JP6334997B2 - Toner for electrostatic image development - Google Patents

Description

  The present invention relates to an electrostatic image developing toner and a method for producing the same.

In the field of electrophotography, with development of an electrophotographic system, development of toner for electrophotography corresponding to high image quality and high speed is demanded. As a method for obtaining a toner having a narrow particle size distribution and a small particle size corresponding to high image quality, an aggregation coalescence method (emulsification) in which fine resin particles are aggregated and fused in an aqueous medium to obtain a toner. A toner is manufactured by an aggregation method or an aggregation fusion method. In particular, a toner having a core-shell structure has been proposed in order to improve thermal characteristics such as low-temperature fixability and heat-resistant storage stability.
For example, a toner for developing an electrostatic charge image having a crystalline polyester (a) and an amorphous polyester (b) in a core portion and an amorphous polyester (c) in a shell portion, the crystalline polyester (a ) Is a crystalline polyester obtained by polycondensation of an alcohol component having an average carbon number of 10 to 12 and an α, ω-alkanediol having 10 to 12 carbon atoms and an acid component containing succinic acid. And an alcohol component in which at least a part of the modified polyester (b) contains an alkyl succinic acid having a branched alkyl group having 9 to 18 carbon atoms and / or an alkenyl succinic acid having a branched alkenyl group having 9 to 18 carbon atoms Is a non-crystalline polyester obtained by polycondensation of the polyester, and the weight ratio ((a) / (b) between the crystalline polyester (a) and the amorphous polyester (b) in the toner. ) Is in a specific range, it is disclosed that both good low-temperature fixability and heat-resistant storage stability are compatible, and the image density of printed matter is excellent (Patent Document 1).

  Further, as a method for producing a toner capable of stably producing a low-temperature fixable toner containing crystalline polyester, an aqueous dispersion of colorant particles containing colorant particles, an aqueous dispersion of wax particles containing wax particles, A mixed liquid preparation step of preparing a mixed liquid by mixing at least a crystalline polyester resin particle aqueous dispersion containing crystalline self-dispersing polyester resin particles containing at least one carboxyl group which is a hydrophilic group; and the mixed liquid A polyvalent metal salt is added as an aggregating agent to agglomerate the colorant particles, the wax particles, and the crystalline self-dispersing polyester resin particles to form an agglomerate, and a mixed liquid containing the agglomerate is formed. An agglomerate forming step of mixing and further aggregating the amorphous polyester resin particle aqueous dispersion, and heating the mixed solution after completion of the agglomerate forming step And a particle forming step for uniformizing the particle size and shape of the aggregates therein, wherein the crystalline self-dispersing polyester resin particles contain polybutylene glycol having a polymerization degree of 2 to 50 as an alcohol component. A method for producing toner is disclosed (Patent Document 2).

  Further, in a toner composed of toner particles containing at least a resin, a colorant, and a release agent, the average value of the circularity of the toner particles and the maximum endothermic peak temperature of the release agent are in a specific range, and the resin A ratio a of a trivalent or higher polyvalent carboxylic acid which contains at least an amorphous polyester and a crystalline polyester, and constitutes either the amorphous polyester and / or the crystalline polyester, and a linear aliphatic diol It is disclosed that a toner whose ratio c satisfies a specific relational expression is a toner that improves low-temperature fixability, suppresses excessive gloss, and has excellent image sharpness and halftone density reproducibility. (Patent Document 3).

JP2013-242509A JP 2010-55032 A JP 2010-262089 A

However, even if a toner having a core-shell structure as in Patent Documents 1, 2, and 3 is obtained, it is still not sufficient in terms of achieving both low-temperature fixability and heat-resistant storage stability. Further, since the resin in the core and the resin in the shell are compatible at the time of fixing, the printed matter after fixing has insufficient document offset resistance, and there is room for improvement in long-term storage.
An object of the present invention is to provide a toner for developing an electrostatic image capable of obtaining a printed matter having both low-temperature fixability and heat-resistant storage stability and excellent dot reproducibility and long-term storage, and a method for producing the same.

  In the toner for developing an electrostatic charge image having a core-shell structure, the inventors of the present invention have a crystalline polyester (a) and an amorphous polyester (b) in the core portion, and an amorphous polyester (c) in the shell portion, respectively. When satisfying a composition containing a specific amount of a specific monomer component, an electrostatic charge image developing toner capable of obtaining a printed matter having both low-temperature fixability and heat-resistant storage stability and excellent dot reproducibility and long-term storage stability. I found it.

That is, the present invention provides the following [1] and [2].
[1] A toner for developing an electrostatic charge image having a core-shell structure, having a crystalline polyester (a) and an amorphous polyester (b) in the core portion, and an amorphous polyester (c) in the shell portion. The crystalline polyester (a) contains an alcohol component containing at least 80 mol% of an aliphatic diol having 2 to 4 carbon atoms and an acid component containing at least 80 mol% of an aliphatic saturated dicarboxylic acid having 4 to 6 carbon atoms. Is an amorphous polyester (b) obtained by polycondensing an alcohol component containing 80 mol% or more of an ethylene oxide adduct of bisphenol A and a polyvalent carboxylic acid component. The resulting amorphous polyester, wherein the amorphous polyester (c) contains 60 mol% or more of a propylene oxide adduct of bisphenol A An amorphous polyester obtained and a polycarboxylic acid component polycondensed, the toner for developing electrostatic images.
[2] The method for producing a toner for developing an electrostatic charge image according to [1], comprising the following steps (1) to (3).
Step (1): Step of aggregating resin particles (A) containing crystalline polyester (a) and amorphous polyester (b) to obtain aggregated particles (1) Step (2): Aggregated particles (1) Step of obtaining aggregated particles (2) by adding resin particles (B) containing amorphous polyester (c) to the process Step (3): Aggregated particles (1) and resin particles in aggregated particles (2) A step of fusing (B) to obtain core-shell particles

  According to the present invention, it is possible to provide an electrostatic charge image developing toner capable of obtaining a printed matter having both low-temperature fixability and heat-resistant storage stability and excellent dot reproducibility and long-term storage, and a method for producing the same.

≪Toner for electrostatic image development≫
The toner for developing an electrostatic charge image of the present invention is a toner for developing an electrostatic charge image having a core-shell structure, and has a crystalline polyester (a) and an amorphous polyester (b) in the core portion. (C) in the shell portion;
The crystalline polyester (a) includes an alcohol component containing 80 mol% or more of an aliphatic diol having 2 to 4 carbon atoms and an acid component containing 80 mol% or more of an aliphatic saturated dicarboxylic acid having 4 to 6 carbon atoms. A crystalline polyester obtained by polycondensation,
The amorphous polyester (b) is an amorphous polyester obtained by polycondensation of an alcohol component containing 80 mol% or more of bisphenol A ethylene oxide adduct and a polyvalent carboxylic acid component,
The amorphous polyester (c) is an amorphous polyester obtained by polycondensation of an alcohol component containing 60 mol% or more of a propylene oxide adduct of bisphenol A and a polyvalent carboxylic acid component.
This is a toner for developing an electrostatic image.
Hereinafter, the electrostatic image developing toner may be simply referred to as “toner”.
An alcohol component containing 80 mol% or more of an aliphatic diol having 2 to 4 carbon atoms in the crystalline polyester (a) may be referred to as “alcohol component (a-al)”. An acid component containing 4 to 6 aliphatic saturated dicarboxylic acid in an amount of 80 mol% or more is sometimes referred to as “acid component (a-ac)”.
The alcohol component containing 80 mol% or more of the ethylene oxide adduct of bisphenol A in the amorphous polyester (b) may be referred to as “alcohol component (b-al)”. The acid component may be referred to as “polycarboxylic acid component (b-ac)”.
The alcohol component containing 60 mol% or more of the propylene oxide adduct of bisphenol A in the amorphous polyester (c) may be referred to as “alcohol component (c-al)”. The acid component may be referred to as “polycarboxylic acid component (c-ac)”.

The reason why the electrostatic image developing toner of the present invention has both good low-temperature fixability and heat-resistant storage stability, and is excellent in dot reproducibility and long-term storage properties of a printed matter obtained using the toner is not clear. It is considered as follows.
The core of the toner of the present invention includes a crystalline polyester (a) having an aliphatic diol unit having 2 to 4 carbon atoms and an aliphatic saturated dicarboxylic acid unit having 4 to 6 carbon atoms, and ethylene oxide of bisphenol A. It has an amorphous polyester (b) whose main component is an adduct. These two kinds of polyesters have good compatibility with each other, so the mixing property is good, and it is considered that the crystalline polyester (a) is not unevenly distributed in the core and is included. Accordingly, at the time of fixing, the crystalline polyester (a) is melted over the entire core even in the low temperature region, so that the state of the toner can be greatly changed, and the low temperature fixing property is considered to be improved.
In addition, since the crystalline polyester (a) has a high ester group concentration and hydrophilicity, resin particles having a narrow particle size distribution can be obtained in the step of producing resin particles containing the crystalline polyester (a) in an aqueous medium. Cheap. Therefore, it is considered that the variation in the particle size of the core portion obtained from the resin particles containing the crystalline polyester (a) is suppressed without special measures such as changing conditions in the aggregation process. Further, since the shell is formed on the obtained core particles having a narrow particle size distribution, the toner particles finally obtained can be obtained without any special modifications such as agglomeration and fusion process at the time of shell formation. It is considered that the variation in the particle size is suppressed, and as a result, the dot reproducibility is improved.
Further, the shell portion of the toner of the present invention has an amorphous polyester (c) whose main unit is a propylene oxide adduct of bisphenol A, and the crystalline polyester (a) and amorphous polyester in the core. The affinity between (b) and amorphous polyester (c) is not high. Therefore, at the time of toner preparation, aggregated particles (1) containing crystalline polyester (a) and amorphous polyester (b), and resin particles containing amorphous polyester (c) covering aggregated particles (1) Even in the step of fusing (B), it is considered that the compatibilization of the aggregated particles (1) and the resin particles (B) is suppressed. Therefore, it is considered that the obtained toner has a core-shell structure and has excellent heat-resistant storage stability.
The amorphous polyester (b) and the amorphous polyester (c) both have a bisphenol skeleton. When the toner is fixed, the polyester is heated to a temperature at which these polyesters are compatibilized. Therefore, the core-shell structure is collapsed and the fixability on the recording medium is excellent. Then, since the amorphous polyesters (b) and (c) are compatibilized on the recording medium, the affinity between the crystalline polyester (a) and the amorphous polyester (b) is reduced and the crystalline polyester ( Since the recrystallization of a) proceeds, it is considered that the document offset property of the fixed image is suppressed and the long-term storage property of the printed matter is improved.
Hereinafter, each component and process used in the present invention will be described.

<Core part>
The core part in the toner for developing an electrostatic charge image of the present invention is a crystalline polyester (a) from the viewpoint of achieving both low-temperature fixability and heat-resistant storage stability of the toner, and improving dot reproducibility and long-term storage of printed matter. ) And amorphous polyester (b).

