JP5685147B2 - Method for producing toner for electrophotography - Google Patents

Description

  The present invention relates to a method for producing an electrophotographic toner and an electrophotographic toner obtained thereby.

In recent years, from the pursuit of high image quality, development of a small particle size toner excellent in fixability has been desired.
For example, Patent Document 1 discloses that an alcohol component, an alkyl succinic acid, and an alkenyl succinic acid are used for manufacturing a toner having a step of forming a raw material component containing at least a polyester-containing binder resin in an aqueous medium or in a solution. An electrophotographic toner obtained by polycondensing a carboxylic acid component containing at least one selected from acids is disclosed.
Patent Document 2 discloses a resin emulsion in an aqueous medium that can be easily emulsified even when a cross-linked polyester is used, hardly causes hydrolysis of the resin, and can obtain a toner having excellent heat-resistant storage stability. A resin emulsion obtained by neutralizing a binder resin having an acid group with a basic compound, wherein the binder resin having an acid group contains 1 to 15 mol% of a trihydric or higher polyhydric alcohol. A resin emulsion containing polyester obtained from raw material monomers is disclosed.

JP 2007-248582 A JP 2008-058950 A

Rather than using a resin emulsion produced by phase inversion emulsification using an organic solvent, a resin emulsion obtained by granulating polyester in an aqueous medium in the presence of a surfactant is used in the step of forming particles in the solution. This is preferable because it generally has less influence on the environment.
However, when a resin emulsion obtained by granulating polyester in the presence of a surfactant is used, there is a problem that the hot offset resistance of the toner is lowered and the printed matter is faded when durable printing is performed.

  Also, depending on the type of paper, the paper temperature differs between the first fixing and the second fixing, and the actual fixing temperature may vary accordingly. However, the fixing process was performed at different fixing temperatures. Even in this case, it is particularly required in business documents that an image having a constant gloss can be obtained without changing the gloss.

  An object of the present invention is to obtain a printed material that is excellent in hot offset resistance and durable printability, and that does not fade even in durable printing, and even when fixing processing is performed at different fixing temperatures. It is an object of the present invention to provide an electrophotographic toner and a method for producing the same.

The present invention provides the following [1] and [2].
[1] A method for producing an electrophotographic toner, comprising the following steps 1 to 4.
Step 1: a carboxylic acid component containing 6 to 50 mol% of an alkyl succinic acid having an alkyl group having 9 to 18 carbon atoms and / or an alkenyl succinic acid having an alkenyl group having 9 to 18 carbon atoms, and a trivalent or higher valent fatty acid A step of obtaining an amorphous polyester A having a weight average molecular weight of 300,000 to 2,000,000 obtained by condensation polymerization with an alcohol component containing 5 to 40 mol% of a group alcohol Step 2: Non-obtained obtained in Step 1 Step of obtaining crystalline aqueous dispersion of amorphous polyester A by crystallizing crystalline polyester A in the presence of a surfactant in aqueous medium Step 3: Aqueous dispersion of amorphous polyester A obtained in Step 2 Step of aggregating with a release agent to obtain aggregated particles Step 4: Step of coalescing the aggregated particles obtained in Step 3 to obtain coalesced particles [2] The toner for electrophotography according to [1] above According to the manufacturing method Obtained, toner for electrophotography.

  The toner for electrophotography obtained by the production method of the present invention is excellent in hot offset resistance and durable printability, and can obtain a printed matter that does not fade even after durable printing. Further, the electrophotographic toner obtained by the production method of the present invention can stably obtain a certain gloss image even when the fixing process is performed at different fixing temperatures.

It is a figure explaining the evaluation method of the gross in an Example.

[Method for producing toner for electrophotography]
The method for producing an electrophotographic toner of the present invention includes the following steps 1 to 4.
Step 1: a carboxylic acid component containing 6 to 50 mol% of an alkyl succinic acid having an alkyl group having 9 to 18 carbon atoms and / or an alkenyl succinic acid having an alkenyl group having 9 to 18 carbon atoms, and a trivalent or higher valent fatty acid To obtain amorphous polyester A having a weight average molecular weight of 300 to 2,000,000 obtained by polycondensation with an alcohol component containing 5 to 40 mol% of a group alcohol Step 2: Amorphous obtained in Step 1 Step of obtaining a water-based dispersion of amorphous polyester A by granulating the polyester A in the presence of a surfactant in an aqueous medium Step 3: separation from the water-based dispersion of amorphous polyester A obtained in Step 2 Step of aggregating the mold and obtaining aggregated particles Step 4: Step of coalescing the aggregated particles obtained in Step 3

When the electrophotographic toner obtained by the production method of the present invention is excellent in hot offset resistance and durable printability, and a printed matter that does not fade even after durable printing is obtained, and the fixing treatment is performed at different fixing temperatures. However, the reason why a constant gloss image can be obtained stably is not clear, but can be considered as follows.
The resin emulsion obtained by granulating polyester in the presence of a surfactant in an aqueous medium is exposed on the particle surface of the aqueous emulsion as compared with a resin emulsion produced by phase inversion emulsification using an organic solvent. This is presumably because the amount of carboxyl groups is relatively small, and in the step of coalescence after aggregation, the coalescence speed is slow, and the wax as the release agent is easily removed from the toner particles. In particular, a polyester having a large weight average molecular weight of 300,000 to 2,000,000 is considered to have a slow coalescence rate.
On the other hand, a non-obtainable product obtained by using a specific amount of a trivalent or higher aliphatic alcohol and an alkyl succinic acid having an alkyl group having 9 to 18 carbon atoms and / or an alkenyl succinic acid having an alkenyl group having 9 to 18 carbon atoms. In the method for producing an electrophotographic toner of the present invention using crystalline polyester, it is considered that the detachment of wax is suppressed.
This is because, by using a trihydric or higher aliphatic alcohol as the raw material monomer of the amorphous polyester, the portion crosslinked with the trihydric or higher aliphatic alcohol has increased mobility due to the combined heat, and the coalescence speed is increased. Affinity with wax is enhanced by using alkyl succinic acid having an alkyl group having 9 to 18 carbon atoms and / or alkenyl succinic acid having an alkenyl group having 9 to 18 carbon atoms. it is conceivable that.
Hereinafter, each step in the method for producing an electrophotographic toner of the present invention will be described.

<Step 1>
Step 1 includes a carboxylic acid component containing 6 to 50 mol% of an alkyl succinic acid having an alkyl group having 9 to 18 carbon atoms and / or an alkenyl succinic acid having an alkenyl group having 9 to 18 carbon atoms, and a trivalent or higher valent component. This is a step of obtaining amorphous polyester A having a weight average molecular weight of 300,000 to 2,000,000 obtained by condensation polymerization with an alcohol component containing 5 to 40 mol% of an aliphatic alcohol.

Here, the crystallinity of a resin such as polyester is the crystallinity defined by the ratio between the softening point and the maximum endothermic peak temperature by a differential scanning calorimeter (DSC), that is, “softening point / maximum endothermic peak temperature”. Expressed by an index. Generally, when the crystallinity index exceeds 1.4, the resin is amorphous, and when it is less than 0.6, the crystallinity is low and there are many amorphous portions. In the present invention, “amorphous polyester” means a polyester having a crystallinity index of more than 1.4 or less than 0.6, and “crystalline polyester” means a crystallinity index of 0.6 to 1. .4, preferably 0.8 to 1.2, more preferably 0.9 to 1.1.
The above “maximum endothermic peak temperature” refers to the temperature of the peak on the highest temperature side among the endothermic peaks observed under the measurement method conditions described in the examples. If the maximum peak temperature is within 20 ° C from the softening point, the maximum peak temperature is the melting point of the crystalline polyester, and the peak with a difference from the softening point exceeding 20 ° C is a peak due to the glass transition of the amorphous polyester. And
The crystallinity of the resin can be adjusted by the type and ratio of the raw material monomers, production conditions (for example, reaction temperature, reaction time, cooling rate) and the like.

(Carboxylic acid component of amorphous polyester A)
The carboxylic acid component of the amorphous polyester A is an alkyl succinic acid having an alkyl group having 9 to 18 carbon atoms and / or an alkenyl having an alkenyl group having 9 to 18 carbon atoms from the viewpoint of hot offset resistance and durable printability. 6 to 50 mol%, preferably 10 to 43 mol%, more preferably 13 to 40 mol%, and still more preferably 15 to 35 mol% of succinic acid (hereinafter also referred to as “succinic acid compound”). When the content of the succinic acid compound is less than 6 mol%, the amount of the release agent taken up is small, the hot offset resistance is lowered and the durable printability is lowered. On the other hand, even when the content of the succinic acid compound exceeds 50 mol%, the durable printability is lowered, which is presumed to be due to the decrease in the hardness of the polyester.

The succinic acid compound may be an alkyl succinic acid and alkenyl succinic anhydride or a lower alkyl ester having 1 to 3 carbon atoms.
The number of carbon atoms of the alkyl group or alkenyl group in the alkyl succinic acid and alkenyl succinic acid is 9 to 18, preferably 9 to 14, more preferably 10 to 12 from the viewpoint of hot offset resistance and durable printability. . These alkyl groups and alkenyl groups may be linear or branched.
The succinic acid compound can be obtained by any production method. For example, an alkylene compound and at least one selected from maleic acid, fumaric acid, and acid anhydrides thereof are mixed and heated to obtain an succinic acid compound. It can be obtained by utilizing a reaction (see Japanese Patent Publication No. 48-23405, Japanese Patent Publication No. 48-23404, US Pat. No. 3,374,285, etc.). As the alkylene compound, a multimer (preferably a 3-5 mer) of ethylene, propylene, isobutylene and / or normal butylene is preferable.

