JP2020109530A - Developing toner for electrostatic charge image - Google Patents

Abstract

To obtain a developing toner for an electrostatic charge image that is excellent in low-temperature fixability and low-temperature fixability after high-temperature and high-humidity storage and excellent in charging stability.SOLUTION: A developing toner for an electrostatic charge image contains a resin composition (C) including a reaction product obtained from reaction in which a crystalline resin (A) and a non-crystalline resin (B) having a component (b1) derived from a hydrocarbon wax (W1) having a hydroxyl group or a carboxyl group and a polyester portion (b2) are at least partially chemically coupled. The reaction uses a polyfunctional compound (S), and the polyfunctional compound (S) is a polyisocyanate compound. The crystalline resin (A) is a crystalline polyester whose hydroxyl value is 3 mgKOH/g to 20 mgKOH/g.SELECTED DRAWING: None

Description

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

In the field of electrophotography, with the development of electrophotographic systems, it has been required to develop a toner for developing an electrostatic image corresponding to high image quality and high speed. In particular, as a method of obtaining a toner having excellent fixability at low temperatures, it is known to use a crystalline resin in addition to the amorphous resin which has been conventionally used as a binder resin. Furthermore, in order to improve basic properties of the toner such as storability, it has been studied to give the resin a specific structure.

For example, Patent Document 1 discloses a toner binder containing a non-crystalline polyester resin, a crystalline polyester resin composed only of crystalline parts, and a block resin composed of crystalline parts and non-crystalline parts. A toner composition is disclosed, and it is described that both low-temperature fixability and hot offset resistance can be achieved, and that storage stability and charge stability are excellent.
Further, Patent Document 2 discloses a toner containing a crosslinked polyester resin and a block copolymer resin, wherein the crosslinked polyester resin contains a diol component as a constituent component, and the diol component has 3 to 10 carbon atoms. It contains 50 mol% or more of an aliphatic diol, and further contains a trivalent or higher valent aliphatic alcohol or acid as a cross-linking component, and the block copolymer resin is composed of a crystalline segment and an amorphous segment. Disclosed is an image forming toner having a glass transition temperature (Tg1st) of 20° C. or more and 50° C. or less at the first temperature increase by scanning calorimetry (DSC), which has excellent low-temperature fixing property and fixing width. It is described that the toner has a wide range of properties, and has both excellent heat resistance and storage stability and excellent abrasion resistance.
Further, Patent Document 3 discloses a binder resin composition for a toner containing an amorphous polyester and a crystalline polyester, wherein the amorphous polyester is an alcohol component in the presence of a hydrocarbon wax having a hydroxyl group. Is a resin obtained by polycondensing a raw material monomer containing a carboxylic acid component and a hydrocarbon wax having a melting point of 60° C. or higher and 110° C. or lower and a number average molecular weight of 600 or higher, and the amount of the hydrocarbon wax. However, a binder resin composition for toner is disclosed, wherein the binder resin composition for toner is 0.5 parts by mass or more and 10 parts by mass or less based on 100 parts by mass of the total amount of the alcohol component and the carboxylic acid component. It is described that the binder resin composition for toner is excellent in storage stability, durability and gloss.

JP, 2015-42737, A JP-A-2015-79240 JP, 2016-4072, A

However, even if the crystalline resin is mixed with the binder resin to improve the low-temperature fixability of the toner, as the toner is stored for a long period of time in an environment of relatively high temperature and high humidity, the low-temperature fixability is deteriorated over time. It turned out that there is a problem that Further, in the prior art such as giving a resin a specific structure, which has been studied in order to improve the basic properties of the toner such as the storage stability, the suppression of the deterioration of the low temperature fixing property with time in the high temperature and high humidity storage is suppressed. Has also been found to be insufficient.
Therefore, it is an object of the present invention to provide a toner for developing an electrostatic charge image, which has excellent low-temperature fixability and low-temperature fixability after storage at high temperature and high humidity, and also excellent charge stability, and a method for producing the same.

The present inventors considered that the factor that affects the characteristics of the toner using the crystalline resin is the dispersed state of the crystalline resin in the toner particles, and conducted the study. As a result, at least the crystalline resin and the amorphous resin having the constituent component derived from the hydrocarbon wax (W1) having a hydroxyl group or a carboxy group and the polyester portion are present at the crystalline resin terminal and the amorphous resin terminal. By including the resin composition obtained by the reaction of chemically bonding a part in the binder resin of the toner, excellent low-temperature fixability and low-temperature fixability after high-temperature and high-humidity storage are obtained, and also the charging stability is obtained. It has been found that an excellent toner for developing an electrostatic image can be obtained.

That is, the present invention relates to the following [1] to [3].
[1] At least one of a crystalline resin (A) and an amorphous resin (B) having a constituent component (b1) derived from a hydrocarbon wax (W1) having a hydroxyl group or a carboxy group and a polyester portion (b2). A toner for developing an electrostatic charge image, which comprises a resin composition (C) containing a reaction product obtained by a reaction of chemically bonding parts.
[2] At least one of the crystalline resin (A) and the amorphous resin (B) having a constituent component (b1) derived from a hydrocarbon wax (W1) having a hydroxyl group or a carboxy group and a polyester portion (b2). A resin composition containing a reaction product obtained by a reaction of chemically bonding parts.
[3] At least one of the crystalline resin (A) and the amorphous resin (B) having a constituent component (b1) derived from a hydrocarbon wax (W1) having a hydroxyl group or a carboxy group and a polyester portion (b2). A method for producing a toner for developing an electrostatic charge image, which comprises a step of obtaining a resin composition (C) containing a reaction product obtained by a reaction of chemically bonding parts.

According to the present invention, it is possible to provide a toner for developing an electrostatic charge image, which has excellent low-temperature fixability and low-temperature fixability after storage at high temperature and high humidity, and also excellent charging stability, and a method for producing the same.

[Toner for developing electrostatic image]
The toner for developing an electrostatic charge image of the present invention (hereinafter, also simply referred to as “toner”) comprises a crystalline resin (A), a constituent component (b1) derived from a hydrocarbon wax (W1) having a hydroxyl group or a carboxy group, and a polyester. A toner for developing an electrostatic charge image, which contains a resin composition (C) containing a reaction product obtained by chemically bonding at least a part of an amorphous resin (B) having a part (b2). Is.

The reason why the toner for developing an electrostatic image of the present invention is excellent in low-temperature fixability and low-temperature fixability after high-temperature and high-humidity storage and also excellent in charging stability is not clear, but is considered as follows.
Since the crystalline resin (A) in the toner does not always have good compatibility with the resin components constituting the other binder resin, the crystalline resin (A) is sufficiently dispersed in the toner base particles during the production of the toner. Even if dispersed, the size of the crystal domain cannot be fixed during storage under high temperature and high humidity after toner production, and the size of the crystal domain tends to gradually increase as crystallization progresses. As a result, the interface between the crystalline resin (A) and another binder resin is relatively reduced, and it becomes difficult to melt the surrounding amorphous resin together with the melting of the crystalline resin (A) during toner fixing. It is considered that the low temperature fixability decreases with time.

The crystalline resin (A), the amorphous resin (B), the end of the crystalline resin (A) and the end of the amorphous resin (B) are chemically bonded to the resin composition (C). It is considered that the block resin (AB) is included. The block resin (AB) forms a block structure in which the end of the amorphous resin (B) and the crystalline resin segment are connected.
The crystalline resin (A) is mixed with the component (b1) derived from the hydrocarbon wax (W1) having a hydroxyl group or a carboxy group and the amorphous resin (B) having the polyester portion (b2) to obtain a hydrocarbon wax ( A fine hydrophobic field is formed together with the hydrocarbon group derived from W1), which facilitates fine dispersion in the toner. Furthermore, the crystalline resin segment bonded to the amorphous resin (B) is finely dispersed by containing a resin in which a crystalline resin segment is bonded to the end of the amorphous resin (B) to form a block structure. Probably because the crystalline resin domain enters the domain of the crystallized crystalline resin, the crystalline resin domain can substantially maintain the bonding state with the amorphous resin component, and is extremely stabilized in the toner. As a result, it is considered that the low temperature fixability is excellent, the expansion of the crystalline resin domain during storage under high temperature and high humidity is suppressed, and the low temperature fixability after high temperature and high humidity storage is also improved.

Further, when the toner of the present invention is produced by an emulsion aggregation method in an aqueous medium, the obtained toner has excellent charge stability. The reason for this is considered as follows. When the emulsion aggregation method is applied, the polyester part (b2) in the relatively hydrophilic amorphous resin (B) is oriented on the interface side with the aqueous medium, and the crystalline resin (A) and the hydroxyl group or the carboxy group are Forming a resin particle having a fine hydrophobic field inside containing a component (b1) derived from a hydrocarbon wax (W1) having, and a crystalline resin (A), which easily causes coarse particles, being finely dispersed and incorporated. Therefore, variations in composition and particle size among the particles are reduced, and the particles are homogenized. As a result, by exposing the crystalline resin (A) to the surface of the toner mother particles by aggregating and fusing the resin particles to form the toner mother particles, the surface composition of the toner becomes stable. It is considered that the charging stability of the toner is improved.
The constituent components of the electrostatic charge developing toner of the present invention will be described below.

<Crystalline resin (A)>
The crystalline resin (A) is preferably a resin having a functional group at its terminal, and from the viewpoint of obtaining a toner having excellent low-temperature fixability and low-temperature fixability after high-temperature and high-humidity storage, and also excellent charge stability, More preferably, it is a crystalline polyester.
Here, in the present invention, whether the resin is crystalline or amorphous is determined by the crystallinity index. The crystallinity index is defined as the ratio between the softening point of the resin and the maximum peak temperature of endotherm (softening point (° C.)/maximum endothermic peak temperature (° C.)) in the measuring method described in Examples described later. The crystalline resin has a crystallinity index of 0.6 or more and 1.4 or less.
The crystalline resin (A) has a crystallization index of 0.6 or more and 1.4 or less, and is excellent in low-temperature fixability and low-temperature fixability after high-temperature and high-humidity storage, and is also excellent in charging stability for electrostatic image development. From the viewpoint of obtaining a toner, it is preferably 0.8 or more, more preferably 0.9 or more, and preferably 1.3 or less, more preferably 1.2 or less.
The crystallinity index can be appropriately adjusted depending on the types and ratios of the raw material monomers, and the production conditions such as reaction temperature, reaction time, and cooling rate.
The crystalline polyester is obtained by polycondensing a polyhydric alcohol component (a-al) and a polyvalent carboxylic acid component (a-ac).

[Polyhydric alcohol component (a-al)]
The polyhydric alcohol component (a-al) is preferably an α,ω-aliphatic diol from the viewpoint of obtaining a toner having excellent low-temperature fixability and low-temperature fixability after high-temperature and high-humidity storage and also excellent charge stability. Contains 80 mol% or more.
The content of the α,ω-aliphatic diol is preferably 80 mol% or more, more preferably 85 mol% or more, still more preferably 90 mol% or more, still more preferably 95 mol% or more in the polyhydric alcohol component. And is 100 mol% or less, and even more preferably 100 mol%.

The carbon number of the α,ω-aliphatic diol is preferably 2 or more, and more preferably 4 or more from the viewpoint of obtaining a toner having excellent low-temperature fixability and low-temperature fixability after storage at high temperature and high humidity, and also excellent charge stability. The above is more preferably 6 or more, still more preferably 8 or more, and preferably 16 or less, more preferably 14 or less, still more preferably 12 or less.
Examples of the α,ω-aliphatic diol include ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,11-undecanediol, 1,12-dodecanediol, 1,13-tridecanediol, 1,14-tetradecanediol, etc. Are listed. Of these, ethylene glycol, 1,6-hexanediol, 1,9-nonanediol, 1,10-decanediol and 1,12-dodecanediol are preferable, 1,6-hexanediol, 1,10-decanediol and 1,12-dodecanediol are more preferable, and 1,10-decanediol is further preferable.

The polyhydric alcohol component (a-al) may contain a polyhydric alcohol component other than the α,ω-aliphatic diol. For example, aliphatic diols other than α,ω-aliphatic diols such as 1,2-propylene glycol and neopentyl glycol; aromatic diols such as alkylene oxide adducts of bisphenol A; glycerin, pentaerythritol, trimethylolpropane, etc. Examples include trihydric or higher alcohols. These polyhydric alcohol components may be used alone or in combination of two or more.

[Polyvalent carboxylic acid component (a-ac)]
The polycarboxylic acid component (a-ac) contains an aliphatic dicarboxylic acid in an amount of 80 mol% or more from the viewpoint of obtaining a toner having excellent low-temperature fixability and low-temperature fixability after high-temperature and high-humidity storage and also excellent charge stability. Those containing are preferable. The content of the aliphatic dicarboxylic acid in the polyvalent carboxylic acid component (a-ac) is preferably 80 mol% or more, more preferably 85 mol% or more, further preferably 90 mol% or more, even more preferably 95 mol%. % And 100 mol% or less, and further preferably 100 mol%.

The number of carbon atoms of the aliphatic dicarboxylic acid is preferably 2 or more, more preferably 4 or more, from the viewpoint of obtaining a toner having excellent low-temperature fixability and low-temperature fixability after high-temperature and high-humidity storage, and also excellent charge stability. It is more preferably 8 or more, still more preferably 10 or more, and preferably 14 or less, more preferably 12 or less.
Examples of the aliphatic dicarboxylic acid include fumaric acid, sebacic acid, dodecanedioic acid, tetradecanedioic acid and the like. Among these, sebacic acid, dodecanedioic acid and tetradecanedioic acid are preferable, and sebacic acid is more preferable.
The polyvalent carboxylic acid component includes not only a free acid but also an anhydride that decomposes to form an acid during the reaction, and an alkyl ester having 1 to 3 carbon atoms of each carboxylic acid.
These polyvalent carboxylic acid components can be used alone or in combination of two or more.

The equivalent ratio (COOH group/OH group) of the polyhydric carboxylic acid component to the polyhydric alcohol component is excellent in low-temperature fixability and low-temperature fixability after storage at high temperature and high humidity, and from the viewpoint of obtaining a toner having excellent charge stability as well. , Preferably 0.7 or more, more preferably 0.8 or more, even more preferably 0.9 or more, and preferably 1.3 or less, more preferably 1.2 or less, still more preferably 1.1 or less. Is.

[Physical properties of crystalline resin (A)]
The softening point of the crystalline resin (A) is preferably 60° C. or higher, more preferably 70° C. or higher, from the viewpoint of obtaining a toner having excellent low-temperature fixability and low-temperature fixability after high-temperature and high-humidity storage and also excellent charge stability. C. or higher, more preferably 80.degree. C. or higher, and preferably 150.degree. C. or lower, more preferably 120.degree. C. or lower, still more preferably 100.degree. C. or lower.

The melting point of the crystalline resin (A) is preferably 50° C. or higher, more preferably 60° C., from the viewpoint of obtaining a toner having excellent low-temperature fixability and low-temperature fixability after high-temperature and high-humidity storage and also excellent charge stability. As described above, the temperature is more preferably 70° C. or higher, and preferably 100° C. or lower, more preferably 90° C. or lower, further preferably 80° C. or lower.

The acid value of the crystalline resin (A) is preferably 5 mgKOH/g or more, and more preferably from the viewpoint of obtaining a toner having excellent low-temperature fixability and low-temperature fixability after high-temperature and high-humidity storage and also excellent charge stability. It is 10 mgKOH/g or more, and preferably 35 mgKOH/g or less, more preferably 25 mgKOH/g or less, even more preferably 20 mgKOH/g or less, even more preferably 15 mgKOH/g or less.

The hydroxyl value of the crystalline resin (A) is preferably 3 mgKOH/g or more, and more preferably from the viewpoint of obtaining a toner having excellent low-temperature fixability and low-temperature fixability after high-temperature and high-humidity storage and also excellent charge stability. It is 5 mgKOH/g or more, and preferably 35 mgKOH/g or less, more preferably 25 mgKOH/g or less, and further preferably 20 mgKOH/g or less.

The ratio of the acid value and the hydroxyl value of the crystalline resin (A) (acid value/hydroxyl value) is excellent in low-temperature fixability and low-temperature fixability after high-temperature and high-humidity storage, and also obtains a toner having excellent charge stability. From the viewpoint, it is preferably 1.00 or more, more preferably more than 1.00, still more preferably 1.05 or more, and preferably 5.00 or less, more preferably 3.00 or less, further preferably 2. It is 00 or less.

