JP5511315B2 - Toner for developing electrostatic image, method for producing the same, developer, image forming method and image forming apparatus - Google Patents

Description

  The present invention relates to a toner for developing an electrostatic image (hereinafter also simply referred to as “toner”), and a method for producing the same, a developer, an image forming method, and an image forming apparatus.

  In recent years, in the market, there has been a demand for toner particle size reduction and low-temperature fixing for energy saving in order to improve the quality of images. In order to reduce the amount of electric power required for the standby time until it becomes possible (warm-up time of the apparatus) as much as possible, it is strongly desired to shorten the standby time.

  As a toner manufacturing method, for example, a kneading and pulverizing method is generally used. However, it is difficult to reduce the particle size of the toner obtained by the above method, the shape is irregular, the particle size distribution is broad, and there are various problems such as high fixing energy.

  In order to solve the problems caused by the kneading and pulverization method, for example, from the extension reaction product of the urethane-modified polyester as a toner binder for the purpose of improving the fluidity of the toner, improving the low-temperature fixing property, and improving the hot offset property as a polymerization method. A dry toner having a practical sphericity of 0.90 to 1.00 has been proposed (see Patent Document 1). In addition, a dry toner has been proposed that has excellent powder flowability and transferability when it is a small particle size toner, and is excellent in all of heat resistant storage stability, low-temperature fixability, and hot offset resistance (Patent Document 2). And Patent Document 3). The toner production methods described therein include a step of increasing the molecular weight of the isocyanate group-containing polyester prepolymer by a polyaddition reaction with an amine in an organic solvent and an aqueous medium. However, in the case of the above-described production method and the toner obtained by the production method, the reaction is inhibited by the influence of the carboxyl group of the polyester resin against the elongation reaction or crosslinking reaction between the prepolymer and the amine, and the degree of polymerization is stable. There is a problem that cannot be obtained. As a result, the fixing properties such as low-temperature fixability and high-temperature offset resistance of the obtained toner are insufficient to always achieve the target level. In particular, the toner production methods described in Patent Document 2 and Patent Document 3 are assumed to be batch production. For stable production and production efficiency, an oil-based dispersion of toner material is used as an aqueous system. It is necessary to subject the isocyanate group-containing polyester prepolymer to a high molecular weight by subjecting the isocyanate group-containing polyester prepolymer to a polyaddition reaction with an amine in an organic solvent and an aqueous medium by continuously heat-treating the dispersion liquid dispersed in the medium.

  In the polymerization of polyester, it has been proposed that a toner binder having a stable molecular weight distribution is produced and an aging step is provided in order to achieve both low-temperature fixability and offset resistance (see Patent Documents 4 and 5). However, the polyester polycondensation, which is a high temperature reaction, is an easy technique, but cannot be applied to a reaction system in which an organic solvent and an aqueous medium are mixed as described above unless various conditions are intensively studied.

  As described above, in order to provide a toner that exhibits stable low-temperature fixability and high-temperature offset resistance and has excellent fixing properties, further improvements are required.

  An object of the present invention is to solve the conventional problems and achieve the following objects. That is, an object of the present invention is to provide a toner having excellent fixing characteristics by exhibiting stable low-temperature fixability and high-temperature offset resistance, and a method for producing the same.

  As a result of intensive studies to achieve the above object, the present inventors have found that it is necessary to control the amount of residual organic solvent before aging in order to achieve both low temperature fixability and high temperature offset resistance. The present invention has been completed.

The present invention is based on the above findings by the present inventors, and means for solving the above problems are as follows. That is,
<1> Oil obtained by dissolving or dispersing a compound having at least an active hydrogen group, a polymer having a site capable of reacting with the compound having an active hydrogen group, a binder resin, a colorant, and a release agent in an organic solvent An aqueous granulation step of emulsifying or dispersing the phase in an aqueous medium, a first desolvation step of removing a part of the solvent of the granulated particles, and a desolvated emulsification or dispersion liquid at 40 ° C to An aging step of heating at 70 ° C. for 0.5 to 25 hours, an emulsification through the aging step, a second desolvation step to remove the solvent in the dispersion, and an emulsification through the second desolvation step A method for producing a toner for an electrostatic charge image phenomenon, comprising: a filtration step of filtering the dispersion; a washing step of washing the filtered particles; and a drying step of drying the washed particles. Residual solvent concentration in the emulsion or dispersion after the solvent removal step Is not less than 10% and not more than 70% with respect to 100 parts pure toner of the emulsified or dispersed liquid, and the residual solvent concentration in the emulsified or dispersed liquid after the second desolvation step is the emulsified or dispersed liquid. In the aging step, the emulsification or dispersion liquid is supplied into an inner tube heated from the bottom of the aging apparatus, and the emulsification or dispersion liquid is supplied from the upper part of the aging apparatus. Is a method for producing a toner for an electrostatic charge image phenomenon.
<2> The method for producing a toner for an electrostatic charge image phenomenon according to <1>, wherein the inner tube has pores and is provided with a rotatable dispersion blade and a baffle plate.
<3> The polymer having a site capable of reacting with a compound having an active hydrogen group is an isocyanate group-containing polymer, and 5 to 40% of the isocyanate group-containing polymer is contained in the electrostatic image developing toner. In the thermal decomposition product generated by thermal decomposition of the electrostatic charge image developing toner from 50 ° C. to 700 ° C., the extraction residual amount of Soxhlet extraction with tetrahydrofuran in the electrostatic charge image developing toner is 2 to 50%. Ratio (B) / (A) of nitrogen content (A) of a compound containing two or more isocyanate groups and nitrogen content (B) of a compound containing one or more isocyanate groups and one or more amino groups Is a method for producing a toner for developing an electrostatic charge image according to any one of <1> to <2>, wherein the toner satisfies 0.1 ≦ (B) / (A) ≦ 6.
<4> An electrostatic charge obtained by granulating toner particles while emulsifying and dispersing in an aqueous medium an oil phase in which at least an isocyanate group-containing polymer, a colorant and a release agent are dissolved or dispersed in an organic solvent. An image developing toner comprising 5 to 40% of the isocyanate group-containing polymer in the electrostatic charge image developing toner, and an extraction residual amount of Soxhlet extraction with tetrahydrofuran in the electrostatic charge image developing toner is 2. In the pyrolyzate generated by thermal decomposition of the electrostatic charge image developing toner from 50 ° C. to 700 ° C., the nitrogen amount (A) of the compound containing two or more isocyanate groups and the isocyanate group are The ratio (B) / (A) of the nitrogen amount (B) of the compound containing one or more and one or more amino groups satisfies 0.1 ≦ (B) / (A) ≦ 6, and the above <1> to <3> A toner for developing electrostatic images which is characterized by being manufactured by the manufacturing method of the electrostatic image developing toner according to any misalignment.
<5> The electrostatic image developing toner according to <4>, wherein the volume average particle size is 3 μm to 9 μm.
<6> The electrostatic image developing toner according to any one of <4> to <5>, wherein the volume average particle diameter Dv / number average particle diameter Dn is 1.20 or less.
<7> The electrostatic image developing toner according to any one of <4> to <6>, wherein the binder resin contains a polyester resin.
<8> The electrostatic image developing toner according to any one of <4> to <7>, wherein the polyester resin has a THF-soluble component having a weight average molecular weight of 1,000 to 30,000.
<9> The electrostatic image developing toner according to any one of <4> to <8>, wherein the isocyanate group-containing polymer has a weight average molecular weight of 10,000 to 200,000.
<10> The electrostatic charge image developing toner according to any one of <4> to <9>, wherein an acid value of the electrostatic charge image developing toner is 0.5 to 40.0 (KOHmg / g).
<11> The electrostatic charge image developing toner according to any one of <4> to <10>, wherein the electrostatic charge image developing toner has a glass transition point of 40 to 70 ° C.
<12> A developer comprising the toner according to any one of <4> to <11> and a carrier.
<13> An electrostatic latent image forming step of forming an electrostatic latent image on the electrostatic latent image carrier, and the electrostatic latent image using the toner according to any one of <4> to <11> An image comprising at least a developing step for developing to form a visible image, a transferring step for transferring the visible image to a recording medium, and a fixing step for fixing the transferred image transferred to the recording medium It is a forming method.
<14> An electrostatic latent image forming unit that forms an electrostatic latent image on the electrostatic latent image carrier, and the toner according to any one of <4> to <11> An image comprising at least developing means for forming a visible image by development, transfer means for transferring the visible image to a recording medium, and fixing means for fixing the transferred image transferred to the recording medium Forming device.
<15> A process cartridge having an electrostatic latent image carrier and developing means for developing a latent image formed on the surface of the electrostatic latent image carrier using a developer to form a visible image In the process cartridge, the developer is the developer described in <12>.
<16> A developer-containing container which is detachable from the image forming apparatus according to <14> or the process cartridge according to <15>, and contains the developer according to <12>. It is.

  According to the present invention, a toner for developing an electrostatic image having stable low-temperature fixability and high-temperature offset resistance can be obtained.

FIG. 1 is a cross-sectional view of an apparatus according to a first embodiment used in an aging process. FIG. 2 is a cross-sectional view of an apparatus according to a second embodiment used in the aging process. FIG. 3 is a top view of the dispersing blade. FIG. 4 is a schematic explanatory view showing an example of a process cartridge used in the present invention. FIG. 5 is a schematic explanatory view showing an example of an image forming apparatus used in the image forming method of the present invention. FIG. 6 is a schematic explanatory view showing another example of an image forming apparatus used in the image forming method of the present invention. FIG. 7 is a schematic explanatory view showing an example of a tandem type color image forming apparatus used in the image forming method of the present invention. FIG. 8 is a partially enlarged schematic explanatory view of the image forming apparatus shown in FIG.

(Static image developing toner)
The electrostatic image developing toner of the present invention comprises at least a compound having an active hydrogen group, a polymer having a site capable of reacting with the compound having an active hydrogen group, a binder resin, a colorant, and a release agent. Further, those containing other components such as a charge control agent as required are preferable.

<Binder resin>
In the present invention, the binder resin can be appropriately selected according to the purpose, and a polyester resin or the like can be used, but an unmodified polyester resin that is not modified is preferable. Thereby, low temperature fixability and glossiness can be improved.
Examples of the unmodified polyester resin include a polycondensate of a polyol and a polycarboxylic acid. The non-modified polyester resin is preferably partially compatible with the urea-modified polyester resin, that is, has a similar structure compatible with each other in terms of low-temperature fixability and hot offset resistance. .

  The weight average molecular weight of the unmodified polyester resin is preferably 1,000 to 30,000, more preferably 1,500 to 15,000. When the weight average molecular weight is less than 1,000, the heat resistant storage stability may be lowered. For this reason, it is preferable that content of the component whose weight average molecular weight is less than 1,000 is 8-28 weight%. On the other hand, when the weight average molecular weight exceeds 30,000, the low-temperature fixability may be lowered.

The glass transition temperature of the unmodified polyester resin is usually 30 to 70 ° C, more preferably 35 to 60 ° C, and still more preferably 35 to 55 ° C. When the glass transition temperature is less than 30 ° C., the heat-resistant storage stability of the toner may be lowered, and when it exceeds 70 ° C., the low-temperature fixability may be lowered.
The hydroxyl value of the unmodified polyester resin is preferably 5 mgKOH / g or more, more preferably 10 to 120 mgKOH / g, and still more preferably 20 to 80 mgKOH / g. When the hydroxyl value is less than 5 mgKOH / g, it may be difficult to achieve both heat-resistant storage stability and low-temperature fixability.
The acid value of the unmodified polyester resin is preferably 1.0 to 50.0 mgKOH / g, and more preferably 1.0 to 30.0 mgKOH / g. Thereby, the toner is easily negatively charged.

  When the toner contains an unmodified polyester resin, the weight ratio of the polyester prepolymer having an isocyanate group to the unmodified polyester resin is preferably 5/95 to 25/75, more preferably 10/90 to 25/75. preferable. When the weight ratio is less than 5/95, the hot offset resistance may be lowered, and when it exceeds 25/75, the low-temperature fixability and the glossiness of the image may be lowered.

  The content of the unmodified polyester resin in the binder resin is preferably 50 to 100% by weight. If it is 50% by weight or less, the low-temperature fixability may deteriorate.

<Polymer having a site capable of reacting with a compound having an active hydrogen group>
The polymer having a site capable of reacting with a compound having an active hydrogen group is preferably a modified polyester resin.

  The active hydrogen group-containing compound acts as an elongation agent, a crosslinking agent, or the like when the polyester capable of reacting with the active hydrogen group-containing compound undergoes an elongation reaction, a crosslinking reaction, or the like in the granulation process in an aqueous medium. The active hydrogen group-containing compound is not particularly limited as long as it has an active hydrogen group, and can be appropriately selected according to the purpose. For example, a modified polyester capable of reacting with the active hydrogen group-containing compound is an isocyanate. A group-containing polymer is preferred.

-Isocyanate group-containing polymer-
Examples of the isocyanate group-containing polymer include reactive modified polyester resins (RMPE) capable of reacting with active hydrogen, and examples thereof include polyester prepolymers having isocyanate groups. The polyester prepolymer is a polycondensate of a polyol (PO) and a polycarboxylic acid (PC), and a polyester having active hydrogen further reacted with a polyisocyanate (PIC) to introduce an isocyanate group, etc. Is mentioned. Examples of the group containing active hydrogen in the polyester include a hydroxyl group (alcoholic hydrogen group and phenolic hydroxyl group), an amino group, a carboxyl group, a mercapto group, and the like. Among these, an alcoholic hydroxyl group is preferable.

  As the compound having an active hydrogen group that reacts with the isocyanate group of the polyester prepolymer, amines are used. Amines act as crosslinkers and extenders for polyester prepolymers with isocyanates that can react with active hydrogen. Modified polyester such as urea-modified polyester obtained by reacting the polyester prepolymer (A) having an isocyanate group with an amine (B) can easily adjust the molecular weight of the polymer component, and is a dry toner, particularly oilless low-temperature fixing. It is convenient to ensure the characteristics (wide releasability and fixability without a release oil application mechanism to the fixing heating medium). Particularly, a polyester prepolymer whose end is modified with urea can suppress adhesion to a heating medium for fixing while maintaining high fluidity and transparency in the fixing temperature range of the unmodified polyester resin itself.

  Examples of the polyol (PO) include diol (DIO) and trivalent or higher polyol (TO), and diol alone or a mixture of diol and a small amount of polyol is preferable. Examples of the diol (DIO) include alkylene glycol (ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butanediol, 1,6-hexanediol, etc.), alkylene ether glycol (diethylene glycol, Triethylene glycol, dipropylene glycol, polyethylene glycol, polypropylene glycol, polytetramethylene ether glycol, etc.), alicyclic diols (1,4-cyclohexanedimethanol, hydrogenated bisphenol A, etc.), bisphenols (bisphenol A, bisphenol F) Bisphenol S, etc.), alkylene oxide (ethylene oxide, propylene oxide, butylene oxide, etc.) adducts of the alicyclic diols, bisphenol Alkylene oxide Le ethers (ethylene oxide, propylene oxide, butylene oxide, etc.) adducts. Among them, preferred are alkylene glycols having 2 to 12 carbon atoms and alkylene oxide adducts of bisphenols, and particularly preferred are alkylene oxide adducts of bisphenols and alkylene glycols having 2 to 12 carbon atoms. It is a combined use. The trivalent or higher polyol (TO) includes 3 to 8 or higher polyhydric aliphatic alcohols (glycerin, trimethylolethane, trimethylolpropane, pentaerythritol, sorbitol, etc.), trivalent or higher phenols (Tris) Phenol PA, phenol novolak, cresol novolak, etc.), and alkylene oxide adducts of the above trivalent polyphenols.

  Examples of the polycarboxylic acid (PC) include dicarboxylic acid (DIC) and trivalent or higher polycarboxylic acid (TC), and dicarboxylic acid alone or a mixture of dicarboxylic acid and a small amount of polycarboxylic acid is preferable. Dicarboxylic acids (DIC) include alkylene dicarboxylic acids (succinic acid, adipic acid, sebacic acid, etc.), alkenylene dicarboxylic acids (maleic acid, fumaric acid, etc.), aromatic dicarboxylic acids (phthalic acid, isophthalic acid, terephthalic acid, naphthalene) Dicarboxylic acid and the like). Of these, preferred are alkenylene dicarboxylic acids having 4 to 20 carbon atoms and aromatic dicarboxylic acids having 8 to 20 carbon atoms. Examples of the trivalent or higher polycarboxylic acid (TC) include aromatic polycarboxylic acids having 9 to 20 carbon atoms (such as trimellitic acid and pyromellitic acid). In addition, as polycarboxylic acid (PC), you may make it react with a polyol (PO) using the above-mentioned acid anhydride or lower alkyl ester (Methyl ester, ethyl ester, isopropyl ester, etc.). The ratio of the polyol (PO) and the polycarboxylic acid (PC) is usually 2/1 to 1/1 as the equivalent ratio [OH] / [COOH] of the hydroxyl group [OH] and the carboxyl group [COOH]. Preferably, it is 1.5 / 1 to 1/1, more preferably 1.3 / 1 to 1.02 / 1.

  Examples of the polyisocyanate (PIC) include aliphatic polyisocyanates (tetramethylene diisocyanate, hexamethylene diisocyanate, 2,6-diisocyanatomethylcaproate, etc.), alicyclic polyisocyanates (isophorone diisocyanate, cyclohexylmethane diisocyanate, etc.), Aromatic diisocyanates (tolylene diisocyanate, diphenylmethane diisocyanate, etc.), araliphatic diisocyanates (α, α, α ′, α′-tetramethylxylylene diisocyanate, etc.), isocyanurates, the above polyisocyanates as phenol derivatives, oximes, caprolactams And a combination of two or more of these. The ratio of the polyisocyanate (PIC) is usually 5/1 to 1/1 as an equivalent ratio [NCO] / [OH] of the isocyanate group [NCO] and the hydroxyl group [OH] of the polyester having a hydroxyl group. 4/1 to 1.2 / 1 is more preferable, and 2.5 / 1 to 1.5 / 1 is particularly preferable. When [NCO] / [OH] exceeds 5, low-temperature fixability deteriorates. When the molar ratio of [NCO] is less than 1, when a modified polyester is used, the urea content in the ester becomes low and the hot offset resistance deteriorates. The content of the polyisocyanate component in the prepolymer (A) having an isocyanate group at the terminal is usually preferably 0.5 to 40% by weight, more preferably 1 to 30% by weight. Particularly preferred is ˜20% by weight. When the content is less than 0.5% by weight, the hot offset resistance is deteriorated and disadvantageous in terms of both heat-resistant storage stability and low-temperature fixability, and when it exceeds 40% by weight, the low-temperature fixability is deteriorated.

  The average number of isocyanate groups contained per molecule in the prepolymer (A) having an isocyanate group is usually preferably 1 or more on average, more preferably 1.5 to 3 on average, and an average of 1.8 It is particularly preferable that the number is ˜2.5. If it is less than 1 per molecule, the molecular weight of the urea-modified polyester will be low, and the hot offset resistance will deteriorate.

  As the amines (B), the diamine (B1), trivalent or higher polyamine (B2), amino alcohol (B3), amino mercaptan (B4), amino acid (B5), and amino groups of B1 to B5 were blocked. (B6) etc. are mentioned. Examples of the diamine (B1) include aromatic diamines (phenylenediamine, diethyltoluenediamine, 4,4′diaminodiphenylmethane, etc.), alicyclic diamines (4,4′-diamino-3,3′dimethyldicyclohexylmethane, diaminecyclohexane). , Isophorone diamine, etc.), and aliphatic diamines (ethylene diamine, tetramethylene diamine, hexamethylene diamine, etc.). Examples of the trivalent or higher polyamine (B2) include diethylenetriamine and triethylenetetramine. Examples of the amino alcohol (B3) include ethanolamine and hydroxyethylaniline. Examples of the amino mercaptan (B4) include aminoethyl mercaptan and aminopropyl mercaptan. Examples of the amino acid (B5) include aminopropionic acid and aminocaproic acid. Examples of the B1-B5 amino group blocked (B6) include ketimine compounds and oxazolidine compounds obtained from the B1-B5 amines and ketones (acetone, methyl ethyl ketone, methyl isobutyl ketone, etc.). Among these amines (B), preferred are B1 and a mixture of B1 and a small amount of B2.

  The ratio of the amines (B) is the equivalent ratio [NCO] / [NHx of the isocyanate group [NCO] in the prepolymer (A) having an isocyanate group and the amino group [NHx] in the amine (B). ] Is generally preferably 1/2 to 2/1, more preferably 1.5 / 1 to 1 / 1.5, and 1.2 / 1 to 1 / 1.2. Particularly preferred. When [NCO] / [NHx] is more than 2 or less than 1/2, the molecular weight of the polyester is lowered and the hot offset resistance is deteriorated.

  Furthermore, if necessary, the molecular weight of the polyester can be adjusted using an elongation terminator. Examples of the elongation terminator include monoamines (diethylamine, dibutylamine, butylamine, laurylamine, etc.), and those obtained by blocking them (ketimine compounds).

  In the pyrolyzate generated by thermal decomposition of the toner from 50 ° C. to 700 ° C., the amount of nitrogen (A) of the compound containing two or more isocyanate groups, one or more isocyanate groups, and one amino group are contained. It is preferable that the ratio (B) / (A) of the nitrogen amount (B) of the compound containing two or more satisfies 0.1 ≦ (B) / (A) ≦ 6, and 0.1 ≦ (B) / (A ) ≦ 4.5 is more preferable, and 0.2 ≦ (B) / (A) ≦ 3 is particularly preferable. When 0.1 ≦ (B) / (A) ≦ 6 is satisfied, stable low-temperature fixability and high-temperature offset resistance are exhibited. In regions higher than that, high-temperature offset resistance cannot be obtained, and in regions lower than that, low-temperature fixability cannot be obtained.

  According to a further study of the present invention, in order to effectively exhibit low-temperature fixability while maintaining heat-resistant storage stability and to provide offset resistance after modification with a prepolymer, The weight average molecular weight is preferably 1,000 to 30,000. This is because when the amount is less than 1,000, the oligomer component increases, the heat-resistant storage stability is deteriorated, and when it exceeds 30,000, the modification with the prepolymer is insufficient due to steric hindrance and the offset resistance is deteriorated.

