JP2017072758A - Electrophotographic toner and manufacturing method of the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an electrophotographic toner that is excellent in balance among low-temperature fixability, heat-resistant storage property, and environmental stability of the toner.SOLUTION: There is provided an electrophotographic toner comprising a crystalline polyester that contains a constitutional unit derived from an alcohol component including 99 mass% or more of ethylene glycol and a constitutional unit derived from a carboxylic acid component including 99 mass% or more of sebacic acid, where the crystalline polyester has a number average molecular weight Mn of 4,500 or more and 7,000 or less, has components with a molecular weight of 500 or less of 2 mass% or less, components with a molecular weight of more than 500 and 1,000 or less of 2 mass% or more and 5 mass% or less, and components with a molecular weight of more than 1,000 and 5,000 or less of 10 mass% or more and 25 mass% or less, and has an acid value of 5 mgKOH/g or more and 20 mgKOH/g or less.SELECTED DRAWING: None

Description

  The present invention relates to an electrophotographic toner and a method for producing the same.

  In recent years, toners are required to have high-temperature offset resistance for high-quality output images, low-temperature fixability for energy saving, and heat-resistant storage stability that can withstand high-temperature and high-humidity during storage and transportation after production. Has been. In particular, since power consumption during fixing accounts for much of the power consumption in the image forming process, it is very important to improve low-temperature fixability.

  Crystalline polyester, unlike other crystalline resins such as polyethylene, is highly compatible with amorphous polyesters, easy to disperse, and has a clear melting point at which crystal parts develop. In recent years, it has attracted attention as a binder resin suitable for improving the low-temperature fixability of toner.

  In Patent Document 1, a crystalline polyester resin and an amorphous polyester resin are used as components for the purpose of providing a toner having no filming and having stable low-temperature fixability, high-temperature offset resistance, and heat-resistant storage stability. The toner includes a binder resin, and the crystalline polyester resin has at least two diffraction peaks detected in a range of 20 ° <2θ <25 ° by X-ray diffraction measurement, and has a melting point of 60 ° C. or higher and 80 ° C. A toner having a diffraction peak less than 1.0 ° / 2θ is disclosed.

Patent Document 2 discloses an increase in differential scanning calorimetry (DSC) for the purpose of providing a toner having excellent low-temperature fixability and heat-resistant storage stability, as well as excellent high-temperature and high-humidity storage stability and image gloss. The glass transition temperature at the first temperature is 20 ° C. or more and 50 ° C. or less, and the glass transition temperature at the second temperature increase in the differential scanning calorimetry (DSC) of the tetrahydrofuran (THF) insoluble matter is −40 ° C. or more and 30 ° C. or less. The storage elastic modulus at 100 ° C. of the THF-insoluble matter is 1.0 × 10 ^{5 to} 1.0 × 10 ⁷ Pa, and the ratio of the storage elastic modulus at 40 ° C. to the storage elastic modulus at 100 ° C. of the THF-insoluble matter is A toner that is 3.5 × 10 or less is disclosed.

  In Patent Document 3, a styrene acrylic resin is provided for the purpose of providing a method for producing toner particles having sufficient low-temperature fixing performance and excellent fluidity in order to cope with high-speed development processes. A method for producing toner particles containing a binder resin as a main component, a colorant and a crystalline resin, wherein the resin particles are produced in a water-based medium after the resin particles are produced by a suspension polymerization method or a dissolution suspension method. Discloses a method for producing toner particles, comprising a step of heating and holding at a temperature not lower than the glass transition temperature of the binder resin and not higher than the melting start temperature of the crystalline resin for not less than 0.5 hours.

JP 2011-242750 A Japanese Patent Laying-Open No. 2015-052697 JP2013-080112A

Laser printers are required to have uniform image quality in various environments, and the toner used in laser printers has environmental stability that exhibits uniform toner chargeability in both high and low humidity environments. Desired.
The present invention relates to an electrophotographic toner excellent in the balance of low-temperature fixability, heat-resistant storage stability and environmental stability of the toner, and a method for producing the same.

The present invention provides the following <1> to <3>.
<1> An electrophotographic toner comprising a crystalline polyester containing a structural unit derived from an alcohol component containing 99% by mass or more of ethylene glycol and a structural unit derived from a carboxylic acid component containing 99% by mass or more of sebacic acid. And
The crystalline polyester has a number average molecular weight Mn of 4,500 or more and 7,000 or less, a molecular weight of 500 or less of 2% by mass or less, a molecular weight of more than 500 or less of 1,000 or less of 2% by mass or more and 5% by mass or less, and a molecular weight of 1, An electrophotographic toner having a content of more than 5,000 and not more than 5,000 and not more than 10% by mass and not more than 25% by mass and an acid value of not less than 5 mgKOH / g and not more than 20 mgKOH / g.
<2> A method for producing an electrophotographic toner, comprising the following steps 1, 2 and 3.
Step 1: A crystalline polyester obtained by polycondensation of an alcohol component containing 99% by mass or more of ethylene glycol and an acid component containing 99% by mass or more of sebacic acid, and having a number average molecular weight Mn of 4,500 or more, 7, The molecular weight of 500 or less is 2% by mass or less, the molecular weight of 500 to 1,000 or less is 2 to 5% by mass, the molecular weight of 1,000 to 5,000 or less is 10 to 25% by mass. A step of obtaining a crystalline polyester dispersion by dispersing a crystalline polyester having an acid value of 5 mgKOH / g or more and 20 mgKOH / g or less in an organic solvent; Step 2: the crystalline polyester dispersion obtained in Step 1; SP value is 10.5 or more and 11.5 or less, softening point is 100 ° C or more and 120 ° C or less, and glass transition temperature Tg is 60 ° C or more and 75 ° C or less. Step of mixing the amorphous polyester to obtain a mixture Step 3: Step of adding an aqueous phase to the mixture obtained in Step 2 and phase-inversion into particles of 4 μm to 7 μm <3> Step 1 below An electrophotographic toner obtained by a process comprising 2 and 3.
Step 1: A crystalline polyester obtained by polycondensation of an alcohol component containing 99% by mass or more of ethylene glycol and an acid component containing 99% by mass or more of sebacic acid, and having a number average molecular weight Mn of 4,500 or more, 7, The molecular weight of 500 or less is 2% by mass or less, the molecular weight of 500 to 1,000 or less is 2 to 5% by mass, the molecular weight of 1,000 to 5,000 or less is 10 to 25% by mass. A step of obtaining a crystalline polyester dispersion by dispersing a crystalline polyester having an acid value of 5 mgKOH / g or more and 20 mgKOH / g or less in an organic solvent; Step 2: the crystalline polyester dispersion obtained in Step 1; SP value is 10.5 or more and 11.5 or less, softening point is 100 ° C or more and 120 ° C or less, and glass transition temperature Tg is 60 ° C or more and 75 ° C or less. Step of mixing the amorphous polyester to obtain a mixture Step 3: Step of adding an aqueous phase to the mixture obtained in Step 2 to invert the particles to particles of 4 μm to 7 μm

  The toner of the present invention has an excellent balance of low-temperature fixability, heat-resistant storage stability and environmental stability, and a fixed image formed using the toner of the present invention has excellent bending strength.

[Electrophotographic toner]
The electrophotographic toner of the present invention includes a crystalline polyester containing a structural unit derived from an alcohol component containing 99% by mass or more of ethylene glycol and a structural unit derived from a carboxylic acid component containing 99% by mass or more of sebacic acid. An electrophotographic toner, wherein the crystalline polyester has a number average molecular weight Mn of 4,500 or more and 7,000 or less, a molecular weight of 500 or less of 2% by mass or less, and a molecular weight of more than 500 to 1,000 or less of 2% by mass or more. 5 mass% or less, molecular weight more than 1,000 and 5,000 or less are 10 mass% or more and 25 mass% or less, and an acid value is 5 or more and 20 or less.

The reason why the electrophotographic toner of the present invention is excellent in the balance of low-temperature fixability, heat-resistant storage stability and environmental stability is not clear, but is estimated as follows.
Normally, even if a crystalline polyester dispersed in a solvent is dispersed in a resin dissolved in a solvent to make the crystalline polyester insoluble, it is difficult to keep the crystalline polyester dispersed in the toner. is there. In contrast, in the present invention, by using a specific crystalline polyester, the crystalline polyester can be highly dispersed in the toner.
The crystalline polyester used in the present invention has a wide SP value with respect to the molecular weight of the crystalline polyester of ethylene glycol / sebacic acid, and is easily crystallized even at a low molecular weight. The crystalline polyester used in the present invention has a specific molecular weight distribution. The component having a molecular weight of 5000 or less in the crystalline polyester is soluble in the organic solvent and is compatible with the amorphous polyester dissolved in the organic solvent, so that it plays a role as a dispersing agent. Can be maintained.

  In the present invention, the term “polyester” includes polyester that has been modified to such an extent that its properties are not substantially impaired. Examples of the modified polyester include a urethane-modified polyester in which the polyester is modified with a urethane bond, an epoxy-modified polyester in which the polyester is modified with an epoxy bond, and two or more resin components including a polyester component and an addition polymerization resin component. And a composite resin having

(Resin crystallinity)
The crystallinity of the resin is expressed by the ratio between the softening point and the maximum endothermic peak temperature measured by a differential scanning calorimeter (DSC), that is, the crystallinity index defined by “softening point / maximum endothermic peak temperature”. 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, the “crystalline resin” refers to a resin having a crystallinity index of 0.6 to 1.4, preferably 0.7 to 1.2, and more preferably 0.9 to 1.2. “Amorphous resin” refers to a resin having a crystallinity index greater than 1.4 or less than 0.6.
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 resin, and the peak exceeding 20 ° C. from the softening point is due to the glass transition temperature of the amorphous resin. Let it be a peak.
The crystallinity of the resin can be adjusted by the types and ratios of the raw material monomers, production conditions (for example, reaction temperature, reaction time, cooling rate) and the like.

