JP6031346B2 - Method for producing magenta toner for developing electrostatic image - Google Patents

Description

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

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.
In order to improve thermal characteristics such as low-temperature fixability and offset resistance in response to higher image quality, attempts have been made to use a mixture of a plurality of types of resins. Further, in order to improve the image quality of a color image, an attempt has been made to use a plurality of colorants in combination with magenta toner, which is important for improving color reproducibility particularly in a color image.

For example, Patent Document 1 discloses a quinacridone pigment whose Ca intensity in a fluorescent X-ray analysis is in a specific range and a colorant which is a naphthol pigment showing a specific X-ray diffraction pattern for the purpose of improving image quality and charging characteristics. An electrophotographic magenta toner containing a binder resin is disclosed.
Patent Document 2 contains a binder resin, a quinacridone colorant, and a monoazo colorant for the purpose of improving color reproducibility, gradation, light resistance, charging characteristics, and matching with an image forming apparatus, A dry toner having a mass ratio of 25:75 to 75:25, a colorant content of 1 to 20% by mass, and an average circularity of 0.950 or more is disclosed.
Patent Document 3 provides a toner masterbatch containing a resin, a colorant, and a plasticizer, a resin emulsion, and the resin emulsion for the purpose of improving emulsification and increasing the image density of the toner. An electrophotographic toner is disclosed.
Patent Document 4 includes a resin containing a specific amount of crystalline polyester and amorphous polyester for the purpose of improving low-temperature fixability, storage stability, and toner scattering property, and having a specific particle size. By holding the particle dispersion for 1 hour or more at a specific temperature, a dispersion of heat-treated resin particles is obtained and aggregated, and a resin fine particle dispersion containing 70% by mass or more of amorphous polyester is added to the resin. A method for producing an electrophotographic toner that obtains and coalesces fine particle adhered aggregated particles is disclosed.

Japanese Patent Laid-Open No. 2006-267641 JP 2002-156895 A JP 2008-70466 A International publication 2011/74674 pamphlet

The toner for electrophotography is desired to have a thermal property (low temperature fixability) for fixing at a low temperature. If the toner is fixed at a low temperature, the power consumption of the printing press can be reduced, and further high-speed printing is possible. As a technique for this, by using crystalline polyester in the toner, the fixing temperature of the obtained toner can be lowered due to its melting characteristics. However, the toner having a low fixing temperature has a problem that the heat-resistant storage stability, which is the stability during high-temperature storage, is lowered, and it is difficult to achieve both low-temperature fixing property and heat-resistant storage stability. Further, there is a problem that the crystalline polyester is liberated or exposed to the toner surface, which is considered to cause a charging failure.
An object of the present invention is to provide a magenta toner for developing an electrostatic image having both good low-temperature fixability and heat-resistant storage stability and excellent chargeability, and a method for producing the same.

  The inventors of the present invention have considered the factors that affect the low-temperature fixability, heat-resistant storage stability, and chargeability in relation to the state of the resin and the colorant constituting the magenta toner and their relationship. As a result, in the core-shell type toner, resin particles containing crystalline polyester, amorphous polyester, and two specific colorants and release agent particles are aggregated to form aggregated particles for the core. For electrostatic image development that has both excellent low-temperature fixability and heat-resistant storage stability and excellent chargeability by adding resin particles containing amorphous polyester to the surface of the agglomerated particles for fusion It has been found that magenta toner can be obtained.

That is, the present invention provides the following [1] and [2].
[1] A method for producing a magenta toner for developing an electrostatic image, comprising the following steps (1) to (3).
Step (1): Crystalline polyester (a), amorphous polyester (b), and C.I. I. Pigment red 122 and C.I. I. Step of obtaining aggregated particles (1) by aggregating resin particles (A) containing a colorant containing Pigment Red 150 and release agent particles containing a release agent in an aqueous medium Step (2) Step of adding resin particles (C) containing amorphous polyester (c) to the aggregated particles (1) to obtain aggregated particles (2) Step (3): Non-aggregated particles (2) A step of obtaining core-shell particles in which the resin particles (C) are fused while maintaining a temperature not lower than the glass transition point of the crystalline polyester (c) and lower than the melting point of the crystalline polyester (a) [2] [1] ] A magenta toner for developing an electrostatic image obtained by the production method.

  According to the present invention, it is possible to provide a method for producing a magenta toner for developing an electrostatic charge image that has both good low-temperature fixability and heat-resistant storage stability and is excellent in chargeability.

The method for producing a magenta toner for developing an electrostatic charge image of the present invention includes the following steps (1) to (3).
Step (1): Crystalline polyester (a), amorphous polyester (b), and C.I. I. Pigment red 122 and C.I. I. Step of obtaining aggregated particles (1) by aggregating resin particles (A) containing a colorant containing Pigment Red 150 and release agent particles containing a release agent in an aqueous medium Step (2) Step of adding resin particles (C) containing amorphous polyester (c) to the aggregated particles (1) to obtain aggregated particles (2) Step (3): Non-aggregated particles (2) A step of obtaining core-shell particles in which the resin particles (C) are fused by holding at a temperature not lower than the glass transition point of the crystalline polyester (c) and lower than the melting point of the crystalline polyester (a).

The reason why the magenta toner for developing an electrostatic image obtained by the production method of the present invention has both good low-temperature fixability and heat-resistant storage stability and is excellent in chargeability is not clear, but is considered as follows.
Crystalline polyester (a), amorphous polyester (b) and release agent are present in the core of the magenta toner obtained by the production method of the present invention, and amorphous polyester (c) is present in the shell. To do. In this way, the crystalline polyester and release agent effective for low-temperature fixability are present in the core, and the amorphous polyester having excellent heat-resistant storage stability is present in the shell, thereby improving low-temperature fixability and heat-resistant storage stability. Although it is possible, it is difficult to achieve both low-temperature fixability and heat-resistant storage stability. That is, the crystalline polyester and the amorphous polyester are excellent in compatibility. If they are completely compatible and the crystalline part of the crystalline polyester disappears, no significant improvement in heat resistant storage stability is observed. Further, if the crystalline polyester and the amorphous polyester are inferior in compatibility, the distribution of the crystalline polyester in the core can be biased, and no significant improvement in low-temperature fixability is observed.
Therefore, in addition to the above configuration, the present invention further includes C.I. I. Pigment red 122 and C.I. I. Pigment Red 150 is included. C. I. Pigment Red 122 has a planar molecular structure with high symmetry. I. Pigment Red 150 has a low molecular structure and is linear because the azo bond between naphthanilide and aminoanisocyanilide in the structure is linked at the para position. It is considered that the interaction is large, each acts as a dispersant, and can be finely dispersed in the resin. Further, C.I. I. Since the pigment red 122 functions as a crystal nucleating agent, the crystalline polyester can be finely recrystallized. As described above, since the crystalline polyester is uniformly dispersed in the toner, it is considered that the heat resistant storage stability is improved while maintaining the low temperature fixability.
As for the chargeability, as described above, the crystalline polyester is present in the toner without being unevenly distributed, so that the exposure of the crystalline polyester to the surface can be prevented, and as a result, the chargeability is improved. it is conceivable that. In addition, C.I. I. Since the pigment red 122 has a highly symmetric structure, when used alone, a large crystal structure is formed, and conjugated electrons in the π-π electron orbit are easily moved. As a result, the charge amount is reduced. It becomes easy to do. However, in the toner of the present invention, as described above, C.I. I. Pigment Red 122 is C.I. I. Since it is used together with CI Pigment Red 150, both colorants are dispersed with each other as described above, and the movement of conjugated electrons is restricted. As a result, it is considered that the chargeability can be greatly improved.
Hereinafter, each component used in the present invention will be described.

[Resin particles (A)]
Resin particles (A) include crystalline polyester (a), amorphous polyester (b), and C.I. I. Pigment red 122 and C.I. I. A coloring agent including CI Pigment Red 150.
The total content of the crystalline polyester (a), the amorphous polyester (b), and the colorant in the resin particles (A) is preferably 90 from the viewpoints of low-temperature fixability, heat-resistant storage stability and chargeability. It is at least mass%.

<Crystalline polyester (a)>
The core contains the crystalline polyester (a) from the viewpoint of achieving both low-temperature fixability and heat-resistant storage stability.
In the present invention, the crystalline polyester is defined as the ratio between the softening point and the maximum endothermic peak temperature measured by a differential scanning calorimeter (DSC), (softening point (° C.)) / (Maximum endothermic peak temperature (° C.)). The crystallinity index is 0.6 to 1.4, and from the viewpoint of low-temperature fixability of the toner, 0.8 to 1.3 is preferable, and 0.9 to 1.2 is more preferable. 0.9 to 1.1 is more preferable.
The crystalline polyester (a) preferably has an acid group at the molecular end from the viewpoint of facilitating the dispersion of the resin particle dispersion during the production of the toner and enhancing the dispersion stability. Examples of the acid group include a carboxy group, a sulfonic acid group, a phosphonic acid group, and a sulfinic acid. Among these, a carboxy group is preferable from the viewpoint of achieving both the dispersibility of the resin and the heat-resistant storage stability of the obtained toner.

(Physical properties of crystalline polyester (a))
The melting point of the crystalline polyester (a) is preferably 70 ° C. or higher, more preferably 72 ° C. or higher, and further preferably 73 ° C. or higher, from the viewpoint of improving the low temperature fixability and heat resistant storage stability of the toner and improving the chargeability. Further, it is preferably 90 ° C. or lower, more preferably 83 ° C. or lower, and further preferably 80 ° C. or lower.
From the same viewpoint, the softening point of the crystalline polyester (a) is preferably 70 ° C. or higher, more preferably 73 ° C. or higher, further preferably 75 ° C. or higher, and preferably 90 ° C. or lower, more preferably 83 ° C. ° C or lower, more preferably 80 ° C or lower.
The number average molecular weight of the crystalline polyester (a) is preferably 1,500 or more, more preferably 2,000 or more, and further preferably 3,000 or more, from the viewpoint of improving the low-temperature fixability and heat-resistant storage stability of the toner. And preferably 50,000 or less, more preferably 10,000 or less, still more preferably 5,000 or less, preferably 1,500 to 50,000, more preferably 2,000 to 10,000, More preferably, it is 3,000 to 5,000.
The acid value of the crystalline polyester (a) is preferably 5 mgKOH / g or more, more preferably 10 mgKOH / g, from the viewpoint of improving the dispersion stability of the resin particle dispersion of the toner and the low-temperature fixability and heat-resistant storage stability of the toner. More preferably, it is 15 mgKOH / g or more, preferably 30 mgKOH / g or less, more preferably 25 mgKOH / g or less, still more preferably 22 mgKOH / g or less, 5-30 mgKOH / g is preferred, 10-25 mgKOH / G is more preferable, and 15-22 mgKOH / g is still more preferable.
In addition, crystalline polyester (a) can be used individually or in combination of 2 or more types.
In the present invention, the melting point, softening point, number average molecular weight and acid value of the crystalline polyester (a) are determined by the methods described in the examples.
In the case where two or more kinds of crystalline polyesters are used as the crystalline polyester (a), the melting point of the crystalline polyester having the largest mass ratio among the crystalline polyesters contained in the obtained toner is determined by the crystallinity in the present invention. It is set as melting | fusing point of polyester (a). When all have the same ratio, the lowest value is set. The softening point, the number average molecular weight, and the acid value of the crystalline polyester (a) are determined by the method described in the examples using a mixture in which all the crystalline polyesters are mixed in a ratio.

(Acid component of crystalline polyester (a))
The crystalline polyester (a) can be produced by subjecting an acid component and an alcohol component to a polycondensation reaction.
Examples of the acid component include aliphatic dicarboxylic acid, alicyclic dicarboxylic acid, aromatic dicarboxylic acid and trivalent or higher carboxylic acid, and among them, from the viewpoint of improving low-temperature fixability, heat-resistant storage stability and chargeability of the toner. Aliphatic dicarboxylic acids are preferred.
In the present specification, the acid includes not only a free acid but also an anhydride that decomposes during the reaction to produce an acid and an alkyl ester having 1 to 3 carbon atoms.
The aliphatic dicarboxylic acid preferably has 2 to 18 carbon atoms and more preferably 8 to 12 carbon atoms from the viewpoint of improving the heat-resistant storage stability of the toner and improving the chargeability.
Examples of the aliphatic dicarboxylic acid having 2 to 18 carbon atoms include oxalic acid, malonic acid, maleic acid, fumaric acid, citraconic acid, itaconic acid, glutaconic acid, succinic acid, adipic acid, sebacic acid, 1,12-dodecanedioic acid. , Azelaic acid, n-dodecyl succinic acid, n-dodecenyl succinic acid and the like. Among them, sebacic acid is preferable from the viewpoint of improving the low-temperature fixability and heat-resistant storage stability of the toner.
Examples of the alicyclic dicarboxylic acid include cyclohexane dicarboxylic acid.
Examples of aromatic dicarboxylic acids include phthalic acid, isophthalic acid, terephthalic acid and the like, with terephthalic acid being preferred.
Examples of the trivalent or higher carboxylic acid include trimellitic acid and pyromellitic acid.
These can be used alone or in combination of two or more.

(Alcohol component of crystalline polyester (a))
Examples of the alcohol component include aliphatic diols, aromatic diols, hydrogenated products of bisphenol A, trivalent or higher alcohols, etc. Among them, the viewpoint of promoting the crystallization of polyester and improving the low-temperature fixability of the toner. Therefore, an aliphatic diol is preferable.
Among the aliphatic diols, α, ω-alkanediol is preferable from the viewpoint of promoting the crystallization of polyester and improving the low-temperature fixability of the toner.
The α, ω-alkanediol preferably has 2 to 18 carbon atoms, more preferably 4 to 12 carbon atoms, and more preferably 4 to 12 carbon atoms from the viewpoint of improving the low-temperature fixability and heat-resistant storage stability of the obtained toner and improving the chargeability. 6-12 are still more preferable.
Examples of the α, ω-alkanediol having 2 to 18 carbon atoms include ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1, Examples include 7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,12-dodecanediol, and the like. Among them, the low-temperature fixability and heat-resistant storage stability of the obtained toner 1,6-hexanediol, 1,4-butanediol and 1,9-nonanediol are preferable from the viewpoint of improving the heat resistance, and 1,9-nonanediol is preferable from the viewpoint of improving the heat resistant storage stability.
The α, ω-alkanediol having 2 to 18 carbon atoms can be used alone or in combination of two or more.
Examples of aromatic diols include alkylene (2 to 3 carbon) oxide adducts (average number of added moles 1 to 16) of bisphenol A.
Examples of trihydric or higher alcohols include glycerin and pentaerythritol.

