JP2011043540A - Toner for electrostatic charge image development and method for producing the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a toner for electrostatic charge image development, capable of forming an image with less offset without using an impurity metal ion when a halftone image is fixed after forming a solid image in an oil-less fixing process, and to provide a method for producing the toner. <P>SOLUTION: The toner for electrostatic charge image development comprising at least a binder resin and a release agent and containing an amino acid and an oxy acid expressed by formula (1) is obtained by: mixing a resin fine particle dispersion liquid in which at least fine particles of a binder resin are dispersed, with a release agent dispersion liquid to which an amino acid and the oxy acid are added; aggregating the mixed liquid to form aggregated particles; and stopping the growth of the aggregated particles followed by heating the aggregated particles at a temperature equal to or higher than the melting temperature of the binder resin to fuse/unify the particles. In formula (1), n represents 1 to 8. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to an electrostatic image developing toner and a method for producing the same.

  A method of visualizing image information through an electrostatic charge image such as electrophotography is currently used in various fields. In electrophotography, an electrostatic charge image is formed on a photoreceptor by charging and exposure processes, and the electrostatic charge image is developed with a developer containing an electrostatic charge image developing toner (hereinafter sometimes referred to simply as “toner”). Then, the electrostatic image is visualized through the transfer and fixing processes.

  As the developer used here, a two-component developer composed of a toner and a carrier, and a one-component developer using a magnetic toner or a non-magnetic toner alone are known. Usually, a kneading and pulverizing method is used in which a thermoplastic resin is melt-kneaded together with a release agent such as a pigment, a charge control agent, and a wax, and after cooling, pulverized and classified. In these toners, if necessary, inorganic and organic fine particles for improving fluidity and cleaning properties may be added to the surface of the toner particles. According to these methods, an excellent toner can be produced, but the stress in the developing unit is caused by the fact that the toner shape is indefinite, fine powder is easily generated, and the release agent is easily exposed on the surface. There are problems such as deterioration in developability, image quality deterioration, and contamination of other members.

  Therefore, in recent years, as a means for intentionally controlling the toner shape and the surface structure of the toner, a toner production method using an emulsion polymerization aggregation method has been proposed (see, for example, Patent Documents 1 and 2). These are generally prepared by dispersing resin fine particles by emulsion polymerization or the like, while preparing a colorant dispersion in which a colorant is dispersed in a solvent, and then mixing these to form aggregated particles corresponding to the toner particle size, This is a method for producing toner by fusing and coalescing by heating. By this method, the toner shape can be controlled to some extent and the chargeability and durability can be improved, but in the oilless fixing process, an offset occurs when fixing a halftone image after solid image formation, Image quality may be degraded. Therefore, in the following Patent Document 3, it is proposed to improve image quality by containing impurity metal ions.

Japanese Patent Laid-Open No. 63-282275 JP-A-6-250439 JP 2007-72327 A

  An object of the present invention is to provide an electrostatic charge image developing toner capable of forming an image with less offset without using impurity metal ions when fixing a halftone image after solid image formation in an oilless fixing step. It is in providing the manufacturing method.

ここで、ｎは１〜８。 In order to achieve the above object, the toner for developing an electrostatic charge image according to claim 1 is characterized in that the toner having at least a binder resin and a release agent contains an amino acid and the following oxyacid. And

Here, n is 1-8.

  The invention according to claim 2 is the invention according to claim 1, wherein the amino acid of the toner is aspartic acid.

  The invention described in claim 3 is the invention described in claim 1 or 2, characterized in that n of the oxyacid of the toner is 1-2.

  According to a fourth aspect of the present invention, in the invention according to any one of the first to third aspects, when the mass% of the amino acid contained in the toner is A and the mass% of the oxyacid is B, A Is 0.01 to 1.5, and the ratio of A and B, C = A / B, is 0.5 to 1.5.

  According to a fifth aspect of the present invention, in the invention according to any one of the first to fourth aspects, the toner binder resin is a polyester resin containing bisphenol A.

  According to a sixth aspect of the present invention, in the invention according to any one of the first to fifth aspects, the toner release agent is an alkyl release agent.

  A seventh aspect of the invention is a method for producing a toner for developing an electrostatic charge image according to the first aspect, in which a resin fine particle dispersion in which fine particles of a binder resin having a volume average particle size of 1 μm or less are dispersed, A mixing step of mixing an amino acid and a release agent dispersion to which the oxyacid is added, and a product of the mixing step are aggregated in the presence of a compound having a monovalent or higher charge to form aggregated particles. An aggregated particle forming step, a particle growth stopping step of stopping the growth of the aggregated particles by adjusting the pH in the system to 5 to 10, and heating the aggregated particles to a temperature equal to or higher than the dissolution temperature of the fine particles of the binder resin And a fusion process of fusing and uniting.

  According to the first aspect of the present invention, when a halftone image is fixed after the solid image is formed in the oilless fixing step, an image with a small offset can be formed without using impurity metal ions.

  According to invention of Claim 2, an amino acid with high reactivity with oxyacid can be used.

  According to the invention of claim 3, it has high hydrophilicity and high reactivity with amino acids.

  According to invention of Claim 4, unreacted oxyacid and an amino acid can be decreased and mold release agent controllability can be improved.

  According to the invention of claim 5, bisphenol A is hardly compatible with the release agent, and the position of the release agent in the toner can be controlled more precisely.

  According to the invention of claim 6, by using the alkyl releasing agent, the compatibility with the resin can be reduced, and the position of the releasing agent in the toner can be controlled more precisely.

  According to the seventh aspect of the present invention, there is provided an electrostatic charge image developing toner capable of forming an image with less offset without using impurity metal ions when fixing a halftone image after solid image formation in an oilless fixing step. Can be manufactured.

1 is a schematic view of an example of an image forming apparatus according to an embodiment.

  Hereinafter, modes for carrying out the present invention (hereinafter referred to as embodiments) will be described.

<Toner for electrostatic image development>
The toner for developing an electrostatic charge image according to the embodiment has at least a binder resin and a release agent, and contains an amino acid and an oxyacid shown below. Here, n (carbon number) is in the range of 0-8.

  In general, in an oilless fixing process or the like, a large amount of release agent is adhered to the surface of the fixing roll after the solid image is formed. In addition, the release agent that composes the toner is present near the toner surface and is easily compatible with the release agent adhering to the fixing roll. Therefore, an offset occurs especially when fixing a halftone image after forming a solid image. It's easy to do. Here, the offset refers to a phenomenon in which a part of the toner image adheres to and is removed from the fixing roll.

  In the toner for developing an electrostatic charge image according to the above-described embodiment (hereinafter sometimes simply referred to as “toner”), at least the oxyacid and the amino acid are added during the production, and the release agent enters the toner particles. By controlling the amount of the release agent on the toner surface, and adjusting the amount of the release agent exuding from the toner particles, the compatibility with the release agent adhering to the fixing roll is suppressed. Yes. In addition, amino acid and oxyacid remain in the vicinity of the release agent, and become an amide compound at the time of fixing, thereby suppressing the softening of the binder resin by suppressing the compatibility between the oxyacid and the binder resin. It prevents the adhesion to the fixing roll from increasing. With the above configuration, the occurrence of offset in the case of fixing a halftone image after solid image formation in an oilless fixing process or the like is suppressed.

  As described above, the electrostatic image developing toner according to the embodiment has at least a binder resin and a release agent, and satisfies the condition that the toner contains an oxyacid and an amino acid. Form. Here, the oxyacid and amino acid are preferably added to the release agent dispersion at the time of production of the electrostatic image developing toner. At this time, it is preferable to add an equal amount of oxyacid and amino acid. The oxyacid and amino acid are extracted by high performance liquid chromatography (HPLC) and identified by NMR analysis. The measurement conditions of HPLC and NMR will be described in Examples described later.

  As described above, it is necessary to add an amino acid and an oxyacid to the toner for developing an electrostatic charge image according to the embodiment. This is because the carboxylic acid of the amino acid, the amino group, and the oxyacid react at the time of fixing to suppress the compatibility of the oxyacid with the binder resin and suppress the offset. The amino acids that can be used in this embodiment are asparagine, serine, aspartic acid, glutamine, glutamic acid, threonine, arginine, histidine, glycine, lysine, tyrosine, tryptophan, cysteine, methionine, proline, phenylalanine, alanine, valine, leucine, isoleucine. Among them, one or more of them can be used. In particular, aspartic acid is more preferable because of its reactivity with oxyacids.

  As described above, n (carbon number) of the oxyacid contained in the electrostatic image developing toner according to the embodiment is in the range of 1 to 8, more preferably 1 to 3. If it is less than 1, the hydrophobicity of the oxyacid is reduced, and a large amount of the release agent is present in the range of 50 nm from the toner surface, which is easily compatible with the release agent adhering to the fixing roll and causes an offset. There is a case. On the other hand, when n is 9 or more, the hydrophobicity of the oxyacid is increased, and a large amount of the release agent is present in the interior of 1 μm or more from the toner surface. The releasability from the fixing roll is lowered, and an offset may occur when fixing a halftone image after solid image formation in an oilless fixing process.

  When the mass% of the amino acid contained in the toner for developing an electrostatic image is A and the mass% of the oxyacid is B, A is 0.01 to 1.5 mass%. A / B ratio A / B = C is preferably 0.5 to 1.5. Furthermore, A is 0.1 to 1.0% by mass, and the ratio A / B = C of A and B is more preferably 0.8 to 1.2. When A is less than 0.01% by mass, the amount of amino acids decreases and a large amount of the release agent is present in the vicinity of the toner surface, and adheres to the fixing roll due to compatibility with the release agent attached to the fixing roll. Since it becomes easy, it is not preferable. On the other hand, when A exceeds 1.5% by mass, the amount of amino acids increases, and the release agent tends to be unevenly distributed near the center of the toner particles, so that the exuding property of the release agent is deteriorated at the time of fixing. Further, when the ratio A / B = C of A and B is less than 0.8, the ratio of oxyacid is high, the binder resin and oxyacid are compatible at the time of fixing, and the compatible binder resin is a fixing roll. It is not preferable because it tends to adhere to the film and offset is likely to occur. Further, when the ratio A / B = C of A / B exceeds 1.5, the ratio of amino acids increases, and the release agent tends to be unevenly distributed in the vicinity of the center of the toner particles, so that the release property of the release agent is reduced. Therefore, it is not preferable.

  The binder resin is preferably a polyester resin containing bisphenol A, and the release agent is preferably an alkyl release agent. When a polyester resin containing bisphenol A and an alkyl release agent are used, bisphenol A and the alkyl release agent are not easily compatible, and as a result, the controllability of the release agent position in the toner particles is enhanced.

  Hereinafter, the electrostatic image developing toner according to the embodiment will be described together with a manufacturing method. Although there is no restriction | limiting in particular as this manufacturing method, The emulsion polymerization aggregation method is preferable. The emulsion polymerization aggregation method includes a mixing step of mixing a resin fine particle dispersion in which fine particles of a binder resin having a volume average particle size of 1 μm or less are dispersed and a release agent dispersion to which an oxyacid and an amino acid are added, and this mixing An agglomerated particle forming step of aggregating the liquid in the presence of a compound having a monovalent or higher charge to form an agglomerated particle, and a particle for adjusting the pH in the system to 5 to 10 to stop the growth of the agglomerated particle A growth stopping step and a fusing step of fusing and coalescing the aggregated particles by heating them to a temperature equal to or higher than the melting temperature of the binder resin fine particles.

  Further, in the aggregated particle forming step, after the aggregated particles (core aggregated particles) are formed, a second resin fine particle dispersion in which the fine particles of the second binder resin are dispersed is added, and the surface of the core aggregated particles is It is also preferable to prepare a toner having a core-shell structure by forming resin-attached aggregated particles to which fine particles of the second binder resin are attached.