(Crystalline polyester)
The crystalline polyester used in the present invention contains a structural unit derived from an alcohol component containing 99% by mass or more of ethylene glycol and a structural unit derived from a carboxylic acid component containing 99% by mass or more of sebacic acid.

<Alcohol unit of crystalline polyester>
The alcohol unit of the crystalline polyester is a structural unit derived from an alcohol component containing 99% by mass or more of ethylene glycol from the viewpoint of improving the heat resistant storage stability and environmental stability of the toner.
The content of ethylene glycol in the alcohol component is 99.0% by mass or more, preferably 99.5% by mass or more, more preferably 99.8%, from the viewpoint of improving the heat resistant storage stability and environmental stability of the toner. It is at least 100% by mass, particularly preferably 100% by mass.

Examples of alcohol components other than ethylene glycol include aliphatic diols having 3 or more carbon atoms, aromatic alcohols, and trivalent or more alcohols.
Examples of the aliphatic diol having 3 or more carbon atoms include 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 2,3- Butanediol, 1,4-butenediol, 1,2-pentanediol, 1,3-pentanediol, 1,4-pentanediol, 1,5-pentanediol, neopentyl glycol, 2,3-pentanediol, 2 , 4-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,12-dodecanediol and the like. It is done. Examples of the aromatic alcohol include polyoxypropylene (2,2) -2,2-bis (4-hydroxyphenyl) propane, polyoxyethylene (2,2) -2,2-bis (4-hydroxyphenyl) propane, and the like Bisphenol A alkylene (2 to 3 carbon atoms) oxide (average added mole number 1 to 10) adduct and the like. Examples of trihydric or higher alcohols include glycerol (also referred to as glycerin), pentaerythritol, trimethylolpropane, and the like.

<Carboxylic acid unit of crystalline polyester>
The carboxylic acid unit of the crystalline polyester is a structural unit derived from a carboxylic acid component containing 99% by mass or more of sebacic acid from the viewpoint of improving low-temperature fixability and heat-resistant storage stability of the toner.
The content of sebacic acid in the carboxylic acid component is 99.0% by mass or more, preferably 99.5% by mass or more, more preferably 99.% by mass, from the viewpoint of improving the low-temperature fixability and heat-resistant storage stability of the toner. It is 8% by mass or more, particularly preferably 100% by mass.

Examples of carboxylic acid components other than sebacic acid include aliphatic dicarboxylic acids other than sebacic acid, alicyclic dicarboxylic acids, aromatic dicarboxylic acids, trivalent or higher polyvalent carboxylic acids, and anhydrides and alkyls thereof (1 carbon number). 3 or less) esters and the like. Of these, aliphatic dicarboxylic acids are preferred.
Aliphatic dicarboxylic acids other than sebacic acid include oxalic acid, malonic acid, fumaric acid, maleic acid, citraconic acid, itaconic acid, glutaconic acid, succinic acid, adipic acid, azelaic acid, n-dodecyl succinic acid, n-dodecenyl succinic acid An acid etc. are mentioned. Examples of the alicyclic dicarboxylic acid include cyclohexane dicarboxylic acid. Examples of the aromatic dicarboxylic acid include phthalic acid, isophthalic acid, terephthalic acid and the like. Examples of the trivalent or higher polyvalent carboxylic acid include 1,2,4-benzenetricarboxylic acid (trimellitic acid), 2,5,7-naphthalenetricarboxylic acid, and pyromellitic acid.

<Physical properties of crystalline polyester>
-Number average molecular weight Mn of crystalline polyester-
The number average molecular weight of the crystalline polyester is 4,500 or more, preferably 5,000 or more, more preferably 5,500 or more, and 7,000 or less, preferably from the viewpoint of improving the environmental stability of the toner. Is 6,800 or less, more preferably 6,500 or less.
In the present invention, the number average molecular weight of the crystalline polyester refers to a value obtained by measuring the chloroform-soluble content, and specifically refers to a value measured by the method shown in the examples.

-Weight average molecular weight Mw of crystalline polyester-
From the viewpoint of improving the environmental stability of the toner, the weight average molecular weight of the crystalline polyester is 9,000 or more, preferably 10,000 or more, more preferably 11,000 or more, and 27,500 or less, preferably Is 25,000 or less, more preferably 22,500 or less.
In the present invention, the weight average molecular weight of the crystalline polyester refers to a value obtained by measuring the chloroform-soluble content, and specifically refers to a value measured by the method shown in the examples.

-Molecular weight distribution of crystalline polyester-
From the viewpoint of improving the environmental stability of the toner, Mw / Mn of the crystalline polyester is preferably 2 or more, more preferably 2.2 or more, still more preferably 2.5 or more, and even more preferably 2.8 or more. Yes, preferably 5 or less, more preferably 4.8 or less, and still more preferably 4.5 or less.

  The molecular weight distribution of the crystalline polyester used in the present invention is 2% by mass or less for components having a molecular weight of 500 or less, 2% by mass to 5% by mass for components having a molecular weight of more than 500, and less than 1,000 for molecular weights of 5, 000 or less component is 10 mass% or more and 25 mass% or less.

  A component having a molecular weight of 500 or less in the crystalline polyester is too hydrophilic and therefore does not act as a dispersant. Further, it tends to appear on the toner surface, and if it exceeds 2 mass% and is contained in the crystalline polyester, it adversely affects the heat resistant storage stability of the toner. Therefore, the component having a molecular weight of 500 or less in the crystalline polyester is 2% by mass or less, preferably 1.9% by mass or less, more preferably 1.8% by mass or less, based on the total amount of the crystalline polyester.

  The component having a molecular weight of more than 500 and less than 1,000 in the crystalline polyester can effectively act as a dispersant, but since it does not recrystallize, if the crystalline polyester contains more than 5% by mass, the heat resistant storage stability of the toner Adversely affect. Therefore, the component having a molecular weight of more than 500 and less than 1,000 in the crystalline polyester is 2% by mass or more, preferably 2.2% by mass or more, more preferably 2. 5 mass% or more, more preferably 2.8 mass% or more, and 5 mass% or less, preferably 4.8 mass% or less, more preferably 4.5 mass% or less, and still more preferably 4.0 mass%. % Or less.

  Components having a molecular weight of more than 1,000 and not more than 5,000 in the crystalline polyester have a high effect as a dispersant. If the amount is less than 10% by mass, a desired effect as a dispersant cannot be obtained. On the other hand, if the amount exceeds 25% by mass, the dispersed particle size of the crystalline polyester is enlarged during recrystallization. Therefore, the component having a molecular weight of more than 1,000 and less than 5,000 in the crystalline polyester is 10% by mass or more, preferably 12% by mass or more, more preferably 15% by mass from the viewpoint of environmental stability or low-temperature fixability of the toner. Further, it is 25% by mass or less, preferably 22% by mass or less, and more preferably 20% by mass or less.

-Acid value of crystalline polyester-
The acid value of the crystalline polyester is 5 mgKOH / g or more, preferably 7 mgKOH / g or more, and 20 mgKOH / g or less, preferably 18 mgKOH / g or less, more preferably from the viewpoint of improving the heat-resistant storage stability of the toner. It is 15 mgKOH / g or less.

-Softening point of crystalline polyester-
The softening point of the crystalline polyester is preferably 60 ° C. or higher, more preferably 70 ° C. or higher, and still more preferably 78 ° C. from the viewpoint of improving reactivity and increasing the molecular weight of the polyester and improving the heat resistant storage stability of the toner. From the viewpoint of improving the low-temperature fixability of the toner, it is preferably 120 ° C. or lower, more preferably 100 ° C. or lower, and still more preferably 90 ° C. or lower.

-Melting point of crystalline polyester-
The peak of melting at 2nd RUN by differential scanning calorimetry (DSC) for the crystalline polyester is preferably 73. From the viewpoint of improving the reactivity and increasing the molecular weight of the polyester and improving the heat resistant storage stability of the toner. 5 ° C. or higher, more preferably 75.0 ° C. or higher, and further preferably 76.0 ° C. or higher. From the viewpoint of improving the low-temperature fixability of the toner, it is preferably 77.0 ° C. or lower, more preferably 76.degree. 9 ° C. or lower, more preferably 76.8 ° C. or lower.
Here, the peak top of melting in 2nd RUN by differential scanning calorimetry (DSC) means that the temperature is raised to 200 ° C. at a heating rate of 10 ° C./min, and cooled from room temperature to 0 ° C. at a cooling rate of 10 ° C./min. Of the endothermic peak obtained when measured at a heating rate of 50 ° C./min after maintaining for 1 minute at a temperature of 1 ° C., and this was taken as the melting point.

-Endotherm amount-
The endothermic amount at 2nd RUN by differential scanning calorimetry (DSC) for the crystalline polyester is preferably 70 J / g or more from the viewpoint of improving the reactivity and increasing the molecular weight of the polyester and improving the heat resistant storage stability of the toner. More preferably, it is 73 J / g or more, more preferably 75 J / g or more. From the viewpoint of improving the low-temperature fixability of the toner, it is preferably 90 J / g or less, more preferably 88 J / g or less, still more preferably. 85 J / g or less.
Here, the endothermic amount in 2nd RUN by differential scanning calorimetry (DSC) is the temperature at which the temperature is increased from room temperature to 200 ° C. at a rate of temperature increase of 10 ° C./min and then cooled from room temperature to 0 ° C. at a rate of temperature decrease of 10 ° C./min. The endothermic area of the endothermic peak obtained when measured at a heating rate of 10 ° C./min after maintaining for 1 minute is calculated.