The softening point, melting point, acid value and hydroxyl value of the crystalline resin (A) can be appropriately adjusted by the kinds and ratios of the raw material monomers, and reaction conditions, reaction time, cooling rate, and other manufacturing conditions. Those values are obtained by the method described in Examples below. When two or more crystalline resins (A) are used in combination, the softening point, melting point, acid value and hydroxyl value obtained as a mixture thereof are preferably within the above ranges.

[Production of crystalline resin (A)]
When the crystalline resin (A) is a crystalline polyester, for example, the polyhydric alcohol component (a-al) and the polyhydric carboxylic acid component (a-ac) may be added in an inert gas atmosphere, if necessary. It can be produced by polycondensation using an esterification catalyst, an esterification co-catalyst and, if necessary, a radical polymerization inhibitor and the like.

Examples of esterification catalysts preferably used in the polycondensation reaction include tin compounds such as dibutyltin oxide and tin(II) di(2-ethylhexanoate), and titanium compounds such as titanium diisopropylate bistriethanolaminate. Can be mentioned. Among these, tin compounds are preferable, and di(2-ethylhexanoic acid)tin(II) is more preferable.
From the viewpoint of reactivity, the amount of the esterification catalyst used is preferably 0.01 parts by mass or more, more preferably 0.1 parts by mass, relative to 100 parts by mass of the total amount of the polyhydric alcohol component and the polycarboxylic acid component. It is at least 5 parts by mass, and preferably at most 5 parts by mass, more preferably at most 2 parts by mass.
As the esterification promoter, pyrogallol, gallic acid (the same as 3,4,5-trihydroxybenzoic acid), pyrogallol compounds such as gallic acid ester; 2,3,4-trihydroxybenzophenone, 2,2', Examples thereof include benzophenone derivatives such as 3,4-tetrahydroxybenzophenone; catechin derivatives such as epigallocatechin and epigallocatechin gallate, and gallic acid is preferable from the viewpoint of reactivity.

As the radical polymerization inhibitor in the polycondensation reaction, 4-tert-butylcatechol or the like can be used.
The temperature of the polycondensation reaction is preferably 120° C. or higher, more preferably 160° C. or higher, even more preferably 180° C. or higher, and preferably 250° C. or lower, more preferably 230° C. or lower, still more preferably 220° C. or lower. Is.

<Amorphous resin (B)>
The amorphous resin (B) of the present invention is a resin having a crystallinity index of more than 1.4 or less than 0.6. The amorphous resin (B) has a constituent component (b1) derived from a hydrocarbon wax (W1) and a polyester portion (b2).
The amorphous resin (B) of the present invention may be a polyester resin having a constituent component (b1) derived from a hydrocarbon wax (W1) and a polyester portion (b2), or a hydrocarbon wax. A composite resin having a constituent component (b1) derived from (W1), an amorphous polyester resin segment composed of a polyester portion (b2), and a vinyl-based resin segment containing a constituent unit derived from a vinyl monomer may be used.

[Constituent component (b1) derived from a hydrocarbon wax (W1) having a hydroxyl group or a carboxy group]
The amorphous resin (B) of the present invention is a hydrocarbon wax having a hydroxyl group or a carboxy group, from the viewpoint of obtaining a toner having excellent low-temperature fixability and low-temperature fixability after high-temperature and high-humidity storage and also excellent charge stability. It has a constituent component (b1) derived from (W1) (hereinafter, also simply referred to as “hydrocarbon wax (W1)”).
The hydrocarbon wax (W1) may have one or both of a hydroxyl group and a carboxy group, but the polyhydric alcohol component (b-al) or polycarboxylic acid of the raw material of the polyester portion (b2) From the viewpoint of reacting with the component (b-ac) during the polycondensation reaction to form a covalent bond with the polyester part (b2) through this, a hydrocarbon wax having both a hydroxyl group and a carboxy group is preferable.
The constituent component derived from the hydrocarbon wax (W1) having a hydroxyl group or a carboxy group contained in the amorphous resin (B) is a portion where the hydrocarbon wax is bonded to a part of the polyester segment via an ester. is there.

The hydrocarbon wax (W1) is obtained by modifying the hydrocarbon wax by a known method. Specific examples of the raw material hydrocarbon wax include paraffin wax, Fischer-Tropsch wax, microcrystalline wax, and polyethylene wax, and paraffin wax and Fischer-Tropsch wax are preferable. Commercially available paraffin wax and Fischer-Tropsch wax, which are reactive hydrocarbon waxes, are "HNP-11", "HNP-9", "HNP-10", "FT-0070", "HNP-51", "FNP". “-0090” (above, manufactured by Nippon Seiro Co., Ltd.) and the like.
Hydrocarbon wax having a hydroxyl group is obtained by modifying hydrocarbon wax such as paraffin wax or Fischer-Tropsch wax by oxidation treatment. Examples of the oxidation treatment method include the methods described in JP-A-62-79267 and JP-A-2010-197979. Specifically, there is a method of liquid-phase oxidizing a hydrocarbon wax with a gas containing oxygen in the presence of boric acid.

Examples of commercially available hydrocarbon waxes having a hydroxyl group include "Unilin 700", "Unilin 425" and "Unilin 550" (all manufactured by Baker Petrolite Co., Ltd.).
Examples of the hydrocarbon wax having a carboxy group include an acid-modified wax, which can be obtained by introducing a carboxy group into the above hydrocarbon wax such as paraffin wax and Fischer-Tropsch wax. Examples of the acid modification method include the methods described in JP 2006-328388 A, JP 2007-84787 A, and the like. Specifically, a carboxy group is introduced by adding an organic peroxide compound (reaction initiator) such as DCP (dicumyl peroxide) and a carboxylic acid compound to a melt of a hydrocarbon wax and reacting them. You can

Examples of commercially available hydrocarbon waxes having a carboxy group include Hiwax 1105A (maleic anhydride-modified ethylene-propylene copolymer, manufactured by Mitsui Chemicals, Inc.).
The hydrocarbon wax having a hydroxyl group and a carboxy group can be obtained, for example, by the same method as the oxidation treatment of the hydrocarbon wax having a hydroxyl group.
Examples of commercially available hydrocarbon waxes having a hydroxyl group and a carboxy group include "Parachol 6420", "Paracoll 6470", and "Paracol 6490" (all manufactured by Nippon Seiro Co., Ltd.).

The hydroxyl value of the hydrocarbon wax (W1) is preferably from the viewpoint of reactivity with polyester, excellent low-temperature fixability and low-temperature fixability after storage at high temperature and high humidity, and also from the viewpoint of obtaining a toner having excellent charge stability. 40 mgKOH/g or more, more preferably 50 mgKOH/g or more, even more preferably 70 mgKOH/g or more, even more preferably 90 mgKOH/g or more, and preferably 180 mgKOH/g or less, more preferably 150 mgKOH/g or less, further It is preferably 120 mgKOH/g or less, more preferably 100 mgKOH/g or less.
From the same viewpoint, the acid value of the hydrocarbon wax (W1) is preferably 1 mgKOH/g or more, more preferably 5 mgKOH/g or more, even more preferably 8 mgKOH/g or more, still more preferably 15 mgKOH/g or more, And it is preferably 30 mgKOH/g or less, more preferably 25 mgKOH/g or less, and further preferably 20 mgKOH/g or less.

From the same viewpoint, the total of the hydroxyl value and the acid value of the hydrocarbon wax (W1) is preferably 41 mgKOH/g or more, more preferably 55 mgKOH/g or more, still more preferably 80 mgKOH/g or more, still more preferably 90 mgKOH/g. g or more, more preferably 110 mgKOH/g or more, and preferably 210 mgKOH/g or less, more preferably 175 mgKOH/g or less, even more preferably 140 mgKOH/g or less, even more preferably 120 mgKOH/g or less.
The hydroxyl value and acid value of the hydrocarbon wax (W1) are determined by the method described in the examples.

The melting point of the hydrocarbon wax (W1) is preferably 50° C. or higher, more preferably 60° C., from the viewpoint of obtaining a toner having excellent low-temperature fixability and low-temperature fixability after storage at high temperature and high humidity, and also excellent charge stability. Or higher, more preferably 70° C. or higher, still more preferably 75° C. or higher, and from the viewpoint of improving the low temperature fixability of the toner, preferably 120° C. or lower, more preferably 110° C. or lower, still more preferably 100° C. Or less, more preferably 95° C. or less, still more preferably 80° C. or less.

The number average molecular weight of the hydrocarbon wax (W1) is preferably 500 or more, more preferably 600 or more from the viewpoint of obtaining a toner having excellent low-temperature fixability and low-temperature fixability after high-temperature and high-humidity storage and also excellent charge stability. Or more, more preferably 700 or more, and preferably 2000 or less, more preferably 1700 or less, further preferably 1500 or less, even more preferably 1200 or less, even more preferably 900 or less.

[Polyester part (b2)]
The polyester portion (b2) has a polyhydric alcohol component (b-al) and a polyhydric carboxylic acid from the viewpoint of obtaining a toner having excellent low-temperature fixability and low-temperature fixability after high-temperature and high-humidity storage and also excellent charge stability. It is obtained by polycondensing the component (b-ac).
(Polyhydric alcohol component (b-al))
The polyhydric alcohol component (b-al) contains 80 mol of an alkylene oxide adduct of bisphenol A from the viewpoint of obtaining a toner having excellent low-temperature fixability and low-temperature fixability after high-temperature and high-humidity storage, and also excellent charge stability. % Or more is preferable. From the same viewpoint, the content of the alkylene oxide adduct of bisphenol A in the polyhydric alcohol component (b-al) is preferably 80 mol% or more, more preferably 90 mol% or more, further preferably 95 mol% or more. , More preferably 98 mol% or more, and 100 mol% or less, even more preferably 100 mol%.

The alkylene oxide adduct of bisphenol A is preferably an ethylene oxide adduct of bisphenol A (polyoxyethylene-2,2-bis(4-hydroxyphenyl)propane) and a propylene oxide adduct of bisphenol A (polyoxypropylene-). 2,2-bis(4-hydroxyphenyl)propane), and more preferably a propylene oxide adduct of bisphenol A.

The average number of moles of alkylene oxide added to the alkylene oxide adduct of bisphenol A is preferably 1. from the viewpoint of obtaining a toner having excellent low-temperature fixability and low-temperature fixability after high-temperature and high-humidity storage and also excellent charge stability. 0 or more, more preferably 1.2 or more, further preferably 1.5 or more, and preferably 16 or less, more preferably 12 or less, further preferably 8 or less, even more preferably 4 or less, even more preferably Is 3 or less.

The polyhydric alcohol component (b-al) may contain a polyhydric alcohol other than the alkylene oxide adduct of bisphenol A. Examples of other polyhydric alcohol components that can be contained in the polyhydric alcohol component (b-al) include aliphatic diols, aromatic diols, alicyclic diols, polyhydric alcohols having 3 or more valences, or those having 2 to 4 carbon atoms. The following alkylene oxide (average addition mole number 1 or more and 16 or less) adduct and the like can be mentioned. Specific examples thereof include ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol and 2,3-butanediol. , Neopentyl glycol, 1,4-butenediol, 1,5-pentanediol, 1,6-hexanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,12 An aliphatic diol such as dodecanediol; an aromatic diol such as bisphenol A (2,2-bis(4-hydroxyphenyl)propane); a hydrogenated bisphenol A (2,2-bis(4-hydroxycyclohexyl)propane) Alicyclic diols thereof, or alkylene oxide adducts thereof having 2 to 4 carbon atoms (average added mole number of 2 to 12); trihydric or higher polyhydric alcohols such as glycerin, pentaerythritol, trimethylolpropane and sorbitol. Or, those alkylene oxides having 2 or more and 4 or less carbon atoms (average added mole number of 1 or more and 16 or less) and the like can be mentioned.
These polyhydric alcohol components may be used alone or in combination of two or more.

(Polyvalent carboxylic acid component (b-ac))
Examples of the polyvalent carboxylic acid component (b-ac) include dicarboxylic acids, trivalent or higher polyvalent carboxylic acids, or their anhydrides and their alkyl esters having 1 to 3 carbon atoms. Among these, a dicarboxylic acid is preferable, and it is more preferable to use a dicarboxylic acid and a polyvalent carboxylic acid having a valence of 3 or more in combination.

Examples of the dicarboxylic acid include aromatic dicarboxylic acid, aliphatic dicarboxylic acid, and alicyclic dicarboxylic acid. Among these, at least one selected from aromatic dicarboxylic acids and aliphatic dicarboxylic acids is preferable.
The polyvalent carboxylic acid component includes not only a free acid but also an anhydride that decomposes to form an acid during the reaction, and an alkyl ester having 1 to 3 carbon atoms of each carboxylic acid.
Examples of the aromatic dicarboxylic acid include phthalic acid, isophthalic acid, terephthalic acid and the like. Among these, isophthalic acid and terephthalic acid are preferable, and terephthalic acid is more preferable, from the viewpoint of obtaining a toner having excellent low-temperature fixability and low-temperature fixability after high-temperature and high-humidity storage and also excellent charge stability.
The aliphatic dicarboxylic acid has a carbon number of preferably 2 or more, more preferably 3 or more, from the viewpoint of obtaining a toner having excellent low-temperature fixability and low-temperature fixability after high-temperature and high-humidity storage and also excellent charge stability. And is preferably 30 or less, more preferably 20 or less.
Examples of the aliphatic dicarboxylic acid having 2 to 30 carbon atoms include oxalic acid, malonic acid, maleic acid, fumaric acid, citraconic acid, itaconic acid, glutaconic acid, succinic acid, adipic acid, sebacic acid, dodecanedioic acid, Examples thereof include azelaic acid and succinic acid substituted with an alkyl group having 1 to 20 carbon atoms or an alkenyl group having 2 to 20 carbon atoms, which are excellent in low-temperature fixability and low-temperature fixability after storage at high temperature and high humidity. From the viewpoint of obtaining a toner having excellent charging stability, fumaric acid and adipic acid are preferable. Specific examples of succinic acid substituted with an alkyl group having 1 to 20 carbon atoms or an alkenyl group having 2 to 20 carbon atoms include dodecyl succinic acid, dodecenyl succinic acid, octenyl succinic acid and the like.
Among these, terephthalic acid, fumaric acid, and adipic acid are preferable, and they are used in combination from the viewpoint of obtaining a toner that is excellent in low-temperature fixability and low-temperature fixability after high-temperature and high-humidity storage and is also excellent in charging stability. Is more preferable.

As the trivalent or higher polyvalent carboxylic acid, a trivalent carboxylic acid is preferable from the viewpoint of obtaining a toner having excellent low-temperature fixability and low-temperature fixability after high-temperature and high-humidity storage and also excellent charge stability, and trimellitic acid. And its acid anhydride are more preferable, and trimellitic acid anhydride is still more preferable.
In addition, the content of the polyvalent carboxylic acid having a valence of 3 or more is determined from the viewpoint of obtaining a toner having excellent low-temperature fixability and low-temperature fixability after high-temperature and high-humidity storage, and also having excellent charging stability. It is preferably 3 mol% or more, more preferably 5 mol% or more, and preferably 20 mol% or less, more preferably 15 mol% or less, still more preferably 12 mol% or less in the acid component.
These polyvalent carboxylic acid components can be used alone or in combination of two or more.

The equivalent ratio (COOH group/OH group) of the polyhydric carboxylic acid component to the polyhydric alcohol component is excellent in low-temperature fixability and low-temperature fixability after storage at high temperature and high humidity, and from the viewpoint of obtaining a toner having excellent charge stability as well. , Preferably 0.7 or more, more preferably 0.8 or more, and preferably 1.3 or less, more preferably 1.2 or less.

[Production of Amorphous Resin (B)]
A polyester resin which is an amorphous resin (B) having a constituent component (b1) derived from a hydrocarbon wax (W1) and a polyester portion (b2) is, for example, a hydrocarbon wax (W1) having a hydroxyl group or a carboxy group. Can be obtained as a polycondensate by a polycondensation reaction between a polyhydric alcohol component and a polycarboxylic acid component.
That is, the method for producing the polyester resin which is the amorphous resin (B) is preferably, for example, the method (i) below.
(I) A method of carrying out a polycondensation reaction with a polyhydric alcohol component and a polyvalent carboxylic acid component in the presence of a hydrocarbon wax (W1) having a hydroxyl group or a carboxy group.
From the viewpoint of reactivity, a catalyst such as an esterification catalyst or an esterification promoter may be used, and further a radical polymerization inhibitor may be used.
It is preferable that a part of the polycarboxylic acid component is used together with the polyhydric alcohol component for polycondensation reaction for a certain period of time, and then the rest is added to the reaction system because the polycondensation reaction can be further advanced. In the method (i), a polyester resin which is an amorphous resin (B) is produced as a polycondensate.