In addition to the succinic acid compound, the carboxylic acid component of the amorphous polyester A may contain a dicarboxylic acid compound or a trivalent or higher polyvalent carboxylic acid compound.
Dicarboxylic acid compounds include oxalic acid, malonic acid, maleic acid, fumaric acid, citraconic acid, itaconic acid, glutaconic acid, succinic acid, adipic acid, sebacic acid, azelaic acid and other aliphatic dicarboxylic acids; phthalic acid, isophthalic acid And aromatic dicarboxylic acids such as terephthalic acid; alicyclic dicarboxylic acids such as cyclohexanedicarboxylic acid; and anhydrides and alkyl (C1 to C3) esters of these acids.
In the present invention, carboxylic acids, their anhydrides and their alkyl (carbon number 1 to 3) esters and the like are collectively referred to as “carboxylic acid compounds”. The alkyl group of the alkyl ester is not included in the carbon number. Examples of the alkyl group in the alkyl ester include a methyl group, an ethyl group, a propyl group, and an isopropyl group.
Examples of the trivalent or higher polyvalent carboxylic acid compounds include 1,2,4-benzenetricarboxylic acid (trimellitic acid), 2,5,7-naphthalenetricarboxylic acid, and aromatic carboxylic acids such as pyromellitic acid, and these Derivatives such as acid anhydrides and alkyl (1 to 3 carbon atoms) esters may be mentioned.
Among these, the carboxylic acid component of the amorphous polyester A preferably contains an aromatic dicarboxylic acid and more preferably contains terephthalic acid from the viewpoint of chargeability.

(Alcohol component of amorphous polyester A)
The alcohol component of the amorphous polyester A is 5 to 40 mol%, preferably 8 to 36 mol%, more preferably 10 to 30 mol of a trihydric or higher aliphatic alcohol from the viewpoint of hot offset resistance and durable printability. It contains in mol%, more preferably 10-25 mol%. When the content of the trihydric or higher aliphatic alcohol is less than 5 mol%, the coalescence speed is slow, the hot offset resistance is lowered, and the durable printability is lowered. On the other hand, when the content of the trihydric or higher aliphatic alcohol exceeds 40 mol%, a highly crosslinked structure is obtained, the amount of the release agent incorporated is small, the hot offset resistance is lowered, and the durable printability is lowered.

  Examples of the trihydric or higher aliphatic alcohol include glycerin, pentaerythritol, and trimethylolpropane, and glycerin is preferable from the viewpoint of durable printability.

  Examples of alcohol components other than trihydric or higher aliphatic alcohols include aromatic diols, aliphatic diols having 2 to 12 carbon atoms, and hydrogenated products of bisphenol A. Among these, among these, From the viewpoint of obtaining a crystalline polyester, an aromatic diol is preferred.

Aromatic diols include polyoxypropylene adducts of 2,2-bis (4-hydroxyphenyl) propane, polyoxyethylene adducts of 2,2-bis (4-hydroxyphenyl) propane, and the following formula (I ) And an alkylene oxide adduct of bisphenol A.
(In the formula, R represents an alkylene group having 2 or 3 carbon atoms. X and y represent the number of added moles of alkylene oxide, each being a positive number, and the average value of the sum of x and y is 1-16. Is preferable, 1-8 are more preferable, and 1.5-4 are still more preferable.)

  Examples of the aliphatic diol having 2 to 12 carbon atoms include ethylene glycol, 1,2-propanediol, 2,3-butanediol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, Examples include 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,12-dodecanediol, and the like.

(Method for producing amorphous polyester A)
The amorphous polyester A is obtained by polycondensation reaction of the carboxylic acid component and the alcohol component. The polycondensation reaction is preferably carried out in the presence of an esterification catalyst, and more preferably carried out in the presence of an esterification catalyst and a pyrogallol compound from the viewpoint of obtaining a polyester with high durable printability of the toner. The same applies to the production of amorphous polyester B and crystalline polyester C described later.

<Esterification catalyst>
Examples of the esterification catalyst suitably used for the condensation polymerization include a titanium compound and a tin (II) compound having no Sn-C bond, and these may be used alone or in combination of two or more. it can.

As a titanium compound, the titanium compound which has a Ti-O bond is preferable, and the compound which has a C1-28 total carbon number alkoxy group, an alkenyloxy group, or an acyloxy group is more preferable.
Specific examples of titanium compounds include titanium diisopropylate bistriethanolamate [Ti (C ₆ H ₁₄ O ₃ N) ₂ (C ₃ H ₇ O) ₂ ], titanium diisopropylate bisdiethanolamate [Ti (C _{4 H 10 O 2 N) 2 (} C 3 H 7 O) 2 ], titanium dipentylate bis triethanolaminate _{[Ti (C 6 H 14 O 3} N) 2 (C 5 H 11 O) 2 ], Chitanjiechi rate bis triethanolaminate _{[Ti (C 6 H 14 O 3} N) 2 (C 2 H 5 O) 2 ], titanium dihydroxy octylate bis triethanolaminate _{[Ti (C 6 H 14 O 3} N) 2 (OHC 8 H ₁₆ O) ₂ ], titanium distearate bistriethanolamate [Ti (C ₆ H ₁₄ O ₃ N) ₂ (C ₁₈ H ₃₇ O) ₂ ], titanium triisopropylate triethanolamate [Ti (C _{6 H 14 O 3 N) 1 (} C 3 ₇ O) _3], and titanium monopropylate tris (triethanolaminate) _{[Ti (C 6 H 14 O 3} N) 3 (C 3 H 7 O) 1 ], and the like. Of these, titanium diisopropylate bistriethanolaminate, titanium diisopropylate bisdiethanolamate, and titanium dipentylate bistriethanolamate are preferred, and these are also available as commercial products of Matsumoto Trading Co., Ltd. It is.

Specific examples of other preferable titanium compounds include tetra-n-butyl titanate [Ti (C ₄ H ₉ O) ₄ ], tetrapropyl titanate [Ti (C ₃ H ₇ O) ₄ ], tetrastearyl titanate [Ti ( C ₁₈ H ₃₇ O) ₄ ], tetramyristyl titanate [Ti (C ₁₄ H ₂₉ O) ₄ ], tetraoctyl titanate [Ti (C ₈ H ₁₇ O) ₄ ], dioctyl dihydroxyoctyl titanate [Ti (C ₈ H ₁₇ O) ₂ (OHC ₈ H ₁₆ O) ₂ ], dimyristyl dioctyl titanate [Ti (C ₁₄ H ₂₉ O) ₂ (C ₈ H ₁₇ O) ₂ ] and the like. Among these, tetrastearyl titanate, tetramyristyl titanate, tetraoctyl titanate, and dioctyl dihydroxy octyl titanate are preferable, and these can be obtained by reacting, for example, titanium halide with a corresponding alcohol. It is also available as a commercial product such as

Examples of the tin (II) compound having no Sn—C bond include a tin (II) compound having a Sn—O bond, a tin (II) compound having a Sn—X (X represents a halogen atom) bond, and the like. Preferred examples include tin (II) compounds having a Sn-O bond.
Examples of tin (II) compounds having a Sn-O bond include tin (II) oxalate, tin (II) diacetate, tin (II) dioctanoate, tin (II) 2-ethylhexanoate, and tin dilaurate (II). ), Tin (II) distearate, tin (II) carboxylate having a carboxylic acid group having 2 to 28 carbon atoms such as tin (II) dioleate; dioctyloxytin (II), dilauroxytin (II), distearoxytin Examples thereof include dialkoxytin (II) having a C2-28 alkoxy group such as (II) and dioleoxytin (II); tin (II) oxide; tin (II) sulfate.
Examples of the compound having a Sn-X (X represents a halogen atom) bond include tin (II) halides such as tin (II) chloride and tin (II) bromide. Among these, fatty acid tin (II) represented by (R ¹ COO) ₂ Sn (wherein R ¹ represents an alkyl group or alkenyl group having 5 to 19 carbon atoms) from the viewpoint of the charge rising effect and catalytic ability. ), (R ² O) ₂ Sn (wherein R ² represents an alkyl group or alkenyl group having 6 to 20 carbon atoms), and tin oxide (II) represented by SnO ), Fatty acid tin (II) and tin oxide (II) represented by (R ¹ COO) ₂ Sn are more preferred, tin (II) dioctanoate, tin (II) 2-ethylhexanoate, tin distearate ( II) and tin (II) oxide are more preferably used.

  The amount of the esterification catalyst present is preferably 0.01 to 1 part by weight, more preferably 0.1 to 0.6 part by weight, based on 100 parts by weight of the total amount of the alcohol component and the carboxylic acid component.

<Pyrogallol compound>
A pyrogallol compound has a benzene ring in which three hydrogen atoms adjacent to each other are substituted with a hydroxyl group, and pyrogallol, gallic acid, gallic acid ester, 2,3,4-trihydroxybenzophenone, 2,2 ′, Examples include benzophenone derivatives such as 3,4-tetrahydroxybenzophenone, and catechin derivatives such as epigallocatechin and epigallocatechin gallate.
The abundance of the pyrogallol compound in the condensation polymerization reaction is preferably 0.001 to 1 part by weight, and preferably 0.005 to 0.005 parts per 100 parts by weight of the total amount of the alcohol component and carboxylic acid component subjected to the condensation polymerization reaction. 4 parts by weight is more preferable, and 0.01 to 0.2 parts by weight is still more preferable. Here, the abundance of the pyrogallol compound means the total amount of the pyrogallol compound subjected to the condensation polymerization reaction.
The weight ratio of the pyrogallol compound to the esterification catalyst (pyrogallol compound / esterification catalyst) is preferably 0.01 to 0.5, more preferably 0.03 to 0.3, from the viewpoint of durable printability. More preferably, it is 05-0.2.