[Crystalline polyester (a)]
The crystalline polyester (a) comprises an alcohol component (a-al) containing an aliphatic diol having 2 to 4 carbon atoms in an amount of 80 mol% and an aliphatic saturated dicarboxylic acid having 4 to 6 carbon atoms in an amount of 80 mol% or more. It is a crystalline polyester obtained by polycondensation with an acid component (a-ac).
In the present invention, the crystalline polyester means 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 (° C)). The defined crystallinity index is 0.6 or more and 1.4 or less, and preferably 0.8 or more, more preferably 0.9 or more, from the viewpoint of improving the low-temperature fixability of the toner. Preferably it is 1.3 or less, More preferably, it is 1.2 or less. 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. In addition, the maximum peak temperature of endotherm refers to the temperature of the peak having the maximum peak area among endothermic peaks observed by 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 core part in the toner for developing an electrostatic charge image of the present invention is a crystalline polyester (a) from the viewpoint of achieving both low-temperature fixability and heat-resistant storage stability of the toner, and improving dot reproducibility and long-term storage of printed matter. ).
The core part may contain a crystalline polyester other than the crystalline polyester (a), but the ratio of the crystalline polyester (a) to the total amount of all the crystalline polyesters contained in the core part is From the viewpoint of achieving both low-temperature fixability and heat-resistant storage stability, and from the viewpoint of improving dot reproducibility and long-term storage properties of printed matter, it is preferably 80% by mass or more, more preferably 90% by mass or more, and still more preferably 95%. % By mass or more, still more preferably 100% by mass, still more preferably 100% by mass.

The content of the crystalline polyester (a) in the core part of the toner for developing an electrostatic charge image of the present invention is preferably 1% by mass or more in the resin constituting the core part from the viewpoint of improving the low-temperature fixability of the toner. More 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%. It is at most 30% by mass, more preferably at most 30% by mass.
The mass ratio ((a) / (b)) between the crystalline polyester (a) and the amorphous polyester (b) in the toner is the same as the viewpoint of achieving both low-temperature fixability and heat-resistant storage stability of the toner. From the viewpoint of improving dot reproducibility and long-term storage, preferably 1/99 to 50/50, more preferably 3/97 to 40/60, still more preferably 5/95 to 35/65, and still more preferably 5 / 95 to 30/70, more preferably 7/93 to 30/70.
The crystalline 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 resin particles containing the crystalline 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, a carboxyl group is preferable from the viewpoint of improving the dispersion stability of the dispersion of the resin particles (A).

The melting point of the crystalline polyester (a) 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 115 ° C. or lower, and still more preferably 110 ° C. or lower.
From the same viewpoint, the softening point of the crystalline polyester (a) is preferably 35 ° C. or higher, more preferably 40 ° C. or higher, still more preferably 45 ° C. or higher, and preferably 150 ° C. or lower, more preferably 130 ° C. ° C or lower, more preferably 120 ° C or lower, still more preferably 110 ° C or lower.
The acid value of the crystalline polyester (a) is preferably 30 mgKOH / g or less, more preferably 28 mgKOH / g, from the viewpoint of improving the dispersion stability of the dispersion of the resin particles (A) containing the crystalline polyester (a). Hereinafter, it is more preferably 27 mgKOH / g or less, preferably 5 mgKOH / g or more, more preferably 10 mgKOH / g or more, and further preferably 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 (a) can be used individually by 1 type or in combination of 2 or more types.

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

  The crystalline polyester (a) comprises an alcohol component (a-al) containing an aliphatic diol having 2 to 4 carbon atoms in an amount of 80 mol% and an aliphatic saturated dicarboxylic acid having 4 to 6 carbon atoms in an amount of 80 mol% or more. It can manufacture by making polycondensation reaction with the acid component (a-ac) containing.

The alcohol component (a-al) is an aliphatic group having 2 or more and 4 or less carbon atoms from the viewpoint of achieving both low-temperature fixability and heat-resistant storage stability of the toner and improving dot reproducibility and long-term storage properties of the printed matter. The diol is contained in the alcohol component (a-al) in an amount of 80 mol% or more, preferably 90 mol% or more, more preferably 95 mol% or more, still more preferably substantially 100 mol%, still more preferably 100 mol%. It is.
Among the aliphatic diols having 2 to 4 carbon atoms, 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, and ethylene glycol, 1,3-propane. Diols and 1,4-butanediol are preferred.

Specific examples of other aliphatic diols having 2 to 4 carbon atoms include 1,2-propanediol, 1,2-butanediol, 1,3-butanediol, 2,3-butanediol, 1,4- Examples include butenediol.
The aliphatic diol having 2 to 4 carbon atoms can be used alone or in combination of two or more.
The alcohol component (a-al) may contain an alcohol other than the aliphatic diol having 2 to 4 carbon atoms. For example, aliphatic diols other than aliphatic diols having 2 to 4 carbon atoms, aromatic diols, alicyclic diols, trivalent or higher polyhydric alcohols, or alkylene oxides having 2 to 4 carbon atoms (average addition) The number of moles is 1 or more and 16 or less). 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 1,5-pentanediol, 1,6-hexanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, and 1,12-dodecanediol. Of bisphenol A such as aliphatic diols such as polyoxypropylene-2,2-bis (4-hydroxyphenyl) propane, polyoxyethylene-2,2-bis (4-hydroxyphenyl) propane, etc. Alkylene oxide (average addition mole number 1 to 16) adduct, alicyclic diol such as hydrogenated bisphenol A, or their alkylene oxides having 2 to 4 carbon atoms (average addition mole number 2 to 12) addition products , Trivalent or higher polyvalent such as glycerin, pentaerythritol, trimethylolpropane, sorbitol Alcohol or their carbon atoms 2 to 4 alkylene oxide (average addition molar number of 1 to 16) adduct, and the like.
Another alcohol can be used individually by 1 type or in combination of 2 or more types.

The acid component (a-ac) is an aliphatic group having 4 to 6 carbon atoms from the viewpoint of achieving both low-temperature fixability and heat-resistant storage stability of the toner and improving dot reproducibility and long-term storage properties of the printed matter. The saturated dicarboxylic acid is contained in the acid component (a-ac) in an amount of 80 mol% or more, preferably 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 aliphatic saturated 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. Acid or adipic acid is preferred, and succinic acid is more preferred.

Aliphatic saturated dicarboxylic acids having 4 to 6 carbon atoms can be used singly or in combination of two or more.
The acid component (a-ac) may contain an acid other than the aliphatic saturated dicarboxylic acid having 4 to 6 carbon atoms. Other acids include dicarboxylic acids other than aliphatic saturated 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. Is 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 (a) 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 acid component (a-ac) to the alcohol component (a-al) in the crystalline polyester (a) is a dispersion of resin particles (A) containing the crystalline polyester (a). 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.

For example, the crystalline polyester (a) polycondenses the alcohol component (a-al) and the carboxylic acid component (a-ac) in an inert gas atmosphere using an esterification catalyst as necessary. Can be manufactured.
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 an acid component (a-ac) and an alcohol component (a-al), More preferably, it is 0. .1 part by mass or more, preferably 1 part by mass or less, more preferably 0.8 part by mass 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 acid component (a-ac) and alcohol component (a-al). In addition, it is preferably 0.5 parts by mass or less, more preferably 0.1 parts by mass or less.

  The polycondensation is preferably first maintained at 130 ° C. or higher and 200 ° C. or lower for 3 hours or longer and 15 hours or shorter, and then an esterification catalyst is added and maintained at 150 ° C. or higher and 220 ° C. or lower for 1 hour or longer and 5 hours or shorter. The pressure is preferably reduced to 0.0 kPa or more and 20 kPa or less and maintained for 1 hour or more and 10 hours or less.

[Amorphous polyester (b)]
The amorphous polyester (b) constitutes the core part of the toner together with the crystalline polyester (a), and contains an alcohol component (b-al) containing 80 mol% or more of bisphenol A ethylene oxide adduct and a polyvalent carboxylic acid component. It is an amorphous polyester obtained by polycondensation with (b-ac).
In the present invention, the amorphous polyester has a crystallinity index of more than 1.4 or less than 0.6, and from the viewpoint of improving the low-temperature fixability and heat-preserving stability of the toner, the amorphous polyester is 0. It is preferably less than 6 or more than 1.4 and 4 or less, more preferably 1.5 or more and 4 or less, further preferably 1.5 or more and 3 or less, and still more preferably 1.5 or more and 2 or less.

The core portion of the toner for developing an electrostatic charge image of the present invention is formed from an amorphous polyester (from the viewpoint of achieving both low-temperature fixability and heat-resistant storage stability of the toner, and improving dot reproducibility and long-term storage of printed matter. b).
The content of the amorphous polyester (b) in the core part of the toner for developing an electrostatic charge image of the present invention is preferably 50% by mass or more in the resin constituting the core part from the viewpoint of improving the heat resistant storage stability of the toner. More preferably, it is 60% by mass or more, more preferably 65% by mass or more, still more preferably 70% by mass or more, and from the viewpoint of improving the low-temperature fixability of the toner, it is preferably 99% by mass or less. Is 97% by mass or less, more preferably 95% by mass or less.
The core part may contain an amorphous polyester other than the amorphous polyester (b), but the ratio of the amorphous polyester (b) to the total amount of all the amorphous polyesters contained in the core part Is preferably 80% by mass or more, more preferably 90% by mass or more, from the viewpoint of achieving both low-temperature fixability and heat-resistant storage stability of the toner, and from the viewpoint of improving dot reproducibility and long-term storage properties of the printed matter. More preferably, it is 95 mass% or more, More preferably, it is substantially 100 mass%, More preferably, it is 100 mass%.

The total amount of the crystalline polyester (a) and the amorphous polyester (b) in the core portion of the toner for developing an electrostatic charge image of the present invention is the viewpoint of achieving both low-temperature fixability and heat-resistant storage stability of the toner, and dots of printed matter. From the viewpoint of improving reproducibility and long-term storage, the resin constituting the core portion 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 98% by mass. As described above, it is more preferably 100% by mass or more, and still more preferably 100% by mass.
The amorphous 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 amorphous 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, a carboxy group is preferable from the viewpoint of improving the dispersion stability of the dispersion of the resin particles (A).

The amorphous polyester (b) is produced by a polycondensation reaction between the acid component (b-ac) and the alcohol component (b-al) in the same manner as the crystalline 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.

  The alcohol component (b-al) of the amorphous polyester (b) is bisphenol A from the viewpoint of achieving both low-temperature fixability and heat-resistant storage stability of the toner and improving dot reproducibility and long-term storage stability of the printed matter. 80 mol% or more of the ethylene oxide adduct (polyoxyethylene-2,2-bis (4-hydroxyphenyl) propane) in the alcohol component (b-al). The content of the bisphenol A ethylene oxide adduct in the alcohol component (b-al) is preferably 90 mol% or more, more preferably 95 mol% or more, still more preferably substantially 100 mol%, still more preferably. 100 mol%. When the alcohol component (b-al) of the amorphous polyester (b) contains 80 mol% or more of an ethylene oxide adduct of bisphenol A, the affinity with the crystalline polyester (a) is improved in the core. Therefore, the crystalline polyester (a) can be encapsulated in the core without being unevenly distributed, and even during fixing at low temperature, the entire core is easily melted, and the low-temperature fixability is excellent.

  The average addition mole number of ethylene oxide of the ethylene oxide adduct of bisphenol A is preferably from the viewpoint of achieving both low-temperature fixability and heat-resistant storage stability of the toner, and from the viewpoint of improving dot reproducibility and long-term storage stability of the printed matter. 1 or more and 16 or less, more preferably 1.2 or more and 12 or less, further preferably 1.5 or more and 8 or less, and still more preferably 1.5 or more and 4 or less.

  The alcohol component (b-al) may contain an alcohol other than the ethylene oxide adduct of bisphenol A. Other alcohols that the alcohol component (b-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 (b-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, aliphatic diols such as 1,10-decanediol and 1,12-dodecanediol, aromatic diols such as bisphenol A, or alkylene oxides having 3 to 4 carbon atoms (average number of added moles of 1 to 16) ) Adducts, alicyclic diols such as hydrogenated bisphenol A, or alkylates thereof having 2 to 4 carbon atoms Oxide (average added mole number 2 to 12) adduct, glycerin, pentaerythritol, trimethylolpropane, sorbitol and other trihydric or higher polyhydric alcohols or alkylene oxides having 2 to 4 carbon atoms (average added mole number) 1 to 16)) adducts and the like.
The other alcohol which an alcohol component (b-al) may contain can be used individually by 1 type or in combination of 2 or more types.