The temperature of the polycondensation reaction is preferably 160° C. or higher, more preferably 180° C. or higher, still more preferably 200° C. or higher, and preferably 260° C. or lower, from the viewpoint of the productivity of the amorphous resin (B). , More preferably 250° C. or lower, still more preferably 245° C. or lower.

Further, it is preferable to accelerate the reaction by reducing the pressure of the reaction system in the latter half of the polymerization.
Examples of esterification catalysts preferably used in the polycondensation reaction include tin compounds such as dibutyltin oxide and tin(II) di(2-ethylhexanoate), and titanium compounds such as titanium diisopropylate bistriethanolaminate. Can be mentioned. Among these, tin compounds are preferable, and di(2-ethylhexanoic acid)tin(II) is more preferable.
From the viewpoint of reactivity, the amount of the esterification catalyst used is preferably 0.01 parts by mass or more, more preferably 0.1 parts by mass, relative to 100 parts by mass of the total amount of the polyhydric alcohol component and the polycarboxylic acid component. It is at least 5 parts by mass, and preferably at most 5 parts by mass, more preferably at most 2 parts by mass.
As the esterification promoter, pyrogallol, gallic acid (the same as 3,4,5-trihydroxybenzoic acid), pyrogallol compounds such as gallic acid ester; 2,3,4-trihydroxybenzophenone, 2,2', Examples thereof include benzophenone derivatives such as 3,4-tetrahydroxybenzophenone; catechin derivatives such as epigallocatechin and epigallocatechin gallate, and gallic acid is preferable from the viewpoint of reactivity.
From the viewpoint of reactivity, the amount of the esterification co-catalyst used is preferably 0.001 part by mass or more, and more preferably 0.01 part by mass based on 100 parts by mass of the total amount of the polyhydric alcohol component and the polycarboxylic acid component. The amount is not less than 0.5 part by mass, and preferably not more than 0.5 part by mass, more preferably not more than 0.2 part by mass.
4-tert-butylcatechol etc. can be used as a radical polymerization inhibitor.
The amount of the radical polymerization inhibitor used is preferably 0.001 parts by mass or more, more preferably 0.005 parts by mass or more based on 100 parts by mass of the total amount of the polyhydric alcohol component and the polycarboxylic acid component. And it is preferably 0.5 parts by mass or less, more preferably 0.2 parts by mass or less, and further preferably 0.1 parts by mass or less.

The amount of the polyester part (b2) in the amorphous resin (B) is preferably 80 from the viewpoint of obtaining a toner having excellent low-temperature fixability and low-temperature fixability after high-temperature and high-humidity storage and also excellent charge stability. The content is at least mass%, more preferably at least 85 mass%, even more preferably at least 88 mass%, and preferably at most 99 mass%, more preferably at most 97 mass%.

The amount of the component (b1) derived from the hydrocarbon wax (W1) having a hydroxyl group or a carboxy group in the amorphous resin (B) is excellent in low-temperature fixability and low-temperature fixability after high-temperature and high-humidity storage, From the viewpoint of obtaining a toner having excellent stability, the content is preferably 1% by mass or more, more preferably 3% by mass or more, and preferably 20% by mass or less, more preferably 15% in the amorphous resin (B). It is not more than 12% by mass, more preferably not more than 12% by mass.

The constitutional unit derived from the hydrocarbon wax (W1) having a hydroxyl group or a carboxy group contained in the amorphous resin (B) is a site in which the hydrocarbon wax is ester-bonded with the polyester portion (b2). Further, the content can be calculated based on the blending amount of the raw materials, assuming that 100% of the hydroxyl groups and carboxy groups derived from each raw material have reacted. At this time, the content of the polyester part (b2) is calculated as a theoretical yield excluding the amount of water generated during the production of the amorphous resin (B).

[Physical Properties of Amorphous Resin (B)]
The softening point of the amorphous resin (B) is preferably 70° C. or higher, more preferably 70° C. or higher, from the viewpoint of obtaining a toner having excellent low-temperature fixability and low-temperature fixability after high-temperature and high-humidity storage and also excellent charge stability. The temperature is 90°C or higher, more preferably 100°C or higher, and preferably 140°C or lower, more preferably 130°C or lower.

From the same viewpoint, the glass transition temperature of the amorphous resin (B) is preferably 30° C. or higher, more preferably 35° C. or higher, further preferably 40° C. or higher, and preferably 70° C. or lower, more preferably Is 60° C. or lower.

The acid value of the amorphous resin (B) is preferably 5 mgKOH/g or more, from the viewpoint of improving the dispersion stability of the resin particles (D) described later and from the viewpoint of improving the low temperature fixability and charging characteristics of the toner. It is preferably 10 mgKOH/g or more, more preferably 15 mgKOH/g or more, and preferably 40 mgKOH/g or less, more preferably 35 mgKOH/g or less, further preferably 30 mgKOH/g or less.

The hydroxyl value of the amorphous resin (B) is preferably 4 mgKOH/g or more, from the viewpoint of improving the dispersion stability of the resin particles (D) described later and from the viewpoint of improving the low-temperature fixability and charging characteristics of the toner. It is preferably 7 mgKOH/g or more, more preferably 10 mgKOH/g or more, and preferably 40 mgKOH/g or less, more preferably 30 mgKOH/g or less, further preferably 20 mgKOH/g or less.

The softening point, glass transition temperature, acid value and hydroxyl value of the amorphous resin (B) can be appropriately adjusted depending on the kinds and ratios of the raw material monomers, and the production conditions such as reaction temperature, reaction time and cooling rate. Also, those values are obtained by the method described in the examples.
When two or more kinds of the amorphous resins (B) are used in combination, the softening point, glass transition temperature and acid value obtained as a mixture thereof are preferably within the above ranges.

<Resin composition (C)>
The resin composition (C) is a crystalline resin (A) and an amorphous resin (B) having a constituent component (b1) derived from a hydrocarbon wax (W1) having a hydroxyl group or a carboxy group and a polyester portion (b2). And a reaction product obtained by the reaction of chemically bonding at least a part of them. Here, the term "chemically bond" means that the crystalline resin (A) and the amorphous resin (B) are linked by a covalent bond. Examples of the bond include an ester group, an ether group, an amide group, a urethane group, and an organic group containing these groups.
"Chemically bonding at least a part" means bonding at least a part of a plurality of crystalline resins (A) and a plurality of amorphous resins (B). That is, the resin composition (C) contains at least a component (block resin (AB)) in which the crystalline resin (A) and the amorphous resin (B) are chemically bonded to each other, and May also include unreacted crystalline resin (A) and amorphous resin (B).
At least a part of the crystalline resin (A) and the amorphous resin (B) having the constituent component (b1) derived from the hydrocarbon wax (W1) and the polyester portion (b2) are chemically bonded. The resin composition (C) containing the reaction product obtained by the reaction is considered to include the block resin (AB), the crystalline resin (A) and the amorphous resin (B) as described above. The actually obtained composition contains various resin structures, and it is the reality that the structure and properties cannot be simply specified and defined. Further, if the structure is to be specified by a known analysis method, extremely complicated analysis such as isolation and purification and establishment of a polymer structure defining method is required. That is, there are circumstances in which the resin composition (C) is almost impractical to directly specify by its structure or characteristics.

<Step (1)>
The resin composition (C) is obtained, for example, by the following step (1).
Step (1): a crystalline resin (A) and an amorphous resin (B) having a constituent component (b1) derived from a hydrocarbon wax (W1) having a hydroxyl group or a carboxy group and a polyester portion (b2), Step of obtaining a resin composition (C) containing a reaction product obtained by a reaction of chemically bonding at least a part

From the viewpoint of obtaining a toner having excellent low-temperature fixability and low-temperature fixability after high-temperature and high-humidity storage, and also excellent charge stability, the step (1) is preferably a crystalline resin (A) and a hydroxyl group or a carboxy group. A hydrocarbon wax (W1)-derived constituent component (b1) and an amorphous resin (B) having a polyester portion (b2), the crystalline resin (A) end and the amorphous resin (B). It is a step of obtaining a resin composition (C) containing a reaction product obtained by a reaction of chemically bonding at least a part of the terminal. The term “amorphous resin (B) end” means the end of the constituent component (b1) derived from the hydrocarbon wax (W1) having a hydroxyl group or a carboxy group or the end of the polyester portion (b2). From the viewpoint of obtaining a toner having excellent low-temperature fixability and low-temperature fixability after high-temperature and high-humidity storage, and also excellent charging stability, the ends of the crystalline resin (A) and the polyester portion (b2) of the amorphous resin (B). It is preferable to obtain a resin composition (C) containing a reaction product obtained by the reaction of chemically bonding the end of (1).
The mass ratio of the crystalline resin (A) and the amorphous resin (B) used in the step (1) is excellent in low-temperature fixability and low-temperature fixability after high-temperature and high-humidity storage, and further has good charging stability. Also from the viewpoint of obtaining an excellent toner, it is preferably 20/80 or more, more preferably 25/75 or more, further preferably 35/65 or more, and preferably 80/20 or less, more preferably 70/30 or less, It is more preferably 60/40 or less.
In the step (1), the crystalline resin (A) terminal and the polyester segment terminal can be condensed and chemically bonded, but it is preferable to use the polyfunctional compound (S) because of easy reaction. preferable.

[Polyfunctional compound (S)]
In the step (1), it is preferable to chemically bond the crystalline resin (A) and the amorphous resin (B) by using the polyfunctional compound (S) from the viewpoint of easy reaction.
The polyfunctional compound (S) is a compound having two or more reactive functional groups. The number of functional groups in the polyfunctional compound (S) is preferably 5 or less, more preferably 4 or less, even more preferably 3 or less, even more preferably 2 or less, and preferably 2.
In the present invention, the functional group means a functional group which reacts with at least one selected from the group consisting of a hydroxyl group and a carboxy group to form a covalent bond.
Examples of the functional group include an isocyanate group, an oxazoline group, a glycidyl group, an amino group, and an aziridine group, and an isocyanate group is preferable.
As the polyfunctional compound (S), a polyisocyanate compound is preferable from the viewpoint of obtaining a toner excellent in easiness of reaction, low-temperature fixability and low-temperature fixability after storage at high temperature and high humidity, and further excellent in charging stability.

As the polyisocyanate compound, a diisocyanate compound is preferable from the viewpoint of reactivity and easiness of handling, for example, aliphatic diisocyanate, aromatic diisocyanate, and prepolymer type, isocyanurate type, urea type, carbodiimide type modification of these diisocyanates. The body.
Examples of the aliphatic diisocyanate include alicyclic diisocyanate and chain aliphatic diisocyanate.
Examples of the alicyclic diisocyanate include isophorone diisocyanate, 4,4′-dicyclohexylmethane diisocyanate, 4-methyl-1,3-cyclohexylene diisocyanate, and 1,2-bis(isocyanatomethyl)cyclohexane.
Examples of the chain aliphatic diisocyanate include hexamethylene diisocyanate.
As the aromatic diisocyanate, for example, 4,4′-diphenylmethane diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, m-phenylene diisocyanate, p-phenylene diisocyanate, 1,3-xylylene diisocyanate, 1,4-xylylene diisocyanate, 1,5-naphthalene diisocyanate, and 3,3'-dimethyl-4,4'-biphenylene diisocyanate are mentioned.
Among these diisocyanate compounds, aliphatic diisocyanates are preferable, alicyclic diisocyanates are more preferable, at least one selected from isophorone diisocyanate and 4,4′-dicyclohexylmethane diisocyanate is further preferable, and isophorone diisocyanate is further preferable.

The step (1) is preferably performed in an organic solvent. The organic solvent is preferably 15 when represented by a solubility parameter (SP value: POLYMER HANDBOOK THIRD EDITION 1989 by John Wiley & Sons, Inc) from the viewpoint of dissolving the resin and facilitating phase inversion into an aqueous medium. .0MPa ^1/2 or more, more preferably 16.0MPa ^1/2, and even more preferably at 17.0MPa ^1/2 or more, and, preferably 26.0MPa ^1/2 or less, more preferably 24.0MPa ^{1 /2} or less, more preferably 22.0 MPa ^1/2 or less.
Specific examples thereof include alcohol solvents such as ethanol (26.0), isopropanol (23.5) and isobutanol (21.5); acetone (20.3), methyl ethyl ketone (19.0), methyl isobutyl ketone ( 17.2), a ketone solvent such as diethyl ketone (18.0); an ether solvent such as dibutyl ether (16.5), tetrahydrofuran (18.6), dioxane (20.5); ethyl acetate (18. 6) and acetic acid ester solvents such as isopropyl acetate (17.4). The numerical value in parentheses after each solvent is the SP value (unit: MPa ^1/2 ) of each. Among these, from the viewpoint of easy removal from the mixed solution after addition of the aqueous medium, preferably one or more selected from ketone solvents and acetic acid ester solvents, more preferably methyl ethyl ketone, ethyl acetate and isopropyl acetate. One or more selected, and more preferably methyl ethyl ketone is used.

The resin composition (C) is preferably obtained by the following steps (1-1) and (1-2).
Step (1-1): Introduce a functional group with a polyfunctional compound (S) into one resin (i) selected from the group X consisting of the crystalline resin (A) and the amorphous resin (B). Step (1-2): reacting the reaction intermediate with a resin (ii) selected from the group X and different from the resin (i)

The resin (i) is one selected from the group X consisting of the crystalline resin (A) and the amorphous resin (B). That is, either the crystalline resin (A) or the amorphous resin (B) is used and a functional group is introduced into the resin.
From the standpoint of easiness of reaction, and from the viewpoint of obtaining a toner having excellent low-temperature fixability and low-temperature fixability after storage at high temperature and high humidity, and also having excellent charge stability, crystalline resin (A), resin It is preferable to select the amorphous resin (B) as (ii).

<<Process (1-1)>>
Step (1-1) is to introduce a functional group with a polyfunctional compound (S) into one resin (i) selected from the group X consisting of the crystalline resin (A) and the amorphous resin (B). Is a step of obtaining a reaction intermediate.
From the viewpoint of easiness of reaction, and also from the viewpoint of obtaining a toner having excellent low-temperature fixability and low-temperature fixability after storage at high temperature and high humidity, and also having excellent charge stability, an isocyanate group is added to the hydroxyl group at the terminal of the crystalline resin (A). It is preferable to select the introduction method, that is, to select the crystalline resin (A) as the resin (i) and the amorphous resin (B) as the resin (ii).
As the polyfunctional compound (S), a diisocyanate compound is preferable from the viewpoint of easy reaction, low-temperature fixability and low-temperature fixability after high-temperature and high-humidity storage, and also a toner having excellent charge stability.
The method of producing the reaction intermediate is not particularly limited, and examples thereof include a method of reacting the resin (i) with a diisocyanate compound in the presence of a urethanization catalyst in an organic solvent. Next, a method of reacting the resin (i) with a diisocyanate compound will be described.

The molar ratio (OH/NCO) of the hydroxyl group of the resin (i) and the isocyanate group of the diisocyanate compound is preferably 1.0 or less, more preferably less than 1.0 from the viewpoint of leaving the isocyanate group in the resin (i). And is preferably 0.1 or more, more preferably 0.25 or more, still more preferably 0.3 or more.
The equivalent ratio of the diisocyanate compound used in the reaction with the hydroxyl group of the resin (i) is preferably 0.70 or more, more preferably 0.80 or more, still more preferably 0.90 or more, still more preferably 1.00. It is above, and preferably 1.20 or less, more preferably 1.10 or less, still more preferably 1.05 or less.
Equivalent ratio of diisocyanate compound={mass of diisocyanate compound (g)/molecular weight of diisocyanate compound}/[{hydroxyl value of resin (i) (mgKOH/g) x blending amount of resin (i)}/ (56×1000)]

As the urethanization catalyst, a tin compound such as dibutyltin oxide or tin(II) di(2-ethylhexanoate), or a titanium compound such as titanium diisopropylate bistriethanolaminate can be used.
The amount of the urethanization catalyst used is not limited, but is preferably 0.01 part by mass or more, more preferably 0.1 part by mass or more, based on 100 parts by mass of the resin (i) and the diisocyanate compound. And it is preferably 1.5 parts by mass or less, more preferably 1.0 parts by mass or less.

