JP2016090598A - Method for manufacturing electrostatic charge image development toner - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for manufacturing an electrostatic charge image development toner excellent in low-temperature fixability, heat-resistant storage and charge stability, with the steps of the method being simple.SOLUTION: A method for manufacturing an electrostatic charge image development toner includes the steps of: (1) aggregating resin particles A and resin particles B, in the presence of an aggregating agent, in an aqueous medium, at a temperature higher than a glass transition temperature Tg(A) of the resin particles A by 5°C or more and at a temperature lower than a glass transition temperature Tg(B) of the resin particles B, to obtain aggregate particles; and (2) heating the aggregate particles obtained in the step (1) to fuse the particles. The glass transition temperature Tg(A) of the resin particles A and the glass transition temperature Tg(B) of the resin particles B are in the relationship of the following formula (1) Tg(A)+10°C<Tg(B). When the solubility parameters according to Fedors method of a resin constituting the resin particles A and a resin constituting the resin particle B are defined as SP(A) and SP(B), respectively, the difference ΔSP(|SP(A)-SP(B)|) between the solubility parameters is 0.3(cal/cm)or more and less than 1.5(cal/cm). In the step (1), a non-metal salt including a monovalent cation is contained as the aggregating agent.SELECTED DRAWING: None

Description

  The present invention relates to a method for producing an electrostatic charge image developing toner.

  In the field of electrophotography, with the development of electrophotographic systems, the development of toner for electrophotography corresponding to high speed and high image quality is required. As a method of obtaining a toner having a small particle size and a uniform particle size that can cope with high image quality, an aggregation coalescence method (emulsion aggregation method, There has been proposed a toner production method using an agglomeration fusion method.

Patent Document 1 includes an amorphous resin obtained by condensation polymerization of a carboxylic acid component containing alkenyl succinic acid and an alcohol component, and a shell portion containing a carboxylic acid component containing alkenyl succinic acid and an alcohol. An electrophotographic toner that is an amorphous resin obtained by polycondensation of the components and the amount of the alkenyl succinic acid component in the core portion and the shell portion satisfies a specific relational expression, has low temperature fixability, heat resistant storage stability, and It is disclosed that the charging stability is excellent.
Patent Document 2 includes a mixing step of mixing a resin particle dispersion in which resin fine particles are dispersed, a colorant particle dispersion in which colorant particles are dispersed, and a release agent particle dispersion in which release agent particles are dispersed. , Agglomeration step of forming an agglomerated particle dispersion of the resin particles, the colorant particles, and the release agent particles, and fusing / merging by heating to a temperature above the glass transition point of the resin fine particles. And a urethane compound dispersion liquid in which a urethane compound having a specific structure is dissolved and mixed in the resin particle dispersion liquid, mixed in the release agent particle dispersion liquid, or in which the urethane compound is dispersed. And a method for producing an electrophotographic toner, characterized in that it is mixed with the agglomerated particle dispersion in the agglomeration step, and has excellent fixability in a high temperature range and excellent image quality and stress resistance. Is shown There.
In patent document 3, the process of obtaining the dispersion liquid of the styrene acrylic modified polyester resin particle whose styrene acrylic content rate is 5-40 mass%, and the content rate of the structural unit derived from a (meth) acrylic acid ester monomer are 40. A step of obtaining a dispersion of vinyl resin particles having a weight average molecular weight of 100,000 to 400,000, a dispersion of the styrene acrylic modified polyester resin particles, and a dispersion of the vinyl resin particles And a process for aggregating the styrene-acrylic modified polyester resin particles and the vinyl resin particles, and a method for producing an electrostatic charge image developing toner, wherein the toner has excellent low-temperature fixability and low gloss Discloses a technique for producing a toner for developing an electrostatic image excellent in the above.

  Further, Patent Document 4 is obtained by agglomerating resin particles having a core-shell structure as an electrostatic charge image developing toner capable of reducing fixing energy even on thick paper while achieving both high image quality and reliability. And the resin constituting the shell contains a polycondensation resin, and the difference between the glass transition point of the resin constituting the core and the glass transition point of the resin constituting the shell is 20 ° C. or more. Toners have been proposed.

JP2013-222002A JP 2006-267508 A JP 2013-195700 A JP 2007-322953 A

However, both are insufficient as high-speed and high-quality toners that have been demanded in recent years, and toners having both low-temperature fixability and storability, and there remain problems in maintaining a high charge amount during printing.
Usually, a resin having a low glass transition temperature Tg is advantageous for improving low-temperature fixability, and a resin having a high glass transition temperature Tg is advantageous for improving heat-resistant storage stability. For this reason, two or more types of resins having different glass transition temperatures are often used. Further, these are core-shell toner particles in which a low Tg resin is arranged on the core side and a high Tg resin is arranged on the shell side. Therefore, both low-temperature fixability and heat-resistant storage stability are achieved. However, in the production of chemical toners, Tg is averaged when compatibility occurs between the resins when the resin particles are heated and fused, so that sufficient low-temperature fixability can be obtained by taking advantage of the characteristics of the resin. It becomes difficult to achieve both heat-resistant storage stability. In addition, the production of the core-shell toner described in Patent Document 1 has a problem that the production process is complicated because the core is formed and then the shell is formed.
An object of the present invention is to provide a production method capable of obtaining a toner for developing an electrostatic image having a simple process and excellent in low-temperature fixability, heat-resistant storage stability, and charging stability.

  The inventor uses at least two types of resin particles having a specific relationship in their characteristics, and agglomerates them under specific conditions and further fuses them to achieve low temperature fixability, heat resistant storage stability, and charge stability. It has been found that an excellent electrostatic charge image developing toner can be obtained.

That is, the present invention is the step (1): in an aqueous medium, in the presence of a flocculant, the resin particles A and the resin particles B are at least 5 ° C. higher than the glass transition temperature Tg (A) of the resin particles A, and A step of agglomerating at a temperature lower than the glass transition temperature Tg (B) of the resin particle B to obtain an agglomerated particle;
Step (2): a step of heating and fusing the aggregated particles obtained in the step (1),
A method for producing an electrostatic charge image developing toner comprising:
The glass transition temperature Tg (A) of the resin particle A and the glass transition temperature Tg (B) of the resin particle B are in the relationship of the following formula (1):
Tg (A) + 10 ° C <Tg (B) (1)
When the solubility parameters by the Fedors method of the resin constituting the resin particle A and the resin constituting the resin particle B are SP (A) and SP (B), respectively.
The solubility parameter difference ΔSP (| SP (A) −SP (B) |) is 0.3 (cal / cm ³ ) ^1/2 or more and less than 1.5 (cal / cm ³ ) ^1/2 ,
In the step (1), there is provided a method for producing a toner for developing an electrostatic image, which contains a nonmetallic salt containing a monovalent cation as an aggregating agent.

  According to the present invention, it is possible to provide a production method capable of obtaining a toner for developing an electrostatic image having a simple process and excellent in low-temperature fixability, heat-resistant storage stability, and charge stability.

The method for producing the toner for developing an electrostatic image of the present invention includes
Step (1): In an aqueous medium, in the presence of an aggregating agent, the resin particles A and the resin particles B are at least 5 ° C. higher than the glass transition temperature Tg (A) of the resin particles A and the glass of the resin particles B Agglomerating at a temperature lower than the transition temperature Tg (B) to obtain agglomerated particles;
Step (2): a step of heating and fusing the aggregated particles obtained in the step (1),
including.
The glass transition temperature Tg (A) of the resin particle A and the glass transition temperature Tg (B) of the resin particle B are in the relationship of the following formula (1).
Tg (A) + 10 ° C <Tg (B) (1)
When the solubility parameters by the Fedors method of the resin constituting the resin particle A and the resin constituting the resin particle B are SP (A) and SP (B), respectively.
The solubility parameter difference ΔSP (| SP (A) −SP (B) |) is 0.3 (cal / cm ³ ) ^1/2 or more and less than 1.5 (cal / cm ³ ) ^1/2 .
Further, in the step (1), the flocculant contains a nonmetallic salt containing a monovalent cation.

The reason why the toner for developing an electrostatic image having excellent low-temperature fixability, heat-resistant storage stability and charging stability can be obtained by the present invention is not clear, but is presumed as follows.
In the present invention, in the method for producing a chemical toner using an aqueous medium, the difference ΔSP (| SP (A) −SP (B) |) of the solubility parameter by the Fedors method of the constituent resin is 0.3 (cal / cm ³ ). ^It contains at least two types of resin particles A and B having a relationship of ^1/2 or more and less than 1.5 (cal / cm ³ ) ^1/2 . Since the SP value difference is less than 1.5 (cal / cm ³ ) ^1/2 , the resin particles A and B can be aggregated and fused together, and the SP value difference is 0.3 ( (cal / cm ³ ) ^1/2 or more, it is considered that the resin particles A and B are not compatible with each other and can maintain the characteristics of the respective resin particles.
Furthermore, in the method for producing a toner for developing an electrostatic charge image of the present invention, there is a difference of 10 ° C. or more between the glass transition temperature Tg (A) of the resin particle A and the glass transition temperature Tg (B) of the resin particle B. is there. When the low Tg resin particles A and the high Tg resin particles B having a SP value difference and a Tg difference of 10 ° C. or more are aggregated, the temperature at the time of aggregation is set to the glass transition temperature Tg (A ) The speed at which aggregated particles are formed using a nonmetallic salt containing a monovalent cation as an aggregating agent while controlling the temperature at a temperature higher than 5 ° C. and lower than the glass transition temperature Tg (B) of the resin particle B. As the resin particles agglomerate, the fusion of only the low Tg resin particles A partially proceeds, so that the cohesion force of the low Tg resin particles A increases, and as a result, the resin particles A partially fused. It is considered that aggregated particles having a core-shell-like structure in which unfused high Tg resin particles B are adhered around the low Tg resin particles A are generated. Thereafter, by fusing, it is considered that toner particles having both low-temperature fixability due to the contribution of the low Tg resin particles A and heat-resistant storage stability due to the contribution of the high Tg resin particles B can be obtained. Further, since it has a core-shell-like structure, it is considered that it is difficult to be destroyed in the machine cartridge even during printing, and the charge amount can be stably maintained.

<< Method for producing toner for developing electrostatic image >>
The method for producing the toner for developing an electrostatic image of the present invention includes
Step (1): In an aqueous medium, in the presence of an aggregating agent, the resin particles A and the resin particles B are at least 5 ° C. higher than the glass transition temperature Tg (A) of the resin particles A and the glass of the resin particles B Agglomerating at a temperature lower than the transition temperature Tg (B) to obtain agglomerated particles;
Step (2): a step of heating and fusing the aggregated particles obtained in the step (1),
including.
Hereafter, each process, component, etc. used for this manufacturing method are demonstrated.

<Step (1)>
In the step (1), in the presence of a flocculant in the aqueous medium, the resin particles A and the resin particles B are at least 5 ° C. higher than the glass transition temperature Tg (A) of the resin particles A and the resin particles B This is a step of agglomerating at a temperature lower than the glass transition temperature Tg (B) to obtain agglomerated particles.
The glass transition temperature Tg (A) of the resin particle A and the glass transition temperature Tg (B) of the resin particle B are in the relationship of the following formula (1).
Tg (A) + 10 ° C <Tg (B) (1)
Further, when the solubility parameters by the Fedors method of the resin constituting the resin particle A and the resin constituting the resin particle B are respectively SP (A) and SP (B),
The solubility parameter difference ΔSP (| SP (A) −SP (B) |) is 0.3 (cal / cm ³ ) ^1/2 or more and less than 1.5 (cal / cm ³ ) ^1/2 .

The glass transition temperature Tg (A) of the resin particle A and the glass transition temperature Tg (B) of the resin particle B are preferably as follows from the viewpoint of improving the low-temperature fixability, heat-resistant storage stability, and charging stability of the toner. It has the relationship of Formula (1-1), and more preferably has the relationship of the following Formula (1-2).
Tg (A) + 15 ° C. <Tg (B) (1-1)
Tg (A) + 20 ° C. <Tg (B) (1-2)
The glass transition temperature of the resin particles is a value obtained by the measurement method “glass transition temperature of the resin particles” described in the examples.
The glass transition temperature Tg (A) of the resin particle A and the glass transition temperature Tg (B) of the resin particle B are preferably in the relationship of the following formula (2) from the viewpoint of improving the low-temperature fixability of the toner. More preferably, it has the relationship of the following formula (2-1).
Tg (B) <Tg (A) + 50 ° C. (2)
Tg (B) <Tg (A) + 40 ° C. (2-1)
Tg (B) <Tg (A) + 30 ° C. (2-2)

The glass transition temperature Tg (A) of the resin particles A is preferably 30 ° C. or higher, more preferably 33 ° C. or higher, and further preferably 35 ° C. or higher, from the viewpoint of improving the heat resistant storage stability and charging stability of the toner. Further, from the viewpoint of improving the low-temperature fixability and charging stability of the toner, it is preferably 50 ° C. or lower, more preferably 46 ° C. or lower, still more preferably 40 ° C. or lower, and further preferably 37 ° C. or lower.
The glass transition temperature Tg (B) of the resin particles B is preferably 45 ° C. or higher, more preferably 50 ° C. or higher, and further preferably 55 ° C. or higher, from the viewpoint of improving the heat resistant storage stability and charging stability of the toner. Further, from the viewpoint of improving the low-temperature fixability and charging stability of the toner, it is preferably 75 ° C. or lower, preferably 70 ° C. or lower, and more preferably 65 ° C. or lower.