  When a toner having a core-shell structure is produced, the amount of the second resin fine particle dispersion used depends on the particle size of the second binder resin fine particles contained therein, but the shell that is finally formed The thickness of the layer is preferably selected so as to be about 20 to 500 nm. In terms of solid content, the amount of the second binder resin used is preferably 1 to 40% by mass and more preferably 5 to 30% by mass in the total amount of toner. When the thickness of the shell layer is less than 20 nm, the colorant is likely to be exposed on the surface, and fogging under high temperature and high humidity may occur. On the other hand, when the thickness of the shell layer exceeds 500 nm, the exuding property of the release agent is lowered and offset may occur.

  Since the binder resin has low compatibility with the release agent, the above-described polyester resin containing bisphenol A is preferable in order to precisely control the position of the release agent in the toner. Crystalline polyester resin fine particles may be added.

  The crystalline polyester resin is synthesized from an acid (dicarboxylic acid) component and an alcohol (diol) component. In the following, “acid-derived component” refers to a component that was an acid component prior to the synthesis of the polyester resin, and “alcohol-derived component” refers to an alcohol component prior to the synthesis of the polyester resin. Refers to the constituent parts.

  When the polyester resin is not crystalline, that is, amorphous, it cannot maintain toner blocking resistance and image storage stability while ensuring good low-temperature fixability. Therefore, the “crystalline polyester resin” refers to a resin having a clear endothermic peak in the differential scanning calorimetry (DSC) instead of a stepwise endothermic change. In the case of a polymer obtained by copolymerizing other components with the main chain of the crystalline polyester resin, when the other components are 50% by mass or less, this copolymer is also called a crystalline polyester resin.

-Acid-derived components-
The acid-derived constituent component is preferably an aliphatic dicarboxylic acid, and particularly preferably a linear carboxylic acid. For example, succinic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelic acid, sebacic acid, 1,9-nonanedicarboxylic acid, 1,10-decanedicarboxylic acid, 1,11-undecanedicarboxylic acid Acid, 1,12-dodecanedicarboxylic acid, 1,13-tridecanedicarboxylic acid, 1,14-tetradecanedicarboxylic acid, 1,16-hexadecanedicarboxylic acid, 1,18-octadecanedicarboxylic acid, etc., or lower alkyl esters thereof, An acid anhydride may be mentioned, but not limited thereto.

  The acid-derived constituent component preferably includes a dicarboxylic acid-derived constituent component having a double bond, a dicarboxylic acid-derived constituent component having a sulfonic acid group, etc. in addition to the aliphatic dicarboxylic acid-derived constituent component described above. . The component derived from a dicarboxylic acid having a double bond is derived from a lower alkyl ester or acid anhydride of a dicarboxylic acid having a double bond in addition to a component derived from a dicarboxylic acid having a double bond. Components are also included. Further, the dicarboxylic acid-derived component having a sulfonic acid group is derived from a dicarboxylic acid having a sulfonic acid group, a lower alkyl ester of a dicarboxylic acid having a sulfonic acid group, an acid anhydride, or the like. Components are also included.

  In addition, the dicarboxylic acid having a double bond can be used to crosslink the entire resin by utilizing the double bond, so that the hot offset at the time of fixing (the toner is overheated and the cohesive force of the toner is increased between the fixing roll and the paper). Can be suitably used to prevent an offset phenomenon that occurs when the toner layer is divided. Examples of such dicarboxylic acids include, but are not limited to, fumaric acid, maleic acid, 3-hexenedioic acid, and 3-octenedioic acid. Moreover, these lower alkyl esters, acid anhydrides, etc. are also mentioned. Among these, fumaric acid and maleic acid are preferable from the viewpoint of versatility.

  The dicarboxylic acid having a sulfonic acid group is effective in that it can favorably disperse a coloring material such as a pigment. In addition, when emulsifying or suspending the entire resin in water to make toner base particles fine particles, if there are sulfonic acid groups, as described later, emulsification or suspension can be performed while suppressing the amount of surfactant used. Is possible. Examples of such a 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. Among these, sodium 5-sulfoisophthalate is preferable from the viewpoint of productivity.

  Content of acid-derived constituent components other than the above-mentioned aliphatic dicarboxylic acid-derived constituent components (dicarboxylic acid-derived constituent components having a double bond and / or dicarboxylic acid-derived constituent components having a sulfonic acid group) in the entire acid-derived constituent components 1 to 20 mol% is preferable, and 2 to 10 mol% is more preferable. When the content is less than 1 constituent mol%, pigment dispersion may not be good, the emulsified particle diameter may be large, and adjustment of the toner diameter by aggregation may be difficult. On the other hand, if it exceeds 20 component mol%, the crystallinity of the polyester resin is lowered, the dissolution temperature is lowered, the storage stability of the image is deteriorated, or the emulsion particle size is too small to dissolve in water, resulting in latex. There may not be. The “constituent mol%” refers to a percentage when each constituent component (acid-derived constituent component, alcohol-derived constituent component) in the polyester resin is defined as one unit (mol).

-Alcohol-derived components-
The alcohol-derived constituent component is preferably an aliphatic diol, such as ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol. 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,11-dodecanediol, 1,12-undecanediol, 1,13-tridecanediol, 1,14-tetradecanediol 1,18-octadecanediol, 1,20-eicosanediol, etc., but are not limited thereto.

  When the alcohol-derived constituent component is an aliphatic diol-derived constituent component, the content of the aliphatic diol-derived constituent component is 80 constituent mol% or more, and other components are included as necessary. Furthermore, when the alcohol-derived constituent component is an aliphatic diol-derived constituent component, the content of the aliphatic diol-derived constituent component is preferably 90 constituent mol% or more. If the content of the aliphatic diol-derived constituent component is less than 80 constituent mol%, the crystallinity of the polyester resin is lowered and the dissolution temperature is lowered, so that toner blocking resistance, image storage stability and low-temperature fixability are deteriorated. There is a case.

  Examples of the other components included as necessary include a diol-derived constituent component having a double bond, a diol-derived constituent component having a sulfonic acid group, and the like.

  Here, examples of the diol having a double bond include 2-butene-1,4-diol, 3-butene-1,6-diol, and 4-butene-1,8-diol.

  Examples of the diol having a sulfonic acid group include 1,4-dihydroxy-2-sulfonic acid benzene sodium salt, 1,3-dihydroxymethyl-5-sulfonic acid benzene sodium salt, and 2-sulfo-1,4-butane. Examples include diol sodium salt.

  Thus, when adding an alcohol-derived component other than the linear aliphatic diol-derived component, that is, when adding a diol-derived component having a double bond and / or a diol-derived component having a sulfonic acid group, The content of the diol-derived constituent component having a double bond and / or the diol-derived constituent component having a sulfonic acid group in the alcohol-derived constituent component is preferably 1-20 constituent mol%, and more preferably 2-10 constituent mol%. In addition, when the content of the alcohol-derived constituent component other than the aliphatic diol-derived constituent component is less than 1 constituent mol% with respect to the total alcohol-derived constituent component, the pigment dispersion is not good or the emulsion particle size is increased. Or adjustment of the toner diameter by aggregation may be difficult. On the other hand, if it exceeds 20 component mol%, the dissolution temperature may be lowered, the image storage stability may be poor, or the emulsified particle size may be too small to dissolve in water, resulting in no latex.

  There is no restriction | limiting in particular as a manufacturing method of crystalline polyester resin mentioned above, It can manufacture by the general polyester polymerization method which makes an acid component and an alcohol component react. For example, direct polycondensation, transesterification, and the like are used depending on the type of monomer. The molar ratio (acid component / alcohol component) when the acid component and alcohol component are reacted is usually about 1/1, although it varies depending on the reaction conditions and the like. The polyester resin can be produced at a polymerization temperature of 180 to 230 ° C., and the reaction system is reduced in pressure as necessary, and the reaction is carried out while removing water and alcohol generated during condensation.

  When the monomer is not dissolved or compatible with the reaction temperature, a solvent having a high boiling point may be added as a solubilizer and dissolved. In the polycondensation reaction, the dissolution aid is distilled off. In the case where a monomer having poor compatibility is present 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 crystalline polyester resin include alkali metal compounds such as sodium and lithium, alkaline earth metal compounds such as magnesium and calcium, zinc, manganese, antimony, titanium, tin, zirconium, germanium and the like. Examples include metal compounds, phosphorous acid compounds, phosphoric acid compounds, and amine compounds. Specifically, sodium acetate, sodium carbonate, lithium acetate, lithium carbonate, calcium acetate, calcium stearate, magnesium acetate, zinc acetate, stearic acid Zinc, zinc naphthenate, zinc chloride, manganese acetate, manganese naphthenate, titanium tetraethoxide, titanium tetrapropoxide, titanium tetraisopropoxide, titanium tetrabutoxide, antimony trioxide, triphenylantimony, tri Tilantimony, tin formate, tin oxalate, tetraphenyltin, dibutyltin dichloride, dibutyltin oxide, diphenyltin oxide, zirconium tetrabutoxide, zirconium naphthenate, zirconyl carbonate, zirconyl acetate, zirconyl stearate, zirconyl octylate, germanium oxide, triphenyl Examples of the compound include phosphite, tris (2,4-di-t-butylphenyl) phosphite, ethyltriphenylphosphonium bromide, triethylamine, and triphenylamine.

  In the emulsion polymerization aggregation method described above, the resin fine particle dispersion is a dispersion of emulsion particles (droplets) of the polyester resin, and includes an aqueous medium, a sulfonated polyester resin, and, if necessary, a colorant. It is formed by applying a shearing force to a solution obtained by mixing a mixed solution (polymer solution).

  In preparing the resin fine particle dispersion, a dispersant may be used for stabilizing the fine particles of the binder resin and increasing the viscosity of the aqueous medium.

  The crystalline polyester resin is preferably used in an amount of 2% to 20% with respect to the toner binder resin. When the crystalline polyester resin is less than 2%, the dispersibility in the toner particles tends to decrease, the colorant and the crystalline polyester tend to aggregate in the toner, and the fog (the toner charge decreases and the polarity decreases). Inverting, a phenomenon in which an image appears as a result of toner adhering to a portion without a latent image where an image does not appear as an original image may occur, and the colorant concentration may decrease. Further, when the crystalline polyester resin exceeds 20%, the crystalline polyester resin is likely to be deposited on the toner particle surface, the exuding property of the release agent is lowered, and offset may occur.

  The toner for developing an electrostatic charge image according to the embodiment preferably uses an amorphous polyester resin together with a crystalline polyester resin. When the crystalline polyester resin is not used, the release agent that is easily compatible with the crystalline polyester resin tends to be unevenly distributed near the surface of the toner particles, and offset is likely to occur. The amorphous polyester resin used in the embodiment may be used alone or in combination of two or more.

  The molecular weight of the amorphous polyester resin is not particularly limited, but when the high molecular component and the low molecular component are respectively synthesized, the weight average molecular weight Mw of the high molecular component is 30000 ≦ Mw ≦ 200000. It is preferable that 30000 ≦ Mw ≦ 100000, and 35000 ≦ Mw ≦ 80000 is particularly preferable. By controlling the molecular weight within this range, it can be more efficiently compatible with the crystalline polyester resin, and the separation of the crystalline polyester resin once compatible can be suppressed, thus inhibiting the exudation of the release agent. do not do. As a result, for example, an offset when fixing a halftone image after solid image formation can be suppressed.

  On the other hand, the low molecular weight component is preferably 8000 ≦ Mw ≦ 25000, more preferably 8000 ≦ Mw ≦ 22000, and particularly preferably 9000 ≦ Mw ≦ 20000. By controlling the molecular weight within this range, the inclusion property of the temporary polymer component in the fusion process is improved, the exposure of the crystalline polyester resin to the toner particle surface is suppressed, and the fogging under high temperature and high humidity is prevented. Can be suppressed.

  When the high molecular component and the low molecular component are mixed and used, the mixing ratio of both is not particularly limited as long as the composition ratio (molar ratio) to the outflow amount in GPC is in the above-described range. Is preferably in the range of polymer / low molecule = 10/90 to 70/30, more preferably 20/80 to 70/30, and particularly preferably 25/75 to 70/30.