The reaction between the resin (i) and the diisocyanate compound is preferably carried out in the above organic solvent. As the organic solvent, various known organic solvents having no functional group capable of reacting with an isocyanate group such as acetone, methyl ethyl ketone, and tetrahydrofuran can be used.

From the viewpoint of reactivity, the amount of the organic solvent used when using an organic solvent is preferably 30 parts by mass or more, and more preferably 50 parts by mass, based on 100 parts by mass of the resin (i) and the diisocyanate compound. As described above, the amount is more preferably 70 parts by mass or more, and preferably 500 parts by mass or less, more preferably 300 parts by mass or less, and further preferably 200 parts by mass or less.

The reaction temperature is preferably 20° C. or higher and 100° C. or lower.
The reaction time is preferably 0.2 hours or longer, more preferably 0.5 hours or longer, still more preferably 1 hour or longer, and preferably 6 hours or shorter, more preferably 5 hours or shorter, still more preferably 4 hours. It is as follows.
<<Process (1-2)>>
In the step (1-2), the reaction intermediate obtained in the step (1-1) is reacted with the hydroxyl group of the resin (ii) different from the resin (i) selected from the group X′. It is a process.
The reaction can be performed, for example, by adding the resin (ii) to the reaction system after the step (1-1) and heating and mixing the reaction intermediate and the resin (ii) in an organic solvent. When the reaction intermediate is obtained by reacting the resin (i) with the diisocyanate compound in step (1-1), it can be produced by subsequently reacting with a urethanization catalyst, if necessary. .. As the urethanization catalyst, the same one as in step (1-1) can be used.
The same organic solvent as that used in step (1-1) can be used. The reaction temperature is preferably 20° C. or higher and 100° C. or lower.
The reaction time of step (1-2) is preferably 0.2 hours or longer, more preferably 0.5 hours or longer, still more preferably 1 hour or longer, and preferably 6 hours or shorter, more preferably 5 hours. It is preferably 4 hours or less, more preferably 4 hours or less.
By going through the steps (1-1) and (1-2), at least a part of the end of the crystalline resin (A) and the end of the amorphous resin (B) are chemically bonded. When a diisocyanate compound is selected as the polyfunctional compound (S), it is linked by a group containing a urethane bond.

The equivalence ratio of the hydroxyl groups of the crystalline resin (A) and the amorphous resin (B) used in the step (1) is excellent in low-temperature fixability and low-temperature fixability after high-temperature and high-humidity storage, and further stable in charging. From the viewpoint of obtaining a toner having excellent properties, the toner content is preferably 0.20 or more, more preferably 0.30 or more, and preferably 1.80 or less, more preferably 1.50 or less, and further preferably 1.30. Or less, more preferably 1.00 or less.
The equivalent ratio of hydroxyl groups is calculated by the following formula.
Equivalent ratio of hydroxyl group = [hydroxyl value of crystalline resin (A) (mgKOH/g) x compounding amount of crystalline resin (A) (g)] / hydroxyl value of amorphous resin (B) (mgKOH/g) )×Amount of amorphous resin (B) (g)]
From the viewpoint of obtaining a toner having excellent low-temperature fixability and low-temperature fixability after high-temperature and high-humidity storage and also excellent charging stability, a crystalline polyester (A) is used as the crystalline resin, and a diisocyanate compound is used as the polyfunctional compound (S). It is preferable to use. That is, it is preferable to have the following steps (1-1′) and (1-2′).
Step (1-1′): Step of Obtaining Reaction Intermediate by Introducing Isocyanate Group with Diisocyanate Compound at Terminal of Crystalline Polyester Step (1-2′): Said Reaction Intermediate and Amorphous Resin (B ) With the end of

The resin composition (C) obtained by the above step (1) includes a block resin (AB) in which a crystalline resin (A) and an amorphous resin (B) are chemically bonded, and a crystalline resin (A). , And an amorphous resin (B) may be included.

[Method for producing toner for developing electrostatic image]
The method for producing the toner for developing an electrostatic image of the present invention comprises a crystalline resin (A), a constituent component (b1) derived from a hydrocarbon wax (W1) having a hydroxyl group or a carboxy group, and a polyester portion (b2). The method includes a step of obtaining a resin composition (C) containing a reaction product obtained by chemically bonding at least a part of the amorphous resin (B), and then the following (1) or (2) including.
(1) A method of producing a toner by obtaining toner mother particles by aggregating and fusing resin particles in a mixture containing a dispersion liquid in which the resin composition (C) is dispersed in an aqueous medium (hereinafter, "Emulsion aggregation method"),
(2) A method of melt-kneading a mixture containing the resin composition (C) and pulverizing the obtained melt-kneaded product to produce a toner (hereinafter, also referred to as “melt-kneading method”),
Etc.
The emulsion aggregation method (1) is preferable from the viewpoint of obtaining a toner having excellent low-temperature fixability and low-temperature fixability after high-temperature and high-humidity storage and also excellent charge stability. Further, the toner may be obtained by the melt kneading method (2).

(1) Emulsion aggregation method The method for producing a toner for electrostatic charge development of the present invention preferably includes the following steps (1) to (4).
Step (1): a crystalline resin (A) and an amorphous resin (B) having a constituent component (b1) derived from a hydrocarbon wax (W1) having a hydroxyl group or a carboxy group and a polyester portion (b2), Step of Obtaining Resin Composition (C) Containing Reaction Product Obtained by Reaction of Chemically Bonding At Least Part Step (2): Resin composition (C) obtained in step (1) in an aqueous medium To obtain a dispersion liquid of the resin particles (D) Step (3): A step of aggregating the resin particles (D) obtained in the Step (2) in an aqueous medium to obtain agglomerated particles Step (4 ): A step of fusing the aggregated particles obtained in the step (3)

The step (1) is as described in the step (1-1) and the step (1-2), or the step (1-1') and the step (1-2') described above.

<Step (2)>
The step (2) is a step of dispersing the resin composition (C) obtained in the step (1) in an aqueous medium to obtain a dispersion liquid of the resin particles (D). As a method for obtaining a resin particle (D) dispersion, a resin composition (C) is added to an aqueous medium and a dispersion treatment is carried out by a disperser, or an aqueous medium is gradually added to the resin composition (C). A method of phase inversion emulsification is preferable from the viewpoint of obtaining a toner having excellent low-temperature fixability and low-temperature fixability after storage at high temperature and high humidity, and also excellent charge stability.
<<Aqueous medium>>
As the aqueous medium, those containing water as a main component are preferable, and the content of water in the aqueous medium is preferably from the viewpoint of improving the dispersion stability of the dispersion liquid of the resin particles (D) and the viewpoint of environmental friendliness. Is 80% by mass or more, more preferably 90% by mass or more, further preferably 95% by mass or more, even more preferably 98% by mass or more, and 100% by mass or less, and even more preferably 100% by mass. .. The water is preferably deionized water or distilled water.
As components other than water that can form an aqueous medium together with water, alkyl alcohols having 1 to 5 carbon atoms; dialkyl ketones having 3 to 5 carbon atoms such as acetone and methyl ethyl ketone; cyclic ethers such as tetrahydrofuran and the like dissolved in water An organic solvent is used. Among these, from the viewpoint of preventing the organic solvent from mixing into the toner, an alkyl alcohol having 1 to 5 carbon atoms that does not dissolve the polyester is preferable, and methanol, ethanol, isopropanol, and butanol are more preferable.

[Phase inversion emulsification]
As the phase inversion emulsification method, after preparing an organic solvent solution of the resin composition (C), an aqueous medium is added to the obtained solution to perform phase inversion emulsification, and to the molten resin composition (C). A method of adding an aqueous medium to carry out phase inversion emulsification can be mentioned. The former method is preferred from the viewpoint of obtaining a homogeneous dispersion of resin particles (D).
During the phase inversion emulsification, other resin components such as the crystalline resin (A) and the amorphous resin (B) may be further added to the organic solvent solution of the resin composition (C).
The preferred embodiment of the organic solvent that can be used is the same as the organic solvent that can be used in the production of the resin composition (C) in step (1). You may produce a resin composition (C) in an organic solvent in a process (1), and you may provide it to a process (2) as an organic solvent solution.
The mass ratio of the organic solvent and the resin constituting the resin particles (D) (organic solvent/resin constituting the resin particles (D)) is a viewpoint of dissolving the resin and facilitating the phase inversion into the aqueous medium, and the resin. From the viewpoint of improving the dispersion stability of the particles (D), it is preferably 0.1 or more, more preferably 0.2 or more, still more preferably 0.4 or more, and preferably 4 or less, more preferably 2 or more. It is as follows.
It is preferable to add a neutralizing agent to the solution of the resin composition (C).
Examples of the neutralizing agent include basic substances. Examples of the basic substance include hydroxides of alkali metals such as lithium hydroxide, sodium hydroxide and potassium hydroxide; nitrogen-containing substances such as ammonia, trimethylamine, ethylamine, diethylamine, triethylamine, diethanolamine, triethanolamine and tributylamine. Basic substances are mentioned. Among these, from the viewpoint of improving the dispersion stability and the cohesiveness of the resin particles (D), an alkali metal hydroxide is preferable, and sodium hydroxide is more preferable.

The equivalent amount (mol %) of the neutralizing agent to the acid group of the resin is preferably 10 mol% or more, more preferably 30 mol% or more, and preferably 150 mol% or less, more preferably 120 mol% or less. , And more preferably 100 mol% or less.
The equivalent amount (mol %) of the neutralizing agent can be calculated by the following formula. The use amount of the neutralizing agent is synonymous with the degree of neutralization when it is 100 mol% or less, and when the use amount of the neutralizing agent is more than 100 mol% in the following formula, the neutralizing agent is an acid group of the resin. Is excessive, and the degree of neutralization of the resin at this time is considered to be 100 mol %.
Equivalent amount of the neutralizing agent (mol %)=[{added mass of neutralizing agent (g)/equivalent amount of neutralizing agent}/[{weighted average acid value of resin constituting resin particles (D) (mgKOH/g) )×mass of resin constituting resin particles (D) (g)}/(56×1000)]]×100

From the viewpoint of improving the dispersion stability of the resin particles (D) and the viewpoint of obtaining uniform aggregated particles in the subsequent step (3), the amount of the aqueous medium to be added is 100 mass% of the resin constituting the resin particles (D). The amount is preferably 100 parts by mass or more, more preferably 150 parts by mass or more, further preferably 200 parts by mass or more, and preferably 900 parts by mass or less, more preferably 600 parts by mass or less.

From the viewpoint of improving the dispersion stability of the resin particles (D), the mass ratio of the aqueous medium and the organic solvent (aqueous medium/organic solvent) is preferably 20/80 or more, more preferably 50/50 or more. , More preferably 60/40 or more, and preferably 97/3 or less, more preferably 93/7 or less, further preferably 90/10 or less.

From the viewpoint of improving the dispersion stability of the resin particles (D), the temperature at which the aqueous medium is added is preferably equal to or higher than the glass transition temperature of the amorphous resin (B) constituting the resin particles (D). The temperature is preferably 50° C. or higher, more preferably 60° C. or higher, even more preferably 70° C. or higher, and preferably 85° C. or lower, more preferably 80° C. or lower, further preferably 75° C. or lower.

From the viewpoint of obtaining resin particles having a small particle diameter, the rate of addition of the aqueous medium is preferably 0.1 parts by mass or more per 100 parts by mass of the resin constituting the resin particles until the phase inversion is completed, More preferably 0.5 part by mass/min or more, still more preferably 1 part by mass/min or more, still more preferably 3 parts by mass/min or more, and preferably 50 parts by mass/min or less, more preferably 30 parts by mass or less. It is not more than 20 parts by mass, preferably not more than 20 parts by mass. There is no limitation on the addition rate of the aqueous medium after the phase inversion.

After the phase inversion emulsification, a step of removing an organic solvent from the obtained dispersion liquid may be included, if necessary. As a method of removing the organic solvent, it is preferable to distill since it dissolves in water. In this case, it is preferable to elevate the temperature to a temperature equal to or higher than the boiling point of the organic solvent used while stirring and distill off. Further, from the viewpoint of maintaining the dispersion stability of the resin particles (D), it is more preferable to distill under reduced pressure, and it is preferable to distill at a constant temperature and pressure. It should be noted that the temperature may be reduced and then raised, or the temperature may be raised and then reduced.
Further, the organic solvent may not be completely removed and may remain in the aqueous dispersion. In this case, the residual amount of the organic solvent in the aqueous dispersion is preferably 1% by mass or less, more preferably 0.5% by mass or less, and further preferably substantially 0%.

The solid content concentration of the obtained dispersion liquid of the resin particles (D) is preferably 5% by mass from the viewpoint of improving the productivity of the toner and the dispersion stability of the dispersion liquid of the resin particles (D). Or more, more preferably 10% by mass or more, further preferably 15% by mass or more, and preferably 50% by mass or less, more preferably 40% by mass or less, further preferably 30% by mass or less, still more preferably 25% by mass or less. It is not more than mass %. The solid content is the total amount of non-volatile components such as resin, colorant and surfactant.

The volume median particle diameter (D ₅₀ ) of the resin particles (D) in the dispersion liquid is preferably 0.05 μm or more, more preferably 0.08 μm or more, from the viewpoint of obtaining a toner capable of obtaining a high-quality image. , And preferably 0.80 μm or less, more preferably 0.40 μm or less, still more preferably 0.20 μm or less.
Here, the volume median particle size (D ₅₀ ) is a particle size at which the cumulative volume frequency calculated by the volume fraction is 50% when calculated from the smaller particle size, and is described in Examples described later. Required by the method.
The coefficient of variation (CV value) (%) of the particle size distribution of the resin particles (D) is preferably 5% or more, more preferably 10 from the viewpoint of improving the productivity of the dispersion liquid of the resin particles (D). % Or more, more preferably 15% or more, and preferably 50% or less, more preferably 40% or less, and further preferably 30% or less from the viewpoint of obtaining a toner capable of obtaining a high-quality image.
The CV value is a value represented by the following formula. The volume average particle diameter in the following formula is the particle diameter obtained by multiplying the particle diameter measured on a volume basis by the ratio of particles having that particle diameter value and dividing the value obtained by the number of particles. is there. The CV value is determined by the method described in the example.
CV value (%)=[standard deviation of particle size distribution (nm)/volume average particle size (nm)]×100
The resin particles (D) include, in addition to the crystalline resin (A), the amorphous resin (B), and the resin composition (C), a resin used in the toner, for example, a crystalline resin (A), Polyester other than the amorphous resin (B), styrene-acrylic copolymer, epoxy, polycarbonate, polyurethane and the like may be contained.
Further, the resin particles (D) may contain a colorant and a charge control agent, if necessary. Further, a reinforcing filler such as a fibrous substance, an additive such as an antioxidant and an anti-aging agent, etc. may be contained within a range not impairing the effects of the present invention.

The mass ratio [(A)/(B)] of the crystalline resin (A) and the amorphous resin (B) is excellent in low-temperature fixability and low-temperature fixability after high-temperature and high-humidity storage, and further has good charging stability. Also from the viewpoint of obtaining an excellent toner, it is preferably 2/98 or more, more preferably 5/95 or more, further preferably 10/90 or more, and preferably 45/55 or less, more preferably 40/60 or less, It is more preferably 35/65 or less, still more preferably 30/70 or less.
The total amount of the crystalline resin (A) and the amorphous resin (B) used is from the viewpoint of obtaining a toner having excellent low-temperature fixability and low-temperature fixability after high-temperature and high-humidity storage, and also excellent charging stability. In the resin component constituting the particles (D), preferably 70% by mass or more, more preferably 90% by mass or more, further preferably 95% by mass or more, still more preferably 98% by mass or more, and preferably 100% by mass or more. It is not more than 100% by mass, more preferably not more than 100% by mass.
The total amount of the crystalline resin (A) used with respect to the total amount of the crystalline resin (A) and the amorphous resin (B) is excellent in low-temperature fixability and low-temperature fixability after high-temperature and high-humidity storage. From the viewpoint of obtaining a toner having excellent stability, it is preferably 5% by mass or more, more preferably 10% by mass or more, further preferably 15% by mass or more, and preferably 45% by mass or less, more preferably 40% by mass. % Or less, more preferably 35% by mass or less.
The "total amount of crystalline resin (A) used" means the amount of the crystalline resin (A) added as a raw material of the resin composition (C) and the raw material of a dispersion liquid of the resin particles (D). Means the total amount of the crystalline resin (A).

