JP5970372B2 - Method for producing toner for developing electrostatic image - Google Patents

Description

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

In the field of electrophotography, with the development of an electrophotographic system, development of toner for electrophotography corresponding to higher image quality and higher speed is required.
From the viewpoint of high image quality, it is necessary to reduce the particle size of the toner, and so-called chemical toners obtained by chemical methods such as a polymerization method and an emulsifying dispersion method have been proposed instead of the conventional melt-kneading method. Furthermore, from the viewpoint of speedup, chemical toners using polyester as a resin have been reported in order to improve low-temperature fixability, thereby reducing the power consumption of the printing press and making the toner suitable for high-speed printing. Yes.

For example, Patent Document 1 discloses an amorphous polyester having 2.0 to 12.0 mol% of a structural unit derived from a trivalent or higher carboxylic acid and crystallinity for the purpose of improving low-temperature fixability and hot offset resistance. A step of emulsifying a raw material polyester containing polyester in an aqueous medium, or after mixing the raw material polyester with an organic solvent, an aqueous medium is added and emulsified to obtain a polyester particle dispersion, and the polyester particle dispersion is obtained. An electrophotographic toner obtained by aggregation and coalescence is disclosed.
Patent Document 2 discloses an alcohol component containing an aliphatic diol having 2 to 12 carbon atoms as a binder resin for toner having excellent carrier contamination resistance and charging rate while maintaining excellent low-temperature fixability. A crystalline polyester obtained by condensation polymerization of a carboxylic acid component containing a specific amount of an aliphatic dicarboxylic acid compound having 8 to 12 carbon atoms, an alcohol component, an alkyl (9 to 18 carbon atoms) succinic acid, and an alkenyl (9 carbon atoms). -18) an amorphous resin (A) obtained by polycondensation with a carboxylic acid component containing a specific amount of at least one succinic acid compound selected from succinic acid, and the shell part is composed of a carboxylic acid component and A binder resin for toner comprising core-shell particles, which is an amorphous resin (B) obtained by condensation polymerization with an alcohol component containing a specific amount of an aliphatic dialcohol having 2 to 5 carbon atoms, is opened. It is.
Patent Document 3 includes a binder resin, a release agent, and silica particles as a toner for developing an electrostatic latent image that is less likely to be bent (hereinafter sometimes referred to as curling) of a fixed image after fixing. The difference between Tm and Tc when the endothermic peak Tm of the release agent in the temperature rising process and the exothermic peak Tc of the release agent in the temperature lowering process were measured by a differential scanning calorimeter (DSC) by the ASTM method. The resin having a ratio of the structural unit derived from the aliphatic monomer within a specific range of the structural units constituting the resin that is 30 ° C. or higher and 50 ° C. or lower occupies a specific ratio of the entire binder resin, and the silica An electrostatic latent image developing toner is disclosed in which a specific amount of particles is contained with respect to the binder resin.

International Publication No. 2010/27071 JP 2011-197193 A JP2010-230990

It is known that when a crystalline polyester is further included in a toner containing an amorphous polyester, the low-temperature fixability is improved. It is also known that low temperature fixability is improved by using an amorphous polyester containing alkenyl succinic acid as a monomer component. This is considered because the amorphous polyester is highly compatible with the crystalline polyester.
However, the amorphous polyester containing an alkenyl succinic acid component lowers the glass transition temperature of the resin, so that the durability and storage stability of the toner are deteriorated. Therefore, it is necessary to suppress the content of the alkenyl succinic acid component to a certain amount or less, and as a result, there is a limit to improving the low-temperature fixability.
An object of the present invention is to provide a method for producing an electrostatic image developing toner and an electrostatic image developing toner that are excellent in low-temperature fixability and durability.

  As a result of intensive studies, the inventors have added a small amount of an amorphous polyester having a high alkenyl succinic acid component content, so that the entire polyester resin has low-temperature fixability even if the alkenyl succinic acid component content is small. It has been found that it can be sufficiently improved, thereby achieving both low-temperature fixability and durability.

That is, the present invention provides the following [1] and [2].
[1] Next steps (1) to (4)
Step (1): Crystalline polyester (a) and amorphous polyester (b) are mixed in an aqueous medium at a temperature equal to or higher than the melting point of crystalline polyester (a), and a dispersion of resin particles (A) Step (2): Step of aggregating resin particles (A) to obtain aggregated particles (1) Step (3): Amorphous polyester (c) is contained in the dispersion of aggregated particles (1) Step of adding aggregated resin particles (B) to obtain aggregated particles (2) Step (4): electrostatic charge image development including the step of fusing the aggregated particles (2) to obtain fused particles The toner for manufacturing a toner according to claim 1, wherein the amorphous polyester (b) is an alkyl succinic acid having an alkyl group having 9 to 14 carbon atoms and / or alkenyl succinic acid having an alkenyl group having 9 to 14 carbon atoms. Acid component and alcohol containing from mol% to 90 mol% The content of the amorphous polyester (b1) in the resin constituting the resin particles (A) is 7% by mass or more and 20% by mass. The content of the alkyl succinic acid and / or alkenyl succinic acid in the total amount of carboxylic acid components of all the polyesters in the resin particles (A) is 5.0 mol% or more and 20 mol% or less. A method for producing a toner for developing an electrostatic image.
[2] A toner for developing an electrostatic image obtained by the production method according to [1].

  ADVANTAGE OF THE INVENTION According to this invention, the manufacturing method of the electrostatic image developing toner excellent in low temperature fixability and durability can be provided.

The method for producing the toner for developing an electrostatic image of the present invention includes
Next steps (1) to (4)
Step (1): Crystalline polyester (a) and amorphous polyester (b) are mixed in an aqueous medium at a temperature equal to or higher than the melting point of crystalline polyester (a), and a dispersion of resin particles (A) Step (2): Step of aggregating resin particles (A) to obtain aggregated particles (1) Step (3): Amorphous polyester (c) is contained in the dispersion of aggregated particles (1) Step of adding aggregated resin particles (B) to obtain aggregated particles (2) Step (4): electrostatic charge image development including the step of fusing the aggregated particles (2) to obtain fused particles The toner for manufacturing a toner according to claim 1, wherein the amorphous polyester (b) is an alkyl succinic acid having an alkyl group having 9 to 14 carbon atoms and / or alkenyl succinic acid having an alkenyl group having 9 to 14 carbon atoms. Acid component and alcohol containing from mol% to 90 mol% The content of the amorphous polyester (b1) in the resin constituting the resin particles (A) is 7% by mass or more and 20% by mass. The content of the alkyl succinic acid and / or alkenyl succinic acid in the total amount of carboxylic acid components of all the polyesters in the resin particles (A) is 5.0 mol% or more and 20 mol% or less. This is a method for producing a toner for developing an electrostatic image.

The reason why the production method of the present invention can produce an electrostatic image developing toner excellent in low-temperature fixability and durability is not clear, but is considered as follows.
By making the content of the alkyl succinic acid and / or alkenyl succinic acid component, which is considered to be highly compatible with both crystalline polyester and amorphous polyester, in a specific range, crystallinity It is considered that the compatibility between the polyester and the amorphous polyester is enhanced, and the crystalline domains of the crystalline polyester can be uniformly dispersed in the resin, and as a result, the low-temperature fixability of the toner is improved. At this time, since a small amount of the amorphous polyester having a high content of the alkyl succinic acid and / or alkenyl succinic acid component is used, the alkyl succinic acid and / or alkenyl succinic acid component is localized in the resin. It is considered that the decrease in the glass transition temperature of the entire resin is suppressed, and the decrease in the durability of the toner is suppressed.
Hereinafter, each component and process used in the present invention will be described.

<Step (1)>
In step (1) in the method for producing a toner for developing an electrostatic charge image of the present invention, crystalline polyester (a) and amorphous polyester (b) are mixed in an aqueous medium at a melting point of crystalline polyester (a) or higher. In the step of obtaining a dispersion of resin particles (A).

[Resin particles (A)]
The resin particles (A) in the present invention contain a crystalline polyester (a) and an amorphous polyester (b) from the viewpoint of improving the low-temperature fixability of the toner.

  The total content of the crystalline polyester (a) and the amorphous polyester (b) in the resin constituting the resin particles (A) is a resin from the viewpoint of improving the low-temperature fixability of the toner and the durability. 80% by mass or more in the resin constituting the particles (A) is preferable, 90% by mass or more is more preferable, 95% by mass or more is further preferable, substantially 100% by mass is still more preferable, and 100% by mass is even more preferable. preferable.

(Crystalline polyester (a))
The crystalline polyester (a) of the present invention has a ratio between a softening point and a maximum endothermic peak temperature measured by a differential scanning calorimeter (DSC), that is, (softening point (° C)) / (maximum endothermic peak temperature (° C)). From the viewpoint of improving the low-temperature fixability of the toner, preferably 0.8 or more, more preferably 0.9 or more, Preferably it is 1.3 or less, More preferably, it is 1.2 or less, More preferably, it is 1.1 or less. The crystallinity index can be appropriately determined according to the production conditions such as the type and ratio of the raw material monomers, the reaction temperature, the reaction time, and the cooling rate. The maximum endothermic peak temperature refers to the temperature of the peak on the highest temperature side among the observed endothermic peaks. The maximum peak temperature is the melting point if the difference from the softening point is within 20 ° C., and the peak due to the glass transition if the difference from the softening point exceeds 20 ° C.

  The crystalline polyester (a) preferably has an acid group at the molecular chain terminal from the viewpoint of improving the dispersion stability of the resin particle dispersion. 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 resin particle dispersion.

The melting point of the crystalline polyester (a) is preferably 50 ° C. or higher, more preferably 60 ° C. or higher, still more preferably 70 ° C. or higher, and even more preferably 75 ° C. or higher, from the viewpoint of improving the low-temperature fixability and durability of the toner. Preferably, 80 degreeC or more is still more preferable. Moreover, 140 degrees C or less is preferable, 120 degrees C or less is more preferable, 100 degrees C or less is still more preferable, 90 degrees C or less is still more preferable, 85 degrees C or less is still more preferable.
From the same viewpoint, the softening point of the crystalline polyester (a) is preferably 50 ° C. or higher, more preferably 60 ° C. or higher, still more preferably 70 ° C. or higher, still more preferably 75 ° C. or higher, and 150 ° C. or lower. Preferably, 120 ° C. or lower is more preferable, 100 ° C. or lower is further preferable, and 95 ° C. or lower is still more preferable.
The acid value of the crystalline polyester (a) is preferably 30 mgKOH / g or less, and preferably 27 mgKOH / g or less from the viewpoint of improving the dispersion stability of the resin particle dispersion and improving the low-temperature fixability and chargeability of the toner. More preferably, 25 mgKOH / g or less is more preferable, 5 mgKOH / g or more is preferable, 10 mgKOH / g or more is more preferable, and 15 mgKOH / g or more is more preferable. The desired softening point and acid value can be obtained by adjusting the charging ratio of alcohol and carboxylic acid, the polycondensation temperature, and the reaction time.
Crystalline polyester (a) can be used individually by 1 type or in combination of 2 or more types.

  In the present invention, the melting point of the crystalline polyester (a) is determined by the method described in the examples. When two or more kinds are used in combination, the melting point of the crystalline polyester (a) having the largest mass ratio in the crystalline polyester (a) contained in the obtained toner is the melting point of the crystalline polyester (a) in the present invention. The melting point. When all have the same ratio, the lowest value is set. 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 raw material monomer of the crystalline polyester (a) is not particularly limited, and an arbitrary alcohol component and an arbitrary carboxylic acid component such as a carboxylic acid, a carboxylic acid anhydride, or a carboxylic acid ester are used.

Examples of the acid component include dicarboxylic acids, trivalent or higher polyvalent carboxylic acids, acid anhydrides thereof, and alkyl esters having 1 to 3 carbon atoms. Among them, dicarboxylic acids are preferable.
Specific examples of the dicarboxylic acid include aliphatic dicarboxylic acid, alicyclic dicarboxylic acid, and aromatic dicarboxylic acid. Among these, aliphatic dicarboxylic acids are preferable from the viewpoint of promoting the crystallinity of the polyester and improving the low-temperature fixability of the toner.
Examples of the aliphatic dicarboxylic acid include sebacic acid, fumaric acid, maleic acid, adipic acid, azelaic acid, succinic acid, an alkyl group having 1 to 20 carbon atoms, or a succinic acid substituted with an alkenyl group having 2 to 20 carbon atoms. Etc. Specific examples of the succinic acid substituted with an alkyl group having 1 to 20 carbon atoms or an alkenyl group having 2 to 20 carbon atoms include dodecyl succinic acid, dodecenyl succinic acid, octenyl succinic acid, and the like. Of these, aliphatic dicarboxylic acids having 4 to 12 carbon atoms are preferred from the viewpoint of improving the low-temperature fixability and storage stability of the toner.

Examples of the aliphatic dicarboxylic acid having 4 to 12 carbon atoms include maleic acid, fumaric acid, citraconic acid, itaconic acid, glutaconic acid, succinic acid, adipic acid, sebacic acid, 1,12-dodecanedioic acid, and azelaic acid. Can be mentioned. Of these, succinic acid, sebacic acid, and 1,12-dodecanedioic acid are preferred, and succinic acid is more preferred from the viewpoint of improving low-temperature fixability and durability of the toner.
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-naphthalenetricarboxylic acid, pyromellitic acid, and the like. Among them, the viewpoint of improving the low-temperature fixability and durability of the toner. Therefore, trimellitic acid and its acid anhydride are preferable, and trimellitic acid anhydride is more preferable.
An acid component can be used individually by 1 type or in combination of 2 or more types.