The polycondensation of the alcohol component and the carboxylic acid component can be performed, for example, at a temperature of 120 to 250 ° C. in an inert gas atmosphere in the presence of the esterification catalyst.
In addition, for example, all monomers are charged together to increase the strength of the resin, or divalent monomers are first reacted to reduce low molecular weight components, and then trivalent or higher monomers are added and reacted. A method may be used. Further, the reaction may be accelerated by reducing the pressure of the reaction system in the latter half of the polymerization.

(Physical properties of amorphous polyester A)
The weight average molecular weight of the amorphous polyester A is 300,000 to 2,000,000, preferably 300,000 to 1,500,000, more preferably 370,000, from the viewpoints of hot offset resistance and durable printing properties and image gloss. To 1,200,000, more preferably 400,000 to 1,000,000, still more preferably 45 to 650,000. When the weight average molecular weight of the amorphous polyester A is less than 300,000, the hot offset resistance is lowered and a constant gloss image cannot be obtained stably. On the other hand, when the weight average molecular weight of the amorphous polyester A exceeds 2 million, the coalescence speed becomes slow, the amount of the release agent taken up is small, and the durable printability is lowered.
In the present invention, the weight average molecular weight of polyester refers to a value measured by a measurement method described later.
Further, the number average molecular weight is preferably 1000 to 7000, more preferably 2000 to 5000, and more preferably 2000 to 4000 from the viewpoint of imparting hardness to the resin to improve the durability printability and not damaging the member of the toner device. Further preferred.

The softening point of the amorphous polyester A is preferably 70 to 180 ° C, more preferably 90 to 150 ° C, and still more preferably 110 to 125 ° C, from the viewpoint of hot offset resistance and durable printability.
The glass transition temperature (Tg) of the amorphous polyester A is preferably 45 to 80 ° C, more preferably 50 to 75 ° C, and still more preferably 54 to 64 ° C, from the viewpoint of hot offset resistance and durable printability. is there.
The acid value of the amorphous polyester A is preferably 2 to 40 mgKOH / g, more preferably 5 to 30 mgKOH / g, and more preferably 10 to 20 mgKOH / g from the viewpoint of improving the cohesiveness of the amorphous polyester A in the aqueous dispersion. g is more preferable.
The weight average molecular weight, softening point, Tg, and acid value can be easily adjusted by adjusting the raw material monomer composition, the polymerization initiator, the molecular weight, the catalyst amount, etc., or by selecting reaction conditions.

[Step 2]
Step 2 is a step in which the amorphous polyester A obtained in Step 1 is granulated in an aqueous medium in the presence of a surfactant to obtain an aqueous dispersion of amorphous polyester A.
Here, the aqueous medium is a medium containing water, and may contain a solvent such as an organic solvent. In the medium, water is preferably 70% by weight or more, preferably 80% by weight or more, and more preferably. Contains 90% by weight or more, more preferably 99% by weight or more, and even more preferably contains essentially 100% by weight of water. In addition, when using a solvent, the solubility of resin is considered and the organic solvent which melt | dissolves in the water mentioned later is preferable. The “aqueous dispersion of amorphous polyester A” refers to a liquid in which amorphous polyester A is dispersed in an aqueous medium. The same applies to an aqueous dispersion of amorphous polyester B and an aqueous dispersion of crystalline polyester C described later.
The aqueous dispersion of amorphous polyester A can be obtained by mixing amorphous polyester A, neutralizing agent, water, surfactant and the like and stirring. In addition, when stirring a mixture, generally used mixing stirring apparatuses, such as an anchor wing | blade, can be used. 30-90 degreeC is preferable and the temperature at the time of stirring a mixture has more preferable 40-80 degreeC.
The degree of neutralization of the amorphous polyester A is preferably 60 to 120 mol%, more preferably 70 to 100 mol%, from the viewpoint of dispersibility of the polyester resin. The degree of neutralization can be calculated by the method described in the examples.

  Examples of the neutralizing agent include alkali metals such as lithium hydroxide, sodium hydroxide, and potassium hydroxide; organic bases such as ammonia, trimethylamine, ethylamine, diethylamine, triethylamine, triethanolamine, and tributylamine.

Examples of the surfactant include anionic surfactants such as sulfate ester, sulfonate, phosphate ester, and soap (such as alkyl ether carboxylate); amine salt type, quaternary ammonium salt Examples include cationic surfactants such as molds; nonionic surfactants described later. In these, it is preferable to contain a nonionic surfactant from a viewpoint of being compatible with resin and improving the dispersibility of resin.
The amount of the surfactant used is preferably 0.1 to 20 parts by weight, more preferably 0.5 to 10 parts by weight, and more preferably 0.5 to 10 parts by weight with respect to 100 parts by weight of the amorphous polyester A from the viewpoint of granulating polyester A. More preferably, it is 1 to 5 parts by weight.

  Nonionic surfactants include, for example, polyoxyethylene alkyl aryl ethers such as polyoxyethylene nonylphenyl ether; polyoxyethylene alkyl ethers such as polyoxyethylene oleyl ether and polyoxyethylene lauryl ether; polyoxyethylene Polyoxyethylene sorbitan esters such as sorbitan monolaurate and polyoxyethylene sorbitan monostearate; Polyoxyethylene fatty acid esters such as polyethylene glycol monolaurate, polyethylene glycol monostearate, and polyethylene glycol monooleate And oxyethylene / oxypropylene block copolymers.

  As the nonionic surfactant, it is preferable to select a nonionic surfactant having good compatibility with the resin. In order to obtain a stable resin dispersion, the HLB of the nonionic surfactant is preferably 12 to 18 (Davies method). Depending on the type of resin, two or more different HLB nonionic interfaces are used. More preferably, an activator is used. For example, in the case of a highly hydrophilic resin, at least one nonionic surfactant having an HLB of 12 to 18 may be used. In the case of a highly hydrophobic resin, a low HLB, for example, 7 to 10 is used. It is preferable to adjust the weighted average of both HLBs to 12 to 18 by using those having the same level and those having a high HLB, for example, 14 to 20 in combination. In this case, it is presumed that those having an HLB of about 7 to 10 can compatibilize the resin, and those having a high HLB can stabilize the dispersion of the resin in water.

  The clouding point of the nonionic surfactant is preferably 70 to 105 ° C, more preferably 80 to 105 ° C when the resin is atomized under normal pressure and water.

(Aqueous dispersion of amorphous polyester A)
The solid content concentration of the aqueous dispersion of the amorphous polyester A is preferably 3 to 50% by weight, more preferably 5 to 30% by weight, and still more preferably 7 to 15% from the viewpoint of cohesion by appropriately adding water. % By weight.
The average particle size of the obtained dispersed particles of amorphous polyester A is preferably 0.05 to 0.8 μm in terms of volume median particle size from the viewpoint of improving hot offset resistance and durable printability, 0.5 micrometer is more preferable and 0.05-0.25 micrometer is still more preferable. The volume-median particle size can be measured by a laser diffraction type particle size measuring device described later.

[Step 3]
Step 3 is a step of aggregating the aqueous dispersion of amorphous polyester A obtained in Step 2 and a release agent to obtain aggregated particles.
In step 3, it is preferable to use an aqueous dispersion of amorphous polyester B and / or an aqueous dispersion of crystalline polyester C from the viewpoint of increasing the coalescence speed in step 4.

(Amorphous polyester B)
From the viewpoint of accelerating the coalescence rate of the amorphous polyester A in the coalescence step of Step 4, the succinic acid having an alkyl group having 9 to 18 carbon atoms and / or the alkenyl having an alkenyl group having 9 to 18 carbon atoms An amorphous material having a weight average molecular weight of 10,000 to 100,000, obtained by polycondensation of a carboxylic acid component containing 6 to 50 mol% of succinic acid and 5 to 30 mol% of a fumaric acid compound and an alcohol component. It is preferable to use an aqueous dispersion of polyester B. The low molecular weight amorphous polyester B is considered to act as a binder when the amorphous polyesters A are joined together.

<Carboxylic acid component of amorphous polyester B>
The carboxylic acid component of the amorphous polyester B is an alkyl succinic acid having an alkyl group having 9 to 18 carbon atoms and / or an alkenyl having an alkenyl group having 9 to 18 carbon atoms from the viewpoint of hot offset resistance and durable printability. It is preferable to contain 6-50 mol% of succinic acid (succinic acid compound) and 5-30 mol% of fumaric acid compound.

Here, as the succinic acid compound, the same succinic acid compound as described for the carboxylic acid component of the amorphous polyester A can be used, and the preferred range is also the same.
The carboxylic acid component of the amorphous polyester B is preferably 6 to 50 mol%, more preferably 10 to 43 mol%, still more preferably 13 to 40 mol% of a succinic acid compound from the viewpoint of hot offset resistance and durable printability. It is contained in a mol%, more preferably 15 to 35 mol%. If the content of the succinic acid compound is 6 mol% or more, it is preferable because a large amount of the release agent is incorporated into the toner particles, and if the content of the succinic acid compound is 50 mol% or less, the durability printability is improved. Also excellent.

The carboxylic acid component of the amorphous polyester B may contain a fumaric acid compound from the viewpoint of increasing the coalescing rate of the aggregated particles and incorporating the release agent into the toner particles to further improve the durable printability. preferable. This is presumably because the use of a fumaric acid compound creates a highly hydrophilic site in the resin and increases the polarity.
From such a viewpoint, the content of the fumaric acid compound in the carboxylic acid component of the amorphous polyester B is preferably 5 to 30 mol%, more preferably 10 to 30 mol%, still more preferably 15 to 25 mol%. It is.
A fumaric acid compound is a C1-C3 lower alkyl ester of fumaric acid, a fumaric acid anhydride, and fumaric acid.