<Step (3)>
In the step (3), the resin particles (D) obtained in the step (2) are aggregated in an aqueous medium to obtain aggregated particles. Specifically, from the viewpoint of obtaining a toner having excellent low-temperature fixability and low-temperature fixability after high-temperature and high-humidity storage, and also excellent charging stability, a dispersion liquid of resin particles (D) and, if necessary, a wax. Wax containing (W2) (W2) Particle dispersion, flocculant, surfactant, colorant, and other optional components are mixed in the aqueous medium to coagulate resin particles (D) and other components The method of obtaining particles is preferred.
The step (3) may include the following step (3A), and the step (3B) may be continuously performed.
Step (3A): A step of aggregating the resin particles (D) obtained in the step (2) in an aqueous medium, preferably in the presence of a wax (W2), to obtain agglomerated particles (1) Step (3B) : Agglomerated particles obtained by adding resin particles (E) containing an amorphous resin (Bs) to the agglomerated particles (1) obtained in the step (3A) and adhering the resin particles (E) ( Step 2) <Step (3A)>
The step (3A) is a step of aggregating the resin particles (D) obtained in the step (2) in an aqueous medium to obtain agglomerated particles (1), preferably obtained in the step (2). In this step, the resin particles (D) are aggregated in an aqueous medium in the presence of the wax (W2) to obtain aggregated particles (1).

[Agglomerated particles (1)]
Aggregated particles (1) are a wax particle dispersion liquid containing a wax (W2) as necessary in the dispersion liquid of resin particles (D) obtained in the step (2), an aggregating agent, a surfactant, and a colorant. It is obtained by mixing and aggregating optional components such as. From the viewpoint of obtaining a toner having excellent low-temperature fixability and low-temperature fixability after storage at high temperature and high humidity, and also excellent charging stability, it is preferable to use a wax particle dispersion liquid containing a wax (W2).
Specifically, first, a dispersion liquid of resin particles (D), a dispersion liquid of wax (W2) particles, and, if necessary, optional components such as a coagulant, a surfactant, and a colorant are mixed in an aqueous medium. It is preferable to obtain a mixed dispersion. Then, when the components in the mixed dispersion liquid are aggregated to obtain a dispersion liquid of aggregated particles (1), it is preferable to add an aggregating agent from the viewpoint of efficiently performing aggregation.
When the colorant is not mixed with the resin particles (D), it is preferable to mix the colorant in the mixed dispersion liquid.
The mixing order of each component is not particularly limited, and each component may be added in any order, or all the components may be added simultaneously.

<<Wax Particle Dispersion>>
The wax particle dispersion can be obtained by using a surfactant, but it can be obtained by mixing the wax (W2) and the resin particles (F) described below after low-temperature fixability and high-temperature high-humidity storage. Is preferable from the viewpoint of obtaining a toner having excellent low-temperature fixability and also excellent charging stability.

(Wax (W2))
Examples of the wax (W2) include mineral or petroleum waxes; synthetic waxes; low molecular weight polyolefins; silicone waxes; fatty acid amides; plant waxes; animal waxes.
Examples of the mineral or petroleum wax include montan wax, paraffin wax, Fischer-Tropsch wax and the like, and paraffin wax is preferable from the viewpoint of improving the releasability and low-temperature fixability of the toner.
As the synthetic wax, ester wax is preferable.
As the low molecular weight polyolefin, polyethylene, polypropylene, polybutene and the like are preferable.
As the fatty acid amide, oleic acid amide, stearic acid amide and the like are preferable.
As the plant wax, carnauba wax, rice wax, candelilla wax and the like are preferable.
As the animal wax, beeswax and the like are preferable.

Among these, mineral or petroleum waxes and synthetic waxes are preferable, one or more kinds selected from ester waxes and paraffin waxes are more preferable, and paraffin waxes are further preferable, from the viewpoint of improving the releasability and low-temperature fixability of the toner. ..
The content of the paraffin wax in the wax (W2) is preferably 95% by mass or more, more preferably 97% by mass or more, further preferably 99% by mass or more from the viewpoint of improving the releasability and low-temperature fixability of the toner. And 100% by mass or less, preferably 100% by mass.
The melting point of the wax (W2) is preferably 60° C. or higher, more preferably 65° C. or higher, further preferably 70° C. or higher from the viewpoint of improving the releasability of the toner, and the low temperature fixability and high temperature of the toner. From the viewpoint of improving the low temperature fixability after high humidity storage, the temperature is preferably 100° C. or lower, more preferably 95° C. or lower, further preferably 90° C. or lower, and further preferably 85° C. or lower. When two or more waxes are used in combination, each melting point is preferably 60° C. or higher and 100° C. or lower, and more preferably both melting points are 60° C. or higher and 90° C. or lower.

The melting point of the wax (W2) is determined by the method described in the examples. When two or more kinds of waxes (W2) are used in combination, the melting point of the wax (W2) having the largest mass ratio among the waxes (W2) contained in the obtained toner is the melting point of the wax (W2) in the present invention. The melting point. When all have the same ratio, the lowest melting point is the melting point of the wax (W2) in the present invention.
The amount of the wax (W2) used is such that the resin in the toner has good releasability, excellent low-temperature fixability and low-temperature fixability after storage at high temperature and high humidity, and from the viewpoint of obtaining a toner having excellent charge stability. With respect to the total amount of 100 parts by mass, preferably 1 part by mass or more, more preferably 2 parts by mass or more, further preferably 3 parts by mass or more, and preferably 30 parts by mass or less, more preferably 20 parts by mass or less, It is more preferably 15 parts by mass or less.

(Resin particles (F))
The resin constituting the resin particles (F) is not particularly limited, but is preferably a resin containing a polyester portion, and is a toner excellent in low-temperature fixability and low-temperature fixability after high-temperature and high-humidity storage, and also excellent in charging stability. From the viewpoint of obtaining the above, it is more preferable to use an amorphous composite resin (Bw) having a polyester segment and a vinyl resin segment.

(Amorphous composite resin (Bw))
The amorphous composite resin (Bw) is a resin having a vinyl resin segment and a polyester segment, and is preferably a graft polymer type resin having a vinyl resin segment in the main chain and a polyester segment side chain.
Here, the “main chain” means the main chain of the graft polymer. "Side chain" means a polymer chain branched from the main chain of the graft polymer.
The amorphous composite resin (Bw) preferably has a constituent portion derived from a bireactive monomer capable of reacting with both the vinyl resin segment and the polyester segment. Further, the amorphous composite resin (Bw) may contain a constituent component derived from the hydrocarbon wax (W1) in addition to the vinyl resin segment and the polyester segment.
The amorphous composite resin of the present invention has the above-mentioned crystallinity index of more than 1.4 or less than 0.6.
The polyester segment is excellent in low-temperature fixability and low-temperature fixability after high-temperature and high-humidity storage, and from the viewpoint of obtaining a toner having excellent charge stability, a polyhydric alcohol component (bw-al) and a polyvalent carboxylic acid component (bw). -Ac) and polycondensation.
The polyhydric alcohol component (bw-al) is an alkylene oxide adduct of bisphenol A in an amount of 80 mol from the viewpoint of obtaining a toner having excellent low-temperature fixability and low-temperature fixability after high-temperature and high-humidity storage and also excellent charge stability. % Or more is preferable. From the same viewpoint, the content of the alkylene oxide adduct of bisphenol A in the polyhydric alcohol component (b-al) is preferably 80 mol% or more, more preferably 90 mol% or more, further preferably 95 mol% or more. , More preferably 98 mol% or more, and 100 mol% or less, even more preferably 100 mol%.

The alkylene oxide adduct of bisphenol A is preferably an ethylene oxide adduct of bisphenol A (polyoxyethylene-2,2-bis(4-hydroxyphenyl)propane) and a propylene oxide adduct of bisphenol A (polyoxypropylene-). 2,2-bis(4-hydroxyphenyl)propane), and more preferably a propylene oxide adduct of bisphenol A.

The average number of moles of alkylene oxide added to the alkylene oxide adduct of bisphenol A is preferably 1. from the viewpoint of obtaining a toner having excellent low-temperature fixability and low-temperature fixability after high-temperature and high-humidity storage and also excellent charge stability. 0 or more, more preferably 1.2 or more, further preferably 1.5 or more, and preferably 16 or less, more preferably 12 or less, further preferably 8 or less, even more preferably 4 or less, even more preferably Is 3 or less.

The polyhydric alcohol component (b-al) may contain a polyhydric alcohol other than the alkylene oxide adduct of bisphenol A. Examples of other polyhydric alcohol components that can be contained in the polyhydric alcohol component (b-al) include aliphatic diols, aromatic diols, alicyclic diols, polyhydric alcohols having 3 or more valences, or those having 2 to 4 carbon atoms. The following alkylene oxide (average addition mole number 1 or more and 16 or less) adduct and the like can be mentioned. Specific examples thereof include ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol and 2,3-butanediol. , Neopentyl glycol, 1,4-butenediol, 1,5-pentanediol, 1,6-hexanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,12 An aliphatic diol such as dodecanediol; an aromatic diol such as bisphenol A (2,2-bis(4-hydroxyphenyl)propane); a hydrogenated bisphenol A (2,2-bis(4-hydroxycyclohexyl)propane) Alicyclic diols thereof, or alkylene oxide adducts thereof having 2 to 4 carbon atoms (average added mole number of 2 to 12); trihydric or higher polyhydric alcohols such as glycerin, pentaerythritol, trimethylolpropane and sorbitol. Or, those alkylene oxides having 2 or more and 4 or less carbon atoms (average added mole number of 1 or more and 16 or less) and the like can be mentioned.
These polyhydric alcohol components may be used alone or in combination of two or more.

Examples of the polyvalent carboxylic acid component (bw-ac) include dicarboxylic acids, trivalent or higher polyvalent carboxylic acids, or their anhydrides and their alkyl esters having 1 to 3 carbon atoms. Among these, a dicarboxylic acid is preferable, and it is more preferable to use a dicarboxylic acid and a trivalent or higher polycarboxylic acid in combination.

Examples of the dicarboxylic acid include aromatic dicarboxylic acid, aliphatic dicarboxylic acid, and alicyclic dicarboxylic acid. Among these, at least one selected from aromatic dicarboxylic acids and aliphatic dicarboxylic acids is preferable.
The polyvalent carboxylic acid component includes not only a free acid but also an anhydride that decomposes to form an acid during the reaction, and an alkyl ester having 1 to 3 carbon atoms of each carboxylic acid.
Examples of the aromatic dicarboxylic acid include phthalic acid, isophthalic acid, terephthalic acid and the like. Among these, isophthalic acid and terephthalic acid are preferable, and terephthalic acid is more preferable, from the viewpoint of obtaining a toner having excellent low-temperature fixability and low-temperature fixability after high-temperature and high-humidity storage and also excellent charge stability.
From the same viewpoint, the aliphatic dicarboxylic acid preferably has 2 or more carbon atoms, more preferably 3 or more carbon atoms, and preferably 30 or less, more preferably 20 or less.
Examples of the aliphatic dicarboxylic acid having 2 to 30 carbon atoms include oxalic acid, malonic acid, maleic acid, fumaric acid, citraconic acid, itaconic acid, glutaconic acid, succinic acid, adipic acid, sebacic acid, dodecanedioic acid, Examples thereof include azelaic acid and succinic acid substituted with an alkyl group having 1 to 20 carbon atoms or an alkenyl group having 2 to 20 carbon atoms, which are excellent in low-temperature fixability and low-temperature fixability after storage at high temperature and high humidity. From the viewpoint of obtaining a toner having excellent charging stability, fumaric acid and adipic acid are preferable. Specific examples of succinic acid substituted with an alkyl group having 1 to 20 carbon atoms or an alkenyl group having 2 to 20 carbon atoms include dodecyl succinic acid, dodecenyl succinic acid, octenyl succinic acid and the like.
Among these, terephthalic acid, fumaric acid, and adipic acid are preferable, and they are used in combination from the viewpoint of obtaining a toner that is excellent in low-temperature fixability and low-temperature fixability after high-temperature and high-humidity storage and is also excellent in charging stability. Is more preferable.

As the trivalent or higher polyvalent carboxylic acid, a trivalent carboxylic acid is preferable from the viewpoint of obtaining a toner having excellent low-temperature fixability and low-temperature fixability after high-temperature and high-humidity storage and also excellent charge stability, and trimellitic acid. And its acid anhydride are more preferable, and trimellitic acid anhydride is still more preferable.
In addition, the content of the polyvalent carboxylic acid having a valence of 3 or more is determined from the viewpoint of obtaining a toner having excellent low-temperature fixability and low-temperature fixability after high-temperature and high-humidity storage, and also having excellent charging stability. It is preferably 3 mol% or more, more preferably 5 mol% or more, and preferably 20 mol% or less, more preferably 15 mol% or less, still more preferably 12 mol% or less in the acid component.
These polyvalent carboxylic acid components can be used alone or in combination of two or more.

The equivalent ratio (COOH group/OH group) of the polyhydric carboxylic acid component to the polyhydric alcohol component is excellent in low-temperature fixability and low-temperature fixability after storage at high temperature and high humidity, and from the viewpoint of obtaining a toner having excellent charge stability as well. , Preferably 0.7 or more, more preferably 0.8 or more, and preferably 1.3 or less, more preferably 1.2 or less.

The amorphous composite resin (Bw) of the present invention is preferably a vinyl group having a hydrocarbon group from the viewpoint of obtaining a toner having excellent low-temperature fixability and low-temperature fixability after storage at high temperature and high humidity, and also excellent charge stability. It has a structural unit derived from a monomer. The vinyl resin segment preferably further contains a structural unit derived from a styrene compound.
The carbon number of the hydrocarbon group of the vinyl monomer having a hydrocarbon group is preferably 4 or more, from the viewpoint of obtaining a toner having excellent low-temperature fixability and low-temperature fixability after high-temperature and high-humidity storage, and also excellent charging stability. More preferably 6 or more, further preferably 8 or more, even more preferably 10 or more, even more preferably 12 or more, even more preferably 14 or more, and preferably 22 or less, more preferably 20 or less, More preferably, it is 18 or less.
It is considered that when the vinyl-based resin segment has a hydrophobic hydrocarbon group, the highly hydrophobic crystalline resin is easily dispersed well.

Examples of the hydrocarbon group include an aliphatic hydrocarbon group such as an alkyl group, an alkynyl group and an alkenyl group, preferably an alkyl group and an alkenyl group, and more preferably an alkyl group.
The hydrocarbon group may be branched or linear.
From the viewpoint of availability and reactivity, the vinyl monomer having a hydrocarbon group is preferably an alkyl ester of (meth)acrylic acid, and more preferably an alkyl (meth)acrylate. In the case of an alkyl ester of (meth)acrylic acid, the hydrocarbon group is the alcohol side residue of the ester. Specifically, (iso)butyl (meth)acrylate, (iso)hexyl (meth)acrylate, cyclohexyl (meth)acrylate, (iso)octyl (meth)acrylate (hereinafter referred to as (meth)acrylic acid 2 -Ethylhexyl), (meth)acrylic acid (iso)decyl, (meth)acrylic acid (iso)dodecyl (hereinafter, also referred to as (meth)acrylic acid (iso)lauryl), (meth)acrylic acid (iso)palmityl , (Meth)acrylic acid (iso)stearyl, (meth)acrylic acid (iso)behenyl and the like can be mentioned, preferably (meth)acrylic acid 2-ethylhexyl, (meth)acrylic acid (iso)decyl, (meth)acrylic. Acid (iso)lauryl, (meth)acrylic acid (iso)stearyl, (meth)acrylic acid (iso)behenyl, more preferably (meth)acrylic acid (iso)decyl, (meth)acrylic acid (iso)lauryl, ( (Iso)stearyl (meth)acrylate, more preferably (iso)lauryl (meth)acrylate, (iso)stearyl (meth)acrylate, and even more preferably (iso)stearyl (meth)acrylate.
Here, “alkyl (meth)acrylate” refers to alkyl acrylate or alkyl methacrylate. Further, “(iso)” for the alkyl moiety means normal alkyl or isoalkyl.
The content of the constituent unit derived from a vinyl monomer having a hydrocarbon group in the vinyl-based resin segment is excellent in low-temperature fixability and low-temperature fixability after high-temperature and high-humidity storage, and from the viewpoint of obtaining a toner having excellent charge stability as well. Therefore, it is preferably 5% by mass or more, more preferably 10% by mass or more, further preferably 15% by mass or more, and preferably 50% by mass or less, more preferably 45% by mass or less, further preferably 40% by mass. It is the following.