The molecular weight according to the present invention is measured by GPC (gel permeation chromatography) as follows. Stabilize the column in a heat chamber at 40 ° C., flow THF at a flow rate of 1 ml / min through the column at this temperature, and prepare a THF sample solution of resin prepared at a sample concentration of 0.05 to 0.6% by weight. Is measured by injecting 50 to 200 μl. In measuring the molecular weight of the sample, the molecular weight distribution of the sample was calculated from the relationship between the logarithmic value of the prepared calibration curve and the count using several types of monodisperse polystyrene standard samples. As a standard polystyrene sample for preparing a calibration curve, for example, Pressure Chemical Co. Or molecular weight made by Toyo Soda Industry Co., Ltd. is 6 × 10 ² , 2.1 × 10 ³ , 4 × 10 ³ , 1.75 × 10 ⁴ , 5.1 × 10 ⁴ , 1.1 × 10 ⁵ , 3.9. It is suitable to use x10 ⁵ , 8.6 × 10 ⁵ , 2 × 10 ⁶ , 4.48 × 10 ⁶ , and use at least about 10 standard polystyrene samples. An RI (refractive index) detector is used as the detector.

  In addition, a polymer having a site capable of reacting with a compound having an active hydrogen group (isocyanate group-containing polymer) is an important binder resin component for realizing low-temperature fixability and high-temperature offset resistance, and its weight The average molecular weight is preferably 10,000 to 200,000. That is, when the weight average molecular weight is less than 10,000, it becomes difficult to control the reaction rate, and problems in production stability begin to occur. On the other hand, when the weight average molecular weight exceeds 200,000, sufficient modified polyester cannot be obtained and the offset resistance starts to be affected.

  The toner preferably contains 5% to 40% of the polymer having an isocyanate group at the time of production, more preferably 8% to 37%, and particularly preferably 10% to 35%. If the polymer is less than 5%, high temperature offset resistance cannot be obtained, and if it exceeds 40%, low temperature fixability may not be obtained.

  In the toner, the extraction residual amount of Soxhlet extraction with tetrahydrofuran in the toner is preferably 2 to 50%, more preferably 5% to 45%, and particularly preferably 8% to 42%. . If the amount of the extraction residue is less than 2%, high temperature offset resistance cannot be obtained, and if it exceeds 50%, low temperature fixability cannot be obtained.

<Release agent>
As the release agent (wax), a low melting point wax having a melting point of 50 to 120 ° C. works more effectively as a release agent in the dispersion with the binder resin between the fixing roller and the toner interface, As a result, the fixing roller is effective against high-temperature offset resistance without applying a release agent such as oil. The melting point of the wax in the present invention was the maximum endothermic peak measured by a differential scanning calorimeter (DSC).

  The following materials can be used as the wax component that functions as the release agent. That is, as specific examples, waxes and waxes include plant waxes such as carnauba wax, cotton wax, wood wax, rice wax, animal waxes such as beeswax and lanolin, mineral waxes such as ozokerite and cercin, And petroleum waxes such as paraffin, microcrystalline, and petrolatum. In addition to these natural waxes, synthetic hydrocarbon waxes such as Fischer-Tropsch wax and polyethylene wax, and synthetic waxes such as esters, ketones and ethers can be used. Furthermore, fatty acid amides such as 12-hydroxystearic acid amide, stearic acid amide, phthalic anhydride imide, chlorinated hydrocarbon, and poly n-stearyl methacrylate, poly n-lauryl methacrylate, which are low molecular weight crystalline polymer resins A crystalline polymer having a long alkyl group in the side chain, such as a polyacrylate homopolymer or copolymer (for example, a copolymer of n-stearyl acrylate-ethyl methacrylate, etc.) can also be used.

<Colorant>
As the colorant, all known dyes and pigments can be used. For example, carbon black, nigrosine dye, iron black, naphthol yellow S, Hansa yellow (10G, 5G, G), cadmium yellow, yellow iron oxide, Ocher, yellow lead, titanium yellow, polyazo yellow, oil yellow, Hansa yellow (GR, A, RN, R), pigment yellow L, benzidine yellow (G, GR), permanent yellow (NCG), Vulcan fast yellow (5G) , R), Tartrazine Lake, Quinoline Yellow Lake, Anthrazan Yellow BGL, Isoindolinone Yellow, Bengala, Red Dan, Lead Zhu, Cadmium Red, Cadmium Mercury Red, Antimon Zhu, Permanent Red 4R, Para Red, Faise red, parachlor ortho Troaniline Red, Resol Fast Scarlet G, Brilliant Fast Scarlet, Brilliant Carmine B, Permanent Red (F2R, F4R, FRL, FRLL, F4RH), Fast Scarlet VD, Belkan Fast Rubin B, Brilliant Scarlet G, Resol Rubin GX, Permanent Red F5R, Brilliant Carmine 6B, Pigment Scarlet 3B, Bordeaux 5B, Tolujing Maroon, Permanent Bordeaux F2K, Helio Bordeaux BL, Bordeaux 10B, Bon Maroon Light, Bon Maroon Medium, Eosin Lake, Rhodamine Lake B, Rhodamine Lake Y, Alizarin Lake , Thioindigo red B, thioindigo maroon, oil red, quinacridone red, pyrazolone , Polyazo Red, Chrome Vermillion, Benzidine Orange, Perinone Orange, Oil Orange, Cobalt Blue, Cerulean Blue, Alkaline Blue Lake, Peacock Blue Lake, Victoria Blue Lake, Metal Free Phthalocyanine Blue, Phthalocyanine Blue, Fast Sky Blue, Indance Ren Blue (RS, BC), Indigo, Ultramarine Blue, Bitumen, Anthraquinone Blue, Fast Violet B, Methyl Violet Lake, Cobalt Purple, Manganese Purple, Dioxane Violet, Anthraquinone Violet, Chrome Green, Zinc Green, Chrome Oxide, Pyridian, Emerald Green , Pigment Green B, Naphthol Green B, Green Gold, Acid Green Lake, Malachite Green Lake, Phthalocyanine green, anthraquinone green, titanium oxide, zinc white, litbon and mixtures thereof can be used. The content of the colorant is usually 1 to 15% by weight, preferably 3 to 10% by weight, based on the toner.

  The colorant can also be used as a master batch combined with a resin. As the binder resin to be kneaded together with the production of the masterbatch or the masterbatch, in addition to the above-mentioned modified and unmodified polyester resins, styrene such as polystyrene, poly p-chlorostyrene and polyvinyltoluene and polymers of substituted products thereof; Styrene-p-chlorostyrene copolymer, styrene-propylene copolymer, styrene-vinyltoluene copolymer, styrene-vinylnaphthalene copolymer, styrene-methyl acrylate copolymer, styrene-ethyl acrylate copolymer Styrene-butyl acrylate copolymer, styrene-octyl acrylate copolymer, styrene-methyl methacrylate copolymer, styrene-ethyl methacrylate copolymer, styrene-butyl methacrylate copolymer, styrene-α- Chloromethyl methacrylate copolymer, steel -Acrylonitrile copolymer, styrene-vinyl methyl ketone copolymer, styrene-butadiene copolymer, styrene-isoprene copolymer, styrene-acrylonitrile-indene copolymer, styrene-maleic acid copolymer, styrene-malein Styrene copolymers such as acid ester copolymers; polymethyl methacrylate, polybutyl methacrylate, polyvinyl chloride, polyvinyl acetate, polyethylene, polypropylene, polyester, epoxy resin, epoxy polyol resin, polyurethane, polyamide, polyvinyl butyral, poly Acrylic resin, rosin, modified rosin, terpene resin, aliphatic or alicyclic hydrocarbon resin, aromatic petroleum resin, chlorinated paraffin, paraffin wax and the like can be mentioned, and these can be used alone or in combination.

  Furthermore, in order to reduce the viscosity of the dispersion medium containing the toner composition, a solvent in which a polyester such as urea-modified polyester or prepolymer (A) is soluble can be used. Use of a solvent is preferable in that the particle size distribution becomes sharp.

  The solvent is preferably volatile with a boiling point of less than 100 ° C. from the viewpoint of easy removal. Examples of the solvent include toluene, xylene, benzene, carbon tetrachloride, methylene chloride, 1,2-dichloroethane, 1,1,2-trichloroethane, trichloroethylene, chloroform, monochlorobenzene, dichloroethylidene, methyl acetate, ethyl acetate, Methyl ethyl ketone, methyl isobutyl ketone and the like can be used alone or in combination of two or more. In particular, aromatic solvents such as toluene and xylene and halogenated hydrocarbons such as methylene chloride, 1,2-dichloroethane, chloroform, and carbon tetrachloride are preferable. The amount of the solvent used relative to 100 parts of the prepolymer (A) is usually preferably 0 to 300 parts, more preferably 0 to 100 parts, and particularly preferably 25 to 70 parts. When a solvent is used, the solvent (solvent) is removed from the obtained reaction product under normal pressure or reduced pressure after the extension and / or crosslinking reaction of the modified polyester (prepolymer) with an amine.

  This master batch can be obtained by mixing and kneading a resin for a master batch and a colorant under a high shear force to obtain a master batch. In this case, an organic solvent can be used in order to enhance the interaction between the colorant and the resin. In addition, a so-called flushing method, which is a wet cake of a colorant, is a method of mixing and kneading an aqueous paste containing water of a colorant together with a resin and an organic solvent, transferring the colorant to the resin side, and removing moisture and organic solvent components. Since it can be used as it is, there is no need to dry it. For mixing and kneading, a high shear dispersion device such as a three-roll mill is preferably used.

  A method for producing an electrophotographic toner in which particles comprising a colorant and a resin and particles comprising at least charge control agent particles are mixed together in a container using a rotating body in order to adhere and immobilize the charge control agent on the toner particle surface. However, in this method, the object of the present invention is to include a step of mixing at a peripheral speed of the rotating body of 40 to 150 m / sec in a container without a fixing member protruding from the inner wall of the container. Toner particles are obtained.

<Charge control agent>
The toner of the present invention may contain a charge control agent as necessary. As the charge control agent, known ones can be used. For example, nigrosine dye, triphenylmethane dye, chromium-containing metal complex dye, molybdate chelate pigment, rhodamine dye, alkoxy amine, quaternary ammonium salt (fluorine) Modified quaternary ammonium salts), alkylamides, phosphorus simple substances or compounds, tungsten simple substances or compounds, fluorine-based activators, salicylic acid metal salts, metal salts of salicylic acid derivatives, and the like. Specifically, Nitronine-based dye Bontron 03, quaternary ammonium salt Bontron P-51, metal-containing azo dye Bontron S-34, oxynaphthoic acid metal complex E-82, salicylic acid metal complex E- 84, E-89 of a phenol-based condensate (manufactured by Orient Chemical Industry Co., Ltd.), TP-302 of a quaternary ammonium salt molybdenum complex, TP-415 (manufactured by Hodogaya Chemical Industry Co., Ltd.), quaternary ammonium Copy charge PSY VP2038 of salt, copy blue PR of triphenylmethane derivative, copy charge of quaternary ammonium salt NEG VP2036, copy charge NX VP434 (manufactured by Hoechst), LRA-901, LR-147 which is a boron complex (Nippon Carlit), copper phthalocyanine, perylene, quinacridone Azo pigments, sulfonate group, carboxyl group, and polymer compounds having a functional group such as a quaternary ammonium salt.

  The amount of the charge control agent used is determined by the toner production method including the type of binder resin, the presence or absence of additives used as necessary, and the dispersion method, and is not uniquely limited. However, it is preferably used in the range of 0.1 to 10 parts by weight, more preferably in the range of 0.2 to 5 parts by weight with respect to 100 parts by weight of the binder resin. When the amount exceeds 10 parts by weight, the chargeability of the toner is too high, the effect of the main charge control agent is reduced, the electrostatic attraction with the developing roller is increased, the developer fluidity is lowered, and the image density is lowered. Invite. These charge control agents and release agents can be melt-kneaded together with the master batch and resin, and may be added when dissolved and dispersed in an organic solvent.

<Other ingredients>
An external additive is used to assist the fluidity, developability, and chargeability of the colored particles obtained in the present invention. As this external additive, inorganic fine particles can be preferably used. The primary particle diameter of the inorganic fine particles is preferably 5 μm to 2 μm, and particularly preferably 5 μm to 500 μm. Moreover, it is preferable that the specific surface area by BET method is 20-500 m < ² > / g. The use ratio of the inorganic fine particles is preferably 0.01 to 5% by weight of the toner, and more preferably 0.01 to 2.0% by weight. Examples of the inorganic fine particles include silica, alumina, titanium oxide, barium titanate, magnesium titanate, calcium titanate, strontium titanate, zinc oxide, tin oxide, silica sand, clay, mica, wollastonite, and diatomaceous earth. , Chromium oxide, cerium oxide, pengala, antimony trioxide, magnesium oxide, zirconium oxide, barium sulfate, barium carbonate, calcium carbonate, silicon carbide, silicon nitride and the like. Among these, as the fluidity imparting agent, it is preferable to use hydrophobic silica fine particles and hydrophobic titanium oxide fine particles in combination. In particular, when stirring and mixing are performed using an average particle size of both fine particles of 50 μm or less, the electrostatic force and van der Waals force with the toner are remarkably improved, so that a desired charge level is obtained. It is clear that even with stirring and mixing inside the developing machine, a fluidity-imparting agent is not detached from the toner, a good image quality that does not generate fireflies and the like can be obtained, and the residual toner can be further reduced. became.

  Titanium oxide fine particles are excellent in environmental stability and image density stability, but have a tendency to deteriorate the charge rise characteristics, and therefore the influence of side effects that the amount of titanium oxide fine particles added is greater than the amount of silica fine particles added is increased. It is possible. However, when the addition amount of the hydrophobic silica fine particles and the hydrophobic titanium oxide fine particles is in the range of 0.3 to 1.5% by weight, the charge rise characteristics are not greatly impaired, and the desired charge rise characteristics can be obtained. Even if the process is repeated, stable image quality can be obtained and toner blowing can be suppressed.

  The toner of the present invention is not particularly limited with respect to various physical properties such as shape and size, and can be appropriately selected according to the purpose. However, the following volume average particle diameter (Dv), volume average It is preferable to have a particle size (Dv) / number average particle size (Dn), a ratio of particles having a particle size of 2 μm or less, an average circularity, and the like.

  The volume average particle diameter Dv of the toner is preferably 3 μm to 9 μm, and particularly preferably 3 μm to 7 μm. In general, it is said that the smaller the particle size of the toner, the more advantageous it is to obtain a high-resolution and high-quality image, but it is disadvantageous for transferability and cleaning properties. is there. When the volume average particle diameter is smaller than the above range, in the case of a two-component developer, the toner is fused to the surface of the carrier during a long period of stirring in the developing device, and the charging ability of the carrier is reduced. When it is used, toner filming on the developing roller and toner fusion to a member such as a blade for thinning the toner are likely to occur. In addition, these phenomena are greatly related to the content of fine powder. Particularly, when the ratio of particles having a particle size of 2 μm or less exceeds 20% by number, it is a problem in the case where adhesion to a carrier or charging stability at a high level is achieved. Become. Conversely, when the toner particle size is larger than the above range, it becomes difficult to obtain a high-resolution and high-quality image, and the toner particle size when the balance of the toner in the developer is performed. In many cases, fluctuations of It was also clarified that the same applies when the volume average particle diameter / number average particle diameter is larger than 1.30.

  In the toner, the ratio (Dv / Dn) of the volume average particle diameter Dv to the number average particle diameter Dn is preferably 1.30 or less, and more preferably 1.00 to 1.20. This makes it possible to obtain high-resolution and high-quality toner. Furthermore, in the case of a two-component developer, even if a long-term balance of the toner is performed, fluctuations in the particle size of the toner in the developer are reduced, and good and stable developability even with long-term stirring in the developing device. Is possible. When the ratio (Dv / Dn) exceeds 1.30, the variation in particle size of individual toner particles is large, and the behavior of the toner varies during development and the reproducibility of minute dots is impaired. As a result, a high-quality image cannot be obtained.

  The average circularity of the toner is preferably 0.94 to 0.99. When the average circularity is less than 0.94, transferability is deteriorated. This phenomenon is because the toner shape is excessively deformed (toner surface unevenness is large), and toner movement during transfer (photosensitive member surface to transfer paper, photosensitive member surface to intermediate transfer belt, first intermediate transfer belt) To the second intermediate transfer belt, etc.) are not smooth, and the toner particles vary in their behavior, so that uniform and high transfer efficiency cannot be obtained. In addition, unstable charging and brittleness of particles begin to appear. Furthermore, it becomes a fine phenomenon in the developer, which causes a decrease in the durability of the developer. The ratio of particles having a particle size of 2 μm or less in the toner of the present invention is preferably 1% by number to 20% by number.

  The ratio of particles having a particle diameter of 2 μm or less and the average circularity of the toner can be measured by, for example, a flow type particle image analyzer FPIA-2000 (manufactured by Sysmex Corporation). As a specific measuring method, 0.1 to 0.5 ml of a surfactant, preferably alkylbenzene sulfonate is added as a dispersant to 100 to 150 ml of water from which impure solids have been removed in advance, and further measurement is performed. Add about 0.1-0.5g of sample. The suspension in which the sample is dispersed is obtained by performing dispersion treatment with an ultrasonic disperser for about 1 to 3 minutes, and measuring the shape and distribution of the toner with the above apparatus at a dispersion concentration of 3000 to 10,000 / μl. .

  The volume average particle diameter Dv and the ratio (Dv / Dn) of the toner can be measured, for example, by a Coulter counter method. Examples of the toner particle size distribution measuring apparatus include Coulter Counter TA-II and Coulter Multisizer II (both manufactured by Coulter). In the present invention, measurement was performed using a Coulter counter TA-II type, connected to an interface (Nichiken Giken Co., Ltd.) that outputs number distribution and volume distribution, and a PC 9801 personal computer (manufactured by NEC).

  The acid value of the toner is derived from the terminal carboxyl group of the unmodified polyester resin. The unmodified polyester resin preferably has an acid value of 0.5 mgKOH / g to 40.0 mgKOH / g in order to control low-temperature fixability (fixing lower limit temperature, hot offset occurrence temperature, etc.) as a toner. More preferably, it is 1 mgKOH / g-35.0 mgKOH / g. When the toner acid value exceeds 40.0 mgKOH / g, the extension or cross-linking reaction of the modified polyester resin becomes insufficient, which may affect the high-temperature offset resistance, and is less than 0.5 mgKOH / g. The dispersion stabilizing effect due to the base compound at the time of production cannot be obtained, the extension or crosslinking reaction of the modified polyester resin tends to proceed, and there may be a problem in production stability. The acid value of the toner can be measured, for example, by a method based on JIS K0070.

  The glass transition temperature of the toner is preferably 40 ° C. to 70 ° C., and more preferably 45 ° C. to 65 ° C. in order to obtain low temperature fixability, heat resistant storage stability and high durability. When the glass transition temperature is less than 40 ° C., blocking in the developing machine and filming to the photosensitive member may easily occur. When the glass transition temperature exceeds 70 ° C., low-temperature fixability may be easily deteriorated. is there.

  The coloration of the toner of the present invention is not particularly limited and can be appropriately selected according to the purpose, and can be at least one selected from black toner, cyan toner, magenta toner and yellow toner. This toner can be obtained by appropriately selecting the type of the colorant.

(Toner production method)
Hereinafter, the method for producing the toner of the present invention will be described. Here, although a preferable manufacturing method is shown, it is not limited to this. The toner production method includes an aqueous granulation step, a first solvent removal step, an aging step, a second solvent removal step, a filtration step, a washing step, and a drying step.

<Water-based granulation process>
The aqueous granulation step is carried out in an organic solvent by using a compound having an active hydrogen group, a polymer having a site capable of reacting with a compound having an active hydrogen group, a binder resin, a colorant, a release agent (hereinafter referred to as active hydrogen). An oil in which a compound having a group, a polymer having a site capable of reacting with a compound having an active hydrogen group, a binder resin, a colorant, a release agent, etc. are collectively referred to as “toner material”) are dissolved or dispersed. This is a step of emulsifying or dispersing the phase in an aqueous medium.

-Preparation of oil phase (dissolution or dispersion of toner material)-
The toner material is dissolved or dispersed in an organic solvent. The organic solvent is not particularly limited as long as it is a solvent that can dissolve or disperse the toner material, and can be appropriately selected according to the purpose. For example, the boiling point is less than 150 ° C. in terms of ease of removal. Volatile ones are preferred, for example, toluene, xylene, benzene, carbon tetrachloride, methylene chloride, 1,2-dichloroethane, 1,1,2-trichloroethane, trichloroethylene, chloroform, monochlorobenzene, dichloroethylidene, methyl acetate, acetic acid Examples include ethyl, methyl ethyl ketone, methyl isobutyl ketone, and the like. These may be used individually by 1 type and may use 2 or more types together. Among these, toluene, xylene, benzene, methylene chloride, 1,2-dichloroethane, chloroform, and carbon tetrachloride are preferable, and ethyl acetate is particularly preferable.

  There is no restriction | limiting in particular as the usage-amount of the said organic solvent, According to the objective, it can select suitably, For example, 40 mass parts-300 mass parts are preferable with respect to 100 mass parts of said toner materials, 60 mass parts- 140 mass parts is more preferable, and 80 mass parts-120 mass parts is still more preferable.

  In the toner material, components other than the modified polyester resin having a site capable of reacting with the active hydrogen group-containing compound may be added and mixed in the aqueous medium in the preparation of the aqueous medium described later. Alternatively, when the solution or dispersion of the toner material is added to the aqueous medium, it may be added to the aqueous medium together with the solution or dispersion.

-Preparation of aqueous medium-
As the aqueous medium, water alone may be used, but a solvent miscible with water may be used in combination. Examples of the miscible solvent include alcohol (methanol, isopropanol, ethylene glycol, etc.), dimethylformamide, tetrahydrofuran, cellosolves (methylcellosolve, etc.), lower ketones (acetone, methyl ethyl ketone, etc.) and the like.