  The polymer component preferably contains alkenyl succinic acid or its anhydride and trimellitic acid or its anhydride as constituent monomers. Alkenyl succinic acid or its anhydride can be more easily compatible with the crystalline polyester resin due to the presence of highly hydrophobic alkenyl groups. Examples of the alkenyl succinic acid component include n-dodecenyl succinic acid, isododecenyl succinic acid, n-octenyl succinic acid, and acid anhydrides, acid chlorides and lower alkyl esters having 1 to 3 carbon atoms. . By containing a trivalent or higher polyvalent carboxylic acid, the polymer chain can take a crosslinked structure. By taking a crosslinked structure, the effect of fixing the crystalline polyester resin once compatible and making it difficult to separate can be obtained, and the low-temperature fixability can be maintained.

  Examples of trivalent or higher polyvalent carboxylic acids include hemimellitic acid, trimellitic acid, trimesic acid, merophanic acid, planitic acid, pyromellitic acid, merit acid, 1,2,3,4-butanetetracarboxylic acid and These acid anhydrides, acid chlorides and lower alkyl esters having 1 to 3 carbon atoms can be mentioned.

  The method for producing the amorphous polyester resin is not particularly limited, as with the method for producing the crystalline polyester resin described above, and can be produced by the general polyester polymerization method as described above. As the carboxylic acid component used for the synthesis of the amorphous polyester resin, various dicarboxylic acids mentioned for the crystalline polyester resin can be similarly used. Also, as the alcohol component, various diols used for the synthesis of the crystalline polyester resin can be used. In addition to the aliphatic diols mentioned for the crystalline polyester resin, bisphenol A, bisphenol A ethylene oxide adduct, bisphenol A propylene oxide adduct, hydrogenated bisphenol A, bisphenol S, bisphenol S ethylene oxide adduct, bisphenol S propylene oxide adduct, and the like can be used. Furthermore, it is particularly preferable to use bisphenol A, bisphenol A ethylene oxide adduct, bisphenol A propylene oxide adduct or hydrogenated bisphenol A in order to improve the manufacturability, heat resistance and transparency of the toner. Further, both the carboxylic acid component and the alcohol component may contain a plurality of components. In particular, since bisphenol A is not particularly compatible with the alkyl type release agent, it is easy to control the position of the release agent in the toner particles. By controlling the bleeding of the mold, it is easy to suppress the offset.

  Next, the crosslinking component of the crystalline polyester resin used as necessary, the copolymerization component that can be used in the synthesis of the binder resin, and the like will be described.

  In synthesizing the polyester resin, other components can be copolymerized and a compound having a hydrophilic polar group can be used. Examples of the polyester resin include dicarboxylic acid compounds in which a sulfonyl group is directly substituted on an aromatic ring such as sulfonyl-terephthalic acid sodium salt and 3-sulfonylisophthalic acid sodium salt. When the binder resin is a vinyl resin, unsaturated aliphatic carboxylic acids such as (meth) acrylic acid and itaconic acid, glycerin mono (meth) acrylate, fatty acid-modified glycidyl (meth) acrylate, and zinc mono (meth) acrylate , Zinc di (meth) acrylate, 2-hydroxyethyl (meth) acrylate, polyethylene glycol (meth) acrylate, esters of (meth) acrylic acid and alcohols such as polypropylene glycol (meth) acrylate, ortho, meta, para Examples include styrene derivatives having a sulfonyl group at any of the positions, sulfonyl group-substituted aromatic vinyls such as sulfonyl group-containing vinyl naphthalene, and the like.

  In addition, a cross-linking agent can be added to the binder resin as necessary for the purpose of preventing uneven glossiness, uneven color development, hot offset, etc. during fixing in a high temperature region.

  Specific examples of the crosslinking agent include aromatic polyvinyl compounds such as divinylbenzene and divinylnaphthalene, divinyl phthalate, divinyl isophthalate, divinyl terephthalate, divinyl homophthalate, divinyl trimesate / trivinyl, divinyl naphthalenedicarboxylate, Polyvinyl esters of aromatic polyvalent carboxylic acids such as diphenyl biphenyl carboxylate, divinyl esters of nitrogen-containing aromatic compounds such as divinyl pyridine dicarboxylate, unsaturated heterocyclic compounds such as pyrrole and thiophene, vinyl pyromumate, Vinyl esters of unsaturated heterocyclic compounds such as vinyl furancarboxylate, vinyl pyrrole-2-carboxylate, vinyl thiophenecarboxylate, butanediol methacrylate, hexanediol acrylate, octanediol methacrylate (Meth) acrylic acid esters of linear polyhydric alcohols such as relate, decanediol acrylate and dodecanediol methacrylate, branching such as neopentylglycol dimethacrylate, 2-hydroxy, 1,3-diacryloxypropane, (Meth) acrylic acid esters of polyhydric alcohols, polyethylene glycol di (meth) acrylate, polypropylene polyethylene glycol di (meth) acrylates, divinyl succinate, divinyl fumarate, vinyl / divinyl maleate, divinyl diglycolate, itaconic acid Vinyl / divinyl, divinyl acetone dicarboxylate, divinyl glutarate, divinyl 3,3′-thiodipropionate, divinyl aconite / trivinyl, divinyl adipate, divinyl pimelate Divinyl suberic, azelaic, divinyl sebacate, divinyl dodecanedioate divinyl, the polyvinyl esters of polycarboxylic acids such as oxalic acid divinyl and the like.

  In addition to the above polymerizable monomer, a compound having a shorter chain alkyl group, alkenyl group, aromatic ring or the like may be used for the purpose of adjusting the melting temperature and molecular weight of the crystalline polyester resin. Specific examples include dicarboxylic acids, alkyl dicarboxylic acids such as succinic acid, malonic acid, and oxalic acid, and phthalic acid, isophthalic acid, terephthalic acid, homophthalic acid, 4,4′-bibenzoic acid, 2,6- Examples include aromatic dicarboxylic acids such as naphthalenedicarboxylic acid and 1,4-naphthalenedicarboxylic acid, and nitrogen-containing aromatic dicarboxylic acids such as dipicolinic acid, dinicotinic acid, quinolinic acid, and 2,3-pyrazinedicarboxylic acid. Short chain alkyl diols such as succinic acid, malonic acid, acetone dicarboxylic acid, diglycolic acid, etc. In the case of short chain alkyl vinyl polymerizable monomers, methyl (meth) acrylate, (meth) Short chain alkyls such as ethyl acrylate, propyl (meth) acrylate, butyl (meth) acrylate, etc. Rylic acid esters, vinyl nitriles such as acrylonitrile and methacrylonitrile, vinyl ethers such as vinyl methyl ether and vinyl isobutyl ether, vinyl methyl ketone, vinyl ethyl ketone, vinyl isopropenyl ketones, ethylene, propylene, butadiene, isoprene, etc. Olefins and the like. These polymerizable monomers may be used individually by 1 type, and may use 2 or more types together.

  As the resin used for the raw material of the electrostatic image developing toner according to the embodiment, a compound having a hydrophilic polar group can be used as long as it is a copolymerizable polyester resin. Specific examples include dicarboxylic acid compounds in which a sulfonyl group is directly substituted on an aromatic ring, such as sulfonyl-terephthalic acid sodium salt and 3-sulfonylisophthalic acid sodium salt. When the resin is a vinyl resin, (meth) Unsaturated aliphatic carboxylic acids such as acrylic acid and itaconic acid, glycerin mono (meth) acrylate, fatty acid-modified glycidyl (meth) acrylate, zinc mono (meth) acrylate, zinc di (meth) acrylate, 2-hydroxyethyl (meth) acrylate, Esters of (meth) acrylic acid and alcohols such as polyethylene glycol (meth) acrylate and polypropylene glycol (meth) acrylate, derivatives of styrene having a sulfonyl group at any of the ortho, meta, and para positions, containing sulfonyl groups Vinylna Sulfonyl group-substituted aromatic vinyl such as array type can be mentioned.

  Examples of the colorant used in the electrostatic image developing toner according to the embodiment include the following pigments.

  Examples of yellow pigments include yellow lead, zinc yellow, yellow iron oxide, cadmium yellow, chrome yellow, hansa yellow, hansa yellow 10G, benzidine yellow G, benzidine yellow GR, selenium yellow, quinoline yellow, and permanent yellow NCG. Is mentioned. Specifically, C.I. I. Pigment yellow 74, C.I. I. Pigment yellow 180, C.I. I. Pigment Yellow 93 and the like, and C.I. I. Pigment Yellow 74 is preferable.

  Examples of the black pigment include carbon black, copper oxide, manganese dioxide, aniline black, activated carbon, nonmagnetic ferrite, and magnetite.

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

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

  Blue pigments include bitumen, cobalt blue, alkali blue rake, Victoria blue rake, fast sky blue, induslen blue BC, aniline blue, ultramarine blue, calco oil blue, methylene blue chloride, phthalocyanine blue, phthalocyanine green, malachite green oxare. Rate and so on.

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

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

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

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

  Moreover, dye can also be used as a coloring agent as needed. Examples of the dye include various dyes such as basic, acidic, dispersed, and direct dyes, such as nigrosine, methylene blue, rose bengal, quinoline yellow, and ultramarine blue. Moreover, these can be used individually or in mixture, and also in the state of a solid solution.

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

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

  The colorant is selected from the viewpoints of hue angle, saturation, brightness, weather resistance, and dispersibility in the toner. The added amount of the colorant is preferably 1 to 15 parts by mass with respect to 100 parts by mass of the binder resin. Further, when a magnetic material is used for the black colorant, it is preferable to add 30 to 100 parts by mass with respect to 100 parts by mass of the binder resin, unlike other colorants.

  The proportion of the colorant contained in the electrostatic image developing toner according to the embodiment is preferably 4 to 15% by mass. When the colorant contained in the toner is less than 4% by mass, the colorant concentration in the fixed image becomes thin, and the color developability may deteriorate. When the colorant contained in the toner exceeds 15%, the colorant may be easily exposed on the surface of the toner particles.

  Specific examples of the release agent that can be used in the electrostatic image developing toner according to the embodiment include low molecular weight polyolefins such as polyethylene, polypropylene, and polybutene, silicones having a softening point, oleic acid amide, erucic acid amide, and ricinol. Fatty acid amides such as acid amide and stearic acid amide, carnauba wax, rice wax, candelilla wax, plant waxes such as tree wax and jojoba oil, animal waxes such as beeswax, montan wax, ozokerite, ceresin, Mineral and petroleum waxes such as paraffin wax, microcrystalline wax, Fischer-Tropsch wax, ester waxes of higher fatty acids and higher alcohols such as stearyl stearate and behenyl behenate, butyl stearate, oleic acid pro , Monostearic glycerides, distearic glycerides, ester waxes of higher fatty acids such as pentaerythritol tetrabehenate and unit or polyhydric lower alcohols, diethylene glycol monostearate, dipropylene glycol distearate, distearic diglyceride, Examples include ester waxes composed of higher fatty acids such as tetrastearic acid triglyceride and polyhydric alcohol multimers, sorbitan higher fatty acid ester waxes such as sorbitan monostearate, and cholesterol higher fatty acid ester waxes such as cholesteryl stearate.

  The release agent is preferably an alkyl release agent. The alkyl release agent has a lower affinity for the polyester resin than the release agent having a polar group, and the position controllability of the release agent is high. That is, offset can be suppressed by improving the controllability of the release agent to exude. Examples of such alkyl release agents include hydrocarbon waxes such as polyethylene wax, Fischer-Tropsch wax, and microcrystalline wax.