In the present invention, the softening point, melting point, and acid value of the above-mentioned crystalline polyester refer to values measured by the methods shown in Examples described later.
In addition, the number average molecular weight, the softening point, the melting point and the acid value of the crystalline polyester are adjusted according to the reaction conditions such as reaction temperature, reaction time, reaction pressure, etc. Can be controlled by selection.

-Particle size of crystalline polyester-
When the crystalline polyester is dispersed in an organic solvent, the volume-median particle size (D ₅₀ ) of the crystalline polyester in the crystalline polyester dispersion is preferably from the viewpoint of highly dispersing the crystalline polyester in the toner. 80 nm or more, more preferably 150 nm or more, further preferably 300 nm or more, still more preferably 450 nm or more, preferably 2,000 nm or less, more preferably 1,500 nm or less, still more preferably 1,200 nm or less, more More preferably, it is 1,000 nm or less.

<Method for producing crystalline polyester>
The crystalline polyester used in the present invention can be obtained by polycondensation of an alcohol component containing 99% by mass or more of ethylene glycol and an acid component containing 99% by mass or more of sebacic acid. This polycondensation reaction is preferably performed in the presence of an esterification catalyst.

The temperature during the polycondensation reaction between the alcohol component and the carboxylic acid component is preferably 190 ° C. or higher from the viewpoint of reactivity, and preferably 250 ° C. or lower from the viewpoint of thermal decomposability.
From the viewpoint of obtaining a crystalline polyester having a desired molecular weight distribution, it is preferable to synthesize gradually from a low temperature. When the temperature is rapidly increased, a large amount of low molecular weight components having a molecular weight of 500 or less may be generated without increasing the molecular weight. For example, it is preferable to raise the temperature from 140 ° C. to 210 ° C. over 12 hours.

  The polycondensation reaction may be performed in the presence of an esterification catalyst, an esterification cocatalyst, a polymerization inhibitor, or the like, if necessary.

Examples of esterification catalysts include tin catalysts and titanium catalysts. From the viewpoint of obtaining a crystalline polyester having a desired molecular weight distribution, it is preferable to use a titanium catalyst.
Examples of the tin catalyst include dibutyltin oxide and di (2-ethylhexanoic acid) tin (II). From the viewpoints of reactivity, molecular weight adjustment, and resin physical property adjustment, di (2-ethylhexanoic acid) tin. Tin (II) compounds having no Sn—C bond such as (II) are preferred. Examples of the titanium catalyst include titanium dihydroxybis (triethanolamate).
The amount of the esterification catalyst used is preferably 0.01 parts by mass or more, more preferably 0.1 parts by mass or more, and preferably 1 with respect to 100 parts by mass of the total amount of the alcohol component and the carboxylic acid component. 0.5 parts by mass or less, more preferably 1.0 parts by mass or less.

  Examples of the esterification promoter include gallic acid. The amount of the esterification cocatalyst used is preferably 0.001 part by mass or more, more preferably 0.01 part by mass or more, and preferably 100 parts by mass or more with respect to the total amount of the alcohol component and the carboxylic acid component. 0.5 parts by mass or less, more preferably 0.1 parts by mass or less.

  From the viewpoint of obtaining a crystalline polyester having a desired molecular weight distribution, it is preferable to perform steam distillation after completion of the reaction to remove low molecular weight components having a molecular weight of 500 or less. For example, after completion of the reaction, 140 ° C. water vapor is preferably blown into the system at a rate of 5 g / min for 1 hour.

  The toner of the present invention contains the crystalline polyester as one of the binder resins. The content of the crystalline polyester in the binder resin is preferably 2.0% by mass or more, more preferably based on the total amount of the binder resin, from the viewpoint of improving the low-temperature fixability, heat-resistant storage stability and environmental stability of the toner. Is 2.5% by mass or more, more preferably 4.0% by mass or more, preferably 20% by mass or less, more preferably 15% by mass or less, and still more preferably 10% by mass or less. The toner of the present invention can suppress moisture absorption of the whole toner even if the content of the crystalline polyester is small.

(Amorphous polyester)
The toner of the present invention preferably further contains an amorphous polyester as a binder resin from the viewpoint of improving the storage stability and durability of the toner.

<Alcohol unit of amorphous polyester>
The alcohol unit of the amorphous polyester is an alcohol containing 70 to 100 mol% of an alkylene oxide adduct of bisphenol A represented by the following formula (I) from the viewpoint of improving the storage stability and durability of the toner. A structural unit derived from a component is preferable.

  In the above formula (I), R represents an alkylene group having 2 or 3 carbon atoms. x and y represent a positive number, and the sum of x and y is preferably 1 or more, more preferably 1.2 or more, still more preferably 1.5 or more, and preferably 16 or less, more preferably Is 10 or less, more preferably 5 or less.

The content of the alkylene oxide adduct of bisphenol A is preferably 70 mol% or more, more preferably 80 mol% or more in the alcohol component of the amorphous polyester, from the viewpoint of improving the storage stability and durability of the toner. More preferably, it is 90 mol% or more, and still more preferably substantially 100 mol%.
Moreover, the alkylene oxide adduct of bisphenol A can be used alone or in combination of two or more.

The alcohol other than the alkylene oxide adduct of bisphenol A that can be contained in the alcohol component is preferably an aliphatic diol having 2 to 10 carbon atoms, and more preferably an aliphatic diol having 2 to 10 carbon atoms. Specific compounds include those used for crystalline polyester.
Moreover, the trivalent or more alcohol similar to what is used for the said crystalline polyester can be illustrated.

<Carboxylic acid unit of amorphous polyester>
The carboxylic acid unit of the amorphous polyester is preferably a structural unit derived from an aromatic dicarboxylic acid compound from the viewpoint of improving the transferability, storage stability and durability of the toner. As the aromatic dicarboxylic acid compound, a terephthalic acid compound is preferable. Examples of the terephthalic acid compound include terephthalic acid, anhydrides thereof, and alkyl (having 1 to 3 carbon atoms) esters, and terephthalic acid is preferable.
When the aromatic dicarboxylic acid compound is contained, the content thereof is preferably 60 mol% or more, more preferably 70 mol% or more, still more preferably 80 mol% or more in the carboxylic acid component of the amorphous polyester. Further, it is preferably 97 mol% or less, more preferably 95 mol% or less, and still more preferably 92 mol% or less.

Examples of carboxylic acids other than terephthalic acid compounds that can be contained in the carboxylic acid component include aliphatic dicarboxylic acids, alicyclic dicarboxylic acids, aromatic dicarboxylic acids other than terephthalic acid, trivalent or higher polyvalent carboxylic acids, and anhydrides thereof. And alkyl (carbon number 1 to 3) ester and the like.
Aliphatic dicarboxylic acids include oxalic acid, malonic acid, fumaric acid, maleic acid, citraconic acid, itaconic acid, glutaconic acid, succinic acid, adipic acid, azelaic acid, sebacic acid, n-dodecyl succinic acid, n-dodecenyl succinic acid Etc. Examples of the alicyclic dicarboxylic acid include cyclohexane dicarboxylic acid. Examples of aromatic dicarboxylic acids other than terephthalic acid include phthalic acid and isophthalic acid. Examples of the trivalent or higher polyvalent carboxylic acid include 1,2,4-benzenetricarboxylic acid (trimellitic acid), 2,5,7-naphthalenetricarboxylic acid, and pyromellitic acid.

<Physical properties of amorphous polyester>
-Acid value of amorphous polyester-
From the viewpoint of improving the storage stability of the toner, the acid value of the amorphous polyester is preferably 5 mgKOH / g or more, more preferably 10 mgKOH / g or more, and preferably 30 mgKOH / g or less, more preferably 20 mgKOH / g. g or less.

-Softening point of amorphous polyester-
The softening point of the amorphous polyester is preferably 100 ° C. or higher, more preferably 105 ° C. or higher, and still more preferably 110 ° C. from the viewpoint of improving reactivity and increasing the molecular weight of the polyester and improving the storage stability of the toner. From the viewpoint of improving the low-temperature fixability of the toner, it is preferably 120 ° C. or lower, more preferably 115 ° C. or lower.

-Glass transition temperature of amorphous polyester-
The glass transition temperature of the amorphous polyester is preferably 60 ° C. or higher, more preferably 63 ° C. or higher from the viewpoint of improving the storage stability of the toner, and preferably from the viewpoint of improving the low-temperature fixability of the toner. 75 ° C. or lower, more preferably 72 ° C. or lower.

-SP value of amorphous polyester-
The SP value of the amorphous polyester when dissolved in the organic solvent is preferably 10.5 or more, more preferably 10.7 or more, and preferably 11.5 or less, more preferably 11.3 or less. is there.
In the present invention, the SP value means a solubility parameter according to the method of Fedors, and is obtained based on the following formula described in [Robert F. Fedors, Polymer Engineering and Science, 14, 147-154 (1974)]. The obtained value δ.
Fedors equation: δ = (ΣΔei / ΣΔvi) ^1/2
[Unit: (cal / cm ³ ) ^1/2 ]
[Where Δei is the evaporation energy (cal / mol) of atoms and atomic groups, and Δvi is the molar volume (cm ³ / mol). ]

<Method for producing amorphous polyester>
The amorphous polyester used in the present invention can be obtained by polycondensation of the above alcohol component and carboxylic acid component.

  The temperature during the polycondensation reaction between the alcohol component and the carboxylic acid component is preferably 190 ° C. or higher from the viewpoint of reactivity, and preferably 250 ° C. or lower from the viewpoint of thermal decomposability.

  The polycondensation reaction may be performed in the presence of an esterification catalyst, an esterification cocatalyst, a polymerization inhibitor, or the like, if necessary. Preferred examples of the esterification catalyst, esterification co-catalyst and polymerization inhibitor are the same as the esterification catalyst, esterification co-catalyst and polymerization inhibitor used in the production of crystalline polyester.