When the solubility parameters of the resin constituting the resin particle A and the resin constituting the resin particle B are SP (A) and SP (B), respectively, the solubility parameter difference ΔSP (| SP (A) −SP ( B) |) is 0.3 (cal / cm ³ ) ^1/2 or more and less than 1.5 (cal / cm ³ ) ^1/2 .
ΔSP indicates an absolute value of a difference value between SP (A) and SP (B).
ΔSP is preferably 0.4 (cal / cm ³ ) ^1/2 or more, more preferably 0.5 (cal / cm ³ ), from the viewpoint of improving low-temperature fixability, heat-resistant storage stability, and charging stability of the toner. ) ^1/2 or more, preferably 1.2 (cal / cm ³ ) ^1/2 or less, more preferably 1.0 (cal / cm ³ ) ^1/2 or less, further preferably 0.8 ( cal / cm ³ ) ^1/2 or less.
When the resin particles contain a plurality of types of resins, the above ΔSP condition is satisfied for the solubility parameter of each resin. That is, when the resin particle A is composed of two types of resins A1 and A2, SP (A1) and SP (A2) are respectively the solubility parameter SP (B) of the resin that constitutes the resin particle B. Satisfy the relationship.
When the resin particles contain a plurality of types of resins, the SP value difference between the plurality of types of resins constituting the same resin particles is from the viewpoint of improving the low-temperature fixability, heat-resistant storage stability, and charging stability of the toner. Preferably 0.3 (cal / cm ³ ) ^1/2 or less, more preferably 0.2 (cal / cm ³ ) ^1/2 or less, and still more preferably 0.1 (cal / cm ³ ) ^1/2 or less. More preferably still substantially 0 (cal / cm ³ ) ^1/2 .

  The mixing mass ratio between the resin particles A and the resin particles B is the mass ratio of the resin constituting the resin particles B to the resin constituting the resin particles A (resin particles B) from the viewpoint of improving the heat resistant storage stability and charging stability of the toner. Resin / resin constituting resin particles A) is preferably 0.1 or more, more preferably 0.15 or more, still more preferably 0.2 or more, and preferably 0.9 or less, more Preferably it is 0.7 or less, More preferably, it is 0.6 or less, More preferably, it is 0.5 or less.

[Resin particles A]
In the present invention, the resin constituting the resin particle A preferably contains an amorphous polyester (a), more preferably non-crystalline polyester, from the viewpoint of improving low-temperature fixability, heat-resistant storage stability, and charging stability of the toner. Crystalline polyester (a) and crystalline polyester (b) are contained. As long as the effects of the present invention are not impaired, a resin other than polyester, for example, a resin such as a styrene-acrylic copolymer, an epoxy resin, a polycarbonate, or a polyurethane may be contained.

In the present invention, the crystalline polyester and the amorphous polyester are the ratio between the softening point and the maximum endothermic peak temperature measured by a differential scanning calorimeter (DSC), that is, (softening point (° C.)) / (Maximum endothermic peak temperature). It is distinguished by the crystallinity index defined by (° C). That is, a crystalline polyester having a crystallinity index of 0.6 or more and 1.4 or less is a crystalline polyester, and an amorphous polyester having a crystallinity index of more than 1.4 or less than 0.6. The crystallinity index can be appropriately adjusted according to the production conditions such as the type and ratio of the raw material monomers, the reaction temperature, the reaction time, and the cooling rate. The maximum endothermic peak temperature refers to the temperature of the peak having the maximum peak area among the endothermic peaks observed with a differential scanning calorimeter (DSC). The maximum peak temperature is the melting point if the difference from the softening point is within 20 ° C., and the peak temperature due to the glass transition if the difference from the softening point exceeds 20 ° C.
The crystallinity index of the amorphous polyester is preferably less than 0.6 or more than 1.4 and 4 or less, more preferably 1.5 or more, from the viewpoint of improving low-temperature fixability and heat-resistant storage stability of the toner. It is 4 or less, more preferably 1.5 or more and 3 or less, and still more preferably 1.5 or more and 2 or less.
The crystallinity index of the crystalline polyester is preferably 0.8 or more, more preferably 0.9 or more, and preferably 1.3 or less, more preferably 1 from the viewpoint of improving the low-temperature fixability of the toner. .2 or less.

[Amorphous polyester (a)]
The content of the amorphous polyester (a) in the resin constituting the resin particle A is preferably 50% by mass or more, more preferably in the resin constituting the resin particle A, from the viewpoint of improving the heat resistant storage stability of the toner. Is 70% by mass or more, more preferably 80% by mass or more, still more preferably 85% by mass or more, and from the viewpoint of improving the low-temperature fixability of the toner, it is preferably 100% by mass or less, more preferably 98% by mass. % Or less, more preferably 97% by mass or less, and still more preferably 95% by mass or less.
The resin particles A may contain an amorphous polyester other than the amorphous polyester (a), but the amorphous polyester (a) with respect to the total amount of all the amorphous polyesters contained in the resin particles A Is preferably 80% by mass or more, more preferably 90% by mass or more, still more preferably 95% by mass or more, and still more preferably substantially from the viewpoint of achieving both low-temperature fixability and heat-resistant storage stability of the toner. Is 100 mass%, more preferably 100 mass%.
The amorphous polyester (a) preferably has an acid group at the end of the molecular chain from the viewpoint of improving the dispersion stability of the dispersion of the resin particles A containing the amorphous polyester (a). Examples of the acid group include a carboxy group, a sulfonic acid group, a phosphonic acid group, and a sulfinic acid group. Among these, from the viewpoint of improving the dispersion stability of the dispersion of the resin particles A, a carboxy group is preferable.

The amorphous polyester (a) can be produced by subjecting an alcohol component (a-al) and an acid component (a-ac) to a polycondensation reaction.
The alcohol component (a-al) of the amorphous polyester (a) is obtained by combining an alkylene oxide adduct of bisphenol A in the alcohol component (a-al) from the viewpoint of achieving both low-temperature fixability and heat-resistant storage stability of the toner. What contains 80 mol% or more is preferable.
The alkylene oxide adduct of bisphenol A is preferably an ethylene oxide adduct of bisphenol A (polyoxyethylene-2,2-bis (4-hydroxyphenyl) propane) and a propylene oxide adduct of bisphenol A (polyoxypropylene- 2,2-bis (4-hydroxyphenyl) propane), more preferably an ethylene oxide adduct of bisphenol A.
The content of the alkylene oxide adduct of bisphenol A in the alcohol component (a-al) is preferably 80 mol% or more, more preferably 90 mol% or more, still more preferably 95 mol% or more, and still more preferably substantially. Is 100 mol%, more preferably 100 mol%.

  The average addition mole number of alkylene oxide of the alkylene oxide adduct of bisphenol A is preferably 1 or more and 16 or less, more preferably 1.2 or more and 12 or less, and more preferably 1.2 or more and 12 or less, from the viewpoint of achieving both low-temperature fixability and heat-resistant storage stability of the toner. Preferably they are 1.5 or more and 8 or less, More preferably, they are 1.5 or more and 4 or less.

  The alcohol component (a-al) may contain alcohol other than the alkylene oxide adduct of bisphenol A. Other alcohols that the alcohol component (a-al) may contain include aliphatic diols, aromatic diols, alicyclic diols, trivalent or higher polyhydric alcohols, or alkylene oxides having 2 to 4 carbon atoms thereof ( Average addition mole number 1-16) and adducts.

Specific examples of other alcohols that the alcohol component (a-al) may contain include ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, neopentyl glycol, 1,4-butenediol, 1,5-pentanediol, 1,6-hexanediol, 1,8-octanediol, 1,9- Nonanediol, 1,10-decanediol, aliphatic diols such as 1,12-dodecanediol, aromatic diols such as bisphenol A (2,2-bis (4-hydroxyphenyl) propane), or those having 3 or more carbon atoms 4 or less alkylene oxide (average added mole number 1 to 16) adduct, hydrogenated bisphenol A (2,2 Alicyclic diols such as bis (4-hydroxycyclohexyl) propane) or their alkylene oxides having 2 to 4 carbon atoms (average added mole number of 2 to 12), glycerin, pentaerythritol, trimethylolpropane, sorbitol And trihydric or higher polyhydric alcohols such as these, or alkylene oxides (average added mole number of 1 to 16) of adducts having 2 to 4 carbon atoms.
The other alcohol which an alcohol component (a-al) may contain can be used individually by 1 type or in combination of 2 or more types.

Examples of the carboxylic acid component (a-ac) of the amorphous polyester (a) include dicarboxylic acids, trivalent or higher polyvalent carboxylic acids, anhydrides thereof, and alkyl esters having 1 to 3 carbon atoms. Can be mentioned. Of these, dicarboxylic acids are preferable, and it is more preferable to use a dicarboxylic acid and a trivalent or higher polyvalent carboxylic acid in combination.
Examples of the dicarboxylic acid include aromatic dicarboxylic acids, aliphatic dicarboxylic acids, and alicyclic dicarboxylic acids. Aromatic dicarboxylic acids and aliphatic dicarboxylic acids are preferable, and aromatic dicarboxylic acids are more preferable.
The carboxylic acid component (a-ac) includes not only a free acid but also an anhydride that decomposes during the reaction to produce an acid, and an alkyl ester having 1 to 3 carbon atoms of each carboxylic acid.
Examples of the aromatic dicarboxylic acid include phthalic acid, isophthalic acid, terephthalic acid and the like. From the viewpoint of improving the heat resistant storage stability of the toner, isophthalic acid and terephthalic acid are preferable, and terephthalic acid is more preferable.
The aliphatic dicarboxylic acid preferably has 2 or more and 30 or less carbon atoms, and more preferably 3 or more and 20 or less carbon atoms, from the viewpoint of improving the low-temperature fixability and heat-resistant storage stability of the toner.
Examples of the aliphatic carboxylic acid having 2 to 30 carbon atoms include oxalic acid, malonic acid, maleic acid, fumaric acid, citraconic acid, itaconic acid, glutaconic acid, succinic acid, adipic acid, sebacic acid, 1,12-dodecanedioic acid. Examples thereof include acid, azelaic acid, succinic acid substituted with an alkyl group having 1 to 20 carbon atoms or an alkenyl group having 2 to 20 carbon atoms. Specific examples of the succinic acid substituted with an alkyl group having 1 to 20 carbon atoms or an alkenyl group having 2 to 20 carbon atoms include dodecyl succinic acid, dodecenyl succinic acid, octenyl succinic acid, and the like. Of these, fumaric acid, adipic acid, and dodecenyl succinic acid are preferable.
As the trivalent or higher polyvalent carboxylic acid, trimellitic acid and its acid anhydride are preferable, and trimellitic acid anhydride is more preferable from the viewpoint of improving low-temperature fixability and heat-resistant storage stability of the toner.
Among these, terephthalic acid is preferable, terephthalic acid and adipic acid are more preferably used in combination, and terephthalic acid, adipic acid and trimellitic anhydride are more preferably used in combination.
The alcohol component (a-al) and the carboxylic acid component (a-ac) can be used singly or in combination of two or more.

  The equivalent ratio (COOH group / OH group) of the carboxylic acid component (a-ac) to the alcohol component (a-al) in the amorphous polyester (a) is the dispersion of the resin particles A containing the amorphous polyester (a). From the viewpoint of improving the dispersion stability of the liquid, it is preferably 0.70 or more, more preferably 0.80 or more, and preferably 1.10 or less, more preferably 1.05 or less.

The softening point of the amorphous polyester (a) is preferably 70 ° C. or higher, more preferably 80 ° C. or higher, and still more preferably 88 ° C. or higher, from the viewpoint of improving the heat resistant storage stability of the toner. From the viewpoint of improving the fixability, it is preferably 165 ° C. or lower, more preferably 140 ° C. or lower, still more preferably 120 ° C. or lower, and still more preferably 105 ° C. or lower.
From the same viewpoint, the glass transition temperature of the amorphous polyester (a) is preferably 35 ° C. or higher, more preferably 40 ° C. or higher, still more preferably 42 ° C. or higher, and preferably 80 ° C. or lower, more preferably Is 70 ° C. or lower, more preferably 65 ° C. or lower.
In addition, when using 2 or more types of amorphous polyester (a) in mixture, the glass transition temperature and softening point are described in an Example as a mixture of 2 or more types of amorphous polyester (a), respectively. It is a value obtained by the method.
The acid value of the amorphous polyester (a) is determined from the viewpoint of improving the dispersion stability of the dispersion of the resin particles A containing the amorphous polyester (a), the viewpoint of improving the low-temperature fixability of the toner, and the charging stability. From the viewpoint of improving, it is preferably 35 mgKOH / g or less, more preferably 30 mgKOH / g or less, still more preferably 25 mgKOH / g or less, preferably 5 mgKOH / g or more, more preferably 10 mgKOH / g or more, still more preferably It is 15 mgKOH / g or more.
Amorphous polyester (a) can be used individually by 1 type or in combination of 2 or more types.

The amorphous polyester (a) is prepared by, for example, adding the alcohol component (a-al) and the carboxylic acid component (a-ac) in an inert gas atmosphere, if necessary, using an esterification catalyst. It can be produced by polycondensation at a temperature of about ~ 250 ° C.
As the esterification catalyst, an esterification catalyst such as a tin compound such as dibutyltin oxide or di (2-ethylhexanoic acid) tin or a titanium compound such as titanium diisopropylate bistriethanolamate can be used.
Although there is no restriction | limiting in the usage-amount of an esterification catalyst, Preferably it is 0.01 mass part or more with respect to 100 mass parts of total amounts of a carboxylic acid component (a-ac) and an alcohol component (a-al), More preferably It is 0.1 mass part or more, Preferably it is 1 mass part or less, More preferably, it is 0.8 mass part or less.
Moreover, a polymerization inhibitor can be used as needed. Examples of the polymerization inhibitor include tert-butylcatechol. The amount of the polymerization inhibitor used is preferably 0.001 parts by mass or more, more preferably 0.005 parts by mass with respect to 100 parts by mass of the total amount of the carboxylic acid component (a-ac) and the alcohol component (a-al). Part or more, preferably 0.5 part by mass or less, more preferably 0.1 part by mass or less.