  The carboxylic acid component of the amorphous polyester B may contain a dicarboxylic acid compound or a trivalent or higher polyvalent carboxylic acid compound in addition to the succinic acid compound and the fumaric acid compound. About these compounds, the same thing as the compound demonstrated by the carboxylic acid component of the amorphous polyester A can be used, and its preferable range is also the same.

<Alcohol component of amorphous polyester B>
The alcohol component of the amorphous polyester B is not particularly limited, but from the viewpoint of obtaining an amorphous polyester, the same alcohol component as described for the alcohol component of the amorphous polyester A can be used, and the preferred range is also It is the same.

(Physical properties of amorphous polyester B)
From the viewpoint of increasing the coalescence rate of the amorphous polyester A, the weight average molecular weight of the amorphous polyester B is preferably 5,000 to 100,000, more preferably 10,000 to 50,000, and still more preferably 10,000 to 30,000. It is. Further, the number average molecular weight is preferably 1000 to 7000, more preferably 2000 to 5000, and more preferably 2000 to 4000 from the viewpoint of imparting hardness to the resin to improve the durability printability and not damaging the member of the toner device. Further preferred.
The softening point of the amorphous polyester B is preferably 70 to 180 ° C, more preferably 90 to 150 ° C, from the viewpoint of increasing the coalescence rate of the amorphous polyester A.
From the viewpoint of increasing the coalescence rate of the amorphous polyester A, the glass transition temperature (Tg) of the amorphous polyester B is preferably 45 to 80 ° C., more preferably 50 to 75 ° C.
The acid value of the amorphous polyester B is preferably 2 to 40 mgKOH / g, more preferably 3 to 30 mgKOH / g, and still more preferably 5 to 25 mgKOH / g from the viewpoint of increasing the coalescence rate of the amorphous polyester A.
The weight average molecular weight, softening point, Tg, and acid value can be easily adjusted by adjusting the raw material monomer composition, the polymerization initiator, the molecular weight, the catalyst amount, etc., or by selecting reaction conditions.

(Aqueous dispersion of amorphous polyester B)
An aqueous dispersion of amorphous polyester B can be produced in the same manner as amorphous polyester A. The solid content concentration of the amorphous polyester B is preferably adjusted to 3 to 50% by weight, more preferably 5 to 30% by weight, and further preferably 7 to 15% by weight from the viewpoint of cohesion by adding water as appropriate. Is done.
The average particle size of the obtained dispersed particles of amorphous polyester B is preferably 0.05 to 0.8 μm in volume median particle size from the viewpoint of improving hot offset resistance and durable printability, 0.5 micrometer is more preferable and 0.05-0.25 micrometer is still more preferable. The volume-median particle size can be measured by a laser diffraction type particle size measuring device described later.

  When an aqueous dispersion of amorphous polyester B is used in the aggregation step of step 3, the weight ratio of amorphous polyester A to amorphous polyester B (amorphous polyester A / amorphous polyester B) From the viewpoint of hot offset property and durable printability, and from the viewpoint of increasing the coalescence speed of the amorphous polyester A, it is preferably 80/20 to 50/50, more preferably 70/30 to 50/40, and even more preferably 65. / 35 to 55/45.

(Crystalline polyester C)
In the coalescence step of Step 4, from the viewpoint of increasing the coalescence rate of the aggregated particles, an alcohol component containing 70 to 100 mol% of an aliphatic diol having 6 to 12 carbon atoms and an aliphatic dicarboxylic acid having 8 to 12 carbon atoms. It is preferable to use an aqueous dispersion of crystalline polyester C obtained by condensation polymerization with a carboxylic acid component containing 70 to 100 mol% of an acid compound.
This is presumably because the crystalline polyester melts at a temporary temperature and acts as a binder when the amorphous polyesters A unit as plasticizers.

<Alcohol component of crystalline polyester C>
The alcohol component of the crystalline polyester C preferably contains 70 to 100 mol% of an aliphatic diol having 6 to 12 carbon atoms from the viewpoint of increasing the coalescence rate and the compatibility with the release agent.

Examples of the aliphatic diol having 6 to 12 carbon atoms include 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,11 -Undecanediol, 1,12-dodecanediol, neopentyl glycol and the like. Among these, an aliphatic diol having 6 to 10 carbon atoms is preferable, and 1,9-nonanediol is more preferable from the viewpoint of increasing the coalescence rate and the compatibility with the release agent.
The content of the aliphatic diol having 6 to 12 carbon atoms is preferably 70 to 100 mol%, more preferably 80 to 100 in the alcohol component of the crystalline polyester C from the viewpoint of further improving the crystallinity of the crystalline polyester. It is mol%, More preferably, it is 90-100 mol%.

  The alcohol component of the crystalline polyester C may contain an aliphatic diol or aromatic diol having 2 to 5 carbon atoms in addition to the aliphatic diol having 6 to 12 carbon atoms. Examples of the aliphatic diol having 2 to 5 carbon atoms include ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol and the like. As the aromatic diol, the same compounds as those described for the alcohol component of the amorphous polyester A can be used.

<Carboxylic acid component of crystalline polyester C>
The carboxylic acid component of the crystalline polyester C preferably contains 70 to 100 mol% of an aliphatic dicarboxylic acid compound having 8 to 12 carbon atoms from the viewpoint of increasing the coalescence rate and compatibility with the release agent. .

Examples of the aliphatic dicarboxylic acid compound having 8 to 12 carbon atoms include suberic acid, azelaic acid, sebacic acid, 1,10-decanedicarboxylic acid and the like. Among these, an aliphatic dicarboxylic acid compound having 10 to 12 carbon atoms is preferable, and sebacic acid is more preferable from the viewpoint of increasing the coalescence rate and the compatibility with the release agent.
The content of the aliphatic dicarboxylic acid compound having 8 to 12 carbon atoms is preferably 70 to 100 mol%, more preferably in the carboxylic acid component of the crystalline polyester C from the viewpoint of further improving the crystallinity of the crystalline polyester. It is 80-100 mol%, More preferably, it is 90-100 mol%, More preferably, it is substantially 100 mol%.

In addition to the aliphatic dicarboxylic acid compound having 8 to 12 carbon atoms, the carboxylic acid component of the crystalline polyester C includes an aliphatic dicarboxylic acid compound or aromatic dicarboxylic acid compound having 3 to 7 carbon atoms and a trivalent or higher polyvalent carboxylic acid. An acid compound or the like may be contained.
Examples of the aliphatic dicarboxylic acid compound having 2 to 7 carbon atoms include oxalic acid, malonic acid, maleic acid, fumaric acid, citraconic acid, itaconic acid, glutaconic acid, succinic acid, and adipic acid. Examples of the aromatic dicarboxylic acid compound include phthalic acid, isophthalic acid, and terephthalic acid. Examples of the trivalent or higher polyvalent carboxylic acid compounds include derivatives of aromatic carboxylic acids such as 1,2,4-benzenetricarboxylic acid (trimellitic acid), 2,5,7-naphthalenetricarboxylic acid, and pyromellitic acid. Can be mentioned.

(Physical properties of crystalline polyester C)
The softening point of the crystalline polyester C is preferably 60 to 160 ° C, more preferably 60 to 120 ° C, still more preferably 65 to 100 ° C, and still more preferably 65 to 90 ° C, from the viewpoint of compatibility with the release agent. preferable.
The melting point of the crystalline polyester C is preferably 60 to 130 ° C, more preferably 65 to 110 ° C, and still more preferably 65 to 90 ° C, from the viewpoint of compatibility with the release agent.

The number average molecular weight of the crystalline polyester C is usually preferably 1,000 or more, more preferably 1,500 or more, from the viewpoint of compatibility with the release agent. However, considering the productivity of the crystalline polyester C, the number average molecular weight is preferably 6,000 or less, more preferably 5,000 or less, and further preferably 4,500 or less. From the above viewpoint, the number average molecular weight of the crystalline polyester C is preferably 1,000 to 6,000, more preferably 1,000 to 5,000, and still more preferably 1,500 to 4,500.
Further, the weight average molecular weight is preferably 3,000 or more, more preferably 5,000 or more, still more preferably 8,000 or more, preferably 100,000 or less, more preferably from the same viewpoint as the number average molecular weight. Is 50,000 or less, more preferably 30,000 or less, and still more preferably 20,000 or less. From the above viewpoint, the weight average molecular weight of the crystalline polyester C is preferably 3,000 to 100,000, more preferably 5,000 to 50,000, still more preferably 5,000 to 30,000, and 8,000 to 20,000 is even more preferable.

The acid value of the crystalline polyester C is preferably 10 to 40 mgKOH / g, more preferably 15 to 35 mgKOH / g, and still more preferably 20 to 30 mgKOH / g, from the viewpoint of compatibility with the release agent.
The hydroxyl value of the crystalline polyester C is preferably 1 to 20 mgKOH / g, more preferably 5 to 15 mgKOH / g, and still more preferably 7 to 13 mgKOH / g, from the viewpoint of compatibility with the release agent.
The softening point, melting point, number average molecular weight, weight average molecular weight, acid value and hydroxyl value can be easily adjusted by adjusting the raw material monomer composition, polymerization initiator, molecular weight, catalyst amount, etc., or by selecting reaction conditions. .