The alcohol component can be used alone or in combination of two or more. From the viewpoint of promoting the crystallization of the polyester, the alcohol component contains 80 to 100 α, ω-alkanediol having 2 to 18 carbon atoms. It is preferably mol%, more preferably 90 to 100 mol%, and still more preferably 100 mol%.
In the crystalline polyester (a), the acid component is preferably an aliphatic dicarboxylic acid and the alcohol component is an aliphatic diol, more preferably the acid component is sebacic acid and the alcohol component is an aliphatic diol, and still more preferably the acid component. Is sebacic acid and the alcohol component is 1,9-nonanediol.

(Production of crystalline polyester (a))
From the viewpoint of improving the efficiency of the polycondensation reaction, the catalyst used for the production of the crystalline polyester (a) is preferably at least one selected from tin compounds and titanium compounds, more preferably tin compounds, and di (2-ethyl). More preferred is at least one selected from hexanoic acid tin and dibutyltin oxide.
Examples of the titanium compound include titanium diisopropylate bistriethanolamate.
The amount of the catalyst used is preferably 0.01 to 1 part by mass, more preferably 0.1 to 0.6 part by mass with respect to 100 parts by mass of the total amount of the acid component and the alcohol component in the crystalline polyester (a). .

  The polycondensation reaction is preferably carried out by putting an acid component and an alcohol component in a reaction vessel and maintaining the reaction at 140 to 250 ° C. for 5 to 15 hours. Further, it is preferable that the pressure is reduced to 5.0 to 20 kPa and maintained for 1 to 10 hours.

<Amorphous polyester (b)>
In the present invention, the amorphous polyester is a resin having a crystallinity index of more than 1.4 or less than 0.6.
The magenta toner of the present invention is a resin particle (A) that serves as a core portion from the viewpoint of improving the adhesion to the shell portion and improving the heat-resistant storage stability and finely dispersing the colorant and improving the chargeability. Contains amorphous polyester (b).

  The amorphous polyester (b) can be produced by polycondensation reaction between an acid component and an alcohol component. A catalyst is preferably used in the polycondensation reaction. Preferred catalysts and polycondensation reaction conditions are the same as those for the crystalline polyester (a).

(Acid component of amorphous polyester (b))
Examples of the acid component of the amorphous polyester (b) include dicarboxylic acids and trivalent or higher carboxylic acids from the viewpoint of improving the chargeability and low-temperature fixability of the toner. Of these, dicarboxylic acids are preferred, and dicarboxylic acids are preferred. More preferably, trivalent or higher carboxylic acid is used in combination.
As the dicarboxylic acid, at least one selected from aliphatic dicarboxylic acids and aromatic dicarboxylic acids is preferable, and the dispersibility of the crystalline polyester in the core is improved, and as a result, the image density and low-temperature fixability of the toner are improved. Therefore, it is more preferable to contain an aliphatic dicarboxylic acid and an aromatic dicarboxylic acid.
An aliphatic dicarboxylic acid is an alkyl succinic acid having an alkyl group having 9 to 14 carbon atoms, an alkenyl succinic acid having an alkenyl group having 9 to 14 carbon atoms, and an alkyl group from the viewpoint of improving the low-temperature fixability and chargeability of the toner. At least one selected from aliphatic dicarboxylic acids having 2 to 12 carbon atoms other than succinic acid and alkenyl succinic acid is preferable. The aliphatic dicarboxylic acid having 2 to 12 carbon atoms is more preferably 2 to 6 carbon atoms.
Examples of the aliphatic dicarboxylic acid having 2 to 12 carbon atoms include oxalic acid, malonic acid, maleic acid, fumaric acid, citraconic acid, itaconic acid, glutaconic acid, succinic acid, adipic acid, sebacic acid, and 1,12-dodecanedioic acid. Examples include at least one selected from acids, and fumaric acid is preferred from the viewpoint of improving the low-temperature fixability and heat-resistant storage stability of the toner.

Among the alkyl succinic acids having an alkyl group having 9 to 14 carbon atoms and the alkenyl succinic acid having an alkenyl group having 9 to 14 carbon atoms, from the viewpoint of increasing the affinity with the crystalline polyester and thus improving the low-temperature fixability of the toner. Alkenyl succinic acid having an alkenyl group having 9 to 14 carbon atoms is preferred.
Further, from the viewpoint of enhancing the affinity with the crystalline polyester and thus enhancing the low-temperature fixability of the toner, the alkyl group or alkenyl group preferably has 10 to 14 carbon atoms, 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 the alkenyl succinic acid having an alkenyl group having 9 to 14 carbon atoms include at least one selected from dodecyl succinic acid, dodecenyl succinic acid and octenyl succinic acid. In view of improving the low-temperature fixability of the toner, dodecenyl succinic acid is preferable.
The alkyl group and alkenyl group of the alkyl succinic acid having an alkyl group having 9 to 14 carbon atoms and the alkenyl succinic acid having an alkenyl group having 9 to 14 carbon atoms are preferably a branched alkyl group and a branched alkenyl group.
The branched structure may exist in any part of the alkyl group and the alkenyl group, but a mixture having a plurality of branched structures is preferable from the viewpoint of enhancing the compatibility with the crystalline polyester.
The acid component preferably further contains an aromatic dicarboxylic acid, and the aromatic dicarboxylic acid is preferably terephthalic acid.

  Examples of the trivalent to pentavalent aromatic carboxylic acid include at least one selected from trimellitic acid, 2,5,7-naphthalenetricarboxylic acid, and pyromellitic acid. Among them, the viewpoint of improving the heat resistant storage stability of the toner. Therefore, trimellitic acid is preferable.

(Alcohol component of amorphous polyester (b))
Examples of the alcohol component include aromatic diols, preferably alkylene (2 to 3 carbon atoms) oxide adducts (average number of added moles 1 to 16) of bisphenol A, and ethylene oxide adducts and propylene oxide adducts of bisphenol A. More preferably, at least one selected from the group consisting of ethylene oxide adduct and propylene oxide adduct of bisphenol A is more preferable, and it is more preferable to use a mixture of these.

(Physical properties of amorphous polyester (b))
The glass transition temperature of the amorphous polyester (b) is preferably 50 ° C. or higher, more preferably 52 ° C. or higher, and further preferably from the viewpoint of improving the durability, low-temperature fixability and heat-resistant storage stability of the toner. Is 54 ° C or higher, preferably 70 ° C or lower, more preferably 68 ° C or lower, and further preferably 66 ° C or lower.
The softening point of the amorphous polyester (b) is preferably 70 ° C. or higher, more preferably 90 ° C. or higher, further preferably 100 ° C. or higher, from the viewpoint of improving the low-temperature fixability and heat-resistant storage stability of the toner. It is preferably 165 ° C. or less, more preferably 140 ° C. or less, and further preferably 130 ° C. or less.

The number average molecular weight of the amorphous polyester (b) is preferably 1,000 or more, more preferably 1,500 or more, from the viewpoint of improving the durability, low-temperature fixability and heat-resistant storage stability of the toner. More preferably, it is 2,000 or more, preferably 50,000 or less, more preferably 10,000 or less, and still more preferably 4,000 or less.
From the viewpoint of easily emulsifying the resin in an aqueous medium, the acid value of the amorphous polyester (b) is preferably 6 mgKOH / g or more, more preferably 10 mgKOH / g or more, and further preferably 15 mgKOH / g. It is above, Preferably it is 35 mgKOH / g or less.
When two or more kinds of amorphous polyesters are used as the amorphous polyester (b), the difference in softening point is preferably 5 ° C. or more, more preferably 7 ° C. or more, and preferably Is 30 ° C. or lower, more preferably 20 ° C. or lower. The softening point, glass transition temperature, number average molecular weight and acid value of the amorphous polyester (b) are determined by the method described in the examples using a mixture in which all the amorphous polyesters are mixed in a ratio. . The same applies to amorphous polyester (c) described later.

<Total amount of crystalline polyester (a) and amorphous polyester (b)>
The total amount of the crystalline polyester (a) and the amorphous polyester (b) in the core portion is the resin constituting the resin particles (A) in the resin constituting the core portion from the viewpoint of improving the low-temperature fixability of the toner. Among these, preferably 50 to 100% by mass, more preferably 80 to 100% by mass, still more preferably 90 to 100% by mass, further preferably substantially 100% by mass, and further preferably 100% by mass. . The mass ratio [(a) / (b)] of the crystalline polyester (a) and the amorphous polyester (b) improves the low-temperature fixability and heat-resistant storage stability of the toner, and improves the chargeability. 5/95 to 50/50 is preferable, 5/95 to 40/60 is more preferable, 5/95 to 30/70 is still more preferable, 10/90 to 30/70 is still more preferable, 15 / 85 to 20/80 is more preferable.

<Colorant>
Examples of the colorant include C.I. I. Pigment red 122 and C.I. I. Pigment Red 150 is used together. This colorant is C.I. I. Pigment red 122 and C.I. I. It is preferable to consist of only two types of CI Pigment Red 150.
C. I. Pigment red 122 and C.I. I. The content of Pigment Red 150 is preferably 1 part by mass or more with respect to 100 parts by mass of the resin constituting the resin particles (A), from the viewpoint of improving the chargeability, low-temperature fixability, and heat-resistant storage stability of the toner. Preferably it is 3 parts by mass or more, more preferably 5 parts by mass or more, preferably 20 parts by mass or less, more preferably 15 parts by mass or less, still more preferably 10 parts by mass or less, and preferably 1 to 20 parts by mass, 3-15 mass parts is more preferable, and 5-10 mass parts is still more preferable.
C. I. Pigment Red 122, C.I. I. Mass ratio to the amount of CI Pigment Red 150 [C.I. I. Pigment red 122 / C.I. I. Pigment Red 150] is preferably 10/90 to 90/10, more preferably 20/80 to 80 /, from the viewpoint of improving the low-temperature fixability and heat-resistant storage stability of the toner, improving the chargeability, and further improving the image density. 20 is more preferable, 30/70 to 70/30 is still more preferable, and 20/80 to 60/40 is still more preferable.
Of these, 10/90 to 60/40 is preferable, 10/90 to 40/60 is more preferable, and 20/80 to 40/60 is still more preferable from the viewpoint of improving the low-temperature fixability and image density of the toner. From the viewpoint of improving the heat resistant storage stability of the toner, 40/60 to 90/10 is preferable, 40/60 to 80/20 is more preferable, and 40/60 to 60/40 is still more preferable. From the viewpoint of improving the chargeability of the toner, 40/60 to 90/10 is preferable, 60/40 to 90/10 is more preferable, and 60/40 to 80/20 is still more preferable.

<Manufacture of resin particles (A)>
Resin particles (A) include crystalline polyester (a), amorphous polyester (b), and C.I. I. Pigment red 122 and C.I. I. It is preferable to manufacture by the method of disperse | distributing the coloring agent containing pigment red 150 in an aqueous medium, and obtaining as a dispersion liquid containing a resin particle (A).
Among these, at least a part of the amorphous polyester (b) and C.I. I. Pigment red 122 and C.I. I. A component containing a colorant including CI Pigment Red 150 is melt-mixed to obtain a colored resin, a so-called masterbatch, and the masterbatch (colored resin) and the crystalline polyester (a) or the crystalline polyester (a) and It is preferable to mix the component containing the remainder of an amorphous polyester (b), add an aqueous medium, and emulsify, and obtain a resin particle (A). Hereinafter, the production by this method will be described.

First, part or all of the amorphous polyester (b) and C.I. I. Pigment red 122 and C.I. I. The colorant containing CI Pigment Red 150 is melt-mixed, that is, the colorant is mixed in a state where the resin is melted, but the resin before melting and the colorant are previously blended and mixed while melting the resin. May be. It is preferable to blend the resin and the colorant in advance and mix while melting the resin from the viewpoint of uniformly including the colorant in the resin. For example, powdery amorphous polyester (b) and a magenta colorant are blended. As an apparatus used for blending, a Henschel mixer can be suitably used.
When using a water-moist paste as the magenta colorant, the content of the colorant in the paste is 10 to 10 from the viewpoint of improving the image density of the obtained toner while being well dispersed when mixed in the resin. 60 mass% is preferable, 20-50 mass% is more preferable, 25-45 mass% is still more preferable.

As a method for melting the amorphous polyester (b) and mixing the colorant, it is preferable to mix the colorant by melting the resin at a temperature equal to or higher than the softening point of the amorphous polyester (b).
The temperature for melting and mixing is preferably a temperature equal to or higher than the softening point of the amorphous polyester (b), specifically, preferably 80 to 180 ° C, more preferably 90 to 150 ° C, and 95 to 130 ° C. Is more preferable.
In addition, when using a colorant paste, it is preferable to mix at 100 degrees C or less until a water | moisture content evaporates, and to mix at the temperature exceeding 100 degreeC after a water | moisture content evaporates.
Although there is no restriction | limiting in particular in the time to melt-mix, From a viewpoint of preventing modification | denaturation of a coloring agent and maintaining the viscosity of resin, 10 to 120 minutes are preferable, 20 to 100 minutes are more preferable, and 30 to 60 minutes are still more preferable. .

Although there is no restriction | limiting in particular in the apparatus to melt-mix, A kneader mixer and a heating three roll are used preferably. When a magenta colorant paste wetted in water is used as the colorant, it is preferable to melt and mix until moisture is removed.
The master batch (colored resin) thus obtained is preferably cooled in order to facilitate use in the subsequent steps, and more preferably pulverized into powder or pellets.
The amount of the colorant in the master batch (colored resin) obtained in this step is 5 to 60% by mass from the viewpoint of improving the chargeability of the obtained toner while maintaining stable dispersibility in the subsequent step. Is preferable, 10-50 mass% is more preferable, and 20-40 mass% is still more preferable.

Next, the component containing the master batch (colored resin), the crystalline polyester (a), and the remainder of the amorphous polyester (b) is preferably melt-mixed and emulsified in the presence of an aqueous alkaline solution, Resin particles (A) are obtained. Of course, when all of the amorphous polyester (b) is used in the production of the masterbatch, the component does not contain the amorphous polyester (b).
The resin particles (A) are preferably produced by a method in which a resin, a colorant and the like are dispersed in an aqueous medium to obtain a dispersion containing the resin particles (A).
Examples of a method for obtaining a dispersion include a method in which a resin or the like is added to an aqueous medium and dispersed using a disperser, and a phase inversion emulsification method in which an aqueous medium is gradually added to a resin or the like to emulsify. From the viewpoint of improving the low-temperature fixability of the toner, the phase inversion emulsification method is preferable. Hereinafter, the phase inversion emulsification method will be described.