[Crystalline polyester (b)]
The content of the crystalline polyester (b) when the resin particles A contain crystalline polyester is preferably 1% by mass or more in the resin constituting the resin particles A from the viewpoint of improving the low-temperature fixability of the toner. Preferably, it is 3% by mass or more, more preferably 5% by mass or more, and from the viewpoint of improving the heat resistant storage stability of the toner, it is preferably 50% by mass or less, more preferably 40% by mass or less, and still more preferably 35% by mass. % Or less, more preferably 30% by mass or less.
The mass ratio ((a) / (b)) between the amorphous polyester (a) and the crystalline polyester (b) in the toner is preferably 99 from the viewpoint of achieving both low-temperature fixability and heat-resistant storage stability of the toner. / 1-50 / 50, more preferably 97 / 3-60 / 40, still more preferably 95 / 5-65 / 35, still more preferably 95 / 5-70 / 30, still more preferably 93 / 7-80 / 20.
The crystalline polyester (b) preferably has an acid group at the end of the molecular chain from the viewpoint of improving the dispersion stability of the dispersion of the resin particles A containing the crystalline polyester (b).
Examples of the acid group include a carboxy group, a sulfonic acid group, a phosphonic acid group, and a sulfinic acid group. Among these, from the viewpoint of improving the dispersion stability of the dispersion of the resin particles A, a carboxy group is preferable.

The melting point of the crystalline polyester (b) is preferably 30 ° C. or higher, more preferably 35 ° C. or higher, still more preferably 40 ° C. or higher, from the viewpoint of improving the heat-resistant storage stability of the toner. From the viewpoint of improving the temperature, it is preferably 140 ° C. or lower, more preferably 120 ° C. or lower, still more preferably 100 ° C. or lower, and still more preferably 80 ° C. or lower.
From the same viewpoint, the softening point of the crystalline polyester (b) is preferably 35 ° C. or higher, more preferably 40 ° C. or higher, further preferably 45 ° C. or higher, and preferably 150 ° C. or lower, more preferably 130 ° C. ° C or lower, more preferably 110 ° C or lower, still more preferably 90 ° C or lower.
The acid value of the crystalline polyester (b) is preferably 35 mgKOH / g or less, more preferably 32 mgKOH / g or less, from the viewpoint of improving the dispersion stability of the dispersion of the resin particles A containing the crystalline polyester (b). More preferably, it is 30 mgKOH / g or less, Preferably it is 5 mgKOH / g or more, More preferably, it is 10 mgKOH / g or more, More preferably, it is 15 mgKOH / g or more. The desired softening point and acid value can be obtained by adjusting the charging ratio of alcohol and carboxylic acid, polycondensation temperature, reaction time, and the like.
Crystalline polyester (b) can be used individually by 1 type or in combination of 2 or more types.

  In this invention, melting | fusing point of crystalline polyester (b) is calculated | required by the method as described in an Example. When two or more crystalline polyesters (b) are used in combination, the melting point is the melting point of the crystalline polyester (b) having the largest mass ratio in the crystalline polyester (b) contained in the obtained toner. It is set as melting | fusing point of crystalline polyester (b). In addition, when all are the same mass ratio, let the value of the lowest melting | fusing point be melting | fusing point of crystalline polyester (b) in this invention. Moreover, the softening point of crystalline polyester (b) is calculated | required by the method as described in an Example as a mixture of crystalline polyester (b).

  The crystalline polyester (b) can be produced by subjecting an alcohol component (b-al) and a carboxylic acid component (b-ac) to a polycondensation reaction.

As the alcohol component (b-al), an aliphatic diol having 2 or more and 12 or less main chain carbon atoms, an aromatic diol, an alicyclic diol, a trivalent or more polyhydric alcohol, or those having 2 to 4 carbon atoms. Examples include adducts of alkylene oxide (average added mole number of 1 to 16). Of these, aliphatic diols having 2 to 12 main chain carbon atoms are preferred from the viewpoint of promoting the crystallinity of the polyester and improving the low-temperature fixability of the toner.
Among the aliphatic diols having 2 to 12 carbon atoms in the main chain, α, ω-linear alkanediol is preferable from the viewpoint of promoting the crystallinity of the polyester and improving the low-temperature fixability of the toner.
The α, ω-linear alkanediol having 2 to 12 main chain carbon atoms is more preferably one having 2 to 6 main chain carbon atoms from the viewpoint of compatibility with other resin components constituting the toner. More preferred are those having 2 to 4 carbon atoms in the main chain.
The content of the α, ω-linear alkanediol having 2 to 4 carbon atoms in the alcohol component (b-al) is preferably 80 mol% or more from the viewpoint of achieving both low-temperature fixability and heat-resistant storage stability of the toner. More preferably, it is 90 mol% or more, more preferably 95 mol% or more, still more preferably substantially 100 mol%, still more preferably 100 mol%.
Specific examples of the α, ω-linear alkanediol having 2 to 4 carbon atoms include ethylene glycol, 1,3-propanediol, and 1,4-butanediol. Ethylene glycol and 1,3-propane Diol is preferred, and 1,3-propanediol is more preferred.
The alcohol component (b-al) may contain an alcohol other than an α, ω-linear alkanediol having 2 to 4 carbon atoms. For example, aliphatic diol other than α, ω-linear alkanediol having 2 to 4 carbon atoms, aromatic diol, alicyclic diol, trivalent or higher polyhydric alcohol, or those having 2 to 4 carbon atoms Examples include adducts of alkylene oxide (average added mole number of 1 to 16). In the present invention, “an alkylene oxide adduct having 2 to 4 carbon atoms of a diol” means “a compound obtained by adding an alkylene oxide having 2 to 4 carbon atoms to a diol”.

Specific examples of other alcohols include 1,2-propanediol, 1,2-butanediol, 1,3-butanediol, 2,3-butanediol, 1,4-butenediol, 1,5-pentanediol. 1,6-hexanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,12-dodecanediol and other aliphatic diols, polyoxypropylene-2,2-bis Alkylene oxide having 2 to 3 carbon atoms (average number of added moles of 1 to 16) of bisphenol A such as (4-hydroxyphenyl) propane and polyoxyethylene-2,2-bis (4-hydroxyphenyl) propane , Alicyclic diols such as hydrogenated bisphenol A (2,2-bis (4-hydroxycyclohexyl) propane) Those alkylene oxides having 2 to 4 carbon atoms (average added mole number 2 to 12) adducts, trivalent or higher polyhydric alcohols such as glycerin, pentaerythritol, trimethylolpropane, sorbitol, or those having 2 or more carbon atoms 4 or less alkylene oxide (average addition mole number 1-16) addition product etc. are mentioned.
Another alcohol can be used individually by 1 type or in combination of 2 or more types.

Examples of the carboxylic acid component (b-ac) include dicarboxylic acids, trivalent or higher polyvalent carboxylic acids, acid anhydrides thereof, alkyl esters having 1 to 3 carbon atoms, and the like. preferable.
Specific examples of the dicarboxylic acid include aliphatic dicarboxylic acid, alicyclic dicarboxylic acid, and aromatic dicarboxylic acid. Of these, aliphatic dicarboxylic acids are preferred from the viewpoint of promoting the crystallinity of the polyester and improving the low-temperature fixability of the toner.
Examples of the aliphatic dicarboxylic acid include aliphatic dicarboxylic acids having 4 to 12 carbon atoms, succinic acid substituted with an alkyl group having 1 to 20 carbon atoms, or an alkenyl group having 2 to 20 carbon atoms. Specific examples of the succinic acid substituted with an alkyl group having 1 to 20 carbon atoms or an alkenyl group having 2 to 20 carbon atoms include dodecyl succinic acid, dodecenyl succinic acid, octenyl succinic acid, and the like. Among these, aliphatic dicarboxylic acids having 4 to 12 carbon atoms are preferable from the viewpoint of promoting the crystallinity of the polyester and improving the low-temperature fixability of the toner.
Among aliphatic dicarboxylic acids having 4 to 12 carbon atoms, those having 4 to 8 main chain carbon atoms are more preferable from the viewpoint of compatibility with other resin components constituting the toner. More preferably 6 or less.
The content of the aliphatic saturated dicarboxylic acid having 4 to 6 carbon atoms in the carboxylic acid component (b-ac) is preferably 80 mol% or more, from the viewpoint of achieving both low-temperature fixability and heat-resistant storage stability of the toner. Preferably it is 90 mol% or more, More preferably, it is 95 mol% or more, More preferably, it is substantially 100 mol%, More preferably, it is 100 mol%.
Specific examples of the aliphatic dicarboxylic acid having 4 to 6 carbon atoms include succinic acid, glutaric acid, adipic acid and the like. From the viewpoint of promoting the crystallinity of the polyester and improving the low-temperature fixability of the toner, succinic acid. Or adipic acid is preferable and succinic acid is more preferable.

Aliphatic dicarboxylic acids having 4 to 6 carbon atoms can be used alone or in combination of two or more.
The carboxylic acid component (b-ac) may contain an acid other than the aliphatic dicarboxylic acid having 4 to 6 carbon atoms. Examples of other acids include dicarboxylic acids other than aliphatic dicarboxylic acids having 4 to 6 carbon atoms, trivalent or more polyvalent carboxylic acids, anhydrides thereof, and alkyl esters having 1 to 3 carbon atoms. Can be mentioned.
In the present invention, “an alkyl ester having 1 to 3 carbon atoms of an acid” means “an ester in which an alkyl group having 1 to 3 carbon atoms is bonded to an acid group”.
Specific examples of the dicarboxylic acid include aliphatic dicarboxylic acid, alicyclic dicarboxylic acid, and aromatic dicarboxylic acid.
Examples of the aliphatic dicarboxylic acid include sebacic acid, fumaric acid, maleic acid, azelaic acid, succinic acid substituted with an alkyl group having 1 to 20 carbon atoms, or an alkenyl group having 2 to 20 carbon atoms. Specific examples of the succinic acid substituted with an alkyl group having 1 to 20 carbon atoms or an alkenyl group having 2 to 20 carbon atoms include dodecyl succinic acid, dodecenyl succinic acid, octenyl succinic acid, and the like.

Specific examples of the aromatic dicarboxylic acid include phthalic acid, isophthalic acid, terephthalic acid and the like.
Specific examples of the alicyclic dicarboxylic acid include cyclohexane dicarboxylic acid.
Specific examples of the trivalent or higher polyvalent carboxylic acid include trimellitic acid, 2,5,7-naphthalene tricarboxylic acid, pyromellitic acid and the like.
Another acid can be used individually by 1 type or in combination of 2 or more types.
The crystalline polyester (b) is preferably a polyester obtained by polycondensation of an α, ω-linear alkanediol having 2 to 4 carbon atoms and an aliphatic dicarboxylic acid having 4 to 6 carbon atoms, more preferably ethylene glycol. Polyester obtained by polycondensation of one or more diols selected from the group consisting of 1,3-propanediol and 1,4-butanediol with one or more dicarboxylic acids selected from succinic acid and adipic acid, more preferably Polyester obtained by polycondensation of 1,3-propanediol and succinic acid.

  The equivalent ratio (COOH group / OH group) of the carboxylic acid component (b-ac) to the alcohol component (b-al) in the crystalline polyester (b) is the dispersion ratio of the resin particles A containing the crystalline polyester (b). From the viewpoint of improving the dispersion stability, it is preferably 0.8 or more, more preferably 0.9 or more, and preferably 1.2 or less, more preferably 1.1 or less.

  The crystalline polyester (b) is produced by a polycondensation reaction between the carboxylic acid component (b-ac) and the alcohol component (b-al) in the same manner as the amorphous polyester (a). be able to. For example, the alcohol component (b-al) and the polyvalent carboxylic acid component (b-ac) in an inert gas atmosphere, if necessary, using an esterification catalyst and a polymerization inhibitor at 130 to 220 ° C. It can be produced by polycondensation at a moderate temperature.

[Resin particles B]
In the present invention, the resin constituting the resin particle B preferably contains an amorphous polyester (c) from the viewpoint of improving low-temperature fixability, heat-resistant storage stability, and charge stability of the toner. The resin particle B may contain crystalline polyester. As long as the effects of the present invention are not impaired, a resin other than polyester, for example, a resin such as a styrene-acrylic copolymer, an epoxy resin, a polycarbonate, or a polyurethane may be contained.

[Amorphous polyester (c)]
The resin particles B preferably contain an amorphous polyester (c) from the viewpoint of achieving both low-temperature fixability and heat-resistant storage stability of the toner and improving the charging stability of the toner.
The content of the amorphous polyester (c) in the resin constituting the resin particle B is preferably 80% by mass or more, more preferably from the viewpoint of improving low-temperature fixability, heat-resistant storage stability, and charge stability of the toner. Is 90% by mass or more, more preferably 95% by mass or more, still more preferably 98% by mass or more, still more preferably substantially 100% by mass, and still more preferably 100% by mass.
The amorphous polyester (c) preferably has an acid group at the end of the molecular chain from the viewpoint of improving the dispersion stability of the dispersion of the resin particles B containing the amorphous polyester (c).
Examples of the acid group include a carboxy group, a sulfonic acid group, a phosphonic acid group, and a sulfinic acid group. Among these, from the viewpoint of improving the dispersion stability of the dispersion of the resin particles B, a carboxy group is preferable.

