispersion a used was changed to 8.3 parts. Obtained. The amount of total nitrogen was 450 mgN / L.

-Preparation of polyester resin dispersion F-
In the preparation of the polyester resin dispersion A, the polyester resin dispersion F was prepared in the same manner as the preparation of the polyester resin dispersion A, except that the amount of ammonium acetate in the used polyester resin dispersion a was changed to 5.5 parts. Obtained. The amount of total nitrogen was 170 mgN / L.

-Preparation of polyester resin dispersion G-
After heating the polyester resin dispersion a to 55 ° C. in a distillation flask,
-50 kPa / min from 101.3 to 60 kPa,
-5 kPa / min from 60 to 35 kPa,
-35 kPa / min up to 35-20 kPa,
-5 kPa / min from 20 to 15 kPa,
Distillation was carried out under the conditions, and after cooling, ion exchange water was added to obtain a polyester resin dispersion G having a solid content concentration of 20%. The amount of total nitrogen was 2000 mgN / L.

-Preparation of colorant dispersion-
・ Black pigment (Regal 330: Cabot Corporation): 50 parts ・ Ionic surfactant Neogen RK (Daiichi Kogyo Seiyaku): 5 parts ・ Ion-exchanged water: 195 parts The above ingredients were mixed and dissolved, and homogenizer (IKA Ultra) (Turrax) for 10 minutes to obtain a colorant dispersion.

-Preparation of release agent dispersion-
・ Polyalkylene wax FNP0092 (melting point: 91 ° C., manufactured by Nippon Seiwa Co., Ltd.): 50 parts ・ Cationic surfactant Neogen RK (Daiichi Kogyo Seiyaku): 5 parts ・ Ion-exchanged water: 195 parts Heat the above ingredients to 95 ° C. Then, after sufficiently dispersing with IKA Ultra Turrax T50, the mixture was dispersed with a pressure discharge type gorin homogenizer to obtain a release agent dispersion having a solid content of 20% by weight.

(Preparation of Toner 1)
-Polyester resin dispersion D: 80 parts-Colorant dispersion: 60 parts-Release agent dispersion: 60 parts The above components were sufficiently mixed and dispersed in a round stainless steel flask with Ultratarax T50. Next, 0.36 parts of polyaluminum chloride was added thereto, and the dispersion operation was continued with Ultra Tarax. The flask was heated to 48 ° C. with stirring in an oil bath for heating. Thereafter, the pH of the system was adjusted to 8.0 with a 0.5 mol / L sodium hydroxide aqueous solution, and then the stainless steel flask was sealed and heated to 95 ° C. while continuing stirring using a magnetic seal. Held for hours. Then, after cooling and sufficiently washing with filtration and ion exchange water, solid-liquid separation was performed by Nutsche suction filtration.
This was further redispersed in 3 L of ion exchanged water at 40 ° C., and stirred and washed at 300 rpm for 15 minutes. This was repeated 5 times. When the pH of the filtrate was 7.01, the electric conductivity was 9.8 μS / cm, and the surface tension was 71.1 Nm, No. Solid-liquid separation was performed using 5A filter paper. Next, vacuum drying was continued at 35 ° C. for 12 hours to obtain toner 1. The obtained toner 1 had a volume average diameter D50 of 6.5 μm and a particle size distribution coefficient GSDv of 1.25. Moreover, it was observed that the shape factor SF1 of the particle | grains calculated | required from the shape observation by Luzex was 113.

(Preparation of Toner 2)
In preparation of toner 1, toner 2 was obtained in the same manner as preparation of toner 1 except that heating to 95 ° C. and holding for 6 hours was changed to heating to 93 ° C. and holding for 5 hours. It was observed that the particle shape factor SF1 obtained from the shape observation of the obtained toner 2 by Luzex was 121.

(Preparation of Toner 3)
In the production of toner 1, toner 3 was produced in the same manner as in the production of toner 1 except that heating to 95 ° C. and holding for 6 hours was changed to heating to 90 ° C. and holding for 3 hours. It was observed that the shape factor SF1 of the particles obtained from the observation of the shape of toner 3 obtained by Luzex was 128.

(Preparation of Toner 4)
In the preparation of toner 1, toner 4 was prepared in the same manner as preparation of toner 1 except that heating to 95 ° C. and holding for 6 hours was changed to heating to 86 ° C. and holding for 2.5 hours. . It was observed that the shape factor SF1 of the particles obtained from the observation of the shape of the toner 4 obtained by Luzex was 138.