Examples of the polyvalent carboxylic acid component (b-ac) of the amorphous polyester (b) include dicarboxylic acids, trivalent or higher polyvalent carboxylic acids, anhydrides thereof, and alkyl esters having 1 to 3 carbon atoms. Etc. 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 polyvalent carboxylic acid component (b-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 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. Among these, adipic acid is 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 (b-al) and the polyvalent carboxylic acid component (b-ac) can be used singly or in combination of two or more.

  The equivalent ratio (COOH group / OH group) of the polyvalent carboxylic acid component (b-ac) to the alcohol component (b-al) in the amorphous polyester (b) is a resin particle containing the amorphous polyester (b) ( From the viewpoint of improving the dispersion stability of the dispersion of A), 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 (b) is preferably 70 ° C. or higher, more preferably 80 ° C. or higher, further preferably 88 ° C. or higher, from the viewpoint of improving the low-temperature fixability and heat-resistant storage stability of the toner. The temperature 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 (b) is preferably 40 ° C. or higher, more preferably 42 ° C. or higher, still more preferably 45 ° C. or higher, and preferably 80 ° C. or lower, more preferably Is 70 ° C. or lower, more preferably 60 ° C. or lower.
In addition, when using 2 or more types of amorphous polyesters (b) in mixture, the glass transition temperature and softening point are described in an Example as a mixture of 2 or more types of amorphous polyesters (b), respectively. It is a value obtained by the method.
The acid value of the amorphous polyester (b) is determined from the viewpoint of improving the dispersion stability of the dispersion of the resin particles (A) containing the amorphous polyester (b), the viewpoint of improving the low-temperature fixability of the toner, and the charging property. From the viewpoint of improving the viscosity, 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. Is 15 mg KOH / g or more.

  Amorphous polyester (b) can be used individually by 1 type or in combination of 2 or more types.

(Release agent)
From the viewpoint of achieving both low-temperature fixability and heat-resistant storage stability of the toner, and improving the dot reproducibility and long-term storage properties of the printed material, it is preferable to have a release agent in the core portion.
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 dot reproducibility and long-term storage of printed matter.
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, from the viewpoint of achieving both low-temperature fixability and heat-resistant storage stability of the toner and improving dot reproducibility and long-term storage properties of the printed matter. Further, it is preferably 70 ° C. or higher, preferably 100 ° C. or lower, more preferably 90 ° C. or lower, still more preferably 85 ° C. or lower. When two or more types are used in combination, the melting point is 60 ° C. or more and 100 ° C. or less from the viewpoint of achieving both low temperature fixability and heat-resistant storage stability of the toner and improving dot reproducibility and long-term storage properties of the printed matter. Preferably there is. 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 lowest value be melting | fusing point.

  The amount of the release agent used is preferably 1 mass with respect to 100 parts by mass of the resin in the toner from the viewpoint of improving the releasability of the toner and the dot reproducibility and long-term storage of the printed matter. Part or more, preferably 2 parts by weight or more, more preferably 5 parts by weight or more, and preferably 20 parts by weight or less, more preferably 15 parts by weight or less from the viewpoint of improving the low-temperature fixability of the toner. .

(Coloring agent)
The toner of the present invention may have a colorant in either the core part or the shell part, from the viewpoint of improving the heat-resistant storage stability of the toner, and from the viewpoint of improving the dot reproducibility and long-term storability of the printed matter. It is preferable to have in the core part.
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 core part 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.

<Shell part>
The shell portion of the toner for developing an electrostatic charge image of the present invention is formed from an amorphous polyester (from the viewpoint of achieving both low-temperature fixability and heat-resistant storage stability of the toner, and improving dot reproducibility and long-term storage stability of printed matter. c).

[Amorphous polyester (c)]
The amorphous polyester (c) is an amorphous product obtained by polycondensation of an alcohol component (c-al) containing 60 mol% or more of a propylene oxide adduct of bisphenol A and a polyvalent carboxylic acid component (c-ac). Quality polyester.
The amorphous polyester (c) preferably has a crystallinity index of less than 0.6 or more than 1.4 and less than 4 from the viewpoint of improving the low-temperature fixability and heat-resistant storage stability of the toner. Preferably it is less than 0.6 or 1.5 or more and 4 or less, More preferably, it is less than 0.6 or 1.5 or more and 3 or less, More preferably, it is less than 0.6 or 1.5 or more and 2 or less. The crystallinity index can be adjusted by the type and ratio of raw material monomers, production conditions (for example, reaction temperature, reaction time, cooling rate, etc.) and the like.

The shell portion in the toner for developing an electrostatic charge image of the present invention is formed from an amorphous polyester (from the viewpoint of achieving both low-temperature fixability and heat-resistant storage stability of the toner and improving dot reproducibility and long-term storage stability of the printed matter. c).
The shell part may contain an amorphous polyester other than the amorphous polyester (c), but the ratio of the amorphous polyester (c) to the total amount of all the amorphous polyesters contained in the shell part Is preferably 80% by mass or more, more preferably 90% by mass or more, from the viewpoint of achieving both low-temperature fixability and heat-resistant storage stability of the toner, and from the viewpoint of improving dot reproducibility and long-term storage properties of the printed matter. More preferably, it is 95 mass% or more, More preferably, it is 98 mass% or more, More preferably, it is substantially 100 mass%, More preferably, it is 100 mass%.

The amorphous polyester (c) having a propylene oxide adduct of bisphenol A as a main unit is not highly compatible with the crystalline polyester (a) and the amorphous polyester (b) in the core portion described above. Therefore, when the toner is produced, the aggregated particles (1) containing the crystalline polyester (a) and the amorphous polyester (b) and the resin particles containing the amorphous polyester (c) covering the aggregated particles (1) ( Even in the step of fusing B), it is considered that the compatibilization of the aggregated particles (1) and the resin particles (B) is suppressed, and that the obtained toner maintains the core-shell structure to improve the heat-resistant storage stability. It is done. The amorphous polyester (b) and the amorphous polyester (c) both have a bisphenol skeleton and are heated to a temperature at which these polyesters become compatible when fixing the toner, so that the core-shell structure collapses. In addition, the fixability on the recording medium is improved. At the same time, since the amorphous polyesters (b) and (c) are compatibilized on the recording medium, the affinity between the crystalline polyester (a) and the amorphous polyester (b) is reduced, so that the crystalline polyester ( It is considered that the recrystallization of a) proceeds, and as a result, the document offset property of the fixed image is suppressed and the printed matter is excellent in long-term storage.
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 resin particles 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, a carboxy group is preferable from the viewpoint of improving the dispersion stability of the dispersion of the resin particles (B).

  The amorphous polyester (c) is obtained by subjecting a polyvalent carboxylic acid component (c-ac) and an alcohol component (c-al) to a polycondensation reaction in the same manner as the crystalline polyester (a). Can be manufactured. For example, the alcohol component (c-al) and the polyvalent carboxylic acid component (c-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.

  The alcohol component (c-al) of the amorphous polyester (c) is bisphenol A from the viewpoint of achieving both low-temperature fixability and heat-resistant storage stability of the toner, and improving dot reproducibility and long-term storage stability of the printed matter. The propylene oxide adduct (polyoxypropylene-2,2-bis (4-hydroxyphenyl) propane) is contained in the alcohol component (c-al) in an amount of 60 mol% or more. The content of the propylene oxide adduct of bisphenol A in the alcohol component (c-al) is preferably 65 mol% or more from the viewpoint of improving the low-temperature fixability of the toner and the dot reproducibility of the printed matter. More preferably, it is 75 mol% or more, More preferably, it is 85 mol% or more, More preferably, it is 95 mol% or more. Further, from the viewpoint of improving the heat resistant storage stability of the toner and improving the long-term storage stability of the printed matter, it is preferably 100 mol% or less, more preferably 95 mol% or less, still more preferably 85 mol% or less, and even more preferably. Is 75 mol% or less. In summary, the content of the propylene oxide adduct of bisphenol A in the alcohol component (c-al) is compatible with both low-temperature fixability and heat-resistant storage stability of the toner, as well as dot reproducibility and long-term storage of the printed matter. From the viewpoint of improving the properties, it is preferably at least 65 mol%, more preferably at least 75 mol%, preferably at most 100 mol%, more preferably at most 95 mol%, still more preferably at most 85 mol%. is there.

  The average number of moles of propylene oxide added to the propylene oxide adduct of bisphenol A is preferably from the viewpoint of achieving both low-temperature fixability and heat-resistant storage stability of the toner, and from the viewpoint of improving dot reproducibility and long-term storage properties of printed matter. 1 or more and 16 or less, more preferably 1.2 or more and 12 or less, further 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 an alcohol other than the propylene 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 or ethylene oxide adducts thereof (average added mole number of 1 to 16), cyclohexanediol, Cycloaliphatic diols such as cyclohexanedimethanol, hydrogenated bisphenol A or the like Alkylene oxide having 2 to 4 carbon atoms (average added mole number 2 to 12) adduct, trihydric or higher polyhydric alcohol such as glycerin, pentaerythritol, trimethylolpropane, sorbitol, or those having 2 to 4 carbon atoms Alkylene oxide (average added mole number 1 to 16) adducts and the like.
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 polyvalent 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, and it is more preferable to use dicarboxylic acid and 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 polyvalent 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 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.
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 low-temperature fixability and heat-resistant storage 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 polyvalent carboxylic acid component (c-ac) to the alcohol component (c-al) in the amorphous polyester (c) is the resin particle containing the amorphous polyester (c) ( From the viewpoint of improving the dispersion stability of the dispersion of B), 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 low-temperature fixability and heat-resistant storage stability of the toner. The temperature 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 70 ° C. or lower, more preferably 65 ° 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 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. Is 35 mgKOH / 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.

  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.

  The core portion and the shell portion may contain a resin other than polyester, for example, a resin such as a styrene-acrylic copolymer, an epoxy resin, a polycarbonate, or a polyurethane as long as the effects of the present invention are not impaired.

  To the electrostatic charge developing toner of the present invention, a charge control agent, a reinforcing filler such as a fibrous substance, an antioxidant, an anti-aging agent, etc. are added as necessary within the range not impairing the effects of the present invention. An agent or the like may be included.

<< Method for producing toner for developing electrostatic image >>
The method for producing an electrostatic charge image developing toner of the present invention includes the following steps (1) to (3).
Step (1): Step of aggregating resin particles (A) containing crystalline polyester (a) and amorphous polyester (b) to obtain aggregated particles (1) Step (2): Aggregated particles (1) Step of obtaining aggregated particles (2) by adding resin particles (B) containing amorphous polyester (c) to the process Step (3): Aggregated particles (1) and resin particles in aggregated particles (2) Step of fusing (B) to obtain core-shell particles Hereinafter, each component and step used in the production method will be described.

<Step (1)>
Step (1): A step of aggregating the resin particles (A) containing the crystalline polyester (a) and the amorphous polyester (b) to obtain aggregated particles (1).
In step (1), mainly
i) mixing a component containing crystalline polyester (a) and amorphous polyester (b) to obtain a resin mixture;
ii) adding an aqueous medium to the resin mixture to obtain a dispersion in which the resin particles (A) are dispersed;
iii) a step of aggregating the resin particles (A) in the dispersion containing the resin particles (A) to obtain a dispersion containing the aggregated particles (1).
Note that iii) a step of aggregating the resin particles (A) in the dispersion containing the resin particles (A) to obtain a dispersion containing the agglomerated particles (1) may be referred to as “aggregation step (1)”.