  In the present invention, a urea-modified polyester (UMPE) or the like can be obtained by reacting a reactive modified polyester such as a polyester prepolymer (A) having an isocyanate group with an amine (B) in an aqueous medium. As a method for stably forming a dispersion comprising a modified polyester such as urea-modified polyester or a reactive modified polyester such as prepolymer (A) in an aqueous medium, a modified polyester such as urea-modified polyester or a pre-polymer can be used in an aqueous medium. Examples thereof include a method in which a composition of a toner raw material composed of reactive modified polyester such as polymer (A) is added and dispersed by shearing force. Reactive modified polyester such as prepolymer (A) and other toner composition (hereinafter referred to as toner raw material), colorant, colorant masterbatch, release agent, charge control agent, unmodified polyester resin, etc. Although mixing may be performed when forming the dispersion in the medium, it is more preferable to mix the toner raw materials in advance and then add and disperse the mixture in the aqueous medium. In the present invention, other toner materials such as a colorant, a release agent, and a charge control agent do not necessarily have to be mixed when forming particles in an aqueous medium, but after the particles are formed. , May be added. For example, after forming particles containing no colorant, the colorant can be added by a known dyeing method.

  The dispersion method is not particularly limited, and known equipment such as a low-speed shear method, a high-speed shear method, a friction method, a high-pressure jet method, and an ultrasonic wave can be applied. In order to make the particle size of the dispersion 2 to 20 μm, a high-speed shearing type is preferable. When a high-speed shearing disperser is used, the number of revolutions is not particularly limited, but is usually 1,000 to 30,000 rpm, preferably 5,000 to 20,000 rpm. The dispersion time is not particularly limited, but in the case of a batch method, it is usually 0.1 to 5 minutes. The temperature during dispersion is usually 0 to 150 ° C. (under pressure), preferably 40 to 98 ° C. Higher temperatures are preferred in that the dispersion of the urea-modified polyester or prepolymer (A) has a low viscosity and is easy to disperse.

  The amount of the aqueous medium used is usually 50 to 2,000 parts by weight, preferably 100 to 1,000 parts by weight based on 100 parts of the toner composition containing a polyester such as urea-modified polyester and prepolymer (A). If the amount is less than 50 parts by weight, the dispersion state of the toner composition is poor, and toner particles having a predetermined particle diameter cannot be obtained. If it exceeds 2,000 parts by weight, it is not economical. Moreover, a dispersing agent can also be used as needed. It is preferable to use a dispersant because the particle size distribution becomes sharp and the dispersion is stable.

  Various dispersants for emulsifying and dispersing the oily phase in which the toner composition is dispersed are used in the liquid containing water. Such a dispersant includes a surfactant, an inorganic fine particle dispersant, a polymer fine particle dispersant and the like. As surfactants, anionic surfactants such as alkylbenzene sulfonates, α-olefin sulfonates, phosphate esters, alkylamine salts, amino alcohol fatty acid derivatives, polyamine fatty acid derivatives, amine salt types such as imidazoline, Quaternary ammonium salt type cationic surfactants such as alkyltrimethylammonium salt, dialkyldimethylammonium salt, alkyldimethylbenzylammonium salt, pyridinium salt, alkylisoquinolinium salt, benzethonium chloride, fatty acid amide derivative, polyhydric alcohol Nonionic surfactants such as derivatives, for example, amphoteric surfactants such as alanine, dodecyldi (aminoethyl) glycine, di (octylaminoethyl) glycine and N-alkyl-N, N-dimethylammonium betaine. It is.

  Further, by using a surfactant having a fluoroalkyl group, the effect can be obtained in a very small amount. Preferred anionic surfactants having a fluoroalkyl group include fluoroalkyl carboxylic acids having 2 to 10 carbon atoms and metal salts thereof, disodium perfluorooctanesulfonyl glutamate, 3- [omega-fluoroalkyl (C6-C11 ) Oxy] -1-alkyl (C3-C4) sodium sulfonate, 3- [omega-fluoroalkanoyl (C6-C8) -N-ethylamino] -1-propanesulfonic acid sodium, fluoroalkyl (C11-C20) carvone Acids and metal salts, perfluoroalkylcarboxylic acids (C7 to C13) and metal salts thereof, perfluoroalkyl (C4 to C12) sulfonic acids and metal salts thereof, perfluorooctanesulfonic acid diethanolamide, N-propyl-N- ( 2-hydroxyethyl) -Fluorooctanesulfonamide, perfluoroalkyl (C6-C10) sulfonamidopropyltrimethylammonium salt, perfluoroalkyl (C6-C10) -N-ethylsulfonylglycine salt, monoperfluoroalkyl (C6-C16) ethyl phosphate, etc. Is mentioned.

  Product names include Surflon S-111, S-112, S-113 (Asahi Glass Co., Ltd.), Florard FC-93, FC-95, FC-98, FC-129 (Sumitomo 3M Co., Ltd.), Unidyne DS-101. DS-102 (Daikin Kogyo Co., Ltd.), MegaFuck F-110, F-120, F-113, F-191, F-812, F-833 (Dainippon Ink Co., Ltd.), Xtop EF-102 , 103, 104, 105, 112, 123A, 123B, 306A, 501, 201, 204 (manufactured by Tochem Products), and Fgentent F-100, F150 (manufactured by Neos).

  Examples of cationic surfactants include aliphatic primary, secondary or secondary amine acids having a fluoroalkyl group, aliphatic quaternary ammonium salts such as perfluoroalkyl (C6-C10) sulfonamidopropyltrimethylammonium salt, benza Luconium salt, benzethonium chloride, pyridinium salt, imidazolinium salt, trade names include Surflon S-121 (Asahi Glass), Florard FC-135 (Sumitomo 3M), Unidyne DS-202 (Daikin Industries) Megafac F-150, F-824 (manufactured by Dainippon Ink, Inc.), Xtop EF-132 (manufactured by Tochem Products), and Footgent F-300 (manufactured by Neos).

  Moreover, tricalcium phosphate, calcium carbonate, acid value titanium, colloidal silica, hydroxyapatite, etc. can be used as an inorganic compound dispersant which is hardly soluble in water.

  Further, the same effect as that of the inorganic dispersant was confirmed for the resin fine particles. For example, MMA polymer fine particles 1 μm and 3 μm, styrene fine particles 0.5 μm and 2 μm, styrene-acrylonitrile fine particle polymer 1 μm, (PB-200H (Kao) SGP (Soken), Technopolymer SB (Sekisui Plastics), SGP-3G (Soken) Micropearl (Sekisui Fine Chemical)).

  In addition, as a dispersant that can be used in combination with the above inorganic dispersant and resin fine particles, the dispersed droplets may be stabilized by a polymeric protective colloid. For example, acrylic acid, methacrylic acid, α-cyanoacrylic acid, α-cyanomethacrylic acid, itaconic acid, crotonic acid, fumaric acid, maleic acid or maleic anhydride and other (meth) acrylic monomers containing hydroxyl groups Bodies such as β-hydroxyethyl acrylate, β-hydroxyethyl methacrylate, β-hydroxypropyl acrylate, β-hydroxypropyl methacrylate, γ-hydroxypropyl acrylate, γ-hydroxypropyl methacrylate, 3-acrylate Chloro-2-hydroxypropyl, 3-chloro-2-hydroxypropyl methacrylate, diethylene glycol monoacrylate, diethylene glycol monomethacrylate, glycerol monoacrylate, glycerol monomethacrylate, N -Methylol acrylamide, N-methylol methacrylamide, etc., vinyl alcohol or ethers with vinyl alcohol, such as vinyl methyl ether, vinyl ethyl ether, vinyl propyl ether, etc., or esters of compounds containing vinyl alcohol and carboxyl groups, such as Vinyl acetate, pinyl propionate, vinyl butyrate, etc., acrylamide, methacrylamide, diacetone acrylamide or their methylol compounds, acid chlorides such as acrylic acid chloride, methacrylic acid chloride, vinyl pyridine, vinyl pyrrolidone, vinyl imidazole, ethylene imine, etc. Homopolymers or copolymers such as those having a nitrogen atom or a heterocyclic ring thereof, polyoxyethylene, polyoxypropylene, Oxyethylene alkylamine, polyoxypropylene alkylamine, polyoxyethylene alkylamide, polyoxypropylene alkylamide, polyoxyethylene nonyl phenyl ether, polyoxyethylene lauryl phenyl ether, polyoxyethylene stearyl phenyl ester, polyoxyethylene nonyl phenyl ester Polyoxyethylenes such as, celluloses such as methyl cellulose, hydroxyethyl cellulose, and hydroxypropyl cellulose can be used.

  The elongation and / or cross-linking reaction time is selected, for example, depending on the reactivity depending on the combination of the isocyanate group structure of the prepolymer (A) and the amines (B), but usually 10 minutes to 40 hours, preferably 2 to 2 hours. 24 hours. The reaction temperature is generally 0 to 150 ° C, preferably 40 to 98 ° C. Moreover, a well-known catalyst can be used as needed. Specific examples include dibutyltin laurate and dioctyltin laurate. In addition, as an extender and / or a crosslinking agent, the above-described amines (B) are used.

-Emulsification or dispersion-
For emulsification or dispersion of the oil phase (dissolution or dispersion of the toner material) in the aqueous medium, the dissolution or dispersion of the toner material is preferably dispersed in the aqueous medium while stirring. The dispersion method is not particularly limited, but a batch type emulsifier such as a homogenizer (manufactured by IKA), polytron (manufactured by Kinematica), TK auto homomixer (manufactured by Tokushu Kika Kogyo Co., Ltd.), Ebara Milder (manufactured by Aihara Seisakusho), TK Fillmix, TK Pipeline Homo Mixer (manufactured by Koki Kogyo Co., Ltd.), Colloid Mill (manufactured by Shinko Pantech Co., Ltd.), Thrasher, Trigonal Wet Mill Machine type), Capitolon (Eurotech Co., Ltd.), fine flow mill (Pacific Kiko Co., Ltd.) and other continuous emulsifiers, microfluidizer (Mizuho Kogyo Co., Ltd.), nanomizer (Nanomizer Co., Ltd.), APV High-pressure emulsifiers such as Gaulin (manufactured by Gaurin), membrane emulsifiers such as membrane emulsifiers (manufactured by Chilling Industries) Vibro mixer (Hiyaka Kogyo Co., Ltd.) vibration type emulsifying machine such as, ultrasonic emulsifier such as an ultrasonic homogenizer (manufactured by Branson Co., Ltd.) and the like. Especially, it is preferable to use APV Gaurin, a homogenizer, TK auto homomixer, Ebara milder, TK fill mix, and TK pipeline homomixer from the viewpoint of uniform particle size.

  In the case where the solution or dispersion contains a modified polyester (prepolymer) that can react with the active hydrogen group-containing compound, the reaction proceeds during the emulsification or dispersion. The reaction conditions are not particularly limited and may be appropriately selected according to the combination of the polymer capable of reacting with the active hydrogen group-containing compound and the active hydrogen group-containing compound. The reaction time is 30 minutes. -25 hours are preferable, and 1 hour to 20 hours are more preferable.

<First solvent removal step>
The first solvent removal step is a step of removing the organic solvent from the emulsification or dispersion prepared in the aqueous granulation step. Specifically, the organic solvent is removed so that the residual solvent concentration in the emulsified or dispersed liquid is 70% or less with respect to 100 parts of pure toner.

  The organic solvent is removed by (1) a method in which the temperature of the entire reaction system is gradually raised to completely evaporate and remove the organic solvent in the oil droplets, and (2) the emulsion dispersion is sprayed into a dry atmosphere. And a method of completely removing the water-insoluble organic solvent in the oil droplets to form toner fine particles and evaporating and removing the aqueous dispersant.

  In the first solvent removal step, the solvent removal is preferably performed at 0 ° C to 40 ° C, more preferably 15 ° C to 40 ° C, and particularly preferably 15 ° C to 35 ° C. When the solvent is removed at a temperature lower than 0 ° C., part of the water in the emulsion may be frozen, and when the solvent is removed at a temperature higher than 40 ° C., the toner fine particles may be aggregated.

  The residual solvent concentration of the toner material in the emulsified or dispersed liquid after the first solvent removal step is preferably 10% or more and 70% or less with respect to 100 parts of the pure toner in the emulsified or dispersed liquid, preferably 50% Is more preferable, and 20% is particularly preferable. If the residual solvent concentration is less than 10%, the high temperature offset resistance of the toner may not be obtained. If the residual solvent concentration exceeds 70%, the toner fine particles may aggregate.

The residual solvent concentration in the emulsified or dispersed liquid after the first desolvation step is measured by a gas chromatograph. For example, in the case of ethyl acetate, it is specifically determined by the following procedure.
Measuring instrument condition measuring device: GC-2010 (Shimadzu Gas Chromatograph)
Injection volume: 2.0 μL
Sample vaporization chamber injection mode: split vaporization chamber temperature: 180 ° C
Carrier gas: He
Pressure: 40.2kPa
Total flow rate: 56.0 mL / min
Column flow rate: 1.04 mL / min
Linear velocity: 20.0 cm / sec
Purge flow rate: 3.0 mL / min
Split ratio: 50.0
Column Column name: ZB-50
Liquid phase film thickness: 0.25 μm
Length: 30.0m
Inner diameter: 0.32 mm ID
Maximum column temperature: 340 ° C
Column oven Column temperature: 60 ° C
Column oven temperature program:
60 ° C hold 6 min → temperature rise rate 60 ° C / min → 230 ° C hold 5 min
Detector Detector temperature: 250 ° C
Make-up gas: N ₂ / Air
Makeup flow rate: 30.0 mL / min
H ₂ flow rate: 47.0 mL / min
Air flow rate: 400 mL / min
Preparation of standard solution in measurement method: Weigh 4 g of toluene in a volumetric flask and dilute to 500 mL with DMF.
Preparation of measurement sample: After 1.5 g of the emulsion to be measured is diluted to about 50 mL with DMF, 10 mL of the internal standard solution is collected with a whole pipette and charged. After stirring the measurement sample with a stirrer at 400 rpm for 4 minutes, the sample is set on the autosampler of the measuring instrument GC and measurement is performed. After the measurement, the amount of ethyl acetate in the emulsion is calculated by the internal standard method from the ratio of toluene and ethyl acetate as the internal standard substance. Next, the emulsion is put into an oven at 150 ° C. for 1 hour, and the solid content of the emulsion is determined from the remaining amount at that time. The solid content of the emulsion is calculated from the following formula (1).

Toner content of emulsion [%] = Emulsion solid content [%] × number of parts of toner material in oil phase / (number of parts of toner material in oil phase + number of parts of solid content in aqueous medium) (1)

The concentration of ethyl acetate with respect to 100 parts of pure toner is calculated from the following formula.

Concentration of ethyl acetate [%] with respect to 100 parts of pure toner
= (Amount of ethyl acetate in emulsion [%] / value of equation (1)) × 100 (2)

<Aging process>
The aging step is a step of heating the desolvated emulsion or dispersion at 40 ° C to 70 ° C. The aging step can be performed by selecting one of the first embodiment and the second embodiment.

-First embodiment-
FIG. 1 is a cross-sectional view of the apparatus of the first embodiment used in the aging step (in the figure, the arrows indicate the flow of emulsification or dispersion). The apparatus shown in FIG. 1 includes an outer tube 1 in which a heat medium (not shown) is accommodated, and an inner tube 2 that is provided inside the outer tube 1 and allows emulsification or dispersion to pass therethrough. An inlet 3 connected to the inner tube 2 is connected to the lower part of the apparatus to supply the emulsified or dispersed liquid into the apparatus, and an emulsified or dispersed liquid connected to the inner pipe 2 is discharged from the apparatus to the upper part of the apparatus. An outlet 4 is provided.
By providing the emulsification or dispersion from the lower part of the apparatus and discharging the overflow from the upper part of the apparatus, the residence time of the emulsification or dispersion can be accurately controlled.

  In the ripening step of the first embodiment, the emulsification or dispersion is supplied from the raw material inlet 3 into the inner tube 2 heated by the heat medium in the outer tube 1, and the emulsification or dispersion in the inner tube 2. Aged. The aged emulsification or dispersion is discharged from the outlet 4.

  The apparatus (ripening apparatus) shown in FIG. 1 is supplied with an emulsified or dispersed liquid from an inlet 3 at the bottom of the apparatus and flows through an inner tube 2 heated by a heat medium in the outer tube 1. By adjusting the flow rate or supply amount of the emulsified or dispersed liquid, the time during which the emulsified or dispersed liquid stays in the heated inner tube 2 can be adjusted. Thereby, the aging process time or aging degree of an emulsification thru | or dispersion liquid can be adjusted.

  The temperature in the inner tube 2 is preferably 40 ° C to 70 ° C, more preferably 40 ° C to 60 ° C, and particularly preferably 50 ° C to 60 ° C. When the temperature is less than 40 ° C., high-temperature offset resistance may not be obtained, and when it exceeds 70 ° C., low-temperature fixability may not be obtained or toner fine particles may aggregate.

  There is no restriction | limiting in particular as a flow volume of the said emulsification thru | or dispersion liquid, According to a use purpose and the apparatus capacity to be used, it can change suitably.

  The residence time of the emulsification or dispersion in the aging apparatus is not particularly limited and may be appropriately changed according to the purpose of use. For example, it is preferably 0.5 to 25 hours, It is more preferably 5 hours to 10 hours, and particularly preferably 0.5 hours to 5 hours. If the residence time is less than 0.5 hours, the high temperature offset resistance of the toner may not be obtained, and if it exceeds 25 hours, the low temperature fixability may not be obtained.

-Second Embodiment-
Hereinafter, the second embodiment of the aging step will be described. In addition, about the location which 1st Embodiment and description overlap, description is abbreviate | omitted suitably. FIG. 2 is a cross-sectional view of the apparatus of the second embodiment used in the ripening step (in the figure, the arrows indicate the flow of emulsification or dispersion). The aging apparatus shown in FIG. 2 includes an outer tube 1 in which a heat medium (not shown) is accommodated, and an inner tube 2 that is provided inside the outer tube 1 and allows emulsification or dispersion to pass therethrough. At the bottom of the ripening device, there is an inlet 3 connected to the inner tube 2 for supplying the emulsion or dispersion into the device. At the top of the ripening device, the aged emulsion or dispersion connected to the inner tube 2 is placed. An outlet 4 is provided for discharging from the device. The inner tube 2 includes at least one dispersion blade 5 for stirring the emulsified or dispersed liquid and a baffle plate 6 for improving the dispersion effect.

  In the aging step of the second embodiment, the emulsified or dispersed liquid is supplied from the raw material inlet 3 into the inner tube 2 heated by the heat medium in the outer tube 1. The cylindrical dispersion blade 5 is rotatable around a stirring shaft, and the supplied emulsification or dispersion liquid is stirred and dispersed through the pores 511 provided in the dispersion blade 5. Further, the baffle plate 6 provided immediately above the dispersion blade 5 improves the dispersion effect, and the emulsified or dispersed liquid is aged in the inner tube 2. The aged emulsification or dispersion is discharged from the outlet 4.

  FIG. 3 is a top view of the dispersion blade 5. The dispersion blade 5 has a cylindrical shape and includes a large number of pores 511 and a stirring shaft 512. It can rotate around the stirring axis, and after the dispersion blade 5 has rotated 45 to 180 degrees clockwise, the emulsified or dispersed liquid has passed through the pores 511 while rotating 45 to 180 degrees counterclockwise. Let A plurality of dispersing blades 5 may be provided in the inner tube 2 as necessary. In the case where a plurality of inner pipes 2 are provided, baffle plates 6 may be provided immediately above each inner pipe 2.

  The inner diameter of the pore 511 is not particularly limited and can be appropriately changed according to the purpose of use. For example, the inner diameter is preferably 0.5 mm to 10 mm, more preferably 1 mm to 5 mm, It is especially preferable that it is 1 mm-3 mm. If the inner diameter is less than 0.5 mm, the pores 511 may be clogged with toner fine particles, and if the inner diameter exceeds 10 mm, the residence time of the emulsified or dispersed liquid in the tube may vary.

  The apparatus shown in FIG. 2 is supplied with an emulsified or dispersed liquid from an inlet 3 at the bottom of the apparatus and flows through the inner tube 2 heated by the heat medium in the outer tube 1. By adjusting the flow rate or supply amount of the emulsified or dispersed liquid, the time during which the emulsified or dispersed liquid stays in the heated inner tube 2 can be adjusted. Thereby, the aging process time or aging degree of an emulsification thru | or dispersion liquid can be adjusted.

  There is no restriction | limiting in particular as a flow volume of the said emulsification thru | or dispersion liquid, According to a use purpose and the apparatus capacity to be used, it can change suitably.

  The residence time of the emulsification or dispersion in the aging apparatus is not particularly limited and may be appropriately changed according to the purpose of use. For example, it is preferably 0.5 to 25 hours, It is more preferably 5 hours to 10 hours, and particularly preferably 0.5 hours to 5 hours. If the residence time is less than 0.5 hours, the high temperature offset resistance of the toner may not be obtained, and if it exceeds 25 hours, the low temperature fixability may not be obtained.

<Second solvent removal step>
The second solvent removal step is a step of completely removing the organic solvent in the emulsification or dispersion after the aging step. By completely removing the organic solvent, toner fine particles are formed. In the second solvent removal step, similar to the first solvent removal step, (1) a method of gradually elevating the temperature of the entire reaction system to completely evaporate and remove the organic solvent in the oil droplets; 2) Spraying the emulsified dispersion into a dry atmosphere to completely remove the water-insoluble organic solvent in the oil droplets to form toner fine particles, and removing the water-based dispersant by evaporation, etc. I do.

  Specifically, the second solvent removal step is preferably carried out until the organic solvent is 10% or less, more preferably 5% or less, based on 100 parts of the pure toner, more preferably 0.5%. It is particularly preferable to carry out the following steps. When the organic solvent is 10% or more, the heat resistant storage stability of the toner may not be obtained.

In the first solvent removal step, the solvent removal is preferably performed at 0 ° C to 50 ° C, more preferably 15 ° C to 50 ° C, and particularly preferably 15 ° C to 40 ° C. If the solvent is removed at a temperature lower than 0 ° C., part of the water in the emulsion may be frozen, and if the solvent is removed at a temperature higher than 50 ° C., the toner fine particles may be aggregated.