In the phase inversion emulsification method, it is preferable to first melt and mix the component containing the master batch (colored resin) and the crystalline polyester (a) in the presence of an aqueous alkali solution to obtain a resin mixture.
When the component contains other resin, a mixture of the component and the other resin may be used in advance, but when the alkaline aqueous solution and the optional component are added, they are added and melted at the same time. It may be obtained by mixing. For example, when the component contains an amorphous polyester (b), the master batch (colored resin), the crystalline polyester (a) and the amorphous polyester (b) are combined in the presence of an aqueous alkaline solution. It is preferable to melt and mix to obtain a resin mixture from the viewpoint of improving the low-temperature fixability of the toner.
In mixing, it is preferable to add a surfactant from the viewpoint of improving the emulsion stability of the resin.

  The alkali in the alkaline aqueous solution is preferably an alkali metal hydroxide such as potassium hydroxide or sodium hydroxide or ammonia, and at least one of potassium hydroxide and sodium hydroxide is more preferable from the viewpoint of improving the dispersibility of the resin. Preferably, potassium hydroxide is more preferable. Moreover, 1-30 mass% is preferable, as for the density | concentration of the alkali in alkaline aqueous solution, 1-25 mass% is more preferable, and 1.5-20 mass% is still more preferable.

Examples of the surfactant include nonionic surfactants, anionic surfactants, cationic surfactants, etc. Among them, nonionic surfactants are preferable, and nonionic surfactants and anionic surfactants or It is more preferable to use a cationic surfactant in combination, and it is more preferable to use a nonionic surfactant and an anionic surfactant in combination from the viewpoint of improving the emulsion stability of the resin.
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 the emulsification of the resin. From the viewpoint of improving stability, 0.3 to 10 is preferable, and 0.5 to 5 is more preferable.

Examples of nonionic surfactants include polyoxyethylene alkyl ethers, polyoxyethylene alkyl aryl ethers, polyoxyethylene fatty acid esters, oxyethylene / oxypropylene block copolymers, among others, improving the emulsion stability of resins. From the viewpoint of making it, polyoxyethylene alkyl ether is preferable.
Examples of the polyoxyethylene alkyl ether include polyoxyethylene oleyl ether and polyoxyethylene lauryl ether.
Examples of the polyoxyethylene alkyl aryl ether include polyoxyethylene nonyl phenyl ether.
Examples of the polyoxyethylene fatty acid ester include polyethylene glycol monolaurate, polyethylene glycol monostearate, polyethylene glycol monooleate and the like.

Examples of anionic surfactants include alkylbenzene sulfonates, alkyl sulfates, alkyl ether sulfates, etc., and alkylbenzene sulfonates and alkyl ether sulfates are preferred from the viewpoint of improving the emulsion stability of the resin. .
As the alkylbenzene sulfonate, an alkali metal salt of alkylbenzene sulfonic acid is preferable, sodium alkylbenzene sulfonate is more preferable, and sodium dodecylbenzene sulfonate is more preferable. As the alkyl sulfate, an alkali metal salt of alkyl sulfate is preferable, and sodium alkyl sulfate is more preferable. As the alkyl ether sulfate, an alkali metal salt of alkyl ether sulfate is preferable, sodium alkyl ether sulfate is more preferable, and sodium dodecylbenzenesulfonate is more preferable.

  The content of the surfactant is preferably 20 parts by mass or less, more preferably 15 parts by mass or less, with respect to 100 parts by mass of the resin constituting the resin particles (A), from the viewpoint of improving the emulsion stability of the resin. 0.1-10 mass parts is still more preferable, and 0.5-10 mass parts is still more preferable.

As a method for obtaining a resin mixture, a component containing the master batch (colored resin), the crystalline polyester (a) and the balance of the amorphous polyester (b), an aqueous alkaline solution, and preferably a surfactant are used. A method in which the resin is melted and mixed uniformly while being put in a container and stirred by a stirrer is preferable.
The temperature at which the resin is melted and mixed is preferably equal to or higher than the melting point of the crystalline polyester (a) from the viewpoint of obtaining homogeneous resin particles, and the resin containing the crystalline polyester (a) is an amorphous polyester (b). When it contains, the glass transition temperature or higher is preferable.

Next, an aqueous medium is added to the resin mixture and phase inversion is performed to obtain a dispersion containing the resin particles (A).
As the aqueous medium, those mainly containing water are preferable.
Examples of components other than water include organic solvents that dissolve in water, such as methanol, ethanol, isopropanol, butanol, acetone, methyl ethyl ketone, and tetrahydrofuran. Among these, from the viewpoint of preventing mixing into the toner, alcohol-based organic solvents such as methanol, ethanol, isopropanol, and butanol, which are organic solvents that do not dissolve the resin, can be used.
From the viewpoint of improving the emulsion stability of the resin, the content of water in the aqueous medium is preferably 80% by mass or more, more preferably 90% by mass or more, still more preferably 95% by mass or more, and further substantially 100% by mass. preferable. The water is preferably deionized water or distilled water.
Components other than water include aliphatic alcohols having 1 to 5 carbon atoms such as ethanol and isopropanol; dialkyl (carbon numbers 1 to 3) ketones such as acetone and methyl ethyl ketone; organic solvents that dissolve in water such as cyclic ethers such as tetrahydrofuran Is used.

The temperature at which the aqueous medium is added is preferably not lower than the glass transition temperature of the amorphous polyester (b), and more preferably not lower than the melting point of the crystalline polyester (a) from the viewpoint of obtaining uniform resin particles.
From the viewpoint of obtaining resin particles having a small particle diameter, the addition rate of the aqueous medium is 0.1 to 50 parts by mass / 100 parts by mass of the resin constituting the resin particles (A) until the phase inversion is completed. Preferably, it is 0.1 to 30 parts by weight / minute, more preferably 0.5 to 10 parts by weight / minute, and 0.5 to 5 parts by weight / minute. Is more preferable. There is no restriction | limiting in the addition rate of the aqueous medium after phase inversion.
The amount of the aqueous medium used is preferably 100 to 2000 parts by mass, and 150 to 1500 parts by mass 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. More preferred is 150 to 500 parts by mass.
From the viewpoint of improving the stability of the resulting resin particle dispersion, the solid content concentration is preferably 7 to 50% by mass, more preferably 10 to 40% by mass, still more preferably 20 to 40% by mass, and still more preferably. It is 25-35 mass%. In addition, solid content is the total amount of non-volatile components, such as resin and surfactant.

The volume median particle size of the resin particles (A) in the dispersion containing the obtained resin particles (A) is preferably 0.02 to 2 μm. From the viewpoint of obtaining a toner capable of obtaining a high quality image, 0.02 to 1.5 μm is preferable, 0.05 to 1 μm is more preferable, and 0.05 to 0.5 μm is still more preferable. Here, the volume-median particle diameter is a particle diameter at which the cumulative volume frequency calculated by the volume fraction is 50% calculated from the smaller particle diameter, and is obtained by the method described in the examples.
Further, the coefficient of variation (CV value) (%) of the particle size distribution of the resin particles is preferably 40% or less, more preferably 39% or less, and more preferably 38% from the viewpoint of obtaining a toner capable of obtaining a high-quality image. The following is more preferable, and 37% or less is more preferable. The CV value is a value represented by the following formula, and is determined by the method described in the examples.
CV value (%) = (standard deviation of particle size distribution / volume average particle size (D _v )) × 100

  The content of the colorant in the resin particles (A) constitutes the resin particles (A) from the viewpoint of improving the image density of the printed matter obtained using the toner and improving the low-temperature fixability of the toner. 1-20 mass parts is preferable with respect to 100 mass parts of resin, 5-15 mass parts is more preferable, and 5-10 mass parts is still more preferable.

From the viewpoint of improving the heat resistant storage stability and low-temperature fixability of the toner, it is preferable to crosslink the polyester resin contained in 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 500 to 2,000,000, more preferably 1,000 to 1,000,000, from the viewpoint of increasing the reactivity with the polyester resin.
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. Also product name).
The content or addition amount of the compound having an oxazoline group is preferably 0 as a solid content with respect to 100 parts by mass of the resin in the resin dispersion from the viewpoint of enhancing the crosslinking reactivity with the resin and improving the productivity. 0.1 to 30 parts by mass, more preferably 0.3 to 10 parts by mass, and still more preferably 0.5 to 5 parts by mass.

  By adding and mixing a compound having an oxazoline group, the polyester resin contained in the resin particles (A) dispersed in the resin dispersion is crosslinked. The temperature at the time of mixing becomes like this. Preferably it is 60-100 degreeC, More preferably, it is 70-98 degreeC. The presence of the crosslink can be confirmed by the amide group.

[Releasing 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.

<Release agent>
The core of the magenta toner of the present invention contains a release agent. Thereby, the effect of imparting releasability and improving the fixing property is obtained.
Release agents include low-molecular-weight polyolefins such as polyethylene, polypropylene, and polybutene; silicone waxes; fatty acid amides such as oleic acid amide and stearic acid amide; plant waxes; animal waxes such as beeswax; mineral and petroleum waxes; esters Synthetic waxes such as waxes may be mentioned.
Examples of plant waxes include carnauba wax, rice wax, and candelilla wax, and carnauba wax is preferred.
Examples of the mineral / petroleum wax include montan wax, paraffin wax, and Fischer-Tropsch wax, and paraffin wax is preferred.
These release agents are preferably used alone or in combination of two or more. From the viewpoint of improving the low-temperature fixability of the toner, it is preferable to use a plant wax and a mineral / petroleum wax in combination, and it is more preferable to use a carnauba wax and a paraffin wax in combination.
The melting point of the release agent is preferably 60 to 100 ° C., more preferably 60 to 90 ° C., further preferably 70 to 90 ° C., and still more preferably 70 to 85 ° C., from the viewpoint of improving the heat resistant storage stability of the toner. . When using 2 or more types together, it is preferable that melting | fusing point of all is 60-90 degreeC from a viewpoint of improving the low temperature fixability of a toner.
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 defined as 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 1 to 20 parts by mass, and 2 to 15 parts by mass with respect to 100 parts by mass of the resin in the toner from the viewpoint of improving the releasability of the toner and improving the low-temperature fixability. 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.
The dispersion of the release agent particles is preferably obtained by dispersing the release agent and the aqueous medium using a disperser in the presence of a surfactant at a temperature equal to or higher than the melting point of the release agent. As the disperser to be used, a homogenizer, an ultrasonic disperser or the like is preferable.
As the aqueous medium used in the present production, those used when obtaining a resin mixture are preferably used.
As the surfactant, an anionic surfactant is preferable, and a polycarboxylate is more preferable.
Examples of polycarboxylates include polyacrylates, acrylic acid-maleic acid copolymer salts, polymaleic acid salts, and the like, from the viewpoint of enhancing cohesiveness during toner preparation, and acrylic acid-maleic acid copolymers. The salt of is preferred. As the salt, an alkali metal salt is preferable, and a sodium salt is preferable.
The sodium salt is preferably sodium polyacrylate, sodium salt of acrylic acid-maleic acid copolymer, sodium polymaleate or the like, and from the same viewpoint, sodium salt of acrylic acid-maleic acid copolymer is more preferable.

The obtained release agent particles preferably contain a surfactant from the viewpoint of cohesiveness. As the surfactant, sodium polycarboxylate is preferable. In the case of using the surfactant, the content is preferably 0.01 to 10 parts by mass with respect to 100 parts by mass of the release agent, from the viewpoint of aggregation properties and chargeability of the obtained toner. Part by mass is more preferable.
Further, the total content of the release agent and the surfactant in the release agent particles is preferably 90% by mass or more, more preferably 95% by mass, from the viewpoint of imparting release properties and improving fixability. % Or more, more preferably 99% by mass or more, and still more preferably 100% by mass.
The volume median particle size of the release agent particles is preferably 0.1 to 1 μm, more preferably 0.1 to 0.7 μm, and more preferably 0.1 to 0 μm from the viewpoint of improving the chargeability of the toner and preventing hot offset. More preferably, it is 5 μm.
The CV value of the release agent particles is preferably 15 to 50%, more preferably 15 to 40%, and still more preferably 15 to 35%, from the viewpoint of improving the chargeability of the toner.

[Resin particles (C)]
In the present invention, the resin particles (C) are used in the step (2) and contain an amorphous polyester (c) from the viewpoint of improving the low-temperature fixability and heat-resistant storage stability of the toner. This resin particle (C) is used for the shell of the core-shell particle.
The amount of the amorphous polyester (c) in the resin particles (C) is preferably 50 to 100% by mass in the resin constituting the resin particles (C), more preferably 80 from the viewpoint of improving the low-temperature fixability of the toner. -100 mass%, More preferably, it is 90-100 mass%, More preferably, it is substantially 100 mass%.

<Amorphous polyester (c)>
The acid component and carboxylic acid component of the amorphous polyester (c) are preferably the same as those of the amorphous polyester (b).

The glass transition temperature of the amorphous polyester (c) is preferably 50 ° C. or higher, more preferably 55 ° C. or higher, and further preferably from the viewpoint of improving the durability, low-temperature fixability and heat-resistant storage stability of the toner. Is 58 ° C or higher, preferably 70 ° C or lower, more preferably 68 ° C or lower, still more preferably 66 ° C or lower.
The softening point of the amorphous polyester (c) is preferably 70 ° C. or higher, more preferably 90 ° C. or higher, further preferably 100 ° C. or higher, and 165 ° C. or lower, from the viewpoint of improving the low-temperature fixability and heat-resistant storage stability of the toner. Is preferable, 140 ° C. or lower is more preferable, and 130 ° C. or lower is further preferable.

The number average molecular weight of the amorphous polyester (c) is preferably 1,000 or more, more preferably 1,500 or more, from the viewpoint of improving the durability, low-temperature fixability and heat-resistant storage stability of the toner. More preferably, it is 2,000 or more, preferably 50,000 or less, more preferably 10,000 or less, and still more preferably 4,000 or less.
From the viewpoint of easily dispersing the resin in the aqueous medium, the acid value of the amorphous polyester (c) is preferably 6 mgKOH / g or more, more preferably 10 mgKOH / g or more, and further preferably 15 mgKOH / g. It is above, Preferably it is 35 mgKOH / g or less.