Examples of the alcohol component include aliphatic diols having 2 to 12 carbon atoms in the main chain, 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). Of these, aliphatic diols having 2 to 12 main chain carbon atoms are preferred from the viewpoint of promoting the crystallinity of polyester and improving the low-temperature fixability of the toner.
Among the aliphatic diols having 2 to 12 carbon atoms in the main chain, α, ω-linear alkanediol is preferable from the viewpoint of promoting the crystallinity of the polyester and improving the low-temperature fixability of the toner.
As the α, ω-linear alkanediol having 2 to 12 main chain carbon atoms, those having 6 to 12 main chain carbon atoms are more preferable from the viewpoint of promoting the crystallinity of the polyester and improving the low-temperature fixability of the toner. preferable.
Specific examples of α, ω-linear alkanediol include ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexane. Diol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,12-dodecanediol, and the like. 8-octanediol, 1,9-nonanediol, 1,10-decanediol and 1,12-dodecanediol are preferred. Among these, 1,10-decanediol and 1,12-dodecanediol are more preferable, and 1,12-dodecanediol is more preferable from the viewpoint of improving the low-temperature fixability and durability of the toner.
Specific examples of other aliphatic diols having 2 to 12 carbon atoms in the main chain include neopentyl glycol and 1,4-butenediol.
Specific examples of other alcohol components include carbon number of bisphenol A such as polyoxypropylene-2,2-bis (4-hydroxyphenyl) propane and polyoxyethylene-2,2-bis (4-hydroxyphenyl) propane. 2 to 3 alkylene oxides (average added mole number 1 to 16) adducts, alicyclic diols such as hydrogenated bisphenol A or alkylene oxides having 2 to 4 carbon atoms (average added mole number 2 to 12) Below), adducts, trihydric or higher polyhydric alcohols such as glycerin, pentaerythritol, trimethylolpropane, sorbitol or their adducts having 2 to 4 carbon atoms of alkylene oxide (average addition mole number of 1 to 16). Can be mentioned.
An alcohol component 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 aliphatic dicarboxylic acid having 4 to 12 carbon atoms and an α, ω-linear alkanediol having 2 to 12 main chain carbon atoms, more preferably succinic acid. At least one dicarboxylic acid selected from the group consisting of acids, sebacic acid and 1,12-dodecanedioic acid, 1,6-hexanediol, 1,8-octanediol, 1,9-nonanediol, 1,10 -Polyester obtained by polycondensation of one or more diols selected from the group consisting of decanediol and 1,12-dodecanediol, more preferably a group consisting of succinic acid, 1,10-decanediol and 1,12-dodecanediol. Polyester obtained by polycondensation of one or more diols selected from

The crystalline polyester (a) can be produced, for example, by polycondensing the alcohol component and the carboxylic acid component in an inert gas atmosphere using an esterification catalyst as necessary.
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 and an alcohol component, More preferably, it is 0.1 mass part or more, Preferably it is 1 mass part or less, More preferably, it is 0.8 mass part or less.
Moreover, a polymerization inhibitor can be used as needed. Examples of the polymerization inhibitor include tert-butylcatechol. The amount of the polymerization inhibitor used is preferably 0.001 part by mass or more, more preferably 0.005 part by mass or more, and preferably 0.000 part by mass or more with respect to 100 parts by mass of the total amount of the acid component and the alcohol component. 5 parts by mass or less, more preferably 0.1 parts by mass or less.

  The polycondensation is preferably carried out by maintaining at 130 to 200 ° C. for 5 to 15 hours. After that, an esterification catalyst is added and the reaction is continued at 150 to 220 ° C. for 1 to 5 hours. A method of obtaining a crystalline polyester by reducing the pressure to 20 kPa and maintaining it for 1 to 10 hours is more preferable.

(Amorphous polyester (b))
The amorphous polyester (b) is an alkyl succinic acid having an alkyl group having 9 to 14 carbon atoms and / or an alkenyl succinic acid having an alkenyl group having 9 to 14 carbon atoms in an amount of 60 mol% to 90 mol%. It contains an amorphous polyester (b1) obtained by polycondensation of an acid component and an alcohol component.

  Here, the amorphous polyester (b) has the above-mentioned crystallinity index of more than 1.4 or less than 0.6. 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 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 resin particle dispersion. 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 resin particle dispersion.

The amorphous polyester (b) can be produced by a polycondensation reaction between an acid component and an alcohol component in the same manner as the crystalline polyester (a). For example, it is produced by polycondensing the alcohol component and the carboxylic acid component at a temperature of about 180 to 250 ° C. in an inert gas atmosphere using an esterification catalyst and a polymerization inhibitor as necessary. Can do.

(Amorphous polyester (b1))
Among the alkyl succinic acid having an alkyl group having 9 to 14 carbon atoms and / or the alkenyl succinic acid having an alkenyl group having 9 to 14 carbon atoms contained in the amorphous polyester (b1), From the viewpoint of increasing the affinity and improving the low-temperature fixability of the toner, alkenyl succinic acid having an alkenyl group having 9 to 14 carbon atoms is preferred.
From the viewpoint of increasing the affinity with the crystalline polyester and improving the low-temperature fixability of the toner, the alkyl group or alkenyl group preferably has 10 to 14 carbon atoms, and more preferably 12 to 14 carbon atoms.
Specific examples of the alkyl succinic acid having an alkyl group having 9 to 14 carbon atoms and / or the alkenyl succinic acid having an alkenyl group having 9 to 14 carbon atoms include dodecyl succinic acid, dodecenyl succinic acid, decenyl succinic acid, and acids thereof. Examples thereof include anhydrides and alkyl esters having 1 to 3 carbon atoms. From the viewpoint of improving the low-temperature fixability of the toner, dodecenyl succinic acid and acid anhydrides thereof are preferable, and dodecenyl succinic acid anhydride is more preferable.
The content of the alkyl succinic acid having an alkyl group having 9 to 14 carbon atoms and / or the alkenyl succinic acid having an alkenyl group having 9 to 14 carbon atoms is selected from the viewpoint of increasing the affinity with the crystalline polyester, and From the viewpoint of improving the low-temperature fixability, it is 60 mol% or more, preferably 65 mol% or more, more preferably 70 mol% or more, and even more preferably 75 mol% or more in the acid component of the amorphous polyester (b1). . Further, from the viewpoint of improving the low-temperature fixability and durability of the toner, it is 90 mol% or less, preferably 87 mol% or less, more preferably 83 mol% or less, in the acid component of the amorphous polyester (b1). 80 mol% or less is still more preferable. When these viewpoints are put together, the content of the alkyl succinic acid having an alkyl group having 9 to 14 carbon atoms and / or the alkenyl succinic acid having an alkenyl group having 9 to 14 carbon atoms is the amorphous polyester (b1). 60 to 90 mol%, preferably 60 to 87 mol%, more preferably 65 to 83 mol%, still more preferably 70 to 80 mol%, and even more preferably 75 to 80 mol%.

As other acid components, aromatic dicarboxylic acids and trivalent or higher polyvalent carboxylic acids are preferable.
The aromatic dicarboxylic acid is preferably terephthalic acid.

  As the trivalent or higher polyvalent carboxylic acid, trimellitic acid and its acid anhydride are preferable, and trimellitic acid anhydride is more preferable.

  Examples of the alcohol component include aliphatic diols having 2 to 12 carbon atoms in the main chain, 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), and the like. Specific examples include those mentioned as the alcohol component of the crystalline polyester (a). You may use the said alcohol component individually by 1 type or in combination of 2 or more types. Examples of the alcohol component include polyoxypropylene-2,2-bis (4-hydroxyphenyl) propane, polyoxyethylene-2,2-bis (4) from the viewpoint of improving the durability of the toner and the charging property. An adduct of bisphenol A such as -hydroxyphenyl) propane having 2 to 3 carbon atoms (average addition mole number of 1 to 16) is preferred.

  The softening point of the amorphous polyester (b1) is preferably 70 ° C. or higher, more preferably 80 ° C. or higher, further preferably 90 ° C. or higher, and more preferably 100 ° C. or higher, from the viewpoint of improving the low-temperature fixability and durability of the toner. More preferably, it is preferably 165 ° C. or lower, more preferably 150 ° C. or lower, still more preferably 130 ° C. or lower, and even more preferably 120 ° C. or lower.

From the same viewpoint, the glass transition temperature of the amorphous polyester (b1) is preferably 10 ° C. or higher, more preferably 20 ° C. or higher, further preferably 25 ° C. or higher, and further preferably 30 ° C. or higher. Further, from the viewpoint of improving the low-temperature fixability of the toner, 80 ° C. or lower is preferable, 70 ° C. or lower is more preferable, 60 ° C. or lower is further preferable, and 50 ° C. or lower is even more preferable.
In addition, when using 2 or more types of amorphous polyester (b1) in mixture, the glass transition temperature and softening point are as described in the examples as a mixture of 2 or more types of amorphous polyester (b1). The value obtained by the method.

  The acid value of the amorphous polyester (b1) is preferably 35 mgKOH / g or less, and preferably 30 mgKOH / g or less from the viewpoint of improving the dispersion stability of the resin particle dispersion and improving the low-temperature fixability and chargeability of the toner. Is more preferable, 25 mgKOH / g or less is more preferable, 5 mgKOH / g or more is preferable, 10 mgKOH / g or more is more preferable, and 15 mgKOH / g or more is more preferable.

(Amorphous polyester (b2))
The amorphous polyester (b) contains an amorphous polyester (b2) in addition to the amorphous polyester (b1).

The raw material monomer of the amorphous polyester (b2) is not particularly limited, and an arbitrary alcohol component and an arbitrary carboxylic acid component are used.
Examples of the acid component include dicarboxylic acids, trivalent or higher polyvalent carboxylic acids, acid anhydrides thereof, and alkyl esters having 1 to 3 carbon atoms, and among them, dicarboxylic acids and trivalent or higher polyvalent carboxylic acids. Divalent carboxylic acids are preferred.
Examples of the dicarboxylic acid include aromatic dicarboxylic acids, aliphatic dicarboxylic acids, and alicyclic dicarboxylic acids, and specifically, those listed above as the acid component of the crystalline polyester (a).
As the dicarboxylic acid, aromatic dicarboxylic acid and aliphatic dicarboxylic acid are preferable, and among these, terephthalic acid and fumaric acid are preferable.
The acid component of the raw material monomer of the amorphous polyester (b2) contains alkyl succinic acid having an alkyl group having 9 to 14 carbon atoms and / or alkenyl succinic acid having an alkenyl group having 9 to 14 carbon atoms. Also good. However, from the viewpoint of achieving both low temperature fixability and durability of the toner, the content of the alkyl succinic acid and / or the alkenyl succinic acid in the acid component of the raw material monomer of the amorphous polyester (b2) is preferably It is less than 60 mol%, more preferably 10 mol% or less, still more preferably 1 mol% or less, still more preferably substantially 0 mol%, still more preferably 0 mol%.
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 durability of the toner.
An acid component can be used individually by 1 type or in combination of 2 or more types.

  The alcohol component of the amorphous polyester (b2) is the same as that of the amorphous polyester (b1).

  The softening point of the amorphous polyester (b2) is preferably 70 ° C. or higher, more preferably 80 ° C. or higher, further preferably 90 ° C. or higher, and more preferably 100 ° C. or higher, from the viewpoint of improving the low-temperature fixability and durability of the toner. More preferably, it is preferably 165 ° C or lower, more preferably 140 ° C or lower, still more preferably 130 ° C or lower, and still more preferably 120 ° C or lower.

From the same viewpoint, the glass transition temperature of the amorphous polyester (b2) is preferably 50 ° C or higher, more preferably 55 ° C or higher, further preferably 60 ° C or higher, more preferably 80 ° C or lower, and 75 ° C or lower. More preferred is 70 ° C. or lower.
In addition, when using 2 or more types of amorphous polyesters (b2) in mixture, the glass transition temperature and the softening point are as described in the examples as a mixture of 2 or more types of amorphous polyesters (b2). The value obtained by the method.
The acid value of the amorphous polyester (b2) is preferably 35 mgKOH / g or less from the viewpoint of improving the dispersion stability of the resin particle dispersion, improving the low-temperature fixability of the toner, and improving the charging property. 30 mgKOH / g or less is more preferable, 28 mgKOH / g or less is more preferable, 5 mgKOH / g or more is preferable, 10 mgKOH / g or more is more preferable, and 15 mgKOH / g or more is more preferable.

  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 and blocking with phenol, urethane, epoxy and the like by the methods 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 a polyester unit.

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

  The resin particles (A) may contain a colorant, a release agent, and a charge control agent as long as the effects of the present invention are not impaired. Moreover, you may contain additives, such as reinforcement fillers, such as a fibrous material, antioxidant, and anti-aging agent, as needed.

(Coloring agent)
The resin particles (A) may be particles composed only of a resin or colorant-containing resin particles containing a colorant. From the viewpoint of obtaining uniform agglomerated particles in the subsequent agglomeration step, From the viewpoint of improving low-temperature fixability and durability, it is preferable to contain a colorant, and colorant-containing resin particles containing a colorant are preferable.
When the resin particles (A) are colorant-containing resin particles, the content of the colorant is based on 100 parts by mass of the resin constituting the resin particles (A) from the viewpoint of improving the image density and low-temperature fixability of the toner. 1 part by mass or more is preferable, 5 parts by mass or more is more preferable, 20 parts by mass or less is preferable, and 10 parts by mass or less is more preferable.

As the colorant, pigments and dyes are used, and pigments are preferable from the viewpoint of improving the image density of the toner.
Specific examples of the pigment include carbon black, inorganic composite oxide, benzidine yellow, brilliantamine 3B, brilliantamine 6B, bengal, aniline blue, ultramarine blue, copper phthalocyanine, and phthalocyanine green. Among these, copper Phthalocyanine is preferred.
Specific examples of the dye include acridine series, azo series, benzoquinone series, azine series, anthraquinone series, indigo series, phthalocyanine series, and aniline black series.
A coloring agent can be used individually by 1 type or in combination of 2 or more types.

(Production of resin particles (A))
Resin particles (A) are prepared by mixing the above-mentioned optional components such as crystalline polyester (a), amorphous polyester (b), surfactant, and colorant in an aqueous medium. It is produced by the method obtained as a dispersion of A).

As the aqueous medium, those containing water as a main component are preferable. From the viewpoint of improving the dispersion stability of the resin particle (A) dispersion and from the viewpoint of environmental properties, the content of water in the aqueous medium is 80% by mass or more. Preferably, 90 mass% or more is more preferable, 95 mass% or more is further preferable, substantially 100 mass% is further more preferable, and 100 mass% is still more preferable. As water, deionized water or distilled water is preferably used.
As components other than water, an organic solvent that dissolves in water such as an alkyl alcohol having 1 to 5 carbon atoms; a dialkyl ketone having 1 to 3 carbon atoms such as acetone and methyl ethyl ketone; and a cyclic ether such as tetrahydrofuran 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 for obtaining a dispersion containing the 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, or an aqueous medium is gradually added to the resin or the like to perform 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 above-mentioned optional components such as crystalline polyester (a), amorphous polyester (b) and, if necessary, surfactant and colorant are melted and mixed to obtain a resin mixture.
When a resin other than polyester is included, a mixture of polyester and other resin may be used in advance, but when adding other components, it is added at the same time, and the resin mixture is melted and mixed. May be obtained.