  When the toner of the present invention contains an amorphous polyester as a binder resin, the mass ratio of the amorphous polyester to the crystalline polyester (amorphous polyester / crystalline polyester) determines the low-temperature fixability of the toner and the heat-resistant storage. From the viewpoint of improving the property and environmental stability, it is preferably 100/20 or more, more preferably 100/15 or more, still more preferably 100/10 or more, and preferably 100/3 or less, more preferably 100 / 5 or less.

(Composite resin)
The toner of the present invention includes a segment (c1) (polyester part) containing amorphous polyester and an addition polymer containing styrene as a structural unit from the viewpoint of improving low-temperature fixability, charging stability and fluidity of the toner. It is preferable to further contain a composite resin having a segment (c2) (styrene acrylic moiety).

The segment (c1) constituting the composite resin contains amorphous polyester. The amorphous polyester is the same as the above-described amorphous polyester.
The SP value of the polyester portion is preferably within a range of ± 0.5 of the SP value of the amorphous polyester.

The segment (c2) constituting the composite resin is composed of an addition polymer containing styrene as a structural unit.
As a raw material monomer which becomes a constituent unit of the segment (c2), styrene alone or styrene and (meth) acrylic is used from the viewpoint of easy availability of the monomer and from the viewpoint of improving low-temperature fixability, charging stability and fluidity of the toner. The combined use of acid esters is preferred, and the combined use of styrene and (meth) acrylic acid esters is more preferred.
The content of the addition polymer containing styrene as a constituent unit in the segment (c2) is preferably 60% by mass or more, more preferably 80% by mass from the viewpoint of improving the low-temperature fixability, charging stability and fluidity of the toner. % Or more, more preferably 90% by mass or more, still more preferably substantially 100% by mass, and still more preferably 100% by mass.
The SP of the styrene acrylic moiety is preferably within the range of ± 0.5 of the SP value of the crystalline polyester.

〔styrene〕
When styrene is used, the content of the structural unit derived from styrene is preferably 60% or more, more preferably in the segment (c2), from the viewpoint of improving low-temperature fixability, charging stability, and fluidity of the toner. 70% by mass or more, more preferably 75% by mass or more, still more preferably 80% by mass or more, and preferably 100% by mass or less, more preferably 90% by mass or less, still more preferably 85% by mass or less. .

[(Meth) acrylic acid ester]
Examples of the (meth) acrylate ester include alkyl (meth) acrylate (alkyl group having 1 to 18 carbon atoms), benzyl (meth) acrylate, and dimethylaminoethyl (meth) acrylate. From the viewpoint of improving the property, charging stability and fluidity, alkyl (meth) acrylates having 1 to 18 carbon atoms in the alkyl group are preferred, and alkyl (meth) acrylates having 4 to 12 carbon atoms in the alkyl group are preferred. More preferably, alkyl (meth) acrylates having 8 to 12 carbon atoms in the alkyl group such as 2-ethylhexyl acrylate are more preferable, and 2-ethylhexyl acrylate is still more preferable.
When (meth) acrylic acid ester is used, the content of the structural unit derived from (meth) acrylic acid ester is in the segment (c2) from the viewpoint of improving low-temperature fixability, charging stability and fluidity of the toner. , Preferably 5% by mass or more, more preferably 10% by mass or more, further preferably 15% by mass or more, and preferably 40% by mass or less, more preferably 30% by mass or less, still more preferably 25% by mass or less. More preferably, it is 20 mass% or less.

[Amotropic monomer]
The segment (c2) preferably contains an amphoteric monomer that becomes a bonding point with the polyester resin of the segment (c1). The bireactive monomer is a monomer capable of both an addition polymerization reaction and a polycondensation reaction.
The both reactive monomers are preferably vinyl monomers having a carboxy group. Specific examples of the vinyl monomer having a carboxy group include acrylic acid, methacrylic acid, crotonic acid, tiglic acid, 2-pentenoic acid, 4-pentenoic acid, 2-methyl-2-pentenoic acid, 4-methyl- Examples include 2-pentenoic acid, 2-hexenoic acid, and 5-hexenoic acid. Among these, at least one of acrylic acid and methacrylic acid is preferable, and acrylic acid is more preferable from the viewpoint of polymerizability.
The amount of both reactive monomers used is the raw material monomer of the polyester resin of the segment (c1) from the viewpoint of dispersibility of the addition polymer containing styrene as a structural unit in the polyester resin and reaction control of the addition polymerization reaction and the polycondensation reaction. Is preferably 1 mol% or more, more preferably 2 mol% or more, still more preferably 3 mol% or more, still more preferably 4 mol% or more with respect to 100 mol% of the total amount of the carboxylic acid component. It is 40 mol% or less, More preferably, it is 30 mol% or less, More preferably, it is 20 mol% or less, More preferably, it is 16 mol% or less.

<Production method of composite resin>
The composite resin is preferably produced by any of the following methods (1) to (3). In addition, it is preferable that both reactive monomers are supplied to a reaction system with the raw material monomer of a vinyl-type resin component from a reactive viewpoint.

(1) A method in which after the step (A) of the polycondensation reaction with the alcohol component and the carboxylic acid component, the step (B) of the addition polymerization reaction with the raw material monomer and the both reactive monomers of the vinyl resin component is performed.
After the step (B), the reaction temperature is raised again, and if necessary, a polycondensation resin component trivalent or higher raw material monomer or the like is added to the polymerization system as a crosslinking agent, and the polycondensation reaction in the step (A) And the reaction with both reactive monomers can be further advanced.

(2) The method of performing the process (A) of the polycondensation reaction by the raw material monomer of a polycondensation-type resin component after the process (B) of the addition polymerization reaction by the raw material monomer and amphoteric monomer of a vinyl-type resin component.
The alcohol component and the carboxylic acid component can be present in the reaction system during the addition polymerization reaction, and the polycondensation reaction can be started by adding an esterification catalyst at a temperature suitable for the polycondensation reaction. The polycondensation reaction can also be started under a temperature condition suitable for the polycondensation reaction by adding it to the system later. In the former case, the molecular weight and molecular weight distribution can be adjusted by adding an esterification catalyst at a temperature suitable for the polycondensation reaction.

(3) A method in which the step (A) of the polycondensation reaction with the alcohol component and the carboxylic acid component and the step (B) of the addition polymerization reaction with the raw material monomer and the both reactive monomers of the vinyl resin component are performed in parallel.
In this method, step (A) and step (B) are performed under reaction temperature conditions suitable for addition polymerization reaction, the reaction temperature is increased, and under temperature conditions suitable for polycondensation reaction, if necessary, It is preferable to add a trivalent or higher valent raw material monomer of the polycondensation resin component to the polymerization system as a crosslinking agent, and further perform the polycondensation reaction in the step (A). At that time, under a temperature condition suitable for the polycondensation reaction, a radical polymerization inhibitor can be added to advance only the polycondensation reaction. Both reactive monomers are involved in the polycondensation reaction as well as the addition polymerization reaction.

Among these, the method (1) is preferable from the viewpoint that the degree of freedom in the reaction temperature of the polycondensation reaction is high.
The temperature suitable for the addition polymerization reaction is preferably 120 ° C. or higher and lower than 180 ° C., more preferably 165 ° C. or higher and lower than 180 ° C. As will be described later, the temperature suitable for the polycondensation reaction is preferably 180 to 250 ° C, more preferably 180 to 230 ° C.
The methods (1) to (3) are preferably performed in the same container.

<Physical properties of composite resin>
The weight average molecular weight of the composite resin is preferably 1,500 or more, more preferably 5,000 or more, still more preferably 10,000 or more, from the viewpoint of low-temperature fixability, charging stability and fluidity of the toner. More preferably, it is 15,000 or more, and preferably 50,000 or less, more preferably 45,000 or less, further preferably 43,000 or less, and still more preferably 40,000 or less.
The number average molecular weight of the composite resin is preferably 800 or more, more preferably 1,000 or more, still more preferably 2,000 or more, and still more preferably 2 from the viewpoints of low-temperature fixability, charging stability and fluidity of the toner. , 500 or more, and preferably 7,000 or less, more preferably 5,000 or less, still more preferably 4,000 or less, still more preferably 3,500 or less, and even more preferably 3,300 or less. .

  The acid value of the composite resin is preferably 5 mgKOH / g or more, more preferably 10 mgKOH / g or more, from the viewpoints of dispersion stability of the resin particle dispersion of the composite resin, obtaining uniform toner particles, and toner chargeability. More preferably, it is 15 mgKOH / g or more, and preferably 40 mgKOH / g or less, more preferably 30 mgKOH / g or less, still more preferably 20 mgKOH / g or less.

  The softening point of the composite resin is preferably 80 ° C. or higher, more preferably 85 ° C. or higher, and further preferably 90 ° C. or higher, from the viewpoint of improving the low-temperature fixability, charging stability and fluidity of the toner. Is 150 ° C. or lower, more preferably 130 ° C. or lower, and still more preferably 120 ° C. or lower.

  The glass transition temperature of the composite resin is preferably 40 ° C. or higher, more preferably 45 ° C. or higher, further preferably 50 ° C. or higher, and preferably from the viewpoint of improving the low-temperature fixability, charging stability and fluidity of the toner. Is 80 ° C. or lower, more preferably 70 ° C. or lower, still more preferably 60 ° C. or lower.

The weight average molecular weight, the number average molecular weight, the acid value, the softening point, the glass transition temperature, and the maximum endothermic peak temperature of the composite resin are measured by the measurement methods described in the examples.
Moreover, a composite resin can be used individually or in combination of 2 or more types. When using 2 or more types together, a softening point is the value which calculated | required the mixture by the method as described in an Example.