(Amorphous polyesters (c-1) and (c-2))
The amorphous polyester (c) may be used singly or in combination of two or more, but it is preferable to use two or more in combination from the viewpoint of heat resistant storage stability of the toner. It is preferable to use crystalline polyester (c-1) or (c-2), more preferably amorphous polyester (c-1), and amorphous polyesters (c-1) and (c-2). ) Is more preferable. Further, the amorphous polyester (c-2) is an amorphous polyester (c-2) having a softening point higher than that of (c-1). The difference in softening point is preferably from 2 to 30 ° C, more preferably from 5 to 25 ° C, and even more preferably from 10 to 20 ° C, from the viewpoints of toner image density, heat-resistant storage stability, and low-temperature fixability.
The amorphous polyester (c) can be produced by polycondensation reaction between an acid component and an alcohol component. In the polycondensation reaction, a catalyst is preferably used, and preferable catalyst and polycondensation reaction conditions are the same as those for the amorphous polyester (a).

(Amorphous polyester (c-1))
As the acid component of the amorphous polyester (c-1), it is preferable to contain an aliphatic dicarboxylic acid from the viewpoint of improving the adhesiveness with the core portion of the obtained toner and thus improving the fluidity of the toner.
The aliphatic dicarboxylic acid preferably has 2 to 12 carbon atoms and more preferably 2 to 6 carbon atoms from the viewpoint of improving the fluidity of the toner.
Examples of the aliphatic dicarboxylic acid having 2 to 12 carbon atoms include those similar to the amorphous polyester (b-1), and fumaric acid is preferable.
The acid component preferably further contains an aromatic dicarboxylic acid, and the aromatic dicarboxylic acid is preferably terephthalic acid.

The proportion of the aliphatic dicarboxylic acid in the carboxylic acid of the amorphous polyester (c-1) is preferably 20 mol% or more, more preferably 40 mol%, from the viewpoint of low-temperature fixability and heat-resistant storage stability of the toner. It is above, More preferably, it is 50 mol% or more, Preferably it is 80 mol% or less, More preferably, it is 70 mol% or less.
The ratio of the aromatic carboxylic acid in the carboxylic acid of the amorphous polyester (c-1) is preferably 20 mol% or more, more preferably 30 mol%, from the viewpoint of low-temperature fixability and heat-resistant storage stability of the toner. It is above, Preferably it is 80 mol% or less, More preferably, it is 60 mol% or less, More preferably, it is 50 mol or less.

  Preferred alcohol components include aromatic diols, alkylene (2 to 3 carbon) oxide adducts of bisphenol A (average addition mole number of 1 to 16) are preferred, ethylene oxide adducts and propylene oxide additions of bisphenol A At least one selected from those is more preferable, and a combination of two is more preferable.

The proportion of the aromatic diol in the alcohol component of the amorphous polyester (c-1) is preferably 60 to 100 mol%, more preferably 80, from the viewpoint of improving the low-temperature fixability and heat-resistant storage stability of the toner. It is -100 mol%, More preferably, it is 90-100 mol%, More preferably, it is substantially 100 mol%, More preferably, it is 100 mol%.
In the amorphous polyester (c-1), it is preferable that the alcohol component is composed of an ethylene oxide adduct of bisphenol A and a propylene oxide adduct, and the acid component is composed of terephthalic acid and fumaric acid.

(Physical properties of amorphous polyester (c-1))
The glass transition temperature of the amorphous polyester (c-1) is preferably 50 ° C. or higher, more preferably 55 ° C. or higher, from the viewpoint of improving the durability, low-temperature fixability and heat-resistant storage stability of the toner. More preferably, it is 58 degreeC or more, Preferably it is 70 degreeC or less, More preferably, it is 68 degreeC or less, More preferably, it is 66 degreeC or less.
The softening point of the amorphous polyester (c-1) is preferably 70 ° C. or higher, more preferably 90 ° C. or higher, still more preferably 100 ° C. or higher, from the viewpoint of improving the low temperature fixability and heat resistant storage stability of the toner. ° C or lower is preferable, 120 ° C or lower is more preferable, and 110 ° C or lower is still more preferable.

The number average molecular weight of the amorphous polyester (c-1) is preferably 1,000 or more, more preferably 1,500 or more, from the viewpoint of improving the durability, low-temperature fixability and heat-resistant storage stability of the toner. More preferably 2,000 or more, preferably 50,000 or less, more preferably 10,000 or less, and still more preferably 4,000 or less.
From the viewpoint of easily dispersing the resin in the aqueous medium, the acid value of the amorphous polyester (c-1) is preferably 6 mgKOH / g or more, more preferably 10 mgKOH / g or more, and further preferably 15 mgKOH. / G or more, preferably 35 mgKOH / g or less.

(Amorphous polyester (c-2))
Examples of the acid component of the amorphous polyester (c-2) include dicarboxylic acids and trivalent or higher carboxylic acids. Of these, dicarboxylic acids are preferable, and dicarboxylic acids and trivalent or higher carboxylic acids may be used in combination. More preferred.
The dicarboxylic acid is preferably at least one selected from alkyl succinic acid having an alkyl group having 9 to 14 carbon atoms, alkenyl succinic acid having an alkenyl group having 9 to 14 carbon atoms, and aromatic dicarboxylic acid. It is more preferable to use an aromatic dicarboxylic acid in combination with at least one selected from alkyl succinic acid having 14 alkyl groups and alkenyl succinic acid having 9 to 14 carbon atoms. The alkyl group and alkenyl group of the alkyl succinic acid having an alkyl group having 9 to 14 carbon atoms and the alkenyl succinic acid having an alkenyl group having 9 to 14 carbon atoms are preferably a branched alkyl group and a branched alkenyl group. Examples of the alkyl succinic acid having an alkyl group having 9 to 14 carbon atoms and the alkenyl succinic acid having an alkenyl group having 9 to 14 carbon atoms include those similar to the amorphous polyester (b-1), and dodecenyl succinic acid is preferable.
In the carboxylic acid of the amorphous polyester (c-2), an alkyl succinic acid having an alkyl group having 9 to 14 carbon atoms and an alkenyl succinic acid having an alkenyl group having 9 to 14 carbon atoms have an affinity for a crystalline polyester. From the viewpoint of enhancing the low-temperature fixability of the toner, and more preferably 1 mol% or more, more preferably 2 mol% or more, still more preferably 3 mol% or more, preferably 40 mol% or less, more preferably 30 mol% or less, More preferably, it is 20 mol% or less, More preferably, it is 10 mol% or less.
As the aromatic dicarboxylic acid, terephthalic acid is preferred.
The ratio of the aromatic carboxylic acid in the carboxylic acid of the amorphous polyester (c-2) is preferably 40 mol% or more, more preferably 50 mol%, from the viewpoint of low-temperature fixability and heat-resistant storage stability of the toner. More preferably, it is 60 mol% or more, preferably 90 mol% or less, more preferably 80 mol% or less, still more preferably 70 mol% or less.

Examples of the trivalent to pentavalent aromatic carboxylic acid include at least one selected from trimellitic acid, 2,5,7-naphthalenetricarboxylic acid, and pyromellitic acid. Therefore, trimellitic acid is preferable.
The content of the trivalent to pentavalent aromatic carboxylic acid in the carboxylic acid of the amorphous polyester (c-2) is preferably 5 mol% or more, more preferably 7 mol% or more from the viewpoint of improving the heat resistant storage stability of the toner. Is more preferably 9 mol% or more, preferably 40 mol% or less, more preferably 35 mol% or less, and even more preferably 30 mol% or less.

  Preferred alcohol components include aromatic diols, alkylene (2 to 3 carbon atoms) oxide adducts (average number of added moles 1 to 16) of bisphenol A are preferred, ethylene oxide adducts and propylene oxide adducts of bisphenol A Are more preferable, and it is more preferable to use a mixture of these.

  The ratio of the aromatic diol in the alcohol component of the amorphous polyester (c-2) is preferably 60 to 100 mol%, more preferably 80 from the viewpoint of improving the low-temperature fixability and heat-resistant storage stability of the toner. It is -100 mol%, More preferably, it is 90-100 mol%, More preferably, it is substantially 100 mol%, More preferably, it is 100 mol%.

  The amorphous polyester (c-2) is preferably composed of an ethylene oxide adduct of bisphenol A and a propylene oxide adduct of the bisphenol A, and an acid component of terephthalic acid, alkenyl succinic acid and trimellitic acid. Is more preferably composed of an ethylene oxide adduct and a propylene oxide adduct of bisphenol A, and the acid component is preferably composed of terephthalic acid, dodecenyl succinic acid and trimellitic acid.

(Physical properties of amorphous polyester (c-2))
The glass transition temperature of the amorphous polyester (c-2) is preferably 50 ° C. or higher, more preferably 55 ° C. or higher, from the viewpoint of improving the durability, low-temperature fixability and heat-resistant storage stability of the toner. More preferably, it is 58 degreeC or more, Preferably it is 70 degreeC or less, More preferably, it is 68 degreeC or less, More preferably, it is 66 degreeC or less.
The softening point of the amorphous polyester (c-2) is preferably 70 ° C. or higher, more preferably 90 ° C. or higher, further preferably 100 ° C. or higher, from the viewpoint of improving the low-temperature fixability and heat-resistant storage stability of the toner. More preferably, it is preferably 165 ° C or lower, more preferably 140 ° C or lower, further preferably 130 ° C or lower, and further preferably 125 ° C or lower.

The number average molecular weight of the amorphous polyester (c-2) is preferably 1,000 or more, more preferably 1,500 or more, from the viewpoint of improving the durability, low-temperature fixability and heat-resistant storage stability of the toner. More preferably 2,000 or more, preferably 50,000 or less, more preferably 10,000 or less, and still more preferably 4,000 or less.
From the viewpoint of easily dispersing the resin in the aqueous medium, the acid value of the amorphous polyester (c-2) is preferably 6 mgKOH / g or more, more preferably 10 mgKOH / g or more, and further preferably 15 mgKOH. / G or more, preferably 35 mgKOH / g or less.

<Manufacture of resin particles (C)>
The resin particles (C) are preferably produced by a method in which a resin containing amorphous polyester (c) is dispersed in an aqueous medium to obtain a dispersion containing the resin particles (C).
As with the resin particles (A), the dispersion is obtained by adding a resin or the like to an aqueous medium and dispersing using a disperser, or by gradually adding an aqueous medium to the resin or the like to emulsify. From the viewpoint of improving the low-temperature fixability of the obtained toner, the phase inversion emulsification method is preferable.

First, a resin containing amorphous polyester (c), an aqueous alkali solution, and the like are melted and mixed to obtain a resin mixture. In mixing, it is preferable to add a surfactant from the viewpoint of improving the emulsion stability of the resin.
Examples of the alkali in the alkaline aqueous solution include hydroxides of alkali metals such as potassium hydroxide and sodium hydroxide, and ammonia. From the viewpoint of improving the dispersibility of the resin, at least potassium hydroxide and sodium hydroxide are used. One type is preferred, and potassium hydroxide is more preferred. Moreover, 1-30 mass% is preferable, as for the density | concentration of the alkali in alkaline aqueous solution, 1-25 mass% is more preferable, and 1.5-20 mass% is still more preferable.

The type of the surfactant is as described in the above-mentioned “Production of the resin particles (A)”, and in particular, the mass ratio of the nonionic surfactant to the anionic surfactant (nonionic surfactant / Anionic surfactant) 0.5 to 5 is preferably used in combination. The nonionic surfactant is preferably polyoxyethylene alkyl ether, and the anionic surfactant is preferably dodecylbenzene sulfonate, and more preferably used in combination.
The content of the surfactant is preferably 20 parts by mass or less, more preferably 15 parts by mass or less, and still more preferably 0.1 to 10 parts by mass with respect to 100 parts by mass of the resin constituting the resin particles (C). 0.5-10 mass parts is still more preferable.
As a method for obtaining a resin mixture, an arbitrary resin such as amorphous polyester (c) or crystalline polyester (d), an alkaline aqueous solution, preferably a surfactant is put in a container, and the resin is stirred while stirring with a stirrer. A method of melting and mixing uniformly is preferable.
The temperature at which the resin is melted and mixed is preferably equal to or higher than the glass transition point of the amorphous polyester (c).

Next, an aqueous medium is added to the resin mixture and phase inversion is performed to obtain a dispersion containing resin particles (C).
About the kind and content of an aqueous medium, it is as having demonstrated in the above-mentioned "manufacture of a resin particle (A)."

The temperature at which the aqueous medium is added is preferably equal to or higher than the glass transition temperature of the amorphous polyester (c) from the viewpoint of obtaining homogeneous resin particles.
From the viewpoint of obtaining resin particles having a small particle size, the addition rate of the aqueous medium is 0.1 to 50 parts by mass / 100 parts by mass of the resin constituting the resin particles (C) until the phase inversion is completed. Preferably, it is 0.1 to 30 parts by weight / minute, more preferably 0.5 to 10 parts by weight / minute, and 0.5 to 5 parts by weight / minute. Is more preferable. There is no restriction | limiting in the addition rate of the aqueous medium after phase inversion.
The amount of the aqueous medium used is preferably 100 to 2000 parts by mass, and 150 to 1500 parts by mass with respect to 100 parts by mass of the resin constituting the resin particles (C) from the viewpoint of obtaining uniform aggregated particles in the subsequent aggregation step. More preferred is 150 to 500 parts by mass. From the viewpoint of improving the stability of the resulting resin particle dispersion, the solid content concentration is preferably 7 to 50% by mass, more preferably 10 to 40% by mass, still more preferably 20 to 40% by mass, and still more preferably. It is 25-35 mass%. In addition, solid content is the total amount of non-volatile components, such as resin and surfactant.

The volume median particle size of the resin particles (C) in the obtained dispersion is preferably 0.02 to 2 μm. From the viewpoint of obtaining a toner capable of obtaining a high quality image, 0.02 to 1.5 μm is preferable, 0.05 to 1 μm is more preferable, and 0.05 to 0.5 μm is still more preferable.
Further, the coefficient of variation (CV value) (%) of the particle size distribution of the resin particles is preferably 40% or less, more preferably 35% or less, and more preferably 30% from the viewpoint of obtaining a toner capable of obtaining a high-quality image. The following is more preferable, and 28% or less is more preferable.
Hereinafter, each process used for this invention is demonstrated.