  As a method for obtaining a resin mixture, the above-mentioned optional components such as crystalline polyester (a), amorphous polyester (b), surfactant, colorant, and alkaline aqueous solution are placed in a container and stirred with a stirrer. A method of melting and uniformly mixing the resin is preferable.

  The dispersion of the resin particles (A) in the present invention preferably contains a surfactant from the viewpoint of improving the dispersion stability of the dispersion of the resin particles (A).

Examples of the surfactant include nonionic surfactants, anionic surfactants, and cationic surfactants. Among them, nonionic surfactants are preferable, and nonionic surfactants and anionic surfactants are preferred. It is more preferable to use an activator or a cationic surfactant in combination. From the viewpoint of improving the dispersion stability of the dispersion of the resin particles (A), a nonionic surfactant and an anionic surfactant are used in combination. More preferably.
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 polyoxyethylene fatty acid esters include polyethylene glycol monolaurate, polyethylene glycol monostearate, polyethylene glycol 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).
The anionic surfactant is preferably at least one selected from the group consisting of alkylbenzene sulfonates, alkyl sulfates, and alkyl ether sulfates. As a kind of salt, at least 1 sort (s) chosen from the group which consists of sodium salt, potassium salt, and ammonium salt is preferable.
Specific examples of the anionic surfactant include sodium dodecylbenzene sulfonate, sodium dodecyl sulfate, sodium lauryl ether sulfate and the like. From the viewpoint of improving the dispersion stability of the dispersion of the resin particles (A), dodecylbenzene. Sodium sulfonate and sodium lauryl ether sulfate are preferable, and sodium dodecylbenzenesulfonate is more preferable.
Specific examples of the cationic surfactant are preferably quaternary ammonium salts such as alkylbenzenedimethylammonium chloride and alkyltrimethylammonium chloride.

  The content of the surfactant is preferably 20 parts by mass or less, and preferably 15 parts by mass or less with respect to 100 parts by mass of the resin constituting the resin particles (A), from the viewpoint of improving the heat resistant storage stability and durability of the toner. More preferably, 10 parts by mass or less is further preferable, and 5 parts by mass or less is even more preferable. Further, from the viewpoint of improving the dispersion stability of the dispersion of the resin particles (A), 0.5 parts by mass or more is preferable with respect to 100 parts by mass of the resin constituting the resin particles (A), and 1 part by mass or more is preferable. More preferred is 2 parts by mass or more.

  Examples of the alkali in the alkaline aqueous solution include alkali metal hydroxides such as potassium hydroxide and sodium hydroxide, and ammonia. From the viewpoint of improving the dispersion stability of the dispersion of the resin particles (A), Potassium hydroxide and sodium hydroxide are preferred. Further, the alkali concentration in the alkaline aqueous solution is preferably 30% by mass or less, more preferably 20% by mass or less, further preferably 10% by mass or less, more preferably 1% by mass or more, and more preferably 1.5% by mass or more. More preferred is 2% by mass or more.

  The temperature at which the resin is melted and mixed is a temperature equal to or higher than the melting point of the crystalline polyester (a), and is preferably a crystal from the viewpoint of mixing the resins finely to achieve both low-temperature fixability and durability of the toner. The temperature is higher than the melting point of the conductive polyester (a) by 10 ° C. or more and 40 ° C. or less, and similarly, it is more preferably 15 ° C. or more and 35 ° C. or less. In addition, from the viewpoint of obtaining uniform resin particles, the glass transition temperature of the resin constituting the amorphous polyester (b) is preferable.

In this step, the mass ratio [(a) / (b)] when the crystalline polyester (a) and the amorphous polyester (b) are mixed is the low-temperature fixability, heat-resistant storage stability, and hot offset resistance of the toner. 5/95 to 45/55 are preferable, 10/90 to 40/60 are more preferable, 10/90 to 30/70 are more preferable, and 13/87 to 20/80 are more preferable. Further preferred.
Thus, by containing more amorphous polyester (b) than crystalline polyester (a), it has a structure in which crystalline polyester (a) is finely dispersed in the amorphous polyester (b) phase, When pressure is applied during low-temperature fixing, the melted crystalline polyester (a) contributes to fixing, and during high-temperature fixing, it is considered that offset can be suppressed by the amorphous polyester (b) present in large amounts on the surface.

  The content of the amorphous polyester (b1) in the resin constituting the resin particles (A) is 7% by mass or more and more preferably 8% by mass or more from the viewpoint of improving the low-temperature fixability of the toner. Further, from the viewpoint of improving low-temperature fixability and durability of the toner, it is 20% by mass or less, preferably 18% by mass or less, more preferably 15% by mass or less, and further preferably 12% by mass or less. And content of the amorphous polyester (b1) in a resin particle (A) is 7-20 mass%, 7-18 mass% is preferable, 7-15 mass% is more preferable, 8-12 mass % Is more preferable.

  The mass ratio ((b1) / (b2)) of the content of the amorphous polyester (b1) and the amorphous polyester (b2) in the resin particles (A) improves the low-temperature fixability and durability of the toner. From the viewpoint, 7/93 to 35/65 are preferable, 8/92 to 25/75 are more preferable, 9/91 to 20/80 are further preferable, and 10/90 to 15/85 are still more preferable.

  The content of the alkyl succinic acid and / or alkenyl succinic acid in the total amount of carboxylic acid components of all the polyesters in the resin particles (A) is 5.0 mol% or more from the viewpoint of improving the low-temperature fixability of the toner. It is preferably 6.0 mol% or more, and more preferably 6.5 mol% or more. Further, from the viewpoint of improving low-temperature fixability and durability of the toner, it is 20 mol% or less, preferably 16 mol% or less, more preferably 12 mol% or less, and even more preferably 8.0 mol% or less. And content of the said alkyl succinic acid and / or alkenyl succinic acid in the total amount of the carboxylic acid component of all the polyesters in a resin particle (A) is 5.0-20 mol%, 5.0-16 Mol% is preferable, 6.0-12 mol% is more preferable, and 6.5-8.0 mol% is still more preferable.

  The mass ratio of the crystalline polyester (a) to the amorphous polyester (b1) (crystalline polyester (a) / amorphous polyester (b1)) is 80 from the viewpoint of improving the low-temperature fixability and durability of the toner. / 20 to 20/80 is preferable, 80/20 to 40/60 is more preferable, 75/25 to 50/50 is further preferable, 70/30 to 55/45 is still more preferable, and 64/36 to 60/40 Is even more preferable.

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

  From the viewpoint of obtaining homogeneous resin particles, the temperature at which the aqueous medium is added is preferably not less than the melting point of the crystalline polyester (a) and less than the boiling point of the lowest boiling solvent contained in the aqueous medium. The glass transition temperature or higher of the crystalline polyester (b) is more preferable.

  From the viewpoint of obtaining resin particles having a small particle diameter, the addition rate of the aqueous medium is preferably 50 parts by mass or less per 100 parts by mass of the resin constituting the resin particles (A) until the phase inversion is completed. , 30 parts by mass or less is more preferable, 10 parts by mass or less is more preferable, 5 parts by mass or less is more preferable, 0.1 parts by mass or more is preferable, and 0.5 parts by mass is preferable. / Min or more is more preferable. 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 preferably 900 parts by mass or less and more preferably 500 parts by mass or less with respect to 100 parts by mass of the resin constituting the resin particles (A) from the viewpoint of obtaining uniform aggregated particles in the subsequent aggregation step. Preferably, 300 parts by mass or less is more preferable, 100 parts by mass or more is preferable, 150 parts by mass or more is more preferable, and 170 parts by mass or more is further preferable.

From the viewpoint of improving the low-temperature fixability and durability of the toner, it is preferable to crosslink the polyester resin constituting the resin particles (A), and it is more preferable to crosslink with a compound having an oxazoline group.
The compound having an oxazoline group preferably contains a plurality of oxazoline groups in the molecule, and more preferably a polymer containing an oxazoline group. The weight average molecular weight of the polymer containing an oxazoline group is preferably 2,000,000 or less, more preferably 1,000,000 or less, and more preferably 500 or more, from the viewpoint of increasing the reactivity with the polyester resin. 1,000 or more is more preferable.
Examples of commercially available polymers containing oxazoline groups include “Epocross WS Series” (water-soluble type, main chain acrylic), “K Series” (emulsion type, main chain styrene / acrylic) manufactured by Nippon Shokubai Co., Ltd. .
The content or addition amount of the compound having an oxazoline group is solid with respect to 100 parts by mass of the total amount of the resin constituting the resin particles (A) from the viewpoint of improving the crosslinking reactivity with the resin and improving the productivity. The amount is preferably 30 parts by mass or less, more preferably 20 parts by mass or less, further preferably 10 parts by mass or less, more preferably 0.1 parts by mass or more, and more preferably 0.5 parts by mass or more.

  By adding and mixing a compound having an oxazoline group, the polyester resin contained in the resin particles (A) dispersed in the dispersion is cross-linked. The temperature during the crosslinking reaction is preferably 100 ° C. or lower, more preferably 98 ° C. or lower, 60 ° C. or higher, more preferably 70 ° C. or higher. The presence of the crosslinking can be confirmed by analyzing the presence of the amide group by a technique such as infrared absorption spectrum analysis.

  The solid content concentration of the obtained dispersion of resin particles (A) is 50% by mass or less from the viewpoint of improving the dispersion stability of the resin particle dispersion, the viewpoint of easy handling, and the improvement of toner productivity. It is preferably 40% by mass or less, more preferably 35% by mass or less, further preferably 10% by mass or more, more preferably 15% by mass or more, and further preferably 20% by mass or more. 25 mass% or more is still more preferable. 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 (A) in the dispersion of the resin particles (A) is preferably 2 μm or less, more preferably 1 μm or less, from the viewpoint of obtaining a high-quality toner. 0.5 μm or less is further preferable, 0.3 μm or less is more preferable, 0.02 μm or more is preferable, 0.05 μm or more is more preferable, 0.08 μm or more is further preferable, and 0.10 μm or more is preferable. Even more preferred. Here, the volume-median particle size (D ₅₀ ) is a particle size at which the cumulative volume frequency calculated by the volume fraction is 50% when calculated from the smaller particle size. The volume median particle diameter (D ₅₀ ) of the resin particles is specifically determined by the method described in the examples.
In addition, the coefficient of variation (CV value) (%) of the particle size distribution of the resin particles (A) is preferably 40% or less, more preferably 35% or less, and 32% from the viewpoint of obtaining a high-quality toner. The following is more preferable. Moreover, 5% or more is preferable from a viewpoint of improving the productivity of the dispersion liquid of the resin particle (A), 10% or more is more preferable, and 15% or more is still more preferable. In addition, the CV value of the resin particles is a value represented by the following formula, and is specifically obtained by the method described in the examples.
CV value (%) = [standard deviation of particle size distribution (μm) / volume median particle size (μm)] × 100

<Step (2)>
Step (2) is a step of aggregating the resin particles (A) to obtain aggregated particles (1). In this step, it is preferable to aggregate the release agent particles shown below together with the resin particles (A) from the viewpoint of improving the low-temperature fixability of the toner. Moreover, it is preferable to agglomerate by mixing a flocculant. That is, it is preferable to obtain the aggregated particles (1) by mixing the resin particles (A), the release agent particles and the flocculant in an aqueous medium and aggregating them.

[Releasing agent particles]
In the present invention, the release agent particles are preferably obtained as a dispersion of release agent particles by dispersing the release agent in an aqueous medium.

(Release agent)
Release agents include low molecular weight polyolefins such as polyethylene, polypropylene and polybutene; silicone waxes that have a softening point upon heating; fatty acid amides such as oleic acid amide and stearic acid amide; carnauba wax, rice wax, and candelilla wax. Plant waxes; animal waxes such as beeswax; mineral and petroleum waxes such as montan wax, paraffin wax, and Fischer-Tropsch wax. Of these, paraffin wax and carnauba wax are preferred from the viewpoint of improving the releasability, low-temperature fixability and durability of the obtained toner. These release agents may be used alone or in combination of two or more, and preferably used in combination of two or more. Among these, from the viewpoint of improving the releasability, low-temperature fixability and durability of the obtained toner, it is preferable to use a plant-based wax and a mineral-based or petroleum-based wax, and to use a paraffin wax and a carnauba wax in combination. Is more preferable.
The melting point of the release agent is preferably 100 ° C. or less, more preferably 95 ° C. or less, still more preferably 90 ° C. or less, still more preferably 85 ° C. or less, from the viewpoint of improving the low-temperature fixability and durability of the toner. 60 ° C. or higher is preferable, 65 ° C. or higher is more preferable, 70 ° C. or higher is further preferable, and 73 ° C. or higher is even more preferable. When two or more types are used in combination, the melting point is preferably 60 ° C. or higher and 100 ° C. or lower from the viewpoint of improving the low-temperature fixability of the toner. That is, the release agent preferably contains at least two release agents having a melting point of 60 ° C. or more and 100 ° C. or less, and more preferably each melting point is 60 ° C. or more and 90 ° C. or less.
In the present invention, the melting point of the release agent is determined by the method described in the examples. 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. When all have the same ratio, the lowest value is set.
The amount of the release agent used is preferably 20 parts by mass or less and more preferably 15 parts by mass or less with respect to 100 parts by mass of the resin in the toner from the viewpoint of improving the releasability, low-temperature fixability and durability of the toner. Preferably, 10 parts by mass or less is more preferable. Moreover, 1 mass part or more is preferable and 2 mass parts or more is more preferable.

(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. More preferably, the dispersion of the release agent particles is obtained by dispersing the release agent in an aqueous medium in the presence of a surfactant at a temperature equal to or higher than the melting point of the release agent using a disperser.
As the disperser to be used, a homogenizer, a high-pressure disperser, an ultrasonic disperser and the like are preferable, and an ultrasonic disperser is more preferable, from the viewpoint of improving low-temperature fixability and durability of the obtained toner. What is necessary is just to set dispersion | distribution time suitably with the disperser to be used.
Examples of the ultrasonic disperser include an ultrasonic homogenizer, and examples of commercially available devices include “US-600T” (manufactured by Nippon Seiki Co., Ltd.).
Further, before using the disperser, it is preferable to preliminarily disperse the mold release agent, optionally the surfactant, and the aqueous medium in advance using a mixer such as a homomixer or a ball mill.

  As an aqueous medium, the thing similar to what is used for the manufacturing method of the said resin particle (A) can be used suitably.

  The dispersion of the release agent particles in the aqueous medium is performed in the presence of a surfactant from the viewpoint of improving the dispersion stability of the release agent particles and obtaining uniform aggregated particles in the subsequent aggregation step. preferable.