  The ratio of the segment (c2) to the total amount of the segment (c1) and the segment (c2) [(c2) / {(c1) + (c2)} × 100] determines the low-temperature fixability, charging stability and fluidity of the toner. From the viewpoint of improving, it is preferably 5% by mass or more, more preferably 10% by mass or more, further preferably 15% by mass or more, and preferably 50% by mass or less, more preferably 45% by mass or less, and still more preferably. 30% by mass or less.

  The mass ratio [(c1) / (c2)] of the segment (c1) to the segment (c2) is preferably 50/50 or more, more preferably from the viewpoint of improving the low-temperature fixability, charging stability and fluidity of the toner. Is 65/35 or more, more preferably 70/30 or more, and is preferably 95/5 or less, more preferably 90/10 or less, and still more preferably 85/15 or less.

  The total amount of the segment (c1) and the segment (c2) in the composite resin is preferably 60% by mass or more, more preferably 80% by mass or more, from the viewpoint of improving the low-temperature fixability, charging stability and fluidity of the toner. More preferably, it is 90 mass% or more, More preferably, it is substantially 100 mass%, More preferably, it is 100 mass%.

  When the toner of the present invention contains a composite resin, the mass ratio of the crystalline polyester to the composite resin (crystalline polyester / composite resin) is selected from the viewpoint of improving the low-temperature fixability, heat-resistant storage stability and environmental stability of the toner. The ratio is preferably 100/300 or more, more preferably 100/200 or more, still more preferably 100/150 or more, and preferably 100/50 or less, more preferably 100/90 or less.

(wax)
The composite resin preferably has a structural unit derived from a hydrocarbon wax having a hydroxyl group from the viewpoint of improving the low-temperature fixability, heat-resistant storage stability and environmental stability of the toner.

  The number average molecular weight of the hydrocarbon wax is preferably 400 or more and preferably 2,000 or less from the viewpoint of improving the low-temperature fixability, charging stability and fluidity of the toner.

  The melting point of the hydrocarbon wax is preferably 70 ° C. or higher, more preferably 80 ° C. or higher, and still more preferably 90 ° C. or higher, from the viewpoint of improving the low-temperature fixability, charging stability and fluidity of the toner. Is 120 ° C. or lower, more preferably 110 ° C. or lower, and still more preferably 100 ° C. or lower.

Specific examples of the hydrocarbon wax include polyolefin waxes such as polyethylene, polypropylene and polybutene, and paraffin wax.
In the present invention, a polyethylene wax having a melting point of 90 ° C. or higher and 120 ° C. or lower is preferable from the viewpoint of improving low-temperature fixability, heat-resistant storage stability and environmental stability of the toner.

  The content of the constituent unit derived from the wax in the composite resin is preferably 1% by mass or more, more preferably 3%, based on the total amount of the composite resin, from the viewpoint of improving the low-temperature fixability, charging stability and fluidity of the toner. It is at least 15% by mass, preferably at most 15 parts by mass, more preferably at most 10 parts by mass, and even more preferably at most 5 parts by mass.

(Additive)
The toner of the present invention includes a colorant, a release agent, a charge control agent, a charge control resin, magnetic powder, a fluidity improver, a conductivity modifier, a reinforcing filler such as a fibrous substance, an antioxidant, and a cleaning property. Additives such as improvers may be contained, and it is preferred that a colorant, a release agent and a charge control agent are contained.

<Colorant>
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 colorants can be used alone or in combination of two or more.
The content of the colorant is preferably 1 part by mass or more, more preferably 2 parts by mass or more, with respect to 100 parts by mass of the binder resin, from the viewpoint of improving the image density and low-temperature fixability of the toner. Preferably it is 20 mass parts or less, More preferably, it is 10 mass parts or less.

<Release agent>
As release agents, low molecular weight polypropylene, low molecular weight polyethylene, low molecular weight polypropylene-polyethylene copolymer, aliphatic hydrocarbon waxes such as microcrystalline wax, paraffin wax, Fischer-Tropsch wax and their oxides, carnauba wax And ester waxes such as montan wax, sazol wax and their deoxidized wax and fatty acid ester wax, fatty acid amides, fatty acids, higher alcohols, fatty acid metal salts and the like. These can be used alone or in admixture of two or more.

  The melting point of the release agent is preferably 60 ° C. or higher, more preferably 70 ° C. or higher, and preferably 100 ° C. or lower, more preferably 90 ° C., from the viewpoint of improving the low-temperature fixability and offset resistance of the toner. It is as follows.

  The number average molecular weight of the release agent is preferably 500 or more and preferably 5,000 or less from the viewpoint of improving low-temperature fixability and offset resistance.

  The content of the release agent is preferably 0.5 mass with respect to 100 parts by mass of the binder resin from the viewpoint of improving the low-temperature fixability and offset resistance of the toner and from the viewpoint of dispersibility in the binder resin. Part or more, more preferably 1 part by weight or more, still more preferably 1.5 parts by weight or more, preferably 10 parts by weight or less, more preferably 8 parts by weight or less, still more preferably 7 parts by weight or less.

<Charge control agent>
Examples of the charge control agent include chromium-based azo dyes, iron-based azo dyes, aluminum-based azo dyes, and salicylic acid metal complexes. These various charge control agents can be used alone or in combination of two or more.

  The content of the charge control agent is preferably 0.01 parts by mass or more, more preferably 0.2 parts by mass or more, and still more preferably from 100 parts by mass of the binder resin from the viewpoint of improving the charging stability of the toner. Is 0.5 parts by mass or more, preferably 10 parts by mass or less, more preferably 5 parts by mass or less, still more preferably 3 parts by mass or less, and still more preferably 2 parts by mass or less.

[Toner Production Method]
The toner production method of the present invention includes the following steps 1, 2, and 3.
Step 1: A crystalline polyester obtained by polycondensation of an alcohol component containing 99% by mass or more of ethylene glycol and an acid component containing 99% by mass or more of sebacic acid, and having a number average molecular weight Mn of 4,500 or more, 7, The molecular weight of 500 or less is 2% by mass or less, the molecular weight of 500 to 1,000 or less is 2 to 5% by mass, the molecular weight of 1,000 to 5,000 or less is 10 to 25% by mass. A step of obtaining a crystalline polyester dispersion by dispersing a crystalline polyester having an acid value of 5 mgKOH / g or more and 20 mgKOH / g or less in an organic solvent; Step 2: the crystalline polyester dispersion obtained in Step 1; SP value is 10.5 or more and 11.5 or less, softening point is 100 ° C or more and 120 ° C or less, and glass transition temperature Tg is 60 ° C or more and 75 ° C or less. Step of mixing the amorphous polyester to obtain a mixture Step 3: Step of adding an aqueous phase to the mixture obtained in Step 2 to invert the particles to particles of 4 μm to 7 μm

<Step 1>
Step 1 is a step of obtaining a crystalline polyester dispersion. Crystalline polyester is dispersed in an organic solvent to obtain a crystalline polyester dispersion. The crystalline polyester is as described above.

  Organic solvents include alcohol solvents such as ethanol, isopropanol, and isobutanol; ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and diethyl ketone; ether solvents such as dibutyl ether, tetrahydrofuran, and dioxane; ethyl acetate Is mentioned. Among these, from the viewpoint of dispersibility of crystalline polyester or amorphous polyester and durability of the toner, methyl ethyl ketone and ethyl acetate are preferable, and ethyl acetate is more preferable.

  The amount of the organic solvent used when mixing with the crystalline polyester is preferably 100 parts by mass or more, more preferably 500 parts by mass or more, and preferably 5,000 parts by mass with respect to 100 parts by mass of the crystalline polyester. Part or less, more preferably 3,000 parts by weight or less.

The volume median particle size (D ₅₀ ) of the crystalline polyester in the crystalline polyester dispersion is preferably 80 nm or more, more preferably 150 nm or more, and still more preferably 300 nm from the viewpoint of highly dispersing the crystalline polyester in the toner. More preferably, the thickness is 450 nm or more, preferably 2,000 nm or less, more preferably 1,500 nm or less, still more preferably 1,200 nm or less, and still more preferably 1,000 nm or less.

<Process 2>
Step 2 is a step of mixing the crystalline polyester dispersion obtained in Step 1 and the amorphous polyester to obtain a mixture. The amorphous polyester is as described above.

  The mass ratio of the amorphous polyester to the crystalline polyester (amorphous polyester / crystalline polyester) is preferably 100/20 or more from the viewpoint of improving low-temperature fixability, heat-resistant storage stability and environmental stability of the toner. More preferably, it is 100/15 or more, More preferably, it is 100/10 or more, Preferably it is 100/3 or less, More preferably, it is 100/5 or less.

In step 2, it is preferable to further mix the composite resin. The composite resin is as described above.
The mass ratio of the crystalline polyester to the composite resin (crystalline polyester / composite resin) is preferably 100/300 or more, more preferably 100, from the viewpoint of improving low-temperature fixability, heat-resistant storage stability and environmental stability of the toner. / 200 or more, more preferably 100/150 or more, preferably 100/50 or less, more preferably 100/90 or less.

<Step 3>
Step 3 is a step in which an aqueous phase is added to the mixture obtained in Step 2 and phase-inversion is performed to particles of 4 μm or more and 7 μm or less.
In this step, it is preferable to add a flocculant for efficient aggregation. As the flocculant, a quaternary salt cationic surfactant, an organic flocculant such as polyethyleneimine; and an inorganic flocculant such as inorganic metal salt and inorganic ammonium salt are used. From the viewpoints of toner particle size distribution, heat resistant storage stability and gloss of printed matter, inorganic flocculants are preferred, and inorganic metal salts are particularly preferred.