(Aqueous dispersion of crystalline polyester C)
The aqueous dispersion of crystalline polyester C can be produced in the same manner as the aqueous dispersion of amorphous polyester A.
The solid content concentration of the aqueous dispersion of crystalline polyester C is preferably 3 to 50% by weight, more preferably 5 to 30% by weight, and further preferably 7 to 15% from the viewpoint of cohesiveness by appropriately adding water. Adjusted to weight percent.
The average particle size of the obtained dispersed particles of crystalline polyester C is preferably 0.05 to 0.8 μm in terms of volume-median particle size from the viewpoint of improving hot offset resistance and durable printability. 0.5 μm is more preferable, and 0.05 to 0.25 μm is still more preferable. The volume-median particle size can be measured by a laser diffraction type particle size measuring device described later.

  When an aqueous dispersion of crystalline polyester C is used in the aggregation step of step 3, the weight ratio of amorphous polyester A to crystalline polyester C (amorphous polyester A / crystalline polyester C) is hot offset resistance. From the viewpoint of durable printability and compatibility with the release agent, it is preferably 95/5 to 60/40, more preferably 90/10 to 70/30.

(Release agent)
Release agents include fatty acid amides such as oleic acid amide, erucic acid amide, ricinoleic acid amide, and stearic acid amide; plant waxes such as carnauba wax, rice wax, candelilla wax, wood wax, and jojoba oil; Animal waxes such as beeswax; waxes such as mineral and petroleum waxes such as montan wax, ozokerite, ceresin, microcrystalline wax, and Fischer-Tropsch wax; polyolefin waxes, paraffin waxes and silicones. Among these, from the viewpoint of improving hot offset resistance and durable printability, at least one selected from the group consisting of polyolefin wax, paraffin wax, and Fischer-Tropsch wax is preferable.
You may use a mold release agent individually by 1 type or in combination of 2 or more types. The melting point of the release agent is preferably 60 to 140 ° C., more preferably 60 to 100 ° C., from the viewpoint of improving hot offset resistance and durable printability.
From the viewpoint of hot offset resistance and durable printability, the release agent is added in an amount of 0.1 parts by weight based on 100 parts by weight of the total amount of all polyesters (total amount of amorphous polyester and crystalline polyester, the same shall apply hereinafter). 5-15 weight part is preferable, 1-10 weight part is more preferable, and 3-8 weight part is still more preferable.
In the aggregation step, the solid content concentration in the system is preferably 5 to 50% by weight, more preferably 5 to 40% by weight, and still more preferably 10 to 30% by weight in order to cause uniform aggregation.

  In the aggregation step of step 3, for example, additives such as a coloring agent, a charge control agent, a conductivity adjusting agent, an extender pigment, a reinforcing filler such as a fibrous substance, an antioxidant, and an anti-aging agent are added. It may be aggregated. The additive can also be used as an aqueous dispersion.

There is no restriction | limiting in particular as a coloring agent, A well-known coloring agent is mentioned, According to the objective, it can select suitably. Specifically, carbon black, inorganic composite oxide, chrome yellow, hansa yellow, benzidine yellow, selenium yellow, quinoline yellow, permanent orange GTR, pyrazolone orange, vulcan orange, watch young red, permanent red, brilliantamine 3B, Brilliantamine 6B, DuPont Oil Red, Pyrazolone Red, Resol Red, Rhodamine B Lake, Lake Red C, Bengal, Aniline Blue, Ultramarine Blue, Calco Oil Blue, Methylene Blue Chloride, Phthalocyanine Blue, Phthalocyanine Green, Malachite Green Oxalate, etc. Various pigments: acridine, xanthene, azo, benzoquinone, azine, anthraquinone, indico, Indigo dyes, phthalocyanine, aniline black, polymethine, triphenylmethane dyes, diphenylmethane dyes, thiazine, and include various dyes of thiazole, and the like. These can be used alone or in combination of two or more.
The amount of the colorant added is preferably 0.1 to 20 parts by weight and more preferably 1 to 10 parts by weight with respect to 100 parts by weight of the total amount of all polyesters.

Examples of charge control agents include chromium azo dyes, iron azo dyes, aluminum azo dyes, and salicylic acid metal complexes. Various charge control agents may be used alone or in combination of two or more.
When the charge control agent is added, the addition amount is preferably 0.1 to 8 parts by weight, and more preferably 0.3 to 5 parts by weight with respect to 100 parts by weight of the total amount of all polyesters.

  The temperature in the system in the coagulation step is not less than “softening point of the mixed resin−60 ° C.” (meaning a temperature lower by 60 ° C. than the softening point of the mixed resin, the same applies hereinafter) and not more than the softening point of the mixed resin. preferable. When using a master batch, the weighted average temperature including the resin used in the master batch is taken as the softening point of the mixed resin. In this specification, the “softening point of the mixed resin” refers to a temperature obtained by weighted averaging of the softening point of the crystalline polyester and the softening point of the amorphous polyester. Specifically, it is preferably maintained at 40 ° C. or more and less than 60 ° C., more preferably 40 to 55 ° C. The time for the aggregation process is preferably 0.5 to 3 hours, more preferably 0.5 to 2 hours.

In addition, additives such as a colorant and a charge control agent may be mixed in advance with an amorphous polyester or a crystalline polyester when preparing resin particles, and each additive is separately dispersed in a dispersion medium such as water. The dispersion may be prepared, mixed with an aqueous dispersion of amorphous polyester and an aqueous dispersion of crystalline polyester, and subjected to an aggregation step.
When preparing a dispersion in which each additive is separately dispersed in a dispersion medium such as water, the amorphous polyester aqueous dispersion, the crystalline polyester aqueous dispersion and the colorant dispersion are subjected to the aggregation step. Thus, it is preferable to obtain aggregated particles.

In the aggregation process, an aggregating agent can be added in order to effectively perform aggregation. As the flocculant, a quaternary salt cationic surfactant, polyethyleneimine, and the like are used in the organic system, and an inorganic metal salt, an inorganic ammonium salt, a divalent or higher metal complex, and the like are used in the inorganic system.
Examples of the inorganic metal salt include metal salts such as sodium sulfate, sodium chloride, calcium chloride, calcium nitrate, barium chloride, magnesium chloride, zinc chloride, aluminum chloride, and aluminum sulfate; polyaluminum chloride, polyaluminum hydroxide, and Examples thereof include inorganic metal salt polymers such as calcium polysulfide. Examples of the inorganic ammonium salt include ammonium sulfate, ammonium chloride, and ammonium nitrate.
When the flocculant is added, the addition amount is preferably 0.3 to 20 parts by weight, and 0.5 to 10 parts by weight with respect to the total amount of 100 parts by weight of the total polyester, from the viewpoint of environmental resistance characteristics of the toner. More preferred is 0.5 to 5 parts by weight.
The flocculant is preferably added after being dissolved in an aqueous medium, and it is preferable that the flocculant is sufficiently stirred at the time of addition of the flocculant and after completion of the addition.

  The amount of the aqueous medium used is preferably from 100 to 3000 parts by weight, more preferably from 200 to 2000 parts by weight, more preferably from 200 to 1000 parts per 100 parts by weight of the total amount of all polyesters, from the viewpoint of obtaining aggregated particles having a uniform particle size. Part by weight is more preferred.

  The volume-median particle size of the aggregated particles obtained in step 3 is preferably 1 to 10 μm, more preferably 2 to 8 μm, and more preferably 3 to 7 μm from the viewpoint of uniformly coalescing in subsequent steps to produce coalesced particles. Is more preferable.

[Step 4]
Step 4 is a step of uniting the aggregated particles obtained in Step 3.
After adding a coagulation terminator to the aqueous dispersion of aggregated particles obtained in step 3 as necessary, coalesced particles can be obtained by a coalescence step of heating.
The temperature in the system in the coalescence process is not less than “softening point of the mixed resin−30 ° C.” or more and “the softening point + 10” from the viewpoint of the target toner particle size, particle size distribution, shape control and particle fusing property. "Softening point-25 ° C" or higher, "softening point + 10 ° C" or lower, more preferably "softening point-20 ° C" or higher, and "softening point + 10 ° C" or lower. Specifically, it is preferably maintained at 60 to 95 ° C, more preferably 70 to 95 ° C. The stirring speed is preferably a speed at which the aggregated particles do not settle. The time for the coalescing step is preferably 5 minutes to 1 hour, more preferably 5 to 30 minutes. Further, the circularity of the coalesced particles is preferably 0.97 or more, and more preferably 0.98 or more.
In addition, when using an aggregation terminator, it is preferable to use a surfactant as the aggregation terminator, and it is more preferable to use an anionic surfactant. Of the anionic surfactants, it is more preferable to use at least one selected from the group consisting of alkyl ether sulfates, alkyl sulfates, and linear alkylbenzene sulfonates.

[Electrophotographic toner]
The resin particles obtained in the coalescence step are appropriately subjected to a solid-liquid separation step such as filtration, a washing step, and a drying step to obtain the electrophotographic toner of the present invention (sometimes simply referred to as a toner). Can do.
In the washing step, it is preferable to use an acid in order to remove metal ions on the surface of the toner in order to ensure sufficient charging characteristics and reliability as the toner. Further, it is preferable to completely remove the added nonionic surfactant by washing, and washing with an aqueous solution below the cloud point of the nonionic surfactant is preferred. The washing is preferably performed a plurality of times.
In the drying step, any method such as a vibration type fluidized drying method, a spray drying method, a freeze drying method, a flash jet method, or the like can be employed. The water content after drying of the toner is preferably adjusted to 1.5% by weight or less, more preferably 1.0% by weight or less, from the viewpoint of chargeability.

(External additive)
Since the toner obtained as described above has low fusing property at the time of external addition treatment, an auxiliary agent such as a fluidizing agent can be easily added to the toner particle surface as an external additive. Examples of external additives include silica fine particles whose surfaces are hydrophobized, titanium oxide fine particles, alumina fine particles, cerium oxide fine particles, and inorganic fine particles such as carbon black; polymer fine particles such as polycarbonate, polymethyl methacrylate, and silicone resin. Fine particles can be used.
The number average particle diameter of the external additive is preferably 4 to 200 nm, more preferably 8 to 50 nm. The number average particle diameter of the external additive is determined using a scanning electron microscope or a transmission electron microscope.