Examples of the styrene compound include substituted or unsubstituted styrene. Examples of the substituent include an alkyl group having 1 to 5 carbon atoms, a halogen atom, an alkoxy group having 1 to 5 carbon atoms, a sulfonic acid group, or a salt thereof. Specific examples thereof include styrenes such as styrene, methylstyrene, α-methylstyrene, β-methylstyrene, t-butylstyrene, chlorostyrene, chloromethylstyrene, methoxystyrene, styrenesulfonic acid and salts thereof. Contains styrene, more preferably styrene.
The content of the structural unit derived from the styrene compound in the vinyl resin segment is preferably 50 from the viewpoint of obtaining a toner having excellent low-temperature fixability and low-temperature fixability after high-temperature and high-humidity storage, and also excellent charge stability. The content is preferably at least mass%, more preferably at least 55 mass%, further preferably at least 60 mass%, and preferably at most 95 mass%, more preferably at most 90 mass%, further preferably at most 85 mass%.
In addition to the above, as raw material vinyl monomers that can be used in the vinyl resin segment, ethylenically unsaturated monoolefins such as ethylene and propylene; conjugated dienes such as butadiene; halovinyls such as vinyl chloride; vinyl acetate, vinyl propionate Vinyl esters such as methacrylic acid dimethylaminoethyl (meth)acrylic acid aminoalkyl esters; vinyl ethers such as methyl vinyl ether; vinylidene halides such as vinylidene chloride; N-vinyl such as N-vinylpyrrolidone Examples thereof include compounds.

The raw material vinyl monomer, which is a component derived from the vinyl-based resin segment, has a carbon number of 4 or more and 22 or less from the viewpoint of obtaining a toner having excellent low-temperature fixability and low-temperature fixability after high-temperature and high-humidity storage and also excellent charge stability. The combined use of a vinyl monomer having a hydrocarbon group and a styrene compound is preferable, and the combined use of an alkyl ester of (meth)acrylic acid having an alkyl group having 4 to 22 carbon atoms with styrene is more preferable.

When a vinyl monomer having a hydrocarbon group and a styrene compound are used in combination, the mass ratio of the constitutional unit derived from the vinyl monomer having a hydrocarbon group in the vinyl resin segment and the constitutional unit derived from the styrene compound [carbonization A constitutional unit derived from a vinyl monomer having a hydrogen group/a constitutional unit derived from a styrene compound] is excellent in low temperature fixing property and low temperature fixing property after high temperature and high humidity storage, and from the viewpoint of obtaining a toner excellent in charging stability, It is preferably 5/95 or more, more preferably 10/90 or more, still more preferably 15/85 or more, and preferably 50/50 or less, more preferably 45/55 or less, further preferably 40/60 or less. is there.

The total content of structural units derived from vinyl monomers and styrene compounds having hydrocarbon groups having a vinyl group in the vinyl resin segment is excellent in low-temperature fixability and low-temperature fixability after high-temperature and high-humidity storage. From the viewpoint of obtaining an excellent toner, the content is preferably 80% by mass or more, more preferably 90% by mass or more, further preferably 95% by mass or more, and preferably 100% by mass or less, and further preferably 100% by mass or less. It is% by mass.

The amorphous composite resin (Bw) preferably has a constitutional unit derived from a bireactive monomer. When a bireactive monomer is used as a raw material monomer of the amorphous composite resin (Bw), the bireactive monomer reacts with both the polyester segment and the vinyl-based resin segment, whereby the amorphous composite resin (Bw) Will be easier to manufacture. Therefore, it is preferable to use a bireactive monomer as a raw material monomer of the amorphous composite resin (Bw). It is preferable that the constitutional unit derived from the bireactive monomer serves as a bonding point between the vinyl resin segment and the polyester segment.
Examples of the bireactive monomer include vinyl monomers having one or more functional groups selected from a hydroxyl group, a carboxy group, an epoxy group, a primary amino group and a secondary amino group in the molecule. Among these, from the viewpoint of reactivity, a vinyl monomer having a hydroxyl group or a carboxy group is preferable, and a vinyl monomer having a carboxy group is more preferable. Examples of the vinyl monomer having a carboxy group include acrylic acid, methacrylic acid, fumaric acid, maleic acid and the like. Among these, acrylic acid and methacrylic acid are preferable, and acrylic acid is more preferable, from the viewpoint of reactivity of both polycondensation reaction and addition polymerization reaction.

From the viewpoint of improving the dispersibility of the wax (W2) and controlling the reaction of the addition polymerization reaction and the polycondensation reaction, the amount of the both-reactive monomer used is 100 mol parts of the total amount of the polyhydric alcohol component as the raw material of the polyester segment. On the other hand, it is preferably 1 part by mole or more, more preferably 5 parts by mole or more, further preferably 10 parts by mole or more, and preferably 30 parts by mole or less, more preferably 25 parts by mole or less, further preferably 20 moles. Below the section. In the case of using a bireactive monomer, when the content of each segment in the amorphous composite resin is calculated, the constitutional unit derived from the bireactive monomer is contained in the constitutional unit of the polyester segment. Calculate as
The content of the polyester segment in the amorphous composite resin (Bw) is preferably 40 mass from the viewpoint of obtaining a toner having excellent low-temperature fixability and low-temperature fixability after high-temperature and high-humidity storage and also excellent charging stability. % Or more, more preferably 50% by mass or more, further preferably 60% by mass or more, and preferably 90% by mass or less, more preferably 80% by mass or less, further preferably 70% by mass or less. From the same viewpoint, the content of the polyester segment in the amorphous composite resin (Bw) is preferably 40 mass% or more, and more preferably 50 mass% with respect to the total content of the polyester segment and the vinyl resin segment. The above is more preferably 60 mass% or more, and preferably 90 mass% or less, more preferably 80 mass% or less, and further preferably 70 mass% or less.
Further, the content of the vinyl-based resin segment in the amorphous composite resin (Bw) is excellent in low-temperature fixability and low-temperature fixability after high-temperature and high-humidity storage, and from the viewpoint of obtaining a toner having excellent charge stability, It is preferably 10% by mass or more, more preferably 20% by mass or more, further preferably 30% by mass or less, and preferably 60% by mass or less, more preferably 50% by mass or less, further preferably 40% by mass or less. is there. From the same viewpoint, the content of the vinyl-based resin segment in the amorphous composite resin (Bw) is preferably 10% by mass or more, more preferably 20% by mass based on the total content of the polyester segment and the vinyl-based resin segment. It is at least mass%, more preferably at least 30 mass%, and preferably at most 60 mass%, more preferably at most 50 mass%, further preferably at most 40 mass%.
In addition, the total content of the polyester segment and the vinyl resin segment in the amorphous composite resin (Bw) is excellent in low-temperature fixability and low-temperature fixability after high-temperature and high-humidity storage, and is also a toner having excellent charge stability. From the viewpoint of obtaining, it is preferably 80% by mass or more, more preferably 90% by mass or more, further preferably 93% by mass or more, still more preferably 95% by mass or more, and preferably 100% by mass or less, and further It is preferably 100% by mass.

The method for producing the amorphous composite resin (Bw) is not particularly limited, but examples thereof include the following methods (i) to (iii).
(I) Method of carrying out polycondensation reaction with polyhydric alcohol component and polycarboxylic acid component, followed by addition polymerization reaction with raw material monomer of vinyl resin segment and bireactive monomer In addition, from the viewpoint of reactivity, vinyl resin It is preferable that the bireactive monomer is supplied to the reaction system together with the raw material monomer of the segment. From the viewpoint of reactivity, a catalyst such as an esterification catalyst or an esterification co-catalyst may be used, and further a radical polymerization initiator and a radical polymerization inhibitor may be used.
From the viewpoint of further promoting the polycondensation reaction and, if necessary, the reaction with the both-reactive monomer, the polyvalent carboxylic acid component is partially subjected to the polycondensation reaction, and then the reaction temperature is raised again after the addition polymerization reaction. It is preferable to add the balance to the reaction system.
It is also possible to manufacture by the following method (ii) or (iii).
(Ii) A method of performing a polycondensation reaction with a raw material monomer of a polyester segment after an addition polymerization reaction with a raw material monomer of a vinyl resin segment and a bireactive monomer. (iii) Polycondensation with a polyhydric alcohol component and a polyvalent carboxylic acid component. Method in which the reaction and the addition polymerization reaction with the raw material monomer of the vinyl resin segment and the bireactive monomer are performed in parallel The polycondensation reaction and the addition polymerization reaction in the above methods (i) to (iii) are both performed in the same container. It is preferable to carry out in-house.
It is preferable that the amorphous composite resin (Bw) is produced by the method (i) because the reaction temperature of the polycondensation reaction is high.

The temperature of the polycondensation reaction is preferably 180° C. or higher, more preferably 200° C. or higher, and preferably 260° C. or lower, more preferably 250° C., from the viewpoint of the productivity of the amorphous composite resin (Bw). It is below.
Examples of esterification catalysts preferably used in the polycondensation reaction include tin compounds such as dibutyltin oxide and tin(II) di(2-ethylhexanoate), and titanium compounds such as titanium diisopropylate bistriethanolaminate. Can be mentioned. Among these, tin compounds are preferable, and di(2-ethylhexanoic acid)tin(II) is more preferable.
From the viewpoint of reactivity, the amount of the esterification catalyst used is preferably 0.01 parts by mass or more, more preferably 0.1 parts by mass, relative to 100 parts by mass of the total amount of the polyhydric alcohol component and the polycarboxylic acid component. It is at least 5 parts by mass, and preferably at most 5 parts by mass, more preferably at most 2 parts by mass.
As the esterification promoter, pyrogallol, gallic acid (the same as 3,4,5-trihydroxybenzoic acid), pyrogallol compounds such as gallic acid ester; 2,3,4-trihydroxybenzophenone, 2,2', Examples thereof include benzophenone derivatives such as 3,4-tetrahydroxybenzophenone; catechin derivatives such as epigallocatechin and epigallocatechin gallate, and gallic acid is preferable from the viewpoint of reactivity.
From the viewpoint of reactivity, the amount of the esterification co-catalyst used is preferably 0.001 part by mass or more, and more preferably 0.01 part by mass based on 100 parts by mass of the total amount of the polyhydric alcohol component and the polycarboxylic acid component. The amount is not less than 0.5 part by mass, and preferably not more than 0.5 part by mass, more preferably not more than 0.2 part by mass.
As the radical polymerization inhibitor in the polycondensation reaction, 4-tert-butylcatechol or the like can be used.
The amount of the radical polymerization inhibitor used is preferably 0.001 parts by mass or more, more preferably 0.005 parts by mass or more based on 100 parts by mass of the total amount of the polyhydric alcohol component and the polycarboxylic acid component. And, it is preferably 0.5 parts by mass or less, more preferably 0.2 parts by mass or less.

The temperature of the addition polymerization reaction varies depending on the type of radical polymerization initiator used and the like, but from the viewpoint of the productivity of the amorphous composite resin (Bw), it is preferably 110° C. or higher, more preferably 130° C. or higher, And it is preferably 220° C. or lower, and more preferably 200° C. or lower.
Further, it is preferable to accelerate the reaction by reducing the pressure of the reaction system in the latter half of the polymerization.

Known polymerization initiators for the addition polymerization reaction include peroxides such as dibutyl peroxide, persulfates such as sodium persulfate, and azo compounds such as 2,2′-azobis(2,4-dimethylvaleronitrile). The radical polymerization initiator of can be used.

The amount of the radical polymerization initiator used is preferably 1 part by mass or more, more preferably 3 parts by mass or more, and preferably 20 parts by mass or less, based on 100 parts by mass of the raw material monomer of the vinyl resin segment. It is preferably 15 parts by mass or less.

[Physical Properties of Amorphous Composite Resin (Bw)]
The softening point of the amorphous composite resin (Bw) is preferably 70° C. or higher, more preferably 70° C. or higher from the viewpoint of obtaining a toner having excellent low-temperature fixability and low-temperature fixability after high-temperature and high-humidity storage and also excellent charge stability. Is 80° C. or higher, and preferably 140° C. or lower, more preferably 120° C. or lower, still more preferably 100° C. or lower.

From the same viewpoint, the glass transition temperature of the amorphous composite resin (Bw) is preferably 30° C. or higher, more preferably 35° C. or higher, still more preferably 40° C. or higher, and preferably 70° C. or lower. It is preferably 60° C. or lower.

The acid value of the amorphous composite resin (Bw) is preferably 5 mgKOH/g or more, from the viewpoint of improving the dispersion stability of the resin particles (D) described later and from the viewpoint of improving the low temperature fixability and charging characteristics of the toner. It is more preferably 10 mgKOH/g or more, still more preferably 15 mgKOH/g or more, and preferably 40 mgKOH/g or less, more preferably 35 mgKOH/g or less, still more preferably 30 mgKOH/g or less.

The hydroxyl value of the amorphous composite resin (Bw) is preferably 4 mgKOH/g or more, from the viewpoint of improving the dispersion stability of the resin particles (D) described later and from the viewpoint of improving the low temperature fixability and charging characteristics of the toner. The amount is more preferably 7 mgKOH/g or more, further preferably 10 mgKOH/g or more, and preferably 40 mgKOH/g or less, more preferably 30 mgKOH/g or less.

The softening point, glass transition temperature, acid value and hydroxyl value of the amorphous composite resin (Bw) may be appropriately adjusted depending on the types and ratios of the raw material monomers and the production conditions such as reaction temperature, reaction time and cooling rate. It is possible, and those values are calculated by the method described in Examples.

The dispersion liquid of the resin particles (F) can be obtained, for example, by the above-mentioned phase inversion emulsification method. For the specific conditions and procedures of phase inversion emulsification, that is, the aqueous medium used, components other than water that can constitute the aqueous medium, the amount of the aqueous medium, the addition temperature, and the addition rate, apply the explanation in step (2). You can
The solid content concentration of the resulting dispersion of the resin particles (F) is preferably 5% by mass from the viewpoint of improving the productivity of the toner and improving the dispersion stability of the aqueous dispersion of the resin particles (F). Or more, more preferably 10% by mass or more, further preferably 15% by mass or more, and preferably 50% by mass or less, more preferably 40% by mass or less, further preferably 30% by mass or less, still more preferably 25% by mass or less. It is not more than mass %. The solid content is the total amount of non-volatile components such as resin, colorant and surfactant.
The volume median particle diameter (D ₅₀ ) of the resin particles (F) in the dispersion is excellent in low-temperature fixability and low-temperature fixability after storage at high temperature and high humidity, and from the viewpoint of obtaining a toner having excellent charge stability, It is preferably 0.01 μm or more, more preferably 0.03 μm or more, and preferably 0.30 μm or less, more preferably 0.15 μm or less, still more preferably 0.10 μm or less.
The coefficient of variation (CV value) (%) of the particle size distribution of the resin particles (F) is preferably 5% or more, more preferably 10 from the viewpoint of improving the productivity of the dispersion liquid of the resin particles (F). % Or more, more preferably 15% or more, preferably 50% or less, more preferably 40% or less, and further preferably 30% or less from the viewpoint of obtaining a toner capable of obtaining a high quality image.
The CV value is a value represented by the following formula.
CV value (%)=[standard deviation of particle size distribution (nm)/volume average particle size (nm)]×100

(Production of wax particle dispersion)
The wax particle dispersion liquid is obtained by mixing the wax (W2) and the dispersion liquid of the resin particles (F).
By preparing the wax particles using the wax (W2) and the resin particles (F), the wax is dispersed in the aqueous medium without using a surfactant because the polyester segment has an appropriate polarity. It is possible to
That is, the wax particles contain wax and resin particles (F). It is considered that in the wax particle dispersion liquid, the wax is dispersed through the resin particles (F) having an appropriate polarity, and a large number of resin particles (F) are adsorbed around the wax particles. It is considered that this makes it easier for the wax particles to be taken into the aggregate of the (binding) resin particles (D) in the subsequent aggregation step.