[Resin particles (A)]
The resin particles (A) contain a crystalline polyester (a) and an amorphous polyester (b).
The mass ratio of the crystalline polyester (a) and the amorphous polyester (b) in the resin particles (A) is the viewpoint of achieving both low-temperature fixability and heat-resistant storage stability of the toner, as well as dot reproducibility and long-term printing. From the viewpoint of improving storage properties, preferably 1/99 to 50/50, more preferably 3/97 to 40/60, still more preferably 5/95 to 35/65, and even more preferably 5/95 to 30 /. 70, more preferably 7/93 to 30/70.
The total content of the crystalline polyester (a) and the amorphous polyester (b) in the resin constituting the resin particles (A) is compatible with the low-temperature fixability and heat-resistant storage stability of the toner, and the dot reproduction of the printed matter. From the viewpoint of improving the property and long-term storage properties, the resin constituting 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. It is 98 mass% or more, More preferably, it is substantially 100 mass%, More preferably, it is 100 mass%.
A resin particle (A) is a dispersion containing resin particles (A) by dispersing the above-mentioned optional components such as a resin containing a crystalline polyester (a) and an amorphous polyester (b) and a colorant in an aqueous medium. It is preferable to manufacture by the method obtained as a liquid.

The aqueous medium is preferably composed mainly of water, and the content of water in the aqueous medium is preferably 80 from the viewpoint of improving the dispersion stability of the dispersion of the resin particles (A) and the environmental aspect. More preferably, it is 90 mass% or more, More preferably, it is 95 mass% or more, More preferably, it is substantially 100 mass%, More preferably, it is 100 mass%. As water, deionized water or distilled water is preferably used.
Components other than water that can form an aqueous medium together with water include alkyl alcohols having 1 to 5 carbon atoms; dialkyl ketones having 1 to 3 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.

  As a method of obtaining a dispersion of resin particles (A), a method of adding a resin or the like to an aqueous medium and performing a dispersion treatment with a disperser or the like, a method of gradually adding an aqueous medium to a resin or the like and performing phase inversion emulsification From the viewpoint of improving the low-temperature fixability of the obtained toner, a method using phase inversion emulsification is preferable. Hereinafter, a method by phase inversion emulsification will be described.

First, the resin component containing the crystalline polyester (a) and the amorphous polyester (b) and, if necessary, the above optional components such as a surfactant and a colorant are melted and mixed to obtain a resin mixture. Get.
Crystalline polyester (a), amorphous polyester (b), and any other resin previously mixed may be used, but when other components are added, they are added simultaneously and melted and mixed. The resin mixture may be obtained.

  As a method for obtaining a resin mixture, crystalline polyester (a), amorphous polyester (b), and any other resin, surfactant, colorant and other optional components described above, and a basic aqueous solution in a container A method of melting and mixing the resin while stirring with a stirrer is preferable.

  Further, at the time of mixing, it is preferable to add a surfactant from the viewpoint of improving the dispersion stability of the resin.

Examples of the surfactant include a nonionic surfactant, an anionic surfactant, and a cationic surfactant. From the viewpoint of improving the dispersion stability of the dispersion of the resin particles (A), the surfactant is nonionic. A surfactant is preferable, a nonionic surfactant and an anionic surfactant or a cationic surfactant are more preferably used in combination, and a nonionic surfactant and an anionic surfactant are used in combination. Is more preferable.
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 dispersion of the resin particles (A), 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 polyoxyethylene alkyl aryl ethers include polyoxyethylene nonylphenyl ether, and specific examples of polyoxyethylene alkyl or alkenyl ethers include polyoxyethylene oleyl ether, polyoxyethylene lauryl ether, and the like. Is mentioned. 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 the resin particles (A).

Examples of the anionic surfactant include alkylbenzene sulfonates, alkyl sulfates, alkyl ether sulfates, etc. From the viewpoint of improving the dispersion stability of the dispersion of the resin particles (A), alkylbenzene sulfonates, alkyls Ether sulfate 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.

  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 15 parts by mass or less, with respect to 100 parts by mass of the resin component constituting the resin particles (A) from the viewpoint of improving the heat resistant storage stability of the toner. Further, more preferably 10 parts by mass or less, still more preferably 5 parts by mass or less, and from the viewpoint of improving the dispersion stability of the dispersion of the resin particles (A), preferably 0.5 parts by mass or more, more Preferably it is 1 mass part or more, More preferably, it is 2 mass parts or more.
The “resin component constituting the resin particles (A)” includes the crystalline polyester (a) and the amorphous polyester (b), and other resins that may optionally be included.

Examples of the basic compound used in the basic aqueous solution include inorganic basic compounds and organic basic compounds.
Examples of inorganic base compounds include hydroxides of alkali metals such as potassium, sodium and lithium, as well as carbonates and bicarbonates. Specific examples thereof include sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, Examples thereof include sodium hydrogen carbonate and potassium hydrogen carbonate. Ammonia is also mentioned. Organic bases include alkanolamines such as diethylethanolamine. From the viewpoint of improving the dispersion stability of the dispersion of the resin particles (A) and from the viewpoint of improving the charging stability of the toner, sodium hydroxide, potassium hydroxide, sodium carbonate, and potassium carbonate are preferred, and potassium hydroxide is preferred. More preferred.

  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 dispersion of the resin particles (A). Further, it is preferably 30% by mass or less, more preferably 25% by mass or less, and further preferably 20% by mass or less.

  The temperature at which the resin is melted and mixed is preferably equal to or higher than the melting point of the crystalline polyester (a) and more preferably equal to or higher than the glass transition temperature of the amorphous polyester (b) from the viewpoint of obtaining uniform resin particles. When the melting point of the crystalline polyester (a) exceeds the boiling point of water, the crystalline polyester (a), the amorphous polyester (b), and any other resin are previously melt-mixed without using an aqueous medium. Then, it is preferable to add aqueous solution components such as a surfactant and a basic aqueous solution and mix them 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 (A).

  The temperature at which the aqueous medium is added constitutes the resin particles (A) from the viewpoint of improving the dispersion stability of the dispersion of the resin particles (A), and improving the low-temperature fixability and heat-resistant storage stability of the toner. It is preferably at least the glass transition temperature of the resin, and preferably below the boiling point of the aqueous medium used in step (1). 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 (A), and improving the low-temperature fixability and heat-resistant storage stability of the toner, the addition speed of the aqueous medium is not limited until the phase inversion is completed. Preferably, it is 0.1 parts by mass or more, more preferably 0.5 parts by mass or more, and preferably 50 parts by mass or less, with respect to 100 parts by mass of the resin component constituting A). More preferably, it is 30 mass parts / min or less, More preferably, it is 10 mass parts / min or less, More preferably, it is 5 mass parts / min or less. There is no restriction | limiting in the addition speed | rate of the aqueous medium after the resin phase is obtained after phase inversion.
The amount of the aqueous medium used is 100 parts by mass of the resin component constituting the resin particles (A) from the viewpoint of improving the productivity of the toner and obtaining uniform aggregated particles (1) in the subsequent aggregation step (1). On the other hand, it is preferably 50 parts by mass or more, more preferably 100 parts by mass or more, still more preferably 150 parts by mass or more, and preferably 900 parts by mass or less, more preferably 500 parts by mass or less, still more preferably 300 parts by mass. Or less.

  The solid content concentration of the resulting dispersion of the resin particles (A) is preferably 10% by mass or more from the viewpoint of improving the productivity of the toner and the dispersion stability of the dispersion of the resin particles (A). More preferably, it is 20 mass% or more, More preferably, it is 25 mass% or more, Preferably it is 50 mass% or less, More preferably, it is 40 mass% or less, More preferably, it is 35 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 (A) in the dispersion of the resin particles (A) is preferably 0.05 μm or more, more preferably from the viewpoint of obtaining a toner capable of obtaining a high-quality image. It is 0.08 μm or more, more preferably 0.10 μm or more, preferably 0.50 μm or less, more preferably 0.40 μm or less, and still more preferably 0.30 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.
The coefficient of variation (CV value) (%) of the particle size distribution of the resin particles (A) is preferably 50% or less, more preferably 45% or less, from the viewpoint of obtaining a toner capable of obtaining a high-quality image. Preferably it is 40% or less. Further, from the viewpoint of improving the productivity of the dispersion liquid of the resin particles (A), it is preferably 5% or more, more preferably 10% or more, and further 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

(Release agent particles)
In the step (1), the release agent particles may be aggregated together with the resin particles (A) to obtain aggregated particles (1).

(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 at a temperature equal to or higher than the melting point of the release agent in the presence of a surfactant or a resin emulsion. Is preferred. As the disperser to be used, a homogenizer, an ultrasonic disperser and the like are preferable from the viewpoint of achieving both low-temperature fixability and heat-resistant storage stability of the toner, and improving dot reproducibility and long-term storage properties of the printed matter.
Examples of the ultrasonic disperser include an ultrasonic homogenizer. Commercially available products include “US-150T”, “US-300T”, “US-600T” (manufactured by Nippon Seiki Seisakusho), SONIFIER 4020-400, SONIFIER 4020-800 (manufactured by Branson; SONIFIER is a registered trademark) ) And the like.
Moreover, 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 before using the disperser.
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 (A).

In the present invention, from the viewpoint of achieving both low-temperature fixability and heat-resistant storage stability of the toner, and from the viewpoint of improving the dot reproducibility and long-term storage properties of the printed matter, the dispersion of the release agent particles in the aqueous medium is performed by releasing the mold. After mixing the agent and the oxazoline group-containing polymer, it is preferable to mix and emulsify the resin emulsion 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, and the polar oxazoline group becomes a dispersion group in an 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.

From the viewpoint of ease of production of the resin emulsion, a surfactant may be used as necessary. 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 the resin content with respect to 100 parts by mass of the release agent from the viewpoint of improving the aggregation property of the release agent particles at the time of toner preparation and preventing the release. The amount is preferably 1 part by mass or more, more preferably 2 parts by mass or more, and even more preferably 3 parts by mass or more. From the viewpoint of improving the low-temperature fixability of the toner, preferably 15 parts by mass or less, more preferably 10 parts by mass. It is as follows.

From the viewpoint of improving the productivity of the toner and the dispersion stability of the release agent particle dispersion, the solid content concentration of the dispersion of the release agent particles is preferably 5% by mass or more, more preferably 10% by mass. % Or more, more preferably 15% by mass or more, preferably 40% by mass or less, more preferably 30% by mass or less, and further preferably 25% by mass or less. 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 determined from the viewpoint of obtaining uniform aggregated particles (1) in the subsequent aggregation step (1), the viewpoint of achieving both low-temperature fixability and heat-resistant storage stability of the toner, From the viewpoint of improving the dot reproducibility and long-term storage properties of the printed material, the thickness is preferably 100 nm or more, more preferably 200 nm or more, and preferably 1 μm or less, more preferably 700 nm or less, and even more preferably 600 nm or less.
The CV value of the release agent particles is preferably 50% or less, more preferably 40, from the viewpoint of obtaining uniform aggregated particles (1) in the subsequent aggregation step (1) and improving the charging stability of the toner. % Or less, more preferably 35% or less, and 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 (1)]
Aggregated particles (1) can be produced by an aggregation step (1) in which the resin particles (A) in the dispersion containing the resin particles (A) are aggregated to obtain a dispersion containing the aggregated particles (1).
In the aggregation step (1), the resin particles (A) and, if necessary, optional components such as an aggregating agent, a releasing agent particle, a surfactant, and a colorant are aggregated in an aqueous medium to obtain aggregated particles. Can do.
In this step, it is preferable to first obtain a mixed dispersion by mixing the dispersion of resin particles (A) and the dispersion of release agent particles in an aqueous medium.
In addition, when a colorant is not mixed in the resin particles (A), it is preferable to mix a colorant in the mixed dispersion.
Further, resin particles other than the resin particles (A) 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) include resin particles (A) and release agent particles from the viewpoint of achieving both low-temperature fixability and heat-resistant storage stability of the toner, and from the viewpoint of improving dot reproducibility and long-term storage properties of the printed matter. In the mixed dispersion, it is preferably 10% by mass or more, more preferably 20% by mass or more, and preferably 40% by mass or less from the viewpoint of controlling aggregation and obtaining aggregated particles (1) having a desired particle size. More preferably, it is 35 mass% or less.