  When the external additive is added, the addition amount is 0.8 to 5 parts by weight with respect to 100 parts by weight of the toner before the processing with the external additive, from the viewpoint of environmental stability of charge degree and weighted storage stability. Is preferred, 1 to 5 parts by weight is more preferred, and 1.5 to 4 parts by weight is even more preferred. However, when hydrophobic silica is used as the external additive, 0.8 to 4.5 parts by weight, preferably 1 to 4 parts by weight of hydrophobic silica is used with respect to 100 parts by weight of the toner before processing with the external additive. By using this, the desired effect can be obtained.

(Physical properties of electrophotographic toner)
The volume median particle size of the electrophotographic toner of the present invention is preferably from 1 to 10 μm, more preferably from 2 to 8 μm, and even more preferably from 3 to 7 μm, from the viewpoints of high image quality and productivity of the toner.
In the toner of the present invention, the weight ratio [crystalline polyester / amorphous polyester] of crystalline polyester and amorphous polyester is 5/95 to 40/60 from the viewpoint of toner transfer efficiency and print storage stability. Preferably, 6 / 94-30 / 70 is more preferable, and 7 / 93-25 / 75 is still more preferable.
The acid value of the binder resin used for the toner is preferably 1 to 40 mgKOH / g, more preferably 2 to 35 mgKOH / g, and more preferably 3 to 30 mgKOH / g from the viewpoints of toner chargeability, transfer efficiency, and print storage stability. Is more preferable.
The softening point of the binder resin used for the toner is preferably 80 to 160 ° C., more preferably 80 to 150 ° C., and further preferably 90 to 140 ° C. from the viewpoints of low-temperature fixability of the toner, transfer efficiency, and print storage stability. preferable. Moreover, 45-80 degreeC is preferable and 50-70 degreeC is more preferable from the same viewpoint as the glass transition temperature of the binder resin.

The electrophotographic toner of the present invention is a known toner binder resin different from the binder resin, for example, a styrene resin such as polyester or styrene-acrylic resin, or an epoxy resin, as long as the effects of the present invention are not impaired. Further, it may contain a resin such as polycarbonate or polyurethane.
The electrophotographic toner of the present invention can be used as a one-component developer or a two-component developer mixed with a carrier.

The alkenyl succinic anhydride compound used in the examples was obtained by the following production method.
(Production of alkylene compounds)
Using propylene tetramer (manufactured by Nippon Oil Corporation, trade name: Light Tetramer), an alkylene compound was obtained by fractional distillation under heating conditions of 183 to 208 ° C. The obtained alkylene compound had 40 peaks in gas chromatography mass spectrometry described later. The distribution of the alkylene compound was as follows: C ₉ H ₁₈ : 0.5 wt%, C ₁₀ H ₂₀ : 4 wt%, C ₁₁ H ₂₂ : 20 wt%, C ₁₂ H ₂₄ : 66 wt%, C ₁₃ H ₂₆ : 9 % By weight and C ₁₄ H ₂₈ : 0.5% by weight.

[Analysis of alkylene compounds by mass spectrometry gas chromatography]
A CI ion source and the following analytical column were attached to a mass spectrometric gas chromatograph (GC / MS) and started up. In addition, CI reaction gas (methane) was flowed, and tuning was performed 24 hours after the evacuation work of the MS part.

(1) GC
Gas chromatograph:
Product name: HP6890N, manufactured by Agilent
Analytical column:
Ultra 1 manufactured by HP (trade name, column length 50 m, inner diameter 0.2 mm, film thickness 0.33 μm)
GC oven temperature rising condition:
Initial temperature 100 ° C (0 min)
First stage heating rate 1 ° C / min (up to 150 ° C)
Second stage heating rate 10 ° C / min (up to 300 ° C)
Final temperature 300 ℃ (10min)
Sample injection volume: 1 μL
Inlet conditions:
Injection mode Split method Split ratio 50: 1
Inlet temperature 300 ° C
Carrier gas:
Gas helium flow 1ml / min (constant flow mode)

(2) Detector mass spectrometer: manufactured by Agilent, trade name: 5973N MSD
Ionization method: Chemical ionization method Reaction gas: Isobutane temperature setting:
Quadrupole 150 ° C
Ion source 250 ℃
Detection condition: Scan scan range: m / z 75-300
Detector ON time: 5 min
Calibration (mass calibration and sensitivity adjustment):
Reaction gas Methane calibrant PFDTD (Perfluoro-5,8-dimethyl-3,6,9-trioxidedecane)
Tuning method Auto tuning

(3) Sample preparation Propylene tetramer was prepared by dissolving in isopropyl alcohol at a concentration of 5% by weight.

(Data processing method)
For the alkene component of each carbon number in the range of 9 to 14 carbon atoms, a mass chromatogram with a mass number corresponding to each molecular ion is extracted, and under the condition of S / N (signal / noise ratio)> 3, Integration was performed according to the integration conditions for each component shown in Tables 2-5. From the detection results shown in Table 1, the ratio of the specific alkyl chain length component was calculated by the following formula.

(4) Integration condition component: C ₉ H ₁₈

Ingredient: C ₁₀ H ₂₀

Ingredients: C ₁₁ H ₂₂ , C ₁₂ H ₂₄ and C ₁₃ H ₂₆

Ingredients: C ₁₄ H ₂₈

  In the present invention, an alkylene compound having 9 to 14 carbon atoms refers to a peak corresponding to a molecular ion in gas chromatography mass spectrometry.

(Production of alkenyl succinic anhydride compound)
In a 1 L Nitto high-pressure autoclave, 542.4 g of the alkylene compound, 157.2 g of maleic anhydride, 0.4 g of triisooctyl phosphite (manufactured by SC Organic Chemical Co., Ltd., trade name: Chelex-O), butyl hydroquinone 0 0.1 g was charged, and pressurized nitrogen substitution (0.2 MPaG) was repeated three times. After stirring was started at 60 ° C., the temperature was raised to 230 ° C. over 1 hour and the reaction was performed for 6 hours. The pressure when the reaction temperature was reached was 0.3 MPaG. After completion of the reaction, the reaction mixture was cooled to 80 ° C., returned to normal pressure (101.3 kPa), and transferred to a 1 L four-necked flask. The temperature was raised while stirring to 180 ° C., and the remaining alkylene compound was distilled off at 1.3 kPa over 1 hour. Subsequently, after cooling to room temperature (25 ° C.), the pressure was returned to normal pressure (101.3 kPa) to obtain 406.1 g of the target alkenyl succinic anhydride compound. The average molecular weight of the alkenyl succinic anhydride compound determined from the acid value was 268.

About each physical-property value of resin etc., it measured with the following method.
<Softening point of resin>
Using a flow tester (manufactured by Shimadzu Corporation, trade name: “CFT-500D”), a 1 g sample was heated at a heating rate of 6 ° C./min, and a load of 1.96 MPa was applied by a plunger. The nozzle was extruded from a nozzle having a length of 1 mm and a length of 1 mm. The amount of plunger drop of the flow tester was plotted against the temperature, and the temperature at which half of the sample flowed out was taken as the softening point.

<Maximum peak temperature and melting point of endothermic resin>
Using a differential scanning calorimeter (DSC; manufactured by TA Instruments Japan Co., Ltd., trade name: “Q-100”), it was cooled from room temperature (20 ° C.) to 0 ° C. at a cooling rate of 10 ° C./min. The sample was allowed to stand for 1 minute as it was, and then measured while heating up to 180 ° C. at a heating rate of 10 ° C./min. Among the observed endothermic peaks, the peak temperature at the highest temperature is the maximum peak temperature of the endotherm, and if the maximum peak temperature is within 20 ° C. of the softening point, the crystalline polyester is used, and the melting point of the crystalline polyester It was.

<Glass transition temperature of amorphous polyester>
Using a differential scanning calorimeter (DSC; manufactured by TA Instruments Japan, trade name: “Q-100”), 0.01 to 0.02 g of a sample was weighed into an aluminum pan, and 200 ° C. The sample was cooled to 0 ° C at a rate of temperature decrease of 10 ° C / min from that temperature, and the sample was heated at a rate of temperature increase of 10 ° C / min. The temperature at the intersection with the tangent indicating the maximum slope from the portion to the peak apex was defined as the glass transition temperature.