<Filtering step, washing step, drying step>
After the second solvent removal step, the toner fine particles are filtered from the aqueous medium (filtration step). After the filtration step, a washing step and a drying step can be performed, and then classification or the like can be performed as desired. The classification can be performed, for example, by removing fine particle portions by a cyclone, a decanter, centrifugation, or the like in a liquid, and the classification operation may be performed after obtaining a powder after drying. When a dispersion stabilizer that is soluble in an acid / alkali such as calcium phosphate is used as the dispersion medium, toner particles are dissolved by a method such as dissolving the dispersion stabilizer with an acid such as hydrochloric acid and washing with water. Can be removed.

(Developer)
The toner of the present invention can be used as a two-component developer. In this case, it may be used by mixing with a magnetic carrier, and the content ratio of the carrier to the toner in the developer is preferably 1 to 10 parts by weight of the toner relative to 100 parts by weight of the carrier. As the magnetic carrier, conventionally known ones such as iron powder, ferrite powder, magnetite powder, magnetic resin carrier having a particle diameter of about 20 to 200 μm can be used. Examples of the coating material include amino resins such as urea-formaldehyde resin, melamine resin, benzoguanamine resin, urea resin, polyamide resin, and epoxy resin. Polyvinyl and polyvinylidene resins such as acrylic resins, polymethyl methacrylate resins, polyacrylonitrile resins, polyvinyl acetate resins, polyvinyl alcohol resins, polyvinyl butyral resins, polystyrene resins and styrene acrylic copolymer resins, Halogenated olefin resins such as vinyl, polyester resins such as polyethylene terephthalate resin and polybutylene terephthalate resin, polycarbonate resins, polyethylene resins, polyvinyl fluoride resins, polyvinylidene fluoride resins, polytrifluoroethylene resins, polyhexafluoro Propylene resin, copolymer of vinylidene fluoride and acrylic monomer, copolymer of vinylidene fluoride and vinyl fluoride, tetrafluoroethylene and vinylidene fluoride And fluoro such as terpolymers of non-fluoride monomers including, and silicone resins. Moreover, you may contain electrically conductive powder etc. in coating resin as needed. As the conductive powder, metal powder, carbon black, titanium oxide, tin oxide, zinc oxide or the like can be used. These conductive powders preferably have an average particle diameter of 1 μm or less. When the average particle diameter is larger than 1 μm, it becomes difficult to control electric resistance. The toner of the present invention can also be used as a one-component magnetic toner that does not use a carrier or a non-magnetic toner.

(Toner container)
The toner-containing container used in the present invention contains the toner or developer of the present invention in a container.

  There is no restriction | limiting in particular as said container, It can select suitably from well-known things, For example, what has a developer container main body and a cap etc. are mentioned suitably.

  The size, shape, structure, material and the like of the container body containing toner are not particularly limited and can be appropriately selected according to the purpose. For example, the shape is preferably cylindrical. The spiral surface irregularities are formed on the peripheral surface, and the toner as the contents can be transferred to the discharge port side by rotating, and part or all of the spiral part has a bellows function, etc. Is particularly preferred.

  The material of the toner-containing container body is not particularly limited, and those having good dimensional accuracy are preferable. For example, a resin is preferably used. Among them, for example, polyester resin, polyethylene resin, polypropylene resin, polystyrene resin, Preferable examples include vinyl chloride resin, polyacrylic acid, polycarbonate resin, ABS resin, polyacetal resin, and the like.

  The toner-containing container of the present invention is easy to store and transport, has excellent handleability, and is detachably attached to the process cartridge and image forming apparatus of the present invention, which will be described later, and is suitable for replenishing toner and developer. Can be used.

(Process cartridge)
The process cartridge used in the present invention develops an electrostatic latent image carrier carrying an electrostatic latent image, and the electrostatic latent image carried on the electrostatic latent image carrier using a toner to develop a visible image. And at least developing means for forming the film, and other means appropriately selected as necessary.
The developing means includes at least a developer container that contains the developer of the present invention, and a developer carrier that carries and conveys the developer contained in the developer container. Furthermore, a layer thickness regulating member for regulating the thickness of the toner layer to be carried may be provided.
The process cartridge can be detachably mounted on various electrophotographic image forming apparatuses, and is preferably detachably mounted on an image forming apparatus used in the present invention described later.

Here, for example, as shown in FIG. 4, the process cartridge includes an electrostatic latent image carrier 101, and includes a charging unit 102, a developing unit 104, a transfer unit 108, and a cleaning unit 107, and further if necessary. And other means. In FIG. 4, reference numeral 103 denotes exposure by exposure means, and 105 denotes a recording medium.
Next, the image forming process using the process cartridge shown in FIG. 4 will be described. The electrostatic latent image carrier 101 is charged by the charging unit 102 while being rotated in the direction of the arrow, and exposure 103 by the exposure unit (not shown). An electrostatic latent image corresponding to the exposure image is formed on the surface. The electrostatic latent image is developed by the developing unit 104, and the obtained visible image is transferred to the recording medium 105 by the transfer unit 108 and printed out. Next, the surface of the latent electrostatic image bearing member after the image transfer is cleaned by the cleaning unit 107, further neutralized by a neutralizing unit (not shown), and the above operation is repeated again.

(Image forming method and image forming apparatus)
The image forming method of the present invention includes at least an electrostatic latent image forming step, a developing step, a transfer step, and a fixing step, and other steps appropriately selected as necessary, for example, a static elimination step, a cleaning step. , Including recycling process, control process, etc. The image forming apparatus used in the present invention includes at least an electrostatic latent image carrier, an electrostatic latent image forming unit, a developing unit, a transfer unit, and a fixing unit, and further appropriately selected as necessary. The other means, for example, a static elimination means, a cleaning means, a recycling means, a control means, etc. are provided.

  The electrostatic latent image forming step is a step of forming an electrostatic latent image on the electrostatic latent image carrier. The electrostatic latent image carrier (sometimes referred to as “electrophotographic photoreceptor”, “photoreceptor”, “image carrier”) is not particularly limited in terms of material, shape, structure, size, and the like. Although it can be appropriately selected from known ones, the shape is preferably a drum shape, and examples of the material thereof include inorganic photoreceptors such as amorphous silicon and selenium, and organic photoreceptors such as polysilane and phthalopolymethine. (OPC), and the like. Among these, amorphous silicon or the like is preferable in terms of long life.

  The formation of the electrostatic latent image can be performed, for example, by uniformly charging the surface of the electrostatic latent image carrier and then performing imagewise exposure, and is performed by the electrostatic latent image forming unit. Can do. The electrostatic latent image forming means includes at least a charger that uniformly charges the surface of the electrostatic latent image carrier and an exposure device that exposes the surface of the electrostatic latent image carrier imagewise. .

  The charging can be performed, for example, by applying a voltage to the surface of the electrostatic latent image carrier using the charger. The charger is not particularly limited and may be appropriately selected depending on the purpose. For example, a known contact charging device including a conductive or semiconductive roll, brush, film, rubber blade, etc. And non-contact chargers using corona discharge such as corotrons and corotrons. Further, the charger is preferably one that is arranged in contact or non-contact with the electrostatic latent image carrier and charges the surface of the electrostatic latent image carrier by applying DC and AC voltages in a superimposed manner. Further, the charger is a charging roller disposed in a non-contact proximity to the electrostatic latent image carrier via a gap tape, and the electrostatic latent image is carried by applying a direct current and an alternating voltage to the charging roller. Those that charge the body surface are preferred.

  The exposure can be performed, for example, by exposing the surface of the latent electrostatic image bearing member imagewise using the exposure device. The exposure device is not particularly limited as long as it can expose the surface of the electrostatic latent image carrier charged by the charger so as to form an image to be formed, and is appropriately selected according to the purpose. For example, various exposure devices such as a copying optical system, a rod lens array system, a laser optical system, and a liquid crystal shutter optical system can be used. In the present invention, a back light system in which imagewise exposure is performed from the back side of the electrostatic latent image carrier may be employed.

-Development process and development means-
The developing step is a step of developing the electrostatic latent image using the toner or developer of the present invention to form a visible image. The visible image can be formed, for example, by developing the electrostatic latent image using the toner or developer of the present invention, and can be performed by the developing unit. The developing means is not particularly limited as long as it can be developed using, for example, the toner or developer of the present invention, and can be appropriately selected from known ones. For example, the toner of the present invention Suitable examples include a developer that contains at least a developer and that can be applied to the electrostatic latent image in a contact or non-contact manner.

  The developing unit may be a dry developing type, a wet developing type, a single color developing unit, or a multi-color developing unit. Well, for example, a developer having a stirrer for charging the developer by frictional stirring and a rotatable magnet roller is preferable.

  In the developing device, for example, the toner and the carrier are mixed and agitated, and the toner is charged by friction at that time, and held on the surface of the rotating magnet roller in a raised state to form a magnetic brush. . Since the magnet roller is disposed in the vicinity of the electrostatic latent image carrier (photoconductor), a part of the toner constituting the magnetic brush formed on the surface of the magnet roller is electrically attracted. It moves to the surface of the electrostatic latent image carrier (photoconductor) by force. As a result, the electrostatic latent image is developed with the toner, and a visible image is formed with the toner on the surface of the electrostatic latent image carrier (photoconductor).

-Transfer process and transfer means-
The transfer step is a step of transferring the visible image onto a recording medium. After the primary transfer of the visible image onto the intermediate transfer member using an intermediate transfer member, the visible image is transferred onto the recording medium. A primary transfer step of forming a composite transfer image by transferring a visible image onto an intermediate transfer body using two or more colors, preferably full color toner as the toner, and a composite transfer image; A mode including a secondary transfer step of transferring the transfer image onto the recording medium is more preferable.

  The transfer can be performed, for example, by charging the latent electrostatic image bearing member (photoconductor) of the visible image using a transfer charger, and can be performed by the transfer unit. The transfer means includes a primary transfer means for transferring a visible image onto an intermediate transfer member to form a composite transfer image, and a secondary transfer means for transferring the composite transfer image onto a recording medium. Embodiments are preferred. The intermediate transfer member is not particularly limited and may be appropriately selected from known transfer members according to the purpose. For example, a transfer belt and the like are preferable.

  The transfer means (the primary transfer means and the secondary transfer means) is a transfer for peeling and charging the visible image formed on the electrostatic latent image carrier (photoconductor) to the recording medium side. It is preferable to have at least a vessel. There may be one transfer means or two or more transfer means.

  Examples of the transfer device include a corona transfer device using corona discharge, a transfer belt, a transfer roller, a pressure transfer roller, and an adhesive transfer device. The recording medium is not particularly limited and can be appropriately selected from known recording media (recording paper).

  The fixing step is a step of fixing the visible image transferred to the recording medium using a fixing unit, and may be performed each time the toner of each color is transferred to the recording medium, or for the toner of each color. You may perform this simultaneously in the state which laminated | stacked this. There is no restriction | limiting in particular as said fixing device, Although it can select suitably according to the objective, A well-known heating-pressing means is suitable. Examples of the heating and pressing means include a combination of a heating roller and a pressure roller, a combination of a heating roller, a pressure roller, and an endless belt. The fixing device includes a heating body including a heating element, a film in contact with the heating body, and a pressure member in pressure contact with the heating body through the film, and the film and the pressure member It is preferably a unit that heats and fixes a recording medium on which an unfixed image is formed. The heating in the heating and pressing means is usually preferably 80 ° C to 200 ° C. In the present invention, for example, a known optical fixing device may be used together with or in place of the fixing step and the fixing unit depending on the purpose.

  The neutralization step is a step of performing neutralization by applying a neutralization bias to the electrostatic latent image carrier, and can be suitably performed by a neutralization unit. The neutralization means is not particularly limited, and may be appropriately selected from known neutralizers as long as it can apply a neutralization bias to the electrostatic latent image carrier. Preferably mentioned.

  The cleaning step is a step of removing the toner remaining on the electrostatic latent image carrier and can be suitably performed by a cleaning unit. The cleaning means is not particularly limited as long as it can remove the electrophotographic toner remaining on the electrostatic latent image carrier, and can be appropriately selected from known cleaners. Suitable examples include brush cleaners, electrostatic brush cleaners, magnetic roller cleaners, blade cleaners, brush cleaners, web cleaners, and the like.

  The recycling step is a step of recycling the toner removed by the cleaning step to the developing unit, and can be suitably performed by the recycling unit. There is no restriction | limiting in particular as said recycling means, A well-known conveyance means etc. are mentioned.

  The control step is a step of controlling each of the steps, and can be suitably performed by a control unit. The control means is not particularly limited as long as the movement of each means can be controlled, and can be appropriately selected according to the purpose. Examples thereof include devices such as a sequencer and a computer.

  One mode for carrying out the image forming method of the present invention by the image forming apparatus will be described with reference to FIG. An image forming apparatus 100 shown in FIG. 2 includes a photosensitive drum 10 as the electrostatic latent image carrier (hereinafter referred to as “photosensitive member 10”), a charging roller 20 as the charging unit, and exposure as the exposure unit. The apparatus 30 includes a developing device 40 as the developing means, an intermediate transfer member 50, a cleaning device 60 as the cleaning means having a cleaning blade, and a static elimination lamp 70 as the static elimination means.

  The intermediate transfer member 50 is an endless belt, and is designed so as to be movable in the direction of the arrow in the figure by three rollers 51 that are arranged on the inner side and stretch the belt. Part of the three rollers 51 also functions as a transfer bias roller that can apply a predetermined transfer bias (primary transfer bias) to the intermediate transfer member 50. An intermediate transfer member cleaning blade 90 is disposed in the vicinity of the intermediate transfer member 50, and a transfer bias for transferring a visible image (toner image) to the recording medium 95 (secondary transfer) is applied. Possible transfer rollers 80 as the transfer means are arranged to face each other. Around the intermediate transfer member 50, a corona charger 58 for applying a charge to the visible image on the intermediate transfer member 50 is connected to the electrostatic latent image carrier 10 in the rotation direction of the intermediate transfer member 50. The contact portion between the intermediate transfer member 50 and the contact portion between the intermediate transfer member 50 and the recording medium 95 is disposed.

  The developing device 40 includes a developing belt 41 as a developer carrying member, and a black developing unit 45K, a yellow developing unit 45Y, a magenta developing unit 45M, and a cyan developing unit 45C provided around the developing belt 41. Yes. The black developing unit 45K includes a developer accommodating portion 42K, a developer supply roller 43K, and a developing roller 44K. The yellow developing unit 45Y includes a developer container 42Y, a developer supply roller 43Y, and a developing roller 44Y. The magenta developing unit 45M includes a developer container 42M, a developer supply roller 43M, and a developing roller 44M. The cyan developing unit 45C includes a developer container 42C, a developer supply roller 43C, and a developing roller 44C. Further, the developing belt 41 is an endless belt, is rotatably stretched by a plurality of belt rollers, and a part thereof is in contact with the electrostatic latent image carrier 10.

  In the image forming apparatus 100 shown in FIG. 5, for example, the charging roller 20 charges the photosensitive drum 10 uniformly. The exposure device 30 performs imagewise exposure on the photosensitive drum 10 to form an electrostatic latent image. The electrostatic latent image formed on the photosensitive drum 10 is developed by supplying toner from the developing device 40 to form a visible image (toner image). The visible image (toner image) is transferred (primary transfer) onto the intermediate transfer member 50 by the voltage applied from the roller 51, and further transferred (secondary transfer) onto the transfer paper 95. As a result, a transfer image is formed on the transfer paper 95. The residual toner on the photoconductor 10 is removed by the cleaning device 60, and the charge on the photoconductor 10 is temporarily removed by the charge eliminating lamp 70.

  Another mode for carrying out the image forming method of the present invention by the image forming apparatus will be described with reference to FIG. The image forming apparatus 100 shown in FIG. 6 does not include the developing belt 41 in the image forming apparatus 100 shown in FIG. 2, and a black developing unit 45K, a yellow developing unit 45Y, a magenta developing unit 45M, and Except for the fact that the cyan developing unit 45C is directly opposed, it has the same configuration as the image forming apparatus 100 shown in FIG. In FIG. 6, the same components as those in FIG. 5 are denoted by the same reference numerals.

Another mode for carrying out the image forming method of the present invention by the image forming apparatus of the present invention will be described with reference to FIG. The tandem image forming apparatus shown in FIG. 7 is a tandem type color image forming apparatus. The tandem image forming apparatus includes a copying apparatus main body 150, a paper feed table 200, a scanner 300, and an automatic document feeder (ADF) 400.
The copying apparatus main body 150 is provided with an endless belt-like intermediate transfer member 50 at the center. The intermediate transfer member 50 is stretched around the support rollers 14, 15 and 16, and can be rotated clockwise in FIG. 4. An intermediate transfer member cleaning device 17 for removing residual toner on the intermediate transfer member 50 is disposed in the vicinity of the support roller 15. The intermediate transfer member 50 stretched between the support roller 14 and the support roller 15 is a tandem type in which four image forming units 18 of yellow, cyan, magenta, and black are arranged to face each other along the conveyance direction. A developing device 120 is disposed. An exposure device 21 is disposed in the vicinity of the tandem developing device 120. A secondary transfer device 22 is disposed on the side of the intermediate transfer member 50 opposite to the side on which the tandem developing device 120 is disposed. In the secondary transfer device 22, a secondary transfer belt 24 that is an endless belt is stretched around a pair of rollers 23, and a recording medium (transfer paper) conveyed on the secondary transfer belt 24 and an intermediate transfer member 50. Can contact each other. A fixing device 25 is disposed in the vicinity of the secondary transfer device 22. The fixing device 25 includes a fixing belt 26 that is an endless belt, and a pressure roller 27 that is pressed against the fixing belt 26. In the tandem image forming apparatus, a sheet reversing device 28 for reversing the transfer paper for image formation on both sides of the transfer paper is disposed in the vicinity of the secondary transfer device 22 and the fixing device 25. .

  Next, formation of a full-color image (color copy) using the tandem developing device 120 will be described. That is, first, a document is set on the document table 130 of the automatic document feeder (ADF) 400, or the automatic document feeder 400 is opened and the document is set on the contact glass 32 of the scanner 300. 400 is closed.

  When a start switch (not shown) is pressed, when the document is set on the automatic document feeder 400, the document is transported and moved onto the contact glass 32, and then the document is set on the contact glass 32. Immediately after that, the scanner 300 is driven, and the first traveling body 33 and the second traveling body 34 travel. At this time, light from the light source is irradiated by the first traveling body 33 and reflected light from the document surface is reflected by the mirror in the second traveling body 34 and is received by the reading sensor 36 through the imaging lens 35 to be color. An original (color image) is read and used as black, yellow, magenta, and cyan image information.

  Each image information of black, yellow, magenta, and cyan is stored in each image forming unit 18 (black image forming unit, yellow image forming unit, magenta image forming unit, and cyan image) in the tandem developing device 120. Each of the image forming units forms black, yellow, magenta, and cyan toner images. That is, each image forming means 18 (black image forming means, yellow image forming means, magenta image forming means, and cyan image forming means) in the tandem type developing device 120 is a static image as shown in FIG. An electrostatic latent image carrier 10 (black electrostatic latent image carrier 10K, yellow electrostatic latent image carrier 10Y, magenta electrostatic latent image carrier 10M, and cyan electrostatic latent image carrier 10C); The electrostatic latent image bearing member 10 is uniformly charged, and the electrostatic latent image bearing member is exposed (L in FIG. 5) for each color image corresponding to each color image information. An exposure device that forms an electrostatic latent image corresponding to each color image on the electrostatic latent image carrier, and each color toner (black toner, yellow toner, magenta toner, and cyan toner) Develop with A developing device 61 for forming a toner image with each color toner, a transfer charger 62 for transferring the toner image onto the intermediate transfer member 50, a cleaning device 63, and a static eliminator 64 are provided. Each single color image (black image, yellow image, magenta image, and cyan image) can be formed based on the color image information. The black image, the yellow image, the magenta image, and the cyan image formed in this way are respectively transferred to the black electrostatic latent image carrier 10K on the intermediate transfer member 50 that is rotationally moved by the support rollers 14, 15, and 16. Black image formed on top, yellow image formed on electrostatic latent image carrier 10Y for yellow, magenta image formed on electrostatic latent image carrier 10M for magenta, and electrostatic latent image carrier for cyan The cyan image formed on 10C is sequentially transferred (primary transfer). Then, the black image, the yellow image, the magenta image, and the cyan image are superimposed on the intermediate transfer member 50 to form a composite color image (color transfer image).

  On the other hand, in the paper feed table 200, one of the paper feed rollers 142 is selectively rotated to feed out a sheet (recording paper) from one of the paper feed cassettes 144 provided in multiple stages in the paper bank 143. Each sheet is separated and sent to the paper feed path 146, transported by the transport roller 147, guided to the paper feed path 148 in the copying machine main body 150, and abutted against the registration roller 49 and stopped. Alternatively, the sheet feed roller 142 is rotated to feed out sheets (recording paper) on the manual feed tray 54, separated one by one by the separation roller 145, put into the manual feed path 53, and abutted against the registration roller 49 and stopped. . The registration roller 49 is generally used while being grounded, but may be used in a state where a bias is applied to remove paper dust from the sheet. Then, the registration roller 49 is rotated in synchronization with the synthesized color image (color transfer image) synthesized on the intermediate transfer member 50, and a sheet (recording paper) is interposed between the intermediate transfer member 50 and the secondary transfer device 22. The secondary color transfer device 22 transfers the composite color image (color transfer image) onto the sheet (recording paper), thereby transferring the color image onto the sheet (recording paper). Is formed. The residual toner on the intermediate transfer member 50 after image transfer is cleaned by the intermediate transfer member cleaning device 17.

  The sheet (recording paper) on which the color image has been transferred is conveyed by the secondary transfer device 22 and sent to the fixing device 25, where the combined color image (color) is generated by heat and pressure. (Transfer image) is fixed on the sheet (recording paper). Thereafter, the sheet (recording paper) is switched by the switching claw 55 and discharged by the discharge roller 56 and stacked on the discharge tray 57, or switched by the switching claw 55 and reversed by the sheet reversing device 28 and transferred again. After being guided to the position and recording an image on the back surface, the image is discharged by the discharge roller 56 and stacked on the discharge tray 57.

  Examples of the present invention will be described below, but the present invention is not limited to these examples.