  The above-mentioned various hydrocarbon waxes more preferably have an endothermic peak maximum value determined by differential thermal analysis in the range of 70 ° C to 95 ° C. When the maximum value of the endothermic peak is less than 70 ° C., the toner tends to block between high temperatures and high humidity. Moreover, when it exceeds 95 degreeC, a mold release agent may become difficult to fuse | melt. It is more preferable that the ratio of the component at 70 ° C. or less obtained from the endothermic peak area to the total endothermic area is 5% or more and 15% or less. When the ratio is less than 5%, the release agent does not fuse with the amorphous polyester resin in the fusion process at the time of toner production, and the rejection (release agent is released from the binder resin and released outside the toner particles. Phenomenon), the releasability may deteriorate during fixing. On the other hand, if it exceeds 15%, the toner may be easily blocked. Furthermore, it is more preferable that the amount of the release agent in the toner determined from the maximum value of the endothermic peak is 6% by mass or more and 15% by mass or less. When the amount of the release agent in the toner is less than 6% by mass, the amount of the release agent may not be sufficient. When the content exceeds 15% by mass, the release agent may not be taken into the toner particles by the emulsion polymerization aggregation method. As a result, the release agent is fused to the toner surface, and the toner may be easily blocked under high temperature and high humidity.

  The release agent has a viscosity of 1.50 mPa · S or more and 5.0 mPa · S or less (more preferably 2.30 mPa · S or less), which is obtained by an E-type viscometer equipped with a cone plate having a cone angle of 1.34 degrees at 140 ° C. 5 mPa · S or more and 4.0 mPa · S or less) is more preferable. When the viscosity is less than 1.5 mPa · S, the viscosity of the release agent is low in the toner combination temporary (fusion process), and the release agent may be unevenly distributed in the toner particles. There is a case. On the other hand, when it exceeds 5.0 mPa · S, the release agent viscosity is high, and the release of the release agent may be insufficient during fixing.

  In the production of the electrostatic image developing toner according to the embodiment, for example, a surfactant is used for the purpose of stabilizing the dispersion of the resin fine particle dispersion, the colorant dispersion, and the release agent dispersion in the emulsion polymerization aggregation method. it can.

  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, etc. And 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.

  In general, anionic surfactants have a strong dispersion power and excellent dispersibility of binder resin fine particles, colorants, and release agents. Therefore, surfactants for dispersing these are anionic interfaces. It is preferred to use an activator.

  The nonionic surfactant is preferably used in combination with the anionic surfactant or the cationic surfactant. These surfactants may be used alone or in combination of two or more.

  The content of the surfactant in each dispersion may be a level that does not hinder the effects of the present invention, and is generally a small amount, specifically in the range of about 0.01 to 10% by mass. Yes, more preferably in the range of 0.05 to 5% by mass, and still more preferably in the range of about 0.1 to 2% by mass. When the content is less than 0.01% by mass, each dispersion such as a resin particle dispersion, a colorant dispersion, and a release agent dispersion becomes unstable, so that aggregation occurs, and each particle during aggregation Because of the different stability between them, the release of specific particles may occur. On the other hand, if it exceeds 10% by mass, the particle size distribution of the particles may become wide, and it may be difficult to control the particle size. In general, a suspension polymerization toner dispersion having a large particle size is stable even if the amount of the surfactant used is small.

  Also, a room temperature solid aqueous polymer or the like can be used as a dispersion stabilizer. Specifically, cellulose compounds such as carboxymethyl cellulose and hydroxypropyl cellulose, polyvinyl alcohol, gelatin, starch, gum arabic and the like can be used.

  When the emulsion polymerization aggregation method is used in the production of the electrostatic charge image developing toner according to the embodiment, the particles can be prepared by causing aggregation by pH change in the aggregation step. At the same time, an aggregating agent may be added to stably and rapidly aggregate the particles, or to obtain aggregated particles having a narrower particle size distribution.

  As the flocculant, a compound having a monovalent or higher charge is preferable. Specific examples of the compound include water-soluble surfactants such as the above-mentioned ionic surfactants and nonionic surfactants, hydrochloric acid, sulfuric acid, Acids such as nitric acid, acetic acid, oxalic acid, magnesium chloride, sodium chloride, aluminum sulfate, calcium sulfate, ammonium sulfate, aluminum nitrate, silver nitrate, copper sulfate, sodium carbonate and other inorganic acid metal salts, sodium acetate, potassium formate, oxalic acid Aliphatic acids such as sodium, sodium phthalate and potassium salicylate, metal salts of aromatic acids, metal salts of phenols such as sodium phenolate, metal salts of amino acids, triethanolamine hydrochloride and aniline hydrochloride And inorganic acid salts of aromatic amines.

  Considering the stability of the agglomerated particles, the stability of the aggregating agent with respect to heat and passage of time, and the ease of removal during washing, the metal salt of an inorganic acid is used as the aggregating agent in terms of performance and ease of use. preferable. Specific examples include metal salts of inorganic acids such as magnesium chloride, sodium chloride, aluminum sulfate, calcium sulfate, ammonium sulfate, aluminum nitrate, silver nitrate, copper sulfate, and sodium carbonate. Further, polyaluminum chloride, polyaluminum hydroxide and the like can also be suitably used.

  The amount of these flocculants to be added varies depending on the valence of the charge, but they are all small, in the case of monovalent, about 3% by mass or less, in the case of divalent, about 1% by mass or less, in the case of trivalent Is about 0.5 mass% or less. Since the amount of the flocculant is preferably small, it is preferable to use a compound having a large valence.

  In addition, when the electrostatic image developing toner according to the embodiment is used as magnetic particles, magnetic powder may be included. As such magnetic powder, a substance magnetized in a magnetic field is used, and examples thereof include ferromagnetic powder such as iron, cobalt, and nickel, or compounds such as ferrite and magnetite. In particular, in this embodiment, it is necessary to pay attention to the water layer transferability of the magnetic material in order to obtain the toner in the water layer, and it is preferable to perform surface modification, for example, hydrophobization treatment.

The toner for developing an electrostatic charge image in this embodiment preferably has a toner shape factor SF1 of 125 ≦ SF1 ≦ 140 (however, toner shape factor SF1 = (ML ² / A) × (π / 4) × 100). Yes, ML is the maximum toner length (μm), and A is the toner projected area (μm ² ). When the shape factor of the toner is between 125 and 140, a stable transfer surface is obtained due to stable transfer properties, and a good image with little offset is obtained. When the shape factor is less than 125, transferability is extremely high under low temperature and low humidity, making it difficult to use, and toner may not be uniformly applied on a fixed image, and offset may occur. When the shape factor exceeds 140, the transferability is deteriorated, the desired toner amount is not placed on the fixed image, the amount of toner applied on the fixed image is uneven, and an offset may occur in a high density portion. .

  The electrostatic image developing toner according to the exemplary embodiment may have at least one or more kinds of metal oxide particles on the surface thereof. Specific examples of the metal oxide particles include silica, titania, zinc oxide, strontium oxide, aluminum oxide, calcium oxide, magnesium oxide, cerium oxide, or a composite oxide thereof. Of these, silica and titania are preferably used from the viewpoints of particle size, particle size distribution, and manufacturability.

  The volume average particle diameter of the metal oxide particles is preferably in the range of 1 nm to 40 nm in terms of primary particle diameter, and more preferably in the range of 5 nm to 20 nm.

  These metal oxide particles may be used alone or in combination of two or more. The amount of addition to these toners is not particularly limited, but is preferably used in the range of 0.1% by mass to 10% by mass. More preferably, it is the range of about 0.2 mass% or more and 8 mass% or less.

  When the addition amount is less than 0.1% by mass, it is difficult to obtain the effect of the added metal oxide or the like (toner fluidity), and when it exceeds 10% by mass, the image density may not be obtained. .

  These metal oxide particles are preferably subjected to surface modification such as hydrophobization because they are easily mixed in the release agent layer at the time of fixing, and the release agent can inhibit fusion to the fixing roll. Conventionally known methods can be used as means for surface modification. Specific examples include coupling treatments such as silane, titanate, and aluminate.

  There are no particular restrictions on the coupling agent used for the coupling treatment, but for example, silane coupling agents such as methyltrimethoxysilane, phenyltrimethoxysilane, methylphenyldimethoxysilane, diphenyldimethoxysilane, vinyltrimethoxysilane, and titanate cups. A ring agent, an aluminate coupling agent, etc. are mentioned as a suitable example.

  In this embodiment, depending on the purpose, in addition to the binder resin, the colorant, and the release agent, other components (particles) such as an internal additive, a charge control agent, an organic granule, a lubricant, and an abrasive. ) Can be added.

  Examples of internal additives include metals such as ferrite, magnetite, reduced iron, cobalt, manganese, and nickel, alloys, and magnetic materials such as compounds containing these metals, and inhibit charging properties as toner characteristics. A small amount can be used.

  The charge control agent is not particularly limited, but when a color toner is used, a colorless or light-colored agent can be preferably used. Examples thereof include quaternary ammonium salt compounds, nigrosine compounds, dyes composed of complexes of aluminum, iron, chromium, and triphenylmethane pigments.

  Examples of the organic particles include all particles usually used as external additives on the toner surface, such as vinyl resins, polyester resins, and silicone resins. These inorganic particles and organic particles can be used as fluidity aids, cleaning aids, and the like.

  Examples of the lubricant include fatty acid amides such as ethylene bis stearic acid amide and oleic acid amide, and fatty acid metal salts such as zinc stearate and calcium stearate.

  As an abrasive | polishing agent, the above-mentioned silica, alumina, cerium oxide etc. are mentioned, for example.

  When the binder resin, the colorant, and the release agent are mixed, the content of the colorant may be 50% by mass or less and is in a range of about 2% by mass to 40% by mass. Is preferred.

  In addition, the content of the other components may be a level that does not hinder the purpose of the present embodiment, and is generally extremely small. Specifically, the content is 0.01% by mass or more and 5% by mass or less. It is a range, Preferably it is the range of 0.5 mass% or more and 2 mass% or less.

  Examples of the dispersion medium in the resin fine particle dispersion, the colorant dispersion, the release agent dispersion, and other components in the present embodiment include an aqueous medium. Examples of the aqueous medium include water such as distilled water and ion exchange water, alcohol, and the like. These may be used individually by 1 type and may use 2 or more types together.

  The particle size distribution index of the electrostatic image developing toner according to the embodiment is such that the volume average particle size distribution index GSDv is 1.30 or less, and the volume average particle size distribution index GSDv and the number average particle size distribution index GSDp are The ratio (GSDp / GSDv) is preferably 0.95 or more. When the volume distribution index GSDv exceeds 1.30, the unevenness of the fixed image increases, and an offset may occur. Further, when the ratio of the volume average particle size distribution index GSDv to the number average particle size distribution index is less than 0.95, it means that the amount of the small particle size toner increases, and unevenness in the applied toner amount tends to occur. May occur.

The specific surface area of the toner for developing an electrostatic charge image according to the embodiment is not particularly limited, and any toner can be used as long as it can be used for a normal toner. Specifically, when the BET method is used, a range of 0.5 m ² / g to 10 m ² / g is preferable, more preferably a range of 1.0 m ² / g to 7 m ² / g, and more preferably. It is the range of about 1.2 m ² / g or more and 5 m ² / g or less. Further, a range of about 1.2 m ² / g or more and 3 m ² / g or less is particularly preferable.

<Electrostatic latent image developer>
The electrostatic latent image developer according to the embodiment is not particularly limited except that it contains the electrostatic charge image developing toner according to the above-described embodiment, and can have an appropriate component composition according to the purpose. The electrostatic latent image developer in the present embodiment becomes a one-component electrostatic latent image developer when an electrostatic charge image developing toner is used alone, and a two-component electrostatic latent image developer when used in combination with a carrier. It becomes an image developer.

  The carrier is not particularly limited, and a known carrier can be used. Examples thereof include resin-coated carriers described in JP-A Nos. 62-39879 and 56-11461. .

  Specific examples of the carrier include the following resin-coated carriers. Examples of the core particle of the carrier include normal iron powder, ferrite, and magnetite molding, and the volume average particle diameter is in the range of about 30 μm to 200 μm.