  The amorphous polyester (c) is produced by subjecting the carboxylic acid component (c-ac) and the alcohol component (c-al) to a polycondensation reaction in the same manner as the amorphous polyester (a). can do.

The alcohol component (c-al) of the amorphous polyester (c) preferably contains an alkylene oxide adduct of bisphenol A from the viewpoint of improving the low-temperature fixability, heat-resistant storage stability, and charge stability of the toner.
The alkylene oxide adduct of bisphenol A is preferably an ethylene oxide adduct of bisphenol A (polyoxyethylene-2,2-bis (4-hydroxyphenyl) propane) and a propylene oxide adduct of bisphenol A (polyoxypropylene- 2,2-bis (4-hydroxyphenyl) propane), more preferably a propylene oxide adduct of bisphenol A.
The content of the alkylene oxide adduct of bisphenol A in the alcohol component (c-al) is preferably 60 mol% or more, preferably 65 mol% or more, more preferably 75, from the viewpoint of improving the low-temperature fixability of the toner. From the viewpoint of improving the heat-resistant storage stability and charge stability of the toner, it is preferably 100 mol% or less, more preferably from mol% or more, more preferably 85 mol% or more, still more preferably 95 mol% or more. It is 95 mol% or less, More preferably, it is 85 mol% or less, More preferably, it is 75 mol% or less.
The average number of moles of alkylene oxide added to the alkylene oxide adduct of bisphenol A is preferably 1.0 or more and 16 or less, more preferably 1 from the viewpoint of improving low-temperature fixability, heat-resistant storage stability, and charge stability of the toner. 2 or more and 12 or less, more preferably 1.5 or more and 8 or less, and still more preferably 1.5 or more and 4 or less.

  The alcohol component (c-al) may contain alcohol other than the alkylene oxide adduct of bisphenol A. Other alcohols that can be contained in the alcohol component (c-al) include aliphatic diols, aromatic diols, alicyclic diols, trivalent or higher polyhydric alcohols, or alkylene oxides having 2 to 4 carbon atoms thereof ( Average addition mole number 1-16) and adducts.

Specific examples of other alcohols that the alcohol component (c-al) may contain include ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, neopentyl glycol, 1,4-butenediol, 1,5-pentanediol, 1,6-hexanediol, 1,8-octanediol, 1,9- Nonanediol, 1,10-decanediol, aliphatic diols such as 1,12-dodecanediol, aromatic diols such as bisphenol A (2,2-bis (4-hydroxyphenyl) propane), or their ethylene oxide adducts (Average addition mole number 1-16), cyclohexanediol, cyclohexanedimethanol, water Alicyclic diols such as added bisphenol A (2,2-bis (4-hydroxycyclohexyl) propane) or their alkylene oxides having 2 to 4 carbon atoms (average number of added moles of 2 to 12), glycerin, Examples thereof include trihydric or higher polyhydric alcohols such as pentaerythritol, trimethylolpropane, and sorbitol, or adducts thereof having 2 to 4 carbon atoms of alkylene oxide (average added mole number of 1 to 16).
Among these, alicyclic diols such as cyclohexanediol, cyclohexanedimethanol, and hydrogenated bisphenol A are preferable, and hydrogenated bisphenol A is more preferable.
The other alcohol which an alcohol component (c-al) may contain can be used individually by 1 type or in combination of 2 or more types.

Examples of the carboxylic acid component (c-ac) of the amorphous polyester (c) include dicarboxylic acids, trivalent or higher polyvalent carboxylic acids, anhydrides thereof, and alkyl esters having 1 to 3 carbon atoms. Among them, dicarboxylic acid is preferable.
Examples of the dicarboxylic acid include aromatic dicarboxylic acids, aliphatic dicarboxylic acids, and alicyclic dicarboxylic acids. Aromatic dicarboxylic acids and aliphatic dicarboxylic acids are preferable, and aromatic dicarboxylic acids are more preferable.
The carboxylic acid component (c-ac) includes not only a free acid but also an anhydride that decomposes to generate an acid during the reaction, and an alkyl ester having 1 to 3 carbon atoms of each carboxylic acid.
Examples of the aromatic dicarboxylic acid include phthalic acid, isophthalic acid, terephthalic acid and the like. From the viewpoint of improving the heat resistant storage stability of the toner, isophthalic acid and terephthalic acid are preferable, and terephthalic acid is more preferable.
The aliphatic dicarboxylic acid preferably has 2 or more and 30 or less carbon atoms, and more preferably 3 or more and 20 or less carbon atoms, from the viewpoint of improving the low-temperature fixability and heat-resistant storage stability of the toner.
Examples of the aliphatic dicarboxylic acid having 2 to 30 carbon atoms include oxalic acid, malonic acid, maleic acid, fumaric acid, citraconic acid, itaconic acid, glutaconic acid, succinic acid, adipic acid, sebacic acid, 1,12-dodecanedioic acid. Examples thereof include acid, azelaic acid, succinic acid substituted with an alkyl group having 1 to 20 carbon atoms or an alkenyl group having 2 to 20 carbon atoms. Specific examples of the succinic acid substituted with an alkyl group having 1 to 20 carbon atoms or an alkenyl group having 2 to 20 carbon atoms include dodecyl succinic acid, dodecenyl succinic acid, octenyl succinic acid, and the like.
Among these, terephthalic acid is preferable, and it is more preferable to use terephthalic acid in combination with at least one selected from the group consisting of fumaric acid, dodecenyl succinic acid and anhydrides thereof.
As the trivalent or higher polyvalent carboxylic acid, trimellitic acid and its acid anhydride are preferable, and trimellitic acid anhydride is more preferable from the viewpoint of improving the heat-resistant storage stability and charging stability of the toner.
The alcohol component (c-al) and the polyvalent carboxylic acid component (c-ac) can be used singly or in combination of two or more.

  The equivalent ratio (COOH group / OH group) of the polycarboxylic acid component (c-ac) to the alcohol component (c-al) in the amorphous polyester (c) is the resin particle B containing the amorphous polyester (c). From the viewpoint of improving the dispersion stability of the above dispersion, it is preferably 0.70 or more, more preferably 0.80 or more, and preferably 1.10 or less, more preferably 1.05 or less.

The softening point of the amorphous polyester (c) is preferably 70 ° C. or higher, more preferably 90 ° C. or higher, further preferably 100 ° C. or higher, from the viewpoint of improving the heat resistant storage stability and charging stability of the toner. From the viewpoint of improving the low-temperature fixability of the toner, it is preferably 165 ° C. or lower, more preferably 140 ° C. or lower, and still more preferably 120 ° C. or lower.
From the same viewpoint, the glass transition temperature of the amorphous polyester (c) is preferably 50 ° C. or higher, more preferably 55 ° C. or higher, still more preferably 60 ° C. or higher, and preferably 80 ° C. or lower, more preferably. Is 75 ° C. or lower, more preferably 70 ° C. or lower.
In addition, when using 2 or more types of amorphous polyester (c) in mixture, the glass transition temperature and softening point are described in an Example as a mixture of 2 or more types of amorphous polyester (c), respectively. It is a value obtained by the method.
The acid value of the amorphous polyester (c) is preferably 35 mg KOH from the viewpoint of improving the dispersion stability of the dispersion of the resin particles B containing the amorphous polyester (c) and improving the heat resistant storage stability of the toner. / G or less, more preferably 30 mgKOH / g or less, still more preferably 27 mgKOH / g or less, preferably 5 mgKOH / g or more, more preferably 10 mgKOH / g or more, still more preferably 15 mgKOH / g or more.
Amorphous polyester (c) can be used individually by 1 type or in combination of 2 or more types.

The amorphous polyester (c) is produced by subjecting the carboxylic acid component (c-ac) and the alcohol component (c-al) to a polycondensation reaction in the same manner as the amorphous polyester (a). can do. For example, the alcohol component (b-al) and the polyvalent carboxylic acid component (b-ac) are 180 to 250 ° C. using an esterification catalyst and a polymerization inhibitor as necessary in an inert gas atmosphere. It can be produced by polycondensation at a moderate temperature.
In the present invention, the polyester includes not only an unmodified polyester as long as it has an acid group, but also a polyester modified to such an extent that the properties are not substantially impaired. Examples of the modified polyester include grafting or blocking with phenol, urethane, epoxy or the like by the method described in JP-A-11-133668, JP-A-10-239903, JP-A-8-20636, and the like. And a composite resin having two or more kinds of resin units including the polyester and the polyester unit.

(Manufacture of resin particles)
Resin particles are prepared by dispersing an optional component such as a resin containing amorphous polyester (hereinafter also referred to as “binder resin”), a surfactant, and a colorant, if necessary, in an aqueous medium. It is preferable to produce by a method obtained as a dispersion.

As the aqueous medium, those containing water as a main component are preferable. From the viewpoint of improving the dispersion stability of the dispersion of resin particles and from the viewpoint of environmental properties, the content of water in the aqueous medium is preferably 80% by mass. Above, more preferably 90% by mass or more, still more preferably 95% by mass or more, still more preferably substantially 100% by mass, and still more preferably 100% by mass. As water, deionized water or distilled water is preferably used.
Non-water components that can form an aqueous medium together with water include alkyl alcohols having 1 to 5 carbon atoms; dialkyl ketones having 3 to 5 carbon atoms such as acetone and methyl ethyl ketone; dissolved in water such as cyclic ethers such as tetrahydrofuran An organic solvent is used. Among these, from the viewpoint of preventing the organic solvent from being mixed into the toner, an alkyl alcohol having 1 to 5 carbon atoms that does not dissolve the polyester is preferable, and methanol, ethanol, isopropanol, and butanol are more preferable.

  Examples of a method for obtaining a dispersion of resin particles include a method in which a resin or the like is added to an aqueous medium and subjected to a dispersion treatment with a disperser or the like, and a method in which an aqueous medium is gradually added to a resin or the like to perform phase inversion emulsification. From the viewpoint of improving emulsifiability and obtaining resin particles having a small particle diameter, and improving the low-temperature fixability of the toner, a method by phase inversion emulsification is preferred. Hereinafter, a method by phase inversion emulsification will be described.

First, it is preferable to melt and mix a binder resin and, if necessary, optional components such as a surfactant and a colorant to obtain a resin mixture.
A mixture in which amorphous polyester and any other resin are mixed in advance may be used. However, a resin mixture may be obtained by simultaneously adding other components and melting and mixing them.
As a method for obtaining a resin mixture, polyester and any other resin, optional components such as a surfactant and a colorant as necessary, and a basic aqueous solution are placed in a container, and the resin is stirred while stirring with a stirrer. A method of melting and mixing is preferred.

From the viewpoint of improving the dispersion stability of the resin dispersion, it is preferable to add a surfactant to the resin particle dispersion in the present invention.
Examples of the surfactant include nonionic surfactants, anionic surfactants, and cationic surfactants. From the viewpoint of improving the dispersion stability of the resin particle dispersion, the nonionic surfactant is used. It is more preferable to use a nonionic surfactant and an anionic surfactant or a cationic surfactant in combination, and it is more preferable to use a nonionic surfactant and an anionic surfactant in combination. .
When a nonionic surfactant and an anionic surfactant are used in combination, the mass ratio of the nonionic surfactant to the anionic surfactant (nonionic surfactant / anionic surfactant) is: From the viewpoint of improving the dispersion stability of the resin particle dispersion, it is preferably 0.3 or more, more preferably 0.5 or more, and preferably 10 or less, more preferably 5 or less.

The nonionic surfactant includes at least one selected from the group consisting of polyoxyethylene alkyl aryl ethers, polyoxyethylene alkyl or alkenyl ethers, polyoxyethylene fatty acid esters, and oxyethylene / oxypropylene block copolymers. preferable.
Specific examples of the polyoxyethylene alkylaryl ethers include polyoxyethylene nonylphenyl ether. Specific examples of polyoxyethylene alkyl or alkenyl ethers include polyoxyethylene oleyl ether and polyoxyethylene lauryl ether. Specific examples of the polyoxyethylene fatty acid esters include polyoxyethylene monolaurate, polyoxyethylene monostearate, polyoxyethylene monooleate and the like. As the nonionic surfactant, polyoxyethylene alkyl or alkenyl ethers are preferable, and polyoxyethylene lauryl ether is more preferable from the viewpoint of improving the dispersion stability of the dispersion of resin particles.

Examples of the anionic surfactant include alkylbenzene sulfonates, alkyl sulfates, alkyl ether sulfates, and the like. From the viewpoint of improving the dispersion stability of the dispersion of resin particles, alkylbenzene sulfonates, alkyl ether sulfates. Is preferred.
As the alkyl benzene sulfonate, an alkali metal salt of dodecyl benzene sulfonic acid is preferable, and sodium dodecyl benzene sulfonate is more preferable. As the alkyl sulfate, an alkali metal salt of dodecyl sulfate is preferable, and sodium dodecyl sulfate is more preferable. As the alkyl ether sulfate, an alkali metal salt of dodecyl ether sulfate is preferable, and sodium dodecyl ether sulfate is more preferable. Among these, sodium dodecylbenzenesulfonate is more preferable from the viewpoint of improving the dispersion stability of the dispersion of resin particles.

  The cationic surfactant is preferably a quaternary ammonium salt, and examples thereof include alkylbenzene trimethyl ammonium chloride, alkyl trimethyl ammonium chloride, dialkyl dimethyl ammonium chloride and the like.