  From the viewpoint of controlling aggregation and obtaining aggregated particles (1) having a desired particle size, the aqueous medium is preferably 60% by mass or more, more preferably in a mixed dispersion containing resin particles (A) and release agent particles. Is 65% by mass or more, and is preferably 90% by mass or less, more preferably 80% by mass or less, from the viewpoint of improving the productivity of the toner.

From the viewpoint of improving the releasability of the toner, from the viewpoint of achieving both low temperature fixability and heat-resistant storage stability of the toner, and from the viewpoint of improving the dot reproducibility and long-term storability of the printed matter, A) It is preferably 1 part by mass or more, more preferably 1.5 parts by mass or more, and still more preferably 2 parts by mass or more with respect to 100 parts by mass, and preferably from the viewpoint of improving the low temperature fixability of the toner Is 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 more and 40 ° C. or less from the viewpoint of controlling aggregation and obtaining aggregated particles (1) having a desired particle size.

  Next, the particles in the mixed dispersion are aggregated to obtain a dispersion of aggregated particles (1). From the viewpoint of efficiently performing the aggregation, it is preferable to add an aggregating agent.

(Flocculant)
The flocculant is preferably an electrolyte, and more preferably a salt, from the viewpoint of obtaining a toner having a desired particle diameter while preventing excessive aggregation.
Examples of the aggregating agent include a quaternary salt cationic surfactant, an organic aggregating agent such as polyethyleneimine; an inorganic aggregating agent such as an inorganic metal salt, an inorganic ammonium salt, and a bivalent or higher metal complex. From the viewpoint of improving the aggregation property and obtaining uniform aggregated particles (1), an inorganic flocculant is preferable, an inorganic metal salt and an inorganic ammonium salt are more preferable, and an inorganic ammonium salt is further preferable.
The valence of the cation of the inorganic flocculant is preferably from 1 to 5 and more preferably from 1 to 2 and more preferably from the viewpoint of obtaining a toner having a desired particle size while preventing excessive aggregation. Is monovalent.

Examples of the monovalent cation of the inorganic flocculant include sodium ion, potassium ion, ammonium ion, etc., from the viewpoint of achieving both low-temperature fixability and heat-resistant storage stability of the toner, as well as dot reproducibility and long-term storage properties of the printed matter. From the viewpoint of improving the pH, ammonium ions are preferred.
Examples of the inorganic metal salt include metal salts such as sodium sulfate, sodium nitrate, sodium chloride, calcium chloride, and calcium nitrate, and inorganic metal salt polymers such as polyaluminum chloride and polyaluminum hydroxide.
Examples of inorganic ammonium salts include ammonium sulfate, ammonium chloride, and ammonium nitrate.
As the flocculant, ammonium sulfate is more preferable.

  The amount of the flocculant used is 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, and from the viewpoint of improving dot reproducibility and long-term storage of printed matter. Is preferably 50 parts by mass or less, more preferably 45 parts by mass or less, and still more preferably 40 parts by mass or less. Further, from the viewpoint of controlling the aggregation of the resin particles to obtain a desired particle size, it is preferably 5 parts by mass or more, more preferably 10 parts by mass or more, and further preferably 20 parts by mass or more.

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 (1) 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% from the viewpoint of controlling aggregation and obtaining aggregated particles (1) having a desired particle size. It is not more than mass%, more preferably not more than 30 mass%, still more preferably not more than 20 mass%, still more preferably not more than 10 mass%.

The dropping time of the aggregating agent is preferably 1 minute or more, more preferably 5 minutes or more from the viewpoint of obtaining aggregation particles (1) having a desired particle size by controlling aggregation, and also improves toner productivity. From the viewpoint of making it possible, it is preferably 120 minutes or less, more preferably 60 minutes or less, still more preferably 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. From the viewpoint of obtaining 1), it is preferably 50 ° C. or lower, more preferably 40 ° C. or lower, and further preferably 30 ° C. or lower.

  Furthermore, from the viewpoint of promoting aggregation and obtaining aggregated particles (1) having a desired particle size and particle size distribution, it is preferable to increase the temperature of the dispersion after adding the flocculant. As a temperature to maintain, it is preferable that it is 50 degreeC or more and the temperature below melting | fusing point of crystalline polyester. It is preferable to confirm the progress of aggregation by monitoring the volume median particle size of the aggregated particles (1) in the temperature range. The lower limit temperature is preferably 50 ° C. or higher, more preferably 51 ° C. or higher, from the viewpoint of achieving both low-temperature fixability and heat-resistant storage stability of the toner, and improving dot reproducibility and long-term storage properties of the printed matter. Preferably it is 52 degreeC or more.

The volume-median particle size (D ₅₀ ) of the obtained aggregated particles (1) is from the viewpoint of achieving both low-temperature fixability and heat-resistant storage stability of the toner, and from the viewpoint of improving dot reproducibility and long-term storage properties of the printed matter. The thickness is preferably 2 μm or more, more preferably 3 μm or more, further preferably 4 μm or more, 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.
Further, the CV value of the aggregated particles (1) is preferably 50% or less, more preferably 40% or less, still more preferably 30% or less, from the viewpoint of obtaining a toner capable of obtaining a high-quality image. Is 5% or more, more preferably 10% or more, and 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 (nm) / volume average particle size (nm)] × 100

<Step (2)>
Step (2) is a step in which the aggregated particles (1) obtained in the step (1) are aggregated with the resin particles (B) containing the amorphous polyester (c) to obtain aggregated particles (2). is there.
In step (2), mainly
iv) mixing the component containing amorphous polyester (c) to obtain a mixture;
v) adding an aqueous medium to the mixture to obtain a dispersion in which the resin particles (B) are dispersed;
vi) Aggregation in which the dispersion liquid containing the agglomerated particles (1) obtained in the step (1) and the dispersion liquid containing the resin particles (B) are mixed to adhere the resin particles (B) to the agglomerated particles (1). Obtaining particles (2).
Vi) The dispersion containing the aggregated particles (1) obtained in step (1) and the dispersion containing the resin particles (B) are mixed to attach the resin particles (B) to the aggregated particles (1). The step of obtaining the aggregated particles (2) may be referred to as “aggregation step (2)”.

[Resin particles (B)]
The resin particles (B) contain amorphous polyester (c).
In addition to the amorphous polyester (c), the resin particles (B) are non-phased with an amorphous polyester other than the amorphous polyester (c), the crystalline polyester (a) and the amorphous polyester (b). You may contain other resin components other than soluble crystalline polyester and polyester.
The content of the amorphous polyester (c) in the resin component constituting the resin particles (B) improves the low-temperature fixability and heat-resistant storage stability of the toner, and improves the dot reproducibility and long-term storage of printed matter. In view of the above, the resin constituting the resin particles (B) is preferably 80% by mass or more, more preferably 90% by mass or more, still more preferably 95% by mass or more, still more preferably 98% by mass or more, and still more. Preferably it is 100 mass% substantially, More preferably, it is 100 mass%.

[Production of resin particles (B)]
The resin particles (B) are obtained by dispersing a resin component containing the amorphous polyester (c) and, if necessary, an optional component such as a surfactant in an aqueous medium. It is preferable to manufacture by the method obtained as follows.
As with the resin particles (A), the dispersion is obtained by adding a resin or the like to an aqueous medium and dispersing using a disperser, or by gradually adding the aqueous medium to the resin or the like and emulsifying the emulsion. From the viewpoint of improving the low-temperature fixability of the obtained toner, the phase inversion emulsification method is preferable.

  First, the resin component containing amorphous polyester (c) and, if necessary, the above-mentioned optional components such as a surfactant and a colorant are melted and mixed to obtain a mixture.

  As a method for obtaining a mixture, the resin component containing amorphous polyester (c), the above-mentioned optional components such as a surfactant and a colorant, and a basic aqueous solution are put in a container, and the resin is stirred with a stirrer. A method of melting and mixing these is preferred.

  As the surfactant, the surfactants exemplified in the aforementioned “resin particles (A)” can be used. 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 dispersion of the resin particles (B), it is preferably 0.3 or more, more preferably 0.5 or more, and preferably 10 or less, more preferably 5 or less.

The addition amount of the surfactant is preferably 20 parts by mass or less, more preferably 10 parts by mass or less, from the viewpoint of improving the heat resistant storage stability of the toner with respect to 100 parts by mass of the resin component constituting the resin particles (B). More preferably, it is 5 parts by mass or less, and from the viewpoint of improving the dispersion stability of the dispersion of the resin particles (B), preferably 0.5 parts by mass or more, more preferably 1 part by mass or more, still more preferably. Is 2 parts by mass or more.
In addition, "the resin component which comprises the resin particle (B)" contains the amorphous polyester (c) and the other resin which can be included arbitrarily.

  As the basic compound used in the basic aqueous solution, the basic compounds exemplified in the aforementioned “resin particles (A)” can be used.

  The temperature for melting and mixing the resin is preferably equal to or higher than the glass transition temperature of the amorphous polyester (c) from the viewpoint of obtaining homogeneous resin particles.

  Next, an aqueous medium is added to the above mixture, and phase inversion is performed to obtain a dispersion containing resin particles (B).

  The temperature at which the aqueous medium is added constitutes the resin particles (B) from the viewpoint of improving the dispersion stability of the dispersion of the resin particles (B), and improving the low-temperature fixability and heat-resistant storage stability of the toner. It is preferably at least the glass transition temperature of the resin and below the boiling point of the aqueous medium. 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 (B), and improving the low-temperature fixability and heat-resistant storage stability of the toner, the addition rate of the aqueous medium is not limited until the phase inversion is completed. Preferably, it is 0.1 parts by weight or more, more preferably 0.5 parts by weight or more, and preferably 50 parts by weight or less, with respect to 100 parts by weight of the resin component constituting B). More preferably, it is 30 mass parts / min or less, More preferably, it is 10 mass parts / min or less, More preferably, it is 5 mass parts / min or less. There is no restriction | limiting in the addition speed | rate of the aqueous medium after the resin phase is obtained after phase inversion.
The amount of the aqueous medium used is based on 100 parts by mass of the resin component constituting the resin particles (B) from the viewpoint of improving toner productivity and obtaining uniform aggregated particles (2) in the aggregation step (2). , Preferably 50 parts by mass or more, more preferably 100 parts by mass or more, still more preferably 150 parts by mass or more, and preferably 900 parts by mass or less, more preferably 500 parts by mass or less, still more preferably 300 parts by mass or less. It is.

  The solid content concentration of the obtained dispersion of the resin particles (B) is preferably 7% by mass or more from the viewpoint of improving the productivity of the toner and the dispersion stability of the dispersion of the resin particles (B). More preferably, it is 10 mass% or more, More preferably, it is 20 mass% or more, Preferably it is 50 mass% or less, More preferably, it is 40 mass% or less, More preferably, it is 35 mass% or less. In addition, solid content is the total amount of non-volatile components, such as resin and surfactant.