  Examples of the coating resin for the resin-coated carrier include styrenes such as styrene, parachlorostyrene, and α-methylstyrene, methyl acrylate, ethyl acrylate, n-propyl acrylate, lauryl acrylate, and acrylic acid 2 -Α-methylene fatty acid monocarboxylic acids such as ethylhexyl, methyl methacrylate, n-propyl methacrylate, lauryl methacrylate, 2-ethylhexyl methacrylate, nitrogen-containing acrylics such as dimethylaminoethyl methacrylate, acrylonitrile, methacrylonitrile, etc. Vinyl nitriles, vinyl pyridines such as 2-vinyl pyridine and 4-vinyl pyridine, vinyl ethers such as vinyl methyl ether and vinyl isobutyl ether, vinyl methyl ketone, vinyl ethyl ketone, vinyl isopropenyl Homopolymers such as vinyl ketones such as ketones, olefins such as ethylene and propylene, vinylidene fluoride, tetrafluoroethylene, hexafluoroethylene and other vinyl-based fluorine-containing monomers, or copolymers comprising two or more types of monomers, Furthermore, silicone resins including methylsilicone, methylphenylsilicone, etc., polyesters containing bisphenol, glycol, etc., epoxy resins, polyurethane resins, polyamide resins, cellulose resins, polyether resins, polycarbonate resins and the like can be mentioned. These resins may be used alone or in combination of two or more. The coating amount of the coating resin is preferably in the range of about 0.1 to 10 parts by weight and more preferably in the range of 0.5 to 3.0 parts by weight with respect to 100 parts by weight of the core particles. preferable.

  For manufacturing the carrier, a heating kneader, a heating Henschel mixer, a UM mixer, or the like can be used. Depending on the amount of the coating resin, a heating fluidized rolling bed, a heating kiln, or the like can be used. .

  Further, the mixing ratio of the electrostatic image developing toner and the carrier in the electrostatic image developer according to the embodiment is not particularly limited and can be appropriately selected according to the purpose.

<Image forming apparatus>
An image forming apparatus according to an embodiment forms an image carrier, a latent image forming unit that forms an electrostatic latent image on the surface of the image carrier, and develops the electrostatic latent image using a developer to form a toner image. Developing means, a transfer means for transferring the developed toner image to the transfer body, and a fixing means for fixing the toner image transferred to the surface of the transfer body, and the electrostatic latent image developer as a developer Is used. The image forming apparatus according to the embodiment may include means other than the above means, for example, a charging means for charging the image holding member, a cleaning means for removing toner remaining on the surface of the image holding member.

  An example of the image forming apparatus according to the embodiment is schematically shown in FIG. The image forming apparatus 1 includes a charging unit 10, an exposure unit 12, an electrophotographic photosensitive member 14 that is an image holding member, a developing unit 16, a transfer unit 18, a cleaning unit 20, and a fixing unit 22.

  In the image forming apparatus 1, the charging unit 10 that is a charging unit that charges the surface of the electrophotographic photosensitive member 14 and the charged electrophotographic photosensitive member 14 are exposed around the electrophotographic photosensitive member 14 according to image information. The exposure unit 12 is a latent image forming unit that forms an electrostatic latent image, the developing unit 16 is a developing unit that develops the electrostatic latent image with toner to form a toner image, and the surface of the electrophotographic photoreceptor 14. A transfer unit 18 that is a transfer unit that transfers the toner image formed on the surface of the transfer target 24, and a cleaning unit 20 that is a cleaning unit that removes toner remaining on the surface of the electrophotographic photosensitive member 14 after transfer. Are arranged in this order. A fixing unit 22 that is a fixing unit that fixes the toner image transferred to the transfer target 24 is arranged on the left side of the transfer unit 18.

  An operation of the image forming apparatus 1 according to the present embodiment will be described. First, the surface of the electrophotographic photosensitive member 14 is uniformly charged by the charging unit 10 (charging process). Next, light is applied to the surface of the electrophotographic photosensitive member 14 by the exposure unit 12, and the charged charges in the irradiated portion are removed, and an electrostatic charge image (electrostatic latent image) is formed according to the image information. (Latent image forming step). Thereafter, the electrostatic charge image is developed by the developing unit 16, and a toner image is formed on the surface of the electrophotographic photosensitive member 14 (developing step). For example, in the case of a digital electrophotographic copying machine using an organic photoconductor as the electrophotographic photoconductor 14 and using a laser beam as the exposure unit 12, the surface of the electrophotographic photoconductor 14 is negatively charged by the charging unit 10. Then, a digital latent image is formed in a dot shape by the laser beam light, and toner is applied to the portion irradiated with the laser beam light by the developing unit 16 to be visualized. In this case, a negative bias is applied to the developing unit 16. Next, a transfer member 24 such as paper is superposed on the toner image at the transfer unit 18, and a charge having a polarity opposite to that of the toner is applied to the transfer member 24 from the back side of the transfer member 24. Is transferred to the transfer target 24 (transfer process). The transferred toner image is heated and pressed by a fixing member in the fixing unit 22 and is fused and fixed to the transfer target 24 (fixing step). On the other hand, toner remaining on the surface of the electrophotographic photoreceptor 14 without being transferred is removed by the cleaning unit 20 (cleaning step). One cycle is completed in a series of processes from charging to cleaning. In FIG. 1, the toner image is directly transferred to the transfer target 24 such as a sheet by the transfer unit 18, but may be transferred via a transfer member such as an intermediate transfer member.

  Hereinafter, the charging unit, the image carrier, the exposure unit, the developing unit, the transfer unit, the cleaning unit, and the fixing unit in the image forming apparatus 1 of FIG. 1 will be described.

(Charging means)
For example, a charging device such as a corotron as shown in FIG. 1 is used as the charging unit 10 as a charging unit, but a conductive or semiconductive charging roll may be used. A contact charger using a conductive or semiconductive charging roll may apply a direct current to the electrophotographic photosensitive member 14 or may superimpose an alternating current. For example, the charging unit 10 charges the surface of the electrophotographic photosensitive member 14 by generating a discharge in a minute space near the contact portion with the electrophotographic photosensitive member 14. Normally, it is charged to -300 to -1000V. The conductive or semiconductive charging roll may have a single layer structure or a multiple structure. Further, a mechanism for cleaning the surface of the charging roll may be provided.

(Image carrier)
The image carrier has a function of forming at least a latent image (electrostatic charge image). As the image carrier, an electrophotographic photosensitive member is preferably exemplified. The electrophotographic photoreceptor 14 has a coating film containing an organic photoreceptor or the like on the outer peripheral surface of a cylindrical conductive substrate. The coating film is a substrate in which a subbing layer and a photosensitive layer including a charge generating layer containing a charge generating material and a charge transporting layer containing a charge transporting material are formed in this order on the substrate as necessary. is there. The order of stacking the charge generation layer and the charge transport layer may be reversed. These are laminated photoconductors in which a charge generation material and a charge transport material are contained in separate layers (charge generation layer, charge transport layer), but both the charge generation material and the charge transport material are the same. A single-layer type photoreceptor included in the above layer may be used, and a laminated photoreceptor is preferable. Further, an intermediate layer may be provided between the undercoat layer and the photosensitive layer. In addition, other types of photosensitive layers such as an amorphous silicon photosensitive film may be used in addition to the organic photoreceptor.

(Exposure means)
There are no particular limitations on the exposure unit 12 that is an exposure means. For example, an optical device that can expose a light source such as semiconductor laser light, LED light, or liquid crystal shutter light on the surface of the image carrier in a desired image-like manner. Can be mentioned.

(Development means)
The developing unit 16 serving as a developing unit has a function of developing a latent image formed on the image carrier with a developer containing toner to form a toner image. Such a developing device is not particularly limited as long as it has the above-mentioned function, and can be appropriately selected according to the purpose. For example, toner for developing an electrostatic image is used using a brush, a roller, or the like. A known developing device having a function of adhering to the electrophotographic photosensitive member 14 may be used. For the electrophotographic photosensitive member 14, a DC voltage is usually used, but an AC voltage may be superimposed and used.

(Transfer means)
As the transfer unit 18 serving as a transfer unit, for example, a charge having a polarity opposite to that of the toner is applied to the transfer target 24 from the back side of the transfer target 24 as shown in FIG. A transfer roll and a transfer roll pressing device using a conductive roll or a semiconductive roll that transfers directly to the surface of the transferred body 24 via the transferred body 24 can be used. . A direct current may be applied to the transfer roll as a transfer current applied to the image carrier, or an alternating current may be applied in a superimposed manner. The transfer roll can be arbitrarily set depending on the width of the image area to be charged, the shape of the transfer charger, the opening width, the process speed (circumferential speed), and the like. Further, a single layer foam roll or the like is suitably used as a transfer roll for cost reduction. As a transfer method, a method of transferring directly to the transfer target 24 such as paper or a method of transferring to the transfer target 24 via an intermediate transfer member may be used.

  A known intermediate transfer member can be used as the intermediate transfer member. Materials used for the intermediate transfer member include polycarbonate resin (PC), polyvinylidene fluoride (PVDF), polyalkylene phthalate, PC / polyalkylene terephthalate (PAT) blend material, ethylene tetrafluoroethylene copolymer (ETFE) / PC, ETFE / PAT, PC / PAT blend materials, and the like can be mentioned. From the viewpoint of mechanical strength, an intermediate transfer belt using a thermosetting polyimide resin is preferable.

(Cleaning means)
The cleaning unit 20 serving as a cleaning unit may be appropriately selected such as one that employs a blade cleaning method, a brush cleaning method, or a roll cleaning method as long as the toner remaining on the image carrier is cleaned. Among these, it is preferable to use a cleaning blade. Examples of the material for the cleaning blade include urethane rubber, neoprene rubber, and silicone rubber. Among them, it is particularly preferable to use a polyurethane elastic body because of its excellent wear resistance. However, there may be a mode in which the cleaning unit 20 is not used when toner having high transfer efficiency is used.

(Fixing means)
The fixing unit 22 that is a fixing unit (image fixing device) fixes the toner image transferred to the transfer medium 24 by heating, pressing, or heating and pressing, and includes a fixing member.

(Transfer)
Examples of the transfer target (paper) 24 to which the toner image is transferred include plain paper, OHP sheet, and the like used in electrophotographic copying machines, printers, and the like. In order to further improve the smoothness of the image surface after fixing, it is preferable that the surface of the transfer target is as smooth as possible. For example, coated paper in which the surface of plain paper is coated with resin, art paper for printing, etc. Can be preferably used.

  Hereinafter, although an example and a comparative example are given and the present invention is explained more concretely, the present invention is not limited to the following examples.

<Each measurement method>
(Toner shape)
The shape factor SF1 was measured as follows using a Luzex image analyzer (manufactured by Nireco Corporation, FT). First, an optical microscopic image of toner spread on a slide glass is taken into a Luzex image analyzer through a video camera, and the maximum length (ML) and projection area (A) of 50 toners are measured. ML2 / A) × (π / 4) × 100 was calculated, and an average value thereof was obtained as the shape factor SF1.

(Toner particle size)
The volume average particle size D50v, the volume average particle size distribution index GSDv, and the number average particle size distribution index GSDp were obtained by measuring with an aperture diameter of 100 μm using a Coulter Multisizer II type (manufactured by Beckman-Coulter). At this time, the measurement was performed after the toner was dispersed in an electrolyte aqueous solution (Isoton aqueous solution) and dispersed by ultrasonic waves for 30 seconds or more. For the particle size range (channel) divided based on the particle size distribution of the toner measured with Coulter Multisizer II, draw the cumulative distribution from the smaller diameter side to the particle size range (channel), and the particle size that will be 16% cumulative Volume D16v, number D16p, particle size that is 50% cumulative is defined as volume D50v, number D50p, and particle size that is 84% cumulative is defined as volume D84v and number D84p. In this case, D50v represents a volume average particle size, the volume average particle size distribution index (GSDv) is determined as (D84v / D16v) 1/2, and the number average particle size distribution index (GSDp) is determined as (D84p / D16p) 1/2. It was.