Examples of the surfactant include nonionic surfactants, anionic surfactants, and cationic surfactants. From the viewpoint of improving the cohesiveness between the release agent particles and the resin particles, the anionic surfactants Is preferred. Among them, from the same viewpoint, the hydrophilic group is more preferably a carboxy group, and a polycarboxylate is more preferable. Preferable specific examples of the polycarboxylic acid salt to be used include polyacrylic acid salt, acrylic acid-maleic acid copolymer salt, from the viewpoint of improving the cohesiveness and releasing of the releasing agent particles during toner preparation, Polymerate and the like are preferable, and an acrylic acid-maleic acid copolymer salt is more preferable. As the salt, an alkali metal salt is preferable, and a sodium salt is more preferable.
The weight average molecular weight of the polycarboxylate is preferably 90,000 or less, more preferably 50,000 or less, and more than 3,000 from the viewpoint of improving the dispersion stability of the release agent particles. It is preferably 10,000 or more.
Commercially available products of polycarboxylates include “Poise 530” (sodium polyacrylate aqueous solution, weight average molecular weight 38000, effective concentration 40% by mass) and “Poise 521” (sodium acrylate-sodium maleate) manufactured by Kao Corporation. Polymer aqueous solution, weight average molecular weight 20000, effective concentration 40% by mass) and the like.

  The content of the surfactant in the release agent dispersion is from the viewpoint of improving the dispersion stability of the release agent particles, from the viewpoint of improving the cohesiveness of the release agent particles during toner preparation, and from the viewpoint of preventing release. 5 mass% or less is preferable, 2 mass% or less is more preferable, 1 mass% or less is further more preferable, 0.05 mass% or more is preferable, 0.1 mass% or more is more preferable, 0.4 mass% The above is more preferable. From the same viewpoint, the content of the surfactant in the release agent dispersion is preferably 15 parts by mass or less, more preferably 10 parts by mass or less, with respect to 100 parts by mass of the total release agent. 0 parts by mass or less is more preferable, 0.2 parts by mass or more is preferable, 1.0 parts by mass or more is more preferable, and 2.0 parts by mass or more is still more preferable.

The volume median particle size (D ₅₀ ) of the release agent particles is preferably 1 μm or less from the viewpoint of obtaining uniform aggregated particles in the subsequent aggregation step and improving the durability and hot offset resistance of the obtained toner. 0.80 μm or less is more preferable, 0.60 μm or less is further preferable, 0.10 μm or more is preferable, 0.20 μm or more is more preferable, and 0.30 μm or more is further preferable.
The CV value of the release agent particles is preferably 50% or less, preferably 40% or less, from the viewpoint of obtaining uniform aggregated particles in the subsequent aggregation process, from the viewpoint of improving the durability of the obtained toner, and from the viewpoint of improving the chargeability. Is more preferable, and 35% or less is still more preferable. Further, from the viewpoint of improving the productivity of the release agent particle dispersion, 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 determined by the same method as that for the resin particles (A), and specifically by the method described in the examples.

  The solid content concentration of the release agent particle dispersion is preferably 50% by mass or less from the viewpoint of improving the dispersion stability of the release agent particles, the viewpoint of easy handling, and the improvement of toner productivity. It is more preferably at most mass%, further preferably at most 30 mass%, more preferably at least 7 mass%, more preferably at least 10 mass%.

[Production of Aggregated Particles (1)]
The agglomerated particles (1) are obtained by a method of obtaining the agglomerated particles (1) by mixing arbitrary components such as the resin particles (A) obtained above, release agent particles, aggregating agents, and colorants in an aqueous medium. To manufacture. Here, when mixing the said component, it is preferable to make it aggregate and obtain as a dispersion liquid of aggregated particle (1).

In this step, first, the resin particles (A) and the release agent particles are mixed in an aqueous medium to obtain a mixed dispersion.
In addition, when a colorant is not mixed with the resin particles (A) in the step (1), it is preferable to mix a colorant in this step.
In this step, resin particles other than the resin particles (A) may be mixed. As resin particles other than resin particles (A), resin particles containing amorphous polyester are preferable, and those having the same composition as resin particles (B) described later are more preferable.
There is no restriction | limiting in order of mixing, You may add any in order and may add simultaneously.

In 100 parts by mass of the mixed dispersion containing the resin particles (A) and the release agent particles, the content of the resin particles (A) is preferably 40 parts by mass or less from the viewpoint of improving the low-temperature fixability and productivity of the toner. 30 parts by mass or less, more preferably 10 parts by mass or more, and more preferably 15 parts by mass or more.
Further, in 100 parts by mass of the mixed dispersion containing the resin particles (A) and the release agent particles, the content of the aqueous medium is preferably 90 parts by mass or less, more preferably 80 parts by mass or less, and 55 parts by mass or more. Preferably, 60 parts by mass or more is more preferable.
The content of the release agent particles is preferably 15 parts by mass or less with respect to 100 parts by mass of the resin particles (A), from the viewpoint of improving the releasability, low-temperature fixability and durability of the toner. Is more preferable. Moreover, 2 mass parts or more are preferable and 3 mass parts or more are more preferable.
When the colorant is mixed in this step, the content of the colorant is 20 with respect to 100 parts by mass of the resin constituting the resin particles (A) from the viewpoint of improving the image density and low-temperature fixability of the toner. It is preferably no greater than 10 parts by mass, more preferably no greater than 10 parts by mass, more preferably no less than 1 part by mass, and even more preferably no less than 5 parts by mass.
The mixing temperature is preferably 0 to 40 ° C. from the viewpoint of controlling aggregation and obtaining aggregated particles having a target particle size.

Next, the particles in the mixed dispersion can be aggregated to obtain a dispersion of aggregated particles (1). It is preferable to add a flocculant for efficient aggregation.
As the aggregating agent, 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, or a bivalent or higher metal complex is used.
Examples of the inorganic metal salt include metal salts such as sodium sulfate, sodium chloride, calcium chloride, magnesium sulfate, 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. The flocculant is preferably an inorganic ammonium salt and more preferably ammonium sulfate from the viewpoint of improving the flocculence and obtaining uniform agglomerated particles.
From the viewpoint of improving the durability of the toner, the use amount of the flocculant is preferably 50 parts by mass or less, more preferably 40 parts by mass or less, and more preferably 35 parts by mass with respect to 100 parts by mass of the resin constituting the resin particles (A). Part or less is more preferable. Further, from the viewpoint of improving the cohesiveness of the resin particles (A), 1 part by mass or more is preferable, 10 parts by mass or more is more preferable, and 20 parts by mass with respect to 100 parts by mass of the resin constituting the resin particles (A). The above is more preferable.

  As an aggregating method, an aggregating agent is preferably added dropwise as an aqueous solution to a container containing a mixed dispersion. The flocculant may be added at one time, or may be added intermittently or continuously. However, it is preferable to perform sufficient stirring at the time of addition and after completion of the addition. The addition time of the flocculant is preferably 1 minute or more, more preferably 10 minutes or more, and still more preferably 20 from the viewpoint of controlling aggregation and obtaining aggregated particles having a target particle diameter and improving the productivity of the toner. Min. Or more, preferably 120 min or less, more preferably 60 min or less, and still more preferably 40 min or less. Further, the dropping temperature is preferably 0 ° C. or higher, more preferably 10 ° C. or higher, still more preferably 20 ° C. or higher, and preferably 50 ° C. from the viewpoint of controlling aggregation and obtaining aggregated particles having a target particle size. ° C or lower, more preferably 40 ° C or lower, still more preferably 30 ° C or lower.

At the time of agglomeration, from the viewpoint of controlling the particle size of the agglomerated particles and suppressing the formation of coarse particles, after adding the aggregating agent, the temperature in the agglomerated system is changed to the glass transition of the resin constituting the resin particles (A). The temperature is preferably 30 ° C or higher than the temperature, more preferably 25 ° C lower than the glass transition temperature and 25 ° C lower than the glass transition temperature. It is preferable to confirm the progress of aggregation by monitoring the volume-median particle size (D ₅₀ ) of the aggregated particles in the temperature range. The volume median particle size (D ₅₀ ) is measured by the method described in the examples.

The volume-median particle size (D ₅₀ ) of the obtained aggregated particles (1) is preferably 10 μm or less, more preferably 8 μm or less, and more preferably 6 μm or less from the viewpoint of reducing the toner particle size and suppressing toner scattering. Is more preferable. Moreover, 1 micrometer or more is preferable, 2 micrometers or more are more preferable, and 3 micrometers or more are still more preferable. Further, the CV value is preferably 30% or less, more preferably 28% or less, and further preferably 25% or less. Moreover, 5% or more is preferable from a viewpoint of improving the productivity of the dispersion liquid of aggregated particle (1), 10% or more is more preferable, and 15% or more is still more preferable. The volume median particle size (D ₅₀ ) and CV value of the aggregated particles (1) are specifically determined by the method described in the examples.

<Step (3)>
Step (3) is a step of obtaining aggregated particles (2) by adding resin particles (B) containing amorphous polyester (c) to the dispersion of aggregated particles (1) and aggregating them.
In this step, the dispersion of resin particles (B) is added to the dispersion of aggregated particles (1) obtained in step (2), and the resin particles (B) are further adhered to the aggregated particles (1). It is preferable to obtain aggregated particles (2).
At this time, the resin particles (B) adhere around the aggregated particles (1). As a result, the portion of the aggregated particles (1) mainly forms the core portion of the toner having the core-shell structure described later, and the resin particles (B) mainly form the shell portion.

[Resin particles (B)]
In the present invention, the resin particles (B) contain an amorphous polyester (c) from the viewpoint of improving the low-temperature fixability and durability of the toner.

  The resin particles (B) preferably contain 80% by mass or more of the amorphous polyester (c) with respect to the resin in the resin particles (B) from the viewpoint of improving the low-temperature fixability and durability of the toner. 90 mass% or more is more preferable, 95 mass% or more is still more preferable, it is still more preferable to contain substantially 100 mass%, and it is still more preferable to contain 100 mass%.

(Amorphous polyester (c))
The amorphous polyester (c) has a crystallinity index of more than 1.4 or less than 0.6, and from the viewpoint of improving low-temperature fixability and durability of the toner, less than 0.6 or It is preferably 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 amorphous polyester (c) may be used alone or in combination of two or more, and the same polyester as the amorphous polyester (b) can be preferably used. A resin made of the same raw material monomer as that of the amorphous polyester (b) may be used, or a resin made of a different raw material monomer may be used. The amorphous polyester (c) can be produced by a polycondensation reaction between an acid component and an alcohol component in the same manner as the amorphous polyester (b).
From the viewpoint of improving low-temperature fixability and durability of the toner, the amorphous polyester (c) has an alkyl succinic acid having an alkyl group having 9 to 14 carbon atoms and / or an alkenyl group having 9 to 14 carbon atoms. It preferably contains an amorphous polyester (c1) obtained by polycondensation of an acid component containing an alkenyl succinic acid and an alcohol component.
Among the alkyl succinic acid having an alkyl group having 9 to 14 carbon atoms and / or the alkenyl succinic acid having an alkenyl group having 9 to 14 carbon atoms contained in the amorphous polyester (c1), From the viewpoint of increasing the affinity and improving the low-temperature fixability of the toner, alkenyl succinic acid having an alkenyl group having 9 to 14 carbon atoms is preferred. Specific examples include dodecyl succinic acid, dodecenyl succinic acid, decenyl succinic acid, and their anhydrides and alkyl esters having 1 to 3 carbon atoms. From the viewpoint of improving the low-temperature fixability of the toner, dodecenyl succinic acid And acid anhydrides thereof are preferred, and dodecenyl succinic anhydride is more preferred.
The content of the alkyl succinic acid having an alkyl group having 9 to 14 carbon atoms and / or the alkenyl succinic acid having an alkenyl group having 9 to 14 carbon atoms is selected from the viewpoint of increasing the affinity with the crystalline polyester, and From the viewpoint of improving the low-temperature fixability, the acid component of the amorphous polyester (c1) is preferably 1 mol% or more, more preferably 3 mol% or more, still more preferably 5 mol% or more, and more preferably 30 mol% or more. More preferably, 60 mol% or more is still more preferable. Further, from the viewpoint of improving the low-temperature fixability and durability of the toner, the acid component of the amorphous polyester (c1) is preferably 90 mol% or less, more preferably 83 mol% or less, still more preferably 80 mol% or less. .
Preferred specific examples of the other acid component and alcohol component are the same as in the case of the amorphous polyester (b1).

  The amorphous polyester (c) preferably contains an amorphous polyester (c2) in addition to the amorphous polyester (c1). The raw material monomer of the amorphous polyester (c2) is not particularly limited, and any alcohol component and any carboxylic acid component can be used. Specific examples of preferred acid components and alcohol components are those described above. The same as in the case of the crystalline polyester (b2).

  The mass ratio ((c1) / (c2)) of the content of the amorphous polyester (c1) and the amorphous polyester (c2) in the resin particles (B) improves the low-temperature fixability and durability of the toner. From the viewpoint, 2/98 to 50/50 is preferable, 5/95 to 45/55 is more preferable, and 8/92 to 40/60 is still more preferable.

  The softening point of the amorphous polyester (c) is preferably 70 ° C. or higher, more preferably 80 ° C. or higher, further preferably 90 ° C. or higher, and more preferably 100 ° C. or higher from the viewpoint of improving the low-temperature fixability and durability of the toner. More preferably, it is preferably 165 ° C. or lower, more preferably 150 ° C. or lower, still more preferably 135 ° C. or lower, and even more preferably 130 ° 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, further preferably 60 ° C or higher, more preferably 75 ° C or lower, and 70 ° C or lower. More preferred is 67 ° C. or lower.
When two or more types of amorphous polyester (c) are used in combination, the glass transition temperature and softening point thereof are as described in the examples as a mixture of two or more types of amorphous polyester (c). The value obtained by the method.
The acid value of the amorphous polyester (c) is preferably 35 mgKOH / g or less, and preferably 30 mgKOH / g or less from the viewpoint of improving the dispersion stability of the resin particle dispersion and improving the low-temperature fixability and chargeability of the toner. Is more preferable, 28 mgKOH / g or less is more preferable, 5 mgKOH / g or more is preferable, 10 mgKOH / g or more is more preferable, and 15 mgKOH / g or more is more preferable.
Resin particles (B) are made of amorphous polyester (c) and a known resin usually used in toners, such as crystalline polyester, styrene-acrylic copolymer, epoxy resin, polycarbonate, polyurethane and the like. You may contain.

