JP2008129478A - Resin particle dispersion and method for preparing the same, electrostatic charge image developing toner and method for manufacturing the same, electrostatic charge image developer and image forming method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a resin particle dispersion that is superior in long-term storage stability of resin particles at high temperatures and high-humidity environment, wherein when the resin particles are used for an electrostatic charge image developing toner, the toner is superior in uniformity of glossiness of a secondary color fixed image, long-term image quality maintaining properties in a high humidity environment, offset resistance, blocking resistance and toner fluidity, a method for preparing the resin particle dispersion, an electrostatic charge image developing toner, using the resin particle dispersion, and to provide a method for manufacturing the same, an electrostatic charge image developer and an image forming method. <P>SOLUTION: In the resin particle dispersion, resin particles containing a polycondensate resin are dispersed, and the resin particle dispersion contains sulfuric acid and a basic substance, while satisfying 1.0×A≤B≤400×A, where A represents the molar quantity of the sulfur acid, and B represents the molar quantity of the basic substance. The resin particle dispersion has a pH of 6-10, and there are also provided the method for preparing the resin particle dispersion, the electrostatic charge image developing toner that uses the resin particle dispersion and the method for manufacturing the same, the electrostatic charge image developer and the image forming method. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a resin particle dispersion and a production method thereof, an electrostatic charge image developing toner and a production method thereof, an electrostatic charge image developer, and an image forming method.

As a general polycondensation method for obtaining a polyester resin for an electrostatic charge image developing toner, particularly an amorphous polyester (hereinafter also referred to as “non-crystalline polyester”), the reactivity of the monomer is low. Therefore, it requires a reaction time far exceeding 10 hours under stirring with high power at a high temperature exceeding 200 ° C. and high vacuum, and is produced by a production method requiring high energy.
In the case of obtaining a polyester resin having low reactivity in this way, a metal catalyst having higher activity in a high temperature region has been generally used.

  However, the technology that uses sulfur acid as a polyester polycondensation catalyst is a technology that can achieve low-temperature polymerization at 150 ° C. or lower, and is extremely important for protecting the global environment in order to reduce the total toner production energy. is there.

  As means for preparing the polyester resin particle aqueous dispersion, there are conventional techniques such as a solvent method, a phase inversion emulsification method, a high temperature emulsification method, etc., but the solvent method is not preferable in terms of environmental safety because it requires a large investment in the recovery equipment, Further, it is difficult to completely remove the solvent, and there is a problem in that it causes bad image quality such as odor generated from the residual solvent of the toner and fogging in the non-image area. In addition, there are hydrophilic polymers having a specific structure for producing self-emulsifiable polyesters, and salts thereof (sulfonylphthalic acid, for example, sulfonic acid and its alkali neutralized salt such as SDSP). When used in a resin, the volume resistance value is lowered, particularly the chargeability in a high temperature and high humidity environment is deteriorated, which has a problem in practical use.

On the other hand, examples of the emulsification technique of polyester without using a solvent include the following examples, but all have problems in quality as described below.
In Patent Document 1, the toner raw material containing polyester is emulsified in water after being heated and melted at a high temperature of 190 ° C. or higher. However, the energy at the time of resin emulsification is enormous and cannot be practically used. Emulsification and dispersion under high-energy conditions can easily lead to decomposition of the resin, causing problems such as the occurrence of uneven distribution of the composition and the uniformity of the particle size distribution of the resin particles in the dispersion. In the toner using the above material, problems occur in the occurrence of fogging in the non-image area and the image quality stability.
Under such circumstances, in the non-solvent system, unlike the high temperature emulsification method and the above method, by adding a heated alkaline solution to the polyester resin to neutralize the resin terminal and thereby having solubility in water. There is also a technique of a neutralization emulsification method (hereinafter sometimes abbreviated as “alkali neutralization method”).

Examples of methods for obtaining a polyester resin particle dispersion using such a neutralization emulsification method include the following.
In Patent Document 2, 1.1 to 1.3 times equivalent of an amine-based neutralizing agent is used for a resin containing polyester to neutralize the resin to produce a resin particle dispersion. About this method, the particle size distribution of the obtained resin particle dispersion is two peaks or the median diameter tends to be as coarse as 1 μm or more, and this method is not suitable as a resin particle dispersion for toner. Is clear.

  Another example of neutralization emulsification is Patent Document 3, in which a polyester resin having an acid value of 2 to 70 KOH · mg / g, a neutralizing agent capable of ionizing the carboxy group of the polyester resin, and an aqueous medium are used. Although the polyester-type water dispersion containing is obtained, there exists an illustration of the alkyl glycidyl ester as a compound which has one functional group for the purpose of reacting with a polyester monomer and providing emulsifying property. In this approach, the polyester is not sufficiently dissolved or finely divided, so that it is difficult to emulsify an amorphous polyester resin suitable as a toner resin to a particle size suitable as a toner resin particle dispersion.

  Patent Document 4 discloses that a resin particle dispersion is prepared after neutralizing a resin using 1.1 to 1.3 equivalents of an amine-based neutralizing agent with respect to a resin containing polyester. Polyester resin particle dispersion with improved particle size distribution is made by jet pulverizing the liquid, but the alkalized amount of carboxy groups at the end of the resin is not constant and some resin remains undissolved. However, when the toner is made using the emulsion as a raw material, the non-image area is fogged in a high humidity environment because the resulting polyester resin particle dispersion has a non-uniform particle size and particle size distribution. There is a problem.

  As described above, in the prior art, even when the polyester resin particle dispersion is prepared using any emulsification method including the neutralization method of the carboxy group at the polyester terminal, the resin particle dispersion is controlled by controlling the amount of alkali added. However, there are no examples of resin particle dispersions for electrostatic charge image developing toner that can control the particle size distribution.

  In addition, when a toner is produced using a polyester resin particle dispersion with uneven or broad particle size distribution as a raw material, it may interfere with aggregation / unification stabilization or charge leakage under high temperature and high humidity environment This is a factor that causes fog in non-image areas or gloss unevenness in a secondary color fixed image. However, the present situation is that no method has been found to improve these.

  Furthermore, a resin polymerized using an acid catalyst has low hue stability over time, and if stored for a long time (≧ 60 days) in a high-humidity environment, the resin is discolored or colored due to the residual acid catalyst. There is a problem in that the brightness of an image having a low area coverage (AC) (AC ≦ 5%) becomes dark or the saturation is lowered in storage in a wet environment. Examples of improving the temporal hue stability of the resin due to such residual catalyst are as follows.

  In Patent Document 5, a polyester polymer obtained by an ester exchange reaction from an aromatic dicarboxylic acid ester derivative and an alkylene glycol is reacted with an alkaline earth metal compound, and then a predetermined amount of a phosphorus compound is added to the alkaline earth metal. After losing the catalytic activity of the metal compound, a certain amount of a polycondensation catalyst system consisting essentially of an unreacted mixture of the titanium compound component and the phosphorus compound component is added, and the aromatic dicarboxylic acid and alkylene in the system are added. A polyester obtained by reacting a diester with glycol is obtained. In this example, it is possible to suppress the addition amount of a titanium compound having a fear of coloring used as a polycondensation catalyst by previously deactivating a large part of the transesterification catalyst by post-adding the phosphorus compound in the middle. Thus, a polyester original fiber having a good color tone with little dullness and color tone fluctuation and excellent in fading color is obtained.

  There are other examples of deactivating a metal catalyst. For example, in Patent Document 6, a titanium compound for polymerizing a polyester resin is used as a polycondensation medium, and the catalyst is deactivated by heat treatment in water. And, because the heat stability of the melt is good and the increase in the cyclic low weight after molding can be reduced, there is an example of obtaining a polyester resin with less mold contamination during molding, or in Patent Document 7, In a composition obtained by melt blending two or more kinds of raw materials, each raw material polymer is polymerized with a metal compound polymerization catalyst such as titanium, antimony or germanium which can be deactivated, and the catalyst is deactivated during the melt molding process. By using a method for producing a polyester in which a catalytic function is substantially deactivated by the action of a compound having an Method for obtaining a high property polyester composed by suppressing property decrease upon melting due to reactions such as exchange are mentioned.

  As described above, there are examples in which a metal catalyst is deactivated by using another metal, or examples in which a metal catalyst is used to improve resin coloring by using a different metal. However, there is no example of obtaining a resin by activating the catalyst and obtaining a resin particle dispersion for a polyester resin produced using an acid catalyst.

JP 2002-351140 A JP-A-9-296100 JP 2000-191892 A JP 2000-26709 A JP 2005-179828 A JP 2005-325368 A JP 2006-28323 A

One problem to be solved by the present invention is that the resin particles are excellent in long-term storage stability in a high-temperature and high-humidity environment, and when the resin particles are used as an electrostatic charge image developing toner, a secondary color fixed image is obtained. It is to provide a resin particle dispersion excellent in uniformity of glossiness and long-term image quality maintainability in a high humidity environment, and a method for producing the same.
Another problem to be solved by the present invention is that the toner for developing an electrostatic charge image having excellent uniformity in the glossiness of the secondary color fixed image and long-term image quality maintenance in a high temperature and high humidity environment, and It is to provide a manufacturing method thereof, an electrostatic charge image developer, and an image forming method.

The above problems have been solved by means <1> to <8> shown below.
<1> A resin particle dispersion in which resin particles containing at least a polycondensation resin are dispersed, wherein the resin particle dispersion contains a sulfur acid and a basic substance, and the molar amount of the sulfur acid is A, the basic When the molar amount of the substance is B, 1.0 × A ≦ B ≦ 400 × A, and the resin particle dispersion has a pH of 6 to 10;
<2> The resin particle dispersion according to <1>, wherein the median diameter of the resin particles is 0.1 to 2.0 μm,
<3> A step of performing a polycondensation reaction of at least a polycondensable monomer using sulfur acid as a catalyst, adding a basic substance to stop the polycondensation reaction, and obtaining a binder resin, and the binder A method for producing a resin particle dispersion comprising a step of further adding a basic substance to a resin and emulsifying and dispersing it in an aqueous medium, wherein the molar amount of the sulfur acid is A and the total number of moles of the basic substance is B. And 1.0 × A ≦ B ≦ 400 × A, and the pH of the resin particle dispersion is 6-10,
<4> The method for producing a resin particle dispersion according to <3>, wherein the basic substance includes a nitrogen element.
<5> A method for producing an electrostatic charge image developing toner comprising a step of aggregating the resin particles in a dispersion containing at least a resin particle dispersion to obtain aggregated particles, and a step of heating and coalescing the aggregated particles. A method for producing an electrostatic charge image developing toner, wherein the resin particle dispersion is a resin particle dispersion produced by the production method according to <3> or <4>.
<6> An electrostatic image developing toner produced by the production method according to <5>,
<7> An electrostatic charge image developer comprising the electrostatic charge image developing toner according to <6> and a carrier,
<8> A latent image forming step of forming an electrostatic latent image on the surface of the latent image holding member, and developing the electrostatic latent image formed on the surface of the latent image holding member with a developer containing toner to form a toner image. An image forming method comprising: a developing step, a transferring step for transferring the toner image formed on the surface of the latent image holding member to the surface of the transfer target, and a fixing step for thermally fixing the toner image transferred to the surface of the transfer target An image forming method using the electrostatic charge image developing toner according to <6> as the toner or the electrostatic charge image developer according to <7> as the developer.

According to the present invention, the resin particles are excellent in long-term storage stability in a high-temperature and high-humidity environment, and when used in an electrostatic charge image developing toner, the uniformity of the glossiness of the secondary color fixed image, and It is possible to provide a resin particle dispersion excellent in long-term image quality maintainability in a high temperature and high humidity environment and a method for producing the same.
Further, according to the present invention, an electrostatic charge image developing toner excellent in uniformity of glossiness of a secondary color fixed image and maintaining long-term image quality in a high-temperature and high-humidity environment, a manufacturing method thereof, and an electrostatic charge image development An agent and an image forming method can be provided.

The resin particle dispersion of the present invention is a resin particle dispersion in which resin particles containing at least a polycondensation resin are dispersed, wherein the resin particle dispersion contains a sulfur acid and a basic substance, and the molar amount of the sulfur acid Where A is the molar amount of the basic substance and B is 1.0 × A ≦ B ≦ 400 × A, and the pH of the resin particle dispersion is 6 to 10.
The method for producing a resin particle dispersion of the present invention includes a step of performing a polycondensation reaction of at least a polycondensable monomer using sulfur acid as a catalyst, and adding a basic substance to stop the polycondensation reaction. A method for producing a resin particle dispersion comprising the steps of obtaining a binder resin, and further adding a basic substance to the binder resin and emulsifying and dispersing in a water-based medium, wherein the molar amount of the sulfur acid Is A, and the total number of moles of the basic substance is B, 1.0 × A ≦ B ≦ 400 × A, and the pH of the resin particle dispersion is 6 to 10.
The resin particle dispersion of the present invention can be suitably used as a resin particle dispersion for an electrostatic image developing toner used in the production of an electrostatic image developing toner.
Hereinafter, the resin particle dispersion and the method for producing the same will be described in detail.

  In order to carry out the polycondensation reaction at a low temperature of 150 ° C. or lower, which is about 100 ° C. lower than the conventional method, a sulfur acid catalyst is used in the production method of the present invention. As the sulfur acid, it is preferable to use a Bronsted acid catalyst containing a sulfur atom. In order to establish a more consistent toner production method with a low environmental load, in addition to using low-temperature polycondensation resin as a raw material, resin particle dispersion at a temperature of 100 ° C. or lower, which is different from conventional emulsification methods The production of the liquid is preferred.