The wax particle dispersion liquid is obtained, for example, by dispersing the wax (W2), the resin particle (F) dispersion liquid, and optionally an aqueous medium at a temperature equal to or higher than the melting point of the wax (W2) using a disperser. can get. From the viewpoint of the stability of the wax particles, the disperser is preferably a homogenizer, a high pressure disperser, an ultrasonic disperser, or the like, and more preferably an ultrasonic disperser. The dispersion time may be set appropriately depending on the disperser used.

Examples of the ultrasonic disperser include an ultrasonic homogenizer. Examples of the commercially available products include "US-150T", "US-300T", "US-600T" (manufactured by Nippon Seiki Co., Ltd.), "SONIFIER (registered trademark) 4020-400", "SONIFIER (registered trademark) 4020. -800" (manufactured by Branson).
In addition, before using the above-mentioned disperser, the wax (W2) and the resin particle (F) dispersion liquid and, if necessary, the aqueous medium may be pre-dispersed in a mixer such as a homomixer or a ball mill. Good.
The preferred embodiment of the aqueous medium used in this production is the same as that used for obtaining the resin particles (D).

From the viewpoint of improving the dispersion stability of the wax particles, obtaining uniform agglomerated particles in the subsequent aggregating step, and including the wax (W2) in the toner even after heating in the fusing step, the wax (W2) 100 The amount of the resin particles (F) with respect to parts by mass is preferably 5 parts by mass or more, more preferably 10 parts by mass or more, further preferably 20 parts by mass or more, further preferably 30 parts by mass or more, and preferably 100 parts by mass. The amount is not more than 70 parts by mass, more preferably not more than 70 parts by mass, further preferably not more than 60 parts by mass, still more preferably not more than 50 parts by mass.
The wax particle dispersion may contain a surfactant, but it is preferable that the wax particle dispersion does not contain a surfactant from the viewpoint of obtaining a toner having excellent low-temperature fixability and stability over time. When a surfactant is contained, the amount of the surfactant is preferably 1 part by mass or less, more preferably 0.5 part by mass or less, further preferably 0.1 part by mass or less, relative to 100 parts by mass of the wax in the wax particles. When used to improve the dispersion stability of the wax particles, it is preferably 0.01 part by mass or more, more preferably 0.02 part by mass or more, still more preferably 0.05 part by mass or more. Is.

It is preferable that the wax (W2) and the dispersion liquid of the resin particles (F) are added to an aqueous medium and dispersed while being heated at a temperature equal to or higher than the melting point of the wax (W2).
Specifically, the heating temperature during the dispersion is preferably from the melting point of the wax (W2) to 80° C. or higher, more preferably 85° C. or higher, and further preferably from the viewpoint of improving the productivity of the wax particle dispersion. It is 90° C. or higher, and preferably 100° C. or lower, more preferably 98° C. or lower, still more preferably 95° C. or lower.
The heating time during dispersion is preferably 5 minutes or more, more preferably 10 minutes or more, further preferably 15 minutes or more, and preferably 3 hours or less, from the viewpoint of improving the productivity of the wax particle dispersion. , More preferably 2 hours or less, still more preferably 1 hour or less.

The solid content concentration of the wax (W2) particle dispersion is preferably 5% by mass or more, from the viewpoint of improving the dispersion stability of the wax particles, facilitating the handling, and improving the productivity of the toner. It is preferably 10% by mass or more, more preferably 15% by mass or more, and preferably 40% by mass or less, more preferably 30% by mass or less, further preferably 25% by mass or less.

The volume median particle diameter (D ₅₀ ) of the wax (W2) particles is excellent from the viewpoint of obtaining uniform agglomerated particles in the subsequent aggregating step, the low temperature fixability and the low temperature fixability after storage at high temperature and high humidity, and further stable charging. From the viewpoint of obtaining a toner having excellent properties, the particle size is preferably 0.05 μm or more, more preferably 0.20 μm or more, still more preferably 0.30 μm or more, still more preferably 0.40 μm or more, and preferably 1. It is not more than 00 μm, more preferably not more than 0.80 μm, still more preferably not more than 0.70 μm, even more preferably not more than 0.65 μm, even more preferably not more than 0.60 μm.
Here, the volume median particle size (D ₅₀ ) is a particle size at which the cumulative volume frequency calculated by the volume fraction is 50% when calculated from the smaller particle size, and is described in Examples described later. Required by the method.
The coefficient of variation (CV value) (%) of the particle size distribution of the wax (W2) particles is preferably 5% or more, more preferably 10% or more, from the viewpoint of improving the productivity of the dispersion liquid of the wax particles. It is more preferably 15% or more, preferably 50% or less, more preferably 40% or less, and further preferably 30% or less from the viewpoint of obtaining a toner capable of obtaining a high quality image.
The CV value is a value represented by the following formula.
CV value (%)=[standard deviation of particle size distribution (nm)/volume average particle size (nm)]×100
Ratio of volume median particle diameter (D ₅₀ ) of wax (W2) particles to volume median particle diameter (D ₅₀ ) of resin particles (F) (volume median particle diameter (D ₅₀ )/wax (W2) particles) The volume median particle diameter (D ₅₀ ) of the resin particles (F) is from the viewpoint of improving the dispersion stability of the wax particles, and the low temperature fixability of the toner and the low temperature fixability after high temperature and high humidity storage. , Preferably 1.0 or more, more preferably 2.0 or more, still more preferably 3.0 or more, and preferably 50 or less, more preferably 30 or less, still more preferably 15 or less, still more preferably 10 or less. It is as follows.

<<Colorant>>
When the colorant is mixed in the mixed dispersion liquid containing the resin particles (D), it is preferable to use a dispersion liquid of the colorant particles in which the colorant is dispersed in an aqueous medium.
As the colorant, a pigment and a dye are used, and the pigment is preferable from the viewpoint of improving the image density of the toner.
Specific examples of the pigment include carbon black, inorganic composite oxide, benzidine yellow, brilliankamine 3B, brilliankamine 6B, bengal, aniline blue, ultramarine blue, copper phthalocyanine, phthalocyanine green, and the like. Phthalocyanine is preferred.

Specific examples of the dye include acridine-based, azo-based, benzoquinone-based, azine-based, anthraquinone-based, indigo-based, phthalocyanine-based, aniline black-based and the like.
The colorants may be used alone or in combination of two or more.
The amount of the colorant used is preferably 2 parts by mass or more, and more preferably 5 parts by mass based on 100 parts by mass of the total amount of the resin in the toner, from the viewpoint of improving the image density of the printed matter and obtaining a high quality image. The amount is at least parts by mass, more preferably at least 7 parts by mass, and preferably at most 30 parts by mass, more preferably at most 20 parts by mass, still more preferably at most 15 parts by mass.

The colorant dispersion liquid is preferably obtained by dispersing the colorant and an aqueous medium using a disperser. As the disperser, a homogenizer, an ultrasonic disperser and the like are preferable.
As the aqueous medium, those mentioned above in the production of the resin particle (D) dispersion are preferable.
From the viewpoint of improving the dispersion stability of the colorant, the colorant is preferably dispersed in the aqueous medium in the presence of a surfactant.
Examples of the surfactant used for producing the colorant dispersion include nonionic surfactants, anionic surfactants, cationic surfactants, etc., from the viewpoint of improving the dispersion stability of the colorant particles, aggregation. From the viewpoint of improving the property, it is preferably an anionic surfactant. Examples of the anionic surfactant include sodium dodecylbenzenesulfonate, sodium dodecylsulfate, sodium lauryl ether sulfate, dipotassium alkenylsuccinate, and the like, and sodium dodecylbenzenesulfonate is preferable.

The content of the surfactant in the colorant dispersion is preferably 1 part by mass or more, more preferably 5 parts by mass or more, relative to 100 parts by mass of the colorant, from the viewpoint of improving the dispersion stability of the colorant. It is more preferably 10 parts by mass or more, and preferably 40 parts by mass or less, more preferably 30 parts by mass or less, still more preferably 25 parts by mass or less.

The solid content concentration of the colorant dispersion is preferably 5% by mass or more, more preferably 10% by mass or more, and further preferably from the viewpoint of improving the productivity of the toner and improving the dispersion stability of the colorant. It is 15% by mass or more, and preferably 50% by mass or less, more preferably 40% by mass or less, and further preferably 30% by mass or less.

The volume median particle diameter (D ₅₀ ) of the colorant particles in the colorant dispersion is preferably 0.050 μm or more, more preferably 0.08 μm or more, still more preferably 0.10 μm or more, and preferably It is 0.30 μm or less, more preferably 0.20 μm or less, still more preferably 0.15 μm or less.
The content of the resin particles (D) in the mixed dispersion is preferably 5% by mass from the viewpoint of obtaining a toner having excellent low-temperature fixability and low-temperature fixability after high-temperature and high-humidity storage and also excellent charging stability. Or more, more preferably 10% by mass or more, further preferably 12% by mass or more, and preferably 40% by mass or less, more preferably 30% from the viewpoint of controlling agglomeration to obtain agglomerated particles having a desired particle size. It is not more than 20% by mass, more preferably not more than 20% by mass.
The mass ratio of the wax (W2) particles to the resin particles (D) in the mixed dispersion (wax (W2) particles/resin particles (D)) is excellent in low-temperature fixability and low-temperature fixability after storage at high temperature and high humidity. Further, from the viewpoint of obtaining a toner having excellent charge stability, it is preferably 0.05 or more, more preferably 0.10 or more, and preferably 1.0 or less, more preferably 0.5 or less, further preferably Is 0.3 or less, and more preferably 0.2 or less.
The mixing temperature is preferably 0° C. or higher, more preferably 10° C. or higher, still more preferably 20° C. or higher, and preferably 40° C. or lower, from the viewpoint of controlling aggregation to obtain aggregated particles having a target particle size. , And more preferably 30° C. or lower.
The mixed dispersion is prepared in the presence of a surfactant from the viewpoint of improving the dispersion stability of the resin particles (D) and optional components such as wax (W2) particles added as necessary. Good.
Examples of the surfactant include anionic surfactants such as sulfuric acid ester-based, sulfonate-based, phosphoric acid ester-based, and soap-based (for example, alkyl ether carboxylate); amine salt-based and quaternary ammonium-based surfactants. Cationic surfactants such as salt type; polyoxyethylene alkylaryl ethers such as polyoxyethylene nonylphenyl ether, polyoxyethylene alkyl ethers and polyoxyethylene alkenyl ethers such as polyoxyethylene oleyl ether and polyoxyethylene lauryl ether , Polyoxyethylene sorbitan monolaurate and polyoxyethylene sorbitan monostearate and other polyoxyethylene sorbitan esters, polyethylene glycol monolaurate, polyethylene glycol monostearate and polyethylene glycol monooleate and other polyoxyethylene fatty acid esters And nonionic surfactants such as oxyethylene/oxypropylene block copolymers. Among these, nonionic surfactants are preferable, polyoxyethylene alkyl ethers and polyoxyethylene alkenyl ethers are preferable, and polyoxyethylene lauryl ether is more preferable.
When a surfactant is used, the amount thereof is preferably 0.1 part by mass or more, more preferably 0.5 part by mass or more, and preferably 100 parts by mass of the resin particles (D). The amount is 10 parts by mass or less, more preferably 5 parts by mass or less, and further preferably 3 parts by mass or less.

<<Flocculant>>
Next, the particles in the mixed dispersion liquid are aggregated to obtain a dispersion liquid of aggregated particles (1) in a suitable manner. It is preferable to add a coagulant in order to efficiently perform coagulation.
As the coagulant, an electrolyte is preferably used, and a salt is more preferably used, from the viewpoint of obtaining a toner having a target particle diameter while preventing excessive coagulation. Specific examples of the aggregating agent include a cationic surfactant of a quaternary salt, an organic aggregating agent such as polyethyleneimine; an inorganic aggregating agent such as an inorganic metal salt, an inorganic ammonium salt and a divalent or higher valent metal complex. To be From the viewpoint of improving the aggregability and obtaining uniform agglomerated particles, an inorganic coagulant is preferred, an inorganic metal salt or an inorganic ammonium salt is more preferred, and an inorganic ammonium salt is even more preferred.

The valence of the cation of the inorganic coagulant is preferably 5 or less, more preferably 2 or less, and further preferably 1 from the viewpoint of obtaining a toner having a desired particle size while preventing excessive aggregation. Examples of the monovalent cation of the inorganic flocculant include sodium ion, potassium ion, ammonium ion and the like. From the viewpoint of improving the low temperature fixability of the obtained toner and the low temperature fixability after high temperature and high humidity storage, the ammonium ion is used. Is preferred.

Examples of the inorganic metal salt include metal salts such as sodium sulfate, sodium nitrate, sodium chloride, calcium chloride and calcium nitrate, and inorganic metal salt polymers such as polyaluminum chloride and polyaluminum hydroxide.
Examples of the inorganic ammonium salt include ammonium sulfate, ammonium chloride, ammonium nitrate and the like.
Ammonium sulfate is more preferable as the aggregating agent.
The amount of the aggregating agent to be used is preferably 5 parts by mass or more, more preferably 5 parts by mass or more based on 100 parts by mass of the resin constituting the aggregating particles (1), from the viewpoint of controlling the aggregation of the resin particles to obtain a target particle size. The amount is preferably 10 parts by mass or more, more preferably 20 parts by mass or more, and is preferably 50 parts by mass from the viewpoint of obtaining a toner having excellent low-temperature fixability and low-temperature fixability after high-temperature and high-humidity storage, and also excellent charging stability. Parts by mass or less, more preferably 45 parts by mass or less, still more preferably 40 parts by mass or less.

The aggregating agent may be added at once, or may be added intermittently or continuously. It is preferable to perform sufficient stirring at the time of addition and after the end of addition.
The coagulant is preferably added dropwise as an aqueous solution from the viewpoint of controlling coagulation to obtain coagulated particles having a desired particle size, and the concentration of the coagulant aqueous solution is preferably 2% by mass or more, and more preferably 4% by mass. The above is more preferably 6 mass% or more, and preferably 40 mass% or less, more preferably 30 mass% or less, and further preferably 20 mass% or less.
Further, from the viewpoint of controlling aggregation to obtain aggregated particles having a desired particle size and particle size distribution, it is preferable to adjust the pH of the aqueous solution of the aggregating agent to 7.0 or more and 9.0 or less before use.
The dropping time of the aggregating agent is preferably 1 minute or more, more preferably 3 minutes or more, from the viewpoint of controlling aggregation to obtain aggregated particles having a desired particle size, and from the viewpoint of improving toner productivity. It is preferably 120 minutes or less, more preferably 30 minutes or less, still more preferably 10 minutes or less.
The temperature at which the aggregating agent is dropped is preferably 0° C. or higher, more preferably 10° C. or higher, further preferably 20° C. or higher, and preferably 40° C. or lower, from the viewpoint of improving toner productivity. The temperature is more preferably 35°C or lower, further preferably 30°C or lower.

Furthermore, from the viewpoint of promoting aggregation and obtaining aggregated particles having a desired particle size and particle size distribution, it is preferable to raise the temperature of the dispersion after adding the aggregating agent. The holding temperature is preferably 45° C. or higher, more preferably 50° C. or higher, and further preferably 55° C. or higher from the viewpoint of improving the low temperature fixability of the obtained toner and the low temperature fixability after high temperature and high humidity storage. , And preferably 70° C. or lower, more preferably 65° C. or lower, still more preferably 60° C. or lower.
It is preferable to confirm the progress of aggregation by monitoring the volume median particle diameter of the aggregated particles in the temperature range.
The volume median particle diameter (D ₅₀ ) of the obtained aggregated particles (1) is preferably 2 μm or more, more preferably from the viewpoint of improving the low temperature fixability of the obtained toner and the low temperature fixability after high temperature and high humidity storage. It is 3 μm or more, more preferably 4 μm or more, and preferably 10 μm or less, more preferably 8 μm or less, still more preferably 6 μm or less. The volume median particle size of the agglomerated particles can be determined by the method described in Examples below.