(Preparation of Toner 5)
A toner 5 was prepared in the same manner as the preparation of the toner 3 except that the polyester resin dispersion D was changed to the polyester resin dispersion E in the preparation of the toner 3. It was observed that the shape factor SF1 of the particle obtained from the observation of the shape of the obtained toner 5 by Luzex was 127.

(Production of Toner 6)
A toner 6 was produced in the same manner as in the production of the toner 3 except that the polyester resin dispersion D was changed to the polyester resin dispersion B in the production of the toner 3. It was observed that the particle shape factor SF1 obtained from the shape observation of the obtained toner 6 by Luzex was 126.

(Preparation of Toner 7)
Toner 7 was prepared in the same manner as in preparation of toner 3 except that polyester resin dispersion D was changed to polyester resin dispersion F in preparation of toner 3. It was observed that the particle shape factor SF1 obtained from the observation of the shape of the toner 7 obtained by Luzex was 126.

(Production of Toner 8)
Toner 8 was produced in the same manner as in Toner 3 except that polyester resin dispersion D was changed to polyester resin dispersion A in the production of toner 3. It was observed that the shape factor SF1 of the particle obtained from the observation of the shape of the toner 8 obtained by Luzex was 127.

(Production of Toner 9)
A toner 9 was prepared in the same manner as in the preparation of the toner 3 except that the polyester resin dispersion D was changed to the polyester resin dispersion C in the preparation of the toner 3. It was observed that the particle shape factor SF1 obtained by observing the shape of the obtained toner 9 with Luzex was 126.

(Production of Toner 10)
In the production of the toner 4, the polyester resin dispersion D is changed to the polyester resin dispersion G, and further heated to 86 ° C. and held for 2.5 hours is changed to be heated to 84 ° C. and held for 2 hours. A toner 10 was produced in the same manner as in the production of the toner 4 except for the above. It was observed that the shape factor SF1 of the particles obtained from the observation of the shape of the toner 10 obtained by Luzex was 144. The volume average diameter D50 was 6.0 μm, the particle size distribution coefficient GSDv was 1.31, and the particle size distribution was larger than those of the toners 1 to 9.

<Preparation of external additive>
AEROSIL200 (manufactured by Nippon Aerosil Co., Ltd .: 16 nm), 100 parts of SZ6070 (manufactured by Toray Dow Corning Silicone Co., Ltd .: methyltrimethoxysilane) and 200 parts of acetone were placed in a flask, stirred for 60 minutes, and then heated to 60 ° C. with a rotary evaporator. While being held, the solution was distilled under reduced pressure, taken out after the solvent was distilled off, and pulverized in a mortar to obtain a coupling agent-treated external additive.

<Preparation of external toner>
To 100 parts of the toners 1 to 10, 2 parts of the coupling agent-treated external additive was added and mixed for 5 minutes at 25 m / s using a Henschel mixer to prepare externally added toners 1 to 10, respectively.

(Development of developer)
The surface of the ferrite particles (volume average particle size: 50 μm) was coated with methyl methacrylate resin (manufactured by Soken Chemical Co., Ltd., Mw: 82000) to prepare a carrier. 100 parts of the prepared carrier is mixed with 8 parts of each of the externally added toners 1 to 10 and mixed with a V-type blender for 20 minutes, and then the aggregates are removed by a vibrating screen having an opening of 212 μm to remove developer 1 10 were obtained respectively.

<Examples 1 to 12, Comparative Example 1>
For each of the externally added toners 1 to 10 shown in Table 1, 300 g of externally added toner is placed in a glass bottle, 0.6 g of 10% aqueous nitric acid solution is added and sealed, and a turbula mixer (T2F, manufactured by Shinmaru Enterprises Co., Ltd.) is sealed. Type) at 100 rpm for 1 hour. Then, the airtightness was released, and drying was performed under reduced pressure at 100 Pa for 12 hours at 25 ° C. in a dryer (Tokyo Rika Kikai Co., Ltd., FD-550P). The toner was then allowed to stand for 12 hours under conditions of an air temperature of 30 ° C.-85% RH, and the angle of repose was measured under the conditions described above (rest angle A). For each of the external toners 1 to 10 not subjected to the above treatment, the angle of repose was measured (rest angle B), and the amount of change in the angle of repose A and the angle of repose B is shown in Table 1 as the amount of change in the angle of repose. Table 1 shows the mass ratio of the total amount of alkali metal and alkaline earth metal to the binder resin as the total amount of metal.