(High-performance liquid chromatograph (HPLC) measurement)
Components such as oxyacids and amino acids in the toner particles are extracted by high performance liquid chromatography (HPLC). The measurement conditions are as follows.

Analyzing device: LC-08 manufactured by Nippon Analytical Industries
Column: JA Engineering GEL-2H (20Φmm × 600mm × 2)
Detector: differential refractometer, ultraviolet absorption detector (254 nm)
Eluent: Chloroform Flow rate 4 mL / min Measurement sample: 1 g of toner was dissolved in 10 mL of chloroform, and the solution was extracted by filtration or the like.
Retention time: In the case of L-aspartic acid, the peak position was 5 minutes.

(NMR (nuclear magnetic resonance) measurement)
Components such as oxyacids and amino acids in various raw materials and toner particles are identified and quantified by 1H-NMR. The 1H-NMR apparatus uses JNM-AL400 (manufactured by JEOL Ltd.), and the measurement conditions are a 5 mm glass tube, a 3 mass% deuterated chloroform solution, and a measurement temperature of 25 ° C. As the measurement sample, a sample in which the carrier is detached from the developer, dissolved from the toner with an organic solvent, and the binder resin is separated by filtration or the like can be used.

<Manufacture of toner>
The toner of this embodiment can be obtained by the following method. That is, the following resin fine particle dispersion, colorant particle dispersion, release agent dispersion, and inorganic particle dispersion were prepared. Next, while a predetermined amount of these were mixed and stirred, a polymer of an inorganic metal salt was added thereto and ionically neutralized to form aggregates of the particles. Before reaching the desired toner particle size, the resin fine particle dispersion was additionally added to obtain a toner particle size. Next, the pH of the system was adjusted from a weakly acidic to a neutral range with an inorganic hydroxide, and then heated above the glass transition temperature of the resin particles to unite and fuse them. After completion of the reaction, a desired toner was obtained through sufficient washing, solid-liquid separation, and drying processes.

(Synthesis of crystalline polyester resin)
In a 5 L (liter) flask, 1982 parts of sebacic acid, 1490 parts of ethylene glycol, 59.2 parts of sodium dimethyl 5-sulfonate and 0.8 parts of dibutyltin oxide were reacted at 180 ° C. for 5 hours in a nitrogen atmosphere. Subsequently, a condensation reaction was performed at 220 ° C. under reduced pressure. The polymer was sampled on the way, and when the molecular weight reached Mw (weight average molecular weight) = 20000 and Mn (number average molecular weight) = 8500 by gel permeation chromatography (GPC), the reaction was stopped to obtain a crystalline polyester resin. It was. The dissolution temperature (DSC peak temperature) was 71 ° C. The measurement result of the content of sodium dimethyl 5-phthalate by NMR was 1 mol% (vs. all components).

(Crystalline polyester resin fine particle dispersion)
Prepare 160 parts of crystalline polyester resin, 233 parts of ethyl acetate, and 0.1 part of sodium hydroxide aqueous solution (0.3N), put them in a 500 ml separable flask and heat at 75 ° C. A resin mixed solution was prepared by stirring with Shinto Kagaku Co., Ltd. While further stirring this resin mixture, 373 parts of ion-exchanged water are gradually added, phase inversion emulsification is performed, the temperature is lowered to 40 ° C. at a temperature lowering rate of 10 ° C./min, and the solvent is removed to remove crystalline polyester resin fine particles. A dispersion (solid content concentration: 30%) was obtained.

(Synthesis of non-crystalline polyester resin)
In a heat-dried two-necked flask, 200 parts of dimethyl terephthalate, 85 parts of 1,3-butanediol, and 0.3 part of dibutyltin oxide as a catalyst were placed, and then the air in the container was removed by a decompression operation. The atmosphere was inert with nitrogen gas, and stirring was performed at 180 rpm with mechanical stirring for 5 hours. Thereafter, the temperature was gradually raised to 230 ° C. under reduced pressure, and the mixture was stirred for 2 hours. When it became viscous, it was air-cooled, the reaction was stopped, and an amorphous polyester resin (a component derived from an aromatic dicarboxylic acid) 240 parts of an amorphous polyester resin containing an acid-derived constituent component with a content of 100 constituent mol% and an alcohol-derived constituent component with an aliphatic diol-derived constituent content of 100 constituent mol%) did.

  As a result of molecular weight measurement (polystyrene conversion) by GPC, the resulting amorphous polyester resin (1) had a weight average molecular weight (Mw) of 9,500 and a number average molecular weight (Mn) of 4,200. Further, when the DSC spectrum of the non-crystalline polyester resin (1) was measured using the above-mentioned differential scanning calorimeter (DSC), no clear peak was shown, and a stepwise endothermic change was observed. The glass transition temperature at the midpoint of the stepwise endothermic change was 55 ° C. The resin acid value was 18 mgKOH / g.

(Non-crystalline polyester resin fine particle dispersion)
Prepare 160 parts of an amorphous polyester resin (1), 233 parts of ethyl acetate, and 0.1 part of an aqueous sodium hydroxide solution (0.3N), put them in a 500 ml separable flask, and heat at 70 ° C. The mixture was stirred with a three-one motor (Shinto Kagaku Co., Ltd.) to prepare a resin mixture. While further stirring this resin mixture, 373 parts of ion exchange water is gradually added, phase inversion emulsification is performed, and the temperature is lowered to 40 ° C. at a temperature lowering rate of 1 ° C./min. A dispersion (solid content concentration: 30%) was obtained.

(Preparation of styrene acrylic resin fine particle dispersion)
(Oil layer)
Styrene (manufactured by Wako Pure Chemical Industries) 30 parts by weight n-butyl acrylate (manufactured by Wako Pure Chemical Industries) 10 parts by weight β-carboethyl acrylate (manufactured by Rhodia Nikka) 1.5 parts by weight Acrylic acid 0.3 part by weight Dodecanethiol (Japanese) 0.2 parts by weight

(Water layer 1)
Ion-exchanged water 17.0 parts by weight Anionic surfactant (manufactured by Rhodia) 0.4 parts by weight

(Water layer 2)
Ion-exchanged water 40 parts by weight Anionic surfactant (manufactured by Rhodia) 0.08 parts by weight Potassium persulfate (manufactured by Wako Pure Chemical Industries) 0.30 parts by weight Ammonium persulfate (manufactured by Wako Pure Chemical Industries) 0.10 parts by weight

  The oil layer component and the water layer 1 component were placed in a flask and mixed with stirring to obtain a monomer emulsified dispersion. The components of the aqueous layer 2 were put into a reaction vessel, and the inside of the vessel was sufficiently replaced with nitrogen and stirred, and then heated in an oil bath until the temperature in the reaction system reached 75 ° C. The monomer emulsion dispersion was gradually dropped into the reaction vessel over 3 hours to carry out emulsion polymerization. After completion of the dropwise addition, the polymerization was further continued at 75 ° C., and the polymerization was terminated after 3 hours.

  The obtained resin particles were 200 nm when the number average particle diameter D50p of the resin particles was measured with a laser diffraction particle size distribution analyzer (LA-700, manufactured by Horiba, Ltd.), and a differential scanning calorimeter (Shimadzu Corporation) was obtained. When the glass transition temperature of the resin was measured at a heating rate of 10 ° C./min using a DSC-50 manufactured by Seisakusho, it was 51.5 ° C., and the weight average molecular weight Mw (polystyrene conversion) was measured using GPC. 30000. As a result, a styrene acrylic resin fine particle dispersion having a number average particle diameter D50p of 200 nm, a solid content of 42% by weight, a glass transition temperature of 51.5 ° C., and an Mw of 30,000 was obtained.

(Preparation of colorant dispersion 1)
Cyan pigment (CI Pigment Blue 15: 3, manufactured by Dainichi Seika) 45 parts by weight Ionic surfactant (Neogen RK, manufactured by Daiichi Kogyo Seiyaku) 5 parts by weight Ion-exchanged water 200 parts by weight

  The above were mixed and dissolved, and dispersed for 10 minutes with a homogenizer (IKA Ultra Tarrax) to obtain a colorant dispersion 1 having a volume average particle size of 170 nm.

(Preparation of amino acid dispersion)
Preparation of amino acid 1 dispersion 20 parts by weight of aspartic acid 60 parts by weight of ion exchange water

  The above was stirred and mixed to obtain an amino acid 1 dispersion having a solid content of 10.2% by weight.

Preparation of Amino Acid 2 Dispersion Glycine 20 parts by weight Ion-exchanged water 60 parts by weight

  The above was stirred and mixed to obtain an amino acid 2 dispersion having a solid content of 10.1% by weight.

Preparation of amino acid 3 dispersion Alanine 20 parts by weight Ion exchange water 60 parts by weight

  The above was stirred and mixed to obtain an amino acid 3 dispersion having a solid content of 10.2% by weight.

Preparation of formic acid dispersion liquid Formic acid 20 parts by weight Deionized water 60 parts by weight

  The above was stirred and mixed to obtain a formic acid dispersion having a solid content of 10.2% by weight.

(Adjustment of oxyacid dispersion)
Preparation of dispersion of oxyacid 1 (n = 2) Oxyacid (n = 2) 20 parts by weight Deionized water 60 parts by weight

  The above was stirred and mixed to obtain an oxyacid 1 (n = 2) dispersion having a solid content of 10.2% by weight.

Preparation of dispersion of oxyacid 2 (n = 1) Oxyacid (n = 1) 20 parts by weight Deionized water 60 parts by weight

  The above was stirred and mixed to obtain an oxyacid 2 (n = 1) dispersion having a solid content of 10.2% by weight.

Preparation of dispersion of oxyacid 3 (n = 8) Oxyacid (n = 8) 20 parts by weight Deionized water 60 parts by weight

  The above was stirred and mixed to obtain an oxyacid 3 (n = 6) dispersion having a solid content of 10.2% by weight.

Preparation of oxyacid 4 (n = 0) dispersion Oxyacid (n = 0) 20 parts by weight Ion-exchanged water 60 parts by weight

  The above was stirred and mixed to obtain an oxyacid 4 (n = 0) dispersion having a solid content of 10.2% by weight.

Preparation of dispersion of oxyacid 5 (n = 9) Oxyacid (n = 9) 20 parts by weight Ion exchange water 60 parts by weight

  The above was stirred and mixed to obtain an oxyacid 5 (n = 9) dispersion having a solid content of 10.2% by weight.

(Preparation of release agent dispersion 1)
Alkyl wax FNP0085 (dissolution temperature 86 ° C., manufactured by Nippon Seiwa Co., Ltd.) 45 parts by weight Cationic surfactant (Neogen RK, manufactured by Daiichi Kogyo Seiyaku) 5 parts by weight Ion-exchanged water 200 parts by weight

  The above was heated to 90 ° C., sufficiently dispersed with IKA Ultra Tarrax T50, and then dispersed with a pressure discharge type gorin homogenizer, and further 5 parts by weight of amino acid 1 dispersion and 5 parts by weight of oxyacid 1 dispersion were added. By adding, release agent dispersion liquid 1 having a volume average particle diameter of 200 nm and a solid content of 24.3% by weight was obtained.

(Preparation of release agent dispersion 2)
A release agent dispersion having a volume average particle size of 200 nm and a solid content of 24.3% by weight was prepared in the same manner as in the release agent dispersion 1 except that an oxyacid 2 dispersion was added instead of the oxyacid 1 dispersion. 2 was obtained.

(Preparation of release agent dispersion 3)
A release agent dispersion having a volume average particle size of 200 nm and a solid content of 24.3% by weight was prepared in the same manner as in the release agent dispersion 1 except that an oxyacid 3 dispersion was added instead of the oxyacid 1 dispersion. 3 was obtained.

(Preparation of release agent dispersion 4)
A release agent dispersion 4 having a volume average particle size of 200 nm and a solid content of 24.3% by weight was prepared except that an amino acid 2 dispersion was added instead of the amino acid 1 dispersion. Obtained.