Production Example 1
<Production of toner material oil dispersion>
-Production of resin fine particle dispersion-
In a reaction vessel equipped with a stirrer and a thermometer, 683 parts of water, 11 parts of sodium salt of ethylene oxide methacrylate adduct sulfate (Eleminol RS-30, manufactured by Sanyo Chemical Industries), 83 parts of styrene, 83 parts of methacrylic acid, When 110 parts of butyl acrylate and 1 part of ammonium persulfate were added and stirred at 400 rpm for 15 minutes, a white emulsion was obtained. The system was heated to raise the system temperature to 75 ° C. and reacted for 5 hours. Further, 30 parts of a 1% ammonium persulfate aqueous solution was added, and the mixture was aged at 75 ° C. for 5 hours, and an aqueous vinyl resin (a copolymer of styrene-methacrylic acid-butyl acrylate-methacrylic acid ethylene oxide adduct sulfate sodium salt). A dispersion [resin fine particle dispersion 1] was obtained. The volume average particle diameter of [resin fine particle dispersion 1] measured with LA-920 was 105 nm. A portion of [resin fine particle dispersion 1] was dried to isolate the resin component. The resin content had a Tg of 59 ° C. and a weight average molecular weight of 150,000.

-Production of low molecular weight polyester-
229 parts by mass of bisphenol A ethylene oxide 2-mole adduct, 529 parts by mass of bisphenol A propion oxide 3-mole adduct, 208 parts by mass of terephthalic acid, 46 parts by mass of isophthalic acid And 2 parts by mass of dibutyltin oxide were added and reacted at 230 ° C. for 5 hours under normal pressure. Next, after reacting the reaction solution under a reduced pressure of 10 to 15 mmHg for 5 hours, 44 parts by weight of trimellitic anhydride was added to the reaction vessel and reacted at 180 ° C. for 2 hours under normal pressure. Low molecular weight polyester 1] was synthesized. The obtained [low molecular weight polyester 1] has a weight average molecular weight (Mw) of 5,200, a glass transition temperature (Tg) of 45 ° C., an acid value of 20 mgKOH / g, and a hydroxyl value of 50 mgKOH / g. Met.

As a measuring method of an acid value, it measured on condition of the following based on the measuring method as described in JIS K0070-1992.
Sample preparation: 0.5 g of polyester (0.3 g for ethyl acetate-soluble component) was added to 120 ml of toluene and dissolved by stirring for about 10 hours at room temperature (23 ° C.). Further, 30 ml of ethanol was added to prepare a sample solution.
The measurement can be calculated by the apparatus described above, but specifically, the calculation was performed as follows. Titration was carried out with N / 10 caustic potash-alcohol solution standardized in advance, and the acid value was determined from the consumption of alcohol potash solution by the following calculation.
Acid value = KOH (ml) x N x 56.1 / sample weight (where N is a factor of N / 10 KOH)

  As a method for measuring the hydroxyl value, 0.5 g of a sample was precisely weighed into a 100 ml volumetric flask, and 5 ml of an acetylating reagent was correctly added thereto. Then, it was heated by being immersed in a bath at 100 ° C. ± 5 ° C. After 1 to 2 hours, the flask was taken out of the bath, allowed to cool, then added with water and shaken to decompose acetic anhydride. Further, in order to complete the decomposition, the flask was again heated in a bath for 10 minutes or more and allowed to cool, and then the wall of the flask was thoroughly washed with an organic solvent. This solution was subjected to potentiometric titration with an N / 2 potassium hydroxide ethyl alcohol solution using the electrode to determine the OH value (according to JISK0070-1966).

  As a measuring method of the glass transition point, Rigaku THRMOFLEX TG8110 manufactured by Rigaku Denki Co., Ltd. was used. A method for measuring Tg will be outlined. As an apparatus for measuring Tg, a TG-DSC system TAS-100 manufactured by Rigaku Corporation was used. First, about 10 mg of a sample was placed in an aluminum sample container, placed on a holder unit, and set in an electric furnace. First, after heating from room temperature to 150 ° C. at a temperature rising rate of 10 ° C./min, the sample was allowed to stand at 150 ° C. for 10 min, the sample was cooled to room temperature and left for 10 min, and the temperature rising rate was again increased to 150 ° C. under a nitrogen atmosphere. DSC measurement was performed by heating at min. Tg was calculated from the contact point between the tangent line of the endothermic curve near the Tg and the base line using the analysis system in the TAS-100 system.

-Production of prepolymer 1-
Into a reaction vessel equipped with a cooling tube, a stirrer, and a nitrogen introduction tube, 795 parts of bisphenol A ethylene oxide 2-mole adduct, 200 parts of isophthalic acid, 65 parts of terephthalic acid, and 2 parts of dibutyltin oxide were added, and atmospheric pressure nitrogen was added. Under an air stream, the condensation reaction was performed at 210 ° C. for 8 hours. Subsequently, the reaction was continued for 5 hours while dehydrating under reduced pressure of 10 to 15 mmHg, then cooled to 80 ° C., reacted with 170 parts of isophorone diisocyanate in 1,500 parts of ethyl acetate for 2 hours, [Prepolymer Solution 1 ] Was obtained. The weight average molecular weight of the prepolymer in the obtained [prepolymer solution 1] was 90,000. Moreover, the prepolymer pure content in the [prepolymer solution 1] was 50%.

-Preparation of toner material oil dispersion 1-
In a beaker, 20 parts of [Prepolymer solution 1], ie, 10 parts of pure prepolymer, 155 parts of [low molecular weight polyester 1], and 80 parts of ethyl acetate were stirred and dissolved. Separately, 15 parts of carnauba wax as a release agent, 20 parts of carbon black pigment, and 110 parts of ethyl acetate were placed in a bead mill and dispersed for 30 minutes. The two liquids were mixed and stirred for 5 minutes at a rotational speed of 12,000 rpm using a TK homomixer, and then dispersed in a bead mill for 10 minutes. 1.2 parts of isophorone diamine was added to the dispersion, and the mixture was stirred for 5 minutes at 12,000 rpm using a TK homomixer to obtain [Oil Material Dispersion Liquid 1].

Example 1
In a beaker, 529.5 parts of ion-exchanged water, 70 parts of [resin fine particle dispersion 1] and 0.5 part of sodium dodecylbenzenesulfonate are added, and this aqueous dispersion is stirred with a TK homomixer at 12,000 rpm. 405.1 parts of the above [Toner material oil dispersion 1] was added to the mixture, and [Toner material oil dispersion 1] was dispersed while stirring for 30 minutes to obtain a dispersion slurry. Subsequently, a first solvent removal step was performed at 25 ° C. until the ethyl acetate concentration (residual solvent concentration) of the dispersion slurry with respect to 100 parts of pure toner became 20%.

  Next, the dispersion slurry which passed through the 1st solvent removal process was supplied in the inner tube | pipe of the ripening apparatus shown in FIG. 1, and the ripening process was performed. At this time, the temperature of the dispersed slurry in the inner tube was 55 ° C., and the slurry was retained in the tube for 3 hours and then discharged out of the tube.

  The dispersion slurry that has been subjected to the aging process is heated at 30 ° C. until the ethyl acetate concentration with respect to 100 parts of the toner is 0.5% or less to perform the second solvent removal process, followed by filtration, washing, drying, and then air classification. As a result, a spherical toner base was obtained. 100 parts of the obtained base particles and 0.25 part of a charge control agent (Bontron E-84 manufactured by Orient Chemical Co., Ltd.) were charged into a Q-type mixer (Mitsui Mining Co., Ltd.), and the peripheral speed of the turbine blades was set to 50 m / sec. And mixed. In this case, the mixing operation was performed for 2 minutes, 5 cycles of 1 minute pause, and the total treatment time was 10 minutes. Further, 0.5 part of hydrophobic silica (H2000, manufactured by Clariant Japan) was added and mixed. In this case, the mixing operation was performed at a peripheral speed of 15 m / sec, and 30 seconds of mixing and rest for 1 minute were carried out for 5 cycles to obtain the final [Toner 1].

Example 2
It was produced in the same manner as in Example 1 except that the residence time in the tube in the aging process was changed to 5 hours.

Example 3
This was produced in the same manner as in Example 1 except that the residence time in the ripening step was 5 hours and the aging temperature was changed to 63 ° C.

<Preparation of toner material oil dispersion 2>
In a beaker, 72 parts of [Prepolymer solution 1], ie, 36 parts of pure prepolymer, 129 parts of [low molecular weight polyester 1], and 80 parts of ethyl acetate were stirred and dissolved. Separately, 15 parts of carnauba wax as a release agent, 20 parts of carbon black pigment, and 84 parts of ethyl acetate were placed in a bead mill and dispersed for 30 minutes. The two liquids were mixed and stirred for 5 minutes at a rotational speed of 12,000 rpm using a TK homomixer, and then dispersed in a bead mill for 10 minutes. 4.4 parts of isophorone diamine was added to the dispersion, and the mixture was stirred for 5 minutes at 12,000 rpm using a TK homomixer to obtain [Oil Material Dispersion 2].

Example 4
In a beaker, 529.5 parts of ion-exchanged water, 70 parts of [resin fine particle dispersion 1] and 0.5 part of sodium dodecylbenzenesulfonate are added, and this aqueous dispersion is stirred with a TK homomixer at 12,000 rpm. 405.1 parts of the above [Toner material oil dispersion 2] was added, and [Toner material oil dispersion 2] was dispersed while stirring for 30 minutes to obtain a dispersion slurry.

  Subsequently, the first solvent removal step was performed at 25 ° C. until the ethyl acetate concentration in the dispersion slurry was 20% with respect to 100 parts of the pure toner.

  Next, the dispersion slurry which passed through the 1st solvent removal process was supplied in the inner tube | pipe of the ripening apparatus shown in FIG. 1, and the ripening process was performed. At this time, the dispersion slurry temperature in the tube was 55 ° C., and the slurry was allowed to stay in the tube for 1.5 hours, and then discharged outside the tube.

  The dispersion slurry that has undergone the aging process is subjected to a second solvent removal process at 30 ° C. until the ethyl acetate concentration with respect to 100 parts of pure toner is 0.5% or less, filtered, washed, dried, then air-classified, A toner base having a shape was obtained. 100 parts of the obtained base particles and 0.25 part of a charge control agent (Bontron E-84 manufactured by Orient Chemical Co., Ltd.) were charged into a Q-type mixer (Mitsui Mining Co., Ltd.), and the peripheral speed of the turbine blades was set to 50 m / sec. And mixed. In this case, the mixing operation was performed for 2 minutes, 5 cycles of 1 minute pause, and the total treatment time was 10 minutes. Further, 0.5 part of hydrophobic silica (H2000, manufactured by Clariant Japan) was added and mixed. In this case, the mixing operation was performed at a peripheral speed of 15 m / sec, and 30 seconds of mixing and resting for 1 minute were carried out for 5 cycles to obtain the final [Toner 4].

Example 5
[Toner 5] was obtained in the same manner as in Example 4 except that the residence time in the ripening step was changed to 3 hours.

Example 6
[Toner 6] was obtained in the same manner as in Example 4 except that the residence time in the ripening step was 3 hours and the aging temperature was changed to 63 ° C.

<Preparation of toner material oil dispersion 3>
In a beaker, 160 parts of [prepolymer solution 1], ie, 80 parts of pure prepolymer, 185 parts of [low molecular weight polyester 1], and 80 parts of ethyl acetate were stirred and dissolved. Separately, 15 parts of carnauba wax as a release agent, 20 parts of carbon black pigment, and 40 parts of ethyl acetate were placed in a bead mill and dispersed for 30 minutes. The two liquids were mixed and stirred for 5 minutes at a rotational speed of 12,000 rpm using a TK homomixer, and then dispersed in a bead mill for 10 minutes. 9.9 parts of isophorone diamine was added to the dispersion, and the mixture was stirred for 5 minutes at 12,000 rpm using a TK homomixer to obtain [Oil Material Dispersion 3].

Example 7
In a beaker, 529.5 parts of ion-exchanged water, 70 parts of [resin fine particle dispersion 1] and 0.5 part of sodium dodecylbenzenesulfonate are added, and this aqueous dispersion is stirred with a TK homomixer at 12,000 rpm. 405.1 parts of the above [Toner material oil-based dispersion liquid 3] was added, and [Toner material oil-based dispersion liquid 3] was dispersed while stirring for 30 minutes to obtain a dispersion slurry. Subsequently, the first solvent removal step was performed at 25 ° C. until the ethyl acetate concentration in the dispersion slurry was 20% with respect to 100 parts of the pure toner.

  Next, the dispersion slurry which passed through the 1st solvent removal process was supplied in the inner tube | pipe of the ripening apparatus shown in FIG. 1, and the ripening process was performed. At this time, the dispersion slurry temperature in the tube was 55 ° C., and the slurry was retained in the tube for 0.5 hour and then discharged outside the tube.

  The dispersion slurry that has undergone the aging process is subjected to a second solvent removal process at 30 ° C. until the ethyl acetate concentration with respect to 100 parts of pure toner is 0.5% or less, filtered, washed, dried, then air-classified, A toner base having a shape was obtained. 100 parts of the obtained base particles and 0.25 part of a charge control agent (Bontron E-84 manufactured by Orient Chemical Co., Ltd.) were charged into a Q-type mixer (Mitsui Mining Co., Ltd.), and the peripheral speed of the turbine blades was set to 50 m / sec. And mixed. In this case, the mixing operation was performed for 2 minutes, 5 cycles of 1 minute pause, and the total treatment time was 10 minutes. Further, 0.5 part of hydrophobic silica (H2000, manufactured by Clariant Japan) was added and mixed. In this case, the mixing operation was performed at a peripheral speed of 15 m / sec, and 30 seconds of mixing and rest for 1 minute were carried out for 5 cycles to obtain the final [Toner 7].

Example 8
[Toner 8] was obtained in the same manner as in Example 7 except that the residence time in the ripening step was changed to 1.5 hours.

<Preparation of toner material oil dispersion 4>
In a beaker, 16 parts of [Prepolymer solution 1], that is, 8 parts of pure prepolymer, 157 parts of [low molecular weight polyester 1], and 80 parts of ethyl acetate were stirred and dissolved. Separately, 15 parts of carnauba wax as a mold release agent, 20 parts of carbon black pigment, and 112 parts of ethyl acetate were placed in a bead mill and dispersed for 30 minutes. The two liquids were mixed and stirred for 5 minutes at a rotational speed of 12,000 rpm using a TK homomixer, and then dispersed in a bead mill for 10 minutes. 1.0 part of isophorone diamine was added to the dispersion, and the mixture was stirred for 5 minutes at 12,000 rpm using a TK homomixer to obtain [Oil Material Dispersion 4].

Example 9
In a beaker, 529.5 parts of ion-exchanged water, 70 parts of [resin fine particle dispersion 1] and 0.5 part of sodium dodecylbenzenesulfonate are added, and this aqueous dispersion is stirred with a TK homomixer at 12,000 rpm. 405.1 parts of the above [Toner material oil dispersion 4] was added, and [Toner material oil dispersion 4] was dispersed while stirring for 30 minutes to obtain a dispersion slurry. Subsequently, a first solvent removal step was performed at 25 ° C. until the ethyl acetate concentration in the dispersion slurry was 70% with respect to 100 parts of the pure toner.

  Next, the dispersion slurry which passed through the 1st solvent removal process was supplied in the inner tube | pipe of the ripening apparatus of FIG. 1, and the ripening process was performed. At this time, the dispersion slurry temperature in the tube was 55 ° C., and the slurry was retained in the tube for 3 hours and then discharged outside the tube.

  The dispersion slurry that has undergone the aging process is subjected to a second solvent removal process at 30 ° C. until the ethyl acetate concentration with respect to 100 parts of pure toner is 0.5% or less, filtered, washed, dried, then air-classified, A toner base having a shape was obtained. 100 parts of the obtained base particles and 0.25 part of a charge control agent (Bontron E-84 manufactured by Orient Chemical Co., Ltd.) were charged into a Q-type mixer (Mitsui Mining Co., Ltd.), and the peripheral speed of the turbine blades was set to 50 m / sec. And mixed. In this case, the mixing operation was performed for 2 minutes, 5 cycles of 1 minute pause, and the total treatment time was 10 minutes. Further, 0.5 part of hydrophobic silica (H2000, manufactured by Clariant Japan) was added and mixed. In this case, the mixing operation was performed at a peripheral speed of 15 m / sec, and 30 seconds of mixing and rest for 1 minute were carried out for 5 cycles to obtain the final [Toner 9].

Example 10
[Toner 10] was obtained in the same manner as in Example 9 except that the residence time in the ripening step was changed to 2 hours.

<Preparation of toner material oil dispersion 5>
In a beaker, 72 parts of [Prepolymer solution 1], ie, 36 parts of pure prepolymer, 129 parts of [low molecular weight polyester 1], and 80 parts of ethyl acetate were stirred and dissolved. Separately, 15 parts of carnauba wax as a release agent, 20 parts of carbon black pigment, and 84 parts of ethyl acetate were placed in a bead mill and dispersed for 30 minutes. The two liquids were mixed and stirred for 5 minutes at a rotational speed of 12,000 rpm using a TK homomixer, and then dispersed in a bead mill for 10 minutes. 1.8 parts of diethylenetriamine was added to the dispersion, and the mixture was stirred for 5 minutes at 12,000 rpm using a TK homomixer to obtain [Oil Material Dispersion 2].

Example 11
In a beaker, 529.5 parts of ion-exchanged water, 70 parts of [resin fine particle dispersion 1] and 0.5 part of sodium dodecylbenzenesulfonate are added, and this aqueous dispersion is stirred with a TK homomixer at 12,000 rpm. 405.1 parts of the above [Toner material oil dispersion 5] was added to the mixture, and [Toner material oil dispersion 5] was dispersed while stirring for 30 minutes to obtain a dispersion slurry. Subsequently, the first solvent removal step was performed at 25 ° C. until the ethyl acetate concentration in the dispersion slurry was 20% with respect to 100 parts of the pure toner.

  Next, the dispersion slurry which passed through the 1st solvent removal process was supplied in the inner tube | pipe of the ripening apparatus shown in FIG. 1, and the ripening process was performed. At this time, the dispersion slurry temperature in the tube was 55 ° C., and the slurry was retained in the tube for 3 hours and then discharged outside the tube.

  Next, the dispersion slurry that has undergone the aging process is subjected to a second solvent removal process at 30 ° C. until the ethyl acetate concentration with respect to 100 parts of the pure toner is 0.5% or less, filtered, washed, dried, and then air classification. As a result, a spherical toner base was obtained. 100 parts of the obtained base particles and 0.25 part of a charge control agent (Bontron E-84 manufactured by Orient Chemical Co., Ltd.) were charged into a Q-type mixer (Mitsui Mining Co., Ltd.), and the peripheral speed of the turbine blades was set to 50 m / sec. And mixed. In this case, the mixing operation was performed for 2 minutes, 5 cycles of 1 minute pause, and the total treatment time was 10 minutes. Further, 0.5 part of hydrophobic silica (H2000, manufactured by Clariant Japan) was added and mixed. In this case, the mixing operation was performed at a peripheral speed of 15 m / sec for 5 cycles of 30-second mixing for 1 minute to obtain the final [Toner 11].

<Preparation of toner material oil dispersion 6>
In a beaker, 72 parts of [Prepolymer solution 1], ie, 36 parts of pure prepolymer, 129 parts of [low molecular weight polyester 1], and 80 parts of ethyl acetate were stirred and dissolved. Separately, 15 parts of carnauba wax as a release agent, 20 parts of carbon black pigment, and 84 parts of ethyl acetate were placed in a bead mill and dispersed for 30 minutes. The two liquids were mixed and stirred for 5 minutes at a rotational speed of 12,000 rpm using a TK homomixer, and then dispersed in a bead mill for 10 minutes. 1.9 parts of triethylenetetramine was added to the dispersion, and the mixture was stirred for 5 minutes at 12,000 rpm using a TK homomixer to obtain [Oil Material Dispersion 6].

Example 12
In a beaker, 529.5 parts of ion-exchanged water, 70 parts of [resin fine particle dispersion 1] and 0.5 part of sodium dodecylbenzenesulfonate are added, and this aqueous dispersion is stirred with a TK homomixer at 12,000 rpm. 405.1 parts of the above [Toner material oil dispersion 6] was added to the mixture, and [Toner material oil dispersion 6] was dispersed while stirring for 30 minutes to obtain a dispersion slurry. Subsequently, the first solvent removal step was performed at 25 ° C. until the ethyl acetate concentration in the dispersion slurry was 20% with respect to 100 parts of the pure toner.

  Next, the dispersion slurry that has undergone the first desolvation step is supplied into the inner tube of the aging apparatus shown in FIG. 1, and the aging step is performed. At this time, the temperature of the dispersion slurry in the tube is 55 ° C. and stays in the tube for 3 hours. And then discharged out of the tube.

  The dispersion slurry that has undergone the aging process is subjected to a second solvent removal process at 30 ° C. until the ethyl acetate concentration with respect to 100 parts of pure toner is 0.5% or less, filtered, washed, dried, then air-classified, A toner base having a shape was obtained. 100 parts of the obtained base particles and 0.25 part of a charge control agent (Bontron E-84 manufactured by Orient Chemical Co., Ltd.) were charged into a Q-type mixer (Mitsui Mining Co., Ltd.), and the peripheral speed of the turbine blades was set to 50 m / sec. And mixed. In this case, the mixing operation was performed for 2 minutes, 5 cycles of 1 minute pause, and the total treatment time was 10 minutes. Further, 0.5 part of hydrophobic silica (H2000, manufactured by Clariant Japan) was added and mixed. In this case, the mixing operation was performed at a peripheral speed of 15 m / sec, and 30 seconds of mixing and rest for 1 minute were performed for 5 cycles to obtain the final [Toner 12].

<Preparation of toner material oil dispersion 7>
In a beaker, 160 parts of [prepolymer solution 1], ie, 80 parts of pure prepolymer, 185 parts of [low molecular weight polyester 1], and 80 parts of ethyl acetate were stirred and dissolved. Separately, 15 parts of carnauba wax as a release agent, 20 parts of carbon black pigment, and 40 parts of ethyl acetate were placed in a bead mill and dispersed for 30 minutes. The two liquids were mixed and stirred for 5 minutes at a rotational speed of 12,000 rpm using a TK homomixer, and then dispersed in a bead mill for 10 minutes. 4.2 parts of triethylenetetramine was added to the dispersion, and the mixture was stirred for 5 minutes at 12,000 rpm using a TK homomixer to obtain [Oil Material Dispersion 7].