Further, using the developers 1 to 10 obtained from the externally added toners 1 to 10 shown in Table 1, the DocuCentre-II C3300 remodeling machine (operates without a developing machine other than black, and the charging voltage is set. 30000 sheets of the following output images under the conditions of 30 ° C. and 85%, with the charging voltage to the charging device (charging means) set to the values shown in Table 1. Output. The paper was R paper manufactured by Fuji Xerox Co., A4 size. The output image was printed on the entire surface with 5 mm × 5 mm characters “Hiki” left and right, up and down, left and right, and visually evaluated according to the following criteria to evaluate fine line reproducibility. The results are shown in Table 1. The evaluation criteria were “G1” to “G5” based on the number of characters in which the characters “Hibi” were crushed. Of “G1” to “G5”, only “G4” is acceptable. In addition, Table 1 shows other changes that occurred in other images.
“G1”: 2 or less “G2”: 3 or more and 5 or less “G3”: 6 or more and 10 or less “G4”: 11 or more and 15 or less “G5”: 16 or more

1 is a schematic configuration diagram illustrating an example of an image forming apparatus of the present invention. It is a schematic block diagram which shows an example of the process cartridge of this invention.

Explanation of symbols

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

Claims (9)

An external additive containing at least a binder resin and treated with a coupling agent is externally added, has a shape factor of 110 to 140, and the rest of the toner before and after being treated in the following steps (1) to (3) An electrostatic charge developing toner, characterized in that the amount of change in angle is from 0 to 3 degrees.
(1) To 100 parts by mass of the toner, 0.2 part of a 10% by mass nitric acid aqueous solution is added and stirred at 100 rpm for 1 hour.
(2) The toner after stirring in (1) is dried under reduced pressure at 100 Pa for 12 hours at 25 ° C.
(3) The toner after drying under reduced pressure in (2) is allowed to stand for 12 hours at a temperature of 30 ° C.-85% RH.   At least one of alkali metal or alkaline earth metal is contained in the toner surface, and the mass ratio of the total amount of alkali metal and alkaline earth metal to the binder resin on the toner surface is 10 ppm or more and 500 ppm or less. The toner for developing an electrostatic charge according to claim 1.   Forming agglomerated particles to prepare an agglomerated particle dispersion in a dispersion containing at least a resin particle dispersion in which binder resin particles are dispersed in a dispersion medium; and heating the agglomerated particle dispersion to agglomerate Including a step of fusing particles, wherein the amount of total nitrogen detected by the fluorescent X-ray method at a solid content concentration of 20% by mass of the resin particle dispersion is 10 mgN / L or more and 500 mgN / L or less. A method for producing a toner for developing an electrostatic charge according to claim 1. Forming agglomerated particles to prepare an agglomerated particle dispersion in a dispersion containing at least a resin particle dispersion in which binder resin particles are dispersed in a dispersion medium; and heating the agglomerated particle dispersion to agglomerate Including the step of fusing particles,
After the resin particle dispersion has dispersed the binder resin particles, the pressure is controlled in the range of 60 Pa to 1 kPa and the saturated vapor pressure of the dispersion medium within a range of ± 3 kPa, and the temperature is adjusted to the binder resin. The electrostatic charge according to claim 1 or 2, wherein the electrostatic charge is a liquid obtained by controlling the glass transition temperature or melting point within a range of ± 20 ° C and further performing distillation under reduced pressure while satisfying the following conditions: A method for producing a developing toner.
0 ≦ | d ² p / dt ² (kPa / min ² ) | ≦ 20
Here, p represents pressure (kPa), and t represents time (min).   An electrostatic charge developing developer comprising: a toner, wherein the toner is the electrostatic charge developing toner according to claim 1.   A toner cartridge containing at least toner, wherein the toner is the electrostatic charge developing toner according to claim 1.   A process cartridge comprising at least a developer holder and containing the developer for electrostatic charge development according to claim 5.   An image carrier, a charging unit that charges the surface of the image carrier, a developing unit that develops an electrostatic image formed on the charged image carrier as a toner image with a developer, and a toner image formed on the image carrier. 6. The electrostatic charge development according to claim 5, further comprising: a transfer unit that transfers the toner image transferred onto the transfer member; and a fixing unit that fixes the toner image transferred onto the transfer member. An image forming apparatus characterized by being a developer.   The image forming apparatus according to claim 8, wherein a charging voltage of the charging unit is 300 V or more and 800 V or less.

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