  Examples of the inorganic metal salt include sodium sulfate, sodium chloride, calcium chloride, calcium nitrate, barium chloride, magnesium chloride, zinc chloride, and aluminum chloride. The valence of the central metal of the inorganic metal salt is preferably 2 or more from the viewpoints of the particle size distribution of the toner, the improvement of heat resistant storage stability and the gloss of the printed matter.

  When the flocculant is added, the addition amount is preferably 0.01 parts by mass or more, more preferably 100 parts by mass with respect to 100 parts by mass of the binder resin, from the viewpoint of improving the heat resistant storage stability of the toner and improving the gloss of the printed matter. It is 0.1 parts by mass or more, more preferably 0.2 parts by mass or more, preferably 10 parts by mass or less, more preferably 5 parts by mass or less, still more preferably 1 part by mass or less, and still more preferably 0. 5 parts by mass or less.

  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. From the viewpoint of uniformly dispersing the flocculant and causing uniform agglomeration, the flocculant is preferably added at 20 ° C. or higher and 40 ° C. or lower until the predetermined particle size is obtained after the flocculant is added. It is preferable to hold at 40 ° C. or higher and 60 ° C. or lower.

  In this step, a colorant, a charge control agent, a release agent, a conductivity adjusting agent, a reinforcing filler such as a fibrous substance, an antioxidant, and an anti-aging agent may be added before aggregation. Good. The additive can also be used as an aqueous dispersion. The additives are as described above.

  In step 3, from the viewpoint of uniformly dispersing a mixture of an aqueous dispersion containing crystalline polyester and an aqueous dispersion containing amorphous polyester, and various additives used as necessary, preferably binding. The dispersion treatment is performed at a temperature lower than the softening point of the resin, more preferably at a temperature not higher than “the softening point−30 ° C.”. Specifically, the temperature is preferably 65 ° C. or less, more preferably 55 ° C. or less, and the dispersion treatment should be performed at a temperature higher than 0 ° C. from the viewpoint of fluidity of the medium and production energy of the aqueous dispersion of the resin. Is preferable, and it is more preferable to carry out at 10 degreeC or more.

  As a method for dispersion treatment, high-speed stirring and mixing devices such as “Ultra Disper” (manufactured by Asada Tekko Co., Ltd.), “Ebara Milder” (manufactured by Ebara Seisakusho Co., Ltd.), and “TK Homomixer” (manufactured by Primix Co., Ltd.); "High-pressure homogenizer" (manufactured by Izumi Food Machinery Co., Ltd.), homo-valve type high-pressure homogenizer represented by "Minilab 8.3H type" (manufactured by Rannie); "Microfluidizer" (manufactured by Microfluidics) and "Nanomizer" Chamber type high-pressure homogenizer, etc.).

The volume-median particle size (D ₅₀ ) of the aggregated particles obtained in Step 3 is preferably 4 μm or more, more preferably 5 μm or more, and preferably 7 μm or less, more preferably 6 μm or less.

An electrophotographic toner can be obtained by subjecting the aggregated particles obtained in Step 3 to a solid-liquid separation step such as filtration, a washing step, and a drying step as appropriate.
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 mass or less, and more preferably 1.0% by mass or less, from the viewpoint of improving the chargeability.

(External additive)
In the toner of the present invention, an external additive is preferably used in order to improve transferability, and inorganic fine particles are preferably used as the external additive. Examples of the inorganic fine particles include silica, alumina, titania, zirconia, tin oxide and zinc oxide, and silica is preferable. As the silica, hydrophobic silica that has been subjected to a hydrophobic treatment is preferable from the viewpoint of improving toner transferability.

  Examples of the hydrophobizing agent for hydrophobizing the surface of silica particles include hexamethyldisilazane (HMDS), dimethyldichlorosilane (DMDS), silicone oil, octyltriethoxysilane (OTES), and methyltriethoxysilane. Of these, hexamethyldisilazane is preferred.

  The volume average particle diameter of the external additive is preferably 10 nm or more, more preferably 15 nm or more, and preferably 250 nm or less, more preferably 200 nm or less, from the viewpoints of chargeability, fluidity, and transferability of the toner. More preferably, it is 90 nm or less.

  The content of the external additive is preferably 0.05 parts by mass or more with respect to 100 parts by mass of the toner before being processed with the external additive, from the viewpoint of environmental stability of charge degree and storage stability under pressure. Preferably it is 0.1 mass part or more, More preferably, it is 0.3 mass part or more, Preferably it is 5 mass parts or less, More preferably, it is 3 mass parts or less.

(Physical properties of toner)
The volume median particle size (D ₅₀ ) of the toner of the present invention is preferably 4 μm or more, more preferably 5 μm or more, and preferably 7 μm or less, more preferably 6 μm or less. In the present specification, the volume-median particle size (D ₅₀ ) means a particle size at which the cumulative volume frequency calculated by the volume fraction is 50% when calculated from the smaller particle size. When the toner is treated with an external additive, the volume median particle size of the toner particles before being treated with the external additive is defined as the volume median particle size of the toner.

  The toner of the present invention can be used as a one-component developing toner or as a two-component developer mixed with a carrier.

  EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples. The physical properties of the resin and the like were measured by the following method.

[Softening point of resin]
Using a flow tester “CFT-500D” (manufactured by Shimadzu Corporation), a 1 g sample was heated at a heating rate of 6 ° C./min, a load of 1.96 MPa was applied by a plunger, a diameter of 1 mm, and a length of 1 mm. Extruded from the nozzle. 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.

[Glass transition temperature of resin]
Using a differential scanning calorimeter “Q-100” (manufactured by TA Instruments Japan Co., Ltd.), 0.01 to 0.02 g of a sample was weighed into an aluminum pan and heated at a rate of 10 ° C./min. The temperature was raised to 200 ° C., and the temperature was cooled to 0 ° C. at a temperature lowering rate of 10 ° C./min. Next, the sample is heated at a heating rate of 10 ° C./min, and the temperature at the intersection of the base line extension below the maximum peak temperature of endotherm and the tangent indicating the maximum slope from the peak rising portion to the peak apex is obtained. The glass transition temperature was taken.

[Maximum peak temperature and melting point of resin endotherm]
Using a differential scanning calorimeter “Q-100” (manufactured by TA Instruments Japan Co., Ltd.), 0.01 to 0.02 g of a sample was weighed into an aluminum pan and heated at a rate of 10 ° C./min. The temperature was raised to 200 ° C., cooled from room temperature to 0 ° C. at a temperature drop rate of 10 ° C./min, and maintained at that temperature for 1 minute. Then, it measured with the temperature increase rate of 50 degreeC / min. Of the endothermic peaks observed, the peak temperature at the highest temperature side was defined as the highest endothermic peak temperature. In crystalline polyester, the highest peak temperature of endotherm was taken as the melting point.

[Endotherm of resin endotherm]
Using a differential scanning calorimeter “Q-100” (manufactured by TA Instruments Japan Co., Ltd.), 0.01 to 0.02 g of a sample was weighed into an aluminum pan and heated at a rate of 10 ° C./min. The temperature was raised to 200 ° C., cooled from room temperature to 0 ° C. at a temperature drop rate of 10 ° C./min, and maintained at that temperature for 1 minute. Then, it measured with the temperature increase rate of 10 degree-C / min. The endothermic area of the observed endothermic peak was calculated and used as the endothermic amount of the crystalline polyester.

[Acid value of the resin]
The acid value of the resin was measured based on the method of JIS K0070. However, only the measurement solvent was changed from a mixed solvent of ethanol and ether specified in JIS K0070 to a mixed solvent of acetone and toluene (acetone: toluene = 1: 1 (volume ratio)).

[Number average molecular weight, weight average molecular weight of polyester]
The molecular weight distribution was measured by the gel permeation chromatography (GPC) method according to the following method, and the number average molecular weight Mn and the weight average molecular weight Mw of the resin were determined.
(1) Preparation of sample solution The resin was dissolved in chloroform so that the concentration was 0.5 g / 100 mL. Subsequently, this solution was filtered using a fluororesin filter “FP-200” (manufactured by Sumitomo Electric Industries, Ltd.) having a pore size of 2 μm to remove insoluble components to obtain a sample solution.
(2) Molecular weight measurement Using the following apparatus, chloroform was flowed as an eluent at a flow rate of 1 ml per minute, and the column was stabilized in a constant temperature bath at 40 ° C. 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. In the calibration curve at this time, several types of monodispersed polystyrenes with known molecular weights (manufactured by Tosoh Corporation; 2.63 × 10 ³ , 2.06 × 10 ⁴ , 1.02 × 10 ⁵ , GL Sciences Corporation); 2.10 × 10 ³ , 7.00 × 10 ³ , 5.04 × 10 ⁴ ) prepared as standard samples were used.
Measuring device: “CO-8010” (manufactured by Tosoh Corporation)
Analytical column: "GMH _XL " + "G3000H _XL " (both manufactured by Tosoh Corporation)

[Melting point of release agent]
Using a differential scanning calorimeter “DSC210” (manufactured by Seiko Instruments Inc.), 0.01 to 0.02 g of sample was weighed into an aluminum pan, heated to 200 ° C., and the temperature decreasing rate was 10 ° C./min. At 0 ° C. Next, the sample was heated at a heating rate of 10 ° C./min, and the maximum peak temperature of the heat of fusion was taken as the melting point of the release agent.