The volume median particle size (D ₅₀ ) of the resin particles (B) in the dispersion of the resin particles (B) is preferably 0.05 μm or more, more preferably from the viewpoint of obtaining a toner capable of obtaining a high-quality image. It is 0.08 μm or more, more preferably 0.10 μm or more, preferably 0.50 μm or less, more preferably 0.40 μm or less, and still more preferably 0.30 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.
The coefficient of variation (CV value) (%) of the particle size distribution of the resin particles (B) is preferably 50% or less, more preferably 45% or less, from the viewpoint of obtaining a toner capable of obtaining a high-quality image. Preferably it is 40% or less. Further, from the viewpoint of improving the productivity of the dispersion of the resin particles (B), it is preferably 5% or more, more preferably 10% or more, and further 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

[Production of Aggregated Particles (2)]
In the step (2), the resin particles (B) are further adhered to the aggregated particles (1) by adding a dispersion containing the resin particles (B) to the dispersion of the aggregated particles (1) described above. It is preferable to obtain a dispersion of particles (2).

  Before adding the dispersion of resin particles (B) to the dispersion of aggregated particles (1), an aqueous medium may be added to the dispersion of aggregated particles (1) for dilution. Further, when the dispersion of resin particles (B) is added to the dispersion of aggregated particles (1), the aggregating agent is added to the aggregated particles (1) in order to efficiently adhere the resin particles (B) to the aggregated particles (1). May be used.

As a preferable addition method in the case of adding the dispersion liquid of the resin particles (B) to the dispersion liquid of the aggregated particles (1), a method of simultaneously adding the aggregation liquid and the dispersion liquid of the resin particles (B), the aggregating agent and the resin Examples thereof include a method of alternately adding a dispersion of particles (B) and a method of adding a dispersion of resin particles (B) while gradually increasing the temperature of the dispersion of aggregated particles (1). By doing in this way, the cohesiveness fall of the aggregated particle (1) and the resin particle (B) by the density | concentration fall of a coagulant | flocculant can be prevented. From the viewpoint of improving the productivity of the toner and from the viewpoint of easy production, it is preferable to add the dispersion of the resin particles (B) while gradually increasing the temperature of the aggregated particles (1).
The temperature at the time of dropping is preferably 40 ° C. or higher, more preferably 45 ° C. or higher, from the viewpoint of achieving both low-temperature fixability and heat-resistant storage stability of the toner, and from the viewpoint of improving dot reproducibility and long-term storage of the printed matter More preferably, it is 50 degreeC or more, Preferably it is 80 degrees C or less, More preferably, it is 70 degrees C or less, More preferably, it is 65 degrees C or less.

The addition amount of the resin particles (B) is selected from the viewpoints of achieving both low-temperature fixability and heat-resistant storage stability of the toner and improving dot reproducibility and long-term storage properties of the printed matter. The mass ratio (resin particles (B) / resin particles (A)) to A) is preferably 0.1 or more, more preferably 0.15 or more, still more preferably 0.2 or more, and still more preferably 0.00. It is 25 or more, preferably 0.9 or less, more preferably 0.7 or less, still more preferably 0.6 or less, and still more preferably 0.5 or less.
The effect of the core portion of the toner of the present invention in which the crystalline polyester (a) and the amorphous polyester (b) are mixed by adding a small amount of the resin particles (B) compared to the resin particles (A). It can be fully expressed, and both low-temperature fixability and heat-resistant storage stability can be achieved.

  The dispersion of the resin particles (B) may be added continuously over a certain period of time, may be added at a time, or may be added in multiple portions. It is preferable to add continuously over several times or to divide and add several times. By adding as described above, the resin particles (B) are likely to selectively adhere to the aggregated particles (1). Among these, from the viewpoint of promoting selective adhesion and improving the productivity of toner, it is preferable to add continuously over a certain period of time. The time for continuous addition is preferably 1 hour or longer and 10 hours or shorter, more preferably 2 hours or longer and 7 hours or shorter from the viewpoint of obtaining uniform aggregated particles (2) and improving the productivity of the toner.

The volume-median particle size (D ₅₀ ) of the obtained aggregated particles (2) is determined from the viewpoint of obtaining a toner capable of obtaining a high-quality image, the viewpoint of achieving both low-temperature fixability and heat-resistant storage stability of the toner, and printed dots From the viewpoint of improving reproducibility and long-term storage, it is preferably at least 2 μm, more preferably at least 3 μm, even more preferably at least 4 μm, preferably at most 10 μm, more preferably at most 8 μm, even more preferably at most 6 μm. is there.
The volume median particle size is measured by the method described in the examples.
Further, the CV value of the agglomerated particles (2) is preferably 50% or less, more preferably 40% or less, still more preferably 30% or less, from the viewpoint of obtaining a toner capable of obtaining a high-quality image. Is 5% or more, more preferably 10% or more, and 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 (nm) / volume average particle size (nm)] × 100

The total amount of the resin particles (B) may be added, and aggregation may be stopped when the toner particles have grown to an appropriate particle size.
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 reliably preventing unnecessary aggregation, a method of stopping aggregation by adding an aggregation stopper is preferable.

As the aggregation terminator, a surfactant is preferable, and an anionic surfactant is more preferable. Examples of the anionic surfactant include alkylbenzene sulfonate, alkyl sulfate, alkyl ether sulfate, polyoxyalkylene alkyl ether sulfate, and the like, preferably polyoxyalkylene alkyl ether sulfate, more preferably polyoxyalkylene alkyl ether sulfate. Oxyethylene lauryl ether sulfate.
An aggregation terminator can be used individually by 1 type or in combination of 2 or more types.
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 resin in the toner, from the viewpoint of reliably 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.

<Step (3)>
Step (3) is a step of obtaining core-shell particles by fusing the agglomerated particles (1) and the resin particles (B) in the agglomerated particles (2) obtained in step (2).
In the aggregated particles (2), the particles that are mainly physically attached to each other are fused and united to form toner particles having a core-shell structure.

In this step, from the viewpoint of improving the fusibility of the agglomerated particles (1), from the viewpoint of achieving both low-temperature fixability and heat-resistant storage stability of the toner, and from the viewpoint of improving dot reproducibility and long-term storage properties of the printed matter, It is held at a temperature equal to or higher than the glass transition temperature of amorphous polyester (c).
At that time, the holding time at a temperature equal to or higher than the glass transition temperature of the amorphous polyester (c) improves the low-temperature fixability and heat-resistant storage stability of the toner, and improves dot reproducibility and long-term storage of the printed matter. From the viewpoint of making it preferable, it is preferably 1 minute or more, more preferably 10 minutes or more, further preferably 30 minutes or more, preferably 240 minutes or less, more preferably 180 minutes or less, still more preferably 120 minutes or less, and still more Preferably it is 90 minutes or less.

The volume-median particle size (D ₅₀ ) of the core-shell particles obtained in the step (3) is a viewpoint that achieves both low-temperature fixability and heat-resistant storage stability of the toner, and a viewpoint that improves dot reproducibility and long-term storability of the printed matter. Therefore, it is preferably 2 μm or more, more preferably 3 μm or more, further preferably 4 μm or more, and preferably 10 μm or less, more preferably 8 μm or less, still more preferably 6 μm or less.
In addition, it is preferable that the volume median particle size of the core-shell particles obtained in the step (3) is not more than the volume median particle size of the aggregated particles (2). That is, in this step (3), it is preferable that aggregation and fusion between the aggregated particles (2) do not occur.
Moreover, the mass ratio (core / shell ratio) of the resin in the core and the resin in the shell of the core-shell particles obtained in this step is preferably 90/10 to 53/47, more preferably 87/13 to 60/40, more preferably 83/17 to 63/37, still more preferably 80/20 to 67/33.

(Post-processing process)
In the present invention, a post-treatment step may be performed after step (3), and it is preferable to obtain toner particles by isolation.
Since the core-shell particles obtained in the step (3) 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, it is preferable to wash with an aqueous medium below the cloud point of the surfactant. 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 core-shell particle itself 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 particles)
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.
The volume-median particle size (D ₅₀ ) of toner particles improves the toner productivity, improves the low-temperature fixability and heat-resistant storage stability of the toner, and improves the dot reproducibility and long-term storage of printed matter. In view of the above, it is preferably 2 μm or more, more preferably 3 μm or more, further preferably 4 μm or more, preferably 10 μm or less, more preferably 8 μm or less, and further preferably 6 μm or less.
The CV value of the toner particles 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 productivity, it is preferably 15% or more, more preferably 18% or more.
The degree of circularity of the toner particles is preferably 0.960 or more, more preferably from the viewpoint of achieving both low-temperature fixability and heat-resistant storage stability of the toner and improving dot reproducibility and long-term storage properties of the printed matter. It is 965 or more. From the same viewpoint, it is preferably 0.990 or less, more preferably 0.985 or less, and still more preferably 0.980 or less.

(External additive)
The toner for developing an electrostatic charge image of the present invention can use the toner particles as a toner as it is, but it is preferable to use a toner obtained by adding a fluidizing agent or the like as an external additive to the surface of the toner particles.
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 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.

The present invention discloses the following toner for developing an electrostatic image with respect to the above-described embodiment.
<1> An electrostatic charge image developing toner having a core-shell structure,
Crystalline polyester (a) and amorphous polyester (b) in the core part, amorphous polyester (c) in the shell part,
The crystalline polyester (a) includes an alcohol component containing 80 mol% or more of an aliphatic diol having 2 to 4 carbon atoms and an acid component containing 80 mol% or more of an aliphatic saturated dicarboxylic acid having 4 to 6 carbon atoms. A crystalline polyester obtained by polycondensation,
The amorphous polyester (b) is an amorphous polyester obtained by polycondensation of an alcohol component containing 80 mol% or more of bisphenol A ethylene oxide adduct and a polyvalent carboxylic acid component,
The amorphous polyester (c) is an amorphous polyester obtained by polycondensation of an alcohol component containing 60 mol% or more of a propylene oxide adduct of bisphenol A and a polyvalent carboxylic acid component.
Toner for developing electrostatic images.

<2> The ratio of the crystalline polyester (a) to the total amount of all the crystalline polyesters contained in the core portion is preferably 80% by mass or more, more preferably 90% by mass or more, and still more preferably 95% by mass. % Or more, more preferably substantially 100% by mass, and still more preferably 100% by mass, the toner for developing an electrostatic charge image according to <1>.
<3> The content of the crystalline polyester (a) in the core part is preferably 1% by mass or more, more preferably 3% by mass or more, and further preferably 5% by mass or more in the resin constituting the core part. Further, it is preferably 50% by mass or less, more preferably 40% by mass or less, still more preferably 35% by mass or less, and still more preferably 30% by mass or less, for developing electrostatic images according to <1> or <2>. toner.
<4> The mass ratio [(a) / (b)] of the crystalline polyester (a) and the amorphous polyester (b) is preferably 1/99 to 50/50, more preferably 3/97 to 40. / 60, more preferably 5/95 to 35/65, still more preferably 5/95 to 30/70, still more preferably 7/93 to 30/70 <1> to <3>. Toner for developing electrostatic images.

<5> The aliphatic diol having 2 to 4 carbon atoms in the crystalline polyester (a) is 80 mol% or more, preferably 90 mol% or more, more preferably 95 mol% or more, and still more preferably in the alcohol component. The toner for developing an electrostatic charge image according to any one of <1> to <4>, which is substantially 100 mol%, more preferably 100 mol%.