  Similarly to the resin particles (A) described above, the resin particles (B) may contain a colorant, a release agent, and a charge control agent as long as the effects of the present invention are not impaired. Moreover, you may contain additives, such as reinforcement fillers, such as a fibrous material, antioxidant, and anti-aging agent, as needed.

(Production of resin particles (B))
The resin particles (B) are preferably obtained as a dispersion of the resin particles (B) by the same method as the method for producing the resin particles (A) described above, and the alkaline aqueous solution, surfactant, aqueous medium, etc. used The thing similar to the manufacturing method of a resin particle (A) can be used suitably. Resin particles (A) can also be used as resin particles (B).

The volume median particle size (D ₅₀ ) of the resin particles (B) in the dispersion of the resin particles (B) is preferably 2 μm or less from the viewpoint of obtaining a toner capable of obtaining a high-quality image. Is more preferably 0.5 μm or less, still more preferably 0.3 μm or less, preferably 0.02 μm or more, more preferably 0.05 μm or more, still more preferably 0.08 μm or more, 0 More preferably, it is 10 μm or more.
Further, the coefficient of variation (CV value) (%) of the particle size distribution of the resin particles (B) is preferably 40% or less, more preferably 35% or less from the viewpoint of obtaining a toner capable of obtaining a high-quality image. Preferably, it is 30% or less. Moreover, 5% or more is preferable from a viewpoint of improving the productivity of the dispersion liquid of the resin particle (B), 10% or more is more preferable, and 15% or more is still more preferable. The volume median particle size (D ₅₀ ) and CV value of the resin particles (B) are determined by the same method as that for the resin particles (A), and specifically by the method described in the examples.

  The solid content concentration of the dispersion of resin particles (B) is 50% by mass or less from the viewpoint of improving the stability of the resulting resin particle dispersion, facilitating handling, and improving toner productivity. It is preferably 40% by mass or less, more preferably 30% by mass or less, more preferably 10% by mass or more, more preferably 15% by mass or more, and still more preferably 20% by mass or more.

[Production of Aggregated Particles (2)]
Aggregated particles (2) are produced by adding resin particles (B) containing amorphous polyester (c) to a dispersion of aggregated particles (1).
Aggregated particles (2) are obtained by adding a dispersion of resin particles (B) to the dispersion of aggregated particles (1) obtained in step (2), and further adding resin particles (1) to aggregated particles (1). B) is preferably adhered and produced as a dispersion of aggregated particles (2).

Before and / or at the same time as adding the dispersion containing the resin particles (B) (resin particle (B) dispersion) to the dispersion containing the aggregated particles (1) (aggregated particles (1) dispersion). It is preferable to dilute the aggregated particle (1) dispersion by adding an aqueous medium, and it is more preferable to add it simultaneously with the resin particle (B) dispersion. By adding the aqueous medium, the resin particles (B) can be more uniformly attached to the aggregated particles (1).
When the resin particle (B) dispersion is added to the aggregated particle (1) dispersion, the aggregating agent may be used in order to efficiently attach the resin particle (B) to the aggregated particle (1).
As a preferable addition method in the case of adding the resin particle (B) dispersion to the aggregated particle (1) dispersion, a method of simultaneously adding the coagulant and the resin particle (B) dispersion, the coagulant and the resin particle (B ) A method of alternately adding the dispersion liquid, and a method of adding the resin particle (B) dispersion liquid while gradually raising the temperature of the aggregated particle (1) dispersion liquid. By doing in this way, the cohesiveness fall of the aggregated particle (1) and the resin particle (B) by the coagulant | flocculant density | concentration fall 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 resin particle (B) dispersion while gradually increasing the temperature of the aggregated particle (1) dispersion.

  The temperature in the system in this step is 5 ° C. or more lower than the melting point of the crystalline polyester (a) contained in the resin constituting the resin particles (A) from the viewpoint of improving the low-temperature fixability and durability of the toner. The glass transition temperature of the amorphous polyester (c) contained in the resin constituting the particles (B) is preferably 3 ° C. or more, more preferably 5 ° C. or more. When the aggregated particles (2) are produced in this temperature range, the low-temperature fixability and durability of the obtained toner are improved. Although the reason is not certain, it is considered that the generation of coarse particles is suppressed because fusion of the aggregated particles (2) does not occur.

  The addition amount of the resin particles (B) is such that the mass ratio of the resin particles (B) to the resin particles (A) (resin particles (B) / resin particles (A) is improved from the viewpoint of improving low-temperature fixability and durability of the toner. )) Is preferably 1.5 or less, more preferably 1.0 or less, still more preferably 0.5 or less, and preferably 0.1 or more, more preferably 0.2 or more.

  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 efficiency of toner production, it is preferable to add continuously over a certain period of time. The time for continuous addition is preferably 1 hour or more, more preferably 2.5 hours, or more preferably 10 hours or less from the viewpoint of obtaining uniform aggregated particles (2) and shortening the toner production time. Is preferable, and 8 hours or less is more preferable.

The total amount of the resin particles (B) is added, and aggregation is stopped when the toner particles have grown to an appropriate particle size.
Particle size to stop the aggregation, ie The particle size of the aggregated particles (2), a volume-median particle size (D _50), from the viewpoint of obtaining a toner image of high image quality is obtained, preferably 10μm or less, 8 [mu] m or less Is more preferably 7 μm or less, still more preferably 6 μm or less, more preferably 1 μm or more, more preferably 2 μm or more, still more preferably 3 μm or more, and even more preferably 4 μm or more.
Methods for stopping the aggregation include a method of cooling the dispersion and a method of adding an aggregation terminator. From the viewpoint of reliably preventing unnecessary aggregation, the aggregation is stopped by adding an aggregation terminator. The method of making it preferable is.
As the aggregation terminator, a surfactant is preferable, and an anionic surfactant is more preferable. Anionic surfactants include alkyl ether sulfates, alkyl sulfates, polyoxyethylene alkyl ether sulfates, and linear alkyl benzene sulfonates. The aggregation terminator can be used alone or in combination of two or more.
The addition amount of the aggregation terminator is preferably 0.1 parts by mass or more, more preferably 1 part by mass or more, and more preferably 3 parts by mass with respect to 100 parts by mass of the total amount of resin in the system, from the viewpoint of reliably stopping aggregation. The above is more preferable, and from the viewpoint of reducing the residual amount in the toner, it is preferably 15 parts by mass or less, more preferably 10 parts by mass or less, and more preferably 8 parts by mass or less with respect to 100 parts by mass of the total resin in the system. Further preferred. The aggregation terminator may be added in any form, but is preferably added as an aqueous solution from the viewpoint of improving toner productivity.

<Step (4)>
Step (4) is a step of fusing the aggregated particles (2) to obtain fused particles.
In this step, the particles in the agglomerated particles (2) obtained in step (3), which are mainly physically attached to each other, are fused and united to form fused particles. The

  From the viewpoint of improving the fusibility of the aggregated particles and improving the productivity of the toner, in this step, the temperature is preferably at least 5 ° C. lower than the glass transition temperature of the amorphous polyester (c), more preferably glass. It is maintained at a temperature not lower than the transition temperature, more preferably not lower than 5 ° C. higher than the glass transition temperature. Further, from the viewpoint of maintaining the core-shell state of the toner and improving the durability of the toner, in this step, the temperature is preferably 30 ° C. or less, more preferably 20 ° C. higher than the glass transition temperature of the amorphous polyester (c). The temperature is kept at a high temperature or lower, more preferably 15 ° C. or higher.

  The holding time in this step is preferably 0.5 to 24 hours from the viewpoint of improving the fusing property of the aggregated particles, improving the low-temperature fixability and durability of the toner, and improving the toner productivity. 0.75-12 hours are more preferable, and 1-8 hours are still more preferable.

The volume median particle size (D ₅₀ ) of the fused particles obtained in this step is preferably 10 μm or less, more preferably 8 μm or less, even more preferably 7 μm or less, from the viewpoint of obtaining a toner capable of obtaining a high-quality image. More preferably, it is 6 μm or less. Moreover, 2 micrometers or more are preferable, 3 micrometers or more are more preferable, and 4 micrometers or more are still more preferable.

  In addition, it is preferable that the average particle diameter of the fusion | melting particle | grains obtained at this process is below the average particle diameter of aggregated particle (2). That is, in this step, it is preferable that the fused particles do not aggregate and fuse.

[Post-processing process]
In the present invention, a post-treatment step may be performed after step (4), and it is preferable to obtain toner particles by isolating the fused particles.
Since the fused particles obtained in the step (4) 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. When a nonionic surfactant is used in the production of the resin particles (A) and (B), it is preferable to remove the added nonionic surfactant, so the cloud point of the nonionic surfactant In the following, it is preferable to wash with an aqueous medium. The washing is preferably performed a plurality of times.
Next, although it is preferable to perform drying, the temperature at the time of drying is 5 ° C. lower than the glass transition temperature of the resin constituting the fused particles, which is higher than the melting point of the crystalline polyester (a). It is preferable to set the temperature to be lower by 5 ° C. or higher, and it is more preferable to set the temperature to be lower by 10 ° C. or higher. 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 volume-median particle size (D ₅₀ ) of the obtained toner particles is preferably 10 μm or less, more preferably 8 μm or less, and more preferably 7 μm or less from the viewpoints of improving the image quality of the toner and improving the productivity of the toner. More preferably, 6 μm or less is still more preferable, 1 μm or more is preferable, 2 μm or more is more preferable, 3 μm or more is further preferable, and 4 μm or more is even more preferable.

From the viewpoint of improving the image quality of the toner, the CV value of the toner particles is preferably 30% or less, more preferably 28% or less, and even more preferably 27% or less. Further, from the viewpoint of improving toner productivity, it is preferably 5% or more, more preferably 10% or more, and further preferably 15% or more.
The volume median particle size (D ₅₀ ) and CV value of the toner particles are determined by the method described in the examples.

<Toner for electrostatic image development>
(toner)
The toner particles obtained by drying or the like can be used as they are as the toner for developing an electrostatic image of the present invention, but the toner particle surface treated as described below is used as a toner for developing an electrostatic image. It is preferable.
The softening point of the obtained toner is preferably 60 ° C. or higher, preferably 140 ° C. or lower, more preferably 130 ° C. or lower, and further preferably 120 ° C. or lower, from the viewpoint of improving the low-temperature fixability and durability of the toner. .

(External additive)
In the toner for developing an electrostatic charge image obtained by the production method of the present invention, the toner particles can be used as the toner as they are, but the toner particles are treated by adding a fluidizing agent or the like as an external additive to the toner particles. It is preferable to use it.
Examples of the external additive include inorganic fine particles such as hydrophobic silica, titanium oxide fine particles, alumina fine particles, cerium oxide fine particles, and carbon black, and polymer fine particles such as polycarbonate, polymethyl methacrylate, and silicone resin. Among these, hydrophobic silica and polymer fine particles are preferable.
When the surface treatment of the toner particles is performed using the external additive, the amount of the external additive added is preferably 1 to 5 parts by mass, and 2 to 5 parts per 100 parts by mass of the toner particles before the treatment with the external additive. A mass part is more preferable, and 3-4.5 mass part is still more preferable.

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.

In this specification, in addition to the above, the following method for producing a toner for developing an electrostatic image is disclosed.
<1> Next steps (1) to (4)
Step (1): Crystalline polyester (a) and amorphous polyester (b) are mixed in an aqueous medium at a temperature equal to or higher than the melting point of crystalline polyester (a), and a dispersion of resin particles (A) Step (2): Step of aggregating resin particles (A) to obtain aggregated particles (1) Step (3): Amorphous polyester (c) is contained in the dispersion of aggregated particles (1) Step of adding aggregated resin particles (B) to obtain aggregated particles (2) Step (4): electrostatic charge image development including the step of fusing the aggregated particles (2) to obtain fused particles A toner manufacturing method, wherein the amorphous polyester (b) is an alkyl succinic acid having an alkyl group having 9 to 14 carbon atoms and / or an alkenyl succinic acid having an alkenyl group having 9 to 14 carbon atoms. An acid component containing 60 mol% or more and 90 mol% or less The amorphous polyester (b1) obtained by polycondensation with an alcohol component is contained, and the content of the amorphous polyester (b1) in the resin constituting the resin particles (A) is 7% by mass or more and 20% by mass. %, And the content of the alkyl succinic acid and / or alkenyl succinic acid in the total amount of carboxylic acid components of all the polyesters in the resin particles (A) is 5 mol% or more and 20 mol% or less A method for producing a toner for developing a charge image.