As a method for realizing low temperature emulsification at 100 ° C. or less in a non-solvent system, for example, by adding an alkaline solution to the resin and immersing and stirring, proton elimination of the molecular chain terminal carboxy group (COOH group) constituting the resin the alkali neutralization (COO ^-) is a method for imparting self-emulsifying capability (. also referred to as "neutralization emulsification method") can be cited with this result the resin.
However, in the conventional neutralization emulsification method, particle size distribution unevenness, composition distribution uneven distribution, and a small amount of hydrophilic components are generated in the resin particle dispersion. Providing a method for producing a resin particle dispersion capable of avoiding the above-mentioned problems because there is a problem that non-image area fogging occurs in a high humidity environment and secondary color gloss unevenness is likely to occur in a fixed image. Was desired.

Examples of a method for obtaining a resin particle dispersion in which this problem has been improved include a method in which the characteristics of the resin particle dispersion are changed to some extent by controlling the amount of alkali used for neutralization.
That is, when the alkali equivalent is extremely insufficient with respect to the resin terminal carboxy group, the alkali neutralization rate of the resin terminal carboxy group is low, so that the resin is hardly dispersed and the resin remains undissolved. , A sufficient solid content concentration (SC) cannot be obtained, and further, it is difficult to obtain a dispersion without a suitable median diameter (0.1 to 2.0 μm) or uneven composition distribution.
On the other hand, if alkali is present in excess relative to the carboxy group contained in the resin, all carboxy groups are neutralized (COO ⁻ ) and all resin molecular chains form salts, so they are completely dissolved in water. As a result, the emulsion cannot be formed or is excessively neutralized, and the dispersed polyester particles are thickened and settled by the formation of aggregates, so that water and polyester are separated.

  In addition, in the polycondensation resin obtained by the polycondensation reaction, there are molecular chains having various molecular weights and acid values. Therefore, there are differences in molecular weight distribution, acid value distribution, and hydrophilicity. Since there are also variations in each characteristic value such as molecular weight, molecular weight distribution, acid value and hydrophilicity among the resins in the inside, in terms of microscopic molecular chains with low molecular weight and high hydrophilicity, For molecular chains that are easily neutralized and dispersed and easily generate hydrophilic components, but for molecular chains with large molecular weights, they are difficult to neutralize and difficult to disperse. The inventors have found that this is a factor in the generation of hydrophilic components.

<Polycondensation resin>
The polycondensation resin used in the present invention is obtained by polycondensation of a polycondensable monomer. Examples of the polycondensable monomer that can be used in the polycondensation reaction include polyvalent carboxylic acids, polyols, hydroxycarboxylic acids, or mixtures thereof, and use at least polyvalent carboxylic acids and polyols. Is preferred. The polycondensable monomer is preferably a polyvalent carboxylic acid and a polyol, and more preferably an ester compound (oligomer and / or prepolymer) thereof. A polyester is obtained through a direct ester reaction or a transesterification reaction. What you get is good. In this case, the polycondensed polyester resin can take any form such as amorphous (amorphous) polyester (non-crystalline polyester), crystalline polyester, or a mixed form thereof.
The polyester that can be used in the present invention is preferably a polyester having a terminal carboxy group, and is preferably an amorphous polyester.

(1) Polyvalent carboxylic acid A polyvalent carboxylic acid is a compound containing two or more carboxy groups in one molecule. Of these, dicarboxylic acid is a compound containing two carboxy groups in one molecule, and is oxalic acid, succinic acid, fumaric acid, maleic acid, adipic acid, β-methyladipic acid, malic acid, malonic acid, pimelic acid. , Tartaric acid, azelaic acid, pimelic acid, sebacic acid, nonanedicarboxylic acid, decanedicarboxylic acid, undecanedicarboxylic acid, dodecanedicarboxylic acid, citraconic acid, cyclohexane-3,5-diene-1,2-carboxylic acid, citric acid, hexa Hydroterephthalic acid, mucous acid, phthalic acid, isophthalic acid, terephthalic acid, tetrachlorophthalic acid, chlorophthalic acid, nitrophthalic acid, p-carboxyphenylacetic acid, p-phenylene dipropionic acid, m-phenylene dipropionic acid, m -Phenylenediacetic acid, p-phenylenediacetic acid, o-pheny Diacetic acid, diphenyldiacetic acid, diphenyl-p, p'-dicarboxylic acid, 1,1-cyclopentenedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 1,2-cyclohexanedicarboxylic acid, 1,2-cyclohexene dicarboxylic acid, norbornene-2,3-dicarboxylic acid, 1,3-adamantane dicarboxylic acid, 1,3-adamantane diacetic acid, naphthalene-1,4-dicarboxylic acid, naphthalene-1,5-dicarboxylic acid , Naphthalene-2,6-dicarboxylic acid, anthracene dicarboxylic acid and the like.
Examples of the polyvalent carboxylic acid other than dicarboxylic acid include trimellitic acid, pyromellitic acid, naphthalenetricarboxylic acid, naphthalenetetracarboxylic acid, pyrenetricarboxylic acid, and pyrenetetracarboxylic acid.
The carboxylic acid may have a functional group other than a carboxy group, and a carboxylic acid derivative such as an acid anhydride or an acid ester may be used.

Among these polycarboxylic acids, monomers preferably used are sebacic acid, nonanedicarboxylic acid, decanedicarboxylic acid, undecanedicarboxylic acid, dodecanedicarboxylic acid, p-phenylenediacetic acid, m-phenylenediacetic acid, p-phenylenediprote. Pionic acid, m-phenylene dipropionic acid, 1,4-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, naphthalene-1,4-dicarboxylic acid, naphthalene-1,5-dicarboxylic acid, naphthalene-2, 6-dicarboxylic acid, trimellitic acid, pyromellitic acid.
Examples of the polyvalent carboxylic acid other than dicarboxylic acid include trimellitic acid, pyromellitic acid, naphthalenetricarboxylic acid, naphthalenetetracarboxylic acid, pyrenetricarboxylic acid, pyrenetetracarboxylic acid, and the like. Examples include lower esters of acids. The acid chloride is not limited to this.
These may be used alone or in combination of two or more.
In addition, a lower ester shows that the carbon number of the alkoxy part of ester is 1-8. Specific examples include methyl ester, ethyl ester, n-propyl ester, isopropyl ester, n-butyl ester, and isobutyl ester.

(2) Polyol A polyol is a compound containing two or more hydroxyl groups in one molecule. Although it does not specifically limit as a polyol, The following monomer can be mentioned.
Diol is a compound containing two hydroxyl groups in one molecule, such as propanediol, butanediol, pentanediol, hexanediol, heptanediol, octanediol, nonanediol, decanediol, dodecanediol, tetradecanediol, octadecanediol, etc. It can be illustrated.
Examples of polyols other than diols include glycol, propanetriol, pentaerythritol, hexamethylol melamine, hexaethylol melamine, tetramethylol benzoguanamine, and tetraethylol benzoguanamine.
Moreover, the following monomer can be mentioned as a polyol which has a cyclic structure. For example, cyclohexanediol, cyclohexanedimethanol, bisphenol A, bisphenol C, bisphenol E, bisphenol F, bisphenol P, bisphenol S, bisphenol Z, hydrogenated bisphenol, biphenol, naphthalenediol, 1,3-adamantanediol, 1,3- Examples thereof include, but are not limited to, adamantane dimethanol and 1,3-adamantane diethanol.
In the present invention, the bisphenols preferably have at least one alkylene oxide group. Examples of the alkylene oxide group include, but are not limited to, an ethylene oxide group, a propylene oxide group, and butylene oxide. Preferably, they are ethylene oxide and propylene oxide, and the added mole number is preferably 1 to 3. When it is within this range, the viscoelasticity and glass transition temperature of the produced polyester can be appropriately controlled for use as a toner.
Among the above-mentioned monomers, hexanediol, cyclohexanediol, octanediol, decanediol, dodecanediol, bisphenol A, bisphenol C, bisphenol E, bisphenol S, bisphenol Z are preferably used. These are alkylene oxide adducts.

(3) Hydroxycarboxylic acid Hydroxycarboxylic acid is a compound containing carboxylic acid and hydroxyl group in one molecule. Polycondensation can also be performed using a hydroxycarboxylic acid compound. Examples include hydroxyoctanoic acid, hydroxynonanoic acid, hydroxydecanoic acid, hydroxyundecanoic acid, hydroxydodecanoic acid, hydroxytetradecanoic acid, hydroxytridecanoic acid, hydroxyhexadecanoic acid, hydroxypentadecanoic acid, hydroxystearic acid, and the like. It is not meant to be limited to this.

You may use a polycondensable monomer combining 2 or more types by arbitrary ratios. In addition, an amorphous resin or a crystalline resin can be easily obtained by combining these polycondensable monomers. The polycondensation resin of the present invention is preferably one obtained by polycondensation of a dicarboxylic acid and a diol, and may have a carboxy group at the molecular end with a slight excess of dicarboxylic acid.
When the dicarboxylic acid is used in a slight excess, it is preferable to make the dicarboxylic acid excessive by 0.1 to 2 mol% with respect to the diol. When the dicarboxylic acid is used in excess of the above range, the resin terminal carboxy group increases and the acid value increases, which is advantageous for obtaining a resin particle dispersion, but there are unreacted residual monomers and reactivity. If the resin is used for toner, offset may occur when fixing in a high temperature region.

(4) Crystalline polyester For example, the polyvalent carboxylic acid used to obtain the crystalline polyester includes oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, peric acid, azelaic acid, sebacin Acid, maleic acid, fumaric acid, citraconic acid, itaconic acid, glutamic acid, n-dodecyl succinic acid, n-dodecenyl succinic acid, isododecyl succinic acid, isododecenyl succinic acid, n-octyl succinic acid, n-octenyl succinic acid These acid anhydrides or lower esters thereof can be exemplified. Furthermore, the acid chloride is not limited to this.

  Furthermore, as the polyol that can be used to obtain the crystalline polyester, ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, 1, Examples include 4-butenediol, neopentyl glycol, 1,5-pentanediol, 1,6-hexanediol, dipropylene glycol, polyethylene glycol, polypropylene glycol, and polytetramethylene glycol.

  Examples of such crystalline polyester include polyesters obtained by reacting 1,9-nonanediol and 1,10-decanedicarboxylic acid, or cyclohexanediol and adipic acid, 1,6-hexanediol and sebacic acid, and the like. Polyester obtained by reacting, polyester obtained by reacting ethylene glycol and succinic acid, polyester obtained by reacting ethylene glycol and sebacic acid, reacting 1,4-butanediol and succinic acid Mention may be made of the polyester obtained. Among these, polyesters obtained by reacting 1,9-nonanediol with 1,10-decanedicarboxylic acid and 1,6-hexanediol with sebacic acid are more preferable, but not limited thereto.

(5) Amorphous polyester Furthermore, polyvalent carboxylic acids that can be used to obtain an amorphous polyester include phthalic acid, isophthalic acid, terephthalic acid, naphthalene-2,6-dicarboxylic acid, and malonic acid. Examples thereof include aromatic dicarboxylic acids such as dibasic acids such as mesaconic acid, and lower esters thereof. Examples of the trivalent or higher carboxylic acid include 1,2,4-benzenetricarboxylic acid, 1,3,5-benzenetricarboxylic acid, 1,2,4-naphthalenetricarboxylic acid, and anhydrides thereof, 2-sulfo Examples include, but are not limited to, sodium terephthalate, sodium 5-sulfoisophthalate, sodium sulfosuccinate and lower esters thereof.

  Examples of the polyhydric alcohol that can be used to obtain an amorphous polyester include aliphatic, alicyclic, and aromatic polyhydric alcohols. Specifically, 1,4-cyclohexanediol, 1 , 4-cyclohexanedimethanol, bisphenol A, bisphenol Z, hydrogenated bisphenol A and the like can be preferably exemplified, but not limited thereto.

  Here, the crystalline melting point Tm in the case of a crystalline resin is preferably 50 to 120 ° C, more preferably 55 to 90 ° C. When the Tm is 50 ° C. or higher, the cohesive force of the binder resin itself in a high temperature range is good, and therefore excellent in releasability and hot offset property during fixing. A Tm of 120 ° C. or lower is preferable because sufficient melting cannot be obtained and the minimum fixing temperature is hardly increased.

  On the other hand, when the polycondensable resin particles are non-crystalline, the glass transition point Tg is preferably 50 to 80 ° C., more preferably 50 to 65 ° C. When the Tg is 50 ° C. or higher, the cohesive force of the binder resin itself in a high temperature range is good, so that it is excellent in hot offset property at the time of fixing. A Tg of 80 ° C. or lower is preferable because sufficient melting can be obtained and the minimum fixing temperature is hardly increased.

  Here, the melting point of the crystalline resin was measured using a differential scanning calorimeter (DSC) according to JIS K-7121: 87 when the measurement was performed from room temperature to 150 ° C. at a heating rate of 10 ° C. per minute. It can be determined as the melting peak temperature of the input compensated differential scanning calorimetry shown. A crystalline resin may show a plurality of melting peaks, but in the present invention, the maximum peak is regarded as the melting point. Here, the glass transition point of an amorphous resin means the value measured by the method (DSC method) prescribed | regulated to ASTMD3418-82. “Crystallinity” as shown in the above “crystalline polyester resin” means that, in differential scanning calorimetry (DSC), it has a clear endothermic peak rather than a stepwise endothermic change. Means that the half-value width of the endothermic peak when measured at a heating rate of 10 ° C./min is within 6 ° C. On the other hand, a resin having an endothermic peak with a half-value width exceeding 6 ° C. or a resin having no clear endothermic peak means non-crystalline (amorphous).