[Step (1)]
Step (1) includes crystalline polyester (a), amorphous polyester (b), and C.I. I. Pigment red 122 and C.I. I. In this step, the resin particles (A) containing the coloring agent containing Pigment Red 150 and the release agent particles containing the release agent are aggregated in an aqueous medium to obtain aggregated particles (1). The aggregated particles (1) thus obtained are used for the core of the core-shell particles. Next, the suitable example of a process (1) is demonstrated.
In this step, first, the resin particles (A) and the release agent particles are mixed in an aqueous medium to obtain a mixed dispersion. There is no restriction | limiting in particular in an aqueous medium, The thing similar to what is used at the time of manufacture of the above-mentioned resin particle (A) can be used conveniently.
There is no restriction | limiting in order of mixing, You may add any in order and may add simultaneously.

In the mixed dispersion, the resin particles (A) are preferably 10 to 35 parts by mass, and more preferably 20 to 30 parts by mass. The aqueous medium is preferably 60 to 85 parts by mass, and more preferably 70 to 80 parts by mass.
Further, the colorant is used in an amount of 1 to 100 parts by mass of the resin constituting the resin particles (A) from the viewpoint of improving the image density of the printed matter obtained using the toner and improving the low-temperature fixability of the toner. 20 mass parts is preferable, 3-15 mass parts is more preferable, and 5-15 mass parts is still more preferable. From the viewpoint of improving the releasability and chargeability of the toner, the release agent particles are preferably 1 to 20 parts by mass, more preferably 2 to 15 parts by mass with respect to 100 parts by mass in total of the resin and the colorant. .
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 are aggregated to obtain a dispersion of aggregated particles (1). It is preferable to add a flocculant for efficient aggregation.
The aggregating agent is preferably an electrolyte, and more preferably a salt, for the purpose of obtaining a toner having a target particle size while preventing excessive aggregation. The valence is preferably 1 to 5, more preferably 1 to 2, and even more preferably 1. That is, a monovalent salt is preferable.
As the monovalent salt, an ammonium salt is preferable.
Specific examples of the flocculant include quaternary salt cationic surfactants, organic flocculants such as polyethyleneimine; inorganic flocculants such as inorganic metal salts, inorganic ammonium salts, and bivalent or higher metal complexes. It is done.
Examples of the inorganic metal salt include metal salts such as sodium sulfate, sodium chloride, calcium chloride and calcium nitrate, and inorganic metal salt polymers such as polyaluminum chloride and polyaluminum hydroxide. Examples of the inorganic ammonium salt include ammonium sulfate, ammonium chloride, ammonium nitrate and the like, and ammonium sulfate is more preferable.
The amount of the flocculant used is preferably 50 parts by mass or less, more preferably 40 parts by mass or less, and still more preferably from 100 parts by mass of the resin constituting the resin particles (A) from the viewpoint of improving the chargeability of the toner. Is 30 parts by mass or less. Further, from the viewpoint of controlling the aggregation of the resin particles to obtain a target particle size, the resin particles (A) are preferably 1 part by mass or more, more preferably 3 parts by mass or more, with respect to 100 parts by mass of the resin. More preferably, it is 5 parts by mass or more.

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. From the viewpoint of controlling the aggregation to obtain a desired particle size and shortening the toner production time, the dropping time of the aggregating agent is preferably 1 to 120 minutes. Moreover, 0-50 degreeC is preferable from a viewpoint of dripping temperature controlling aggregation and obtaining the target particle size.
Further, from the viewpoint of promoting aggregation and obtaining aggregated particles having a target particle size and particle size distribution, it is preferable to increase the temperature of the dispersion after adding the aggregating agent. As temperature to maintain, 50-70 degreeC is preferable.

The volume median particle size of the obtained aggregated particles (1) is preferably 1 to 10 μm, more preferably 2 to 9 μm, and further preferably 3 to 6 μm, from the viewpoint of suppressing toner scattering. The coefficient of variation (CV value) is preferably 30% or less, more preferably 28% or less, and still more preferably 25% or less.
The volume-median particle size ratio of the aggregated particles (1) to the resin particles (C) [aggregated particles (1) / resin particles (C)] is such that the aggregated particles (1) are mainly present on the core side, From the viewpoint of improving the low-temperature fixability, heat-resistant storage stability and chargeability of the toner, C) is mainly core-shell particles present mainly on the shell side, and is preferably 2 or more, more preferably 5 or more, still more preferably 10 or more, Preferably it is 15 or more, More preferably, it is 20 or more, Preferably it is 60 or less, More preferably, it is 50 or less, More preferably, it is 40 or less, More preferably, it is 35 or less, More preferably, it is 20 ~ 30.

  The agglomerated particles (1) may contain other components in addition to the resin particles (A), the release agent particles, and the aggregating agent as long as the object of the present invention is not impaired. The total content of the resin particles (A), the release agent particles and the flocculant in 1) is preferably 90% by mass or more, more preferably 95% by mass or more, and further preferably 99% by mass or more. Yes, more preferably 100% by mass.

[Step (2)]
Step (2) is a step of obtaining aggregated particles (2) by adding resin particles (C) containing amorphous polyester (c) to the aggregated particles (1).
Thus, by adding the resin particles (C) to the aggregated particles (1), the aggregated particles (1) are present inside and the resin particles (C) are present outside, the aggregated particles (2) Is obtained. Next, the suitable example of a process (2) is demonstrated.
In this step, the dispersion of resin particles (C) is added to the dispersion of aggregated particles (1) obtained in step (1), and the resin particles (C) are further adhered to the aggregated particles (1). It is preferable to obtain aggregated particles (2).

Before adding the dispersion liquid (resin particle (C) dispersion liquid) containing the resin particles (C) to the dispersion liquid (aggregated particle (1) dispersion liquid) containing the aggregated particles (1), the aggregated particle (1) An aqueous medium may be added to the dispersion for dilution, and an aqueous medium is preferably added. By adding an aqueous medium to obtain a predetermined coagulant concentration, the resin particles (C) can be more uniformly adhered to the aggregated particles (1).
When the resin particle (C) dispersion is added to the aggregated particle (1) dispersion, the aggregating agent may be used in order to efficiently attach the resin particle (C) to the aggregated particle (1).
As a preferable addition method in the case of adding the resin particle (C) dispersion to the aggregated particle (1) dispersion, a method of simultaneously adding the coagulant and the resin particle (C) dispersion, the coagulant and the resin particle (C ) A method of alternately adding the dispersion liquid, and a method of adding the resin particle (C) dispersion liquid while gradually raising the temperature of the aggregated particle (1) dispersion liquid. By doing in this way, the cohesiveness fall of the coagulated particle (1) and the resin particle (C) by the coagulant | flocculant density | concentration fall can be prevented. From the viewpoint of toner productivity and manufacturing simplicity, it is preferable to add the resin particle (C) dispersion while gradually raising the temperature of the aggregated particle (1) dispersion.

  The temperature in the system in this step is to improve the low-temperature fixability and heat-resistant storage stability of the toner, and from the viewpoint of improving the low-temperature fixability and heat-resistant storage stability of the toner, the crystalline polyester (a ) Is 5 ° C. or more lower than the melting point of the amorphous polyester (c), 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 heat-resistant storage stability of the obtained toner are improved. The reason for this is not clear, but because the agglomeration of the aggregated particles (2) does not occur, the generation of coarse particles is suppressed, and the crystallinity of the crystalline polyester (a) can be maintained. Conceivable.

The addition amount of the resin particles (C) improves the low temperature fixability and heat resistant storage stability of the toner, and from the viewpoint of improving the low temperature fixability and heat resistant storage stability of the toner, the resin particles (C) and the resin particles (A) Mass ratio (resin particles (C) / resin particles (A)) is preferably 0.1 to 0.9, more preferably 0.1 to 0.5, and still more preferably 0.2 to 0.4. Is preferred.
Compared with the resin particles (A), by adding a small amount of the resin particles (C), the effect of the core portion of the toner of the present invention in which the crystalline polyester (a) and the amorphous polyester (b) are mixed is sufficiently obtained. And can improve heat-resistant storage stability.

  The resin particle (C) dispersion may be added continuously over a certain period of time, may be added at a time, or may be added in a plurality of divided portions. It is preferable to add them continuously or in several divided portions. By adding as described above, the resin particles (C) are likely to selectively adhere to the aggregated particles (1). Among these, it is preferable to add continuously over a certain time from the viewpoint of promoting selective adhesion and efficient production. The time for continuous addition is preferably 1 to 10 hours, more preferably 2 to 7 hours from the viewpoint of obtaining uniform aggregated particles (2) and shortening the production time.

The total amount of the resin particles (C) is added, and the aggregation is stopped when the toner particles grow to an appropriate particle size.
As a particle size for stopping the aggregation, the volume median particle size is preferably 1 to 10 μm, more preferably 2 to 10 μm, still more preferably 3 to 9 μm, and further preferably 4 to 6 μm.
Examples of the method for stopping the aggregation include a method of cooling the dispersion, a method of adding an aggregation stopper, and a method of diluting the dispersion. From the viewpoint of reliably preventing unnecessary aggregation, the aggregation stopper A method of stopping the aggregation by adding is preferable.
As the aggregation terminator, a surfactant is preferable, and an anionic surfactant is more preferable. Examples of the anionic surfactant include alkyl ether sulfates such as sodium alkyl ether sulfate, alkyl sulfates, and linear alkylbenzene sulfonates. The aggregation terminators can be used alone or in combination of two or more.
The addition amount of the aggregation terminator is preferably 0.1 to 15 parts by mass, more preferably 100 parts by mass with respect to 100 parts by mass of the total amount of resin in the system, from the viewpoint of stopping aggregation and reducing residual toner. 0.1-10 mass parts, More preferably, it is 0.1-8 mass parts. The aggregation terminator is preferably added as an aqueous solution from the viewpoint of improving productivity.

The volume median particle size of the agglomerated particles (2) obtained in the step (2) is preferably 1 to 10 μm, more preferably 2 to 10 μm, and more preferably 3 to 9 μm from the viewpoint of obtaining a high-quality printed material with toner. Is more preferable, and 4 to 6 μm is more preferable.
The circularity of the core-shell aggregated particles is preferably from 0.93 to 0.96, more preferably from 0.93 to 0.95, from the viewpoint of obtaining a high-quality printed material with toner.
The agglomerated particles (2) may contain other components in addition to the agglomerated particles (1), the resin particles (C) and the aggregating agent as long as they do not impair the object of the present invention. The total content of the agglomerated particles (1), the resin particles (C) and the aggregating agent in (2) is preferably 90% by mass or more, more preferably 95% by mass or more, and further preferably 99% by mass. It is above, More preferably, it is 100 mass%.

[Step (3)]
In the step (3), the aggregated particles (2) obtained in the step (2) are maintained at a temperature not lower than the glass transition point of the amorphous polyester (c) and lower than the melting point of the crystalline polyester (a). , A step of obtaining core-shell particles in which the resin particles (C) are fused, and the particles in the agglomerated particles (2) that are mainly physically attached to each other are fused and integrated. Core-shell particles are formed. Next, the suitable example of a process (3) is demonstrated.

From the viewpoint of promoting fusing and improving toner productivity, in this step, the temperature is preferably not less than the glass transition temperature of the amorphous polyester (c), more preferably not less than 5 ° C. higher than the glass transition temperature. Hold on. From the viewpoint of improving the heat-resistant storage stability while maintaining the core-shell state of the toner and maintaining the low-temperature fixability, it is preferably maintained at a temperature below the melting point of the crystalline polyester (a) in this step.
Further, from the viewpoint of improving the low-temperature fixability of the toner, in this step, it is preferably maintained at a temperature not higher than the melting point of the release agent, more preferably not higher than 3 ° C., more preferably not higher than 5 ° C.
In this step, the temperature is preferably maintained at 55 to 85 ° C, more preferably 60 to 80 ° C, and still more preferably 65 to 75 ° C from the viewpoint of promoting particle fusion.
The holding time in this step is preferably 0.5 to 24 hours, more preferably 0.7 to 18 hours, from the viewpoint of improving particle fusing property, heat-resistant storage stability of toner, chargeability and toner productivity. More preferably, it is 1 to 12 hours.

From the viewpoint of obtaining a high-quality image, the volume-median particle size of the core-shell particles obtained in this step is preferably 2 to 10 μm, more preferably 2 to 8 μm, more preferably 2 to 7 μm, still more preferably 3 to 8 μm. More preferably, it is 4-6 micrometers.
The average particle size of the fused core-shell particles obtained in this step is preferably equal to or less than the average particle size of the aggregated particles (2). That is, in this step, it is preferable that the core shell particles do not aggregate and fuse.

[Post-processing process]
In the present invention, a post-treatment step may be performed after step (3), and it is preferable to obtain toner particles by isolating the core-shell particles.
Since the core-shell particles obtained in the step (3) are present in the aqueous medium, it is preferable to first perform solid-liquid separation. For solid-liquid separation, a suction filtration method or the like is preferably used.
It is preferable to perform washing after the solid-liquid separation. When a nonionic surfactant is used in the production of the resin particles (A) and (C), it is preferable to remove the added nonionic surfactant, so that it is aqueous below the cloud point of the nonionic surfactant. Washing with a solution is preferred. The washing is preferably performed a plurality of times.
Next, although it is preferable to dry, the temperature at the time of drying is preferably such that the temperature of the core-shell particle itself is 5 ° C. or more lower than the melting point of the crystalline polyester, and preferably 10 ° C. or more. More preferred. As a drying method, it is preferable to use a vibration type fluidized drying method, a spray drying method, a freeze drying method, a flash jet method, or the like. The water content after drying is preferably adjusted to 1.5% by mass or less, more preferably 1.0% by mass or less, from the viewpoint of suppressing toner scattering and improving the chargeability.