Example 13
In a beaker, 529.5 parts of ion-exchanged water, 70 parts of [resin fine particle dispersion 1] and 0.5 part of sodium dodecylbenzenesulfonate are added, and this aqueous dispersion is stirred with a TK homomixer at 12,000 rpm. 405.1 parts of [Toner Material Oily Dispersion 7] was added to the mixture, and [Toner Material Oily Dispersion 7] was dispersed while stirring for 30 minutes to obtain a dispersion slurry. Subsequently, the first solvent removal step was performed at 25 ° C. until the ethyl acetate concentration in the dispersion slurry was 20% with respect to 100 parts of the pure toner.

  Next, the dispersion slurry which passed through the 1st solvent removal process was supplied in the inner tube | pipe of the ripening apparatus of FIG. 1, and the ripening process was performed. At this time, the dispersion slurry temperature in the tube was 55 ° C., and the slurry was retained in the tube for 3 hours and then discharged outside the tube.

  Next, the dispersion slurry that has undergone the aging process is subjected to a second solvent removal process at 30 ° C. until the ethyl acetate concentration with respect to 100 parts of the pure toner is 0.5% or less, filtered, washed, dried, and then air classification. As a result, a spherical toner base was obtained. 100 parts of the obtained base particles and 0.25 part of a charge control agent (Bontron E-84 manufactured by Orient Chemical Co., Ltd.) were charged into a Q-type mixer (Mitsui Mining Co., Ltd.), and the peripheral speed of the turbine blades was set to 50 m / sec. And mixed. In this case, the mixing operation was performed for 2 minutes, 5 cycles of 1 minute pause, and the total treatment time was 10 minutes. Further, 0.5 part of hydrophobic silica (H2000, manufactured by Clariant Japan) was added and mixed. In this case, the mixing operation was performed at a peripheral speed of 15 m / sec, and 30 seconds of mixing and rest for 1 minute were performed for 5 cycles to obtain final [Toner 13].

<Preparation of toner material oil dispersion 8>
In a beaker, 72 parts of [Prepolymer solution 1], ie, 36 parts of pure prepolymer, 129 parts of [low molecular weight polyester 1], and 80 parts of ethyl acetate were stirred and dissolved. Separately, 15 parts of carnauba wax as a release agent, 20 parts of carbon black pigment, and 84 parts of ethyl acetate were placed in a bead mill and dispersed for 30 minutes. The two liquids were mixed, stirred for 5 minutes at 12,000 rpm using a TK homomixer, then dispersed for 10 minutes using a bead mill, and 5 at 12,000 rpm using a TK homomixer. The mixture was stirred for a while to obtain [Toner material oil dispersion 8].

Example 14
In a beaker, 529.5 parts of ion-exchanged water, 70 parts of [resin fine particle dispersion 1] and 0.5 part of sodium dodecylbenzenesulfonate are added, and this aqueous dispersion is stirred with a TK homomixer at 12,000 rpm. 405.1 parts of the above [Toner material oil dispersion 8] was added, and [Toner material oil dispersion 8] was dispersed while stirring for 30 minutes to obtain a dispersion slurry. Subsequently, the first solvent removal step was performed at 25 ° C. until the ethyl acetate concentration in the dispersion slurry was 20% with respect to 100 parts of the pure toner.

  Next, the dispersion slurry which passed through the 1st solvent removal process was supplied in the inner tube | pipe of the ripening apparatus of FIG. 1, and the ripening process was performed. At this time, the dispersion slurry temperature in the tube was 55 ° C., and the slurry was retained in the tube for 3 hours and then discharged outside the tube.

  Next, the dispersion slurry that has undergone the aging process is subjected to a second solvent removal process at 30 ° C. until the ethyl acetate concentration with respect to 100 parts of the pure toner is 0.5% or less, filtered, washed, dried, and then air classification. As a result, a spherical toner base was obtained. 100 parts of the obtained base particles and 0.25 part of a charge control agent (Bontron E-84 manufactured by Orient Chemical Co., Ltd.) were charged into a Q-type mixer (Mitsui Mining Co., Ltd.), and the peripheral speed of the turbine blades was set to 50 m / sec. And mixed. In this case, the mixing operation was performed for 2 minutes, 5 cycles of 1 minute pause, and the total treatment time was 10 minutes. Further, 0.5 part of hydrophobic silica (H2000, manufactured by Clariant Japan) was added and mixed. In this case, the mixing operation was performed at a peripheral speed of 15 m / sec, and 30 seconds of mixing and rest for 1 minute were carried out for 5 cycles to obtain the final [Toner 14].

Example 15
[Toner 5] was obtained in the same manner as in Example 14 except that the residence time in the ripening step was changed to 1.7 hours.

Example 16
A toner was produced in the same manner as in Example 4 except that the ethyl acetate concentration in the first solvent removal step was changed to 10%, the dispersion slurry temperature in the aging step was changed to 40 ° C., and the residence in the tube was changed to 0.5 hour. ] Was obtained.

Example 17
[Toner 17] was produced in the same manner as in Example 4 except that the ethyl acetate concentration in the first solvent removal step was changed to 70%, the dispersion slurry temperature in the aging step was changed to 70 ° C., and the residence in the tube was changed to 20 hours. Obtained.

Example 18
[Toner 18] was obtained in the same manner as in Example 4 except that the ethyl acetate concentration in the second solvent removal step was changed to 5%.

Example 19
In Example 1, [Toner 19] was obtained in the same manner as in Example 1 except that the aging step was performed with an apparatus as shown in FIG.

Example 20
In Example 2, [Toner 20] was obtained in the same manner as in Example 2 except that the aging step was performed with an apparatus as shown in FIG.

Example 21
In Example 3, [Toner 21] was obtained in the same manner as in Example 3 except that the aging step was performed using an apparatus as shown in FIG.

Example 22
In Example 4, [Toner 22] was obtained in the same manner as in Example 4 except that the aging step was performed with an apparatus as shown in FIG.

Example 23
In Example 5, [Toner 23] was obtained in the same manner as in Example 5 except that the aging step was performed with an apparatus as shown in FIG.

Example 24
In Example 6, [Toner 24] was obtained in the same manner as in Example 6 except that the aging step was performed with an apparatus as shown in FIG.

Example 25
In Example 7, [Toner 25] was obtained in the same manner as in Example 7 except that the aging step was performed with an apparatus as shown in FIG.

Example 26
In Example 8, [Toner 26] was obtained in the same manner as in Example 8 except that the aging step was performed with an apparatus as shown in FIG.

Example 27
In Example 9, [Toner 27] was obtained in the same manner as in Example 9 except that the aging step was performed with an apparatus as shown in FIG.

Example 28
In Example 10, [Toner 28] was obtained in the same manner as in Example 10 except that the aging step was performed using an apparatus as shown in FIG.

Example 29
In Example 11, [Toner 29] was obtained in the same manner as in Example 11 except that the aging step was performed with an apparatus as shown in FIG.

Example 30
In Example 12, [Toner 30] was obtained in the same manner as in Example 12 except that the aging step was performed using an apparatus as shown in FIG.

Example 31
In Example 13, [Toner 31] was obtained in the same manner as in Example 13 except that the aging step was performed using an apparatus as shown in FIG.

Example 32
In Example 14, [Toner 32] was obtained in the same manner as in Example 14 except that the aging step was performed with an apparatus as shown in FIG.

Example 33
In Example 15, [Toner 33] was obtained in the same manner as in Example 15 except that the aging step was performed with an apparatus as shown in FIG.

Example 34
A toner was produced in the same manner as in Example 22 except that the ethyl acetate concentration in the first solvent removal step was changed to 10%, the dispersion slurry temperature in the aging step was changed to 40 ° C., and the residence time in the tube was changed to 0.5 hour. ] Was obtained.

Example 35
[Toner 35] was produced in the same manner as in Example 22 except that the ethyl acetate concentration in the first solvent removal step was changed to 70%, the dispersion slurry temperature in the aging step was changed to 70 ° C., and the residence in the tube was changed to 20 hours. Obtained.

Example 36
[Toner 36] was produced in the same manner as in Example 22 except that the ethyl acetate concentration in the second solvent removal step was changed to 5%.

Example 37
[Toner 37] was produced in the same manner as in Example 27 except that the ethyl acetate concentration in the first solvent removal step was changed to 20%.

<Preparation of Toner Material Oily Dispersion 9>
In a beaker, 200 parts of [Prepolymer solution 1], that is, 100 parts of pure prepolymer, 65 parts of [low molecular weight polyester 1] and 100 parts of ethyl acetate were stirred and dissolved. Separately, 15 parts of carnauba wax as a mold release agent, 20 parts of carbon black pigment, and 112 parts of ethyl acetate were placed in a bead mill and dispersed for 30 minutes. The two liquids were mixed and stirred for 5 minutes at a rotational speed of 12,000 rpm using a TK homomixer, and then dispersed in a bead mill for 10 minutes. To this dispersion was added 12.3 parts of isophorone diamine, and the mixture was stirred for 5 minutes at 12,000 rpm using a TK homomixer to obtain [Oil Material Dispersion Liquid 5].

  In a beaker, 529.5 parts of ion-exchanged water, 70 parts of [resin fine particle dispersion 1] and 0.5 part of sodium dodecylbenzenesulfonate are added, and this aqueous dispersion is stirred with a TK homomixer at 12,000 rpm. 405.1 parts of [Toner Material Oily Dispersion 9] was added to [Toner Material Oily Dispersion 9] while being stirred for 30 minutes to obtain a dispersion slurry. Subsequently, the first solvent removal step was performed at 25 ° C. until the ethyl acetate concentration in the dispersion slurry was 20% with respect to 100 parts of the pure toner.

  Next, the dispersion slurry which passed through the 1st solvent removal process was supplied in the inner tube | pipe of the ripening apparatus of FIG. 1, and the ripening process was performed. At this time, the dispersion slurry temperature in the tube was 55 ° C., and the slurry was allowed to stay in the tube for 1.5 hours, and then discharged outside the tube.

  Next, the dispersion slurry that has undergone the aging process is subjected to a second solvent removal process at 30 ° C. until the ethyl acetate concentration with respect to 100 parts of the pure toner is 0.5% or less, filtered, washed, dried, and then air classification. As a result, a spherical toner base was obtained. 100 parts of the obtained base particles and 0.25 part of a charge control agent (Bontron E-84 manufactured by Orient Chemical Co., Ltd.) were charged into a Q-type mixer (Mitsui Mining Co., Ltd.), and the peripheral speed of the turbine blades was set to 50 m / sec. And mixed. In this case, the mixing operation was performed for 2 minutes, 5 cycles of 1 minute pause, and the total treatment time was 10 minutes. Further, 0.5 part of hydrophobic silica (H2000, manufactured by Clariant Japan) was added and mixed. In this case, the mixing operation was performed at a peripheral speed of 15 m / sec, and 30 seconds of mixing and rest for 1 minute were carried out for 5 cycles to obtain the final [Toner 38].

Example 39
[Toner 39] was obtained in the same manner as in Example 30 except that the residence time in the ripening step was changed to 5 hours.

Example 40
[Toner 40] was obtained in the same manner as in Example 5 except that the stirring time of the TK homomixer was changed to 6 minutes.

Example 41
[Toner 41] was obtained in the same manner as in Example 5 except that the stirring time of the TK homomixer was changed to 4 minutes.

Example 42
[Toner 42] was obtained in the same manner as in Example 5 except that the stirring time of the TK homomixer was changed to 7 minutes.

Example 43
[Toner 43] was obtained in the same manner as in Example 5 except that the stirring time of the TK homomixer was changed to 3 minutes.

-Production of low molecular weight polyester 2-
229 parts by mass of bisphenol A ethylene oxide 2-mole adduct, 529 parts by mass of bisphenol A propion oxide 3-mole adduct, 208 parts by mass of terephthalic acid, 46 parts by mass of isophthalic acid And 2 parts by mass of dibutyltin oxide were added and reacted at 230 ° C. for 5 hours under normal pressure. Next, after the reaction solution was reacted for 2 hours under reduced pressure of 10 to 15 mmHg, 44 parts by mass of trimellitic anhydride was added to the reaction vessel, and the reaction was performed at 180 ° C. for 2 hours under normal pressure. Low molecular weight polyester 2] was synthesized. The obtained [low molecular weight polyester 2] had a THF-soluble component weight average molecular weight (Mw) of 1000, a glass transition temperature (Tg) of 47 ° C., an acid value of 24 mgKOH / g, and a hydroxyl value of 52 mgKOH / g. It was.

<Preparation of Toner Material Oily Dispersion 10>
In a beaker, 72 parts of [Prepolymer solution 1], ie, 36 parts of pure prepolymer, 129 parts of [low molecular weight polyester 2], and 164 parts of ethyl acetate were stirred and dissolved. Separately, 15 parts of carnauba wax as a mold release agent, 20 parts of carbon black pigment, and 112 parts of ethyl acetate were placed in a bead mill and dispersed for 30 minutes. The two liquids were mixed and stirred for 5 minutes at a rotational speed of 12,000 rpm using a TK homomixer, and then dispersed in a bead mill for 10 minutes. 12.3 parts of isophorone diamine was added to the dispersion, and the mixture was stirred for 5 minutes at 12,000 rpm using a TK homomixer to obtain [Oil Material Dispersion 10].

Example 44
[Toner 44] was produced in the same manner as in Example 23 except that [Toner material oil dispersion 2] was changed to [Toner material oil dispersion 10].

-Production of low molecular weight polyester 3-
229 parts by mass of bisphenol A ethylene oxide 2-mole adduct, 529 parts by mass of bisphenol A propion oxide 3-mole adduct, 208 parts by mass of terephthalic acid, 46 parts by mass of isophthalic acid And 2 parts by mass of dibutyltin oxide were added and reacted at 230 ° C. for 5 hours under normal pressure. Next, after reacting the reaction solution under a reduced pressure of 10 to 15 mmHg for 8 hours, 44 parts by mass of trimellitic anhydride was added to the reaction vessel, and the reaction was performed at 180 ° C. for 2 hours under normal pressure. Low molecular weight polyester 3] was synthesized. The obtained [low molecular weight polyester 3] had a weight average molecular weight (Mw) of 30,000, a glass transition temperature (Tg) of 48 ° C., an acid value of 21 mgKOH / g, and a hydroxyl value of 53 mgKOH / g. It was.

<Preparation of Toner Material Oily Dispersion 11>
In a beaker, 72 parts of [Prepolymer solution 1], that is, 36 parts of pure prepolymer, 129 parts of [low molecular weight polyester 3], and 164 parts of ethyl acetate were stirred and dissolved. Separately, 15 parts of carnauba wax as a mold release agent, 20 parts of carbon black pigment, and 112 parts of ethyl acetate were placed in a bead mill and dispersed for 30 minutes. The two liquids were mixed and stirred for 5 minutes at a rotational speed of 12,000 rpm using a TK homomixer, and then dispersed in a bead mill for 10 minutes. 12.3 parts of isophorone diamine was added to the dispersion, and the mixture was stirred for 5 minutes at 12,000 rpm using a TK homomixer to obtain [Toner Material Oily Dispersion 11].

Example 45
[Toner 44] was produced in the same manner as in Example 23 except that [Toner material oil dispersion 2] was changed to [Toner material oil dispersion 11].

-Production of low molecular weight polyester 4-
229 parts by mass of bisphenol A ethylene oxide 2-mole adduct, 529 parts by mass of bisphenol A propion oxide 3-mole adduct, 208 parts by mass of terephthalic acid, 46 parts by mass of isophthalic acid And 2 parts by mass of dibutyltin oxide were added and reacted at 230 ° C. for 5 hours under normal pressure. Next, after the reaction solution was reacted for 1 hour under reduced pressure of 10 to 15 mmHg, 44 parts by mass of trimellitic anhydride was added to the reaction vessel and reacted at 180 ° C. for 2 hours under normal pressure. Low molecular weight polyester 4] was synthesized. The obtained [low molecular weight polyester 4] had a weight-average molecular weight (Mw) of 900, a glass transition temperature (Tg) of 44 ° C., an acid value of 20 mgKOH / g, and a hydroxyl value of 49 mgKOH / g. It was.

<Preparation of Toner Material Oily Dispersion 12>
In a beaker, 72 parts of [Prepolymer solution 1], that is, 36 parts of pure prepolymer, 129 parts of [low molecular weight polyester 3], and 164 parts of ethyl acetate were stirred and dissolved. Separately, 15 parts of carnauba wax as a mold release agent, 20 parts of carbon black pigment, and 112 parts of ethyl acetate were placed in a bead mill and dispersed for 30 minutes. The two liquids were mixed and stirred for 5 minutes at a rotational speed of 12,000 rpm using a TK homomixer, and then dispersed in a bead mill for 10 minutes. 12.3 parts of isophorone diamine was added to the dispersion, and the mixture was stirred for 5 minutes at 12,000 rpm using a TK homomixer to obtain [Toner Material Oily Dispersion 12].

Example 46
[Toner 45] was produced in the same manner as in Example 23 except that [Toner material oil-based dispersion liquid 2] was changed to [Toner material oil-based dispersion liquid 12].

-Production of low molecular weight polyester 5-
229 parts by mass of bisphenol A ethylene oxide 2-mole adduct, 529 parts by mass of bisphenol A propion oxide 3-mole adduct, 208 parts by mass of terephthalic acid, 46 parts by mass of isophthalic acid And 2 parts by mass of dibutyltin oxide were added and reacted at 230 ° C. for 5 hours under normal pressure. Next, after the reaction solution was reacted for 9 hours under a reduced pressure of 10 to 15 mmHg, 44 parts by mass of trimellitic anhydride was added to the reaction vessel, and the reaction was performed at 180 ° C. for 2 hours under normal pressure. Low molecular polyester 5] was synthesized. The obtained [low molecular weight polyester 5] had a weight-average molecular weight (Mw) of 35,000, a glass transition temperature (Tg) of 49 ° C., an acid value of 18 mgKOH / g, and a hydroxyl value of 51 mgKOH / g. It was.

<Preparation of Toner Material Oily Dispersion 13>
In a beaker, 72 parts of [Prepolymer solution 1], that is, 36 parts of pure prepolymer, 129 parts of [low molecular weight polyester 4] and 164 parts of ethyl acetate were stirred and dissolved. Separately, 15 parts of carnauba wax as a mold release agent, 20 parts of carbon black pigment, and 112 parts of ethyl acetate were placed in a bead mill and dispersed for 30 minutes. The two liquids were mixed and stirred for 5 minutes at a rotational speed of 12,000 rpm using a TK homomixer, and then dispersed in a bead mill for 10 minutes. 12.3 parts of isophorone diamine was added to the dispersion, and the mixture was stirred for 5 minutes at 12,000 rpm using a TK homomixer to obtain [Toner Material Oily Dispersion 13].

Example 47
[Toner 46] was produced in the same manner as in Example 23 except that [Toner material oil-based dispersion 2] was changed to [Toner material oil-based dispersion 13].

-Production of prepolymer 2-
Into a reaction vessel equipped with a cooling tube, a stirrer, and a nitrogen introduction tube, 795 parts of bisphenol A ethylene oxide 2-mole adduct, 200 parts of isophthalic acid, 65 parts of terephthalic acid, and 2 parts of dibutyltin oxide were added, and atmospheric pressure nitrogen was added. Under an air stream, the condensation reaction was carried out at 210 ° C. for 5 hours. Next, the reaction was continued for 5 hours while dehydrating under reduced pressure of 10 to 15 mmHg, then cooled to 80 ° C., reacted with 170 parts of isophorone diisocyanate in 1,500 parts of ethyl acetate, and [prepolymer solution 2 ] Was obtained. The weight average molecular weight of the prepolymer in the obtained [prepolymer solution 2] was 10,000. Moreover, the prepolymer pure content in the [prepolymer solution 2] was 50%.

<Preparation of Toner Material Oily Dispersion 14>
In a beaker, 72 parts of [Prepolymer solution 2], ie, 36 parts of pure prepolymer, 129 parts of [low molecular weight polyester 1], and 164 parts of ethyl acetate were stirred and dissolved. Separately, 15 parts of carnauba wax as a mold release agent, 20 parts of carbon black pigment, and 112 parts of ethyl acetate were placed in a bead mill and dispersed for 30 minutes. The two liquids were mixed and stirred for 5 minutes at a rotational speed of 12,000 rpm using a TK homomixer, and then dispersed in a bead mill for 10 minutes. 12.3 parts of isophoronediamine was added to the dispersion, and the mixture was stirred for 5 minutes at 12,000 rpm using a TK homomixer to obtain [Oil Material Dispersion 14].

Example 48
[Toner 48] was produced in the same manner as in Example 23 except that [Toner material oil-based dispersion liquid 2] was changed to [Toner material oil-based dispersion liquid 14].

-Production of prepolymer 3-
Into a reaction vessel equipped with a cooling tube, a stirrer, and a nitrogen introduction tube, 795 parts of bisphenol A ethylene oxide 2-mole adduct, 200 parts of isophthalic acid, 65 parts of terephthalic acid, and 2 parts of dibutyltin oxide were added, and atmospheric pressure nitrogen was added. Under an air stream, the condensation reaction was performed at 210 ° C. for 10 hours. Subsequently, the reaction was continued for 5 hours while dehydrating under reduced pressure of 10 to 15 mmHg, then cooled to 80 ° C., reacted with 170 parts of isophorone diisocyanate in 1,500 parts of ethyl acetate for 2 hours, [Prepolymer Solution 3 ] Was obtained. The weight average molecular weight of the prepolymer in the obtained [prepolymer solution 3] was 200,000. Moreover, the prepolymer pure content in the [prepolymer solution 3] was 50%.

<Preparation of Toner Material Oily Dispersion 15>
In a beaker, 72 parts of [Prepolymer solution 3], ie, 36 parts of pure prepolymer, 129 parts of [low molecular weight polyester 1], and 164 parts of ethyl acetate were stirred and dissolved. Separately, 15 parts of carnauba wax as a mold release agent, 20 parts of carbon black pigment, and 112 parts of ethyl acetate were placed in a bead mill and dispersed for 30 minutes. The two liquids were mixed and stirred for 5 minutes at a rotational speed of 12,000 rpm using a TK homomixer, and then dispersed in a bead mill for 10 minutes. 12.3 parts of isophoronediamine was added to the dispersion, and the mixture was stirred for 5 minutes at 12,000 rpm using a TK homomixer to obtain [Oil Material Dispersion 14].