<Resin acid value, hydroxyl value>
The acid value of the resin was measured based on the method of JIS K 0070. However, only the measurement solvent was changed from the mixed solvent of ethanol and ether specified in JIS K 0070 to a mixed solvent of acetone and toluene (acetone: toluene = 1: 1 (volume ratio)).
Moreover, the hydroxyl value of resin was measured on condition of the following based on JISK1557.
Sample amount: 2g
Acetylating reagent: 10 mL of a mixed solution of 65 mL of acetic anhydride and 935 mL of pyridine
Catalyst: None Reaction temperature: 99 ° C
Reaction time: 2 hours Solvent: Mixed solvent of acetone and toluene (acetone: toluene = 1: 1 (volume ratio))
Titration solution: 0.5 mol / L KOH ethanol solution

<Number average molecular weight and weight average molecular weight of resin>
By the following method, the molecular weight distribution was measured by gel permeation chromatography (GPC) method, and the number average molecular weight M _n and the weight average molecular weight M _w of the resin were determined.
(1) Preparation of sample solution The resin was dissolved in chloroform (crystalline polyester) or tetrahydrofuran (amorphous polyester) so that the concentration was 0.5 g / 100 mL. Subsequently, this solution was filtered using a fluororesin filter having a pore size of 2 μm (manufactured by Sumitomo Electric Industries, Ltd., trade name: FP-200) to remove insoluble components to obtain a sample solution.
(2) Molecular weight measurement Chloroform (crystalline polyester) or tetrahydrofuran (amorphous polyester) is flowed as an eluent at a flow rate of 1 ml per minute using the following apparatus, and the column is stabilized in a constant temperature bath at 40 ° C. It was. Measurement was performed by injecting 100 μl of the sample solution. The molecular weight of the sample was calculated based on a calibration curve prepared in advance. The calibration curve at this time includes several types of monodisperse polystyrene (monodisperse polystyrene manufactured by Tosoh Corporation; 2.63 × 10 ³ , 2.06 × 10 ⁴ , 1.02 × 10 ⁵ , GL Sciences Inc.) Monodispersed polystyrenes made from 2.10 × 10 ³ , 7.00 × 10 ³ , 5.04 × 10 ⁴ (number average molecular weight)) were used as standard samples.
Measuring device: CO-8010 (trade name, manufactured by Tosoh Corporation)
Analytical column: GMH _XL + G3000H _XL (both trade names, manufactured by Tosoh Corporation)

<Degree of neutralization of resin>
The degree of neutralization (mol%) of the resin was determined by the following formula.
Degree of neutralization (mol%) = {[weight of neutralizer (g) / equivalent of neutralizer] / [[acid value of resin (KOH mg / g) × resin weight (g)] / (56 × 1000 )]} × 100

<Volume Median Particle Size (D ₅₀ ) of Resin Particles, Colorant Fine Particles, Release Agent Fine Particles, and Charge Control Agent Fine Particles>
Using a laser diffraction particle size analyzer (Horiba, Ltd., trade name: “LA-920”), distilled water is added to the measurement cell, and the volume-median particle size is adjusted so that the absorbance is in the proper range. (D ₅₀ ) was measured.

<Volume-median particle size of the aggregated particles (D _50)>
The volume median particle size of the aggregated particles was measured as follows.
Measuring instrument: Coulter Multisizer III (trade name, manufactured by Beckman Coulter)
・ Aperture diameter: 50μm
・ Analysis software: Multisizer III version 3.51 (trade name, manufactured by Beckman Coulter)
Electrolyte: Isoton II (trade name, manufactured by Beckman Coulter)
Measurement conditions: 30,000 particles are measured after adjusting the particle size of 30,000 particles to a concentration that can be measured in 20 seconds by adding a sample dispersion containing aggregated particles to 100 mL of the electrolyte. The volume-median particle size (D ₅₀ ) was determined from the particle size distribution.

<Volume Median Particle Size (D ₅₀ ) and Particle Size Distribution of Toner Particles>
The volume median particle size of the toner particles was measured as follows.
The measuring instrument, aperture diameter, analysis software, and electrolyte solution were the same as the volume median particle diameter of the aggregated particles.
-Dispersion: Polyoxyethylene lauryl ether (trade name, Emulgen 109P, HLB: 13.6, manufactured by Kao Corporation) was dissolved in the electrolytic solution to obtain a dispersion having a concentration of 5% by weight.
Dispersion condition: 10 mg of a toner measurement sample is added to 5 mL of the dispersion, and dispersed for 1 minute with an ultrasonic disperser (manufactured by SND Co., Ltd.), and then 25 mL of an electrolyte is added. For 1 minute to prepare a sample dispersion.
Measurement conditions: The sample dispersion is added to 100 mL of the electrolytic solution to adjust the particle size of 30,000 particles to a concentration that can be measured in 20 seconds, and then 30,000 particles are measured and the particle size distribution thereof. From this, the volume median particle size (D ₅₀ ) was determined.

[Production of Amorphous Polyesters A-1 to A-14]
Into a 10 L four-necked flask equipped with a nitrogen introduction tube, a dehydration tube, a stirrer, and a thermocouple, raw material monomers other than alkenyl succinic anhydride compounds of the types and blending amounts shown in Table 6, tin 2-ethylhexanoate ( II) 40 g and 2 g of gallic acid monohydrate were added, reacted at 230 ° C. for 10 hours, cooled to 215 ° C., added with an alkenyl succinic anhydride compound and reacted at normal pressure for 3 hours. The reaction was continued at 8 kPa until the softening point shown in Table 6 was reached.

[Production of Amorphous Polyester A-15]
A 10-L four-necked flask equipped with a nitrogen inlet tube, a dehydrating tube, a stirrer, and a thermocouple is mixed with raw material monomers other than trimellitic acid of the types and blending amounts shown in Table 6, tin 2-ethylhexanoate (II) 40 g and 2 g of gallic acid monohydrate were added, reacted at 230 ° C. for 10 hours, cooled to 215 ° C., reacted with trimellitic acid for 1 hour at normal pressure, and then expressed at 8 kPa. The reaction was continued until the softening point shown in FIG.

[Production of Amorphous Polyesters B-1 to B-3]
A 10 L four-necked flask equipped with a nitrogen inlet tube, a dehydrating tube, a stirrer, and a thermocouple is mixed with BPA-PO and terephthalic acid, 40 g of tin (II) 2-ethylhexanoate and gallic acid shown in Table 7. 2 g of acid monohydrate was added, the reaction was performed at 230 ° C. for 10 hours, the temperature was lowered to 210 ° C., the remaining raw material monomers were added, and the reaction was performed at normal pressure for 3 hours. The reaction was allowed to reach the softening point indicated.

[Production of Crystalline Polyester C-1]
After a monomer of the type and blending amount shown in Table 8 is placed in a 10 L four-necked flask equipped with a nitrogen introducing tube, a dehydrating tube, a stirrer, and a thermocouple, and reacted at 140 ° C. for 6 hours. The temperature was raised from 140 ° C. to 200 ° C. over 6 hours, and then 20 g of tin (II) 2-ethylhexanoate and 2 g of gallic acid were added and reacted at normal pressure for 1 hour, and then at 8 kPa for 3 hours. The reaction was allowed to proceed.

[Preparation of aqueous dispersion of polyesters A to C]
In a 5 L flask equipped with a stirrer, 600 g of each polyester, polyoxyethylene alkyl ether (nonionic surfactant, trade name: Emulgen 150, manufactured by Kao Corporation), 8.5 g, 15 wt% sodium dodecylbenzenesulfonate Aqueous solution (anionic surfactant, trade name: Neoperex G-15, manufactured by Kao Corporation) 80 g, 5 wt% aqueous potassium hydroxide solution was added in an amount equivalent to 95 mol% neutralization, and the temperature was raised to 98 ° C. with stirring. The mixture was warmed and melted and mixed at 98 ° C. for 2 hours to obtain resin mixtures, respectively.
Next, 1116 g of deionized water was added dropwise at a rate of 6 g / min while stirring to obtain an emulsion. Next, the obtained emulsion was cooled to 25 ° C., and a resin particle dispersion was obtained through a 200-mesh (mesh 105 μm) wire mesh. The solid content concentration was measured, and ion-exchanged water was added so that the solid content concentration was 20% by weight to obtain aqueous dispersions of polyesters A to C, respectively. The volume median particle size (D ₅₀ ) of the fine particles was 150 nm.

[Preparation of aqueous dispersion of colorant]
50 g of copper phthalocyanine (manufactured by Dainichi Seika Kogyo Co., Ltd., model number: “ECB-301”), 5 g of nonionic surfactant (manufactured by Kao Corporation, trade name: “Emulgen (registered trademark) 150”) and ion exchange 195 g of water was mixed, copper phthalocyanine was dispersed, and dispersed for 10 minutes using a homogenizer to obtain an aqueous dispersion (solid content concentration: 20% by weight) of a colorant containing fine colorant particles. The volume median particle size (D ₅₀ ) of the colorant fine particles was 120 nm.

[Preparation of aqueous dispersion of release agent]
Paraffin wax (manufactured by Nippon Seiwa Co., Ltd., trade name: “HNP-9”, melting point: 75 ° C.) 50 g, cationic surfactant (manufactured by Kao Corporation, trade name: “Sanisol (registered trademark) B50” ) 5 g and 195 g of ion-exchanged water were heated to 95 ° C., and the paraffin wax was dispersed using a homogenizer, followed by dispersion treatment using a pressure discharge homogenizer, and an aqueous dispersion of a release agent containing release agent fine particles. A liquid (solid content concentration: 20% by weight) was obtained. The volume median particle size (D ₅₀ ) of the release agent fine particles was 550 nm.

[Preparation of dispersion of charge control agent]
50 g of charge control agent (Orient Chemical Industries, trade name: “Bontron E-84”), 5 g of nonionic surfactant (trade name: “Emulgen (registered trademark) 150”, manufactured by Kao Corporation) And 195 g of ion-exchanged water are mixed, glass beads are used and dispersed for 10 minutes using a sand grinder, and an aqueous dispersion of the charge control agent containing the charge control agent fine particles (solid content concentration: 20% by weight). Obtained. The volume median particle size (D ₅₀ ) of the charge control agent fine particles was 500 nm.

Examples 1-10 and Comparative Examples 1-7
(Manufacture of toner)
A toner was produced using an aqueous dispersion of polyesters A to C in combinations shown in Table 9. 300 g of aqueous dispersion of amorphous polyester A, 210 g of aqueous dispersion of amorphous polyester B, 90 g of aqueous dispersion of crystalline polyester C, 30 g of aqueous dispersion of colorant, 40 g of aqueous dispersion of release agent, charge 6 g of an aqueous dispersion of a control agent and 1.5 g of a cationic surfactant (Sanisol B50, trade name, manufactured by Kao Corporation) were stirred at 100 r / min with a chi-type stirrer in a round stainless steel flask. After mixing and dispersing, the flask was heated to 48 ° C. with stirring in an oil bath for heating. Furthermore, it hold | maintained at 48 degreeC for 1 hour, and the aggregated particle was formed. The volume-median particle size (D ₅₀ ) of the aggregated particles at this time was 5.1 μm.