[Magenta toner for electrostatic image development]
<Toner>
Although the toner particles obtained by drying or the like can be used as they are as the toner of the present invention, it is preferable to use toner particles whose surfaces have been treated as described below as electrostatic charge image developing toner.
The softening point of the obtained toner is preferably 60 to 140 ° C., more preferably 60 to 130 ° C., and still more preferably 60 to 120 ° C. from the viewpoint of improving the low-temperature fixability and heat-resistant storage stability of the toner. The glass transition temperature is preferably 30 to 80 ° C., more preferably 40 to 70 ° C., from the viewpoint of improving the low-temperature fixability, durability, and heat-resistant storage stability of the toner.
The volume-median particle size of the toner is preferably 1 to 10 μm, more preferably 2 to 8 μm, still more preferably 3 to 7 μm, and still more preferably 4 from the viewpoint of obtaining a high-quality printed matter with the toner and improving productivity. ~ 6 μm.
The CV value of the toner is preferably 30% or less, more preferably 27% or less, still more preferably 25% or less, and further preferably 22% or less from the viewpoint of obtaining a high-quality printed matter.
The degree of circularity of the toner is preferably 0.955 to 0.990, more preferably 0.960 to 0.980, and more preferably 0.965 to 0.975 from the viewpoint of suppressing toner scattering and improving cleaning properties. Further preferred.
The BET specific surface area of the toner is preferably 0.8 to 2.5, more preferably 1.0 to 2.5, and more preferably 1.3 to 2.0 from the viewpoint of suppressing toner scattering and improving heat-resistant storage stability. Is more preferable.

<External additive>
In the toner for developing an electrostatic charge image of the present invention, the toner particles can be used as the toner as they are, but it is preferable to use a toner obtained by adding a fluidizing agent or the like to the toner particle surface as an external additive.
Examples of the external additive include hydrophobic silica, titanium oxide fine particles, alumina fine particles, cerium oxide fine particles, inorganic fine particles such as carbon black, and polymer fine particles such as polycarbonate, polymethyl methacrylate, and silicone resin. Among these, hydrophobic Silica is preferred.
When the surface treatment of toner particles is performed using an external additive, the amount of the external additive added is preferably 1 to 5 parts by mass, more preferably 2 to 4 parts by mass with respect to 100 parts by mass of the toner particles. .

  The magenta toner for developing an electrostatic image obtained by the present invention can be used as a one-component developer or mixed with a carrier and used as a two-component developer.

The present invention discloses the following magenta toner for developing an electrostatic image and a method for producing the same with respect to the above-described embodiments.
<1> A method for producing a magenta toner for developing an electrostatic charge image, comprising the following steps (1) to (3).
Step (1): Crystalline polyester (a), amorphous polyester (b), and C.I. I. Pigment red 122 and C.I. I. Step of obtaining aggregated particles (1) by aggregating resin particles (A) containing a colorant containing Pigment Red 150 and release agent particles containing a release agent in an aqueous medium Step (2) Step of adding resin particles (C) containing amorphous polyester (c) to the aggregated particles (1) to obtain aggregated particles (2) Step (3): Non-aggregated particles (2) A step of obtaining core-shell particles in which the resin particles (C) are fused by holding at a temperature not lower than the glass transition point of the crystalline polyester (c) and lower than the melting point of the crystalline polyester (a).

<2> The resin particles (A) are a master batch obtained by melt-mixing a mixture containing at least a part of the amorphous polyester (b) and the colorant, the crystalline polyester (a), and the amorphous The method for producing a magenta toner for developing an electrostatic charge image according to <1>, wherein the remainder of the polyester (b) is mixed and emulsified by adding an aqueous medium.
<3> The amount of the colorant in the masterbatch (colored resin) is 5 to 60% by mass, preferably 10 to 50% by mass, and more preferably 20 to 40% by mass. <1> or <2> A method for producing a magenta toner for developing an electrostatic charge image according to claim 1.
<4> Resin particles (A) include a step of obtaining a resin mixture by melting and mixing the components containing the master batch and the crystalline polyester (a) in the presence of an aqueous alkali solution, and an aqueous system for the resin mixture. An electrostatic charge image according to any one of <1> to <3>, which is obtained by adding a medium and performing phase inversion to obtain a dispersion containing resin particles (A). A method for producing a magenta toner for development.
<5> C.I. in resin particles (A) I. Pigment red 122 and C.I. I. The total content of CI Pigment Red 150 is preferably 1 part by mass or more, more preferably 3 parts by mass or more, still more preferably 5 parts by mass or more, with respect to 100 parts by mass of the resin constituting the resin particles (A). Preferably it is 20 mass parts or less, More preferably, it is 15 mass parts or less, More preferably, it is 10 mass parts or less, Preferably it is 1-20 mass parts, More preferably, it is 3-15 mass parts, More preferably, it is 5-10 mass parts. The method for producing a magenta toner for developing an electrostatic image according to any one of <1> to <4>.

<6> C.I. I. Pigment red 122, C.I. I. Mass ratio to CI Pigment Red 150 [C.I. I. Pigment red 122 / C.I. I. Pigment Red 150] is 10/90 to 90/10, preferably 20/80 to 80/20, more preferably 30/70 to 70/30, still more preferably 20/80 to 60/40, <1 The method for producing a magenta toner for developing an electrostatic charge image according to any one of> to <5>.
<7> C.I. I. Pigment red 122, C.I. I. Mass ratio to CI Pigment Red 150 [C.I. I. Pigment red 122 / C.I. I. Pigment Red 150] is preferably 10/90 to 60/40, more preferably 10/90 to 40/60, and still more preferably 20/80 to 40/60, any one of <1> to <5> A method for producing a magenta toner for developing an electrostatic image as described in 1.
<8> C.I. I. Pigment red 122, C.I. I. Mass ratio to CI Pigment Red 150 [C.I. I. Pigment red 122 / C.I. I. Pigment Red 150] is 40/60 to 90/10, preferably 40/60 to 80/20, more preferably 40/60 to 60/40, according to any one of <1> to <5>. A method for producing a magenta toner for developing an electrostatic image.
<9> C.I. I. Pigment red 122, C.I. I. Mass ratio to CI Pigment Red 150 [C.I. I. Pigment red 122 / C.I. I. Pigment Red 150] is preferably 40/60 to 90/10, more preferably 60/40 to 90/10, and still more preferably 60/40 to 80/20, any one of <1> to <5> A method for producing a magenta toner for developing an electrostatic image as described in 1.
<10> The amorphous polyester (b) is an alkyl succinic acid having an alkyl group having 9 to 14, preferably 10 to 14, more preferably 12 to 14 carbon atoms, and 9 to 14 carbon atoms, preferably 10 to 14 carbon atoms. More preferably, it is an amorphous polyester obtained by condensation polymerization of an acid component containing at least one selected from alkenyl succinic acids having 12 to 14 alkenyl groups and an alcohol component, <1> to <9 The method for producing a magenta toner for developing an electrostatic image according to any one of the above.

<11> The mass ratio [(a) / (b)] of the crystalline polyester (a) and the amorphous polyester (b) is preferably 5/95 to 50/50, more preferably 5/95 to 40. / 60, more preferably 5/95 to 30/70, more preferably 10/90 to 30/70, still more preferably 15/85 to 20/80, <1> to <10> A method for producing a magenta toner for developing electrostatic images.
<12> The crystalline polyester (a) is a crystalline polyester obtained by polycondensing an α, ω-alkanediol having 2 to 18 carbon atoms and an aliphatic dicarboxylic acid having 8 to 12 carbon atoms, <1> A method for producing a magenta toner for developing an electrostatic charge image according to any one of to <11>.
<13> The method for producing a magenta toner for developing an electrostatic charge image according to any one of <1> to <12>, wherein the crystalline polyester (a) has a melting point of 70 to 90 ° C.
<14> The melting point of the crystalline polyester (a) is preferably 70 ° C or higher, more preferably 72 ° C or higher, still more preferably 73 ° C or higher, and preferably 90 ° C or lower, more preferably 83 ° C or lower, More preferably, it is 80 degrees C or less, The manufacturing method of the magenta toner for electrostatic image development in any one of <1>-<13>.
<15> The softening point of the crystalline polyester (a) is preferably 70 ° C or higher, more preferably 73 ° C or higher, still more preferably 75 ° C or higher, and preferably 90 ° C or lower, more preferably 83 ° C or lower. More preferably, the method for producing a magenta toner for developing an electrostatic charge image according to any one of <1> to <14>, which is 80 ° C. or lower.

<16> The number average molecular weight of the crystalline polyester (a) is preferably 1,500 or more, more preferably 2,000 or more, still more preferably 3,000 or more, and preferably 50,000 or less. Preferably it is 10,000 or less, More preferably, it is 5,000 or less, Preferably it is 1,500-50,000, More preferably, it is 2,000-10,000, More preferably, it is 3,000-5,000. , <1> to <15>, a method for producing a magenta toner for developing an electrostatic charge image.
<17> The acid value of the crystalline polyester (a) is preferably 5 mgKOH / g or more, more preferably 10 mgKOH / g or more, still more preferably 15 mgKOH / g or more, and preferably 30 mgKOH / g or less, more preferably Is 25 mg KOH / g or less, more preferably 22 mg KOH / g or less, preferably 5 to 30 mg KOH / g, more preferably 10 to 25 mg KOH / g, still more preferably 15 to 22 mg KOH / g, <1> to <16 The method for producing a magenta toner for developing an electrostatic charge image according to any one of the above.
<18> Crystalline polyester (a) is an aliphatic dicarboxylic acid having 2 to 18 carbon atoms, preferably an acid component containing sebacic acid, and α, ω-alkanediol, preferably α, ω having 2 to 18 carbon atoms. An alcohol component containing an alkanediol, more preferably an α, ω-alkanediol having 4 to 12 carbon atoms, still more preferably an α, ω-alkanediol having 6 to 12 carbon atoms, still more preferably 1,9-nonanediol. The method for producing a magenta toner for developing an electrostatic charge image according to any one of <1> to <17>, which is obtained by polycondensation reaction.
<19> Amorphous polyester (b) is an acid component and an alkylene oxide (2 to 3 carbon atoms) oxide adduct (average number of added moles 1 to 16) of bisphenol A, preferably an ethylene oxide adduct of bisphenol A and At least one selected from propylene oxide adducts, more preferably at least one of bisphenol A ethylene oxide adduct and propylene oxide adduct, more preferably two types of bisphenol A ethylene oxide adduct and propylene oxide adduct. The method for producing a magenta toner for developing an electrostatic charge image according to any one of <1> to <18>, which is obtained by polycondensation reaction with an alcohol component.
<20> The production of a magenta toner for developing an electrostatic charge image according to <19>, wherein the acid component of the amorphous polyester (b) contains a dicarboxylic acid, preferably a dicarboxylic acid and a trivalent or higher carboxylic acid. Method.

<21> The acid component of the amorphous polyester (b) is an alkyl succinic acid having an alkyl group having 9 to 14 carbon atoms, an alkenyl succinic acid having an alkenyl group having 9 to 14 carbon atoms, and alkyl succinic acid and alkenyl. Production of a magenta toner for developing electrostatic images according to <19> or <20>, comprising at least one selected from aliphatic dicarboxylic acids having 2 to 12 carbon atoms, preferably 2 to 6 carbon atoms other than succinic acid. Method.
<22> The amorphous polyester (b) contains at least one of terephthalic acid, dodecenyl succinic acid, trimellitic acid and fumaric acid, preferably contains terephthalic acid and dodecenyl succinic acid, more preferably terephthalic acid, dodecenyl succinic acid and The method for producing a magenta toner for developing electrostatic images according to <1> to <21>, comprising trimellitic acid.
<23> The glass transition temperature of the amorphous polyester (b) is preferably 50 ° C. or higher, more preferably 52 ° C. or higher, still more preferably 54 ° C. or higher, preferably 70 ° C. or lower, The method for producing a magenta toner for developing an electrostatic charge image according to <1> to <22>, which is more preferably 68 ° C. or lower, and further preferably 66 ° C. or lower.
<24> The softening point of the amorphous polyester (b) is preferably 70 ° C or higher, more preferably 90 ° C or higher, still more preferably 100 ° C or higher, preferably 165 ° C or lower, and more. The method for producing a magenta toner for developing electrostatic images according to <1> to <23>, which is preferably 140 ° C. or lower, more preferably 130 ° C. or lower.
The number average molecular weight of <25> amorphous polyester (b) is preferably 1,000 or more, more preferably 1,500 or more, still more preferably 2,000 or more, preferably 50,000. The method for producing a magenta toner for developing electrostatic images according to <1> to <24>, which is preferably 10,000 or less, more preferably 4,000 or less.

The acid value of <26> amorphous polyester (b) is preferably 6 mgKOH / g or more, more preferably 10 mgKOH / g or more, still more preferably 15 mgKOH / g or more, preferably 35 mgKOH / g or less. The method for producing a magenta toner for developing an electrostatic charge image according to <1> to <25>.
<27> C.I. I. Pigment red 122 and C.I. I. The content of Pigment Red 150 is preferably 1 part by mass or more, more preferably 3 parts by mass or more, and still more preferably 5 parts by mass or more, with respect to 100 parts by mass of the resin constituting the resin particles (A). Is 20 parts by mass or less, more preferably 15 parts by mass or less, still more preferably 10 parts by mass or less, preferably 1 to 20 parts by mass, more preferably 3 to 15 parts by mass, and 5 to 10 parts by mass. The method for producing a magenta toner for developing an electrostatic charge image according to 1> to <26>.
<28> A magenta toner for developing an electrostatic image obtained by the production method according to any one of <1> to <28>.

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

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

[Polyester softening point, crystallinity index, endothermic maximum peak temperature, melting point and glass transition point]
(1) Softening point Using a flow tester “CFT-500D” (manufactured by Shimadzu Corporation), a 1 g sample was heated at a heating rate of 6 ° C./min, and a load of 1.96 MPa was applied by a plunger. The nozzle was extruded from a nozzle having a diameter of 1 mm and a length of 1 mm. A flow tester drop amount of the flow tester was plotted against the temperature, and the temperature at which half of the sample flowed out was defined as the softening point.

(2) Maximum endothermic peak temperature, melting point and glass transition temperature The temperature was raised to 200 ° C. using a differential scanning calorimeter (manufactured by PerkinElmer, trade name: Pyris 6 DSC), and the temperature lowering rate was 50 ° C./min. The sample cooled to 0 ° C. was heated at a heating rate of 10 ° C./min, and the endothermic peak was measured. Among the observed endothermic peaks, the temperature of the peak having the maximum peak area was defined as the maximum endothermic temperature (1). In the case of crystalline polyester, the peak temperature was taken as the melting point. In the case of an amorphous polyester, when an endothermic peak is observed, the temperature of the peak is measured, and when a step is observed without a peak being observed, the tangent indicating the maximum slope of the curve of the step and the step The temperature of the intersection with the extended line of the base line on the high temperature side was taken as the glass transition temperature.