The addition amount of the surfactant is preferably 20 parts by mass or less, more preferably 10 parts by mass or less, and still more preferably from 100 parts by mass of the resin component constituting the resin particles, from the viewpoint of improving the heat resistant storage stability of the toner. Is 5 parts by mass or less, and from the viewpoint of improving the dispersion stability of the dispersion of resin particles, preferably 0.5 parts by mass or more, more preferably 1 part by mass or more, and even more preferably 1.5 parts by mass. That's it.
The “resin component constituting the resin particles” includes other resins such as amorphous polyester and crystalline polyester which can be optionally included.

Examples of the basic compound used in the basic aqueous solution include inorganic basic compounds and organic basic compounds.
Examples of the inorganic base compound include alkali metal hydroxides such as potassium, sodium, and lithium, carbonates, bicarbonates, etc., and specific examples thereof include sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, and carbonate. Examples thereof include sodium hydrogen and potassium hydrogen carbonate. Ammonia may be used. Examples of the organic base include alkanolamines such as diethylethanolamine. From the viewpoint of improving the dispersion stability of the dispersion of resin particles and the viewpoint of improving the charging stability of the toner, sodium hydroxide, potassium hydroxide, sodium carbonate, and potassium carbonate are preferable, and potassium hydroxide is more preferable.
The concentration of the basic compound in the basic aqueous solution is preferably 1% by mass or more, more preferably 3% by mass or more, from the viewpoint of improving the dispersion stability and productivity of the resin particle dispersion. Is 30% by mass or less, more preferably 20% by mass or less, and still more preferably 10% by mass or less.

  The temperature at which the resin is melted and mixed is preferably equal to or higher than the glass transition temperature of the amorphous polyester from the viewpoint of obtaining homogeneous resin particles. If the glass transition temperature of the amorphous polyester exceeds the boiling point of water, melt and mix the amorphous polyester and any other resin such as crystalline polyester in advance without using an aqueous medium. It is preferable to add an aqueous solution component such as an activator or a basic aqueous solution and mix to obtain a resin mixture.

Next, an aqueous medium is added to the resin mixture and phase inversion is performed to obtain a dispersion containing resin particles.
The temperature at which the aqueous medium is added is equal to or higher than the glass transition temperature of the resin constituting the resin particles from the viewpoint of improving the dispersion stability of the dispersion of the resin particles, and improving the low-temperature fixability and heat-resistant storage stability of the toner. The boiling point of the aqueous medium used in the step (1) is preferable. Specifically, it is preferably 70 ° C. or higher, more preferably 80 ° C. or higher, still more preferably 85 ° C. or higher, and preferably less than 100 ° C., more preferably 98 ° C. or lower.

From the viewpoint of improving the dispersion stability of the dispersion of the resin particles, and improving the low-temperature fixability and heat-resistant storage stability of the toner, the addition rate of the aqueous medium is a resin constituting the resin particles until the phase inversion is completed. Preferably it is 0.1 mass part / min or more with respect to 100 mass parts of components, More preferably, it is 0.5 mass part / min or more, Preferably it is 50 mass parts / min or less, More preferably, it is 30 mass parts / Min or less, more preferably 10 parts by mass / min or less, and even more preferably 5 parts by mass / min or less. There is no restriction | limiting in the addition rate of the aqueous medium after the resin phase is obtained after phase inversion.
The amount of the aqueous medium used is preferably 50 parts by mass or more with respect to 100 parts by mass of the resin component constituting the resin particles from the viewpoint of improving the productivity of the toner and obtaining uniform aggregated particles in the subsequent step. More preferably, it is 100 parts by mass or more, more preferably 150 parts by mass or more, preferably 900 parts by mass or less, more preferably 500 parts by mass or less, and still more preferably 300 parts by mass or less.
The solid content concentration of the obtained resin particle dispersion is preferably 10% by mass or more, more preferably 15% by mass from the viewpoint of improving the productivity of the toner and the dispersion stability of the resin particle dispersion. % Or more, more preferably 20% by mass or more, preferably 50% by mass or less, more preferably 40% by mass or less, and still more preferably 35% by mass or less. In addition, solid content is the total amount of non-volatile components, such as resin, a coloring agent, and surfactant.

The volume median particle size (D ₅₀ ) of the resin particles in the resin particle dispersion is preferably 0.05 μm or more, more preferably 0.08 μm or more from the viewpoint of obtaining a toner capable of obtaining a high-quality image. Further, it is preferably 0.50 μm or less, more preferably 0.30 μm or less, and still more preferably 0.20 μm or less. Here, the volume-median particle size is a particle size at which the cumulative volume frequency calculated by the volume fraction is 50% when calculated from the smaller particle size, and is obtained by the method described in the examples.
Further, the coefficient of variation (CV value) (%) of the particle size distribution of the resin particles is preferably 50% or less, more preferably 45% or less, and still more preferably 40, from the viewpoint of obtaining a toner capable of obtaining a high-quality image. From the viewpoint of improving the productivity of the resin particle dispersion, it is preferably 5% or more, more preferably 10% or more, and even more preferably 15% or more. The CV value is a value represented by the following formula. Here, the volume average particle diameter is obtained by multiplying the particle diameter measured on a volume basis by the ratio of particles having the particle diameter value. It is a particle size obtained by dividing the obtained value by the number of particles, and is determined by the method described in the examples.
CV value (%) = [standard deviation of particle size distribution (nm) / volume average particle size (nm)] × 100

  The toner obtained by the production method of the present invention preferably contains a colorant and a release agent. Moreover, you may contain additives, such as a charge control agent, reinforcing fillers, such as a fibrous substance, antioxidant, anti-aging agent, as needed.

(Coloring agent)
The toner obtained by the production method of the present invention may have a colorant in either resin particle A or resin particle B, and is preferably included in resin particle A from the viewpoint of improving the heat resistant storage stability of the toner. .
The content of the colorant is preferably 1 part by mass or more, more preferably 5 parts by mass or more with respect to 100 parts by mass of the resin constituting the resin particles A from the viewpoint of improving the image density of the printed matter. From the viewpoint of improving the low-temperature fixability, it is preferably 20 parts by mass or less, more preferably 10 parts by mass or less.

Examples of the colorant used in the present invention include pigments and dyes, and pigments are preferable from the viewpoint of improving the image density of printed matter.
Examples of the pigment include a cyan pigment, a yellow pigment, a magenta pigment, and a black pigment.
The cyan pigment is preferably a phthalocyanine pigment, and more preferably copper phthalocyanine. The yellow pigment is preferably a monoazo pigment, isoindoline pigment, or benzimidazolone pigment, and the magenta pigment is preferably a soluble azo pigment such as a quinacridone pigment or a BONA lake pigment, or an insoluble azo pigment such as a naphthol AS pigment. The black pigment is preferably carbon black.
Examples of the dye include acridine dyes, azo dyes, benzoquinone dyes, azine dyes, anthraquinone dyes, indigo dyes, phthalocyanine dyes, aniline black dyes, and the like.
A coloring agent can be used individually by 1 type or in combination of 2 or more types.

(Release agent particles)
The toner obtained by the production method of the present invention preferably contains a release agent from the viewpoint of improving the releasability and low-temperature fixability of the toner. Examples of the method for adding the release agent include a method of mixing with the resin in the production of the resin particles, a method of dispersing the release agent particles in an aqueous medium to obtain a dispersion, and aggregating the resin particles with the resin particles. From the viewpoint of improving the dispersion stability of the resin particle dispersion, from the viewpoint of facilitating aggregation with the resin particles, from the viewpoint of improving the low-temperature fixability, heat-resistant storage stability and charging stability of the toner, in step (1), A method of aggregating the release agent particles together with the resin particles A and B to obtain aggregated particles is preferable.

(Release agent)
Release agents include low molecular weight polyolefins such as polyethylene, polypropylene and polybutene; silicone waxes; fatty acid amides such as oleic acid amides and stearic acid amides; plant waxes; animal waxes such as beeswax; mineral or petroleum waxes; esters Synthetic waxes such as waxes may be mentioned.
Examples of plant-based waxes include carnauba wax, rice wax, and candelilla wax. Carnauba wax is preferred from the viewpoint of improving toner releasability and low-temperature fixability.
Examples of the mineral or petroleum-based wax include montan wax, paraffin wax, and Fischer-Tropsch wax. Paraffin wax is preferable from the viewpoint of improving toner releasability and low-temperature fixability.
These release agents can be used singly or in combination of two or more, and it is preferable to use two or more in combination. From the viewpoint of improving the releasability and low-temperature fixability of the toner, it is preferable to use a plant-based wax and a mineral-based or petroleum-based wax in combination, and it is more preferable to use a carnauba wax and a paraffin wax in combination.

The melting point of the release agent is preferably 60 ° C. or higher, more preferably 65 ° C. or higher, further preferably 70 ° C. or higher, and preferably 100 ° C. from the viewpoint of achieving both low-temperature fixability and heat-resistant storage stability of the toner. Below, it is 90 degrees C or less more preferably, More preferably, it is 85 degrees C or less. When two or more types are used in combination, the melting point is preferably 60 ° C. or higher and 100 ° C. or lower from the viewpoint of achieving both low temperature fixability and heat resistant storage stability of the toner. That is, the release agent preferably contains at least two release agents having a melting point of 60 ° C. or more and 100 ° C. or less, and more preferably each melting point is 60 ° C. or more and 90 ° C. or less.
In this invention, melting | fusing point of a mold release agent is calculated | required by the method as described in an Example. When two or more kinds are used in combination, the melting point of the release agent having the largest mass ratio among the release agents contained in the obtained toner is the melting point of the release agent in the present invention. In addition, when all are the same ratio, let the value of the lowest melting | fusing point be melting | fusing point of the mold release agent in this invention.
The amount of the release agent used is preferably 1 part by mass or more, more preferably 2 parts by mass or more, and further preferably 5 parts by mass with respect to 100 parts by mass of the resin in the toner from the viewpoint of improving the releasability of the toner. Part or more, preferably 20 parts by mass or less, more preferably 15 parts by mass or less.

(Manufacture of release agent particles)
The release agent particles are preferably obtained as a dispersion of release agent particles by dispersing the release agent in an aqueous medium.
A dispersion of release agent particles is obtained by dispersing a release agent and an aqueous medium using a disperser in the presence of a surfactant or a resin emulsion at a temperature equal to or higher than the melting point of the release agent. Is preferred. As the disperser to be used, a homogenizer, an ultrasonic disperser and the like are preferable from the viewpoint of improving the dispersion stability of the release agent particles.
Examples of the ultrasonic disperser include an ultrasonic homogenizer. As the commercially available products, “US-150T”, “US-300T”, “US-600T” (manufactured by Nippon Seiki Seisakusho Co., Ltd.), “SONIFIER 4020-400”, “SONIFIER 4020-800” (manufactured by Branson; SONIFIER is a registered trademark).
Further, before using the disperser, it is preferable to preliminarily disperse the release agent, optionally the resin particles and the surfactant, and the aqueous medium in advance using a mixer such as a homomixer or a ball mill.
A preferred embodiment of the aqueous medium used in the production is the same as the aqueous medium used when obtaining the dispersion of the resin particles.

In the present invention, from the viewpoint of achieving both low-temperature fixability and heat-resistant storage stability of the toner, the release agent particles are dispersed in the aqueous medium by mixing the release agent and the oxazoline group-containing polymer and then mixing the resin emulsion. And then emulsifying to obtain an aqueous dispersion of release agent particles.
The oxazoline group-containing polymer is used from the viewpoint of dispersing the release agent in an aqueous medium. By using an oxazoline group-containing polymer, the polymer main chain is adsorbed on a hydrophobic wax, the polar oxazoline group becomes a dispersing group in the aqueous medium, and the release agent can be dispersed in the aqueous medium. Become. And since the reaction active site | part in the resin in the resin emulsion to mix next and an oxazoline group couple | bond together chemically, it can be set as the particle | grains which the resin particle adhered firmly to the mold release agent particle surface. In addition, when the release agent contains a functional group such as a carboxy group, it reacts with the oxazoline group, more easily adheres to the surface of the release agent, and improves the dispersion stability of the release agent particles. Conceivable.
The number average molecular weight of the oxazoline group-containing polymer is preferably 1,000 or more, more preferably 5,000 or more, and preferably 1,000,000 from the viewpoint of increasing the reactivity with the release agent and the resin. 000 or less, more preferably 100,000 or less.
Commercially available oxazoline group-containing polymers include “Epocross (registered trademark) WS series” such as Epocross (registered trademark) WS-300, WS-500, WS-700, etc. Chain acryl), “K series” (manufactured by Nippon Shokubai Co., Ltd., emulsion type, main chain styrene / acrylic) and the like.

  The amount of the oxazoline group-containing polymer to be used is preferably 0.00 with respect to 100 parts by mass of the release agent from the viewpoint of increasing the reactivity with the release agent and the resin and improving the dispersion stability of the release agent particles. 1 part by mass or more, more preferably 0.3 part by mass or more, further preferably 0.5 part by mass or more, and preferably 10 parts by mass or less from the viewpoint of improving the productivity of the release agent particle dispersion. More preferably, it is 5 mass parts or less, More preferably, it is 2 mass parts or less, More preferably, it is 1 mass part or less.

The resin emulsion is preferably a resin emulsion having a carboxy group as an acidic group, and the acid value of the resin is preferably a carboxy group. Examples of the resin emulsion include one or more selected from a vinyl chloride resin emulsion, an acrylic resin emulsion, and a polyester resin emulsion.
The vinyl chloride resin emulsion preferably contains a resin obtained by polymerization (preferably emulsion polymerization) of a vinyl chloride monomer and, if necessary, at least one copolymerizable monomer. Examples of the monomer that can be copolymerized with the vinyl chloride monomer include acrylic monomers and vinyl acetate. In addition, as shown in International Publication No. 2010-140647, a vinyl chloride monomer and at least one copolymerizable monomer are polymerized in the presence of a styrene / acryl oligomer and / or an acrylate oligomer (preferably Or vinyl chloride resin obtained by emulsion polymerization).
A commercially available resin emulsion may be used as the vinyl chloride resin emulsion. Commercially available resin emulsions are commercially available as so-called soap-free types that do not use surfactants, such as VINYBRAN 700 and VINYBRAN 701 (both vinyl chloride copolymer emulsions manufactured by Nissin Chemical Industry Co., Ltd .; VINYBRAN is a registered trademark) ) And the like.