The amount of the basic substance contained in the resin particle dispersion is required to have the following relationship (1) when the molar amount of the sulfur acid is A and the molar amount of the basic substance is B. .
1.0 × A ≦ B ≦ 400 × A (1)
Furthermore, it is preferable that 1.05 × A ≦ B ≦ 180 × A,
It is more preferable that 1.1 × A ≦ B ≦ 150 × A.
When B is less than 1.0 (the amount of basic substance is small), a sufficient deactivation effect cannot be obtained, the hue stability of the resin cannot be obtained, and the area is low under high temperature and high humidity storage. The phenomenon that the brightness of the coverage image sample decreases cannot be sufficiently suppressed. When B exceeds 400 A (the amount of the basic substance is large), the acid catalyst is not only sufficiently deactivated, but also the terminal carboxyl group of the resin is excessively neutralized. For this reason, a suitable resin particle dispersion cannot be obtained.

  The pH of the resin particle dispersion in the present invention is 6 or more and 10 or less. The pH of the resin particle dispersion is preferably 6.5 or more and 9.8 or less, and more preferably 6.8 or more and 9.5 or less. When the pH is less than 6, the neutralization rate of the carboxy group at the end of the resin is not controlled within a suitable range, and a sufficient solid content concentration cannot be obtained or is necessary for use in a resin particle dispersion for toner. A large particle size distribution may not be obtained. On the other hand, when the pH exceeds 10, the resin terminal carboxy group is also excessively neutralized, so that a resin particle dispersion suitable for use in toner may not be obtained.

  The median diameter (center diameter) of the resin particles in the resin particle dispersion of the present invention is preferably 0.1 μm or more and 2.0 μm or less, more preferably 0.1 μm or more and 1.0 μm or less, and 0.15 μm. The thickness is particularly preferably 0.8 μm or less. When the median diameter is in the above range, the dispersion state of the resin particles in the aqueous medium is stabilized, and the toner obtained from the toner is difficult to release a release agent such as wax. Excellent in properties. The median diameter of the resin particles can be measured, for example, with a laser diffraction particle size distribution measuring device (LA-920, manufactured by Horiba, Ltd.).

  In addition, the resin particle dispersion of the present invention has a median diameter of 0.03 μm or less or 5.0 μm or more from the viewpoint of not having the above-mentioned median diameter and generation of ultrafine powder or ultracoarse powder. The ratio of the particles is preferably 10% or less, and more preferably 5% or less. This ratio can be obtained, for example, by plotting the relationship between the particle diameter and the frequency integration in the measurement result in LA-920 and obtaining from the frequency integration amount of 0.03 μm or less or 5.0 μm or more.

The resin particle dispersion of the present invention is obtained by collecting the dispersion in a small amount of a test tube (for example, a 50 mL centrifuge tube made of polypropylene (30 mm diameter × 1 height 118 mm) and centrifuging at 2,000 rpm × 10 minutes. When the sample is collected with a dropper from the supernatant and the bottom of each sample and the particle size is measured, the ratio between the _{median diameter at the} top of the dispersion (upper _{median diameter} ) and the median diameter at the bottom of the dispersion (lower _{median diameter} ) (upper _{median diameter)} / Lower _{median diameter} ) is preferably 0.80 to 1, more preferably 0.90 to 1. As the centrifuge that can be used for the centrifugation, a Hitachi small tabletop centrifuge (himac CT4i) (manufactured by Hitachi High-Tech) can be preferably used.

  Moreover, the weight average molecular weight of the polyester obtained by polycondensation of a polycondensable monomer is preferably 1,500 to 55,000, and more preferably 3,000 to 45,000. When the weight average molecular weight is 1,500 or more, the cohesive force of the binder resin is good and the hot offset property is excellent, and when it is 55,000 or less, the minimum hot offset property fixing temperature is preferable. Further, it may be partially branched or cross-linked by selecting the carboxylic acid valence or alcohol valence of the monomer.

  The dispersion medium of the resin particle dispersion of the present invention is an aqueous medium. Examples of the aqueous medium that can be used in the present invention include water such as distilled water and ion exchange water, and alcohols such as ethanol and methanol. Among these, ethanol and water are preferable, and water such as distilled water and ion-exchanged water is particularly preferable. These may be used individually by 1 type and may use 2 or more types together. The aqueous medium may contain a water-miscible organic solvent. Examples of the water-miscible organic solvent include acetone and acetic acid.

  The solid content in the aqueous medium in the resin particle dispersion of the present invention is preferably 5 to 50 parts by weight, more preferably 10 to 45 parts by weight, and still more preferably 10 to 45 parts by weight with respect to 100 parts by weight of the resin particle dispersion. 40 parts by weight, most preferably 15-40 parts by weight. When the solid content is 50 parts by weight or less, the fluidity of the latex is good and the cream mousse is not deteriorated depending on the storage conditions. When the amount is 5% by weight or more, when the toner is prepared using the present dispersion, the ratio of the present dispersion in the total composition does not increase, the composition can be easily adjusted, and the cost during transportation can be suppressed. In the polymerization in the aqueous medium, in addition to the monomer components before polymerization, a colorant, wax and the like described later can be mixed in advance. By such a method, resin particles can be obtained in a form incorporating a colorant or wax.

  When the polyester is dispersed in an aqueous medium, the above materials are dispersed in the aqueous medium using, for example, mechanical shear or ultrasonic waves. In this dispersion, a surfactant or a polymer is used as necessary. It is also possible to add a dispersant, an inorganic dispersant and the like to the aqueous medium. Further, an aqueous medium may be added to a mixture (oil phase) containing polyester, and finally the polyester may be emulsified and dispersed in the aqueous medium.

  In order to increase the dispersion efficiency and improve the stability of the resin particle dispersion, a surfactant described later can be added to the resin particle dispersion of the present invention. Examples of the surfactant that can be used in the present invention include anionic surfactants such as sulfate ester, sulfonate, and phosphate ester; cationic surfactants such as amine salt type and quaternary ammonium salt type. Agents: Nonionic surfactants such as polyethylene glycol, alkylphenol ethylene oxide adducts, polyhydric alcohols, and the like. Among these, anionic surfactants and cationic surfactants are preferable. The nonionic surfactant is preferably used in combination with the anionic surfactant or the cationic surfactant. The said surfactant may be used individually by 1 type, and may use 2 or more types together.

  Anionic surfactants include sodium dodecylbenzenesulfonate, sodium alkylnaphthalenesulfonate, sodium arylalkylpolyethersulfonate, 3,3′-disulfonediphenylurea-4,4′-diazo-bis-amino-8-naphthol Sodium 6-sulfonate, ortho-carboxybenzene-azo-dimethylaniline, 2,2 ′, 5,5′-tetramethyltriphenylmethane-4,4′-diazo-bis-β-naphthol-6-sulfonic acid Sodium, sodium dialkylsulfosuccinate, sodium dodecyl sulfate, sodium tetradecyl sulfate, sodium pentadecyl sulfate, sodium octyl sulfate, sodium oleate, sodium laurate, sodium caprate, sodium caprylate, Sodium Ron, potassium stearate, and the like calcium oleate.

  Examples of the cationic surfactant include alkylbenzene dimethyl ammonium chloride, alkyl trimethyl ammonium chloride, distearyl ammonium chloride and the like.

  Nonionic surfactants include, for example, polyethylene oxide, polypropylene oxide, combinations of polypropylene oxide and polyethylene oxide, esters of polyethylene glycol and higher fatty acids, alkylphenol polyethylene oxide, esters of higher fatty acids and polyethylene glycol, higher fatty acids and polypropylene. Examples include oxide esters and sorbitan esters.

Further, a polymer dispersant or a stabilizing aid may be added to the resin particle dispersion of the present invention.
Examples of the polymer dispersant include sodium polycarboxylate and polyvinyl alcohol, and examples of the inorganic dispersant include calcium carbonate. However, these do not limit the present invention.

  Further, in order to prevent the Ostwald Ripping phenomenon of the monomer emulsion particles in an ordinary aqueous medium, a higher alcohol represented by heptanol or octanol or a higher aliphatic hydrocarbon represented by hexadecane is often added as a stabilizer. It is also possible.

  Further, in the present invention, in addition to the polycondensable monomer, an addition polymerizable monomer, preferably a radical polymerizable monomer, may be added as necessary, so that polycondensation and addition polymerization are performed simultaneously. Alternatively, it may be performed separately and combined. Examples of the addition polymerizable monomer include a cationic polymerizable monomer and a radical polymerizable monomer, and a radical polymerizable monomer is preferable.

  Specific examples of the radical polymerizable monomer used in this case include α-substituted styrene such as styrene, α-methylstyrene, α-ethylstyrene, m-methylstyrene, p-methylstyrene, 2 , Vinyl aromatics such as nucleus-substituted styrene such as 5-dimethylstyrene, nucleus-substituted halogenated styrene such as p-chlorostyrene, p-bromostyrene and dibromostyrene, (meth) acrylic acid (in addition, “(meth) acrylic” "Means acrylic and methacrylic, and the same shall apply hereinafter.), Unsaturated carboxylic acids such as crotonic acid, maleic acid, fumaric acid, citraconic acid, itaconic acid, methyl (meth) acrylate, ethyl ( (Meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, pentyl (meth) acrylate Unsaturated carboxylic acid esters such as hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, glycidyl (meth) acrylate, benzyl (meth) acrylate, (meth) acrylaldehyde, (meth) acrylonitrile, (meth) acrylamide, etc. Unsaturated carboxylic acid derivatives, N-vinyl compounds such as N-vinyl pyridine and N-vinyl pyrrolidone, vinyl esters such as vinyl formate, vinyl acetate and vinyl propionate, vinyl chloride, vinyl bromide, vinylidene chloride, etc. Halogenated vinyl compounds, N-methylol acrylamide, N-ethylol acrylamide, N-propanol acrylamide, N-methylol maleamic acid, N-methylol maleamic acid ester, N-methylol maleimide, N-ethylo N-substituted unsaturated amides such as lumaleimide, conjugated dienes such as butadiene and isoprene, polyfunctional vinyl compounds such as divinylbenzene, divinylnaphthalene and divinylcyclohexane, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate , Propylene glycol di (meth) acrylate, tetramethylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, hexamethylene glycol di (meth) acrylate, trimethylolpropane di (meth) acrylate, trimethylolpropane tri ( (Meth) acrylate, glycerol di (meth) acrylate, glycerol tri (meth) acrylate, pentaerythritol di (meth) acrylate, pentaerythrito Tritrimethacrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol di (meth) acrylate, dipentaerythritol tri (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, Examples include polyfunctional acrylates such as dipentaerythritol hexa (meth) acrylate, sorbitol tri (meth) acrylate, sorbitol tetra (meth) acrylate, sorbitol penta (meth) acrylate, and sorbitol hexa (meth) acrylate. Among these, N-substituted unsaturated amides, conjugated dienes, polyfunctional vinyl compounds, polyfunctional acrylates, and the like can also cause a crosslinking reaction in the produced polymer. These can be used alone or in combination.

  The addition polymerizable monomer, particularly a radical polymerizable monomer, can be polymerized by a method using a radical polymerization initiator, a self-polymerization by heat, a method using ultraviolet irradiation, or a known polymerization method. In this case, the radical initiator may be oil-soluble or water-soluble as a method using a radical initiator, but either initiator may be used. Specifically, for example, 2,2′-azobis (2-methylpropionitrile), 2,2′-azobis (2-methylbutyronitrile), 2,2′-azobisisobutyronitrile, 2 , 2'-azobis (2,4-dimethylvaleronitrile), 2,2'-azobis (2,4-dimethyl-4-methoxyvaleronitrile), 1,1'-azobis (cyclohexanecarbonitrile), 2,2 Azobisnitriles such as' -azobis (2-amidinopropane) hydrochloride, acetyl peroxide, octanoyl peroxide, 3,5,5-trimethylhexanoyl peroxide, decanoyl peroxide, lauroyl peroxide, benzoyl peroxide Diacyl peroxide such as oxide, di-t-butyl peroxide, t-butyl-α-kumi Dialkyl peroxides such as peroxide and dicumyl peroxide, t-butyl peroxyacetate, α-cumyl peroxypivalate, t-butyl peroxyoctoate, t-butylperoxyneodecanoate, t-butylperoxide Peroxyesters such as oxylaurate, t-butylperoxybenzoate, di-t-butylperoxyphthalate, di-t-butylperoxyisophthalate, t-butylhydroperoxide, 2,5-dimethylhexane-2 , 5-dihydroperoxide, cumene hydroperoxide, hydroperoxide such as di-isopropylbenzene hydroperoxide, organic peroxides such as peroxycarbonate such as t-butylperoxyisopropyl carbonate, hydrogen peroxide, etc. Inorganic excess Products such as potassium persulfate, sodium persulfate, radical polymerization initiators such as persulfates such as ammonium persulfate. A redox polymerization initiator may be used in combination. Moreover, you may use a chain transfer agent at the time of addition polymerization. There is no restriction | limiting in particular as a chain transfer agent, Specifically, what has the covalent bond of a carbon atom and a sulfur atom is preferable, For example, thiols are mentioned preferably.