(3) Crystallinity Index Using a differential scanning calorimeter (manufactured by PerkinElmer, trade name: Pyris 6 DSC), a sample cooled from room temperature (20 ° C.) to 0 ° C. at a temperature decrease rate of 10 ° C./min is left still for 1 minute. Thereafter, the temperature was raised to 180 ° C. at a temperature rising rate of 10 ° C./min, and the endothermic peak was measured. Of the observed peaks, the peak temperature with the maximum peak area is defined as the endothermic maximum peak temperature (2), and the crystallinity is expressed by (softening point (° C)) / (maximum endothermic peak temperature (2) (° C)). The index was determined.

[Number average molecular weight of polyester]
The molecular weight distribution was measured by gel permeation chromatography and the number average molecular weight was calculated by the following method.
(1) Preparation of sample solution Polyester was dissolved in chloroform so that the concentration was 0.5 g / 100 ml. Subsequently, this solution was filtered using a fluororesin filter “FP-200” (manufactured by Sumitomo Electric Industries, Ltd.) having a pore size of 2 μm to remove insoluble components to obtain a sample solution.
(2) Molecular weight distribution measurement Chloroform was allowed to flow as a lysis solution at a flow rate of 1 ml / min, and the column was stabilized in a constant temperature bath at 40 ° C. Measurement was performed by injecting 100 μl of the sample solution. The molecular weight of the sample was calculated based on a calibration curve prepared in advance. The calibration curve at this time includes several types of monodisperse polystyrene (monodisperse polystyrene manufactured by Tosoh Corporation; 2.63 × 10 ³ , 2.06 × 10 ⁴ , 1.02 × 10 ⁵ (weight average molecular weight), A monodisperse polystyrene manufactured by GL Sciences Inc .; 2.10 × 10 ³ , 7.00 × 10 ³ , 5.04 × 10 ⁴ (weight average molecular weight)) was used as a standard sample.
Measuring device: CO-8010 (manufactured by Tosoh Corporation)
Analysis column: GMHXL + G3000HXL (manufactured by Tosoh Corporation)

[Melting point of release agent]
A differential scanning calorimeter “DSC210” (manufactured by Seiko Denshi Kogyo Co., Ltd.) is used to measure from 20 ° C. at a rate of temperature increase of 10 ° C./min, and the maximum peak temperature is taken as the melting point.

[Volume Median Particle Size (D ₅₀ ), Volume Average Particle Size (D _v ), and Particle Size Distribution of Resin Particles, Release Agent Particles, and Colorant 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.
Further, as the particle size distribution, the CV value (%) was calculated according to the following formula from the volume average particle size (D _v ) and standard deviation displayed by the particle size measuring instrument.
CV value (%) = (standard deviation of particle size distribution / volume average particle size (D _v )) × 100

[Solid content concentration of resin particle dispersion and release agent particle dispersion]
Using an infrared moisture meter “FD-230” (manufactured by Kett Scientific Laboratory), 5 g of a measurement sample is set at a drying 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)

[Softening point of resin particles]
After weighing 20 g of the resin particle dispersion in an aluminum dish, it is put into a shelf dryer “DRC-1000” (manufactured by EYELA) connected to a freeze dryer “FDU-2100” (manufactured by EYELA) at room temperature and normal pressure, and −25 After maintaining at 1 ° C. for 1 hour, the pressure is reduced at −10 ° C. and 8.0 Pa for 9 hours. Then, after hold | maintaining at 25 degreeC for 5 hours, it returned to the normal pressure and obtained the resin particle.
The softening point of the obtained resin particles was measured by the same method as that for the polyester.

[Toner circularity]
-Preparation of dispersion: Toner dispersion was prepared by adding 50 mg of toner to 5 ml of 5% by weight polyoxyethylene lauryl ether (Emulgen 109P) aqueous solution and dispersing for 1 minute with an ultrasonic disperser, and then adding 20 ml of distilled water. And the mixture was further dispersed for 1 minute using an ultrasonic disperser.
Measurement device: Flow type particle image analyzer “FPIA-3000” (manufactured by Sysmex Corporation)
・ Measurement mode: HPF measurement mode

[BET specific surface area of toner]
Using a Micromeritics FlowSorb III (manufactured by Shimadzu Corporation), the BET specific surface area was measured under the following conditions.
Toner sample amount: 0.09 to 0.11 g
・ Deaeration condition: 40 ° C., 10 minutes ・ Adsorption gas: Nitrogen gas

[Volume Median Particle Size (D ₅₀ ), Volume Average Particle Size (D _v ), and Particle Size Distribution of Toner and Aggregated Particles]
The volume median particle size of the toner and aggregated particles was measured as follows.
Measuring instrument: 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 conditions: 10 mg of a measurement sample was added to 5 mL of the dispersion, and dispersed for 1 minute with an ultrasonic disperser. Then, 25 mL of electrolyte was added, and further dispersed for 1 minute with an ultrasonic disperser. A sample dispersion was prepared.
Measurement conditions: The sample dispersion is added to 100 mL of the electrolytic solution to adjust the particle size of 30,000 particles to a concentration that can be measured in 20 seconds, and then 30,000 particles are measured and the particle size distribution thereof. From this, the volume median particle size (D ₅₀ ) was determined.
Further, as the particle size distribution, the CV value (%) was calculated from the volume average particle size (D _v ) and standard deviation displayed by the analysis software according to the following formula.
CV value (%) = (standard deviation of particle size distribution / volume average particle size (D _v )) × 100

[Evaluation of low-temperature fixability of toner]
Using a commercially available printer “Microline 5400” (manufactured by Oki Data Co., Ltd.) on high-quality paper “J paper A4 size” (manufactured by Fuji Xerox Co., Ltd.), the toner adhesion amount on the paper is 0.42 to 0.48 mg / A solid image of cm ² was output without being fixed at a length of 50 mm, leaving a margin of 5 mm from the top edge of the A4 paper.
Next, the same printer with the temperature-variable fixing device prepared was prepared, the temperature of the fixing device was set to 90 ° C., and fixing was performed at a speed of 1.5 seconds per sheet in the A4 longitudinal direction, thereby obtaining a printed matter.
In the same manner, the temperature of the fixing device was increased by 5 ° C., and the fixing was performed to obtain a printed matter.
A 500 g weight is applied to the margin at the top of the printed image, after lightly pasting a piece of mending tape (product name: Scotch mending tape 810, width 18 mm) cut to a length of 50 mm. It was loaded and pressed once and again 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 a speed of 10 mm / second to obtain a printed matter after the tape was peeled off. Thirty sheets of “Excellent White Paper A4 Size” (manufactured by Oki Data Co., Ltd.) are placed under the printed material before and after the tape is applied, and the reflected image density of the fixed image portion before and after the tape is applied to each printed material. Is measured using a colorimeter “SpectroEye” (manufactured by Gretag-Macbeth, light condition: standard light source D ₅₀ , observation field of view 2 °, density standard DINNB, absolute white standard), Calculated.
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 heat-resistant storage stability of toner]
20 g of toner was put in a wide-mouthed polybin with an internal volume of 100 ml, sealed, and allowed to stand for 24 hours in an environment at a temperature of 53 ° C. Thereafter, it was allowed to stand for 12 hours or more while being sealed at a temperature of 25 ° C. and cooled. Subsequently, a sieve having a mesh size of 250 μm was set on a vibrating table of a powder tester (manufactured by Hosokawa Micron Co., Ltd.), 20 g of the toner was placed thereon, and the mixture was vibrated for 30 seconds, and the amount of toner remaining on the sieve was measured. The smaller the value, the better the heat resistant storage stability of the toner.

[Charge amount of toner at normal temperature and humidity (NN charge amount)]
At a temperature of 25 ° C. and a relative humidity of 50%, 2.1 g of toner and 27.9 g of a silicone ferrite carrier (manufactured by Kanto Denka Kogyo Co., Ltd., average particle size: 40 μm) are placed in a 50 ml cylindrical polypropylene bottle (Nikko Corporation The product was shaken 10 times vertically and horizontally, and then the amount of charge at a mixing time of 1 hour was measured with a ball mill using a q / m meter (manufactured by EPPING). The charge amount was defined as “charge amount under normal temperature and normal humidity (NN charge amount)”. The higher the absolute value of the charge amount, the better the chargeability.
Measurement equipment, settings, etc. are as follows.
Measuring instrument: q / m-meter manufactured by EPPING
Setting: Mesh Size: 635 mesh (Aperture: 24 μm, made of stainless steel)
Soft blow, blow pressure (600V)
Suction time: 90 seconds Charge amount (μC / g) = Total amount of electricity after 90 seconds (μC) / Amount of toner sucked (g)

[Charge amount (HH charge amount) and charge amount retention rate of toner at high temperature and high humidity]
After the chargeability evaluation under normal temperature and normal humidity, the toner was placed at a temperature of 30 ° C. and a relative humidity of 85% (high temperature and high humidity environment), and held for 12 hours. Thereafter, the mixture was placed in a high temperature and high humidity environment at a temperature of 25 ° C. and a relative humidity of 50%. The charge amount was defined as “charge amount under high temperature and high humidity (HH charge amount)”. The higher the absolute value of the charge amount, the better the chargeability.
Using the value of the charge amount, the charge amount retention rate was calculated according to the following formula. The chargeability is better as the value of the charge retention rate is larger.
Charge amount retention rate [%] = (charge amount under high temperature and high humidity environment / charge amount under normal temperature and humidity environment) × 100

[Image density]
Using a commercially available printer “Microline 5400” (manufactured by Oki Data Co., Ltd.) on high-quality paper “J paper A4 size” (manufactured by Fuji Xerox Co., Ltd.), the toner adhesion amount on the paper is 0.42 to 0.48 mg / A solid image of cm ² was output to obtain a printed matter.
30 sheets of high quality paper “Excellent White Paper A4 Size” (Oki Data Co., Ltd.) are laid under the printed material, and the reflected image density of the solid image portion of the printed material is measured by the colorimeter “SpectroEye” (Gretag-Macbeth) Manufactured, light emission conditions: standard light source D ₅₀ , observation field of view 2 °, density standard DINNB, absolute white standard), and measured values of three arbitrary points on the image were averaged to obtain an image density. The larger the value of the reflected image density, the better the image density.

[Production of polyester]
Production Examples 1 and 2
(Production of crystalline polyesters X1 and X2)
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 the raw material monomers shown in Table 1 were added. While stirring, the temperature was raised to 140 ° C., maintained at 140 ° C. for 3 hours, and then heated from 140 ° C. to 200 ° C. over 10 hours. Thereafter, di (2-ethylhexanoic acid) tin was added, and the mixture was further maintained at 200 ° C. for 1 hour, and then the pressure in the flask was lowered and maintained at 8.3 kPa for 4 hours to obtain crystalline polyesters X1 and X2. It was. The physical properties are shown in Table 1.

Production Example 3
(Production of amorphous polyester Y1)
The inside of a four-necked flask equipped with a nitrogen introduction tube, dehydration tube, stirrer, and thermocouple was replaced with nitrogen, and the raw material monomers and esterification catalyst excluding trimellitic anhydride shown in Table 1 were placed in a nitrogen atmosphere. While stirring, the temperature was raised to 230 ° C. and maintained at 230 ° C. 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, trimellitic anhydride was added and maintained at 215 ° C. for 1 hour, then the pressure in the flask was further lowered and maintained at 8.3 kPa for 3 hours. Amorphous polyester Y1 was obtained. The physical properties are shown in Table 1.

Production Example 4
(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 is purged with nitrogen, and the raw material monomer and esterification catalyst excluding fumaric acid shown in Table 1 are added and stirred in a nitrogen atmosphere. However, after raising the temperature to 230 ° C. and maintaining at 230 ° C. for 5 hours, the pressure in the flask was further lowered and maintained at 8.3 kPa for 1 hour. Then, after cooling to 210 ° C. and returning to atmospheric pressure, fumaric acid and tert-butylcatechol were added and maintained at a temperature of 210 ° C. for 5 hours, and then the pressure in the flask was further lowered at 8.3 kPa. The polyester resin Y2 was obtained by maintaining for 4 hours. The physical properties are shown in Table 1.

Production Example 5
(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 purged with nitrogen, and the raw material monomer and esterification catalyst shown in Table 1 were placed and stirred at 220 ° C. in a nitrogen atmosphere. The temperature was then maintained at 220 ° C. for 5 hours, and after confirming that the softening point measured according to ASTM D36-86 had reached 120 ° C., the reaction was stopped by lowering the temperature to obtain polyester resin Y3. The physical properties are shown in Table 1.

Production Example 6
(Production of amorphous polyester Y4)
A raw material monomer, a polymerization inhibitor and an esterification catalyst shown in Table 1 were put into a four-necked flask equipped with a nitrogen introduction tube, a dehydration tube, a stirrer and a thermocouple, and stirred at 230 ° C. in a nitrogen atmosphere. ASTM D36- It was made to react until the softening point measured according to 86 reached 100 degreeC, and polyester resin Y4 was obtained. The physical properties are shown in Table 1.

[Manufacture of master batch]
Production Example 7
(Manufacture of master batch A1)
1400 g of fine powder of polyester resin Y4 of Production Example 6, magenta pigment C.I. I. Pigment Red 122 (manufactured by Dainichi Seika Kogyo Co., Ltd.) and magenta pigment C.I. I. 300 g of Pigment Red 150 (manufactured by Toyo Ink Manufacturing Co., Ltd.) was charged into a Henschel mixer and mixed for 5 minutes. Next, this mixture was kneaded with a kneader type mixer at a kneading temperature of 100 ° C. for 20 minutes, and further kneaded at a kneading temperature of 120 ° C. for 20 minutes. The obtained kneaded product was cooled and then kneaded with a heated three roll, cooled and crushed to obtain a master batch A1 containing a pigment (colorant) at a concentration of 30% by mass.

Production Examples 8-13
(Manufacture of master batches A2 to A4, C1, D1 and E1)
Master batches A2 to A4, C1, D1, and E1 were obtained in the same manner as in Production Example 7, except that the magenta pigment was changed to the composition shown in Table 2. In Production Example 12, the magenta pigment C.I. I. Pigment Red 238 was manufactured by Sanyo Dye Co., Ltd. I. Pigment Violet 19 manufactured by Dainichi Seika Kogyo Co., Ltd. was used.