The acrylic resin emulsion preferably includes an acrylic resin obtained by polymerization (for example, emulsion polymerization) of an acrylic monomer alone or an acrylic monomer and at least one copolymerizable monomer.
As acrylic resin emulsion, acrylic resin emulsion, styrene-acrylic copolymer resin emulsion, vinyl acetate-acrylic copolymer resin emulsion, silicone-acrylic resin emulsion, polyester-acrylic resin emulsion, urethane-acrylic resin emulsion, modified acrylic Examples thereof include at least one selected from a resin emulsion, a self-crosslinking acrylic acid ester resin emulsion, and an ethylene-vinyl acetate-acrylic resin emulsion. Among these, from the viewpoint of improving the dispersion stability of the release agent particles, an acrylic resin emulsion and a styrene-acrylic copolymer resin emulsion are preferable.
The polyester resin used in the polyester resin emulsion used for producing the dispersion of the release agent particles may be either a crystalline polyester resin or an amorphous polyester resin. It can be produced by subjecting an acid component and an alcohol component to a polycondensation reaction in the same manner as in the production of the constituting polyester.

In addition, from the viewpoint of ease of production of the resin emulsion, a surfactant may be used as necessary. However, if the content of the surfactant in the resin emulsion is large, the resin may be used when emulsifying the wax. There is a risk of inhibiting the emulsion from adsorbing to the wax interface. Therefore, the content of the surfactant in the resin emulsion is preferably 10% by mass or less, more preferably 5% by mass or less, still more preferably 3% by mass or less, and still more preferably substantially, in the solid content of the resin emulsion. 0 mass%.
The addition amount of the resin emulsion in the dispersion of the release agent particles is, as a resin component, from the viewpoint of improving the cohesiveness of the release agent particles at the time of toner preparation and preventing the release with respect to 100 parts by mass of the release agent. The amount is preferably 1 part by mass or more, more preferably 2 parts by mass or more, and further preferably 3 parts by mass or more. From the viewpoint of improving the low-temperature fixability of the toner, it is preferably 15 parts by mass or less, more preferably 10 parts by mass or less. It is.

The solid content concentration of the release agent particle dispersion is preferably 5% by mass or more, more preferably 10% from the viewpoint of improving the productivity of the toner and the dispersion stability of the release agent particle dispersion. It is at least 15% by mass, more preferably at least 15% by mass, preferably at most 40% by mass, more preferably at most 30% by mass, still more preferably at most 25% by mass. In addition, solid content is the total amount of non-volatile components, such as a mold release agent and resin.
The volume median particle size (D ₅₀ ) of the release agent particles is preferably 100 nm or more, more preferably from the viewpoint of facilitating aggregation with the resin particles, and achieving both low-temperature fixability and heat-resistant storage stability of the toner. It is 200 nm or more, preferably 1 μm or less, more preferably 700 nm or less, and still more preferably 600 nm or less.
The CV value of the release agent particles is preferably 50% or less, more preferably 40% or less, and still more preferably 35%, from the viewpoint of facilitating aggregation with the resin particles and improving the charging stability of the toner. From the viewpoint of improving toner productivity, it is preferably 15% or more, more preferably 20% or more, and further preferably 25% or more. The volume median particle size and CV value of the release agent particles are specifically determined by the method described in the examples.

(Production of aggregated particles)
The agglomerated particles agglomerate the resin particles A and the resin particles B at a temperature of 5 ° C. higher than the glass transition temperature Tg (A) of the resin particles A and lower than the glass transition temperature Tg (B) of the resin particles B. Obtained.
In step (1), resin particles A, resin particles B, an aggregating agent, and optional components such as a release agent particle, a surfactant, and a colorant are aggregated in an aqueous medium to obtain aggregated particles. be able to.
In this step, it is preferable to first mix a dispersion of resin particles A, a dispersion of resin particles B, and a dispersion of release agent particles in an aqueous medium to obtain a mixed dispersion.
In addition, when a coloring agent is not mixed in the resin particle A, it is preferable to mix a coloring agent in this mixed dispersion liquid.
Further, resin particles other than the resin particles A and the resin particles B may be mixed in the mixed dispersion.
There is no restriction | limiting in order of mixing, You may add any in order and may add simultaneously.

The resin particles A are preferably 10% by mass or more, more preferably 20% by mass or more in the mixed dispersion containing the resin particles A and the resin particles B from the viewpoint of achieving both low-temperature fixability and heat-resistant storage stability of the toner. In addition, from the viewpoint of controlling aggregation and obtaining aggregated particles having a desired particle diameter, it is preferably 40% by mass or less, more preferably 35% by mass or less.
The aqueous medium is preferably 60% by mass or more, more preferably 65% by mass or more in the mixed dispersion containing the resin particles A and the resin particles B from the viewpoint of controlling aggregation and obtaining aggregated particles having a desired particle size. In addition, from the viewpoint of improving the productivity of the toner, it is preferably 90% by mass or less, and more preferably 80% by mass or less.

The release agent particles are preferably 1 part by mass or more, more preferably from 100 parts by mass of the resin particles A, from the viewpoint of improving the releasability of the toner and from the viewpoint of achieving both low temperature fixability and heat resistant storage stability of the toner. From the viewpoint of improving the low-temperature fixability of the toner, it is preferably 20 parts by mass or less, more preferably 15 parts by mass or less, and still more preferably 10 parts by mass. Or less.
The mixing temperature is preferably 0 ° C. or higher and 40 ° C. or lower from the viewpoint of controlling aggregation and obtaining aggregated particles having a desired particle size.

  Next, the particles in the mixed dispersion are aggregated to obtain a dispersion of aggregated particles. From the viewpoint of efficiently performing the aggregation, it is preferable to add an aggregating agent.

[Flocculant]
The flocculant contains a non-metallic salt containing a monovalent cation.
Examples of the flocculant include organic flocculants such as quaternary ammonium salts; inorganic flocculants such as inorganic ammonium salts. From the viewpoint of improving the cohesiveness and obtaining uniform aggregated particles, an inorganic coagulant is preferable.
Examples of the monovalent cation include quaternary ammonium ions such as ammonium ion (NH ₄ ⁺ ), tetraalkylammonium, pyridinium ion, and among these, ammonium ion is preferable.
Examples of the non-metal salt containing a monovalent cation include ammonium salts such as ammonium sulfate, ammonium chloride, and ammonium nitrate, and ammonium sulfate is more preferable.
The amount of the flocculant used is preferably 50 parts by mass or less, more preferably 45 parts by mass or less, with respect to 100 parts by mass of the resin constituting the resin particles A, from the viewpoint of achieving both low-temperature fixability and heat-resistant storage stability of the toner. More preferably, it is 40 parts by mass or less, and from the viewpoint of obtaining the desired particle size by controlling the aggregation of the resin particles, preferably 5 parts by mass or more, more preferably 10 parts by mass or more, and still more preferably 20 parts by mass. More than a part.

The flocculant is preferably added dropwise to the mixture dispersion. The flocculant may be added at once, or may be added intermittently or continuously. It is preferable to perform sufficient stirring during and after the addition.
The flocculant is preferably added dropwise as an aqueous solution from the viewpoint of controlling aggregation and obtaining aggregated particles having a desired particle size. The concentration of the aqueous solution of the flocculant is preferably 2% by mass or more, more preferably 4% by mass or more, and preferably 40% by mass or less from the viewpoint of controlling aggregation and obtaining aggregated particles having a desired particle size. More preferably, it is 30 mass% or less, More preferably, it is 20 mass% or less, More preferably, it is 10 mass% or less.
The dropping time of the flocculant is preferably 1 minute or more from the viewpoint of obtaining aggregation particles having a desired particle size by controlling the aggregation, and preferably 120 minutes or less from the viewpoint of improving the productivity of the toner. More preferably, it is 60 minutes or less, More preferably, it is 30 minutes or less.
The temperature at which the flocculant is dropped is preferably 0 ° C. or higher, more preferably 10 ° C. or higher from the viewpoint of improving the productivity of the toner. Therefore, it is preferably 50 ° C. or lower, more preferably 40 ° C. or lower, and further preferably 30 ° C. or lower.
Further, from the viewpoint of promoting aggregation and obtaining aggregated particles having a desired particle size and particle size distribution, it is preferable to add the flocculant and then raise the temperature of the dispersion to cause aggregation.

The agglomeration temperature is at least 5 ° C. higher than the glass transition temperature Tg (A) of the resin particle A and the glass of the resin particle B from the viewpoint of improving the low-temperature fixability, heat-resistant storage stability, and charging stability of the toner. The temperature is lower than the transition temperature Tg (B).
The aggregation temperature is preferably at least 6 ° C. higher than the glass transition temperature Tg (A) of the resin particles A, more preferably resin particles, from the viewpoint of improving low-temperature fixability, heat-resistant storage stability, and charging stability of the toner. When the glass transition temperature of A is 8 ° C. higher than the glass transition temperature Tg (A) and Tg (A) and Tg (B) are in the relationship of the formula (1-1), the glass transition temperature of the resin particles A is more preferable. When the temperature is 12 ° C. higher than Tg (A) and Tg (A) and Tg (B) are in the relationship of the formula (1-2), more preferably from the glass transition temperature Tg (A) of the resin particle A From the viewpoint of improving the low-temperature fixability, heat-resistant storage stability, and charging stability of the toner, it is preferably 2 ° C. or lower than the glass transition temperature Tg (B) of the resin particle B. More preferably, the glass transition temperature of the resin particle B The temperature is 4 ° C. or lower than the temperature Tg (B), more preferably 6 ° C. or lower than the glass transition temperature Tg (B) of the resin particle B.

The volume-median particle size (D ₅₀ ) of the obtained aggregated particles is preferably 2 μm or more, more preferably 3 μm or more, and even more preferably 4 μm or more, from the viewpoint of achieving both low-temperature fixability and heat-resistant storage stability of the toner. Further, it is preferably 10 μm or less, more preferably 8 μm or less, and further preferably 6 μm or less.
The volume median particle size is measured by the method described in the examples.
The CV value of the aggregated particles is preferably 50% or less, more preferably 40% or less, still more preferably 30% or less, and preferably 5% from the viewpoint of obtaining a toner capable of obtaining a high-quality image. Above, more preferably 10% or more, still more preferably 15% or more. The CV value is a value represented by the following formula and is determined by the method described in the examples.
CV value (%) = [standard deviation of particle size distribution (μm) / volume average particle size (μm)] × 100

Aggregation is stopped when the aggregated particles grow to an appropriate particle size as a toner.
Examples of the method for stopping the aggregation include a method of cooling the dispersion, a method of adding an aggregation stopper, and a method of diluting the dispersion. From the viewpoint of surely preventing unnecessary aggregation, the aggregation stopper A method of stopping the aggregation by adding is preferable.

(Flocculation terminator)
As the aggregation terminator, a surfactant is preferable, and an anionic surfactant is more preferable. Examples of the anionic surfactant include alkyl ether sulfates, alkyl sulfates, and linear alkylbenzene sulfonates. The aggregation terminator can be used alone or in combination of two or more.
The addition amount of the aggregation terminator is preferably 0.1 parts by mass or more, more preferably 1 part by mass or more, with respect to 100 parts by mass of the total amount of the resin in the toner, from the viewpoint of surely preventing unnecessary aggregation. More preferably, it is 2 parts by mass or more, and from the viewpoint of reducing residual toner, it is preferably 15 parts by mass or less, more preferably 10 parts by mass or less, and further preferably 6 parts by mass or less. The aggregation terminator is preferably added as an aqueous solution from the viewpoint of improving toner productivity.
The temperature at which the aggregation terminator is added is preferably the same as the temperature at which the aggregated particle dispersion is retained, and is preferably 50 ° C. or higher and 75 ° C. or lower from the viewpoint of improving toner productivity.
The obtained aggregated particles can be further aggregated with other resin particles to obtain core-shell structured aggregated particles. In this case, it is preferable to aggregate so that the obtained aggregated particles are on the core side and the other resin particles are on the shell side.

<Step (2)>
Step (2) is a step in which the aggregated particles obtained in step (1) are heated and fused.
In the aggregated particles, the particles that are mainly physically attached to each other are fused and united to form toner particles.

In this step, the temperature is preferably maintained at a temperature equal to or higher than the glass transition temperature Tg (B) of the resin particle B from the viewpoint of improving the fusing property of the aggregated particles and achieving both low temperature fixability and heat resistant storage stability of the toner. To be fused.
The fusing temperature is more preferably 3 ° C. or more from the glass transition temperature Tg (B) of the resin particles B, and more preferably 5 ° C. from the Tg (B), from the viewpoint of achieving both low-temperature fixability and heat-resistant storage stability of the toner. In addition, the temperature is preferably 15 ° C. or higher than Tg (B), preferably 12 ° C. or lower, more preferably 10 ° C. or lower than Tg (B).
When a release agent is contained, the fusing temperature is preferably a temperature lower than the melting point of the release agent, more preferably from the viewpoint of suppressing the release of the release agent and improving the charging stability of the toner. Is 2 ° C. or lower than the melting point of the release agent, more preferably 4 ° C. or lower than the melting point of the release agent.
The time for holding the resin particles B at a temperature equal to or higher than the glass transition temperature is preferably 1 minute or more, more preferably 10 minutes or more, and still more preferably 30 from the viewpoint of achieving both low-temperature fixability and heat-resistant storage stability of the toner. Min. Or more, preferably 240 min or less, more preferably 180 min or less, still more preferably 120 min or less, and still more preferably 90 min or less.