Example 49
[Toner 49] was produced in the same manner as in Example 23 except that [Toner material oil dispersion 2] was changed to [Toner material oil dispersion 15].

-Production of prepolymer 4-
Into a reaction vessel equipped with a cooling tube, a stirrer, and a nitrogen introduction tube, 795 parts of bisphenol A ethylene oxide 2-mole adduct, 200 parts of isophthalic acid, 65 parts of terephthalic acid, and 2 parts of dibutyltin oxide were added, and atmospheric pressure nitrogen was added. Under an air stream, the condensation reaction was carried out at 210 ° C. for 4 hours. Next, the reaction was continued for 5 hours while dehydrating under a reduced pressure of 10 to 15 mmHg, then cooled to 80 ° C., reacted with 170 parts of isophorone diisocyanate in 1,500 parts of ethyl acetate, and [prepolymer solution 4 ] Was obtained. The weight average molecular weight of the prepolymer in the obtained [prepolymer solution 4] was 9,000. Moreover, the prepolymer pure content in the [prepolymer solution 4] was 50%.

<Preparation of Toner Material Oily Dispersion 16>
In a beaker, 72 parts of [Prepolymer solution 4], ie, 36 parts of pure prepolymer, 129 parts of [low molecular weight polyester 1], and 164 parts of ethyl acetate were stirred and dissolved. Separately, 15 parts of carnauba wax as a mold release agent, 20 parts of carbon black pigment, and 112 parts of ethyl acetate were placed in a bead mill and dispersed for 30 minutes. The two liquids were mixed and stirred for 5 minutes at a rotational speed of 12,000 rpm using a TK homomixer, and then dispersed in a bead mill for 10 minutes. To this dispersion was added 12.3 parts of isophoronediamine, and the mixture was stirred for 5 minutes at 12,000 rpm using a TK homomixer to obtain [Toner Material Oily Dispersion 16].

Example 50
[Toner 50] was produced in the same manner as in Example 23 except that [Toner material oil-based dispersion liquid 2] was changed to [Toner material oil-based dispersion liquid 16].

-Production of prepolymer 5-
Into a reaction vessel equipped with a cooling tube, a stirrer, and a nitrogen introduction tube, 795 parts of bisphenol A ethylene oxide 2-mole adduct, 200 parts of isophthalic acid, 65 parts of terephthalic acid, and 2 parts of dibutyltin oxide were added, and atmospheric pressure nitrogen was added. Under an air stream, the condensation reaction was performed at 210 ° C. for 6 hours. Subsequently, the reaction was continued for 5 hours while dehydrating under a reduced pressure of 10 to 15 mmHg, then cooled to 80 ° C., reacted with 170 parts of isophorone diisocyanate in 1,500 parts of ethyl acetate for 2 hours [Prepolymer Solution 5 ] Was obtained. The weight average molecular weight of the prepolymer in the obtained [prepolymer solution 5] was 250,000. Moreover, the prepolymer pure content in the [prepolymer solution 5] was 50%.

<Preparation of Toner Material Oily Dispersion 17>
In a beaker, 72 parts of [Prepolymer solution 5], that is, 36 parts of pure prepolymer, 129 parts of [low molecular weight polyester 1], and 164 parts of ethyl acetate were stirred and dissolved. Separately, 15 parts of carnauba wax as a mold release agent, 20 parts of carbon black pigment, and 112 parts of ethyl acetate were placed in a bead mill and dispersed for 30 minutes. The two liquids were mixed and stirred for 5 minutes at a rotational speed of 12,000 rpm using a TK homomixer, and then dispersed in a bead mill for 10 minutes. 12.3 parts of isophorone diamine was added to the dispersion, and the mixture was stirred for 5 minutes at 12,000 rpm using a TK homomixer to obtain [Oil Material Dispersion 17].

Example 51
[Toner 51] was obtained in the same manner as in Example 23 except that [Toner material oil dispersion 2] was changed to [Toner material oil dispersion 17].

-Production of low molecular weight polyester 6-
229 parts by mass of bisphenol A ethylene oxide 2-mole adduct, 529 parts by mass of bisphenol A propion oxide 3-mole adduct, 208 parts by mass of terephthalic acid, 46 parts by mass of isophthalic acid And 2 parts by mass of dibutyltin oxide were added and reacted at 230 ° C. for 5 hours under normal pressure. Next, the reaction solution was reacted for 5 hours under a reduced pressure of 10 to 15 mmHg, and then 5 parts by mass of trimellitic anhydride was added to the reaction vessel and reacted at 180 ° C. for 2 hours under normal pressure. Low molecular weight polyester 6] was synthesized. The obtained [low molecular weight polyester 6] has a weight average molecular weight (Mw) of THF-soluble content of 5,500, a glass transition temperature (Tg) of 45 ° C., an acid value of 1.5 mgKOH / g, and a hydroxyl value of 80 mgKOH. / G.

<Preparation of Toner Material Oily Dispersion 18>
In a beaker, 72 parts of [Prepolymer solution 1], ie, 36 parts of pure prepolymer, 129 parts of [low molecular weight polyester 6], and 164 parts of ethyl acetate were stirred and dissolved. Separately, 15 parts of carnauba wax as a mold release agent, 20 parts of carbon black pigment, and 112 parts of ethyl acetate were placed in a bead mill and dispersed for 30 minutes. The two liquids were mixed and stirred for 5 minutes at a rotational speed of 12,000 rpm using a TK homomixer, and then dispersed in a bead mill for 10 minutes. 12.3 parts of isophorone diamine was added to the dispersion, and the mixture was stirred for 5 minutes at 12,000 rpm using a TK homomixer to obtain [Oil Material Dispersion 18].

Example 52
[Toner 52] was produced in the same manner as in Example 23 except that [Toner material oil-based dispersion liquid 2] was changed to [Toner material oil-based dispersion liquid 18].

-Production of low molecular weight polyester 7-
229 parts by mass of bisphenol A ethylene oxide 2-mole adduct, 529 parts by mass of bisphenol A propion oxide 3-mole adduct, 208 parts by mass of terephthalic acid, 46 parts by mass of isophthalic acid And 2 parts by mass of dibutyltin oxide were added and reacted at 230 ° C. for 5 hours under normal pressure. Next, the reaction solution was reacted for 5 hours under a reduced pressure of 10 to 15 mmHg, and then 80 parts by weight of trimellitic anhydride was added to the reaction vessel and reacted at 180 ° C. for 2 hours under normal pressure. Low molecular weight polyester 7] was synthesized. The obtained [low molecular weight polyester 7] has a weight average molecular weight (Mw) of THF-soluble content of 5,500, a glass transition temperature (Tg) of 46 ° C., an acid value of 40 mgKOH / g, and a hydroxyl value of 20 mgKOH / g. Met.

<Preparation of Toner Material Oily Dispersion 19>
In a beaker, 72 parts of [Prepolymer solution 1], ie, 36 parts of pure prepolymer, 129 parts of [low molecular weight polyester 7], and 164 parts of ethyl acetate were stirred and dissolved. Separately, 15 parts of carnauba wax as a mold release agent, 20 parts of carbon black pigment, and 112 parts of ethyl acetate were placed in a bead mill and dispersed for 30 minutes. The two liquids were mixed and stirred for 5 minutes at a rotational speed of 12,000 rpm using a TK homomixer, and then dispersed in a bead mill for 10 minutes. To this dispersion was added 12.3 parts of isophoronediamine, and the mixture was stirred for 5 minutes at 12,000 rpm using a TK homomixer to obtain [Oil Material Dispersion 19].

Example 53
[Toner 53] was obtained in the same manner as in Example 23 except that [Toner material oil-based dispersion 2] was changed to [Toner material oil-based dispersion 19].

-Production of low molecular polyester 8-
229 parts by mass of bisphenol A ethylene oxide 2-mole adduct, 529 parts by mass of bisphenol A propion oxide 3-mole adduct, 208 parts by mass of terephthalic acid, 46 parts by mass of isophthalic acid And 2 parts by mass of dibutyltin oxide were added and reacted at 230 ° C. for 5 hours under normal pressure. Next, after reacting the reaction solution under a reduced pressure of 10 to 15 mmHg for 5 hours, 2 parts by weight of trimellitic anhydride was added to the reaction vessel, and the reaction was performed at 180 ° C. for 2 hours under normal pressure. Low molecular weight polyester 8] was synthesized. The obtained [Low molecular weight polyester 8] has a weight-average molecular weight (Mw) of THF-soluble content of 5,400, a glass transition temperature (Tg) of 47 ° C., an acid value of 0.8 mgKOH / g, and a hydroxyl value of 91 mgKOH. / G.

<Preparation of Toner Material Oily Dispersion 20>
In a beaker, 72 parts of [Prepolymer solution 1], ie, 36 parts of pure prepolymer, 129 parts of [low molecular weight polyester 8], and 164 parts of ethyl acetate were stirred and dissolved. Separately, 15 parts of carnauba wax as a mold release agent, 20 parts of carbon black pigment, and 112 parts of ethyl acetate were placed in a bead mill and dispersed for 30 minutes. The two liquids were mixed and stirred for 5 minutes at a rotational speed of 12,000 rpm using a TK homomixer, and then dispersed in a bead mill for 10 minutes. 12.3 parts of isophorone diamine was added to the dispersion, and the mixture was stirred for 5 minutes at 12,000 rpm using a TK homomixer to obtain [Toner Material Oily Dispersion 20].

Example 54
[Toner 54] was produced in the same manner as in Example 23 except that [Toner material oil dispersion 2] was changed to [Toner material oil dispersion 20].

-Production of low molecular weight polyester 9-
229 parts by mass of bisphenol A ethylene oxide 2-mole adduct, 529 parts by mass of bisphenol A propion oxide 3-mole adduct, 208 parts by mass of terephthalic acid, 46 parts by mass of isophthalic acid And 2 parts by mass of dibutyltin oxide were added and reacted at 230 ° C. for 5 hours under normal pressure. Next, after reacting the reaction solution under a reduced pressure of 10 to 15 mmHg for 5 hours, 90 parts by mass of trimellitic anhydride was added to the reaction vessel, and the reaction was performed at 180 ° C. for 2 hours under normal pressure. Low molecular polyester 9] was synthesized. The obtained [low molecular weight polyester 9] has a weight-average molecular weight (Mw) of 5,400, a glass transition temperature (Tg) of 45 ° C., an acid value of 45 mgKOH / g, and a hydroxyl value of 18 mgKOH / g. Met.

<Preparation of Toner Material Oily Dispersion 21>
In a beaker, 72 parts of [Prepolymer solution 1], that is, 36 parts of pure prepolymer, 129 parts of [low molecular weight polyester 9], and 164 parts of ethyl acetate were stirred and dissolved. Separately, 15 parts of carnauba wax as a mold release agent, 20 parts of carbon black pigment, and 112 parts of ethyl acetate were placed in a bead mill and dispersed for 30 minutes. The two liquids were mixed and stirred for 5 minutes at a rotational speed of 12,000 rpm using a TK homomixer, and then dispersed in a bead mill for 10 minutes. 12.3 parts of isophorone diamine was added to the dispersion, and the mixture was stirred for 5 minutes at 12,000 rpm using a TK homomixer to obtain [Toner Material Oily Dispersion 21].

Example 55
[Toner 55] was obtained in the same manner as in Example 23 except that [Toner material oil-based dispersion liquid 2] was changed to [Toner material oil-based dispersion liquid 21].

-Production of low molecular weight polyester 10-
163 parts of bisphenol A ethylene oxide 2-mole adduct, 470 parts of bisphenol A propylene oxide 2-mole adduct, 277 parts of terephthalic acid and 18 parts of isophthalic acid are charged into a reaction vessel equipped with a cooling pipe, a stirrer and a nitrogen introduction pipe. The condensation reaction was carried out at 210 ° C. for 8 hours under a normal pressure nitrogen stream. Subsequently, 73 parts of salicylic acid was added, and the condensation reaction was continued at 210 ° C. for 5 hours. Further, the reaction was continued for 5 hours while dehydrating under a reduced pressure of 10 to 15 mmHg, followed by cooling to obtain [Low Molecular Polyester 10]. The obtained [Low molecular weight polyester 10] had a weight-average molecular weight of 5700, a glass transition temperature of 40 ° C., an acid value of 21 KOH mg / g, and a hydroxyl value of 48 mg KOH / g.

<Preparation of Toner Material Oily Dispersion 22>
In a beaker, 72 parts of [Prepolymer solution 1], ie, 36 parts of pure prepolymer, 129 parts of [low molecular weight polyester 10], and 164 parts of ethyl acetate were stirred and dissolved. Separately, 15 parts of carnauba wax as a mold release agent, 20 parts of carbon black pigment, and 112 parts of ethyl acetate were placed in a bead mill and dispersed for 30 minutes. The two liquids were mixed and stirred for 5 minutes at a rotational speed of 12,000 rpm using a TK homomixer, and then dispersed in a bead mill for 10 minutes. 12.3 parts of isophorone diamine was added to the dispersion, and the mixture was stirred for 5 minutes at 12,000 rpm using a TK homomixer to obtain [Toner Material Oily Dispersion 22].

Example 56
[Toner 56] was produced in the same manner as in Example 23 except that [Toner material oil-based dispersion liquid 2] was changed to [Toner material oil-based dispersion liquid 22].

-Production of low molecular weight polyester 11-
Into a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen introducing tube, 668 parts of bisphenol A propylene oxide 2-mole adduct, 304 parts of terephthalic acid, and 5 parts of trimellitic anhydride are introduced, and under an atmospheric pressure nitrogen stream. The condensation reaction was carried out at 210 ° C. for 5 hours. Subsequently, 40 parts of salicylic acid was added, and the condensation reaction was continued at 210 ° C. for 5 hours. Furthermore, the reaction was continued for 5 hours while dehydrating under reduced pressure of 10 to 15 mmHg, and then cooled to obtain [Polyester 11]. The obtained [Low molecular weight polyester 11] had a weight average molecular weight of 5600, a glass transition temperature of 60 ° C., an acid value of 22 KOH mg / g, and a hydroxyl value of 49 mg KOH / g.

<Preparation of Toner Material Oily Dispersion 23>
In a beaker, 72 parts of [Prepolymer solution 1], ie, 36 parts of pure prepolymer, 129 parts of [low molecular weight polyester 11], and 164 parts of ethyl acetate were stirred and dissolved. Separately, 15 parts of carnauba wax as a mold release agent, 20 parts of carbon black pigment, and 112 parts of ethyl acetate were placed in a bead mill and dispersed for 30 minutes. The two liquids were mixed and stirred for 5 minutes at a rotational speed of 12,000 rpm using a TK homomixer, and then dispersed in a bead mill for 10 minutes. 12.3 parts of isophorone diamine was added to the dispersion, and the mixture was stirred for 5 minutes at 12,000 rpm using a TK homomixer to obtain [Oil Material Dispersion Liquid 23].

Example 57
[Toner 57] was produced in the same manner as in Example 23 except that [Toner material oil-based dispersion liquid 2] was changed to [Toner material oil-based dispersion liquid 23].

-Production of low molecular weight polyester 12-
270 parts of bisphenol A ethylene oxide 2-mole adduct, 260 parts of bisphenol A propylene oxide 2-mole adduct, 277 parts of terephthalic acid and 18 parts of isophthalic acid are charged into a reaction vessel equipped with a cooling pipe, a stirrer and a nitrogen introduction pipe. The condensation reaction was carried out at 210 ° C. for 8 hours under a normal pressure nitrogen stream. Subsequently, 73 parts of salicylic acid was added, and the condensation reaction was continued at 210 ° C. for 5 hours. Further, the reaction was continued for 5 hours while dehydrating under a reduced pressure of 10 to 15 mmHg, followed by cooling to obtain [Low Molecular Polyester 12]. The obtained [Low molecular weight polyester 12] had a weight-average molecular weight of 5,500, a glass transition temperature of 37 ° C., an acid value of 23 mgKOH / g, and a hydroxyl value of 51 mgKOH / g.

<Preparation of Toner Material Oily Dispersion 24>
In a beaker, 72 parts of [Prepolymer solution 1], that is, 36 parts of pure prepolymer, 129 parts of [low molecular weight polyester 12], and 164 parts of ethyl acetate were stirred and dissolved. Separately, 15 parts of carnauba wax as a mold release agent, 20 parts of carbon black pigment, and 112 parts of ethyl acetate were placed in a bead mill and dispersed for 30 minutes. The two liquids were mixed and stirred for 5 minutes at a rotational speed of 12,000 rpm using a TK homomixer, and then dispersed in a bead mill for 10 minutes. 12.3 parts of isophorone diamine was added to the dispersion, and the mixture was stirred for 5 minutes at 12,000 rpm using a TK homomixer to obtain [Toner Material Oily Dispersion 24].

Example 58
[Toner 58] was produced in the same manner as in Example 23 except that [Toner material oil dispersion 2] was changed to [Toner material oil dispersion 24].

-Production of low molecular polyester 13-
750 parts of bisphenol A propylene oxide 2-mole adduct, 320 parts of terephthalic acid, and 8 parts of trimellitic anhydride are put into a reaction vessel equipped with a cooling pipe, a stirrer, and a nitrogen introduction pipe. The condensation reaction was carried out at 210 ° C. for 5 hours. Subsequently, 44 parts of salicylic acid was added, and the condensation reaction was continued at 210 ° C. for 5 hours. Further, the reaction was continued for 5 hours while dehydrating under a reduced pressure of 10 to 15 mmHg, followed by cooling to obtain [Polyester 13]. The obtained [low molecular weight polyester 13] had a weight-average molecular weight of 5,700, a glass transition temperature of 68 ° C., an acid value of 22 mgKOH / g, and a hydroxyl value of 50 mgKOH / g.

<Preparation of toner material oil dispersion 25>
In a beaker, 72 parts of [Prepolymer solution 1], that is, 36 parts of pure prepolymer, 129 parts of [low molecular weight polyester 13], and 164 parts of ethyl acetate were stirred and dissolved. Separately, 15 parts of carnauba wax as a mold release agent, 20 parts of carbon black pigment, and 112 parts of ethyl acetate were placed in a bead mill and dispersed for 30 minutes. The two liquids were mixed and stirred for 5 minutes at a rotational speed of 12,000 rpm using a TK homomixer, and then dispersed in a bead mill for 10 minutes. To this dispersion was added 12.3 parts of isophoronediamine, and the mixture was stirred for 5 minutes at 12,000 rpm using a TK homomixer to obtain [Toner Material Oily Dispersion 25].

Example 59
[Toner 59] was produced in the same manner as in Example 23 except that [Toner material oil-based dispersion liquid 2] was changed to [Toner material oil-based dispersion liquid 25].

Comparative Example 1
In a beaker, 529.5 parts of ion-exchanged water, 70 parts of [resin fine particle dispersion 1] and 0.5 part of sodium dodecylbenzenesulfonate are added to the aqueous dispersion while stirring with a TK homomixer at 12000 rpm. [Toner material oil-based dispersion liquid 3] 405.1 parts was added, and [toner material oil-based dispersion liquid 3] was dispersed while stirring for 30 minutes to obtain a dispersion slurry.

  The dispersion solvent was subjected to a first desolvation step at 25 ° C. until the ethyl acetate concentration with respect to 100 parts of the pure toner became 20%.

  Next, the dispersion slurry which passed through the 1st solvent removal process was supplied in the inner tube | pipe of the ripening apparatus shown in FIG. 1, and the ripening process was performed. At this time, the temperature of the dispersed slurry in the tube was 50 ° C., and the slurry was retained in the tube for 0.3 hours and then discharged outside the tube.

  Next, the dispersion slurry that has undergone the aging process is subjected to a second solvent removal process at 30 ° C. until the ethyl acetate concentration with respect to 100 parts of the pure toner is 0.5% or less, filtered, washed, dried, and then air classification. As a result, a spherical toner base was obtained. 100 parts of the obtained base particles and 0.25 part of a charge control agent (Bontron E-84 manufactured by Orient Chemical Co., Ltd.) were charged into a Q-type mixer (Mitsui Mining Co., Ltd.), and the peripheral speed of the turbine blades was set to 50 m / sec. And mixed. In this case, the mixing operation was performed for 2 minutes, 5 cycles of 1 minute pause, and the total treatment time was 10 minutes. Further, 0.5 part of hydrophobic silica (H2000, manufactured by Clariant Japan) was added and mixed. In this case, the mixing operation was performed at a peripheral speed of 15 m / sec, and 30 seconds of mixing and rest for 1 minute were carried out for 5 cycles to obtain the final [Toner 60].

(Adjustment of toner material oil dispersion 9)
In a beaker, 200 parts of [prepolymer solution 1], that is, 100 parts of pure prepolymer, 65 parts of [low molecular weight polyester 1], and 80 parts of ethyl acetate were stirred and dissolved. Separately, 15 parts of carnauba wax as a release agent, 20 parts of carbon black pigment, and 20 parts of ethyl acetate were placed in a bead mill and dispersed for 30 minutes. The two liquids were mixed and stirred for 5 minutes at a rotational speed of 12,000 rpm using a TK homomixer, and then dispersed in a bead mill for 10 minutes. 12.3 parts of isophorone diamine was added to the dispersion, and the mixture was stirred for 5 minutes at 12,000 rpm using a TK homomixer to obtain [Oil Material Dispersion 9].

Comparative Example 2
In a beaker, 529.5 parts of ion-exchanged water, 70 parts of [resin fine particle dispersion 1] and 0.5 part of sodium dodecylbenzenesulfonate are added to the aqueous dispersion while stirring with a TK homomixer at 12000 rpm. [Toner Material Oily Dispersion 9] 405.1 parts were added and [Toner Material Oily Dispersion 9] was dispersed while stirring for 30 minutes to obtain a dispersion slurry.

  The dispersion solvent was subjected to a first desolvation step at 25 ° C. until the ethyl acetate concentration with respect to 100 parts of the pure toner became 20%.

  Next, the dispersion slurry that has undergone the first desolvation step is supplied into the inner tube of the aging apparatus shown in FIG. 1, and the aging step is performed. At this time, the temperature of the dispersion slurry in the tube is 40 ° C. After staying for a while, it went out of the tube.