[Production of resin particles]
Production Example 14
(Production of resin particle dispersion Em-1)
In a flask equipped with a stirrer, 90 g of crystalline polyester X1, 374 g of amorphous polyester Y1, 195 g of master batch A1, 9.5 g of polyoxyethylene alkyl ether “Emulgen 150” (manufactured by Kao Corporation), 15 mass% dodecyl Sodium benzenesulfonate aqueous solution “Neopelex G-15” (manufactured by Kao Co., Ltd.) 80 g, 238 g of 5 mass% potassium hydroxide aqueous solution was added, and the mixture was heated to 98 ° C. with stirring and melted. Mixing for a time, a resin mixture was obtained.
Next, with stirring at 98 ° C., 1242 g of deionized water was added dropwise at a rate of 6 g / min to obtain an emulsion. Next, the obtained emulsion was cooled to 25 ° C. and stirred at 25 ° C., while the oxazoline group-containing polymer aqueous solution “Epocross WS-700” (manufactured by Nippon Shokubai Co., Ltd., solid content 25% by mass, acrylic main chain) 23 g (5.75 g in terms of solid content) was added, and then the temperature was raised to 95 ° C. and held at 95 ° C. for 1 hour. Next, after cooling to 25 ° C., the obtained emulsion was passed through a 200 mesh (mesh 105 μm) wire mesh, deionized water was added to adjust the solid content to 28% by mass, and the resin particle dispersion Em-1 was obtained. Physical properties are shown in Table 3-1.

Production Examples 15-20
(Production of resin particle dispersions Em-2 to Em-7)
Resin particle dispersions Em-2 to Em-7 were obtained in the same manner as in Production Example 14 except that the master batch A1 was changed as shown in Table 3-1. Physical properties are shown in Table 3-1.

Production Example 21
(Production of resin particle dispersion Em-8)
195 g of master batch A1 of Production Example 14 was added to 136 g of amorphous polyester Y4 and magenta pigment C.I. I. Pigment Red 122 (manufactured by Dainichi Seika Kogyo Co., Ltd.) 17.5 g, and magenta pigment C.I. I. A resin particle dispersion Em-8 was obtained in the same manner except that it was changed to 41 g of CI Pigment Red 150 (manufactured by Toyo Ink Manufacturing Co., Ltd.). The physical properties are shown in Table 3-2.

Production Example 22
(Production of resin particle dispersion Em-9)
In a flask having an internal volume of 5 liters, 390 g of amorphous polyester Y2, 210 g of amorphous polyester Y3, 6 g of polyoxyethylene alkyl ether “Emulgen 430” (manufactured by Kao Corporation), 15% by mass aqueous sodium dodecylbenzenesulfonate “ 40 g of Neoperex G-15 "(manufactured by Kao Corporation) and 268 g of 5% by mass potassium hydroxide are added, and the mixture is heated to 95 ° C. with stirring and melted, and mixed at 95 ° C. for 2 hours. Got.
Next, 1145 g of deionized water was added dropwise at a rate of 6 g / min while stirring to obtain an emulsion. Next, the obtained emulsion was cooled to 25 ° C., passed through a 200-mesh wire mesh, deionized water was added to adjust the solid content to 28% by mass, and a resin particle dispersion Em-9 was obtained. . The physical properties are shown in Table 3-2.

Production Example 23
(Production of resin particle dispersion Em-10)
Resin particle dispersion Em according to the same procedure as in Production Example 22 except that the raw materials used were changed to 254 g of amorphous polyester Y2, 210 g of amorphous polyester Y3 and 195 g of master batch A2 as shown in Table 3-2. -10 was obtained. The physical properties are shown in Table 3-2.

Production Example 24
(Production of resin particle dispersion Em-11)
In a 5-liter flask, crystalline polyester X2 90 g, amorphous polyester Y1 374 g, amorphous polyester Y4 136 g, polyoxyethylene alkyl ether “Emulgen 150” (manufactured by Kao Corporation) 8.5 g, 15 mass A 80% aqueous solution of sodium dodecylbenzenesulfonate “Neopelex G-15” (manufactured by Kao Corporation) and 238 g of 5% by mass potassium hydroxide were added and heated to 98 ° C. with stirring to melt. For 2 hours to obtain a resin mixture.
Next, 1105 g of deionized water was added dropwise at a rate of 6 g / min while stirring to obtain an emulsion. Next, the obtained emulsion was cooled to 25 ° C., passed through a 200-mesh wire mesh, deionized water was added, and the solid content was adjusted to 28% by mass to obtain a resin particle dispersion Em-11. . The physical properties are shown in Table 3-2.

[Production of colorant particles]
Production Example 25
(Colorant particle dispersion P-1)
In a beaker having an internal volume of 1 liter, 134 g of deionized water and 100 g of a 15% by mass sodium dodecylbenzenesulfonate aqueous solution “Neopelex G-15” (manufactured by Kao Corporation) were weighed, and magenta pigment Pigment Red 122 (Ohnissei) (Chemical Industry Co., Ltd.) 73.1 g and magenta pigment Pigment Red 185 (Clariant Japan Co., Ltd.) 73.1 g were added, followed by stirring at 25 ° C. for 2 minutes at 5000 r / min using a TK homomixer. Then, the number of rotations was increased to 12,000 and stirring was continued for 2 hours. The obtained colorant dispersion was passed through a 200-mesh wire mesh, deionized water was added to adjust the pigment solid content to 25% by mass, and colorant particle dispersion P-1 was obtained. The volume median particle size (D ₅₀ ) of the colorant particles in the colorant particle dispersion P-1 was 650 nm, and the CV value was 60%.

[Manufacture of release agent particles]
Production Example 26
(Production of release agent particle dispersion W-1)
In a 1 liter beaker, 3.8 g of sodium acrylate-sodium maleate copolymer aqueous solution “Poise 521” (manufactured by Kao Corporation, effective concentration: 40% by mass) is added as sodium polycarboxylate aqueous solution to 200 g of deionized water. After dissolution, 5 g of carnauba wax “Carnauba Wax No. 1” (manufactured by Hiroyuki Kato, melting point 83 ° C.) and paraffin wax “HNP-9” (manufactured by Nippon Seiki Co., Ltd., melting point 75) 45 g) was added, melted while maintaining the temperature at 90 to 95 ° C., and stirred to obtain a molten mixture in which carnauba wax and paraffin wax were melted together.
The aqueous solution containing the obtained molten mixture was further subjected to a dispersion treatment for 30 minutes with an ultrasonic homogenizer “US-600T” (manufactured by Nippon Seiki Co., Ltd.) while maintaining the temperature at 90 to 95 ° C. and then cooled to room temperature. Then, deionized water was added thereto to adjust the release agent 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 in the release agent particle dispersion was 450 nm, and the CV value was 30%.

[Production of toner]
Example 1
(Preparation of magenta toner A)
Into a four-necked flask having an internal volume of 5 liters equipped with a dehydrating tube, a stirrer, and a thermocouple, 300 g of resin particle dispersion Em-1, 27 g of deionized water, and 20 g of release agent particle dispersion W-1 were heated to 25. Mixed under ℃. Next, while stirring the mixture, an aqueous solution in which 22 g of ammonium sulfate was dissolved in 210 g of deionized water was added dropwise at 25 ° C. over 10 minutes, and then the temperature was raised to 62 ° C. so that the volume median particle size of the aggregated particles was 4 It was kept at 62 ° C. until it became 7 μm to obtain a dispersion liquid (1) containing aggregated particles.
The temperature of the aggregated particle dispersion (1) was cooled to 58 ° C. Subsequently, 82 g of resin particle dispersion Em-9 was dropped at a rate of 0.6 ml / min until the volume median particle size of the aggregated particles became 5.2 μm while maintaining 58 ° C., and the aggregated particle dispersion ( 2) was obtained.
An aqueous solution in which 17 g of sodium alkyl ether sulfate “Emal (registered trademark) E27C” (manufactured by Kao Corporation, effective concentration: 27 mass%) and 3337 g of deionized water were added to the aggregated particle dispersion (2). Thereafter, the temperature was raised to 68 ° C. over 1.5 hours and held at 68 ° C. for 1 hour to fuse the aggregated particles to obtain core-shell particles.
The obtained core-shell particle dispersion was cooled to 25 ° C., the solid content of the dispersion was separated by suction filtration, washed with deionized water, and dried at 33 ° C. to obtain toner particles. 100 parts by mass of the toner particles, 2.5 parts by mass of hydrophobic silica (manufactured by Nippon Aerosil Co., Ltd., trade name: RY50, average particle size; 0.04 μm), and hydrophobic silica (manufactured by Cabot, trade name: Cabo Seal TS720) , Average particle diameter: 0.012 μm) 1.0 part by mass was placed in a Henschel mixer, stirred, and passed through a 150-mesh sieve to obtain magenta toner A. Table 4 shows the physical properties and evaluation of magenta toner A.

Examples 2 to 4 and Comparative Examples 1 to 5
(Production of magenta toners B, C, D, E, F, G, H, and I)
In Example 1, the magenta toners B, C, D, E, F, G, and H were used in the same manner as in Example 1 except that the resin particle dispersion Em-1 was changed to the resin particle dispersion shown in Table 4. And I were obtained. Table 4 shows the physical properties and evaluation of the toner.

Comparative Example 6
(Production of magenta toner J)
In a three-liter four-necked flask equipped with a dehydration tube, a stirrer and a thermocouple, 300 g of resin particle dispersion Em-11, 33 g of colorant particle dispersion P-1, 8 g of deionized water, and a release agent 20 g of particle dispersion W-1 was mixed at a temperature of 25 ° C. Next, while stirring the mixture, an aqueous solution in which 22 g of ammonium sulfate was dissolved in 210 g of deionized water was added dropwise at 25 ° C. over 10 minutes, and then the temperature was raised to 62 ° C. so that the volume median particle size of the aggregated particles was 4 It was kept at 62 ° C. until it became 7 μm to obtain a dispersion liquid (1) containing aggregated particles.
The temperature of the aggregated particle dispersion (1) was cooled to 58 ° C. Subsequently, 82 g of resin particle dispersion Em-9 was dropped at a rate of 0.6 ml per minute while maintaining the temperature at 58 ° C. until the volume median particle size of the aggregated particles reached 5.1 μm. 2) was obtained.
An aqueous solution in which 17 g of sodium alkyl ether sulfate “Emal (registered trademark) E27C” (manufactured by Kao Corporation, effective concentration: 27 mass%) and 3337 g of deionized water were added to the aggregated particle dispersion (2). Thereafter, the temperature was raised to 68 ° C. over 1.5 hours and held at 68 ° C. for 1 hour to fuse the aggregated particles to obtain core-shell particles.
The obtained core-shell particle dispersion was cooled to 25 ° C., the solid content of the dispersion was separated by suction filtration, washed with deionized water, and dried at 33 ° C. to obtain toner particles. 100 parts by mass of the toner particles, 2.5 parts by mass of hydrophobic silica “RY50” (manufactured by Nippon Aerosil Co., Ltd., average particle size: 0.04 μm), and hydrophobic silica “Caboseal TS720” (manufactured by Cabot, average particle size) 0.012 μm) 1.0 part by mass was placed in a Henschel mixer, stirred, and passed through a 150-mesh sieve to obtain magenta toner J. Table 4 shows the physical properties and evaluation of Magenta Toner J.

  From Table 4, the magenta toner for developing an electrostatic image of the example has both excellent low-temperature fixability and heat-resistant storage stability and excellent charging properties as compared with the magenta toner for developing an electrostatic image of the comparative example. I understand that.

  The electrostatic image developing magenta toner obtained by the production method of the present invention has both good low-temperature fixability and heat-resistant storage stability and is excellent in chargeability, and therefore can be suitably used as a toner used in electrophotography. . According to the method of the present invention, a toner having such characteristics can be produced efficiently.

Claims (8)

A method for producing a magenta toner for developing an electrostatic charge image, comprising the following steps (1) to (3):
Step (1): Crystalline polyester (a), amorphous polyester (b), and C.I. I. Pigment red 122 and C.I. I. Step of obtaining aggregated particles (1) by aggregating resin particles (A) containing a colorant containing Pigment Red 150 and release agent particles containing a release agent in an aqueous medium Step (2) Step of adding resin particles (C) containing amorphous polyester (c) to the aggregated particles (1) to obtain aggregated particles (2) Step (3): Non-aggregated particles (2) A step of obtaining core-shell particles in which the resin particles (C) are fused by holding at a temperature not lower than the glass transition point of the crystalline polyester (c) and lower than the melting point of the crystalline polyester (a).   The resin particles (A) include a master batch obtained by melt-mixing a mixture containing at least a part of the amorphous polyester (b) and the colorant, the crystalline polyester (a), and the amorphous polyester (b The method for producing a magenta toner for developing an electrostatic charge image according to claim 1, which is obtained by mixing the remainder of (2) and emulsifying by adding an aqueous medium.   C. in the resin particles (A) I. Pigment red 122 and C.I. I. The method for producing a magenta toner for developing an electrostatic charge image according to claim 1 or 2, wherein the total content of Pigment Red 150 is 1 to 20 parts by mass with respect to 100 parts by mass of the resin constituting the resin particles (A). .   C. I. Pigment red 122, C.I. I. Mass ratio to CI Pigment Red 150 [C.I. I. Pigment red 122 / C.I. I. The method of producing a magenta toner for developing an electrostatic charge image according to any one of claims 1 to 3, wherein CI Pigment Red 150] is 10/90 to 90/10.   An acid component and an alcohol component in which the amorphous polyester (b) contains at least one selected from alkyl succinic acid having an alkyl group having 9 to 14 carbon atoms and alkenyl succinic acid having an alkenyl group having 9 to 14 carbon atoms The method for producing a magenta toner for developing an electrostatic charge image according to any one of claims 1 to 4, which is an amorphous polyester obtained by condensation polymerization.   The static mass according to any one of claims 1 to 5, wherein the mass ratio [(a) / (b)] of the crystalline polyester (a) and the amorphous polyester (b) is 5/95 to 30/70. A method for producing a magenta toner for developing a charge image.   The crystalline polyester (a) is a crystalline polyester obtained by condensation polymerization of an α, ω-alkanediol having 2 to 18 carbon atoms and an aliphatic dicarboxylic acid having 8 to 12 carbon atoms. A method for producing a magenta toner for developing an electrostatic image according to any one of the above.   The method for producing a magenta toner for developing an electrostatic charge image according to any one of claims 1 to 7, wherein the crystalline polyester (a) has a melting point of 70 to 90 ° C.