The volume median particle size (D ₅₀ ) of the toner particles obtained in the step (2) is preferably 2 μm or more, more preferably 3 μm or more, and still more preferably from the viewpoint of achieving both low-temperature fixability and heat-resistant storage stability of the toner. It is 4 μm or more, preferably 10 μm or less, more preferably 8 μm or less, and still more preferably 6 μm or less.

(Post-processing process)
In the present invention, a post-treatment step may be performed after the step (2), and it is preferable to obtain toner particles by isolation.
Since the toner particles obtained in the step (2) are present in the aqueous medium, it is preferable to first perform solid-liquid separation. For solid-liquid separation, a suction filtration method or the like is preferably used.
It is preferable to perform washing after the solid-liquid separation. At this time, since it is preferable to remove the added surfactant, when a nonionic surfactant is used in the production of the resin particles, the aqueous surfactant is used below the cloud point of the nonionic surfactant. It is preferable to wash. The washing is preferably performed a plurality of times.
Next, it is preferable to perform drying. The drying temperature is preferably such that the temperature of the toner particles themselves is 5 ° C. or more lower than the melting point of the crystalline polyester, and more preferably 10 ° C. or more. As a drying method, it is preferable to use a vacuum low temperature drying method, a vibration type fluidized drying method, a spray drying method, a freeze drying method, a flash jet method, or the like. The water content after drying is preferably adjusted to 1.5% by mass or less, more preferably 1.0% by mass or less, from the viewpoint of improving the chargeability of the toner.

[toner]
Although the toner particles obtained by drying or the like can be used as they are as the toner of the present invention, it is preferable to use toner particles whose surfaces have been treated as described below as electrostatic charge image developing toner.

(External additive)
In the toner for developing an electrostatic charge image of the present invention, the toner particles can be used as the toner as they are, but it is preferable to use a toner obtained by adding a fluidizing agent or the like to the toner particle surface as an external additive.
Examples of the external additive include hydrophobic silica, titanium oxide fine particles, alumina fine particles, cerium oxide fine particles, inorganic fine particles such as carbon black, and polymer fine particles such as polycarbonate, polymethyl methacrylate, and silicone resin. Among these, hydrophobic Silica is preferred.
When the surface treatment of the toner particles is performed using an external additive, the amount of the external additive added 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 toner particles. , Preferably 5 parts by mass or less, more preferably 4.5 parts by mass or less.

The volume median particle size (D ₅₀ ) of the obtained toner is preferably 2 μm or more, more preferably 3 μm or more, from the viewpoint of improving the productivity of the toner and the viewpoint of achieving both low temperature fixability and heat resistant storage stability of the toner. More preferably, it is 4 micrometers or more, Preferably it is 10 micrometers or less, More preferably, it is 8 micrometers or less, More preferably, it is 6 micrometers or less.
The CV value of the toner is preferably 30% or less, more preferably 27% or less, still more preferably 25% or less, and still more preferably 23% or less, from the viewpoint of obtaining a high-quality image. From the viewpoint of improving the property, it is preferably 15% or more, more preferably 18% or more.
The degree of circularity of the toner is preferably 0.960 or more, more preferably 0.965 or more from the viewpoint of achieving both low-temperature fixability and heat-resistant storage stability of the toner, and preferably 0.990 from the same viewpoint. Below, more preferably 0.985 or less, and still more preferably 0.980 or less.
The electrostatic image developing toner obtained by the present invention can be used as a one-component developer or mixed with a carrier and used as a two-component developer.

  Each property value of polyester, resin particles, toner, etc. was measured and evaluated by the following method.

[Acid value of polyester]
It measured according to JIS K0070. However, the measurement solvent was chloroform.

[Resin softening point, crystallinity index, maximum peak temperature of endotherm, melting point and glass transition temperature]
(1) Softening point Using a flow tester “CFT-500D” (manufactured by Shimadzu Corporation), 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.

(2) Crystallinity Index Using a differential scanning calorimeter “Q100” (manufactured by TA Instruments Japan Co., Ltd.), 0.01 to 0.02 g of a sample was weighed into an aluminum pan and room temperature (20 ° C. ) To 0 ° C. at a temperature drop rate of 10 ° C./min. Next, the sample was allowed to stand still for 1 minute, and then heated to 180 ° C. at a heating rate of 10 ° C./min, and the amount of heat was measured. Of the observed endothermic peaks, the temperature of the peak with the largest peak area is defined as the maximum endothermic peak temperature (1), and (softening point (° C)) / (maximum endothermic peak temperature (1) (° C)), The crystallinity index was determined.

(3) Melting point and glass transition temperature (Tg)
Using a differential scanning calorimeter “Q100” (manufactured by TA Instruments Japan Co., Ltd.), 0.01 to 0.02 g of a sample was weighed into an aluminum pan, heated to 200 ° C., and from that temperature It cooled to 0 degreeC with the temperature-fall rate 10 degreeC / min. Next, the sample was heated at a heating rate of 10 ° C./min, and the amount of heat was measured. Among the observed endothermic peaks, the temperature of the peak having the maximum peak area was defined as the maximum endothermic temperature (2). In the case of crystalline polyester, the peak temperature was taken as the melting point. In the case of an amorphous polyester, when an endothermic peak is observed, the temperature of the peak is measured, and when a step is observed without a peak being observed, the tangent indicating the maximum slope of the curve of the step and the step The temperature of the intersection with the extended line of the base line on the high temperature side was taken as the glass transition temperature.

[Melting point of release agent]
Using a differential scanning calorimeter “DSC210” (manufactured by Seiko Denshi Kogyo Co., Ltd.), 0.01 to 0.02 g of a 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 from 20 ° C. to 180 ° C. at a heating rate of 10 ° C./min, the amount of heat was measured, and the maximum peak temperature of the endotherm was taken as the melting point.

[Volume Median Particle Size (D ₅₀ ) and CV Value of Resin Particles and Release Agent Particles]
(1) Measuring apparatus: Laser diffraction type particle size measuring instrument “LA-920” (manufactured by Horiba, Ltd.)
(2) Measurement conditions: Distilled water was added to the measurement cell, and the volume-median particle size (D ₅₀ ) and the volume average particle size were measured at a concentration where the absorbance was in an appropriate range. The CV value (coefficient of variation of particle size distribution) was calculated according to the following formula.
CV value (%) = (standard deviation of particle size distribution / volume average particle size) × 100

[Solid content concentration of resin particle dispersion and release agent particle dispersion]
Using an infrared moisture meter “FD-230” (manufactured by Kett Scientific Laboratory), a measurement sample 5 g was dried at a temperature of 150 ° C. and in a measurement mode 96 (monitoring time 2.5 min / variation width 0.05%). Moisture (mass%) was measured. The solid content concentration was calculated according to the following formula.
Solid content concentration (% by mass) = 100-water content (% by mass)

[Volume Median Particle Size (D ₅₀ ) and CV Value of Aggregated Particles]
The volume-median particle size (D ₅₀ ) of the aggregated particles was measured as follows.
Measuring instrument: “Coulter Multisizer (registered trademark) III” (manufactured by Beckman Coulter, Inc.)
・ Aperture diameter: 50μm
Analysis software: “Multisizer (registered trademark) III version 3.51” (manufactured by Beckman Coulter, Inc.)
Electrolyte: “Isoton (registered trademark) II” (manufactured by Beckman Coulter, Inc.)
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. From the particle size distribution, the volume median particle size (D ₅₀ ) and the volume average particle size were determined.
The CV value (%) was calculated according to the following formula.
CV value (%) = (standard deviation of particle size distribution / volume average particle size) × 100

[Volume Median Particle Size (D ₅₀ ) and CV Value of Toner]
The volume median particle size of the toner 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 "Emulgen (registered trademark) 109P" (manufactured by Kao Corporation, HLB: 13.6) was dissolved in the electrolytic solution to obtain a dispersion having a concentration of 5% by mass.
-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, and then 25 mL of electrolyte is added, and further dispersed for 1 minute with an ultrasonic disperser. A sample dispersion was prepared.
Measurement conditions: After adding the sample dispersion to 100 mL of the electrolyte solution, the particle size of 30,000 particles is adjusted to a concentration that can be measured in 20 seconds, and then 30,000 particles are measured. The volume-median particle size (D ₅₀ ) and the volume average particle size were determined from the distribution.
The CV value (%) was calculated according to the following formula.
CV value (%) = (standard deviation of particle size distribution / volume average particle size) × 100

[Glass transition temperature of resin particles]
20 g of resin particle dispersion was weighed in an aluminum pan, and then a shelf dryer “DRC-1000” (manufactured by Tokyo Rika Kikai Co., Ltd.) connected to a freeze dryer “FDU-2100” (manufactured by Tokyo Rika Kikai Co., Ltd.) at room temperature and normal pressure. ) And held at −25 ° C. for 1 hour, and then reduced in pressure at −10 ° C. and 8.0 Pa for 9 hours.
The glass transition temperature of the obtained resin particles was measured by the same method as the glass transition temperature of the resin.

[Toner circularity]
50 mg of toner particles were added to 5 ml of a 5% by mass aqueous solution of polyoxyethylene lauryl ether “Emulgen (registered trademark) 109P” (manufactured by Kao Corporation, HLB: 13.6) and dispersed for 1 minute by an ultrasonic disperser. Thereafter, 20 ml of distilled water was added, and the mixture was further dispersed for 1 minute using an ultrasonic disperser. Measurement was performed on 1000 particles by the following measuring apparatus, and the average value thereof was defined as the circularity of the toner.
Measurement device: Flow type particle image analyzer “FPIA (registered trademark) -3000” (manufactured by Sysmex Corporation)
・ Measurement mode: HPF measurement mode ・ Objective lens: 10 times (standard lens)
-Number of observation samples: 1000

[Low-temperature fixability of toner]
Using a commercially available printer “Microline (registered trademark) 5400” (manufactured by Oki Data Corporation) on high-quality paper “J paper A4 size” (manufactured by Fuji Xerox Co., Ltd.), the toner adhesion amount on the paper is 0.42 to 0. A solid image of .48 mg / cm ² was output without being fixed at a length of 50 mm, leaving a margin of 5 mm from the top edge of the A4 paper.
Next, the same printer with the temperature-variable fixing device prepared was prepared, the temperature of the fixing device was set to 90 ° C., and fixing was performed at a speed of 1.5 seconds per sheet in the A4 longitudinal direction, thereby obtaining a printed matter.
In the same manner, the temperature of the fixing device was increased by 5 ° C. and fixed, and a printed matter was obtained.
From the margin at the top edge of the printed image to the solid image, lightly paste a 50 mm long mending tape “Scotch (registered trademark) mending tape 810” (manufactured by Sumitomo 3M Limited, width 18 mm). After that, a weight of 500 g was placed and pressed once back and forth at a speed of 10 mm / sec. Thereafter, the affixed tape was peeled off from the lower end side at a peeling angle of 180 degrees and at a speed of 10 mm / sec to obtain a printed matter after the tape was peeled off. 30 sheets of high quality paper “Excellent White Paper A4 Size” (made by Oki Data Co., Ltd.) is laid under the printed material before and after the tape is applied, and the reflected image density of the fixed image portion before and after the tape is applied to each printed material. The measurement was performed using a colorimeter “SpectroEye” (manufactured by GretagMacbeth, Inc., light emission condition: standard light source D50, observation field of view 2 °, density standard DINNB, absolute white standard), and the fixing ratio was calculated from the following formula.
Fixing rate (%) = (Reflected image density after peeling tape / Reflected image density before applying tape) × 100
The lowest temperature at which the fixing rate was 90% or more was defined as the minimum fixing temperature. The lower the minimum fixing temperature, the better the low temperature fixing property.

[Heat resistant storage stability of toner]
10 g of toner was placed in a 100 ml wide mouthed polybin and sealed, placed in a thermostat kept at 45 ° C., 47 ° C., 50 ° C., 53 ° C., and 55 ° C., respectively, and left in that environment for 48 hours. Thereafter, it was allowed to stand for 12 hours or more while being sealed at a temperature of 25 ° C. and cooled. Next, a powder tester (registered trademark) (manufactured by Hosokawa Micron Co., Ltd.) is set on a vibrating table having a mesh size of 250 μm, and 10 g of the toner is placed on the vibrating table, and the toner is vibrated for 30 seconds. The mass was measured. The smaller the value, the better the heat resistant storage stability of the toner.

[Toner charging stability]
(1) Initial charge amount Q / d of toner
0.6 g of toner and 19.4 g of ferrite carrier (ferrite core, silicone coat, saturation magnetization: 71 Am ^{2 /} kg) are placed in a polypropylene bottle “PP sampler bottle wide mouth 50 ml” (manufactured by Sampratec Co., Ltd.), and 20 minutes by a ball mill. After mixing, 5 g was collected and measured with a charge amount measuring device “q-test” (manufactured by Epping), and median q / d was defined as a toner charge amount Q / d (fC / 10 μm). At that time, the Specific Density was 1.2 g / cm ^3, and the median diameter was a value of the volume median particle size (D ₅₀ ) of the toner.
Measurement was performed under the following measurement conditions.
Toner Flow (ml / min): 160
Electrode Voltage (V): 4000
Deposition Time (s): 2

(2) Charge amount Q / d after printing 5,000 sheets of toner
Using a commercially available printer “Microline (registered trademark) 5400” (manufactured by Oki Data Corporation) on high-quality paper “J paper A4 size” (manufactured by Fuji Xerox Co., Ltd.), 5000 images with a printing rate of 5% are continuously displayed. After printing, the toner in the toner cartridge was collected, and the charge amount Q / d after printing 5,000 sheets was determined by the method described in [Initial charge amount Q / d of toner].
The smaller the change in the charge amount after printing 5,000 sheets compared to the initial charge amount of the toner, the better the charging stability.