<2> The total content of the crystalline polyester (a) and the amorphous polyester (b) in the resin constituting the resin particles (A) is 80% by mass or more in the resin constituting the resin particles (A). The toner for developing an electrostatic charge image according to <1>, preferably 90% by mass or more, more preferably 95% by mass or more, substantially more preferably 100% by mass, and still more preferably 100% by mass. Production method.
<3> The melting point of the crystalline polyester (a) is preferably 50 ° C. or higher, more preferably 60 ° C. or higher, still more preferably 70 ° C. or higher, still more preferably 75 ° C. or higher, still more preferably 80 ° C. or higher, The electrostatic charge image according to <1> or <2>, preferably 140 ° C. or lower, more preferably 120 ° C. or lower, still more preferably 100 ° C. or lower, still more preferably 90 ° C. or lower, and still more preferably 85 ° C. or lower. A method for producing a developing toner.
<4> The softening point of the crystalline polyester (a) is preferably 50 ° C. or higher, more preferably 60 ° C. or higher, still more preferably 70 ° C. or higher, still more preferably 75 ° C. or higher, and preferably 150 ° C. or lower, The method for producing a toner for developing an electrostatic charge image according to any one of <1> to <3>, preferably 120 ° C. or lower, more preferably 100 ° C. or lower, and still more preferably 95 ° C. or lower.
<5> The acid value of the crystalline polyester (a) is preferably 30 mgKOH / g or less, more preferably 27 mgKOH / g or less, further preferably 25 mgKOH / g or less, more preferably 5 mgKOH / g or more, and 10 mgKOH / g or more. Is more preferable, and 15 mgKOH / g or more is still more preferable, The manufacturing method of the electrostatic image developing toner in any one of <1>-<4>.
<6> The crystalline polyester (a) contains a polyester obtained by polycondensation of an α, ω-alkanediol having 2 to 12 carbon atoms and an aliphatic carboxylic acid having 4 to 12 carbon atoms. The method for producing a toner for developing an electrostatic charge image according to any one of 1> to <5>.
<7> The crystalline polyester (a) is preferably a polyester obtained by polycondensation of an aliphatic dicarboxylic acid having 4 to 12 carbon atoms and an α, ω-linear alkanediol having 2 to 12 main chain carbon atoms. Preferably, at least one dicarboxylic acid selected from the group consisting of succinic acid, sebacic acid and 1,12-dodecanedioic acid, 1,6-hexanediol, 1,8-octanediol, 1,9-nonanediol, Polyester obtained by polycondensation of one or more diols selected from the group consisting of 1,10-decanediol and 1,12-dodecanediol, more preferably succinic acid, 1,10-decanediol and 1,12-dodecanediol The electrostatic image according to any one of <1> to <6>, which is a polyester obtained by polycondensation of one or more diols selected from the group consisting of A method for producing a developing toner.
<8> An alkyl succinic acid having an alkyl group having 9 to 14 carbon atoms and / or an alkenyl succinic acid having an alkenyl group having 9 to 14 carbon atoms has an alkyl group or an alkenyl group having 10 to 14 carbon atoms. Preferably, 12 or more and 14 or less are more preferable, dodecenyl succinic acid and its acid anhydride are preferable, and dodecenyl succinic acid anhydride is more preferable, The manufacturing method of the electrostatic image developing toner in any one of <1>-<7> .
<9> The content of the alkyl succinic acid having an alkyl group having 9 to 14 carbon atoms and / or the alkenyl succinic acid having an alkenyl group having 9 to 14 carbon atoms is in the acid component of the amorphous polyester (b1). 60 mol% or more, preferably 65 mol% or more, more preferably 70 mol% or more, more preferably 75 mol% or more, and 90 mol% or less, preferably 87 mol% or less, 83 mol%. The following is more preferable, 80 mol% or less is more preferable, 60-90 mol% is preferable, 60-87 mol% is preferable, 65-83 mol% is more preferable, 70-80 mol% is still more preferable, 75 The method for producing a toner for developing an electrostatic charge image according to any one of <1> to <8>, wherein ˜80 mol% is even more preferable.
<10> The softening point of the amorphous polyester (b1) is preferably 70 ° C. or higher, more preferably 80 ° C. or higher, still more preferably 90 ° C. or higher, still more preferably 100 ° C. or higher, and preferably 165 ° C. or lower. The method for producing a toner for developing an electrostatic charge image according to any one of <1> to <9>, wherein 150 ° C. or lower is more preferable, 130 ° C. or lower is further preferable, and 120 ° C. or lower is even more preferable.

<11> The glass transition temperature of the amorphous polyester (b1) is preferably 10 ° C. or higher, more preferably 20 ° C. or higher, further preferably 25 ° C. or higher, more preferably 30 ° C. or higher, and 80 ° C. or lower. The method for producing a toner for developing an electrostatic charge image according to any one of <1> to <10>, preferably 70 ° C. or lower, more preferably 60 ° C. or lower, and still more preferably 50 ° C. or lower.

<12> The acid value of the amorphous polyester (b1) is preferably 35 mgKOH / g or less, more preferably 30 mgKOH / g or less, further preferably 25 mgKOH / g or less, more preferably 5 mgKOH / g or more, and 10 mgKOH / g. The method for producing an electrostatic charge image developing toner according to any one of <1> to <11>, wherein the above is more preferable, and 15 mgKOH / g or more is further preferable.
<13> The amorphous polyester (b) contains the amorphous polyester (b2) in addition to the amorphous polyester (b1), and the acid component of the raw material monomer of the amorphous polyester (b2) is carbon. An acid component of the raw material monomer of the amorphous polyester (b2), which may contain an alkyl succinic acid having an alkyl group of 9 to 14 and / or an alkenyl succinic acid having an alkenyl group of 9 to 14 carbon atoms The content of the alkyl succinic acid and / or the alkenyl succinic acid is preferably less than 60 mol%, more preferably 10 mol% or less, still more preferably 1 mol% or less, and still more preferably substantially. The method for producing a toner for developing an electrostatic charge image according to any one of <1> to <12>, which is 0 mol%, and more preferably 0 mol%.

<14> The dispersion of resin particles (A) preferably contains a surfactant, and examples of the surfactant include a nonionic surfactant, an anionic surfactant, and a cationic surfactant. Among them, nonionic surfactants are preferable, and it is more preferable to use a nonionic surfactant and an anionic surfactant or a cationic surfactant in combination, and the nonionic surfactant and the anionic interface are used in combination. It is more preferable to use an active agent in combination, and when using a nonionic surfactant and an anionic surfactant in combination, the mass ratio of the nonionic surfactant to the anionic surfactant (nonionic interface) (Activator / anionic surfactant) is preferably 0.3 or more, more preferably 0.5 or more, and preferably from the viewpoint of improving the dispersion stability of the dispersion of the resin particles (A). 0 or less, more preferably 5 or less, <1> to <13> any method for producing a toner according to the.

<15> The nonionic surfactant is at least selected from the group consisting of polyoxyethylene alkylaryl ethers, polyoxyethylene alkyl or alkenyl ethers, polyoxyethylene fatty acid esters, oxyethylene / oxypropylene block copolymers The method for producing a toner for developing an electrostatic charge image according to <14>, wherein one kind is preferable, polyoxyethylene alkyl or alkenyl ether is preferable, and polyoxyethylene lauryl ether is more preferable.
<16> The anionic surfactant is preferably at least one selected from the group consisting of alkylbenzene sulfonates, alkyl sulfates, and alkyl ether sulfates, sodium dodecylbenzene sulfonate and sodium lauryl ether sulfate are preferable, and dodecyl The method for producing a toner for developing an electrostatic charge image according to <14> or <15>, wherein sodium benzenesulfonate is more preferable.

The content of <17> surfactant is preferably 20 parts by mass or less, more preferably 15 parts by mass or less, and still more preferably 10 parts by mass or less, with respect to 100 parts by mass of the resin constituting the resin particles (A). 5 parts by mass or less is more preferable, 0.5 parts by mass or more is preferable, 1 part by mass or more is more preferable, and 2 parts by mass or more is more preferable, The static according to any one of <14> to <16> A method for producing a toner for developing a charge image.

<18> The mass ratio [(a) / (b)] when the crystalline polyester (a) and the amorphous polyester (b) are mixed is preferably 5/95 to 45/55, and 10/90 to 40/60 is more preferred, 10/90 to 30/70 is more preferred, and 13/87 to 20/80 is still more preferred. Production of an electrostatic charge image developing toner according to any one of <1> to <17> Method.

<19> The content of the amorphous polyester (b1) in the resin constituting the resin particles (A) is 7% by mass or more, more preferably 8% by mass or more, and 20% by mass or less. 18 mass% or less is preferable, 15 mass% or less is more preferable, 12 mass% or less is still more preferable, and it is 7-20 mass%, 7-18 mass% is preferable, 7-15 mass% is more preferable, The method for producing a toner for developing an electrostatic charge image according to any one of <1> to <18>, wherein 8 to 12% by mass is further preferable.

The mass ratio ((b1) / (b2)) of the amorphous polyester (b1) and the amorphous polyester (b2) in the <20> resin particles (A) is 7/93 to 35/65. Preferably, 8/92 to 25/75 is more preferable, 9/91 to 20/80 is still more preferable, and 10/90 to 15/85 is still more preferable, Static according to any one of <1> to <19> A method for producing a toner for developing a charge image.

The content of the alkyl succinic acid and / or alkenyl succinic acid in the total amount of carboxylic acid components of all the polyesters in <21> resin particles (A) is 5.0 mol% or more, and 6.0 mol%. The above is preferable, 6.5 mol% or more is more preferable, 20 mol% or less, 16 mol% or less is preferable, 12 mol% or less is more preferable, 8.0 mol% or less is more preferable, and 5.0 to 20 mol%, preferably 5.0 to 16 mol%, more preferably 6.0 to 12 mol%, and even more preferably 6.5 to 8.0 mol%, <1> to <20 The method for producing a toner for developing an electrostatic charge image according to any one of the above.
<22> The mass ratio of the crystalline polyester (a) to the amorphous polyester (b1) (crystalline polyester (a) / amorphous polyester (b1)) is preferably 80/20 to 20/80, 20-40 / 60 is more preferable, 75 / 25-50 / 50 is still more preferable, 70 / 30-55 / 45 is still more preferable, and 64 / 36-60 / 40 is still more preferable, <1>-<21 The method for producing a toner for developing an electrostatic charge image according to any one of the above.
<23> The electrostatic charge image development according to any one of <1> to <22>, wherein the polyester resin constituting the resin particles (A) is preferably crosslinked, and more preferably crosslinked with a compound having an oxazoline group. Of manufacturing toner.
<24> The content or addition amount of the compound having an oxazoline group is preferably 30 parts by mass or less, and 20 parts by mass or less as a solid content with respect to 100 parts by mass of the total amount of the resin constituting the resin particles (A). More preferably, 10 parts by mass or less, further preferably 0.1 parts by mass or more, and more preferably 0.5 parts by mass or more, and the method for producing a toner for developing an electrostatic charge image according to <23>.
The solid content concentration of the dispersion of <25> resin particles (A) is preferably 50% by mass or less, more preferably 40% by mass or less, still more preferably 35% by mass or less, and 10% by mass or more. The electrostatic image developing toner according to any one of <1> to <24>, preferably 15% by mass or more, more preferably 20% by mass or more, and still more preferably 25% by mass or more. Production method.

The volume median particle size (D ₅₀ ) of the resin particles (A) in the dispersion of <26> resin particles (A) is preferably 2 μm or less, more preferably 1 μm or less, and further 0.5 μm or less. Preferably, 0.3 μm or less is more preferable, 0.02 μm or more is preferable, 0.05 μm or more is more preferable, 0.08 μm or more is further preferable, and 0.10 μm or more is further preferable, <1 The method for producing a toner for developing an electrostatic charge image according to any one of <25> to <25>.
<27> The coefficient of variation (CV value) (%) of the particle size distribution of the resin particles (A) is preferably 40% or less, more preferably 35% or less, still more preferably 32% or less, and 5%. The method for producing a toner for developing an electrostatic charge image according to any one of <1> to <26>, preferably 10% or more, more preferably 15% or more.
<28> The step (2) preferably aggregates the release agent particles together with the resin particles (A), preferably mixes and aggregates the flocculant, and the resin particles (A), the release agent particles and The method for producing a toner for developing an electrostatic charge image according to any one of <1> to <27>, wherein the coagulant is mixed and aggregated in an aqueous medium to obtain aggregated particles (1).
<29> The method for producing a toner for developing an electrostatic charge image according to <28>, wherein the release agent is preferably paraffin wax and carnauba wax, and more preferably used in combination with paraffin wax and carnauba wax.
The volume median particle size (D ₅₀ ) of <30> aggregated particles (1) is preferably 10 μm or less, more preferably 8 μm or less, further preferably 6 μm or less, more preferably 1 μm or more, and more preferably 2 μm or more, The method for producing a toner for developing an electrostatic charge image according to any one of <1> to <29>, further preferably 3 μm or more.
<31> The CV value of the aggregated particles (1) is preferably 30% or less, more preferably 28% or less, further preferably 25% or less, more preferably 5% or more, more preferably 10% or more, and 15%. The method for producing an electrostatic image developing toner according to any one of <1> to <30>, wherein the above is more preferable.

<32> In step (3), a dispersion of resin particles (B) is added to the dispersion of aggregated particles (1) obtained in step (2), and resin particles (1) are further added to aggregated particles (1). The method for producing a toner for developing an electrostatic charge image according to any one of <1> to <31>, wherein B) is preferably adhered to obtain aggregated particles (2).
<33> The resin particles (B) preferably contain 80% by mass or more, more preferably 90% by mass or more, and 95% by mass of the amorphous polyester (c) with respect to the resin in the resin particles (B). The method for producing a toner for developing an electrostatic charge image according to <32>, wherein the above is further preferable, the content is more preferably substantially 100% by mass, and still more preferably 100% by mass.

<34> The amorphous polyester (c) is an acid component and an alcohol containing an alkyl succinic acid having an alkyl group having 9 to 14 carbon atoms and / or an alkenyl succinic acid having an alkenyl group having 9 to 14 carbon atoms. The method for producing a toner for developing an electrostatic charge image according to <33>, preferably containing an amorphous polyester (c1) obtained by polycondensation with a component.
<35> The content of the alkyl succinic acid having an alkyl group having 9 to 14 carbon atoms and / or the alkenyl succinic acid having an alkenyl group having 9 to 14 carbon atoms is in the acid component of the amorphous polyester (c1). 1 mol% or more is preferable, 3 mol% or more is more preferable, 5 mol% or more is further preferable, 30 mol% or more is further more preferable, 60 mol% or more is further more preferable, and 90 mol% or less is preferable. 83 mol% or less is more preferable, and 80 mol% or less is more preferable, The manufacturing method of the electrostatic image developing toner as described in <34>.

<36> The amorphous polyester (c) preferably contains an amorphous polyester (c2) in addition to the amorphous polyester (c1), and the amorphous polyester (c1) in the resin particles (B) ) And amorphous polyester (c2) content mass ratio ((c1) / (c2)) is preferably 2/98 to 50/50, more preferably 5/95 to 45/55, and 8/92. The method for producing a toner for developing an electrostatic charge image according to any one of <33> to <35>, wherein ˜40 / 60 is further preferred.
<37> The glass transition temperature of the amorphous polyester (c) is preferably 50 ° C. or higher, more preferably 55 ° C. or higher, further preferably 60 ° C. or higher, more preferably 75 ° C. or lower, and more preferably 70 ° C. or lower. 67. The method for producing a toner for developing an electrostatic charge image according to any one of <33> to <36>, further preferably 67 ° C. or lower.
<38> The mass ratio of the resin particles (B) to the resin particles (A) (resin particles (B) / resin particles (A)) is preferably 1.5 or less, more preferably 1.0 or less, and 5 or less is more preferable, 0.1 or more is preferable, and 0.2 or more is more preferable, The manufacturing method of the electrostatic image developing toner in any one of <32>-<37>.

<39> The volume median particle size (D ₅₀ ) of the toner or toner particles is preferably 10 μm or less, more preferably 8 μm or less, further preferably 7 μm or less, still more preferably 6 μm or less, and preferably 1 μm or more. The method for producing a toner for developing an electrostatic charge image according to any one of <1> to <38>, preferably 2 μm or more, more preferably 3 μm or more, and still more preferably 4 μm or more.

The CV value of <40> toner or toner particles is preferably 30% or less, more preferably 28% or less, and even more preferably 27% or less. The method for producing a toner for developing an electrostatic charge image according to any one of <1> to <39>, preferably 5% or more, more preferably 10% or more, and further preferably 15% or more.