  Next, the dispersion slurry that has undergone the aging process is subjected to a second solvent removal process at 30 ° C. until the ethyl acetate concentration with respect to 100 parts of the pure toner is 0.5% or less, filtered, washed, dried, and then air classification. As a result, a spherical toner base was obtained. 100 parts of the obtained base particles and 0.25 part of a charge control agent (Bontron E-84 manufactured by Orient Chemical Co., Ltd.) were charged into a Q-type mixer (Mitsui Mining Co., Ltd.), and the peripheral speed of the turbine blades was set to 50 m / sec. And mixed. In this case, the mixing operation was performed for 2 minutes, 5 cycles of 1 minute pause, and the total treatment time was 10 minutes. Further, 0.5 part of hydrophobic silica (H2000, manufactured by Clariant Japan) was added and mixed. In this case, the mixing operation was performed at a peripheral speed of 15 m / sec, and 30 seconds of mixing and rest for 1 minute were carried out for 5 cycles to obtain the final [Toner 61].

Comparative Example 3
A “toner 62” was obtained in the same manner as in Example 4 except that the residence time in the aging process was changed to 25 hours.

Comparative Example 4
In a beaker, 529.5 parts of ion-exchanged water, 70 parts of [resin fine particle dispersion 2] and 0.5 part of sodium dodecylbenzenesulfonate are added, and this aqueous dispersion is stirred with a TK homomixer at 12,000 rpm. 405.1 parts of the above [Toner material oil dispersion 2] was added, and [Toner material oil dispersion 2] was dispersed while stirring for 30 minutes to obtain a dispersion slurry. Subsequently, the first solvent removal step was performed at 25 ° C. until the ethyl acetate concentration in the dispersion slurry was 75% with respect to 100 parts of the pure toner.

  Next, the dispersion slurry which passed through the 1st solvent removal process was supplied in the inner tube | pipe of the ripening apparatus shown in FIG. 1, and the ripening process was performed. At this time, the temperature of the dispersed slurry in the tube was 55 ° C., and the slurry was allowed to stay in the tube for 1.5 hours and then discharged out of the tube.

Comparative Example 5
[Toner 64] was produced in the same manner as in Example 4 except that the ethyl acetate concentration in the first solvent removal step was changed to 9%, the dispersion slurry temperature in the aging step was changed to 70 ° C., and the residence time in the tube was changed to 20 hours. Obtained.

Comparative Example 6
In a beaker, 529.5 parts of ion-exchanged water, 70 parts of [resin fine particle dispersion 2] and 0.5 part of sodium dodecylbenzenesulfonate are added, and this aqueous dispersion is stirred with a TK homomixer at 12,000 rpm. 405.1 parts of the above [Toner material oil dispersion 2] was added, and [Toner material oil dispersion 2] was dispersed while stirring for 30 minutes to obtain a dispersion slurry. Subsequently, the first solvent removal step was performed at 25 ° C. until the ethyl acetate concentration in the dispersion slurry was 20% with respect to 100 parts of the pure toner.

  Next, the dispersion slurry which passed through the 1st solvent removal process was supplied in the inner tube | pipe of the ripening apparatus shown in FIG. 1, and the ripening process was performed. At this time, the temperature of the dispersed slurry in the tube was 80 ° C., and the slurry was allowed to stay in the tube for 1.5 hours and then discharged outside the tube.

Comparative Example 7
[Toner 66] was produced in the same manner as in Example 4 except that the dispersion slurry temperature in the aging step was changed to 30 ° C. and the residence time in the tube was changed to 20 hours.

Comparative Example 8
[Toner 67] was produced in the same manner as in Example 4 except that the ethyl acetate concentration in the second solvent removal step was 10%.

Comparative Example 9
In a beaker, 529.5 parts of ion-exchanged water, 70 parts of [resin fine particle dispersion 1] and 0.5 part of sodium dodecylbenzenesulfonate are added, and this aqueous dispersion is stirred with a TK homomixer at 12,000 rpm. 405.1 parts of the above [Toner material oil dispersion 2] was added, and [Toner material oil dispersion 2] was dispersed while stirring for 30 minutes to obtain a dispersion slurry.

  Subsequently, the first solvent removal step was performed at 25 ° C. until the ethyl acetate concentration in the dispersion slurry was 20% with respect to 100 parts of the pure toner.

  Next, the dispersion solvent is subjected to a second solvent removal step at 30 ° C. until the ethyl acetate concentration with respect to 100 parts of toner is 0.5% or less, filtered, washed, dried, then air-classified, and spherical Toner base was obtained. 100 parts of the obtained base particles and 0.25 part of a charge control agent (Bontron E-84 manufactured by Orient Chemical Co., Ltd.) were charged into a Q-type mixer (Mitsui Mining Co., Ltd.), and the peripheral speed of the turbine blades was set to 50 m / sec. And mixed. In this case, the mixing operation was performed for 2 minutes, 5 cycles of 1 minute pause, and the total treatment time was 10 minutes. Further, 0.5 part of hydrophobic silica (H2000, manufactured by Clariant Japan) was added and mixed. In this case, the mixing operation was performed at a peripheral speed of 15 m / sec, and 30 seconds of mixing and resting for 1 minute were carried out for 5 cycles to obtain the final [Toner 68].

Comparative Example 10
[Comparative Example 1] [Toner 69] was obtained in the same manner as Comparative Example 1 except that the aging process was performed using an apparatus as shown in Fig. 2.

Comparative Example 11
[Comparative Example 2] [Toner 70] was obtained in the same manner as Comparative Example 2 except that the aging step was performed using an apparatus as shown in Fig. 2.

Comparative Example 12
In Comparative Example 3, [Toner 71] was obtained in the same manner as in Comparative Example 3 except that the aging step was performed with an apparatus as shown in FIG.

Comparative Example 13
In Comparative Example 4, production was carried out in the same manner as in Comparative Example 4 except that the ripening step was carried out with an apparatus as shown in FIG. 2, but the result was the same as in Comparative Example 4, and no toner was obtained.

Comparative Example 14
In Comparative Example 5, [Toner 73] was obtained in the same manner as in Comparative Example 5 except that the aging step was performed with an apparatus as shown in FIG.

Comparative Example 15
In Comparative Example 6, production was carried out in the same manner as in Comparative Example 6 except that the aging step was carried out with the apparatus as shown in FIG. 2, but the result was the same as in Comparative Example 6, and no toner was obtained.

Comparative Example 16
[Comparative Example 7] [Toner 75] was obtained in the same manner as in Comparative Example 7, except that the aging step was performed with an apparatus as shown in Fig. 2.

Comparative Example 17
[Comparative Example 8] [Toner 76] was obtained in the same manner as in Comparative Example 8, except that the aging step was performed using the apparatus shown in FIG.

  Tables 1 to 4 show the content of polyester as the raw material of the toner, the weight average molecular weight (Mw) of the THF soluble component, the glass transition temperature (Tg), the acid value, the hydroxyl value, the isocyanate group [NCO], and the hydroxyl group. Equivalent ratio ([NCO] / [OH]) of the hydroxyl group [OH] of the polyester having the isocyanate group [NCO] in the prepolymer (A) having an isocyanate group and the amino group [NHx] in the amine (B) Equivalent ratio ([NCO] / [NHx]), and the isocyanate group contained per molecule in the prepolymer (A) having an isocyanate group.

(Evaluation)
Using the obtained [Toner 1] to [Toner 76], the following items were evaluated. The results are shown in Tables 5-8.

<Volume average particle diameter Dv and ratio (Dv / Dn)>
The volume average particle diameter Dv and the ratio (Dv / Dn) of the toner are obtained by using an Coulter Counter TA-II type (manufactured by Coulter, Inc.), an interface for outputting the number distribution and the volume distribution (Nikka Giken Co., Ltd.) Measurement was performed by connecting a PC 9801 personal computer (manufactured by NEC).

  First, 0.1 to 5 ml of a surfactant (alkylbenzene sulfonate) was added as a dispersing agent to 100 to 150 ml of an electrolytic aqueous solution. The electrolytic aqueous solution is prepared by preparing a 1% by mass NaCl aqueous solution using primary sodium chloride, and ISOTON-II (manufactured by Coulter, Inc.) can be used. Next, 2 to 20 mg of a measurement sample was added. The electrolytic aqueous solution in which the measurement sample is suspended is subjected to a dispersion treatment for 1 to 3 minutes with an ultrasonic disperser, and the volume and number of toners are measured with the measurement apparatus using a 100 μm aperture as an aperture. The number distribution was calculated.

  As a channel, it is 2.00 micrometers or more and less than 2.52 micrometers; 2.52 micrometers or more and less than 3.17 micrometers; 3.17 micrometers or more and less than 4.00 micrometers; 4.00 micrometers or more and less than 5.04 micrometers; 5.04 micrometers or more and less than 6.35 micrometers; .35 μm or more and less than 8.00 μm; 8.00 μm or more and less than 10.08 μm; 10.08 μm or more and less than 12.70 μm; 12.70 μm or more and less than 16.00 μm; 16.00 μm or more and less than 20.20 μm; Less than 40 μm; 25.40 μm or more and less than 32.00 μm; 3 channels of 32.00 μm or more and less than 40.30 μm are used, and particles having a particle size of 2.00 μm or more and less than 40.30 μm are targeted. The volume-based volume average particle diameter Dv obtained from the volume distribution, the number average particle diameter Dn obtained from the number distribution and the ratio (Dv / Dn) were obtained.

<Acid value>
It was measured by the method specified in JISK0070. However, when the sample did not dissolve, dioxane or tetrahydrofuran was used as a solvent. The acid value was specifically determined by the following procedure.
Measuring device: automatic potentiometric titrator DL-53 Titrator (manufactured by METTLER TOLEDO)
Electrode used: DG113-SC (Metler Toledo)
Analysis software: LabX Light Version 1.00.000
Calibration of the apparatus: Use a mixed solvent of 120 ml of toluene and 30 ml of ethanol.
Measurement temperature: 23 ° C
The measurement conditions are as follows.
Still
Speed [%] 25
Time [s] 15
EQP titration
Titrant / Sensor
Titrant CH ₃ ONa
Concentration [mol / L] 0.1
Sensor DG115
Unit of measurement mV
Predispensing to volume
Volume [mL] 1.0
Wait time [s] 0
Titrant addition Dynamic
dE (set) [mV] 8.0
dV (min) [mL] 0.03
dV (max) [mL] 0.5
Measurement mode Equilibrium controlled
dE [mV] 0.5
dt [s] 1.0
t (min) [s] 2.0
t (max) [s] 20.0
Recognition
Threshold 100.0
Steppes jump only No
Range No
Tendency None
Termination
at maximum volume [mL] 10.0
at potential No
at slope No
after number EQPs Yes
n = 1
comb. termination conditions No
Evaluation
Procedure Standard
Potential 1 No
Potentialial 2 No
Stop for revaluation No

<Glass transition point Tg>
The glass transition point was measured with a Rigaku THRMOFLEX TG8110 manufactured by Rigaku Corporation under the condition of a heating rate of 10 ° C./min. A method for measuring Tg will be outlined. As an apparatus for measuring Tg, a TG-DSC system TAS-100 manufactured by Rigaku Corporation was used.

  First, about 10 mg of a sample is placed in an aluminum sample container, which is placed on a holder unit and set in an electric furnace. First, after heating from room temperature to 150 ° C. at a temperature rising rate of 10 ° C./min, the sample was allowed to stand at 150 ° C. for 10 min, the sample was cooled to room temperature and left for 10 min, and the temperature rising rate was again increased to 150 ° C. under a nitrogen atmosphere. DSC measurement was performed by heating at min. Tg was calculated from the contact point between the tangent line of the endothermic curve near the Tg and the base line using the analysis system in the TAS-100 system.

<Extraction residue (THF insoluble matter)>
The extraction residue amount is obtained by subjecting 0.30 g of the toner to Soxhlet extraction with tetrahydrofuran for 7 hours, measuring the weight of the extraction residue, and calculating the extraction residue amount [%] in the toner by the following formula.

Extraction residue amount [%] = Extraction residue weight [g] /0.30 [g] × 100

<Compound containing a nitrogen content (A) of a compound containing two or more isocyanate groups generated by thermal decomposition at a decomposition temperature of 50 ° C. to 700 ° C. and containing one or more isocyanate groups and one or more amino groups Nitrogen content (B) ratio (B) / (A)>
In the pyrolyzate generated by thermal decomposition of the toner from 50 ° C. to 700 ° C., the amount of nitrogen of the compound containing two or more isocyanate groups (A) and one or more isocyanate groups and one amino group The ratio (B) / (A) of the nitrogen content (B) of the compound contained above was measured as follows.

  100 μg of toner was weighed into a measuring cup, the cup was capped with inert wool, and the resultant was subjected to a thermal decomposition apparatus. The pyrolyzate generated by pyrolysis was trapped with liquid nitrogen, then sent to a gas chromatograph column, and each pyrolyzate was separated and detected by a nitrogen phosphorus detector.

The equipment conditions are as follows.
Gas chromatograph: HP6890 manufactured by Hewlett-Packard Company
Column: UltraALLOY ⁺ -5
Detector: Nitrogen phosphorus detector Pyrolysis device: PY-2020D manufactured by Frontier Laboratories
Thermal decomposition temperature: Start temperature 50 ° C Temperature increase rate 10 ° C / min Final temperature 700 ° C
Oven temperature: After holding at a starting temperature of 50 ° C. for 10 minutes, the temperature is raised to 250 ° C. at a temperature rising rate of 5 ° C./min. After reaching 250 ° C., the temperature is raised to 300 ° C. at a temperature rising rate of 25 ° C./min.
Injection temperature: 320 ° C
Sample amount: 100 μg

  The peak area (S1) of a compound containing two or more isocyanate groups detected by a nitrogen phosphorus detector and the peak area (S2) containing one or more isocyanate groups and one or more amino groups were determined. .

From the following formula, in the pyrolyzate generated by thermal decomposition of the toner from 50 ° C. to 700 ° C., the compound contains two or more isocyanate groups containing a nitrogen amount (A) and one or more isocyanate groups, and The ratio (B) / (A) of the nitrogen amount (B) of the compound containing one or more amino groups was calculated.
(B) / (A) = (S2) / (S1)

  The toners of Examples 1 to 59 and Comparative Examples 1 to 17 were evaluated as follows. Tables 9 to 12 show the performance evaluation results.

<Low-temperature fixability (fixing lower limit temperature and hot offset property)>
Ricoh Copier Co., Ltd. using a Teflon (registered trademark) roller as a fixing roller MF2200 A machine having a modified fixing unit was set with Ricoh type 6200 paper and subjected to a copying test. The cold offset temperature (fixing lower limit temperature) and the hot offset temperature (hot offset resistant temperature) were determined by changing the fixing temperature. The minimum fixing temperature of the conventional low-temperature fixing toner is about 140 to 150 ° C. The evaluation conditions for low-temperature fixing are as follows: the paper feed linear velocity is 120 to 150 mm / sec, the surface pressure is 1.2 kgf / cm ² , the nip width is 3 mm, and the high temperature offset is the evaluation condition for the paper feed linear velocity is 50 mm / sec. The surface pressure was set to 2.0 kgf / cm ² and the nip width was 4.5 mm. The criteria for each characteristic evaluation are as follows.

-Evaluation criteria for minimum fixing temperature-
A: Less than 140 ° C. O: 140-149 ° C.
□: 150-159 ° C
Δ: 160-170 ° C.
× 170 ℃ or more

-Evaluation criteria for hot offset-
◎: 201 ° C or higher ○: 200-191 ° C
□: 190-181 ° C
Δ: 180-171 ° C.
×: 170 ° C. or less

<Heat resistant storage stability>
After the toner was stored at 50 ° C. for 8 hours, it was sieved with a 42 mesh sieve for 2 minutes, and the residual ratio on the wire mesh was regarded as heat resistant storage stability. A toner having better heat-resistant storage stability has a lower residual ratio.

-Evaluation criteria for heat-resistant storage stability-
A: Less than 10% B: 10-20%
Δ: 20-30%
×: 30% or more

<Soil dirt>
Using a digital full-color copier (ImagioColor 2800, manufactured by Ricoh Co., Ltd.), running 30,000 image charts with a 50% image area in single-color mode, then stopping the blank image during development, and developing on the photoreceptor after development The agent was transferred to tape, and the difference from the image density of the untransferred tape was measured with a 938 spectrodensitometer (manufactured by X-Rite). The smaller the difference in image density, the better the background stain, and the better ones were ranked in the order of “◎”, “◯”, “Δ”, “×”.

<Toner scattering>
After continuous printing of 50,000 sheets using a digital full-color copying machine (imageColor 2800 manufactured by Ricoh), the degree of toner contamination in the machine was confirmed. A problem-free level was indicated by “◯”, a toner was observed, but a problem-free level was indicated by “Δ”, and a markedly contaminated and problematic problem was indicated by “X”.

<Image graininess, sharpness>
Using an evaluator, a photographic image was output in a single color, and the degree of graininess and sharpness was visually evaluated. In order from the best, “◎” is equivalent to offset printing, “○” is slightly worse than offset printing, “△” is much worse than offset printing, “×” is about the same as conventional electrophotographic images (very much Bad).

  As can be seen from the tables, Examples 1 to 59 show that the fixing minimum temperature and the hot offset property are good, and the heat-resistant storage stability is also excellent. On the other hand, Comparative Example 1 to Comparative Example 17 did not show good results for all of the minimum fixing temperature, hot offset property, and heat resistant storage stability, and an electrostatic charge image having stable low temperature fixability and high temperature offset resistance. It can be seen that the toner is not a developing toner.

  The toner of the present invention and the manufacturing method thereof are suitably used for high-quality electrophotographic image formation. The developer of the present invention using the toner of the present invention and the image forming method can be widely used for full-color copying machines, full-color laser printers, full-color plain paper fax machines and the like using a direct or indirect electrophotographic multicolor image development system. .

DESCRIPTION OF SYMBOLS 1 Outer tube 2 Inner tube 3 Inlet 4 Outlet 5 Dispersion blade 511 Fine hole 512 Stirring shaft 6 Baffle plate 10 Photoconductor (photoconductor drum)
10K electrostatic latent image carrier for black 10Y electrostatic latent image carrier for yellow 10M electrostatic latent image carrier for magenta 10C electrostatic latent image carrier for cyan 14 support roller 15 support roller 16 support roller 17 intermediate transfer cleaning device DESCRIPTION OF SYMBOLS 18 Image forming means 20 Charging roller 21 Exposure apparatus 22 Secondary transfer apparatus 23 Roller 24 Secondary transfer belt 25 Fixing apparatus 26 Fixing belt 27 Pressure roller 28 Sheet reversing apparatus 30 Exposure apparatus 32 Contact glass 33 1st traveling body 34 2nd Traveling body 35 Imaging lens 36 Reading sensor 40 Developing device 41 Developing belt 42K Developer container 42Y Developer container 42M Developer container 42C Developer container 43K Developer supply roller 43Y Developer supply roller 43M Developer supply roller 43C Developer supply roller 44K Development roller 44Y developing roller 44M developing roller 44C developing roller 45K black developing unit 45Y yellow developing unit 45M magenta developing unit 45C cyan developing unit 49 registration roller 50 intermediate transfer member 51 roller 52 corona charger 53 constant current source 55 switching claw 56 Ejection roller 57 Ejection tray 58 Separation roller 60 Cleaning device 61 Developer 62 Transfer charger 63 Photoconductor cleaning device 64 Electrification device 70 Electrification lamp 80 Transfer roller 90 Cleaning device 95 Transfer paper 100 Image forming device 120 Tandem type development device 130 Document table 142 paper feed roller 143 paper bank 144 paper feed cassette 145 separation roller 146 paper feed path 147 transport roller 148 paper feed path 150 copier main body 200 paper feed table 300 scanner 400 original Automatic transfer device (ADF)

Japanese Patent Laid-Open No. 11-133665 JP 2002-287400 A JP 2002-351143 A Japanese Patent No. 2579150 JP 2001-158819 A

Claims (3)

In an organic solvent, an aqueous phase is prepared by dissolving or dispersing a compound having at least an active hydrogen group, a polymer having a site capable of reacting with the compound having an active hydrogen group, a binder resin, a colorant, and a release agent. An aqueous granulation step for emulsifying or dispersing in a medium;
A first desolvation step of removing a part of the solvent of the granulated particles;
An aging step of heating the desolvated emulsion or dispersion at 40 ° C. to 70 ° C. for 0.5 to 25 hours;
A second desolvation step for removing the solvent in the emulsification or dispersion that has undergone the aging step;
A filtration step of filtering the emulsification or dispersion that has undergone the second solvent removal step;
A washing step for washing the filtered particles;
A drying step of drying the washed particles, and a method for producing a toner for an electrostatic charge image phenomenon, comprising:
The residual solvent concentration in the emulsification or dispersion after the first solvent removal step is 10% or more and 70% or less with respect to 100 parts of pure toner in the emulsion or dispersion, and the second solvent removal step. The residual solvent concentration in the subsequent emulsification or dispersion is 5% or less with respect to 100 parts of pure toner in the emulsification or dispersion;
The aging step, the emulsified or supplying a dispersion liquid in a tube within which is heated from the bottom of the soaker, an electrostatic image current image to the top, characterized in that for discharging the emulsion or dispersion of the soaker Toner manufacturing method. Have pores in the inner tube, a manufacturing method of the electrostatic image a toner for the current image according to claim 1, rotatable dispersing blades and baffles are provided. The polymer having a site capable of reacting with the compound having an active hydrogen group is an isocyanate group-containing polymer, and 5 to 40% of the isocyanate group-containing polymer is contained in the toner for developing an electrostatic image, and the electrostatic charge is contained. In the thermal decomposition product generated by thermal decomposition of the electrostatic charge image developing toner from 50 ° C. to 700 ° C., the extraction residue amount of Soxhlet extraction with tetrahydrofuran in the image developing toner is 2 to 50%. The ratio (B) / (A) of the amount of nitrogen (A) of the compound containing two or more and the amount of nitrogen (B) of the compound containing one or more isocyanate groups and one or more amino groups is 0. The method for producing a toner for developing an electrostatic charge image according to claim 1, wherein 1 ≦ (B) / (A) ≦ 6 is satisfied.