[Volume-median particle diameter of toner (D ₅₀ )]
Measuring machine: “Coulter Multisizer II” (Beckman Coulter, Inc.)
Aperture diameter: 50 μm
Analysis software: “Coulter Multisizer AccuComp version 1.19” (Beckman Coulter, Inc.)
Electrolyte: “Isoton II” (Beckman Coulter, Inc.)
Dispersion: “Emulgen 109P” (polyoxyethylene lauryl ether, manufactured by Kao Corporation, HLB: 13.6) 5% electrolyte dispersion condition: 10 mg of a measurement sample was added to 5 ml of the dispersion, and 1 with an ultrasonic disperser. The sample dispersion was prepared by dispersing for 25 minutes, and then adding 25 ml of the electrolyte and further dispersing for 1 minute by an ultrasonic disperser.
Measurement conditions: 100 ml of electrolyte and dispersion were added to a beaker, the dispersion was added so that the particle size of 30,000 particles could be measured in 20 seconds, and 30,000 particles were measured. The volume-median particle size (D ₅₀ ) was determined from the distribution.

<Manufacture of resin>
Production Examples 1, 2, 3, 5, 8, and 9
(Production of crystalline polyesters A1, A2, A3, A5, A8 and A9)
The raw material monomers shown in Table 1 were put into a 10 L four-necked flask equipped with a nitrogen introduction tube, a dehydration tube equipped with a fractionating tube through which hot water of 98 ° C. was passed, a stirrer and a thermocouple, and under a nitrogen atmosphere. The temperature was raised from 140 ° C. to 210 ° C. over 12 hours. After the temperature was lowered to 180 ° C., 140 ° C. water (water vapor) was blown into the resin at a rate of 5 g / min for 1 hour while stirring at 40 kPa at the same temperature and added. After completion of the blowing, the reaction was further carried out at 8 kPa for 0.5 hour to sufficiently remove the water in the system, 20 g of titanium dihydroxybis (triethanolaminate) was added, and the reaction was further carried out at 210 ° C. for 1 hour. The reaction was continued at 8 kPa until a predetermined molecular weight was reached.

Production Example 4
(Production of crystalline polyester A4)
The raw material monomers shown in Table 1 were put into a 10 L four-necked flask equipped with a nitrogen introduction tube, a dehydration tube equipped with a fractionating tube through which hot water of 98 ° C. was passed, a stirrer and a thermocouple, and under a nitrogen atmosphere. The temperature was raised from 140 ° C. to 210 ° C. over 12 hours. Titanium dihydroxybis (triethanolaminate) 20 g was added and reacted at 210 ° C. for an additional hour, and then reacted at 8 kPa until a predetermined molecular weight was reached.

Production Examples 6 and 7
(Production of crystalline polyesters A6 and A7)
Raw material monomer shown in Table 1 and 2-ethylhexanoic acid tin (II) 20 g, 10 L capacity equipped with nitrogen introduction tube, dehydration tube equipped with a fractionating tube through which hot water of 98 ° C. was passed, agitator and thermocouple Was heated from 140 ° C. to 210 ° C. over 12 hours in a nitrogen atmosphere. After the temperature was lowered to 180 ° C., 140 ° C. water (water vapor) was blown into the resin at a rate of 5 g / min for 1 hour while stirring at 40 kPa at the same temperature and added. After completion of the blowing, the reaction was further carried out at 8 kPa for 0.5 hours to sufficiently remove the water in the system, 20 g of titanium dihydroxybis (triethanolaminate) was added, and the reaction was further carried out at 210 ° C. for 1 hour. The reaction was continued at 8 kPa until the predetermined molecular weight was reached.

Production Examples 10, 11 and 12
(Production of amorphous polyesters B1, B2 and B3)
Raw material monomers other than trimellitic anhydride shown in Table 2 and 40 g of titanium diisopropylate bis (triethanolaminate) and 2 g of gallic acid were added to a 10 L volume equipped with a nitrogen introduction tube, a dehydration tube, a stirrer and a thermocouple. The flask was placed in a four-necked flask, heated to 230 ° C. under a nitrogen atmosphere, and reacted at 230 ° C. for 6 hours. Then, after adding trimellitic anhydride at 210 ° C., the mixture was reacted for 2 hours, reacted at 210 ° C. for 1 hour at normal pressure, and then reacted at 8 kPa until the softening point shown in Table 2 was reached. Thus, an amorphous polyester was obtained.

Production Examples 13, 14 and 15
(Production of composite resins C1, C2 and C3)
A thermometer containing raw material monomers of polycondensation resin components other than trimellitic anhydride shown in Table 3, hydrocarbon wax having a hydroxyl group and polyethylene wax, 20 g of titanium diisopropylate bis (triethanolamate) and 2 g of gallic acid , Put into a 10 L four-necked flask equipped with a stainless steel stir bar, dehydration tube, flow-down condenser, and nitrogen inlet tube, and rise from 180 ° C to 235 ° C over 6 hours in a mantle heater in a nitrogen atmosphere. After warming, it reacted at 235 ° C. for 4 hours. Then, it reacted at 8 kPa for 1 hour.
Next, the temperature was lowered to 160 ° C. while maintaining the reduced pressure condition of 8 kPa, and a mixed solution of the vinyl resin raw material monomer, the radical polymerization initiator and acrylic acid shown in Table 3 was added dropwise over 1 hour. After completion of the dropping, the reaction was aged for 1 hour, and then the pressure was reduced at 8 kPa for 1 hour to remove the remaining vinyl resin raw material monomer and the like.
And trimellitic anhydride was added, maintaining the pressure reduction conditions of 8 kPa, and it heated up at 200 degreeC. After reacting at 200 ° C. for 3 hours, the reaction was carried out at 20 kPa until the desired softening point was reached to obtain a composite resin.

Examples 1 to 13 and Comparative Examples 1 to 5
<Production of crystalline polyester dispersion>
The crystalline polyester obtained in each of Production Examples 1 to 9 was pulverized to 10 μm with a jet mill pulverizer.
In a 500 mL container, 100 g of ethyl acetate and 10 g of each crystalline polyester are added, and further 300 g of 0.3 mmφ zirconia beads are added. After shaking for 5 hours with a paint shaker (manufactured by Asada Steel Corporation), a stainless steel wire mesh is used. The zirconia beads were filtered through (200 mesh) to obtain crystalline polyester dispersions.

<Manufacture of wax dispersion>
In a 500 mL container, 100 g of ethyl acetate and 10 g of paraffin wax “HNP-9” (manufactured by Nippon Seiki Co., Ltd., melting point: 75 ° C.) are heated to 70 ° C. and confirmed to be completely dissolved. It was immersed in a water bath and cooled to 20 ° C. in 10 minutes. Then, 300 g of 0.3 mmφ zirconia beads were added and shaken for 5 hours to obtain a wax dispersion. The particle size of the wax was 350 nm.

<Manufacture of pigment master batch>
After stirring 100 parts by mass of amorphous polyester and 20 parts by mass of colorant “ECB-301” (CI Pigment Blue 15: 3, manufactured by Dainichi Seika Kogyo Co., Ltd.) with a Henschel mixer, Melt kneading was performed using a co-rotating twin screw extruder having a total length of 1560 mm, a screw diameter of 42 mm, and a barrel inner diameter of 43 mm.

<Preparation of developing toner>
(Preparation of polyester mixture)
After 100 parts by weight of amorphous polyester, 10 parts by weight of composite resin, 20 parts by weight of pigment masterbatch, and 150 parts by weight of ethyl acetate are dissolved in a 2 L flask equipped with a paddle type stirring blade, crystalline polyester dispersion 100 Part by mass and 50 parts by mass of the wax dispersion were added, and sufficiently mixed and dispersed using an attritor (manufactured by Nippon Coke Industries, Ltd.).

(Creation of aqueous dispersion)
On the other hand, 300 parts by mass of ion-exchanged water and 390 parts by mass of a 0.1 M Na ₃ PO ₄ aqueous solution were put into a 4 L four-necked vessel equipped with a high-speed agitator “TK homomixer” (manufactured by Primex Corporation). Warmed to ° C. To this was added 60 parts by mass of a 1.0 M CaCl ₂ aqueous solution, and the mixture was stirred at a rotational speed of 10,000 rpm to prepare an aqueous medium containing a fine hardly water-soluble dispersion stabilizer Ca ₃ (PO ₄ ) ₂ . .

(Create toner)
The polyester mixed solution was poured into an aqueous medium, and the mixture was stirred at 10,000 rpm for 4 minutes while being kept at 40 ° C. under a nitrogen stream, and granulated. Thereafter, the stirring was switched to a paddle type stirring blade, and ethyl acetate was recovered under reduced pressure at 40 ° C. for 2 hours.
After completion of the distillation under reduced pressure, the contents in the container were cooled to room temperature, hydrochloric acid was added thereto to dissolve the hardly water-soluble dispersion stabilizer, and toner particles were obtained through filtration, washing with water and drying. The volume-median particle size (D ₅₀ ) of the toner particles was 5.8 μm.

<External processing>
To 100 parts by mass of the obtained toner particles, 1.0 part by mass of hydrophobic silica “NAX-50” (manufactured by Nippon Aerosil Co., Ltd., average particle size 40 nm), hydrophobic silica “R972” (Japan Aerosil Co., Ltd.) Manufactured, average particle diameter of 16 nm) 0.6 parts by mass, ST, AO A 10-liter Henschel mixer (Mitsui Mining Co., Ltd.) equipped with stirring blades was added and stirred at 3,000 r / min for 2 minutes. A toner was obtained.

[Evaluation of toner]
(1) Heat-resistant storage stability of toner 20 g of toner was put in a wide-mouthed polybin having an internal volume of 100 mL, sealed, and allowed to stand for 48 hours in an environment of any temperature. Thereafter, it was allowed to stand for 12 hours or more while being sealed at a temperature of 25 ° C. and cooled. Next, a sieve having a mesh size of 250 μm is set on a vibrating table of “Powder Tester (registered trademark)” (manufactured by Hosokawa Micron Co., Ltd.), and 20 g of the toner is placed thereon, and the mixture is vibrated for 30 seconds. The maximum value of the arbitrary temperature of those that did not agglomerate (those that did not agglomerate) was defined as the maximum temperature at which no agglomeration occurred, and was used as an index for heat resistant storage stability. The larger the value, the more excellent the heat resistant storage stability of the toner.