<41> The softening point of the toner or toner particles is preferably 60 ° C. or higher, preferably 140 ° C. or lower, more preferably 130 ° C. or lower, and further preferably 120 ° C. or lower, any one of <1> to <40> A method for producing a toner for developing an electrostatic image as described in 1.
<42> An electrostatic charge image developing toner obtained by the production method according to any one of <1> to <41>.

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

[Softening point of polyester and toner]
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, and the diameter was 1 mm and the length was 1 mm. Extruded from the nozzle. The amount of plunger drop of the flow tester was plotted against the temperature, and the temperature at which half of the sample flowed out was taken as the softening point.

[Maximum endothermic peak temperature, crystallinity index, melting point and glass transition temperature of polyester]
Using a differential scanning calorimeter “Pyris 6 DSC” (manufactured by PerkinElmer), the sample cooled from room temperature (20 ° C.) to 0 ° C. at a temperature decreasing rate of 10 ° C./min was allowed to stand still for 1 minute. The temperature was raised to 180 ° C at a rate of ° C / min and measured. 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.
In the case of crystalline polyester, the peak temperature was taken as the melting point. In the case of amorphous polyester, the endothermic peak is observed when the peak temperature is observed, and when the step is observed without the peak being observed, the tangent line indicating the maximum slope of the step portion 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.

[Acid value of polyester]
It measured according to JIS K0070. However, the measurement solvent was a mixed solvent of acetone and toluene (acetone: toluene = 1: 1 (volume ratio)).

[Melting point of release agent]
A differential scanning calorimeter “Pyris 6 DSC” (manufactured by PerkinElmer) was used to measure from 20 ° C. at a heating rate of 10 ° C./min, and the maximum peak temperature was taken as the melting point.

[Average primary particle size of inorganic fine particles]
The particle size (average value of major axis and minor axis) of 500 particles was measured from a scanning electron microscope (SEM) photograph, and the average value was defined as the average primary particle size.

[Volume Median Particle Size (D ₅₀ ) and CV Value of Resin Particles, Release Agent Particles]
(1) Measuring apparatus: Laser diffraction 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 ) was measured at a concentration at which the absorbance was in an appropriate range. The CV value was calculated according to the following formula.
CV value (%) = (standard deviation of particle size distribution / volume median particle size (D ₅₀ )) × 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), 5 g of a measurement sample was dried at a temperature of 150 ° C. and in a measurement mode 96 (monitoring time 2.5 minutes / variation width 0.05%). The moisture percentage was measured. The solid content concentration was calculated according to the following formula.
Solid content concentration (% by mass) = 100-M
M: moisture (%) = [(W−W ₀ ) / W] × 100
W: Sample mass before measurement (initial sample mass)
W ₀ : Mass of sample after measurement (absolute dry mass)

[Volume Median Particle Size (D ₅₀ ) and CV Value of Toner Particles, Aggregated Particles, and Fused Particles]
The volume median particle size of the toner particles was measured as follows.
-Measuring machine: Coulter Multisizer III (Beckman Coulter, Inc.)
・ Aperture diameter: 50μm
・ Analysis software: Multisizer III version 3.51 (Beckman Coulter, Inc.)
・ Electrolyte: Isoton II (Beckman Coulter)
Dispersion: Polyoxyethylene lauryl ether “Emulgen 109P” (manufactured by Kao Corporation, HLB: 13.6) was dissolved in the electrolytic solution to obtain a dispersion having a concentration of 5% by mass.
-Dispersion condition: 10 mg of a toner measurement sample is added to 5 mL of the dispersion, and dispersed for 1 minute with an ultrasonic disperser, and then 25 mL of electrolyte is added, and further dispersed for 1 minute with an ultrasonic disperser. A sample dispersion was prepared.
Measurement conditions: After adding the sample dispersion to 100 mL of the electrolyte solution, the particle size of 30,000 particles is adjusted to a concentration that can be measured in 20 seconds, and then 30,000 particles are measured. The volume-median particle size (D ₅₀ ) was determined from the distribution.
The CV value (%) was calculated according to the following formula.
CV value (%) = (standard deviation of particle size distribution / volume median particle size (D ₅₀ )) × 100
The volume median particle size of the aggregated particles (1), aggregated particles (2), and fused particles is determined by measuring the volume median particle size of the toner particles as the sample dispersion liquid. ), And the same measurement was performed using dispersion liquids each containing fused particles.

[Evaluation of low-temperature fixability of toner]
Using a commercially available printer “Microline 5400” (Oki Data Co., Ltd.) on high quality paper “J paper A4 size” (Fuji Xerox Co., Ltd.), the toner adhesion amount on the paper is 0.42 to 0.48 mg / cm ^2. The solid image was output without fixing at a length of 50 mm, leaving a margin of 5 mm from the top edge of the A4 paper.
Next, the same printer with the temperature-variable fixing device prepared was prepared, the temperature of the fixing device was set to 90 ° C., and fixing was performed at a speed of 1.5 seconds per sheet in the A4 longitudinal direction, thereby obtaining a printed matter.
In the same manner, the temperature of the fixing device was increased by 5 ° C. and fixed, and a printed matter was obtained.
A 500 g weight is applied to the solid image from the top margin of the printed image and a solid image with a 50 mm long mending tape “Scotch Mending Tape 810” (18 mm wide by 3M). And reciprocally pressed 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 high-quality paper “Excellent White Paper A4 Size” (manufactured by Oki Data Co., Ltd.) is laid under the printed matter 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 matter. Measurement was performed using a colorimeter “SpectroEye” (manufactured by GretagMacbeth, Inc., light emission condition: standard light source D ₅₀ , observation visual field 2 °, density reference DINNB, absolute white reference), 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 more was defined as the minimum fixing temperature. The lower the minimum fixing temperature, the better the low-temperature fixing property.

[Evaluation of toner durability]
The toner is put into the developing cartridge of the non-magnetic one-component developing device “Microline 5400” (manufactured by Oki Data Co., Ltd.). The occurrence of uneven stripes on the roll surface was visually observed, and the time (Hr) until the occurrence of uneven stripes was measured. In the one-component developing device, the toner is charged by passing through the blade portion. At this time, if the toner is weak against external factors, the toner adheres to the blade portion and the developing roll, and unevenness occurs. Observed. Therefore, a toner having a longer time until occurrence of unevenness is more excellent in durability.

[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 replaced with nitrogen, and 5050 g of 1,12-dodecanediol and 2950 g of succinic acid were added. And maintained for 3 hours. Thereafter, the temperature was raised from 135 ° C. to 200 ° C. over 10 hours, 16 g of di (2-ethylhexanoic acid) tin was added, and maintained at 200 ° C. for 1 hour, and then the pressure in the flask was further lowered to 8.3 kPa. For 1 hour to obtain crystalline polyester X1. Table 1 shows the physical properties of the obtained crystalline polyester X1.

Production Example 2
(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 purged with nitrogen, and 2042 g of polyoxypropylene (2.2) -2,2-bis (4-hydroxyphenyl) propane, Put 813 g of polyoxyethylene (2.0) -2,2-bis (4-hydroxyphenyl) propane, 1742 g of dodecenyl succinic anhydride and 25 g of di (2-ethylhexanoic acid) tin, and stir in a nitrogen atmosphere. The temperature was raised to 220 ° C. and maintained for 5 hours. Thereafter, the mixture was cooled to 215 ° C., 336 g of trimellitic anhydride was added, and maintained at 215 ° C. for 1 hour, and then the pressure in the flask was further lowered and maintained at 8.3 kPa for 1 hour to obtain amorphous polyester Y1 Got. Table 1 shows the physical properties of the obtained amorphous polyester Y1.

Production Example 3
(Production of amorphous polyester Y2)
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 3773 g of polyoxypropylene (2.2) -2,2-bis (4-hydroxyphenyl) propane, Put 1502 g of polyoxyethylene (2.0) -2,2-bis (4-hydroxyphenyl) propane, 256 g of terephthalic acid, 2806 g of dodecenyl succinic anhydride, and 45 g of di (2-ethylhexanoic acid) tin under a nitrogen atmosphere. While stirring, the temperature was raised to 230 ° C. and maintained for 6 hours, and then the pressure in the flask was further lowered and maintained at 8.3 kPa for 1 hour. Then, after cooling to 215 ° C. and returning to atmospheric pressure, 621 g of trimellitic anhydride was added and maintained at a temperature of 215 ° C. for 1 hour, and then the pressure in the flask was further reduced to 3 at 8.3 kPa. Amorphous polyester Y2 was obtained by maintaining the time. Table 1 shows the physical properties of the obtained amorphous polyester Y2.

Production Example 4
(Production of amorphous polyester Y3)
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 3651 g of polyoxypropylene (2.2) -2,2-bis (4-hydroxyphenyl) propane, While adding 1453 g of polyoxyethylene (2.0) -2,2-bis (4-hydroxyphenyl) propane, 3394 g of dodecenyl succinic anhydride and 45 g of di (2-ethylhexanoic acid) tin, stirring under a nitrogen atmosphere The temperature was raised to 220 ° C. and maintained for 7 hours. Thereafter, the mixture was cooled to 215 ° C., 429 g of trimellitic anhydride was added and maintained at a temperature of 215 ° C. for 1 hour, and then the pressure in the flask was further lowered and maintained at 8.3 kPa for 1 hour to obtain amorphous. Quality polyester Y3 was obtained. Table 1 shows the physical properties of the obtained amorphous polyester Y3.

Production Example 5
(Production of amorphous polyester Y4)
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 3920 g of polyoxypropylene (2.2) -2,2-bis (4-hydroxyphenyl) propane, Polyoxyethylene (2.0) -2,2-bis (4-hydroxyphenyl) propane (1560 g), terephthalic acid (1142 g), and di (2-ethylhexanoic acid) tin (45 g) were added, and the mixture was stirred under a nitrogen atmosphere. The temperature was raised to ° C. and maintained for 6 hours. Thereafter, 1972 g of dodecenyl succinic anhydride and 369 g of trimellitic anhydride were added and maintained at 230 ° C. for 2 hours, then the pressure in the flask was further lowered and maintained at 8.3 kPa for 2 hours to obtain amorphous polyester Y4 Got. Table 1 shows the physical properties of the obtained amorphous polyester Y4.

Production Example 6
(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 purged with nitrogen, and 3626 g of polyoxypropylene (2.2) -2,2-bis (4-hydroxyphenyl) propane, A mixture of 1443 g of polyoxyethylene (2.0) -2,2-bis (4-hydroxyphenyl) propane, 3927 g of dodecenyl succinic anhydride and 45 g of di (2-ethylhexanoic acid) tin is added with stirring under a nitrogen atmosphere. The temperature was raised to 220 ° C. and maintained for 8 hours, and then the pressure in the flask was further reduced and maintained at 8.3 kPa for 2 hours to obtain amorphous polyester Y5. Table 1 shows the physical properties of the obtained amorphous polyester Y5.

Production Example 7
(Production of amorphous polyester Y6)
The inside of a four-necked flask equipped with a nitrogen introduction tube, a dehydration tube, a stirrer, and a thermocouple was replaced with nitrogen, and 3374 g of polyoxypropylene (2.2) -2,2-bis (4-hydroxyphenyl) propane, Put 33 g of polyoxyethylene (2.0) -2,2-bis (4-hydroxyphenyl) propane, 672 g of terephthalic acid, and 10 g of dibutyltin oxide, and raise the temperature to 230 ° C. with stirring in a nitrogen atmosphere. Maintained for 5 hours. Thereafter, the pressure in the flask was further reduced and maintained at 8.3 kPa for 1 hour. After cooling to 210 ° C. and returning to atmospheric pressure, 696 g of fumaric acid and 0.49 g of tert-butylcatechol were added and maintained at 210 ° C. for 5 hours, and then the pressure in the flask was further reduced to 4 at 8.3 kPa. Amorphous polyester Y6 was obtained by maintaining the time. Table 1 shows the physical properties of the obtained amorphous polyester Y6.

Production Example 8
(Production of amorphous polyester Y7)
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 1750 g of polyoxypropylene (2.2) -2,2-bis (4-hydroxyphenyl) propane, A nitrogen atmosphere containing 1625 g of polyoxyethylene (2.0) -2,2-bis (4-hydroxyphenyl) propane, 1145 g of terephthalic acid, 161 g of dodecenyl succinic anhydride, 480 g of trimellitic anhydride, and 10 g of dibutyltin oxide Under stirring, the temperature was raised to 220 ° C. and maintained for 5 hours. After confirming that the softening point measured in accordance with ASTM D36-86 reached 120 ° C., the temperature was lowered to stop the reaction. Quality polyester Y7 was obtained. Table 1 shows the physical properties of the obtained amorphous polyester Y7.

[Production of release agent particle dispersion]
Production Example 9
(Production of release agent particle dispersion)
In a beaker with an internal volume of 1 liter, 200 g of deionized water and 3.8 g of a sodium acrylate-sodium maleate copolymer aqueous solution “Poise 521” (made by Kao Corporation, effective concentration 40% by mass) as a sodium polycarboxylate aqueous solution are dissolved. After that, 5 g of carnauba wax “Carnauba wax No. 1” (manufactured by Kato Yoko Co., Ltd., melting point 83 ° C.) and 45 g of paraffin wax “HNP-9” (manufactured by Nippon Seiki Co., Ltd., melting point 75 ° C.) are added. The mixture was melted while maintaining the temperature at 90 to 95 ° C. to obtain a molten mixture in which carnauba wax and paraffin wax were fused together.
The aqueous solution containing the obtained molten mixture was further subjected to a dispersion treatment for 30 minutes using an ultrasonic homogenizer “US-600T” (manufactured by Nippon Seiki Seisakusyo) while maintaining the temperature at 90 to 95 ° C. After cooling to 25 ° C., deionized water was added to adjust the solid content to 20% by mass to obtain a release agent particle dispersion. The volume median particle size (D ₅₀ ) of the release agent particles was 0.450 μm, and the CV value was 30%.