In the present invention, a cosurfactant can be used in combination in order to keep the average particle size of the polyester-containing material (oil phase) containing the addition polymerizable monomer within a specific range. As the co-surfactant, those which are water-insoluble or hardly soluble and monomer-soluble, and those used in the conventionally known “miniemulsion polymerization” described later in detail can be used.
Examples of suitable cosurfactants include alkanes having 8 to 30 carbon atoms such as dodecane, hexadecane and octadecane, alkyl alcohols having 8 to 30 carbon atoms such as lauryl alcohol, cetyl alcohol and stearyl alcohol, lauryl (meta C8-C30 alkyl (meth) acrylates such as acrylate, cetyl (meth) acrylate, stearyl (meth) acrylate, C8-C30 alkyl mercaptans such as lauryl mercaptan, cetyl mercaptan, stearyl mercaptan, and the like. Other examples include polymers such as polystyrene and polymethyl methacrylate, polyadducts, carboxylic acids, ketones, and amines.

<Polycondensation catalyst>
In the polycondensation of the polycondensable monomer in the present invention, a polycondensation catalyst is preferably used because the reaction rate of the polycondensation reaction can be increased. At the time of polycondensation, a known polycondensation catalyst can be blended in the polycondensable monomer in advance if necessary. In order to polycondense a polycondensable monomer at a low temperature of 150 ° C. or lower or 100 ° C. or lower, a polycondensation catalyst is usually used. As the polycondensable catalyst having catalytic activity at a low temperature, an acid catalyst, a rare earth-containing catalyst, a hydrolase, or the like can be used, and among these, an acid catalyst is preferable.

(1) Acid-based catalyst As the acid-based catalyst, sulfur acid is used, but sulfur acid which is Bronsted acid is preferable, and salts thereof can also be used.
Furthermore, an acid having a surface active effect may be used. The acid having a surface-active effect has a chemical structure composed of a hydrophobic group and a hydrophilic group, and has an acid structure in which at least a part of the hydrophilic group is composed of protons.

  Examples of the sulfur acid include inorganic sulfur acid and organic sulfur acid. Examples of the inorganic sulfur acid include sulfuric acid, sulfurous acid, and salts thereof, and examples of the organic sulfur acid include sulfonic acids such as alkyl sulfonic acid, aryl sulfonic acid, and salts thereof, alkyl sulfuric acid, Organic sulfuric acids such as aryl sulfuric acid and salts thereof are mentioned. The sulfur acid is preferably an organic sulfur acid, and more preferably an organic sulfur acid having a surface active effect.

  Examples of the organic sulfur acid having a surface active effect include alkylbenzene sulfonic acid, alkyl sulfonic acid, alkyl disulfonic acid, alkyl phenol sulfonic acid, alkyl naphthalene sulfonic acid, alkyl tetralin sulfonic acid, alkyl allyl sulfonic acid, petroleum sulfonic acid, alkyl benzoic acid. Imidazole sulfonic acid, higher alcohol ether sulfonic acid, alkyl diphenyl sulfonic acid, long chain alkyl sulfate, higher alcohol sulfate, higher alcohol ether sulfate, higher fatty acid amide alkylol sulfate, higher fatty acid amide alkylated sulfate, sulfate Fat, sulfosuccinic acid ester, resin acid alcohol sulfuric acid, and all salt compounds thereof may be mentioned, and a plurality of them may be combined as necessary. Among these, a sulfonic acid having an alkyl group or an aralkyl group, a sulfate ester having an alkyl group or an aralkyl group, or a salt compound thereof is preferable, and the alkyl group or the aralkyl group has 7 to 20 carbon atoms. More preferably. Specific examples include dodecylbenzenesulfonic acid, isopropylbenzenesulfonic acid, camphorsulfonic acid, paratoluenesulfonic acid, monobutylphenylphenol sulfate, dibutylphenylphenol sulfate, dodecyl sulfate, naphthenyl alcohol sulfate, and the like.

Examples of acids having surface-active effects other than the above that can be used in combination with sulfur acids include various fatty acids, sulfonated higher fatty acids, higher alkyl phosphates, resin acids, naphthenic acids, and all salt compounds thereof. Etc. can be exemplified.
These polycondensation catalysts may be used alone or in combination. Further, these catalysts can be recovered and regenerated if necessary.

Further, as the polycondensation catalyst at the time of polycondensation, the above-mentioned sulfur acid and a basic substance may be used in combination. For example, a salt of sulfur acid and a basic substance, a mixture of sulfur acid and a basic substance, or the like is used. be able to.
When sulfur acid and a basic substance are used in combination at the time of polycondensation, they may be mixed at the time of polycondensation or premixed, and the sulfur acid and basic substance may be reacted in advance, You may isolate and use as a salt, and you may produce | generate and use by salt exchange etc. in a polycondensation reaction system.
When the sulfur acid and the basic substance are used in combination, coloring can be suppressed more than in the case of using only the sulfur acid, and the environmental dependency of charging in the toner using the polyester resin as a binder resin can be suppressed. It is preferable because it can prevent the dependency of the toner on the environment due to the deterioration of the chargeability due to the sulfur acid. This is presumably because the basic substance reacts with the sulfur acid remaining in the reaction system to suppress the coordination of the sulfur acid to the ester bond site, thereby preventing coloring.
The basic substance that can be used in combination with the sulfur acid at the time of polycondensation can preferably be a basic substance that can be used at the time of polycondensation stoppage described below, at the time of dispersion, at the time of emulsion dispersion, etc. Alternatively, they may be the same as or different from the basic substances used for dispersion, emulsification dispersion, and the like. Moreover, when using together a sulfuric acid and a basic substance at the time of polycondensation, it is preferable that the basic substance used at the time of polycondensation is a thing with a basicity smaller than the basic substance used at the time of a polymerization stop.
Specifically, triethylamine, tributylamine, trioctylamine, tripropylamine, triphenylamine, dibenzylmethylamine, N, N-dimethylbenzylamine and the like can be mentioned more preferably. N, N-dimethylbenzylamine Can be more preferably used.
Further, the basic substance that can be used in combination with the sulfur acid at the time of polycondensation is preferably a tertiary amine, which has less steric hindrance and is easy to coordinate to the monomer in view of the ease of coordination to the monomer. More preferably, the three substituents on the nitrogen atom are tertiary amines independently selected from the group consisting of a methyl group, a phenyl group, a benzyl group and a toluyl group.
The ratio of sulfur acid and basic substance used during polycondensation is in the range of (acid amount in sulfur acid) :( base amount in basic substance) = 1: 0.1 to 1: 1 as a molar ratio. It is particularly preferable that the ratio is in the range of 1: 0.1 to 1: 0.5.

<Method for producing resin particle dispersion>
The resin particle dispersion of the present invention is preferably produced by the production method shown below.
The method for producing a resin particle dispersion of the present invention includes a step of obtaining a polyester having a terminal carboxy group by polycondensation of a polycondensable monomer (hereinafter also referred to as “polycondensation step”), and adding a basic substance. Then, the step of stopping the polycondensation reaction to obtain a binder resin (hereinafter also referred to as “polycondensation stopping step”), the step of dispersing the polyester in an aqueous medium (hereinafter also referred to as “dispersing step”). And it is preferable that it is a method including the process (henceforth a "neutralization process") which neutralizes a part of terminal carboxy group in the said polyester.
Moreover, the manufacturing method of the resin particle dispersion of this invention may include the other process mentioned later and the arbitrary processes well-known as needed.

(1) Polycondensation Step The method for producing a resin particle dispersion of the present invention preferably includes a step of obtaining a polyester having a terminal carboxy group by polycondensation of a polycondensable monomer.

  The reaction temperature of the polycondensation reaction in the polycondensation step is preferably reacted at a temperature lower than the conventional reaction temperature. The reaction temperature is preferably 70 to 150 ° C, more preferably 70 ° C to 140 ° C, and further preferably 80 ° C to less than 140 ° C. It is preferable that the reaction temperature is 70 ° C. or higher because the solubility of the monomer and the catalyst activity are not lowered, the reactivity is sufficiently high, and the molecular weight elongation is not suppressed. Moreover, it is preferable for the reaction temperature to be 150 ° C. or lower because the purpose of the low energy production method can be achieved. Furthermore, it is preferable because coloring of the resin due to high temperature and decomposition of the produced polyester are difficult to occur. Moreover, although the reaction time at the time of polycondensation is dependent also on reaction temperature, 0.5 to 72 hours are preferable and 1 to 48 hours are more preferable.

  The polycondensation reaction in the polycondensation step of the present invention can be carried out by general polycondensation methods such as underwater polymerization such as bulk polymerization, emulsion polymerization and suspension polymerization, solution polymerization and interfacial polymerization. Bulk polymerization or water polymerization is used. Although the reaction is possible under atmospheric pressure, general conditions such as reduced pressure and nitrogen flow can be widely used for the purpose of increasing the molecular weight of the polyester.

  The polycondensation reaction in the polycondensation step may be performed in an aqueous medium. The aqueous medium that can be used for the polycondensation reaction is the same as the above-mentioned aqueous medium, and the preferred range is also the same.

  The polycondensation reaction in the polycondensation step may be performed using an organic solvent. Specific examples of the organic solvent that can be used in the present invention include, for example, hydrocarbon solvents such as toluene, xylene, mesitylene, chlorobenzene, bromobenzene, iodobenzene, dichlorobenzene, 1,1,2,2-tetrachloroethane. Halogen solvents such as p-chlorotoluene, ketone solvents such as 3-hexanone, acetophenone and benzophenone, dibutyl ether, anisole, phenetole, o-dimethoxybenzene, p-dimethoxybenzene, 3-methoxytoluene, dibenzyl ether, Ether solvents such as benzyl phenyl ether, methoxynaphthalene and tetrahydrofuran, thioether solvents such as phenyl sulfide and thioanisole, ethyl acetate, butyl acetate, pentyl acetate, methyl benzoate, methyl phthalate, phthalic acid Ester solvents such as chill and cellosolve acetate, diphenyl ether, or alkyl-substituted diphenyl ethers such as 4-methylphenyl ether, 3-methylphenyl ether, and 3-phenoxytoluene, or 4-bromophenyl ether, 4-chlorophenyl ether, 4 -Halogen-substituted diphenyl ethers such as bromodiphenyl ether and 4-methyl-4'-bromodiphenyl ether, or alkoxy such as 4-methoxydiphenyl ether, 4-methoxyphenyl ether, 3-methoxyphenyl ether, 4-methyl-4'-methoxydiphenyl ether Examples thereof include diphenyl ether solvents such as substituted diphenyl ethers and cyclic diphenyl ethers such as dibenzofuran and xanthene, and these may be used in combination. A solvent that can be easily separated from water is preferable. In order to obtain a polyester having a high average molecular weight, an ester solvent, an ether solvent, and a diphenyl ether solvent are more preferable, and an alkyl-aryl ether solvent and an ester are preferable. System solvents are particularly preferred.

  Furthermore, in the present invention, in order to obtain a binder resin having a high average molecular weight, a dehydration and demonomer agent may be added to the organic solvent. Specific examples of the dehydration and demonomer include, for example, molecular sieves such as molecular sieve 3A, molecular sieve 4A, molecular sieve 5A, molecular sieve 13X, alumina, silica gel, calcium chloride, calcium sulfate, diphosphorus pentoxide, concentrated Examples include sulfuric acid, magnesium perchlorate, barium oxide, calcium oxide, potassium hydroxide, sodium hydroxide, metal hydrides such as calcium hydride, sodium hydride, lithium aluminum hydride, or alkali metals such as sodium. It is done. Among these, molecular sieves are preferable because of easy handling and regeneration.

(2) Polycondensation stop, neutralization step Since the acid catalyst remains in the polyester polycondensation resin using the acid catalyst, the hue stability of the resin with time is low. Therefore, when a resin particle dispersion is prepared using the resin and a toner is obtained, especially when stored for a long time under a high temperature and high humidity environment, the resin particle dispersion has a constant resin terminal neutralization rate as described above. Even so, when a print with a low area coverage (AC ≦ 5%) is obtained, a phenomenon occurs in which the lightness (L ^* ) becomes dark or the saturation falls. The change in hue of the resin over time is caused by the fact that protons released from the acid catalyst form hydrogen bonds with the oxygen atoms of the carboxy group and weaken the double bond properties of the carboxy group. Because it changes. The above-described hue stability over time can be improved by allowing a basic substance capable of deactivating the acid catalyst to coexist in the resin particle dispersion. The basic substance is not particularly limited as long as it is a basic substance that can react with the acid used for the catalyst. The basic substance will be described later. Nitrogen-containing basic substances such as triethanolamine, 2-vinylpyridine, aniline and N, N-diethylbenzylamine can be preferably used in the polycondensation termination step.

In the present invention, the basic substance can be used not only for deactivating the acid catalyst, but also as a neutralizing emulsifier for neutralizing the terminal carboxy group of the polyester. The neutralizing emulsifier is not particularly limited as long as it is a basic compound capable of causing a neutralization reaction with the carboxy group of the polyester resin, and M (OH) _n (M is an alkali metal or an alkaline earth metal, Examples thereof include a metal hydroxide having a chemical formula of n = 1 to 3) and an ammonium compound.
Among the above neutralizing emulsifiers, when a metal hydroxide or an aqueous solution thereof is used, there is a concern of coloring due to residual metal. When a metal hydroxide aqueous solution is used as a deactivation / emulsifier, since a part of the resin may start to be emulsified earlier than the deactivation reaction, a resin particle dispersion is prepared without sufficient deactivation. Sometimes.