<6> The aliphatic saturated dicarboxylic acid having 4 to 6 carbon atoms in the crystalline polyester (a) is preferably 90 mol% or more, more preferably 95 mol% or more, and still more preferably substantially, in the acid component. The toner for developing an electrostatic charge image according to any one of <1> to <5>, containing 100 mol%, more preferably 100 mol%.
<7> The aliphatic saturated dicarboxylic acid having 4 to 6 carbon atoms is any one or more selected from the group consisting of succinic acid, glutaric acid, and adipic acid, preferably at least of succinic acid and adipic acid On the other hand, the electrostatic image developing toner according to any one of <1> to <6>, which is more preferably succinic acid.
<8> The equivalent ratio of the acid component to the alcohol component (COOH group / OH group) in the crystalline polyester (a) is preferably 0.8 or more, more preferably 0.9 or more, and preferably 1. The toner for developing an electrostatic charge image according to any one of <1> to <7>, which is 2 or less, more preferably 1.1 or less.

<9> The ratio of the amorphous polyester (b) to the total amount of all the amorphous polyesters contained in the core portion is preferably 80% by mass or more, more preferably 90% by mass or more, and still more preferably. The toner for developing an electrostatic charge image according to any one of <1> to <8>, which is 95% by mass or more, more preferably substantially 100% by mass, and still more preferably 100% by mass.
<10> The content of the amorphous polyester (b) in the core part is preferably 50% by mass or more, more preferably 60% by mass or more, further preferably 65% by mass or more, in the resin constituting the core part. More preferably, it is 70% by mass or more, preferably 99% by mass or less, more preferably 97% by mass or less, and still more preferably 95% by mass or less, according to any one of <1> to <9>. Toner for charge image development.
<11> The total amount of the crystalline polyester (a) and the amorphous polyester (b) in the core part is preferably 80% by mass or more, more preferably 90% by mass or more, and still more preferably 95% in the resin constituting the core part. The electrostatic charge image according to any one of <1> to <10>, which is at least mass%, more preferably at least 98 mass%, still more preferably at least 100 mass%, even more preferably at least 100 mass%. Development toner.

<12> The content of the bisphenol A ethylene oxide adduct in the alcohol component is preferably 90 mol% or more, more preferably 95 mol% or more, still more preferably substantially 100 mol%, still more preferably 100 mol. %. The toner for developing an electrostatic charge image according to any one of <1> to <11>.
<13> The polyvalent carboxylic acid component of the amorphous polyester (b) is dicarboxylic acid, trivalent or higher polyvalent carboxylic acid, dicarboxylic acid anhydride, trivalent or higher polyvalent carboxylic acid anhydride, dicarboxylic acid <1> to <12, which are any one or more selected from the group consisting of an alkyl ester having 1 to 3 carbon atoms and an alkyl ester having 1 to 3 carbon atoms of a trivalent or higher polyvalent carboxylic acid. > The toner for developing an electrostatic charge image according to any one of the above.
<14> The polyvalent carboxylic acid component of the amorphous polyester (b) is
Preferably, it contains terephthalic acid, more preferably contains terephthalic acid and adipic acid, and more preferably contains terephthalic acid, adipic acid, and trimellitic anhydride in any one of <1> to <13> The toner for developing an electrostatic image according to the description.
<15> The equivalent ratio (COOH group / OH group) of the polyvalent carboxylic acid component to the alcohol component in the amorphous polyester (b) is preferably 0.70 or more, more preferably 0.80 or more, The toner for developing an electrostatic charge image according to any one of <1> to <14>, which is preferably 1.10 or less, more preferably 1.05 or less.

<16> Having a mold release agent in the core part, it is preferable to use two or more types of mold release agents in combination, and it is preferable to use a plant-based wax and a mineral-based or petroleum-based wax in combination, and carnauba wax The toner for developing an electrostatic charge image according to any one of <1> to <15>, which is more preferably used in combination with paraffin wax.
<17> The electrostatic image developing toner according to any one of <1> to <16>, wherein the toner has a colorant in at least one of a core portion and a shell portion, and preferably has a colorant in the core portion.

<18> The ratio of the amorphous polyester (c) to the total amount of all the amorphous polyesters contained in the shell portion is preferably 80% by mass or more, more preferably 90% by mass or more, and still more preferably. The electrostatic charge image according to any one of <1> to <17>, which is 95% by mass or more, more preferably 98% by mass or more, still more preferably substantially 100% by mass, and still more preferably 100% by mass. Development toner.
<19> The content of the propylene oxide adduct of bisphenol A in the alcohol component is preferably 65 mol% or more, more preferably 75 mol% or more, still more preferably 85 mol% or more, still more preferably 95 mol% or more. The toner for developing an electrostatic charge image according to any one of <1> to <18>.
<20> The content of the propylene oxide adduct of bisphenol A in the alcohol component is preferably 100 mol% or less, more preferably 95 mol% or less, still more preferably 85 mol% or less, and even more preferably 75 mol% or less. <1> to <19> according to any one of <1> to <19>.
<21> The polyvalent carboxylic acid component of the amorphous polyester (c) is a dicarboxylic acid, a trivalent or higher polyvalent carboxylic acid, a dicarboxylic acid anhydride, a trivalent or higher polyvalent carboxylic acid anhydride, or a dicarboxylic acid. <1> to <20, which is any one or more selected from the group consisting of an alkyl ester having 1 to 3 carbon atoms and an alkyl ester having 1 to 3 carbon atoms of a trivalent or higher polyvalent carboxylic acid. > The toner for developing an electrostatic charge image according to any one of the above.
<22> The equivalent ratio (COOH group / OH group) of the polyvalent carboxylic acid component to the alcohol component in the amorphous polyester (c) is preferably 0.70 or more, more preferably 0.80 or more, The toner for developing an electrostatic charge image according to any one of <1> to <21>, which is preferably 1.10 or less, more preferably 1.05 or less.

<23> The method for producing a toner for developing an electrostatic charge image according to any one of <1> to <22>, comprising the following steps (1) to (3).
Step (1): Step of aggregating resin particles (A) containing crystalline polyester (a) and amorphous polyester (b) to obtain aggregated particles (1) Step (2): Aggregated particles (1) Step of obtaining aggregated particles (2) by adding resin particles (B) containing amorphous polyester (c) to the process Step (3): Aggregated particles (1) and resin particles in aggregated particles (2) A step of fusing (B) to obtain core-shell particles

<24> Step (1)
i) mixing a component containing crystalline polyester (a) and amorphous polyester (b) to obtain a resin mixture;
ii) adding an aqueous medium to the resin mixture to obtain a dispersion in which the resin particles (A) are dispersed;
and iii) an aggregation step (1) in which the resin particles (A) in the dispersion containing the resin particles (A) are aggregated to obtain a dispersion containing the aggregated particles (1). A method for producing a toner for image development.
<25> The aggregation step (1) is a step of adding an aggregating agent to the dispersion containing the resin particles (A), and the amount of the aggregating agent used is 100 parts by mass of the resin constituting the resin particles (A). Preferably, it is 50 parts by mass or less, more preferably 45 parts by mass or less, further preferably 40 parts by mass or less, preferably 5 parts by mass or more, more preferably 10 parts by mass or more, still more preferably 20 parts by mass. <24> The method for producing an electrostatic charge image developing toner according to <24>.

<26> Step (2)
iv) mixing the component containing amorphous polyester (c) to obtain a mixture;
v) adding an aqueous medium to the mixture to obtain a dispersion in which the resin particles (B) are dispersed;
vi) Aggregation in which the dispersion liquid containing the agglomerated particles (1) obtained in the step (1) and the dispersion liquid containing the resin particles (B) are mixed to adhere the resin particles (B) to the agglomerated particles (1). A method for producing a toner for developing an electrostatic charge image according to any one of <22> to <25>, further comprising an aggregation step (2) for obtaining particles (2).

  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.

[Polyester 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. Extruded from a nozzle of 1 mm length 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. The sample cooled to 0 ° C. at a temperature decrease rate of 10 ° C./min was allowed to stand still for 1 minute, and then heated to 180 ° C. at a temperature increase rate of 10 ° C./min. Of the observed peaks, the peak temperature with the maximum peak area is defined as the endothermic maximum peak temperature (1), and the crystallinity by (softening point (° C)) / (maximum endothermic peak temperature (1) (° C)). The index was determined.

(3) Melting point and glass transition temperature 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 200 ° C. The sample was cooled to 0 ° C. at a temperature decrease rate of 10 ° C./min from that temperature and measured at a temperature increase rate of 10 ° C./min. 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 measured from 20 ° C. to 180 ° C. at a heating rate of 10 ° C./min, and the maximum peak temperature was taken as the melting point.

[Volume Median Particle Size (D ₅₀ ) and Particle Size Distribution (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 (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 Science Laboratory Co., Ltd.), a measurement sample 5 g was dried at a temperature of 150 ° C. 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 Particle Size Distribution (CV Value) of Aggregated Particles, Core Shell 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.
Moreover, CV value (%) was calculated according to the following formula as particle size distribution.
CV value (%) = (standard deviation of particle size distribution / volume average particle size) × 100

[Volume Median Particle Size (D ₅₀ ) and Particle Size Distribution (CV Value) of Toner Particles]
The volume median particle size of the toner particles was measured as follows.
The measuring instrument, aperture diameter, analysis software, and electrolyte solution were the same as the volume median particle diameter of the aggregated particles.
-Dispersion: Polyoxyethylene lauryl ether "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 particle 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. Thus, 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

[Toner particle circularity]
-Preparation of dispersion: Toner particle dispersion was added 50 mg of toner particles to 5 ml of 5% by weight aqueous solution of polyoxyethylene lauryl ether “Emulgen (registered trademark) 109P” (manufactured by Kao Corporation, HLB: 13.6). Then, after dispersing for 1 minute with an ultrasonic disperser, 20 ml of distilled water was added and further dispersed for 1 minute with an ultrasonic disperser.
Measurement device: Flow type particle image analyzer “FPIA (registered trademark) -3000” (manufactured by Sysmex Corporation)
・ Measurement mode: HPF measurement mode

[Minimum fixing temperature 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 0.42-0 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 a variable temperature fixing device was prepared, the fixing device temperature was set to 90 ° C., and fixing was performed at a speed of 1.5 seconds per sheet in the A4 longitudinal direction to obtain a printed matter.
In the same manner, the temperature of the fixing device was increased by 5 ° C., and the fixing was performed to obtain a printed matter.
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 temperature at which the fixing rate was 90% or higher 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]
20 g of toner was put in a wide-mouthed polybin having an internal volume of 100 ml, sealed, and allowed to stand for 48 hours in an environment at a temperature of 55 ° C. 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 20 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.

[Dot reproducibility of printed matter]
Using a high-quality paper “J paper A4 size” (Fuji Xerox Co., Ltd.) and a commercially available printer “Microline (registered trademark) 5400” (made by Oki Data Corporation, resolution 600 × 600 dpi), 2 by 2 (2 dots 2 spaces) The halftone image was output without fixing, and 5 × 5 dots of the unfixed image were enlarged and observed using an optical microscope “VHX-100” (manufactured by Keyence Corporation). A dot having a portion where the underlying paper is exposed was regarded as missing a dot, and the degree of missing dot was evaluated based on the number of dots. The dot reproducibility of the printed material indicates that the smaller the dot missing, the better.