(Preparation of release agent dispersion 5)
A release agent dispersion 5 having a volume average particle size of 200 nm and a solid content of 24.3% by weight was prepared except that an amino acid 3 dispersion was added instead of the amino acid 1 dispersion. Obtained.

(Preparation of release agent dispersion 6)
Instead of adding 5 parts by weight of the amino acid 1 dispersion and 5 parts by weight of the oxyacid 1 dispersion, 0.2 parts by weight of the amino acid 1 dispersion and 0.2 parts by weight of the oxyacid 1 dispersion were added. Prepared in the same manner as the release agent dispersion 1, and a release agent dispersion 6 having a volume average particle size of 200 nm and a solid content of 24.3% by weight was obtained.

(Preparation of release agent dispersion liquid 7)
Instead of adding 5 parts by weight of the amino acid 1 dispersion and 5 parts by weight of the oxyacid 1 dispersion, 40 parts by weight of the amino acid 1 dispersion and 40 parts by weight of the oxyacid 1 dispersion were added. Prepared in the same manner as Liquid 1, and a release agent dispersion 7 having a volume average particle size of 200 nm and a solid content of 24.3% by weight was obtained.

(Preparation of release agent dispersion 8)
Instead of adding 5 parts by weight of oxyacid 1 dispersion, it was prepared in the same manner as release agent dispersion 1, except that 12.5 parts by weight of oxyacid 1 dispersion was added. Volume average particle size 200 nm, solid content 24.3% by weight of release agent dispersion 8 was obtained.

(Preparation of release agent dispersion 9)
Instead of adding 5 parts by weight of oxyacid 1 dispersion, it was prepared in the same manner as release agent dispersion 1, except that 3.13 parts by weight of oxyacid 1 dispersion was added. A release agent dispersion 9 having an amount of 24.3% by weight was obtained.

(Preparation of mold release agent dispersion 10)
Instead of adding 45 parts by weight of the alkyl wax FNP0085, it was prepared in the same manner as the release agent dispersion 1, except that 45 parts by weight of ester wax WEP5 (manufactured by Nippon Seiwa Co., Ltd.) was added and the heating temperature was 80 ° C. A release agent dispersion 10 having a volume average particle size of 200 nm and a solid content of 24.3% by weight was obtained.

(Preparation of mold release agent dispersion 11)
Except for not adding 5 parts by weight of the amino acid 1 dispersion, it was prepared in the same manner as the release agent dispersion 1, and a release agent dispersion 11 having a volume average particle size of 200 nm and a solid content of 24.3% by weight was obtained.

(Preparation of release agent dispersion 12)
Prepared in the same manner as the release agent dispersion 1, except that 5 parts by weight of the oxyacid 4 dispersion was added instead of the oxyacid 1 dispersion, and the release was performed with a volume average particle size of 200 nm and a solid content of 24.3% by weight. An agent dispersion 12 was obtained.

(Preparation of mold release agent dispersion 13)
Except for adding 5 parts by weight of oxyacid 5 dispersion instead of oxyacid 1 dispersion, it was prepared in the same manner as release agent dispersion 1, and was released from a mold having a volume average particle size of 200 nm and a solid content of 24.3% by weight. An agent dispersion 13 was obtained.

(Preparation of mold release agent dispersion 14)
A release agent dispersion liquid 14 having a volume average particle size of 200 nm and a solid content of 24.3% by weight was obtained except that the oxyacid 1 dispersion liquid was not added.

(Preparation of release agent dispersion 15)
A release agent dispersion having a volume average particle size of 200 nm and a solid content of 24.3% by weight was prepared in the same manner as in the release agent dispersion 1 except that 5 parts by weight of a formic acid dispersion was added instead of the amino acid 1 dispersion. 15 was obtained.

(Preparation of release agent dispersion 16)
It was prepared in the same manner as the mold release agent dispersion 1 except that 5 parts by weight of the amino acid 1 dispersion and 5 parts by weight of the oxyacid 1 dispersion were not added, and a release having a volume average particle size of 200 nm and a solid content of 24.3% by weight. A mold dispersion 16 was obtained.

(Toner Production Example 1)
Crystalline polyester resin fine particle dispersion 15 parts by weight Amorphous polyester resin fine particle dispersion 80 parts by weight Colorant dispersion 18 parts by weight Release agent dispersion 1 18 parts by weight

  Ion exchange water was added to the above components so that the solid content was 16% by weight, and the mixture was sufficiently mixed and dispersed in a round stainless steel flask with an Ultra Turrax T50. Next, 0.36 parts by weight of polyaluminum chloride was added thereto, and the dispersion operation was continued with an ultra turrax. The flask was heated to 47 ° C. with stirring in an oil bath for heating. After maintaining at 47 ° C. for 60 minutes, 46 parts by weight of the amorphous polyester resin fine particle dispersion was gradually added thereto. Thereafter, the pH of the system was adjusted to 9.0 with a 0.55 mol / L sodium hydroxide aqueous solution, and then the stainless steel flask was sealed, and heated to 90 ° C. while continuing stirring using a magnetic seal. Hold for 5 hours.

  After completion of the above treatment, the mixture was cooled, filtered, sufficiently washed with ion exchange water, and then subjected to solid-liquid separation by Nutsche suction filtration. This was further redispersed in 3 L of ion exchange water at 40 ° C., and stirred and washed at 300 rpm for 15 minutes. This was repeated five more times, and when the pH of the filtrate was 7.01, the electric conductivity was 9.7 μS / cm, and the surface tension was 71.2 Nm, solid-liquid separation was performed using No5A filter paper by Nutsche suction filtration. It was. Next, vacuum drying was continued for 12 hours to obtain toner base particles 1. When the particle size at this time was measured, the volume average particle size was 6.1 μm, the volume average particle size distribution index GSDv was 1.26, and the number average particle size distribution index GSDp was 1.25. The ratio (GSDp / GSDv) to the number average particle size distribution index GSDp was 0.99. The toner shape factor SF1 was 134.

  Further, 1.0 part by weight of hydrophobic silica (TS720: manufactured by Cabot) and 2.0 parts by weight of hydrophobic silica (X24: manufactured by Shin-Etsu Chemical Co., Ltd.) with respect to 50 parts by weight of the prepared toner base particles 1. And blended in a sample mill. This was weighed so that the toner concentration was 5% by weight with respect to a ferrite carrier having a volume average particle diameter of 50 μm coated with 1% of methacrylate (manufactured by Soken Chemical Co., Ltd.), stirred and mixed in a ball mill for 5 minutes to develop developer 1. Adjusted.

(Toner Production Example 2)
Release agent dispersion 2 A toner mother particle 2 was obtained in the same manner as in Toner Production Example 1 except that the dispersion was changed to 18 parts by weight.

  When the particle size at this time was measured, the volume average particle size was 6.0 μm, the volume average particle size distribution index GSDv was 1.26, and the number average particle size distribution index GSDp was 1.25. The ratio (GSDp / GSDv) to the number average particle size distribution index GSDp was 0.99. Further, the toner shape factor SF1 was 133. Further, the developer 2 was prepared in the same manner as in Toner Production Example 1.

(Toner Production Example 3)
Release agent dispersion 3 A toner mother particle 3 was obtained in the same manner as in Toner Production Example 1 except that the dispersion was changed to 18 parts by weight.

  When the particle size at this time was measured, the volume average particle size was 5.9 μm, the volume average particle size distribution index GSDv was 1.25, and the number average particle size distribution index GSDp was 1.25. The ratio (GSDp / GSDv) to the number average particle size distribution index GSDp was 1.00. The toner shape factor SF1 was 132. Further, the developer 3 was prepared in the same manner as in Toner Production Example 1.

(Toner Production Example 4)
Release agent dispersion 4 Toner base particles 4 were obtained in the same manner as in Toner Production Example 1 except that the dispersion was changed to 18 parts by weight.

  When the particle size at this time was measured, the volume average particle size was 6.1 μm, the volume average particle size distribution index GSDv was 1.26, and the number average particle size distribution index GSDp was 1.26. The ratio (GSDp / GSDv) to the number average particle size distribution index GSDp was 1.00. The toner shape factor SF1 was 134. Further, the developer 4 was prepared in the same manner as in Toner Production Example 1.

(Toner Production Example 5)
Release agent dispersion 5 A toner mother particle 5 was obtained in the same manner as in Example 1 except that the dispersion was changed to 18 parts by weight.

  When the particle size at this time was measured, the volume average particle size was 6.3 μm, the volume average particle size distribution index GSDv was 1.25, and the number average particle size distribution index GSDp was 1.25. The ratio (GSDp / GSDv) to the number average particle size distribution index GSDp was 1.00. The toner shape factor SF1 was 135. Further, the developer 5 was prepared in the same manner as in Toner Production Example 1.

(Toner Production Example 6)
Toner base particles 6 were obtained in the same manner as in Toner Production Example 1 except that 18 parts by weight of the release agent dispersion 6 dispersion was used.

  When the particle size at this time was measured, the volume average particle size was 6.1 μm, the volume average particle size distribution index GSDv was 1.26, and the number average particle size distribution index GSDp was 1.25. The ratio (GSDp / GSDv) to the number average particle size distribution index GSDp was 0.99. The toner shape factor SF1 was 134. Further, the developer 6 was prepared in the same manner as in Toner Production Example 1.

(Toner Production Example 7)
Release toner dispersion 7 Dispersion 18 Except for 18 parts by weight, toner mother particles 7 were obtained in the same manner as in Toner Production Example 1.

  When the particle size at this time was measured, the volume average particle size was 6.1 μm, the volume average particle size distribution index GSDv was 1.26, and the number average particle size distribution index GSDp was 1.25. The ratio (GSDp / GSDv) to the number average particle size distribution index GSDp was 0.99. The toner shape factor SF1 was 134. At this time, it was confirmed that aspartic acid and oxyacid (n = 0) were contained by HPLC. Further, a developer 7 was prepared in the same manner as in Toner Production Example 1.

(Toner Production Example 8)
Release agent dispersion 8 Dispersing liquid was used in the same manner as in Toner Production Example 1 except that 18 parts by weight of dispersion was used to obtain toner mother particles 8.

  When the particle size at this time was measured, the volume average particle size was 6.1 μm, the volume average particle size distribution index GSDv was 1.26, and the number average particle size distribution index GSDp was 1.25. The ratio (GSDp / GSDv) to the number average particle size distribution index GSDp was 0.99. The toner shape factor SF1 was 134. Further, the developer 8 was prepared in the same manner as in Toner Production Example 1.

(Toner Production Example 9)
Toner base particles 9 were obtained in the same manner as in Toner Production Example 1 except that the release agent dispersion 9 was changed to 18 parts by weight.

  When the particle size at this time was measured, the volume average particle size was 6.1 μm, the volume average particle size distribution index GSDv was 1.26, and the number average particle size distribution index GSDp was 1.25. The ratio (GSDp / GSDv) to the number average particle size distribution index GSDp was 0.99. The toner shape factor SF1 was 134. Further, a developer 9 was prepared in the same manner as in Toner Production Example 1.

(Toner Production Example 10)
Release agent dispersion 10 A toner mother particle 10 was obtained in the same manner as in Toner Production Example 1 except that the dispersion was changed to 18 parts by weight.

  When the particle size at this time was measured, the volume average particle size was 6.1 μm, the volume average particle size distribution index GSDv was 1.26, and the number average particle size distribution index GSDp was 1.25. The ratio (GSDp / GSDv) to the number average particle size distribution index GSDp was 0.99. The toner shape factor SF1 was 134. Further, the developer 10 was prepared in the same manner as in Toner Production Example 1.

(Toner Production Example 11)
Instead of 15 parts by weight of the crystalline polyester resin fine particle dispersion and 80 parts by weight of the noncrystalline polyester resin fine particle dispersion, 95 parts by weight of styrene acrylic resin fine particle dispersion, and 80 parts by weight of noncrystalline polyester resin fine particle dispersion Were produced in the same manner as in Toner Production Example 1 to obtain toner mother particles 11.