(3) Dispersing Step The method for producing a resin particle dispersion of the present invention is preferably a step of dispersing the polyester in an aqueous medium. In the dispersion step, it is preferable to perform dispersion by adding a surfactant or the like in order to increase the dispersion efficiency or improve the stability of the resin particle dispersion.

  The method for dispersing and granulating the polyester in an aqueous medium can be selected from known methods such as forced emulsification, self-emulsification, and phase inversion emulsification. Of these, the self-emulsification method and the phase inversion emulsification method are preferably applied in consideration of the energy required for emulsification, the particle size controllability of the obtained emulsion, stability, and the like. The self-emulsification method and the phase inversion emulsification method are described in “Application Technology of Ultrafine Particle Polymer (CMC Publishing)”. Moreover, since the said polyester has a terminal carboxy group and also neutralizes a part thereof, the self-emulsification method is more preferably used.

  When an organic solvent is used in the dispersion step, the method for producing a resin particle dispersion of the present invention may include a step of removing at least a part of the organic solvent and a step of forming resin particles. For example, after emulsifying the content of the polyester having a terminal carboxy group, it is preferable to solidify as particles by removing a part of the organic solvent. As a specific method of solidification, after the polyester content is emulsified and dispersed in an aqueous medium, an inert gas such as air or nitrogen is sent in while stirring the solution, and the organic solvent at the gas-liquid interface is mixed. A method of drying (waste wind drying method), a method of drying while holding under reduced pressure and bubbling an inert gas as necessary (pressure reduction topping method), and further, polyester-containing material in an aqueous medium For example, there is a method of discharging an emulsified dispersion or an emulsified dispersion of a polyester-containing material into a shower-like shape from a pore, and dropping it into a dish-shaped receiver and drying it repeatedly (shower-type solvent removal method). It is preferable to remove the solvent by selecting or combining these methods as appropriate based on the evaporation rate of the organic solvent to be used, the solubility in water, and the like.

  Examples of a method for dispersing and granulating the polyester in an aqueous medium include, for example, a suspension polymerization method, a dissolution suspension method, a miniemulsion method, a microemulsion method in an aqueous medium when the polyester is produced. Examples of the method include a multistage swelling method and an emulsion polymerization method including seed polymerization.

  There is no particular limitation on the basic substance used when the polycondensation resin is dispersed in an aqueous medium, and alkali hydroxides (NaOH, KOH, LiOH), organic amines and the like can be used. As a basic substance used for emulsification dispersion immediately after the completion of polycondensation, a basic substance containing no hydroxyl group is preferably used as a main component rather than an alkali hydroxide, and an organic amine material is particularly preferable. Examples of the organic amine materials include dimethylethanolamine, diethylethanolamine, triethanolamine, tripropanolamine, tributanolamine, triethylamine, propylamine, butylamine, isopropylamine, monomethanolamine, morpholine, methoxypropylamine, and pyridine. The organic amines such as vinyl pyridine are not particularly limited, but considering the combined use as an emulsifier, a material having high water solubility such as triethanolamine is more preferable.

In the case of using basicity at the time of polycondensation, for example, after obtaining a polyester resin by performing polycondensation using an amount of acid catalyst larger than the amount of basic substance, the amount of acid catalyst equal to or more than the amount of acid catalyst after polycondensation is completed A method of adding and emulsifying later is also possible.
Further, in the present invention, as described above, the method for deactivating the acid catalyst is to add a basic substance at the end of the polycondensation reaction to stop the polycondensation, and then to add the basic substance again during emulsification of the resin. It is also possible to take additional methods. At this time, the basic substance added at the end of the polycondensation reaction and the basic substance added at the time of emulsification may be the same or different.

<Electrostatic image developing toner and production method thereof>
The method for producing an electrostatic charge image developing toner (hereinafter also simply referred to as “toner”) of the present invention comprises a step of aggregating the resin particles in a dispersion containing at least a resin particle dispersion to obtain aggregated particles, and A method for producing an electrostatic charge image developing toner comprising the step of heating and aggregating the aggregated particles, wherein the resin particle dispersion is the resin particle dispersion described above.

  The method for producing an electrostatic charge image developing toner of the present invention includes, for example, mixing the resin particle dispersion prepared in the present invention with a colorant particle dispersion and a release agent particle dispersion, and further adding a flocculant to heteroaggregation. Then, aggregated particles having a toner diameter are formed, and then heated to a temperature equal to or higher than the glass transition point or the melting point of the resin particles to fuse and coalesce the aggregated particles, and then washed and dried. An electrostatic charge image developing toner is obtained. The toner shape is preferably from irregular to spherical. In addition to surfactants, inorganic salts and divalent or higher metal salts can be suitably used as the flocculant. In particular, when a metal salt is used, it is preferable in terms of aggregation control and toner charging characteristics.

  Further, in the agglomeration step, the resin particle dispersion and the colorant particle dispersion of the present invention are aggregated in advance, and after the formation of the first aggregated particles, the resin particle dispersion of the present invention or another resin particle dispersion is added. It is also possible to form a second shell layer on the first particle surface. In this illustration, the colorant dispersion is separately adjusted, but naturally, a colorant may be blended in advance with the resin particles in the resin particle dispersion of the present invention.

  In the present invention, the formation method of the aggregated particles is not particularly limited, and a known aggregation method conventionally used in the emulsion polymerization aggregation method of electrostatic charge image developing toner, for example, temperature increase, pH change, salt A method of reducing the stability of the emulsion by addition or the like and stirring with a disperser or the like is used. Further, after the agglomeration treatment, the particle surface may be cross-linked by heat treatment or the like for the purpose of suppressing leaching of the colorant from the particle surface. In addition, you may remove the used surfactant etc. by water washing | cleaning, acid washing | cleaning, or alkali washing | cleaning as needed.

  In addition, in the method for producing an electrostatic charge image developing toner of the present invention, a charge control agent used for this kind of toner may be used, if necessary. An aqueous dispersion or the like may be used at the start of production of the emulsion, at the start of polymerization, or at the start of aggregation of the resin particles. The addition amount of the charge control agent is preferably 1 to 25 parts by weight, more preferably 5 to 15 parts by weight with respect to 100 parts by weight of the monomer or polymer.

  As the charge control agent, for example, nigrosine dye, quaternary ammonium salt compound, triphenylmethane compound, imidazole compound, positive charge control agent such as polyamine resin, or chromium, cobalt, aluminum, Loads of metal-containing azo dyes such as iron, metal salts and metal complexes of hydroxycarboxylic acids such as salicylic acid or akilsalicylic acid and benzylic acid, such as chromium, zinc and aluminum, amide compounds, phenolic compounds, naphtholic compounds and phenolamide compounds Known materials such as an electric charge control agent can be used.

  In addition, in the method for producing an electrostatic charge image developing toner of the present invention, if necessary, waxes as a release agent used for this type of toner may be used. It may be added as an aqueous dispersion or the like at the start of production of the monomer emulsion, at the start of polymerization, or at the start of aggregation of the polymer particles. The amount of the release agent to be used is preferably 1 to 25 parts by weight, more preferably 5 to 15 parts by weight with respect to 100 parts by weight of the monomer or polymer.

  Examples of the release agent include polyolefin waxes such as low molecular weight polyethylene, low molecular weight polypropylene, and ethylene-propylene copolymers, plant waxes such as paraffin wax, hydrogenated castor oil, carnauba wax, rice wax, and stearic acid. Higher fatty acid ester waxes such as esters, behenic acid esters and montanic acid esters, higher alcohols such as alkyl-modified silicones and higher fatty acid stearyl alcohols such as stearic acid, higher fatty acid amides such as oleic acid amide and stearic acid amide, distearyl ketone Well-known things, such as a ketone which has long-chain alkyl groups, such as, can be used.

  Furthermore, in the method for producing an electrostatic charge image developing toner of the present invention, various known internal additives such as antioxidants and ultraviolet absorbers used for this type of toner may be used as necessary.

  The toner obtained by the method for producing an electrostatic charge image developing toner of the present invention preferably has an average particle diameter of 1 to 10 μm, and preferably 0.1% to 100 parts by weight of the polyester in the particles. 1 to 50 parts by weight, more preferably 0.5 to 40 parts by weight, particularly preferably 1 to 25 parts by weight of a colorant is contained.

<Addition polymerization resin particle dispersion>
In addition to the crystalline polyester resin particle dispersion and the non-crystalline polyester resin particle dispersion, addition polymerization resin particle dispersions prepared using conventionally known emulsion polymerization can be used together. The median diameter of the resin particles in the addition polymerization resin particle dispersion that can be used in the present invention is preferably 0.1 μm or more and 2.0 μm or less as in the resin particle dispersion of the present invention.

  As an example of the addition polymerizable monomer for preparing these addition polymerization type resin particle dispersions, the aforementioned addition polymerizable monomer can be preferably exemplified. In the case of addition polymerization monomers, emulsion polymerization can be carried out using an ionic surfactant or the like to produce a resin particle dispersion, and in the case of other resins, it is oily and the solubility in water is compared. If it is soluble in a low solvent, the resin is dissolved in those solvents and dispersed in an aqueous medium with a disperser such as a homogenizer together with an ionic surfactant or polymer electrolyte, and then heated or decompressed. Then, the resin particle dispersion can be obtained by evaporating the solvent. Moreover, the above-mentioned polymerization initiator and chain transfer agent can also be used at the time of the polymerization of the addition polymerization monomer.

<Colorant>
Examples of the colorant that can be used in the toner of the present invention include carbon black, chrome yellow, hansa yellow, benzidine yellow, sren yellow, quinoline yellow, permanent orange GTR, pyrazolone orange, vulcan orange, watch young red, and permanent red. , Brilliantamine 3B, brilliantamine 6B, dapon oil red, pyrazolone red, risor red, rhodamine B rake, lake red C rose bengal, aniline blue, ultramarine blue, calco oil blue, methylene blue chloride, phthalocyanine blue, phthalocyanine green, Various pigments such as malachite green oxalate, titanium black, acridine, xanthene, azo, benzox , Azine, anthraquinone, thioindico, dioxazine, thiazine, azomethine, indico, thioindico, phthalocyanine, aniline black, polymethine, triphenylmethane, diphenylmethane, thiazine, thiazole And various dyes such as xanthene series. Specific examples of the colorant include carbon black, nigrosine dye (CI No. 50415B), aniline blue (CI No. 50405), calco oil blue (CI No. azoic Blue 3), chrome yellow (CI No. 14090), ultra Marine Blue (CINo.77103), DuPont Oil Red (CINo.26105), Quinoline Yellow (CINo.47005), Methylene Blue Chloride (CINo.52015), Phthalocyanine Blue (CINo.74160), Malachite Green Oxalate (CINo.42000) Lamp black (CI No. 77266), Rose Bengal (CI No. 45435), a mixture thereof, and the like can be preferably used.

The amount of the colorant used is usually 0.1 to 20 parts by weight, particularly preferably 0.5 to 10 parts by weight, based on 100 parts by weight of the toner. Moreover, as a coloring agent, these pigments, dyes, etc. can be used individually by 1 type, or 2 or more types can be used together.
As these dispersion methods, any method such as a general dispersion method such as a rotary shear type homogenizer, a ball mill having media, a sand mill, or a dyno mill can be used, and is not limited at all. These colorant particles may be added to the mixed solvent at the same time as other particle components, or may be divided and added in multiple stages.

  The electrostatic charge image developing toner of the present invention may contain a magnetic material and a property improving agent as necessary. As the magnetic substance, metals or alloys exhibiting ferromagnetism such as ferrite, magnetite, iron, cobalt, nickel, etc., compounds containing these elements, or containing no ferromagnetic elements, but subjected to appropriate heat treatment Examples thereof include alloys that exhibit ferromagnetism, for example, a type of alloy called Heusler alloy containing manganese and copper, such as manganese-copper-aluminum and manganese-copper-tin, or chromium dioxide. For example, in the case of obtaining a black toner, it is particularly preferable to use magnetite which is black in itself and also functions as a colorant. In the case of obtaining a color toner, it is preferable to use a material with little blackness such as metallic iron. Some of these magnetic materials also function as a colorant, and in that case, they may also be used as a colorant. When the magnetic toner is used, the content of these magnetic materials is preferably 20 to 70 parts by weight, more preferably 40 to 70 parts by weight per 100 parts by weight of the toner.

  Examples of the property improver include a fixability improver and a charge control agent. Examples of fixability improvers include polyolefins, fatty acid metal salts, fatty acid esters and fatty acid ester waxes, partially saponified fatty acid esters, higher fatty acids, higher alcohols, fluid or solid paraffin waxes, polyamide waxes, and polyhydric alcohol esters. Silicon varnish, aliphatic fluorocarbon, and the like can be used. In particular, a wax having a softening point (ring and ball method: JIS K2531) of 60 to 150 ° C. is preferable. As the charge control agent, those conventionally known can be used, and examples thereof include nigrosine dyes and metal-containing dyes.