(2) Toner environmental stability (2-1) Charge stability under normal temperature and low humidity (NL) environment 0.4 g (4 parts by mass) of toner and a silicone coated ferrite carrier (manufactured by Kanto Denka Kogyo Co., Ltd., average particle) 9.6 g (96 parts by mass) of a diameter of 90 μm) was put into a 20 mL polypropylene container, left to stand for 12 hours in an environment of 20 ° C. and 20% RH, and then mixed for 10 minutes by a ball mill. After mixing, the amount of charge in an NL environment was measured using “q / m Meter MODEL 210HS” (manufactured by TREK).

(2-2) Charge stability in a room temperature and high humidity (NH) environment 0.4 g (4 parts by mass) of toner and 9.6 g of a silicone-coated ferrite carrier (manufactured by Kanto Denka Kogyo Co., Ltd., average particle size 90 μm) 96 parts by mass) was put into a 20 mL polypropylene container, left open in an environment of 20 ° C. and 80% RH for 12 hours, and then mixed in a ball mill for 10 minutes. After mixing, the charge amount in an NH environment was measured using “q / m Meter MODEL 210HS” (manufactured by TREK).

  The closer the value of the charge amount in the NH environment / the charge amount in the NL environment is to 1, the better the toner is in environmental stability. 0.60 or more is practically preferable, and 0.80 or more is more preferable. .

(3) Low-temperature fixability of toner Toner is mounted on an apparatus in which the fixing machine of the copier “AR-505” (manufactured by Sharp Corporation) is improved so that fixing can be performed outside the apparatus, and paper manufactured by Sharp Corporation. On [CopyBond SF-70NA (75 g / m ² )], a printed matter was obtained in an unfixed state so that the toner adhesion amount was 0.6 mg / cm ² . Using a fixing machine (fixing speed 200 mm / sec) adjusted so that the total fixing pressure becomes 40 kgf, the fixing roller temperature is increased from 100 ° C. to 240 ° C. in 5 ° C. increments, and the unfixed state at each temperature. The fixing test of the printed material was conducted.
A sand eraser with a bottom of 15 mm x 7.5 mm under a load of 500 g. The image fixed through the fixing machine is rubbed 5 times, and the optical reflection density before and after rubbing is measured by a reflection densitometer “RD-915” (Gretag Macbeth) The temperature of the fixing roller in which the ratio between the two (after rubbing / before rubbing) first exceeded 70% was defined as the minimum fixing temperature. The lower the minimum fixing temperature, the better the low-temperature fixability of the toner.

(4) Bending strength of printed matter Toner is mounted on a copier “AR-505” (manufactured by Sharp Corporation) in which the fixing machine is improved so that fixing can be performed outside the apparatus, and J paper (Fuji Xerox Co., Ltd.) A printed matter was obtained in an unfixed state so that the toner adhesion amount was 0.6 mg / cm ² . Fixing was performed at a fixing roller temperature of 140 ° C. using a fixing machine (fixing speed: 100 mm / sec) adjusted so that the total fixing pressure was 40 kgf.
Further, the printed material is folded in a mountain so that the printing surface is on top, and after passing through a fixing machine (fixing speed 200 mm / sec, 40 ° C.) adjusted so that the total fixing pressure is 40 kgf, the image of the crease portion is displayed. Observed and evaluated according to the following criteria.
5: No damage 4: Observed at several white spots 3: Some cracks 2: White lines of 0.5 mm or less in the fold 1: White lines of 1 mm or more in the folds The higher the numerical value, the printed matter Represents a high bending strength, and 3 or more is practically preferable, and 4 or more is more preferable.

From the above results, it can be seen that the toners of the examples are all excellent in the balance of low-temperature fixability, heat-resistant storage stability and environmental stability as compared with the toners of the comparative examples.
It can also be seen that the use of the toner of the present invention improves the bending strength of the printed matter. This is considered that the impact is absorbed by the fine dispersion of the crystalline polyester in the toner of the present invention.

  The electrophotographic toner of the present invention can be suitably used as an electrophotographic toner used in electrophotography, electrostatic recording method, electrostatic printing method and the like.

Claims (13)

An electrophotographic toner comprising a crystalline polyester containing a structural unit derived from an alcohol component containing 99% by mass or more of ethylene glycol and a structural unit derived from a carboxylic acid component containing 99% by mass or more of sebacic acid,
The crystalline polyester has a number average molecular weight Mn of 4,500 or more and 7,000 or less, a molecular weight of 500 or less of 2% by mass or less, a molecular weight of more than 500 or less of 1,000 or less of 2% by mass or more and 5% by mass or less, and a molecular weight of 1, An electrophotographic toner having a content of more than 5,000 and not more than 5,000 and not more than 10% by weight and not more than 25% by weight, and an acid value of not less than 5 mgKOH / g and not more than 20 mgKOH / g.   The toner for electrophotography according to claim 1, wherein Mw / Mn of the crystalline polyester is 2 or more and 5 or less.   The peak top of melting at 2nd RUN by differential scanning calorimetry (DSC) for the crystalline polyester is 73.5 ° C. or higher and 77.0 ° C. or lower, and the endothermic amount is 70 J / g or higher and 90 J / g or lower. Item 3. The toner for electrophotography according to Item 1 or 2.   The amorphous polyester having an SP value of 10.5 to 11.5, a softening point of 100 ° C to 120 ° C, and a glass transition temperature Tg of 60 ° C to 75 ° C is further included. The toner for electrophotography as described in any one of -3.   The toner for electrophotography according to claim 4, wherein a mass ratio of the amorphous polyester to the crystalline polyester (amorphous polyester / crystalline polyester) is in a range of 100/20 or more and 100/3 or less. .   Styrene in which the SP of the styrene acrylic part is within the range of ± 0.5 of the SP value of the crystalline polyester, and the SP value of the polyester part is within the range of ± 0.5 of the SP value of the amorphous polyester The toner for electrophotography according to claim 1, further comprising a composite resin having an acrylic moiety and a polyester moiety.   7. The composite resin according to claim 6, wherein the composite resin contains 1% by mass or more and 15% by mass or less of a structural unit derived from a hydrocarbon wax having a hydroxyl group having a molecular weight of 400 or more and 2,000 or less and a melting point of 70 ° C. or more and 120 ° C. or less. Toner for electrophotography.   The electrophotographic toner according to claim 7, wherein the hydrocarbon wax is a polyethylene wax having a melting point of 90 ° C. or higher and 120 ° C. or lower.   The electron according to any one of claims 6 to 8, wherein a mass ratio between the crystalline polyester and the composite resin (crystalline polyester / composite resin) is in a range of 100/300 or more and 100/50 or less. Toner for photography. A method for producing an electrophotographic toner, comprising the following steps 1, 2 and 3.
Step 1: A crystalline polyester obtained by polycondensation of an alcohol component containing 99% by mass or more of ethylene glycol and an acid component containing 99% by mass or more of sebacic acid, and having a number average molecular weight Mn of 4,500 or more, 7, The molecular weight of 500 or less is 2% by mass or less, the molecular weight of 500 to 1,000 or less is 2 to 5% by mass, the molecular weight of 1,000 to 5,000 or less is 10 to 25% by mass. A step of obtaining a crystalline polyester dispersion by dispersing a crystalline polyester having an acid value of 5 mgKOH / g or more and 20 mgKOH / g or less in an organic solvent; Step 2: the crystalline polyester dispersion obtained in Step 1; SP value is 10.5 or more and 11.5 or less, softening point is 100 ° C or more and 120 ° C or less, and glass transition temperature Tg is 60 ° C or more and 75 ° C or less. Step of mixing the amorphous polyester to obtain a mixture Step 3: Step of adding an aqueous phase to the mixture obtained in Step 2 to invert the particles to particles of 4 μm to 7 μm   The method for producing an electrophotographic toner according to claim 10, wherein a particle size of the crystalline polyester in the crystalline polyester dispersion is 80 nm or more and 2,000 nm or less.   In step 2, the SP of the styrene acrylic part is within the range of ± 0.5 of the SP value of the crystalline polyester, and the SP value of the polyester part is ± 0.5 of the SP value of the amorphous polyester. The method for producing an electrophotographic toner according to claim 10 or 11, wherein a composite resin having a styrene acrylic part and a polyester part, which is within the range, is mixed. An electrophotographic toner obtained by a process comprising the following processes 1, 2 and 3.
Step 1: A crystalline polyester obtained by polycondensation of an alcohol component containing 99% by mass or more of ethylene glycol and an acid component containing 99% by mass or more of sebacic acid, and having a number average molecular weight Mn of 4,500 or more, 7, The molecular weight of 500 or less is 2% by mass or less, the molecular weight of 500 to 1,000 or less is 2 to 5% by mass, the molecular weight of 1,000 to 5,000 or less is 10 to 25% by mass. A step of obtaining a crystalline polyester dispersion by dispersing a crystalline polyester having an acid value of 5 mgKOH / g or more and 20 mgKOH / g or less in an organic solvent; Step 2: the crystalline polyester dispersion obtained in Step 1; SP value is 10.5 or more and 11.5 or less, softening point is 100 ° C or more and 120 ° C or less, and glass transition temperature Tg is 60 ° C or more and 75 ° C or less. Step of mixing the amorphous polyester to obtain a mixture Step 3: Step of adding an aqueous phase to the mixture obtained in Step 2 to invert the particles to particles of 4 μm to 7 μm