[Production of resin particle dispersion: Step (1)]
Production Example P1
(Preparation of resin particle (1) dispersion)
In a 5 l stainless steel flask equipped with a stirrer, 90 g of crystalline polyester X1, 51 g of amorphous polyester Y1, 459 g of amorphous polyester Y6, 45 g of copper phthalocyanine pigment “ECB-301” (manufactured by Daiichi Seika Kogyo Co., Ltd.) , Polyoxyethylene lauryl ether “Emulgen 150” (nonionic surfactant, manufactured by Kao Corporation) 8.5 g, 15 mass% sodium dodecylbenzenesulfonate aqueous solution “Neopelex G-15” (anionic surfactant, Kao) 80 g) and 278.5 g of 5% by mass aqueous potassium hydroxide solution were added and mixed at 95 ° C. for 2 hours with stirring. While maintaining the temperature of the system at 95 ° C., 1222 g of deionized water was added dropwise at a rate of 6 g / min while stirring to obtain an emulsion. The obtained emulsion was cooled to 25 ° C., and stirred at 25 ° C., 28 g of an oxazoline group-containing polymer aqueous solution “Epocross WS-700” (manufactured by Nippon Shokubai Co., Ltd., nonvolatile content 25% by mass, acrylic main chain) was added. Thereafter, the temperature was raised to 95 ° C. and held at 95 ° C. for 1 hour. Next, the mixture was cooled to 25 ° C. and passed through a 200 mesh (mesh opening 105 μm) wire mesh to obtain a resin particle (1) dispersion. Table 2 shows the solid content concentration of the obtained resin particle (1) dispersion, the volume median particle size of the resin particle (1), and the CV value.

Production Example P2
(Preparation of resin particle (2) dispersion)
In Production Example P1, except that 51 g of amorphous polyester Y1 was changed to 60 g of amorphous polyester Y2, and 459 g of amorphous polyester Y6 was changed to 450 g of amorphous polyester Y6, resin particles ( 2) A dispersion was obtained. Table 2 shows the solid content concentration of the obtained resin particle (2) dispersion, the volume median particle size (D ₅₀ ), and the CV value of the resin particle (2).

Production Example P3
(Preparation of resin particle (3) dispersion)
In Production Example P1, except that 51 g of amorphous polyester Y1 was changed to 48 g of amorphous polyester Y3 and 459 g of amorphous polyester Y6 were changed to 462 g of amorphous polyester Y6, resin particles ( 3) A dispersion was obtained. Table 2 shows the solid content concentration of the obtained resin particle (3) dispersion, the volume median particle size (D ₅₀ ), and the CV value of the resin particle (3).

Production Example P4
(Preparation of resin particle (4) dispersion)
In Production Example P1, except that 51 g of amorphous polyester Y1 was changed to 120 g of amorphous polyester Y1 and 459 g of amorphous polyester Y6 was changed to 390 g of amorphous polyester Y6, resin particles ( 4) A dispersion was obtained. Table 2 shows the solid content concentration of the obtained resin particle (4) dispersion, the volume median particle size (D ₅₀ ), and the CV value of the resin particle (4).

Production Example P5
(Preparation of resin particle (5) dispersion)
In Production Example P1, except that 51 g of amorphous polyester Y1 was changed to 60 g of amorphous polyester Y1 and 459 g of amorphous polyester Y6 was changed to 450 g of amorphous polyester Y6, resin particles ( 5) A dispersion was obtained. Table 2 shows the solid content concentration of the obtained resin particle (5) dispersion, the volume median particle size (D ₅₀ ), and the CV value of the resin particle (5).

Production Example P6
(Preparation of resin particle (6) dispersion)
In Production Example P1, except that 51 g of amorphous polyester Y1 was changed to 60 g of amorphous polyester Y3 and 459 g of amorphous polyester Y6 was changed to 450 g of amorphous polyester Y6, resin particles ( 6) A dispersion was obtained. Table 2 shows the solid content concentration of the obtained resin particle (6) dispersion, the volume median particle size (D ₅₀ ), and the CV value of the resin particle (6).

Production Example P7
(Preparation of resin particle (7) dispersion)
Resin particles (Production Example P1) were the same as Production Example P1 except that 51 g of amorphous polyester Y1 was changed to 90 g of amorphous polyester Y2, and 459 g of amorphous polyester Y6 was changed to 420 g of amorphous polyester Y6. 7) A dispersion was obtained. Table 2 shows the solid content concentration of the obtained resin particle (7) dispersion, the volume median particle size (D ₅₀ ), and the CV value of the resin particle (7).

Production Example P8
(Preparation of resin particle (8) dispersion)
Resin particles (Production Example P1) were the same as Production Example P1 except that 51 g of amorphous polyester Y1 was changed to 90 g of amorphous polyester Y4 and 459 g of amorphous polyester Y6 was changed to 420 g of amorphous polyester Y6. 8) A dispersion was obtained. Table 2 shows the solid content concentration of the obtained resin particle (8) dispersion, the volume median particle size (D ₅₀ ), and the CV value of the resin particle (8).

Production Example P9
(Preparation of resin particle (9) dispersion)
In Production Example P1, the same procedure as in Production Example P1, except that 51 g of amorphous polyester Y1 was changed to 40.8 g of amorphous polyester Y5 and 459 g of amorphous polyester Y6 was changed to 469.2 g of amorphous polyester Y6. A resin particle (9) dispersion was obtained. Table 2 shows the solid content concentration of the obtained resin particle (9) dispersion, the volume median particle size (D ₅₀ ), and the CV value of the resin particle (9).

Production Example P10
(Preparation of resin particle (10) dispersion)
In Production Example P1, except that 51 g of amorphous polyester Y1 was changed to 36 g of amorphous polyester Y1 and 459 g of amorphous polyester Y6 were changed to 474 g of amorphous polyester Y, resin particles ( 10) A dispersion was obtained. Table 2 shows the solid content concentration of the obtained resin particle (10) dispersion, the volume median particle size (D ₅₀ ), and the CV value of the resin particles (10).

Production Example P11
(Preparation of resin particle (11) dispersion)
Resin particles (Production Example P1) were the same as Production Example P1 except that 51 g of amorphous polyester Y1 was changed to 180 g of amorphous polyester Y1, and 459 g of amorphous polyester Y6 was changed to 330 g of amorphous polyester Y6. 11) A dispersion was obtained. Table 2 shows the solid content concentration of the obtained resin particle (11) dispersion, the volume median particle size (D ₅₀ ), and the CV value of the resin particles (11).

Production Example P12
(Preparation of resin particle (12) dispersion)
In Production Example P1, except that 51 g of amorphous polyester Y1 was changed to 132 g of amorphous polyester Y4 and 459 g of amorphous polyester Y6 was changed to 330 g of amorphous polyester Y6, resin particles ( 12) A dispersion was obtained. Table 2 shows the solid content concentration of the obtained resin particle (12) dispersion, the volume median particle size (D ₅₀ ), and the CV value of the resin particles (12).

Production Example P13
(Preparation of resin particle (13) dispersion)
In Production Example P1, except that 51 g of amorphous polyester Y1 was changed to 60 g of amorphous polyester Y5 and 459 g of amorphous polyester Y6 was changed to 450 g of amorphous polyester Y6, resin particles ( 13) A dispersion was obtained. Table 2 shows the solid content concentration of the obtained resin particle (13) dispersion, the volume median particle size (D ₅₀ ), and the CV value of the resin particles (13).

Production Example P14
(Preparation of resin particle (14) dispersion)
5. In a 5 l stainless steel flask equipped with a stirrer, 210 g of amorphous polyester Y7, 390 g of amorphous polyester Y6, polyoxyethylene oleyl ether “Emulgen 430” (nonionic surfactant, manufactured by Kao Corporation) 0 g, 20.0 g of 15 mass% sodium dodecylbenzenesulfonate aqueous solution “Neopelex G-15” (anionic surfactant, manufactured by Kao Corporation), and 278.5 g of 5 mass% potassium hydroxide aqueous solution were added and stirred. The mixture was mixed at 95 ° C. for 2 hours. While maintaining the temperature of the system at 95 ° C., 1222 g of deionized water was added dropwise at a rate of 6 g / min while stirring to obtain an emulsion. The obtained emulsion was cooled to 25 ° C. and passed through a 200 mesh (mesh opening 105 μm) wire mesh to obtain a resin particle (14) dispersion. Table 3 shows the solid content concentration of the obtained resin particle (14) dispersion, the volume median particle size of the resin particle (14), and the CV value.

Production Example P15
(Preparation of resin particle (15) dispersion)
Production Example P1 except that the crystalline polyester X1 was not used, except that 51 g of the amorphous polyester Y1 was changed to 60 g of the amorphous polyester Y1, and 459 g of the amorphous polyester Y6 was changed to 540 g of the amorphous polyester Y6. Resin particle (15) dispersion was obtained in the same manner as P1. Table 3 shows the solid content concentration of the obtained resin particle (15) dispersion, the volume median particle size (D ₅₀ ), and the CV value of the resin particles (15).

[Production of toner]
Example 1
(Preparation of Toner 1)
<Step (2): Production of Aggregated Particle (1)>
Into a 2 l four-necked flask equipped with a dehydration tube, a stirrer and a thermocouple, 250 g of resin particle (1) dispersion, 54 g of deionized water, and 18 g of release agent particle dispersion were placed at a temperature of 25 ° C. Mixed. Next, an aqueous solution obtained by dissolving 20.1 g of ammonium sulfate in 196 g of deionized water was added dropwise over 30 minutes while stirring at 25 ° C., and then the mixture was heated to 58 ° C. Was kept at 58 ° C. until the particle size became 4.8 μm to obtain a dispersion liquid containing aggregated particles (1).

<Step (3): Production of Aggregated Particle (2)>
After cooling the temperature of the agglomerated particles (1) dispersion (total amount) obtained in step (2) to 50 ° C., 70 g of the dispersion of resin particles (14) while increasing the temperature at a rate of 1 ° C./h, A mixed liquid obtained by mixing 22 g of deionized water was added dropwise over 180 minutes to obtain a dispersion containing aggregated particles (2). The volume-average particle size (D ₅₀ ) of the obtained aggregated particles (2) was 5.2 μm. 15.6 g of polyoxyethylene lauryl ether sodium sulfate aqueous solution “Emar E-27C” (anionic surfactant, manufactured by Kao Corporation, solid content: 28% by mass) was deionized in the dispersion of the obtained aggregated particles (2). An aqueous solution mixed with 1231 g of water was added to stop aggregation.

<Step (4): Preparation of fused particles>
The dispersion (total amount) of the aggregated particles (2) obtained in the step (3) is heated to 70 ° C. over 2 hours and held at 70 ° C. for 1 hour, so that the volume-median particle size is 5.1 μm. A dispersion containing the fused particles was obtained. Then, it cooled to 25 degreeC.

<Post-processing process>
While maintaining the fused particle dispersion obtained in step (4) at 25 ° C., the solid content is separated by suction filtration, washed with deionized water, and the vacuum low-temperature dryer “DRV622DA” (manufactured by ADVANTEC Toyo) Was dried at 33 ° C. to obtain toner particles. Table 4 shows the volume-median particle size and CV value of the obtained toner particles. To 100 parts by mass of the toner particles, 2.5 parts by mass of hydrophobic silica “RY50” (manufactured by Nippon Aerosil Co., Ltd., average primary particle size; 0.04 μm), hydrophobic silica “Cabo Seal TS720” (manufactured by Cabot Corp., average) 1.0 part by mass of primary particle size: 0.012 μm and 0.8 part by mass of fine polymer particle “Finesphere P2000” (manufactured by Nippon Paint Co., Ltd., average primary particle size: 0.5 μm) are placed in a Henschel mixer and stirred. The toner 1 was obtained by passing through a 150 mesh sieve. Table 4 shows the physical properties and evaluation of the obtained toner.

Examples 2-7 and Comparative Examples 1-6
(Preparation of toners 2-7 and 10-15)
Toners 2 to 7 and 10 to 15 were obtained in the same manner as in Example 1 except that the resin particle (1) dispersion was changed to the resin particle dispersion shown in Table 4 in Example 1. Table 4 shows the physical properties and evaluation of the obtained toner.

Example 8
(Production of Toner 8)
In Example 1, the resin particle (1) dispersion was changed to the resin particle (5) dispersion, and the resin particle (14) dispersion was changed to the resin particle (15) dispersion. Toner 8 was obtained. Table 4 shows the physical properties and evaluation of the obtained toner.

Example 9
(Preparation of Toner 9)
In Example 1, except that the resin particle (1) dispersion was changed to the resin particle (5) dispersion and the resin particle (14) dispersion was changed to the resin particle (5) dispersion, the same as in Example 1. Toner 9 was obtained. Table 4 shows the physical properties and evaluation of the obtained toner.

  From Table 4, it can be seen that the toners of Examples 1 to 9 are all excellent in low-temperature fixability and durability as compared with the toners of Comparative Examples 1 to 6.

  The toner for developing an electrostatic image obtained by the production method of the present invention is excellent in low-temperature fixability and durability. Therefore, the toner for developing an electrostatic image used in electrophotography, electrostatic recording, electrostatic printing, etc. It can be used suitably. According to the method of the present invention, a toner having such characteristics can be produced efficiently.

Claims (3)

Next steps (1) to (4)
Step (1): Crystalline polyester (a) and amorphous polyester (b) are mixed in an aqueous medium at a temperature equal to or higher than the melting point of crystalline polyester (a), and a dispersion of resin particles (A) Step (2): Step of aggregating resin particles (A) to obtain aggregated particles (1) Step (3): Amorphous polyester (c) is contained in the dispersion of aggregated particles (1) Step of adding aggregated resin particles (B) to obtain aggregated particles (2) Step (4): electrostatic charge image development including the step of fusing the aggregated particles (2) to obtain fused particles A toner manufacturing method comprising:
60 to 90 mol% of the amorphous polyester (b) is an alkyl succinic acid having an alkyl group having 9 to 14 carbon atoms and / or an alkenyl succinic acid having an alkenyl group having 9 to 14 carbon atoms. Containing an amorphous polyester (b1) obtained by polycondensation of an acid component and an alcohol component,
The content of the amorphous polyester (b1) in the resin constituting the resin particles (A) is 7% by mass or more and 20% by mass or less,
The content of the alkyl succinic acid and / or alkenyl succinic acid in the total amount of carboxylic acid components of all polyesters in the resin particles (A) is 5.0 mol% or more and 20 mol% or less.
A method for producing a toner for developing an electrostatic image.   The crystalline polyester (a) contains a polyester obtained by polycondensation of an α, ω-alkanediol having 2 to 12 carbon atoms and an aliphatic carboxylic acid having 4 to 12 carbon atoms. A method for producing the toner for developing an electrostatic image according to claim 1.   The mass ratio of the crystalline polyester (a) to the amorphous polyester (b1) (crystalline polyester (a) / amorphous polyester (b1)) is 80/20 to 20/80. A method for producing the toner for developing an electrostatic image according to claim 1.