Furthermore, the toner of the present invention is preferably used by mixing inorganic particles such as a fluidity improver. The inorganic particles used in the present invention are particles having a primary particle diameter of 5 nm to 2 μm, preferably 5 nm to 500 nm. Moreover, it is preferable that the specific surface area by BET method is 20-500 m < ² > / g. The proportion mixed with the toner is 0.01 to 5% by weight, preferably 0.01 to 2.0% by weight. Examples of such inorganic particles include silica powder, alumina, titanium oxide, barium titanate, magnesium titanate, calcium titanate, strontium titanate, zinc oxide, silica sand, clay, mica, wollastonite, diatomaceous earth, Examples thereof include chromium oxide, cerium oxide, bengara, antimony trioxide, magnesium oxide, zirconium oxide, barium sulfate, barium carbonate, calcium carbonate, silicon carbide, and silicon nitride, and silica powder is particularly preferable.

The silica powder here is a powder having a Si—O—Si bond, and includes both those produced by a dry method and a wet method. In addition to anhydrous silicon dioxide, any of aluminum silicate, sodium silicate, potassium silicate, magnesium silicate, zinc silicate and the like may be used, but those containing SiO _{2 in an amount} of 85% by weight or more are preferable. Specific examples of these silica powders include various commercially available silicas, but those having a hydrophobic group on the surface are preferable. For example, AEROSIL R-972, R-974, R-805, R-812 (manufactured by Aerosil Co., Ltd.) ), Thalax 500 (manufactured by Tarco) and the like. In addition, silica powder treated with a silane coupling agent, a titanium coupling agent, silicon oil, silicon oil having an amine in the side chain, or the like can be used.

The cumulative volume average particle diameter D ₅₀ of the toner obtained by the method for producing an electrostatic charge image developing toner of the present invention is preferably 3.0 to 9.0 μm, and more preferably 3.0 to 5.0 μm. Is more preferable. Within the above numerical range, the adhesion is moderate, the developability is good, and the resolution of the image is excellent.

  Further, the volume average particle size distribution index GSDv of the obtained toner is preferably 1.30 or less, more preferably 1.24 or less, and further preferably 1.20 or less. When GSDv is 1.30 or less, the resolution is excellent, and image defects such as toner scattering and fogging do not occur.

Here, the cumulative volume average particle size D ₅₀ and the average particle size distribution index are, for example, the particle size distribution measured by a measuring instrument such as Coulter Counter TAII (manufactured by Beckman Coulter), Multisizer II (manufactured by Beckman Coulter). The particle size range (channel) divided on the basis of the volume and number are cumulatively distributed from the small diameter side, and the particle size that becomes 16% is the particle size that is the volume D _16v , the number D _16P , and the particle size that is 50% cumulative The diameter is _defined as a volume D _50v and a number D _50P , and the particle diameter at a cumulative 84% is defined as a volume D _84v and a number D _84P . Using these, the volume average particle size distribution index (GSDv) is calculated as (D _84v / D _16V ) ^1/2 and the number average particle size distribution index (GSDp) is calculated as (D _84P / D _16P ) ^1/2 .

  The shape factor SF1 of the obtained toner is preferably from 100 to 140, more preferably from 110 to 135, from the viewpoint of image formability. The shape factor SF1 is digitized mainly by analyzing a microscope image or a scanning electron microscope image with an image analyzer, and is obtained as follows, for example. For the measurement of the shape factor SF1, first, an optical microscope image of toner spread on a slide glass is taken into a Luzex image analyzer through a video camera, and SF1 of the following formula is calculated for 50 or more toners to obtain an average value. Can be obtained.

ここでＭＬはトナー粒子の絶対最大長、Ａはトナー粒子の投影面積である。

Here, ML is the absolute maximum length of the toner particles, and A is the projected area of the toner particles.

  The obtained toner is dried in the same manner as a normal toner for the purpose of imparting fluidity and improving cleaning properties, and then inorganic particles such as silica, alumina, titania and calcium carbonate, and resins such as vinyl resins, polyesters and silicones. The particles can be added to the surface of the toner particles while being sheared in a dry state.

  In addition, when adhering to the toner surface in an aqueous medium, examples of inorganic particles include silica, alumina, titania, calcium carbonate, magnesium carbonate, tricalcium phosphate, etc. Can be used by dispersing with an ionic surfactant, polymer acid, or polymer base.

<Electrostatic image developer>
The toner obtained by the method for producing an electrostatic charge image developing toner of the present invention described above can be used as an electrostatic charge image developer. The developer is not particularly limited except that it contains the electrostatic image developing toner, and can have an appropriate component composition depending on the purpose. When the electrostatic image developing toner is used alone, it is prepared as a one-component electrostatic image developer, and when used in combination with a carrier, it is prepared as a two-component electrostatic image developer. The carrier that can be used in the present invention is not particularly limited. Usually, magnetic particles such as iron powder, ferrite, iron oxide powder, and nickel; magnetic particles are used as a core material, and the surface thereof is a styrene resin or vinyl resin. A resin-coated carrier formed by coating a resin, an ethylene-based resin, a rosin-based resin, a polyester-based resin, a melamine-based resin or the like, or a wax such as stearic acid, and forming a resin-coated layer; magnetic particles in the binder resin And a magnetic material-dispersed carrier in which is dispersed. Among them, the resin-coated carrier is particularly preferable because the chargeability of the toner and the resistance of the entire carrier can be controlled by the configuration of the resin coating layer. The mixing ratio of the toner of the present invention and the carrier in the two-component electrostatic image developer is usually 2 to 10 parts by weight of the toner with respect to 100 parts by weight of the carrier. Moreover, the preparation method of a developing agent is not specifically limited, For example, the method of mixing with a V blender etc. is mentioned.

<Image forming method>
The image forming method of the present invention includes a latent image forming step of forming an electrostatic latent image on the surface of the latent image holding member, and development with a developer containing electrostatic latent image toner formed on the surface of the latent image holding member. A developing step for forming a toner image, a transfer step for transferring the toner image formed on the surface of the latent image holding member to the surface of the transfer target, and a fixing step for thermally fixing the toner image transferred on the surface of the transfer target. The electrostatic charge image developing toner of the present invention is used as the toner, or the electrostatic charge image developer of the present invention is used as the developer. In the image forming method of the present invention, a developer is prepared using the specific toner as described above, and an electrostatic image is formed and developed with a conventional electrophotographic copying machine using the developer. The image is electrostatically transferred onto the transfer paper, and is fixed by a heating roller fixing device in which the temperature of the upper heating roller is set to a constant temperature to form a copy image. The image forming method of the present invention is particularly preferably used when performing high-speed fixing such that the contact time between the toner on the transfer paper and the heating roller is within 1 second, particularly within 0.5 seconds.

  The electrostatic image developer (electrostatic image developing toner) of the present invention can be used in an image forming method of a normal electrostatic image developing system (electrophotographic system). Specifically, the image forming method of the present invention includes, for example, an electrostatic latent image forming step, a toner image forming step, a transfer step, and a cleaning step. Each of the above steps is a general step per se, and is described in, for example, JP-A-56-40868 and JP-A-49-91231. The image forming method of the present invention can be carried out using an image forming apparatus such as a copier or a facsimile machine known per se.

  The electrostatic latent image forming step is a step of forming an electrostatic latent image on the electrostatic latent image carrier. The toner image forming step is a step of developing the electrostatic latent image with a developer layer on a developer carrier to form a toner image. The developer layer is not particularly limited as long as it contains the electrostatic image developer of the present invention containing the electrostatic image developing toner of the present invention. The transfer step is a step of transferring the toner image onto a transfer body. The cleaning step is a step of removing the electrostatic charge image developer remaining on the electrostatic latent image carrier.

  In the image forming method of the present invention, an embodiment that further includes a recycling step is preferable. The recycling step is a step of transferring the electrostatic charge image developing toner collected in the cleaning step to a developer layer. The image forming method including the recycling step can be performed using an image forming apparatus such as a toner recycling system type copying machine or facsimile machine. The present invention can also be applied to a recycling system in which the cleaning process is omitted and toner is collected simultaneously with development.

  Hereinafter, the present invention will be described in detail with reference to examples. “Part” represents “part by weight”.

(Example 1)
<Preparation of resin P1>
-Bisphenol A ethylene oxide 2-mol adduct 24.84 parts-Bisphenoxyethanol fluorene 8.48 parts-1,4-cyclohexanedicarboxylic acid 16.67 parts-Dodecylbenzenesulfonic acid 0.127 parts The above materials are mixed and stirred. And a polycondensation reaction was performed for 16 hours so that the resin temperature became 120 ° C. in an open system, to obtain a uniform transparent amorphous polyester resin P1.
Thereafter, 0.06 part of triethanolamine was added and stirred for 1 hour to stop the polycondensation reaction.
The resin was collected as a small sample and the following physical properties were measured.
・ GPC weight average molecular weight Mw 16,500
・ Glass transition temperature Tg (onset) 63 ℃

For the measurement of the molecular weight, the weight average molecular weight Mw and the number average molecular weight Mn were measured by gel permeation chromatography (GPC) under the conditions described below. At a temperature of 40 ° C., a solvent (tetrahydrofuran) was flowed at a flow rate of 1.2 ml per minute, and 3 mg of a tetrahydrofuran sample solution having a concentration of 0.2 g / 20 ml was injected as a sample weight for measurement. In measuring the molecular weight of the sample, the measurement conditions included in the range in which the logarithm of the molecular weight of the prepared calibration curve and the count number are linear are selected with several monodisperse polystyrene standard samples having a molecular weight of the sample. . In addition, the reliability of the measurement results is that the NBS706 polystyrene standard sample performed under the above measurement conditions is
Weight average molecular weight Mw = 28.8 × 10 ⁴
Number average molecular weight Mn = 13.7 × 10 ⁴
Can be confirmed. Further, as the GPC column, TSK-GEL, GMH (manufactured by Tosoh Corporation), etc. satisfying the above conditions were used. A differential scanning calorimeter (Shimadzu Corporation, DSC50) was used to measure the glass transition temperature Tg of the polyester.

In addition, 5 g of P1 resin was taken out and crushed into a powder. Among the powdered samples, 2.5 g was then pelletized, and the value of L ^* was measured with X-Rite 404 (manufactured by X-Rite). For the remaining 2.5 g, the value of L ^* was measured after storing the P1 resin in a high temperature and high humidity environment (35 ° C./85% RH) for 60 days. Before and after storage, no color change was visually confirmed. (Refer to ΔL = 0.21 table)
Judgment criteria are as follows.
○: ΔL ^* = L ^* (before storage) −L ^* (after 60 days storage) <0.5
Δ: ΔL ^* = 0.5 to 0.6
×: ΔL ^* > 0.6

<Preparation of resin particle dispersion L1>
30 parts of the resin P1 obtained as described above was weighed and charged into a reactor equipped with the same stirrer, and then 0.002 part of triethanolamine was added, followed by stirring at 120 ° C. for 0.5 hour. Thereafter, 45 parts of ion-exchanged water heated to 90 ° C. was added to the resin, and stirring was continued for 2 hours to obtain a polyester aqueous dispersion. Then, the presence or absence of the resin dispersion residue in the resin particle dispersion after stirring for 3 minutes with a homogenizer (IKA Corporation, Ultra Turrax T50) was confirmed. There was no residue, and a resin particle dispersion having a solid content of 40% was obtained.
By the above method, an amorphous polyester resin particle dispersion L1 having a particle center diameter of 310 nm and a pH of 6.95 was obtained.
In addition, the particle diameter of the resin particle dispersion was measured with a laser diffraction particle size distribution analyzer (LA-920, manufactured by Horiba, Ltd.).
In this production method, the number of moles of sulfuric acid A and the number of moles of basic substance B were as follows. B = 1.26A

(Example 2)
<Preparation of resin P2>
-Bisphenol A propylene oxide 2-mole adduct 28.49 parts-Bisphenoxyethanol fluorene 7.25 parts-1,4-cyclohexanedicarboxylic acid 14.26 parts-Dodecylbenzene sulfonic acid 0.060 parts The polycondensation was carried out for 16 hours so that the resin temperature was 120 ° C. in an open system, whereby a uniform transparent amorphous polyester resin P1 was obtained.