  When the particle size at this time was measured, the volume average particle size was 6.1 μm, the volume average particle size distribution index GSDv was 1.26, and the number average particle size distribution index GSDp was 1.25. The ratio (GSDp / GSDv) to the number average particle size distribution index GSDp was 0.99. The toner shape factor SF1 was 134. Further, the developer 11 was prepared in the same manner as in Toner Production Example 1.

(Toner Production Example 12)
The toner base particles 12 were obtained in the same manner as in Toner Production Example 1 except that the release agent dispersion 11 was changed to 18 parts by weight.

  When the particle size at this time was measured, the volume average particle size was 6.2 μm, the volume average particle size distribution index GSDv was 1.26, and the number average particle size distribution index GSDp was 1.25. The ratio (GSDp / GSDv) to the number average particle size distribution index GSDp was 0.99. The toner shape factor SF1 was 134. Further, the developer 12 was prepared in the same manner as in Toner Production Example 1.

(Toner Production Example 13)
The toner base particles 13 were obtained in the same manner as in Toner Production Example 1 except that the release agent dispersion 12 was changed to 18 parts by weight.

  When the particle size at this time was measured, the volume average particle size was 6.2 μm, the volume average particle size distribution index GSDv was 1.26, and the number average particle size distribution index GSDp was 1.25. The ratio (GSDp / GSDv) to the number average particle size distribution index GSDp was 0.99. The toner shape factor SF1 was 134. Further, the developer 13 was prepared in the same manner as in Toner Production Example 1.

(Toner Production Example 14)
A toner base particle 14 was obtained in the same manner as in Toner Production Example 1 except that the release agent dispersion 13 was changed to 18 parts by weight.

  When the particle size at this time was measured, the volume average particle size was 6.2 μm, the volume average particle size distribution index GSDv was 1.26, and the number average particle size distribution index GSDp was 1.25. The ratio (GSDp / GSDv) to the number average particle size distribution index GSDp was 0.99. The toner shape factor SF1 was 134. Further, the developer 14 was prepared in the same manner as in Toner Production Example 1.

(Toner Production Example 15)
Toner base particles 15 were obtained in the same manner as in Toner Production Example 1 except that the release agent dispersion 14 was changed to 18 parts by weight.

  When the particle size at this time was measured, the volume average particle size was 6.2 μm, the volume average particle size distribution index GSDv was 1.26, and the number average particle size distribution index GSDp was 1.25. The ratio (GSDp / GSDv) to the number average particle size distribution index GSDp was 0.99. The toner shape factor SF1 was 134. Further, the developer 15 was prepared in the same manner as in Toner Production Example 1.

(Toner Production Example 16)
Toner base particles 16 were obtained in the same manner as in Toner Production Example 1 except that the release agent dispersion 15 was changed to 18 parts by weight.

  When the particle size at this time was measured, the volume average particle size was 6.2 μm, the volume average particle size distribution index GSDv was 1.26, and the number average particle size distribution index GSDp was 1.25. The ratio (GSDp / GSDv) to the number average particle size distribution index GSDp was 0.99. The toner shape factor SF1 was 134. Further, the developer 16 was prepared in the same manner as in Toner Production Example 1.

(Toner Production Example 17)
Toner base particles 17 were obtained in the same manner as in Toner Production Example 1 except that the release agent dispersion 16 was changed to 18 parts by weight.

  When the particle size at this time was measured, the volume average particle size was 6.2 μm, the volume average particle size distribution index GSDv was 1.26, and the number average particle size distribution index GSDp was 1.25. The ratio (GSDp / GSDv) to the number average particle size distribution index GSDp was 0.99. The toner shape factor SF1 was 134. Further, the developer 17 was prepared in the same manner as in Toner Production Example 1.

(Evaluation of toner)
Image quality evaluation: DocuCenterColor400CP (manufactured by Fuji Xerox Co., Ltd.) as the evaluator and C2 paper (manufactured by Fuji Xerox Co., Ltd.) as the paper to produce an image, and then the image density at 100% input density was adjusted to 5.0 After the fixing of the image, the offsets of the 50% and 20% halftone images when the image density with an input density of 100% was adjusted to 1.5 were confirmed and evaluated according to the following criteria. Fixing was performed using an external fixing device (fixing roll surface was PFA coated, oil-less specification) with a nip width of 6.5 mm, a fixing speed of 220 mm / sec, and a fixing temperature of 160 ° C. The above developers 1 to 17 were used as developers.

(Halftone evaluation)
In the halftone evaluation, the above machine was used to form an image by adjusting the toner applied amount to 0.5 g / m2 using fine paper (J paper) manufactured by Fuji Xerox Co., and fixing the image at 160 ° C. Visual evaluation was made. The evaluation index is as follows.

◎: Vivid halftone with no offset.
○: Halftone of fixing offset area 0 to 5%, which cannot be recognized as offset.
Δ: Minor halftone with a fixing offset area of 6 to 15%.
X: Halftone that can be clearly recognized as 16% or more of the fixing offset area.

  The above results are summarized in Table 1. Developer 1 to Developer 11 (using toners 1 to 11 produced in Toner Production Examples 1 to 11) are Examples 1 to 11 of the present invention, and Developer 12 to Developer 17 (Toner Production). Comparative Examples 1 to 6 are toners 12 to 17 produced in Examples 12 to 17.

  In Table 1, Example 1 uses aspartic acid as an amino acid, n of oxyacid is 2, amino acid is 0.2 mass%, oxyacid is 0.2 mass%, and amino acid and oxyacid The ratio (denoted as C = A / B ratio) is 1. Further, polyester was used as the binder resin, and alkyl wax was used as the release agent.

  Example 2 uses aspartic acid as the amino acid, n of the oxyacid is 1, the ratio of amino acid to oxyacid using 0.2% by mass of amino acid and 0.2% by mass of oxyacid (C = A / B ratio) is 1. Further, polyester was used as the binder resin, and alkyl wax was used as the release agent.

  Example 3 uses aspartic acid as the amino acid, n of the oxyacid is 8, and the amino acid / oxyacid ratio (C) using 0.2% by mass of amino acid and 0.2% by mass of oxyacid. = A / B ratio) is 1. Further, polyester was used as the binder resin, and alkyl wax was used as the release agent.

  Example 4 uses glycine as an amino acid, the n of the oxyacid is 2, the ratio of amino acid to oxyacid using 0.2% by mass of amino acid and 0.2% by mass of oxyacid (C = A / B ratio) is 1. Further, polyester was used as the binder resin, and alkyl wax was used as the release agent.

  Example 5 uses alanine as the amino acid, n of the oxyacid is 2, the ratio of the amino acid to the oxyacid using 0.2% by mass of amino acid and 0.2% by mass of oxyacid (C = A / B ratio) is 1. Further, polyester was used as the binder resin, and alkyl wax was used as the release agent.

  Example 6 uses aspartic acid as the amino acid, n of the oxyacid is 2, the ratio of amino acid to oxyacid (0.009% by mass of amino acid and 0.009% by mass of oxyacid) (C = A / B ratio) is 1. Further, polyester was used as the binder resin, and alkyl wax was used as the release agent.

  Example 7 uses aspartic acid as an amino acid, n of oxyacid is 2, ratio of amino acid to oxyacid (C) using 1.6% by mass of amino acid and 1.6% by mass of oxyacid = A / B ratio) is 1. Further, polyester was used as the binder resin, and alkyl wax was used as the release agent.

  Example 8 uses aspartic acid as an amino acid, n of oxyacid is 2, ratio of amino acid to oxyacid (C) using 0.2% by mass of amino acid and 0.5% by mass of oxyacid = A / B ratio) is 0.4. Further, polyester was used as the binder resin, and alkyl wax was used as the release agent.

  Example 9 uses aspartic acid as the amino acid, n of the oxyacid is 2, the ratio of amino acid to oxyacid (0.2% by weight of amino acid and 0.125% by weight of oxyacid (C = A / B ratio) is 1.6. Further, polyester was used as the binder resin, and alkyl wax was used as the release agent.

  Example 10 uses aspartic acid as an amino acid, n of oxyacid is 2, ratio of amino acid to oxyacid (C) using 0.2% by mass of amino acid and 0.2% by mass of oxyacid = A / B ratio) is 1. Further, polyester was used as the binder resin, and ester wax was used as the release agent.

  Example 11 uses aspartic acid as the amino acid, n of the oxyacid is 2, the ratio of amino acid to oxyacid using 0.2% by mass of amino acid and 0.2% by mass of oxyacid (C = A / B ratio) is 1. Further, styrene acrylic was used as the binder resin, and alkyl wax was used as the release agent.

  In Comparative Example 1, no amino acid was used, n of oxyacid was 2, and 0.2% by mass of oxyacid was used. Further, polyester was used as the binder resin, and alkyl wax was used as the release agent.

  Comparative Example 2 uses aspartic acid as an amino acid, n of oxyacid is 0, 0.2% by mass of amino acid and 0.2% by mass of oxyacid are used. = A / B ratio) is 1. Further, polyester was used as the binder resin, and alkyl wax was used as the release agent.

  Comparative Example 3 uses aspartic acid as the amino acid, n of the oxyacid is 9, the ratio of amino acid to oxyacid (C) using 0.2% by mass of amino acid and 0.2% by mass of oxyacid = A / B ratio) is 1. Further, polyester was used as the binder resin, and alkyl wax was used as the release agent.

  In Comparative Example 4, aspartic acid was used as an amino acid, oxyacid was not used, and 0.2% by mass of amino acid was used. Further, polyester was used as the binder resin, and alkyl wax was used as the release agent.

  Comparative Example 5 uses formic acid instead of amino acid, n of oxyacid is 2, ratio of formic acid to oxyacid using 0.2% by mass of formic acid and 0.2% by mass of oxyacid ( C = A / B ratio) is 1. Further, polyester was used as the binder resin, and alkyl wax was used as the release agent.

  In Comparative Example 6, amino acids and oxyacids were not used, polyester was used as the binder resin, and alkyl wax was used as the release agent.

  As shown in Table 1, when the developers of Examples 1 to 11 were used, images with little offset were obtained. On the other hand, when the developers of Comparative Examples 1 to 6 were used, an offset occurred.

  DESCRIPTION OF SYMBOLS 1 Image forming apparatus, 10 charging part, 12 exposure part, 14 electrophotographic photosensitive member, 16 developing part, 18 transfer part, 20 cleaning part, 22 fixing part, 24 to-be-transferred body.

Claims (7)

A toner for developing an electrostatic image, wherein the toner has at least a binder resin and a release agent, and contains an amino acid and an oxyacid shown below.

Here, n is 1-8.   The toner for developing an electrostatic image according to claim 1, wherein the amino acid of the toner is aspartic acid.   3. The electrostatic image developing toner according to claim 1, wherein n of the oxyacid of the toner is 1 to 2.   When the mass% of amino acids contained in the toner is A and the mass% of oxyacid is B, A is 0.01 to 1.5, and the ratio of A and B C = A / B is 0.5. The electrostatic image developing toner according to claim 1, wherein the toner is an electrostatic charge image developing toner.   The electrostatic charge image developing toner according to any one of claims 1 to 4, wherein the binder resin of the toner is a polyester resin containing bisphenol A.   6. The electrostatic image developing toner according to claim 1, wherein the toner release agent is an alkyl release agent. A method for producing an electrostatic charge image developing toner according to claim 1,
A mixing step of mixing a resin fine particle dispersion in which fine particles of a binder resin having a volume average particle size of 1 μm or less are dispersed and a release agent dispersion to which the amino acid and the oxyacid are added;
An aggregated particle forming step of aggregating the product of the mixing step in the presence of a compound having a monovalent or higher charge to form aggregated particles;
A particle growth stopping step of adjusting the pH in the system to 5 to 10 to stop the growth of the aggregated particles,
And a fusing step of fusing and coalescing the aggregated particles by heating them to a temperature equal to or higher than the dissolution temperature of the fine particles of the binder resin.

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