[Long-term storage of printed materials]
For each toner, using a commercially available printer “Microline (registered trademark) 5400” (manufactured by Oki Data Corporation, resolution 600 × 600 dpi) on high-quality paper “J paper A4 size” (Fuji Xerox Co., Ltd.), the minimum fixing temperature One unfixed image was fixed at a temperature of + 10 ° C. 100 sheets of paper were placed on the fixed image, and a 2 kg weight was placed thereon, placed on a 50 ° C. hot plate, and left under four conditions of 1 hour, 5 hours, 24 hours, and 48 hours. From the degree of fusion of the fixed image to the paper, the long-term storage property of the printed matter was evaluated according to the following evaluation criteria.
〔Evaluation criteria〕
A: It was not fused even after being left for 48 hours.
B: Although it was not fused when left for 24 hours, it was partly fused when left for 48 hours.
C: Although it was not fused when left for 5 hours, it was partly fused when left for 24 hours.
D: It was not fused when left for 1 hour, but was partially fused when left for 5 hours.
E: Partially fused or completely fused after standing for 1 hour, and the paper did not peel off.

[Production of polyester]
Production Example 1
(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 Examples 2-8
(Production of crystalline polyesters X2 to X8)
Crystalline polyesters X2 to X8 were obtained in the same manner as in Production Example 1 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 9
(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 the terephthalic acid and di (2-ethylhexanoic acid) among the alcohol components and acid components shown in Table 2 Put tin and. While stirring the mixture in a nitrogen atmosphere, the temperature was raised to 230 ° C., held at 230 ° C. for 5 hours, then cooled to 180 ° C., and an acid component other than terephthalic acid was added among the acid components shown in Table 2, The temperature was raised to 10 ° C. 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 2.

Production Examples 10-12, 15
(Production of amorphous polyesters Y2 to Y4 and Y7)
Amorphous polyesters Y2 to Y4 and Y7 were obtained in the same manner as in Production Example 9 except that the raw material monomer and mass parts of the amorphous polyester were changed as shown in Table 2. The physical properties are shown in Table 2.

Production Example 13
(Production of amorphous polyester Y5)
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 5900 g of polyoxypropylene (2.2) -2,2-bis (4-hydroxyphenyl) propane was substituted. Then, 1301 g of terephthalic acid and 41 g of di (2-ethylhexanoic acid) tin were added. While stirring the mixture in a nitrogen atmosphere, the temperature was raised to 230 ° C. and maintained for 5 hours, and then the pressure in the flask was further reduced and maintained at 8.0 kPa for 1 hour. Then return to atmospheric pressure, cool to 190 ° C., add 711 g of fumaric acid, 275 g of trimellitic anhydride, and 1.5 g of tert-butylcatechol, maintain at 190 ° C. for 1 hour, then take 2 hours. The temperature was raised to 210 ° C. Further, the pressure in the flask was lowered and maintained at 8.0 kPa for 4 hours to obtain amorphous polyester Y5. The physical properties are shown in Table 2.

Production Example 14
(Production of amorphous polyester Y6)
Table 2 shows the physical properties of amorphous polyester Y6 obtained in the same manner as in Production Example 13, except that the raw material monomer and mass parts of amorphous polyester were changed as shown in Table 2.

[Production of resin particles]
Production Example 16
(Production of resin particle dispersion A-1)
In a flask equipped with a stirrer, 60 g (10 parts by mass) of crystalline polyester X1, 540 g (90 parts by mass) of amorphous polyester Y1, and 45 g of copper phthalocyanine pigment “ECB301” (manufactured by Dainichi Seika Kogyo Co., Ltd.) , 12 g of nonionic surfactant “Emulgen (registered trademark) 150” (manufactured by Kao Corporation, polyoxyethylene (50 mol) lauryl ether), anionic surfactant “Neopelex (registered trademark) G-15” ( 80 g of 15 mass% sodium dodecylbenzenesulfonate aqueous solution manufactured by Kao Corporation) and 225 g of 6 mass% potassium hydroxide aqueous solution were added respectively, and the mixture was heated to 98 ° C. with stirring and melted, and mixed at 98 ° C. for 2 hours. Thus, a resin mixture was obtained.
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. Next, the 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. Table 3 shows the physical properties.

Production Examples 17 to 19 and 22 to 26
(Production of resin particle dispersions A-2 to A-4 and A-7 to A-11)
Resin particle dispersions A-2 to A-4 and A-7 to A in the same manner as in Production Example 16 except that the types and parts by mass of crystalline polyester and amorphous polyester were changed as shown in Table 3. -11 was obtained. Table 3 shows the physical properties. In addition, it manufactured so that 100 mass parts might be 600 g.

Production Example 20
(Production of resin particle dispersion A-5)
In a flask equipped with a stirrer, 60 g (10 parts by mass) of crystalline polyester X1, 540 g (90 parts by mass) of amorphous polyester Y1, and 45 g of copper phthalocyanine pigment “ECB301” (manufactured by Dainichi Seika Kogyo Co., Ltd.) While being stirred, the mixture was heated to 120 ° C. and melted with stirring, and mixed at 120 ° C. for 30 minutes to obtain a molten mixture. After cooling the obtained molten mixture to 98 ° C., 12 g of a nonionic surfactant “Emulgen (registered trademark) 150” (manufactured by Kao Corporation, polyoxyethylene (50 mol) lauryl ether), an anionic surfactant “ Neoperex (registered trademark) G-15 "(manufactured by Kao Corporation, 15% by weight sodium dodecylbenzenesulfonate aqueous solution) 80g, 6% by weight potassium hydroxide aqueous solution 225g was added and 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. Next, the 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-5 was obtained. Table 3 shows the physical properties.

Production Example 21
(Production of resin particle dispersion A-6)
Resin particle dispersion A-6 was obtained in the same manner as in Production Example 20, except that the types and parts by mass of crystalline polyester and amorphous polyester were changed as shown in Table 3. Table 3 shows the physical properties.

Production Example 27
(Production of resin particle dispersion B-1)
In a flask equipped with a stirrer, 600 g of amorphous polyester Y3, 6 g of nonionic surfactant “Emulgen (registered trademark) 150” (manufactured by Kao Corporation, polyoxyethylene (50 mol) lauryl ether), anionic Surfactant “Neopelex (registered trademark) G-15” (manufactured by Kao Corporation, 15 mass% sodium dodecylbenzenesulfonate aqueous solution) 40 g and 6 mass% potassium hydroxide aqueous solution 225 g were added and stirred. The temperature was raised to 0 ° C. and the mixture was melted 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. Next, the emulsion was cooled to 25 ° C., and the obtained emulsion was 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 4 shows the physical properties.

Production Examples 28-31
(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 27 except that the type of amorphous polyester was changed as shown in Table 4. Table 4 shows the physical properties.

[Manufacture of release agent particles]
Production Example 32
(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 mgKOH / g, glass transition point 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)
250 g of resin particle dispersion A-1, 42 g of deionized water, and 35 g of release agent particle dispersion were charged into a three-liter four-necked flask equipped with a dehydrating tube, a stirrer, and a thermocouple. And mixed at a temperature of 25 ° C. Next, while stirring the mixture, an aqueous solution in which 21 g of ammonium sulfate was dissolved in 216 g of deionized water was added dropwise at 25 ° C. over 5 minutes, and then the temperature was raised to 52 ° C. over 2 hours. The mixture was kept at 52 ° C. until the particle size became 4.3 μm to obtain a dispersion of aggregated particles (1).
While increasing the temperature of the dispersion of the aggregated particles (1) from 52 ° C. at a rate of 0.8 ° C./hr, the resin particle dispersion B-1 (93 g) is dropped at a rate of 0.4 ml / min. As a result, a dispersion of aggregated particles (2) was obtained. Moreover, the temperature of the dispersion liquid after completion | finish of dripping was 57 degreeC.

In a dispersion of the agglomerated particles (2), 15 g of anionic surfactant “Emar (registered trademark) E27C” (manufactured by Kao Corporation, sodium polyoxyethylene lauryl ether sulfate, effective concentration 27 mass%) and 1183 g of deionized water The mixed aqueous solution was added. Thereafter, the temperature was raised to 70 ° C. and held at 70 ° C. for 1 hour to fuse the aggregated particles to obtain a dispersion of core-shell particles.
The obtained dispersion of core-shell particles was cooled to 30 ° C., the solid content of the dispersion was separated by suction filtration, washed with deionized water, and dried at 33 ° C. to obtain toner particles. 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 “Cabo Seal TS720” (manufactured by Cabot, number average) Toner 1 was obtained by putting 1.0 part by mass of (particle diameter: 0.012 μm) into a Henschel mixer, stirring, and passing through a 150-mesh sieve. Table 5 shows the physical properties and evaluation of the toner particles.

Examples 2-9 and Comparative Examples 1-6
(Production of toners 2 to 15)
Toners 2 to 15 were obtained in the same manner as in Example 1 except that the resin particle dispersions A-1 and B-1 in Example 1 were changed to the resin particle dispersions shown in Tables 5 and 6. The physical properties and evaluation of the toner particles are shown in Tables 5 and 6.

  From Tables 5 and 6, the toners of Examples 1 to 9 have both low-temperature fixability and heat-resistant storage stability as compared with the toners of Comparative Examples 1 to 6, and the printed matter using the toner has dot reproducibility and long-term storage. It turns out that it is excellent in property.

Claims (7)

An electrostatic charge image developing toner having a core-shell structure,
Crystalline polyester (a) and amorphous polyester (b) in the core part, amorphous polyester (c) in the shell part,
The crystalline polyester (a) comprises an alcohol component containing 80 mol% or more of an α, ω-linear alkanediol having 2 to 4 carbon atoms and an aliphatic saturated dicarboxylic acid having 4 to 6 carbon atoms in an amount of 80 mol% or more. It is a crystalline polyester obtained by polycondensation with an acid component containing,
The amorphous polyester (b) is an amorphous polyester obtained by polycondensation of an alcohol component containing 80 mol% or more of bisphenol A ethylene oxide adduct and a polyvalent carboxylic acid component,
Amorphous polyester (c) is, Ri amorphous polyester der obtained an alcohol component and a polycarboxylic acid component comprising propylene oxide adduct of bisphenol A 60 mol% or more polycondensation,
The mass ratio (core / shell ratio) of the resin in the core and the resin in the shell is 90/10 to 53/47,
The mass ratio ((a) / (b)) between the crystalline polyester (a) and the amorphous polyester (b) in the toner is 1/99 to 50/50,
The ratio of the crystalline polyester (a) to the total amount of all the crystalline polyesters contained in the core part is 80% by mass or more and 100% by mass or less,
The toner for developing an electrostatic charge image , wherein the ratio of the amorphous polyester (c) to the total amount of all the amorphous polyesters contained in the shell portion is 80% by mass or more and 100% by mass or less .   The electrostatic image developing toner according to claim 1, wherein the polyvalent carboxylic acid component of the amorphous polyester (c) contains an aromatic dicarboxylic acid.   The electrostatic image developing toner according to claim 1, wherein the polyvalent carboxylic acid component of the amorphous polyester (c) contains a trivalent or higher polyvalent carboxylic acid.   The electrostatic image developing toner according to claim 1, wherein the polyvalent carboxylic acid component of the amorphous polyester (b) contains terephthalic acid and adipic acid.   The toner for developing electrostatic images according to claim 1, wherein the aliphatic saturated dicarboxylic acid having 4 to 6 carbon atoms of the crystalline polyester (a) is succinic acid or adipic acid.   The mass ratio [(a) / (b)] of the crystalline polyester (a) and the amorphous polyester (b) is 7/93 to 30/70, according to any one of claims 1 to 5. Toner for developing electrostatic images. The method for producing a toner for developing an electrostatic image according to claim 1, comprising the following steps (1) to (3).
Step (1): Step of aggregating resin particles (A) containing crystalline polyester (a) and amorphous polyester (b) to obtain aggregated particles (1) Step (2): Aggregated particles (1) Step of obtaining aggregated particles (2) by adding resin particles (B) containing amorphous polyester (c) to the process Step (3): Aggregated particles (1) and resin particles in aggregated particles (2) A step of fusing (B) to obtain core-shell particles