Thereafter, 0.19 part of 2-vinylpyridine was added and stirred for 1 hour to stop the polycondensation reaction.
The resin was collected as a small sample and the following physical properties were measured.
-Weight average molecular weight by GPC 14,650
・ Glass transition temperature (onset) 64 ℃

Under the same conditions as in Example 1, L ^* of the P2 resin was measured.
Before and after storage, no color change was visually confirmed. (Refer to ΔL = 0.22 table)

<Preparation of resin particle dispersion L2>
30 parts of the resin P2 obtained as described above was weighed and charged into a reactor equipped with a stirrer, and then 6.19 parts of triethanolamine was added, followed by stirring at 120 ° C. for 0.5 hour. It was. Thereafter, 45 g of ion-exchanged water heated to 90 ° C. was added to the resin, and stirring was continued for 2 hours to obtain a polyester aqueous dispersion. Then, the presence or absence of the resin dispersion residue in the resin particle dispersion after stirring for 3 minutes with a homogenizer (IKA Corporation, Ultra Turrax T50) was confirmed. There was no residue, and a resin particle dispersion having a solid content of 40% was obtained.
By the above method, an amorphous polyester resin particle dispersion L2 having a particle central diameter of 190 nm and a pH of 9.50 was obtained. In this production method, the number of moles of sulfuric acid A and the number of moles of basic substance B were as follows. B = 367A

(Example 3)
<Preparation of resin P3>
-Bisphenol A propylene oxide 2-mole adduct 28.8 parts-Bisphenoxyethanol fluorene 7.33 parts-Phenylenediacetic acid 13.89 parts-Dodecylbenzenesulfonic acid 0.120 parts A reactor equipped with the above ingredients and equipped with a stirrer The polycondensation reaction was carried out for 16 hours so that the resin temperature was 120 ° C. in an open system, and a uniform transparent amorphous polyester resin P3 was obtained. Thereafter, 0.084 parts of aniline was added and stirred for 1 hour to stop the polycondensation reaction.
The resin was collected as a small sample and the following physical properties were measured.
・ GPC weight average molecular weight 13,950
・ Glass transition temperature (onset) 63 ℃

Under the same conditions as in Example 1, L ^* of the P3 resin was measured. Before and after storage, no color change was visually confirmed. (Refer to ΔL = 0.22 table)

<Preparation of resin particle dispersion L3>
30 parts by weight of the resin P3 obtained as described above was weighed and charged into a reactor equipped with the same stirrer, and then 0.048 parts by weight of morpholine was added, followed by stirring at 120 ° C. for 0.5 hours. It was. Thereafter, 45 parts by weight of ion-exchanged water heated to 90 ° C. was added to the resin, and stirring was continued for 2 hours to obtain a polyester resin particle dispersion. Then, the presence or absence of the resin dispersion residue in the resin particle dispersion after stirring for 3 minutes with a homogenizer (IKA Corporation, Ultra Turrax T50) was confirmed. There was no residue, and a resin particle dispersion having a solid content of 40% was obtained.
By the above method, an amorphous polyester resin particle dispersion L3 having a particle central diameter of 220 nm and a pH of 8.20 was obtained.
In this production method, the number of moles of sulfuric acid A and the number of moles of basic substance B were as follows. B = 7.4A

Example 4
<Preparation of resin P4>
-Bisphenol A ethylene oxide 2-mole adduct 23.64 parts-Bisphenoxyethanol fluorene 8.19 parts-Phenylenediacetic acid 18.16 parts-Dodecylbenzenesulfonic acid 0.122 parts A reactor equipped with the above ingredients and equipped with a stirrer The polycondensation was carried out for 16 hours so that the resin temperature was 120 ° C. in an open system, and a uniform transparent amorphous polyester resin P4 was obtained. Thereafter, 0.06 part of triethanolamine was added and stirred for 1 hour to stop the polycondensation reaction, and then a small resin sample was taken and the following physical properties were measured.
-Weight average molecular weight by GPC 16,010
・ Glass transition temperature (onset) 63 ℃

Under the same conditions as in Example 1, L ^* of P4 resin was measured. Before and after storage, no color change was visually confirmed. (Refer to ΔL = 0.4 table)

<Preparation of resin particle dispersion L4>
30 parts of the resin P4 obtained as described above was weighed and charged into a reactor equipped with a stirrer, 0.04 part of triethanolamine was added, and the mixture was stirred at 120 ° C. for 0.5 hour. Thereafter, 45 parts of ion-exchanged water heated to 90 ° C. and 2 parts of a 1N NaOH aqueous solution were added to the resin, and stirring was continued for 2 hours to obtain a polyester resin particle dispersion. Then, the presence or absence of the resin dispersion residue in the resin particle dispersion after stirring for 3 minutes with a homogenizer (IKA Corporation, Ultra Turrax T50) was confirmed. There was no residue, and a resin particle dispersion having a solid content of 40% was obtained.
By the above method, an amorphous polyester resin particle dispersion L4 having a particle central diameter of 230 nm and a pH of 7.90 was obtained.
In this production method, the number of moles of sulfuric acid A and the number of moles of basic substance B were as follows. B = 15.2A

(Example 5)
<Preparation of resin particle dispersion L5>
30 parts of the resin P4 was weighed and charged into a reactor equipped with a stirrer, and then 0.06 part of triethanolamine was added, followed by stirring at 120 ° C. for 0.5 hour. After adding 3.0 parts of styrene and further stirring for 0.5 hour, 45 parts of ion-exchanged water heated to 90 ° C. and 2 parts of 1N NaOH aqueous solution were then added to the resin, and stirring was continued for 2 hours. A resin particle dispersion was obtained. Then, after stirring for 3 minutes with a homogenizer (manufactured by IKA, Ultra Tarrax T50), 0.035 parts of ammonium persulfate was added, radical polymerization was performed at 80 ° C. for 2 hours, and then the resin particle dispersion was quenched. To stop the polymerization reaction. Thereafter, it was confirmed whether or not there was a resin dispersion residue in the resin particle dispersion, but all the resin was dispersed in water, and there was no resin dispersion residue, and a resin particle dispersion with a solid content of 40% was obtained.
By the above method, an amorphous polyester resin particle dispersion L5 having a particle central diameter of 300 nm and a pH of 8.00 was obtained.

(Example 6)
<Preparation of resin P5>
-Bisphenol A ethylene oxide 2 mol adduct 27.44 parts-Bisphenoxyethanol (2 mol adducts at both ends) 7.61 parts-Cyclohexanedicarboxylic acid 14.95 parts-Dodecylbenzenesulfonic acid 0.125 parts-N, N-dimethyl Benzylamine 0.0712 parts The above materials were mixed, put into a reactor equipped with a stirrer, and subjected to polycondensation for 16 hours so that the resin temperature was 120 ° C in an open system. Resin P5 was obtained. Thereafter, 0.167 part of N, N-diethylbenzylamine was added and stirred for 1 hour to stop the polycondensation reaction.
The resin was collected as a small sample and the following physical properties were measured.
・ GPC weight average molecular weight 16,800
・ Glass transition temperature (onset) 63 ℃

Under the same conditions as in Example 1, L ^* of the P5 resin was measured. Before and after storage, no color change was visually confirmed. (See ΔL = 0.1 table)

<Preparation of resin particle dispersion L6>
30 parts of the resin P5 obtained as described above was weighed and charged into a reactor equipped with a stirrer, 0.88 part of dodecanoic acid was added, and the mixture was stirred at 120 ° C. for 0.5 hour. Thereafter, 1.16 parts of triethanolamine was added, followed by stirring at 120 ° C. for 0.5 hour. Thereafter, 45 parts of ion-exchanged water heated to 90 ° C. was added to the resin, and stirring was continued for 2 hours to obtain a polyester resin particle dispersion. Then, the presence or absence of the resin dispersion residue in the resin particle dispersion after stirring for 3 minutes with a homogenizer (IKA Corporation, Ultra Turrax T50) was confirmed. There was no residue, and a resin particle dispersion having a solid content of 40% was obtained. By the above method, an amorphous polyester resin particle dispersion L6 having a particle central diameter of 240 nm and a pH of 8.10 was obtained.
In this production method, the number of moles of sulfuric acid A and the number of moles of basic substance B were as follows. B = 293A

(Comparative Example 1)
<Preparation of resin P6>
・ Bisphenol A propylene oxide 4 mol adduct 34.49 parts ・ Phenylenediacetic acid 15.51 parts ・ Dodecylbenzenesulfonic acid 0.104 parts The above materials are mixed and charged into a reactor equipped with a stirrer, and the resin is used in an open system. When polycondensation was carried out for 16 hours so that the temperature became 120 ° C., a uniform transparent amorphous polyester resin P6 was obtained. Thereafter, 0.023 parts of aniline was added and stirred for 1 hour to stop the polycondensation reaction.
The resin was collected as a small sample and the following physical properties were measured.
・ GPC weight average molecular weight 19,800
・ Glass transition temperature (onset) 53 ℃

Under the same conditions as in Example 1, L ^* of P6 resin was measured. The coloration of the resin progressed so that the color change could be confirmed visually before and after storage, and the color changed from pale yellow to brown. (ΔL * = 1.6)

<Preparation of resin particle dispersion L7>
30 parts of the resin P6 obtained as described above was measured and charged into a reactor equipped with a stirrer, and then 0.002 part of aniline was added and stirred at 120 ° C. for 0.5 hour. Thereafter, 45 parts of ion-exchanged water heated to 90 ° C. was added to the resin, and stirring was continued for 2 hours to obtain a polyester resin particle dispersion. Thereafter, the presence or absence of resin dispersion residue in the resin particle dispersion after stirring for 3 minutes with a homogenizer (IKA, Ultra Tarrax T50) was confirmed. A dispersion residue remained. As a result, a resin particle dispersion having a solid content of 5.5% was obtained. By the above method, an amorphous polyester resin particle dispersion L7 having a particle center diameter of 6,600 nm and a pH of 5.8 was obtained.
In this production method, the number of moles of sulfuric acid A and the number of moles of basic substance B were as follows. B = 0.71A

(Comparative Example 2)
<Preparation of resin particle dispersion L8>
30 parts of the resin P6 obtained as described above was weighed and charged into a reactor equipped with a stirrer, and then 3.9 parts of morpholine was added, followed by stirring at 120 ° C. for 0.5 hour. Thereafter, 45 parts by weight of ion-exchanged water heated to 90 ° C. was added to the resin, and stirring was continued for 2 hours to obtain a polyester resin particle dispersion. Thereafter, the presence or absence of residual resin dispersion in the resin particle dispersion after stirring for 3 minutes with a homogenizer (Ultra Turrax T50 manufactured by IKA) was confirmed. The rest was left. As a result, a resin particle dispersion having a solid content of 6.9% was obtained.
The resin was collected as a small sample and the following physical properties were measured.
By the above method, an amorphous polyester resin particle dispersion L8 having a particle center diameter of 15,500 nm and a pH of 12.6 was obtained.
In this production method, the number of moles of sulfuric acid A and the number of moles of basic substance B were as follows. B = 408A

(Comparative Example 3)
<Preparation of resin P7>
-Bisphenol A ethylene oxide 4 mol adduct 35.43 parts-Phenylenediacetic acid 14.57 parts-Dodecylbenzene sulfonic acid 0.111 parts The above materials are mixed, put into a reactor equipped with a stirrer, and resin is opened in an open system When polycondensation was carried out for 16 hours so that the temperature became 120 ° C., a uniform transparent amorphous polyester resin P7 was obtained. Thereafter, 0.03 weight of dimethylaminomethanol was added and stirred for 1 hour to stop the polycondensation reaction.
The resin was collected as a small sample and the following physical properties were measured.
-Weight average molecular weight by GPC 20,510
・ Glass transition temperature (onset) 50 ℃

Under the same conditions as in Example 1, L ^* of the P7 resin was measured. The coloration of the resin progressed so that a slight color change could be visually confirmed before and after storage, and the color changed from light yellow to light orange. Almost no color change was visually observed before and after storage. (Refer to ΔL = 0.4 table)

<Preparation of resin particle dispersion L9>
30 parts of the resin P7 obtained as described above was weighed and charged into a reactor equipped with a stirrer, and then 5.82 parts of triethanolamine was added, followed by stirring at 120 ° C. for 0.5 hour. . Thereafter, 45 parts of ion-exchanged water heated to 90 ° C. and 12 parts of 1N NaOHOH were added to the resin, and stirring was continued for 2 hours to obtain a polyester resin particle dispersion. Thereafter, the presence or absence of residual resin dispersion in the resin particle dispersion after stirring for 3 minutes with a homogenizer (Ultra Turrax T50 manufactured by IKA) was confirmed. The rest was left. As a result, a resin particle dispersion having a solid content of 6.8% was obtained.
By the above method, an amorphous polyester resin particle dispersion L9 having a particle center diameter of 16,600 nm and a pH of 10.9 was obtained.
In this production method, the number of moles of sulfuric acid A and the number of moles of basic substance B were as follows. B = 18.7A

(Comparative Example 4)
<Preparation of resin particle dispersion L10>
30 parts of the obtained resin P7 was weighed and charged into a reactor equipped with a stirrer, 0.88 parts of butanoic acid was added, and the mixture was stirred at 120 ° C. for 0.5 hour. Thereafter, 0.002 g of aniline was added and stirred at 120 ° C. for 0.5 hour.
Thereafter, 45 parts by weight of ion-exchanged water heated to 90 ° C. was added to the resin, and stirring was continued for 2 hours to obtain a polyester resin particle dispersion. Thereafter, the presence or absence of residual resin dispersion in the resin particle dispersion after stirring for 3 minutes with a homogenizer (Ultra Turrax T50, manufactured by IKA) was confirmed. The rest was left. As a result, a resin particle dispersion having a solid content of 14.5% was obtained. By the above method, an amorphous polyester resin particle dispersion L10 having a particle center diameter of 20,500 nm and a pH of 5.70 was obtained.
In this production method, the number of moles of sulfuric acid A and the number of moles of basic substance B were as follows. B = 1.1A

(Comparative Example 5)
<Preparation of resin P8>
Bisphenol A ethylene oxide 4 mol adduct 32.59 parts Terephthalic acid 17.41 parts of dibutyltin oxide _{{(C 4 H 9) 2} SnO = 248.94} was mixed 0.17 parts of the material, the stirrer When the polycondensation was carried out in an atmosphere of 0.5 MPa under reduced pressure for 48 hours so that the resin temperature was 220 ° C. in an open system, a uniform transparent amorphous polyester resin P8 was obtained.
The resin was collected as a small sample and the following physical properties were measured.
・ GPC weight average molecular weight 13,560
・ Glass transition temperature (onset) 65 ℃

Under the same conditions as in Example 1, L ^* of the P8 resin was measured. Large discoloration was observed after storage.