Next, 3 g of an anionic surfactant (Perex SS-L, trade name, manufactured by Kao Corporation, sodium alkyldiphenyl ether disulfonate) was added, and a reflux tube was attached to the stainless steel flask while stirring was continued. The sample was heated to 90 ° C. at a rate of 0.1 ° C./min, the degree of circularity was measured every 30 minutes, and the degree of circularity was maintained at 0.98, and the aggregated particles were coalesced and fused. Then, it cooled to 30 degreeC, hold | maintained for 20 minutes, heated up to 50 degreeC, and hold | maintained for 2 hours. Thereafter, the mixture was cooled again, the coalesced particles were filtered, thoroughly washed with ion exchange water, and then dried to obtain toner particles.
The obtained toner particles each had a volume-median particle size (D ₅₀ ) of about 5.0 μm.

  Further, hydrophobic silica “NAX-50” (trade name, manufactured by Nippon Aerosil Co., Ltd., number average particle size 40 nm) 2.0 parts by weight, hydrophobic silica “R972” (trade name) with respect to 100 parts by weight of toner particles. , Nippon Aerosil Co., Ltd., number average particle diameter 16 nm) 1.5 parts by weight to a 10 L Henschel mixer (Mitsui Mine Co., Ltd.), ST (upper blade) -A0 (lower blade) type stirring blade The toner was obtained by stirring for 2 minutes at 3000 r / min for external addition.

[Evaluation]
<Unified speed>
In the above stainless steel flask, 50 g of the aggregated particles (solid content 20%) obtained above were added to an anionic surfactant (solid content 100%) (Perex SS-L, trade name, manufactured by Kao Corporation, alkyldiphenyl ether. Sodium disulfonate (0.22 g) was added, and the mixture obtained by stirring and mixing was diluted with deionized water so that the solid concentration was 0.001 to 0.05% to prepare a sample dispersion. . The circularity of the sample dispersion was measured using a flow type particle image analyzer (manufactured by Sysmex Corporation, trade name: FPIA-3000, measurement mode: HPF measurement mode) and found to be 0.955.
The sample dispersion (48 ° C.) was heated to 90 ° C. at a rate of 0.1 ° C./min while stirring and held at 90 ° C. for 10 minutes, and then the circularity of the sample dispersion was measured.
The coalescence speed was evaluated from the circularity before and after heating at 90 ° C. for 10 minutes. The greater the circularity after heating, the higher the coalescence speed.

<Releasing agent content in toner when circularity reaches 0.98>
Using a differential scanning calorimeter (manufactured by TA Instruments Japan Co., Ltd., trade name: Q-100), the release agent used for the toner was heated from 0 to 150 ° C. at 5 ° C./min, The endothermic amount of the release agent was measured. The value of (endothermic amount of release agent) × (theoretical weight ratio of release agent in core-shell particles (excluding surfactant and external additive)) is the theoretical value of endothermic amount of release agent. .
Next, the obtained toner (circularity: 0.98) was heated from 0 ° C. to 200 ° C. at 5 ° C./min, then rapidly cooled to 0 ° C. at 100 ° C./min, and then from 0 ° C. to 150 ° C. The temperature was increased at a rate of 5 ° C./min until the endothermic amount of the release agent contained in the toner was measured. This value is taken as an actual measurement value of the release agent content in the toner. In addition, the influence of the peak caused by the resin can be removed by rapid cooling.
Based on the measured value and the theoretical value of the endothermic amount of the release agent, the content of the release agent in the toner was evaluated according to the following evaluation criteria.
Release agent content in toner = ratio of measured value and theoretical value of endothermic amount of release agent [actual value / theoretical value × 100] (%)

<Durable printability (fading during durable printing)>
A toner was mounted on a non-magnetic one-component developing device (trade name: MicroLine 9300PS, manufactured by Oki Data Co., Ltd.), and an image having a printing rate of 5% was printed on 1000 sheets of A4 paper in an environment of 25 ° C. and 60% RH. Later, a solid image was printed on A4 paper.
For the A4 paper on which a solid image is printed, the reflection density meter (product name: RD-915, manufactured by Gretag Macbeth Co., Ltd.) is used for the optical reflection density of the A part (one place) and the B part (two places) shown in FIG. Measured. Based on the measurement result, (concentration of the A portion) − (average value of the concentrations of the two portions of the B portion) was calculated. A smaller value is preferred.

<Hot offset resistance>
The toner was mounted on an apparatus in which the fixing machine of the copying machine “AR-505” (trade name, manufactured by Sharp Corporation) was improved so that fixing was possible outside the apparatus, and images were printed without fixing (printing) Area: 2 cm × 12 cm, adhesion amount: 0.5 mg / cm ² ). Using the fixing device of the copying machine adjusted so that the total fixing pressure becomes 40 kgf, the fixing roller temperature is increased from 70 ° C. to 200 ° C. by 5 ° C., and the unfixed image is 300 mm / sec. Fixed on paper. As the fixing paper, “Xerox P paper” (trade name, manufactured by Fuji Xerox Co., Ltd., 64 g / m ² ) was used. The temperature at which hot offset was first observed on the fixing roller was measured. It shows that it is excellent in hot-off resistance, so that temperature is high.

<Gloss>
The toner was mounted on an apparatus in which the fixing machine of the copying machine “AR-505” (trade name, manufactured by Sharp Corporation) was improved so that fixing was possible outside the apparatus, and images were printed without fixing (printing) Area: 2 cm × 12 cm, adhesion amount: 0.5 mg / cm ² ). Using the fixing machine of the copying machine adjusted so that the total fixing pressure was 40 kgf, the temperature of the fixing roller was 150 ° C. and 180 ° C., and the unfixed image was fixed on the paper at 300 mm / sec. For the fixing paper, “CopyBond SF-70NA (trade name, manufactured by Sharp Corporation, 75 g / m ² )” was used.
Using the gloss meter (trade name: “IG-330”, manufactured by Horiba, Ltd.), the glossiness of the obtained image was measured under a light irradiation condition of 60 ° with a cardboard under the image. did. Based on the measurement result, (Glossiness of image at fixing temperature 180 ° C.) − (Glossiness of image at fixing temperature 150 ° C.) was calculated. The smaller the value, the smaller the change in the gloss value accompanying the change in the fixing temperature.

  As is apparent from Table 9, the toner obtained by the production method of the present invention is excellent in hot offset resistance and durable printability, and can obtain a printed material that does not fade even when durable printed, and has different fixing temperatures. Even when the fixing process is performed, a constant gloss image can be stably obtained.

  The toner obtained by the production method of the present invention is excellent in hot offset resistance and durable printability, and can obtain a printed material that does not fade even after durable printing, and is constant even when fixing processing is performed at different fixing temperatures. The gloss image can be obtained stably. Therefore, it can be suitably used as an electrophotographic toner used in electrophotography, electrostatic recording method, electrostatic printing method and the like.

Claims (7)

A method for producing an electrophotographic toner, comprising the following steps 1 to 4.
Step 1: a carboxylic acid component containing 6 to 50 mol% of an alkyl succinic acid having an alkyl group having 9 to 18 carbon atoms and / or an alkenyl succinic acid having an alkenyl group having 9 to 18 carbon atoms, and a trivalent or higher valent fatty acid A step of obtaining an amorphous polyester A having a weight average molecular weight of 300,000 to 2,000,000 obtained by condensation polymerization with an alcohol component containing 5 to 40 mol% of a group alcohol Step 2: Non-obtained obtained in Step 1 Step of obtaining crystalline aqueous dispersion of amorphous polyester A by crystallizing crystalline polyester A in the presence of a surfactant in aqueous medium Step 3: Aqueous dispersion of amorphous polyester A obtained in Step 2 Step of aggregating with release agent to obtain aggregated particles Step 4: Step of integrating aggregated particles obtained in step 3 to obtain coalesced particles   The method for producing an electrophotographic toner according to claim 1, wherein the trihydric or higher aliphatic alcohol is glycerin.   The method for producing an electrophotographic toner according to claim 1, wherein the release agent is at least one selected from the group consisting of polyolefin wax, paraffin wax, and Fischer-Tropsch wax.   In the agglomeration step of Step 3, an alkyl succinic acid having an alkyl group having 9 to 18 carbon atoms and / or an alkenyl succinic acid having an alkenyl group having 9 to 18 carbon atoms is further added to 6 to 50 mol% and a fumaric acid compound. An aqueous dispersion of amorphous polyester B having a weight average molecular weight of 10,000 to 100,000, obtained by condensation polymerization of 5 to 30 mol% of a carboxylic acid component and an alcohol component is used. 4. The method for producing an electrophotographic toner according to any one of 3 above.   The toner for electrophotography according to claim 4, wherein the weight ratio of amorphous polyester A to amorphous polyester B (amorphous polyester A / amorphous polyester B) is 80/20 to 50/50. Manufacturing method.   In the agglomeration step of the step 3, a carboxylic acid containing an alcohol component containing 70 to 100 mol% of an aliphatic diol having 6 to 12 carbon atoms and 70 to 100 mol% of an aliphatic dicarboxylic acid compound having 8 to 12 carbon atoms. The method for producing an electrophotographic toner according to claim 1, wherein an aqueous dispersion of crystalline polyester C obtained by condensation polymerization with an acid component is used.   An electrophotographic toner obtained by the method for producing an electrophotographic toner according to claim 1.