[Production of polyester]
Production Example X1
(Production of crystalline polyester X1)
The inside of a four-necked flask equipped with a nitrogen introduction tube, a dehydration tube, a stirrer, and a thermocouple was purged with nitrogen, and 3078 g of 1,3-propanediol as an alcohol component and 4922 g of succinic acid as an acid component were added. While stirring, the temperature was raised to 135 ° C., maintained at 135 ° C. for 3 hours, and then heated from 135 ° C. to 200 ° C. over 10 hours. Thereafter, 16 g of di (2-ethylhexanoic acid) tin was added, and the mixture was further maintained at 200 ° C. for 1 hour. Then, the pressure in the flask was lowered and maintained at 8.3 kPa for 1 hour to obtain crystalline polyester X1. . The physical properties are shown in Table 1.

Production Example X2
(Production of crystalline polyester X2)
Crystalline polyester X2 was obtained in the same manner as in Production Example X1, except that the alcohol component, acid component, and esterification catalyst were changed as shown in Table 1. The physical properties are shown in Table 1.

Production Example Y1
(Production of amorphous polyester Y1)
The inside of a four-necked flask equipped with a nitrogen introduction tube, a dehydration tube, a stirrer, and a thermocouple was replaced with nitrogen, and polyoxyethylene (2.0) -2,2-bis (4-hydroxyphenyl) propane as an alcohol component 6500 g, among the acid components, 1660 g of terephthalic acid and 47 g of di (2-ethylhexanoic acid) tin were added. While stirring in a nitrogen atmosphere, the temperature was raised to 230 ° C., maintained at 230 ° C. for 5 hours, then cooled to 180 ° C., and 876 g of adipic acid and 384 g of trimellitic acid anhydride were added out of the acid components to 220 ° C. The temperature was raised at 10 ° C./hr. Thereafter, the reaction was carried out at 10 kPa to the desired softening point to obtain amorphous polyester Y1. The physical properties are shown in Table 1.

Production Examples Y2 to Y5
(Production of amorphous polyesters Y2 to Y5)
Amorphous polyesters Y2 to Y5 were obtained in the same manner as in Production Example Y1, except that the raw material monomer and mass of the amorphous polyester were changed as shown in Table 1. The physical properties are shown in Table 1.

Production Example Y6
(Production of amorphous polyester Y6)
The inside of a four-necked flask equipped with a nitrogen introduction tube, a dehydration tube, a stirrer, and a thermocouple was replaced with nitrogen, and polyoxyethylene (2.0) -2,2-bis (4-hydroxyphenyl) as an alcohol component 5635 g of propane, 1338 g of terephthalic acid among the acid components, and 41 g of di (2-ethylhexanoic acid) tin were added. While stirring in a nitrogen atmosphere, the temperature was raised to 230 ° C. and maintained at 230 ° C. for 5 hours, and then the pressure in the flask was further reduced and maintained at 8.0 kPa for 1 hour. Then, after returning to atmospheric pressure and cooling to 190 ° C., 744 g of fumaric acid, 283 g of trimellitic anhydride and 1.5 g of tert-butylcatechol were added and maintained at 190 ° C. for 1 hour. The temperature was raised to 210 ° C. over 2 hours. Further, the pressure in the flask was lowered and maintained at 8.0 kPa for 4 hours to obtain amorphous polyester Y6. The physical properties are shown in Table 1.

Production Examples Y7, Y8
(Production of amorphous polyesters Y7 and Y8)
Amorphous polyesters Y7 and Y8 were obtained in the same manner as in Production Example Y6 except that the raw material monomers and mass of the amorphous polyester were changed as shown in Table 1. The physical properties are shown in Table 1.

[Production of resin particles]
Production Example A1
(Production of resin particle dispersion A-1)
In a flask equipped with a stirrer, crystalline polyester X1 60 g (10 parts by mass), amorphous polyester Y1 540 g (90 parts by mass), copper phthalocyanine pigment “ECB-301” (manufactured by Dainichi Seika Kogyo Co., Ltd.) 45 g, Nonionic surfactant “Emulgen (registered trademark) 150” (manufactured by Kao Corporation, polyoxyethylene (50 mol) lauryl ether) 12 g, anionic surfactant “Neopelex (registered trademark) G-15” (Kao Corporation) 80 g of 15% by weight sodium dodecylbenzenesulfonate aqueous solution manufactured by company) and 225 g of 6% by weight potassium hydroxide aqueous solution were added, the temperature was raised to 98 ° C. with stirring, and the mixture was mixed at 98 ° C. for 2 hours to obtain a resin mixture. Got.
Next, 1000 g of deionized water was added dropwise at a rate of 6 g / min while stirring the resin mixture to obtain an emulsion. The obtained emulsion was cooled to 25 ° C., deionized water was added to adjust the solid content to 30% by mass, and a resin particle dispersion A-1 was obtained. The physical properties are shown in Table 2.

Production Examples A2 to A5
(Production of resin particle dispersions A-2 to A-5)
Resin particle dispersions A-2 to A-5 were obtained in the same manner as in Production Example A1, except that the types and parts by mass of crystalline polyester and amorphous polyester were changed as shown in Table 2. The physical properties are shown in Table 2. In addition, it manufactured so that 100 mass parts might be 600 g.

Production Example B1
(Production of resin particle dispersion B-1)
In a flask equipped with a stirrer, amorphous polyester Y4 600 g, nonionic surfactant “Emulgen (registered trademark) 150” (manufactured by Kao Corporation, polyoxyethylene (50 mol) lauryl ether) 6 g, anionic surfactant 40 g of the agent “Neopelex (registered trademark) G-15” (manufactured by Kao Corporation, 15 mass% sodium dodecylbenzenesulfonate aqueous solution) and 225 g of 6 mass% potassium hydroxide aqueous solution were added and stirred at 98 ° C. The temperature was raised and mixed at 98 ° C. for 2 hours to obtain a resin mixture.
Next, 1150 g of deionized water was added dropwise at a rate of 6 g / min while stirring the resin mixture to obtain an emulsion. The obtained emulsion was cooled to 25 ° C. and passed through a wire mesh of 200 mesh (aperture 105 μm). Thereafter, deionized water was added to the filtrate to adjust the solid content to 24% by mass to obtain a resin particle dispersion B-1. Table 3 shows the physical properties.

Production Examples B2 to B5
(Production of resin particle dispersions B-2 to B-5)
Resin particle dispersions B-2 to B-5 were obtained in the same manner as in Production Example B1, except that the type of amorphous polyester and the number of parts by mass were changed as shown in Table 3. Table 3 shows the physical properties.

Production Example W1
(Production of release agent particle dispersion)
In a 1 liter beaker, 225 g of deionized water, 5 g of carnauba wax “carnauba wax 1” (manufactured by Hiroyuki Kato, melting point 83 ° C.), and paraffin wax “HNP-9” (manufactured by Nippon Seiwa Co., Ltd.) , Melting point 75 ° C.) was added, and the mixture was melted while stirring at 90 to 95 ° C. to obtain a molten mixture in which carnauba wax and paraffin wax were melted together. Next, 1.7 g of an aqueous oxazoline group-containing polymer aqueous solution “Epocross (registered trademark) WS-700” (manufactured by Nippon Shokubai Co., Ltd., nonvolatile content 25 mass%, number average molecular weight 20,000) was added, and the temperature was adjusted to 90 to 95 ° C. Was held for 15 minutes using an ultrasonic homogenizer “US-600T” (manufactured by Nippon Seiki Seisakusho Co., Ltd.). 8. Here, vinyl chloride copolymer emulsion “Viniblanc (registered trademark) 701” (manufactured by Nissin Chemical Industry Co., Ltd., solid content 30% by mass, acid value 46 mg KOH / g, glass transition temperature 70 ° C., average particle size 30 nm) 0 g was added, and after dispersing for 15 minutes with an ultrasonic homogenizer, the mixture was cooled to room temperature. Deionized water was added to the resulting dispersion to adjust the solid content concentration to 20% by mass to obtain a release agent particle dispersion. The obtained release agent particle dispersion had a particle size of 440 nm and a particle size distribution CV value of 30%.

[Production of toner]
Example 1
(Preparation of Toner 1)
In a flask having an internal volume of 2 liters, 250 g of resin particle dispersion A-1, 56 g of resin particle dispersion B-2, 36 g of deionized water, and 31 g of release agent particle dispersion were placed. K. The mixture was stirred and mixed under the condition of 6000 rpm with a homomixer (2M-03 model manufactured by Tokushu Kika Kogyo Co., Ltd.). Next, an aqueous solution in which 19 g of ammonium sulfate was dissolved in 286 g of deionized water was added dropwise at 25 ° C. over 1 minute while stirring was continued, and the mixture was further stirred for 5 minutes to obtain a mixture.
The mixture was placed in a 4-liter flask having an internal volume of 2 liters equipped with a dehydrating tube, a stirrer, and a thermocouple, heated to 55 ° C. over 2 hours, and the volume-median particle size of the aggregated particles was 4.8 μm. It was kept at 55 ° C. until it became an agglomerated particle dispersion.
To the resulting aggregated particle dispersion, 12 g of anionic surfactant “Emar (registered trademark) E-27C” (manufactured by Kao Corporation, sodium polyoxyethylene lauryl ether sulfate, effective concentration 27 mass%) is added 469 g of deionized water. 1 mol / L sulfuric acid (manufactured by Kishida Chemical Co., Ltd.) was added to adjust the pH in the system to 4.8. Thereafter, the temperature was raised to 70 ° C. over 1 hour and held at 70 ° C. for 1 hour to obtain a dispersion of fused particles having a volume median particle size of 5.1 μm.
The obtained fused particle dispersion was cooled to 30 ° C. and the solid content was separated by suction filtration, washed with deionized water, and dried at 25 ° C. to obtain toner particles. To 100 parts by mass of the toner particles, 2.5 parts by mass of hydrophobic silica “RY50” (manufactured by Nippon Aerosil Co., Ltd., number average particle size; 0.04 μm) and hydrophobic silica “Caboseal TS720” (manufactured by Cabot) , Number average particle diameter; 0.012 μm) 1.0 part by mass was externally added to a Henschel mixer and passed through a 150-mesh sieve to obtain toner 1. Table 4 shows the physical properties and evaluation of the toner.

Examples 2-6 and Comparative Examples 1-6
(Production of toners 2 to 6 and C1 to C6)
Example 1 except that the resin particle dispersions A-1 and B-2, the coagulant used, and the coagulation temperature were changed to the resin particle dispersions, coagulant, and coagulation temperature shown in Tables 4 and 5 in Example 1. In the same manner, toners 2 to 6 and C1 to C6 were obtained. The physical properties and evaluation of the toner are shown in Tables 4 and 5.

  From Tables 4 and 5, it can be seen that the toners of Examples 1 to 6 are toners having both low-temperature fixability and heat-resistant storage stability and good charging stability as compared with the toners of Comparative Examples 1 to 6. .

  According to the production method of the present invention, it is possible to provide a production method capable of obtaining a toner for developing an electrostatic charge image that has a simple process and is excellent in low-temperature fixability, heat-resistant storage stability, and charge stability.

Claims (6)

Step (1): In an aqueous medium, in the presence of an aggregating agent, the resin particles A and the resin particles B are at least 5 ° C. higher than the glass transition temperature Tg (A) of the resin particles A and the glass of the resin particles B Agglomerating at a temperature lower than the transition temperature Tg (B) to obtain agglomerated particles;
Step (2): a step of heating and fusing the aggregated particles obtained in the step (1),
A method for producing an electrostatic charge image developing toner comprising:
The glass transition temperature Tg (A) of the resin particle A and the glass transition temperature Tg (B) of the resin particle B are in the relationship of the following formula (1):
Tg (A) + 10 ° C <Tg (B) (1)
When the solubility parameters by the Fedors method of the resin constituting the resin particle A and the resin constituting the resin particle B are SP (A) and SP (B), respectively.
The solubility parameter difference ΔSP (| SP (A) −SP (B) |) is 0.3 (cal / cm ³ ) ^1/2 or more and less than 1.5 (cal / cm ³ ) ^1/2 ,
A method for producing a toner for developing an electrostatic charge image, which comprises a non-metal salt containing a monovalent cation as an aggregating agent in the step (1).   The method for producing a toner for developing an electrostatic charge image according to claim 1, wherein the step (2) is a step of fusing the resin particles B by holding them at a temperature equal to or higher than the glass transition temperature Tg (B).   The method for producing a toner for developing an electrostatic charge image according to claim 1, wherein the nonmetallic salt is an ammonium salt.   The mass ratio of the resin constituting the resin particle B to the resin constituting the resin particle A (resin constituting the resin particle B / resin constituting the resin particle A) is 0.1 or more and 0.9 or less. A method for producing a toner for developing an electrostatic charge image according to any one of 1 to 3.   The toner for developing an electrostatic charge image according to any one of claims 1 to 4, wherein in the step (1), an aqueous solution of a flocculant of 2% by mass or more and 40% by mass or less is dropped over a period of 1 minute or more and 120 minutes or less. Manufacturing method.   The method for producing a toner for developing an electrostatic charge image according to claim 1, wherein the resin constituting the resin particles A and B contains 80% by mass or more of amorphous polyester.