<Preparation of resin particle dispersion L11>
30 parts of the resin P8 obtained as described above was weighed and charged into a reactor equipped with a stirrer, 0.5 parts by weight of soft sodium dodecylbenzenesulfonate was further added as a surfactant, and acetic acid was further added. A uniform oil phase was prepared by dissolving in 300 parts by weight of ethyl. Water was gradually added to this oil phase to carry out phase inversion emulsification. In the phase inversion emulsification, water was added while being sufficiently mixed and dispersed with a homogenizer (manufactured by IKA, Ultra Turrax T50) in the reactor while heating to 60 ° C. When stirring with the homogenizer was continued, an emulsion dispersion of polyester resin particles was obtained. This dispersion was put into a rotary evaporator, and solvent removal was continued for 10 hours under reduced pressure.
By the above method, an amorphous polyester resin particle dispersion L11 having a particle central diameter of 160 nm, a pH of 7.9, and a solid content concentration of 40% was obtained.

In preparing toner using the resin particle dispersion prepared as described above as a raw material, the following release agent particle dispersion W1 and colorant particle dispersion C1 were prepared. “Parts” represents parts by weight.
<Preparation of release agent particle dispersion W1>
・ Polyethylene wax (Toyo Petrolite, Polywax 725, melting point 103 ° C.) 30 parts ・ Cationic surfactant (Kao Corporation, Sanizol B50) 3 parts ・ Ion-exchanged water 67 parts The above ingredients are homogenizer (IKA, Ultra The mixture was sufficiently dispersed while being heated to 95 ° C. with Thalax T50), and then dispersed with a pressure discharge type homogenizer (Gorin homogenizer, manufactured by Gorin Co., Ltd.) to prepare a release agent particle dispersion (W1). The number average particle diameter D _50n of the release agent particles in the obtained dispersion was 460 nm. Thereafter, ion exchange water was added to adjust the solid concentration of the dispersion to 30%.

<Preparation of Cyan Pigment Dispersion C1>
Cyan pigment (Daiichi Seika Kogyo Co., Ltd., CI Pigment Blue PB15: 3)
20 parts ・ Anionic surfactant (Daiichi Kogyo Seiyaku Co., Ltd., Neogen R) 2 parts ・ Ion-exchanged water 78 parts Mix and dissolve the above ingredients, homogenizer (IKA, Ultra Tarrax) for 5 minutes and ultrasonic bath Was dispersed for 10 minutes to obtain a cyan pigment dispersion C1 (colorant particle dispersion C1). The number average particle diameter D _50n of the pigment in the dispersion was 121 nm. Thereafter, ion exchange water was added to adjust the solid content concentration of the dispersion to 15%.

<Preparation of yellow colorant particle dispersion Y1 for measuring secondary color gloss unevenness>
-Yellow pigment (Clariant Japan, CI Pigment Yellow 74) 20 parts-Anionic surfactant (Daiichi Kogyo Seiyaku, Neogen R)-2 parts-Ion-exchanged water 78 parts A colorant particle dispersion Y1 was prepared in the same manner as the particle dispersion C1. The number average particle diameter D _50n of the pigment in the dispersion was 118 nm. Thereafter, ion exchange water was added to adjust the solid content concentration of the dispersion to 15%.

(Toner Example 1 (Production of toner using resin particle dispersion L1))
<Preparation of toner particles>
-Resin particle dispersion L1 160 parts-Release agent particle dispersion (W1) 33 parts-Cyan pigment dispersion (C1) 60 parts-Polyaluminum chloride 10 wt% aqueous solution (PAC100W manufactured by Asada Chemical Co., Ltd.)
15 parts, 1% aqueous nitric acid solution 3 parts The above ingredients were dispersed in a round stainless steel flask at 5,000 rpm for 3 minutes using a homogenizer (IKA, Ultra Turrax T50), and then magnetically applied to the flask. Put a cap equipped with a stirrer with a seal, a thermometer and a pH meter, set a heating mantle heater, and stir by appropriately adjusting the minimum number of rotations at which the entire dispersion in the flask is stirred. While heating to 62 ° C. at 1 ° C./min and holding at 62 ° C. for 30 minutes, the particle size of the aggregated particles was confirmed with a Coulter counter (TAII, manufactured by Nikka Kisha Co., Ltd.). Immediately after the temperature increase was stopped, 50 parts by weight of the resin particle dispersion (L1) was added and held for 30 minutes. Then, an aqueous sodium hydroxide solution was added until the pH in the system reached 6.5, and then at 1 ° C./min. Heated to 97 ° C. After the temperature rise, an aqueous nitric acid solution was added to adjust the pH in the system to 5.0, and the aggregated particles were heated and fused by holding for 10 hours.
Thereafter, the temperature in the system was lowered to 50 ° C., an aqueous sodium hydroxide solution was added to adjust the pH to 12.0, and the mixture was maintained for 10 minutes. After removing from the flask, sufficiently filtering with ion-exchanged water and washing with water, dispersed in ion-exchanged water so that the solid content becomes 10% by weight, and added with nitric acid and stirred at pH 3.0 for 10 minutes. Then, the slurry obtained by sufficiently filtering and washing with water through ion exchange water again was freeze-dried to obtain a cyan toner (toner C1).

Silica colored particles, silica (SiO ₂ ) particles having an average primary particle size of 40 nm and surface hydrophobized with hexamethyldisilazane (hereinafter sometimes abbreviated as “HMDS”), metatitanic acid and isobutyltrimethoxysilane 1 wt% each of the metatitanic acid compound particles having an average primary particle diameter of 20 nm, which is a reaction product of the above reaction product, was mixed with a Henschel mixer to prepare a cyan externally added toner.

Thus, the particle diameter of the toner particles was measured with a Coulter counter. As a result, the cumulative volume average particle diameter D ₅₀ was 4.46 μm, and the volume average particle size distribution index GSDv was 1.20. Further, the shape factor SF1 of the toner particles obtained from the shape observation by Luzex was 134 potato shapes.

(Toner Example 2 (Production of toner using resin particle dispersion L2))
In Toner Example 1, except for changing the resin particle dispersion L2 is obtained cyan colored particles in a similar manner, the cumulative volume-average particle diameter D ₅₀ and the volume average particle size distribution index GSDv, the shape factor were measured. An external additive was externally added to the toner in the same manner as in Toner Example 1 to obtain a cyan externally added toner.
As a result, in Example 2, D ₅₀ was 4.61 μm, and the volume average particle size distribution index GSDv was 1.20. The shape factor SF1 was 131 potato shapes.

(Toner Examples 3 to 6)
Hereinafter, the toner described below was obtained in the same manner as in Example 1 except that the resin particle dispersion was changed to L3 to L6. Further, an external additive was externally added to the obtained toner in the same manner as in Toner Example 1 to obtain a cyan externally added toner.
In Toner Example 3 using resin particle dispersion L3, D ₅₀ is 4.97, GSDv of 1.20, a shape factor SF1 124 toner was obtained.
In Toner Example 4 using resin particle dispersion L4, D ₅₀ is 4.57, GSDv of 1.20, a shape factor SF1 of the toner 133 was obtained.
In Toner Example 5 using resin particle dispersion L5, D ₅₀ is 4.55, GSDv of 1.20, a shape factor SF1 of the toner 127 was obtained.
In Toner Example 6 using resin particle dispersion L6, a toner having a D ₅₀ of 4.75, a GSDv of 1.20, and a shape factor SF1 of 133 was obtained.

(Toner Comparative Examples 1 to 5 (Preparation of toner using resin particle dispersions L7 to L11))
In Toner Example 1, except for changing the respective resin particle dispersion L7~L11 obtain a cyan colored particles in a similar manner, the cumulative volume-average particle diameter D ₅₀ and the volume average particle size distribution index GSDv, and measuring the shape factor . An external additive was externally added to the toner in the same manner as in Toner Example 1 to obtain a cyan externally added toner.
as a result,
· In Comparative Example 1 using resin particle dispersion L7, D ₅₀ is 5.48, GSDv is 1.33, a shape factor SF1 of the toner 137 was obtained.
- Comparative Example 2 resin particle dispersion L8 used, D ₅₀ is 5.17, GSDv is 1.41, a shape factor SF1 is obtained toner 130.
In Comparative Example 3 using resin particle dispersion L9, D ₅₀ is 4.65, GSDv is 1.26, a shape factor SF1 of the toner 133 was obtained.
In Comparative Example 4 using the resin particle dispersion L10, a toner having a D ₅₀ of 4.75, a GSDv of 1.28, and a shape factor SF1 of 133 was obtained.
· In Comparative Example 5 using resin particle dispersion L11, D ₅₀ is 4.99, GSDv is 1.22, a shape factor SF1 of the toner 126 was obtained.

<Creation of carrier>
A methanol solution containing 0.1 part by weight of γ-aminopropyltriethoxysilane was added to 100 parts by weight of Cu—Zn ferrite particles having a volume average particle diameter of 35 μm and coated with a kneader. The silane compound was completely cured by heating at 0 ° C. for 2 hours. To this particle, a perfluorooctylethyl methacrylate-methyl methacrylate copolymer (copolymerization ratio 40:60) dissolved in toluene was added, and perfluorooctylethyl methacrylate-methyl was added using a vacuum reduced pressure kneader. A resin-coated carrier was produced so that the coating amount of the methacrylate copolymer was 0.5% by weight.

<Production of developer>
8 parts by weight of each toner prepared as described above was put into 100 parts by weight of the obtained resin-coated carrier and mixed by a V blender to prepare an electrostatic charge image developer.
The following toner evaluation and image quality evaluation were performed using each developer prepared as described above.

<Evaluation of toner particles and image quality>
<Fixing evaluation>
For fixing and image quality evaluation with the developer obtained by the method described above, the following fixing evaluation was performed using a Docu Center Color 500CP remodeling machine manufactured by Fuji Xerox Co., Ltd. at a fixing temperature of 140 ° C. and a process speed of 240 mm / sec. went. The evaluation by high temperature and high humidity environment storage was performed after storing the modified machine in an environment of 35 ° C. and 65% RH.

(1): Gloss unevenness evaluation of secondary color (ΔGloss)
Secondary color fixing by changing the colorant particle dispersion from C1 to Y1 using the resin particle dispersions L1 to L11 in the same manner as in the cyan toners produced in Examples 1 to 6 and Comparative Examples 1 to 5. A yellow toner was prepared for use.
After forming the green non-fixed solid image of 5 × 5 cm formed by the secondary color of the obtained cyan toner and yellow toner, and fixing by the above fixing method, the central portion of the solid image forming portion Then, Gloss measurement was performed on five points including the periphery thereof, and the determination was made as follows based on the difference value (ΔGloss) between the maximum value and the minimum value of the five points.
○: ΔGloss = (Gloss maximum value) − (Gloss minimum value) ≦ 4
Δ: 4 <ΔGloss <5
×: 5 ≦ ΔGloss

  As a result of performing the above evaluation on each of the obtained toners, ΔGloss when a fixed solid image of the secondary color of the toner produced by the methods of Examples 1 to 6 was prepared and the gloss of 5 points was measured is described in the table. Thus, it was 4 or less, and gloss nonuniformity was not confirmed visually. On the other hand, as for the toners of Comparative Examples 1 to 5, although the gloss unevenness was not confirmed for the toner of Comparative Example 5 using the resin particle dispersion L11 prepared by the phase inversion emulsification method, the toners of Comparative Examples 1 to 4 were used. Gloss unevenness evaluation of the secondary color with respect to was Δ or ×.

(2): ΔID (AC 5% image density difference) image quality evaluation of cyan low area coverage image before and after storage in a high humidity environment The toners produced in the examples and comparative examples are the above-mentioned Docu Center in the room temperature environment.
Using a Color500CP remodeling machine, a single cyan image was printed with an area coverage of 5% (A4 size), and the value of L ^* was measured.
Thereafter, after storing in a high temperature and high humidity environment for 60 days, 50,000 sheets of area coverage 5% (A4 size) were printed as described above, and the L ^* value of the sample printed on the 50,001 sheet was measured. The evaluation criteria are shown below.
Based on the result of ΔL = L ^* (before storage) −L ^* (after 60 days storage), three-level evaluation was performed based on the following criteria.
○: ΔL ^* <0.6
Δ: ΔL ^* = 0.6 to 0.7
×: ΔL ^* > 0.7

As a result of performing the above evaluation on each of the obtained toners, the toners of Examples 1 to 6 all had a change in L ^* of less than 0.6, and no difference in image brightness was visually confirmed. The toner had a brightness change of 0.6 or more, and a difference in brightness was observed visually before and after storage.

The evaluation results of Examples 1 to 6 and Comparative Examples 1 to 5 are shown in Table 1.
In the figure, DBSA represents dodecylbenzenesulfonic acid, and Bn ₂ SnO represents acid value dibutyltin.

  Table 2 shows the evaluation results of Toner Examples 1 to 6 and Toner Comparative Examples 1 to 5.

Claims (1)

A resin particle dispersion in which resin particles containing at least a polycondensation resin are dispersed,
The resin particle dispersion contains a sulfur acid and a basic substance,
When the molar amount of the sulfur acid is A and the molar amount of the basic substance is B,
1.0 × A ≦ B ≦ 400 × A,
PH of the said resin particle dispersion liquid is 6-10, The resin particle dispersion liquid characterized by the above-mentioned.