<Process (3B)>
In the step (3B), the resin particles (E) containing the amorphous resin (Bs) are added to the agglomerated particles (1) obtained in the step (3A), and the resin particles are added to the agglomerated particles (1). In this step, (E) is attached to obtain agglomerated particles (2).
The step (3) can improve the low temperature fixability of the toner and the low temperature fixability after high temperature and high humidity storage, which are the effects of the present invention, only by the step (3A), but by further performing the step (3B). The crystalline resin (A) and the wax (W2) finely dispersed in the agglomerated particles (1) become more difficult to detach during fusion of the particles in the agglomerated particles in the next step (4). It is considered that the exposure of the wax (W2) to the surface of the obtained toner mother particles can be further suppressed.
[Agglomerated particles (2)]
The aggregated particles (1) can be aggregated with the resin particles (E) containing the amorphous resin (Bs) to obtain the aggregated particles (2). By passing through the aggregated particles (2), it is possible to obtain toner mother particles having a core-shell structure in which the component of the aggregated particles (1) is contained in the core portion and the amorphous resin is contained in the shell portion.

<<Resin particles (E)>>
The resin particles (E) are preferably obtained as a dispersion liquid of the resin particles (E) by dispersing a resin component containing an amorphous polyester as the amorphous resin (Bs) in an aqueous medium.
The amorphous polyester can be obtained by polycondensing a polyhydric alcohol component (bs-al) and a polyvalent carboxylic acid component (bs-ac).
(Polyhydric alcohol component (bs-al))
The polyhydric alcohol component (bs-al) contains 80 mol of an alkylene oxide adduct of bisphenol A from the viewpoint of obtaining a toner having excellent low-temperature fixability and low-temperature fixability after high-temperature and high-humidity storage and also excellent charge stability. % Or more is preferable. From the same viewpoint, the content of the alkylene oxide adduct of bisphenol A in the polyhydric alcohol component (bs-al) is preferably 80 mol% or more, more preferably 90 mol% or more, still more preferably 95 mol% or more. , More preferably 98 mol% or more, and 100 mol% or less, even more preferably 100 mol%.

The alkylene oxide adduct of bisphenol A is preferably an ethylene oxide adduct of bisphenol A (polyoxyethylene-2,2-bis(4-hydroxyphenyl)propane) and a propylene oxide adduct of bisphenol A (polyoxypropylene-). 2,2-bis(4-hydroxyphenyl)propane), and more preferably an ethylene oxide adduct of bisphenol A.

The average number of moles of alkylene oxide added to the alkylene oxide adduct of bisphenol A is preferably 1 or more from the viewpoint of obtaining a toner having excellent low-temperature fixability and low-temperature fixability after high-temperature and high-humidity storage and also excellent charge stability. , More preferably 1.2 or more, still more preferably 1.5 or more, and preferably 16 or less, more preferably 12 or less, even more preferably 8 or less, even more preferably 4 or less.

The polyhydric alcohol component (bs-al) may contain a polyhydric alcohol other than the alkylene oxide adduct of bisphenol A. The other polyhydric alcohol component that may be contained in the polyhydric alcohol component (bs-al) is a polyhydric alcohol component (b) that is a raw material for producing the polyester portion (b2) of the amorphous resin (B) described above. -Al) are exemplified.
The polyhydric alcohol component may be used alone or in combination of two or more.

(Polyvalent carboxylic acid component (bs-ac))
As the polyvalent carboxylic acid component (bs-ac), those exemplified in the polyvalent carboxylic acid component (b-ac) which is a raw material for producing the polyester portion (b2) of the amorphous resin (B) described above. Is mentioned. Among the exemplified dicarboxylic acids, terephthalic acid, fumaric acid, dodecenylsuccinic acid and the like are used as the dicarboxylic acid from the viewpoint of obtaining a toner having excellent low-temperature fixability and low-temperature fixability after high-temperature and high-humidity storage, and also excellent charge stability. Anhydride is preferable, and as the trivalent or higher polycarboxylic acid, trimellitic anhydride is preferable. From the same viewpoint, it is more preferable to use these in combination.
The equivalent ratio (COOH group/OH group) of the polyhydric carboxylic acid component to the polyhydric alcohol component is excellent in low-temperature fixability and low-temperature fixability after storage at high temperature and high humidity, and from the viewpoint of obtaining a toner having excellent charge stability. , Preferably 0.7 or more, more preferably 0.8 or more, and preferably 1.3 or less, more preferably 1.2 or less.
As the reaction conditions such as the reaction temperature of the polycondensation reaction, the esterification catalyst, and the esterification cocatalyst, the conditions shown in the production of the polyester segment of the amorphous resin (B) can be applied.

[Physical Properties of Amorphous Resin (Bs)]
The softening point of the amorphous resin (Bs) is preferably 90° C. or higher, and more preferably from the viewpoint of obtaining a toner having excellent low-temperature fixability and low-temperature fixability after high-temperature and high-humidity storage, and also excellent charge stability. It is 100° C. or higher, more preferably 110° C. or higher, and preferably 160° C. or lower, more preferably 140° C. or lower, still more preferably 130° C. or lower.

From the same viewpoint, the glass transition temperature of the amorphous resin (Bs) is preferably 40° C. or higher, more preferably 50° C. or higher, further preferably 60° C. or higher, and preferably 90° C. or lower, more preferably Is 80° C. or lower, and more preferably 70° C. or lower.

The acid value of the amorphous resin (Bs) is excellent from the viewpoint of improving the dispersion stability of the resin particles (E), the low-temperature fixability and the low-temperature fixability after high-temperature and high-humidity storage, and also the charge stability. From the viewpoint of obtaining a toner, it is preferably 5 mgKOH/g or more, more preferably 10 mgKOH/g or more, further preferably 15 mgKOH/g or more, and preferably 35 mgKOH/g or less, more preferably 30 mgKOH/g or less, further preferably Is 25 mgKOH/g or less.

The hydroxyl value of the amorphous resin (Bs) is preferably 4 mgKOH/g or more, and more preferably from the viewpoint of obtaining a toner having excellent low-temperature fixability and low-temperature fixability after high-temperature and high-humidity storage and also excellent charge stability. Is 7 mgKOH/g or more, more preferably 10 mgKOH/g or more, and preferably 40 mgKOH/g or less, more preferably 25 mgKOH/g or less, further preferably 15 mgKOH/g or less.

The softening point, glass transition temperature, acid value and hydroxyl value of the amorphous resin (Bs) can be appropriately adjusted according to the types and ratios of the raw material monomers, and the production conditions such as reaction temperature, reaction time and cooling rate. Also, those values are obtained by the method described in the examples.
When two or more amorphous resins are used in combination, it is preferable that the softening point, glass transition temperature and acid value obtained as a mixture thereof are within the above ranges.

As in the case of the resin particles (D), the method for obtaining the dispersion is preferably a method in which an aqueous medium is gradually added to an organic solvent solution of a resin and the like to perform phase inversion emulsification.
Also as the phase inversion emulsification method, as in the case of the resin particles (D), a method of performing phase inversion emulsification by adding an aqueous medium to a solution obtained by dissolving the resin and other optional components described above in an organic solvent. preferable. Preferred embodiments of the aqueous medium and the organic solvent that can be used are the same as the aqueous medium and the organic solvent used in the method for producing the resin particles (D). The mass ratio of the aqueous medium and the organic solvent, the temperature at which the aqueous medium is added, and the addition rate of the aqueous medium are the same as in the method for producing the resin particles (D).

In the step (3B), the resin particles (E) are added to the agglomerated particles (1) obtained in the step (3A), and the resin particles (E) are attached to the agglomerated particles (1) ( In the step of obtaining 2), the resin particles (E) are further adhered to the aggregated particles (1) by adding the dispersion liquid of the resin particles (E) to the dispersion liquid of the above-mentioned aggregated particles (1), It is preferred to obtain a dispersion of aggregated particles (2).
Before adding the dispersion liquid of the resin particles (E) to the dispersion liquid of the aggregated particles (1), an aqueous medium may be added to the dispersion liquid of the aggregated particles (1) to dilute it. When the dispersion liquid of the resin particles (E) is added to the dispersion liquid of the agglomerated particles (1), in order to efficiently attach the resin particles (E) to the agglomerated particles (1), the aggregating agent is added. It may be used in the step (3B).
The temperature at which the dispersion liquid of the resin particles (E) is added is preferably 40° C. or higher from the viewpoint of obtaining a toner having excellent low-temperature fixability and low-temperature fixability after high-temperature and high-humidity storage and also excellent charging stability. , More preferably 45° C. or higher, still more preferably 50° C. or higher, and preferably 80° C. or lower, more preferably 70° C. or lower, still more preferably 65° C. or lower.

The dispersion liquid of the resin particles (E) may be added continuously over a certain period of time, may be added at one time, or may be divided and added in a plurality of times. It is preferable to add them continuously over a period of time or to divide them into a plurality of times for addition. By adding as described above, the resin particles (E) are likely to selectively adhere to the aggregated particles (1). Above all, from the viewpoint of promoting selective adhesion and improving the productivity of the toner, it is preferable to continuously add them over a certain period of time.

The addition rate in the case of continuous addition is from the viewpoint of obtaining uniform aggregated particles (2) and the viewpoint of improving the productivity of the toner, with respect to 100 parts by weight of aggregated particles (1), resin particles (E) are added. Is preferably 0.03 parts by mass/min or more, more preferably 0.07 parts by mass/min or more, and preferably 1.0 parts by mass/min or less, more preferably 0.5 parts by mass/min. Below, it is 0.3 mass part/min or less more preferably.
From the viewpoint of obtaining a toner having excellent low-temperature fixability and low-temperature fixability after high-temperature and high-humidity storage and also excellent charge stability, the addition amount of the resin particles (E) and the resin particles (E) are And the mass ratio [(E)/(D)] is preferably 0.05 or more, more preferably 0.1 or more, still more preferably 0.13 or more, still more preferably 0.15 or more, and The amount is preferably 0.5 or less, more preferably 0.3 or less, still more preferably 0.2 or less.
The volume median particle diameter (D ₅₀ ) of the aggregated particles (2) improves the viewpoint of obtaining a toner capable of obtaining a high quality image, and the low temperature fixability of the obtained toner and the low temperature fixability after high temperature and high humidity storage. From the viewpoint, it is preferably 2 μm or more, more preferably 3 μm or more, still more preferably 4 μm or more, and preferably 10 μm or less, more preferably 9 μm or less, further preferably 8 μm or less.
In the step (3), the aggregation may be stopped when the aggregated particles have grown to have an appropriate particle size as a toner.
Examples of the method of stopping the aggregation include a method of cooling the dispersion liquid, a method of adding an aggregation stopper, a method of diluting the dispersion liquid, and the like. From the viewpoint of surely preventing unnecessary aggregation, a method of adding an aggregation stopper to stop the aggregation is preferable.

<<Flocculating agent>>
As the aggregation stopper, a surfactant is preferable, and an anionic surfactant is more preferable. Examples of the anionic surfactant include alkylbenzene sulfonate, alkyl sulfate, alkyl ether sulfate, polyoxyalkylene alkyl ether sulfate and the like. Among these, polyoxyalkylene alkyl ether sulfate is preferable, polyoxyethylene lauryl ether sulfate is more preferable, and sodium polyoxyethylene lauryl ether sulfate is further preferable.

The aggregation terminator may be used alone or in combination of two or more kinds.
The addition amount of the aggregation terminator is preferably 0.1 parts by mass or more, and more preferably 1 part by mass or more, based on 100 parts by mass of the total amount of the resin in the toner, from the viewpoint of reliably preventing unnecessary aggregation. The amount is more preferably 2 parts by mass or more, and preferably 15 parts by mass or less, more preferably 10 parts by mass or less, and further preferably 7 parts by mass or less from the viewpoint of reducing the residue on the toner. The aggregation stopper is preferably added as an aqueous solution from the viewpoint of improving the productivity of the toner.

From the viewpoint of improving the productivity of the toner, the temperature at which the aggregation stopper is added is preferably the same as the temperature at which the dispersion liquid of aggregated particles is held. The temperature is preferably 40° C. or higher, more preferably 45° C. or higher, even more preferably 50° C. or higher, and preferably 80° C. or lower, more preferably 70° C. or lower, further preferably 65° C. or lower.
Further, from the viewpoint of stabilizing the aggregated particles and preventing the particles that have once aggregated from being dispersed before fusion bonding, it is preferable to add an acid together with the termination of aggregation to make the dispersion liquid of the aggregated particles neutral to acidic. ..
The acid to be added is not limited and, for example, sulfuric acid, hydrochloric acid, nitric acid, phosphoric acid, acetic acid and the like are preferably mentioned, but from the viewpoint of rapid pH change with respect to addition, hydrochloric acid, sulfuric acid, nitric acid and acetic acid are preferable. At least one selected from the group consisting of hydrochloric acid, sulfuric acid, and nitric acid, and more preferably sulfuric acid.
The acid is preferably added as an aqueous solution. Further, it may be added together with the aggregation stopper.

<Step (4)>
Step (4) is a step of fusing the aggregated particles obtained in step (3).
Here, the "aggregated particles obtained in the step (3)" means the aggregated particles (1) obtained in the step (3A) when the step (3B) is not carried out, and the step (3B) When carrying out, it means the aggregated particles (2) obtained in the step (3B).
In this step, the particles in the agglomerated particles obtained in the step (3), which were mainly in a state of physically adhering to each other, are fused and integrated to form fused particles.
When the aggregated particles (2) are fused, toner base particles having a core-shell structure can be obtained.

In this step, the crystalline resin (from the viewpoint of improving the fusion property of the agglomerated particles, and from the viewpoint of obtaining a toner having excellent low-temperature fixability and low-temperature fixability after high-temperature and high-humidity storage and also excellent charging stability, It is preferable to maintain the temperature at 10° C. or more lower than the melting point of A).
The holding temperature is more preferably 5° C. or more lower than the melting point of the crystalline resin (A), and further preferably a crystalline resin, from the viewpoint of improving the fusion property of the aggregated particles and the productivity of the toner. It is equal to or higher than the melting point of (A).

At that time, from the viewpoint of obtaining a toner excellent in low-temperature fixability and low-temperature fixability after high-temperature and high-humidity storage, a time of holding at a temperature 10° C. lower than the melting point of the crystalline resin (A) is obtained. , Preferably 1 minute or more, more preferably 10 minutes or more, further preferably 30 minutes or more, and preferably 240 minutes or less, more preferably 180 minutes or less, still more preferably 120 minutes or less, even more preferably 90 minutes or less. It is less than a minute.

The volume median particle size (D ₅₀ ) of the fused particles in the dispersion obtained in the step (4) is excellent in low-temperature fixability and low-temperature fixability after high-temperature and high-humidity storage, and is also excellent in charging stability. From the viewpoint of obtaining the above, it is preferably 2 μm or more, more preferably 3 μm or more, still more preferably 4 μm or more, and preferably 10 μm or less, more preferably 8 μm or less, still more preferably 6 μm or less. Further, the circularity of the fused particles in the dispersion liquid is preferably 0.955 or more, from the viewpoint of obtaining a toner having excellent low-temperature fixability and low-temperature fixability after high-temperature and high-humidity storage, and also excellent charging stability. It is more preferably 0.960 or more, still more preferably 0.965 or more, and preferably 0.990 or less, more preferably 0.985 or less, still more preferably 0.980 or less.

<Post-treatment process>
A post-treatment step may be carried out after the step (4), and it is preferable to obtain fused toner particles as toner mother particles by isolating the fused particles from the dispersion liquid obtained in the step (4).
Since the fused particles in the dispersion liquid obtained in the step (4) are present in the aqueous medium, it is preferable to first perform solid-liquid separation. A suction filtration method or the like is preferably used for solid-liquid separation.
It is preferable to perform washing after solid-liquid separation. At this time, since it is preferable to remove the added surfactant, it is preferable to wash with an aqueous medium below the cloud point of the surfactant. It is preferable to perform the washing a plurality of times.

Next, it is preferable to perform drying. The temperature at the time of drying is preferably such that the temperature of the fused particles themselves is lower than the minimum value of the glass transition temperature of the resin constituting the resin particles. As a drying method, it is preferable to use a vacuum low temperature drying method, a vibration type fluidized drying method, a spray drying method, a freeze drying method, a flash jet method, or the like. The water content after drying is adjusted to preferably 1.5% by mass or less, more preferably 1.0% by mass or less, from the viewpoint of improving the charging property of the toner.
By drying the fused particles, toner mother particles can be obtained.

(2) Melt-kneading method The method (2) is preferably a step of melt-kneading a mixture containing a resin composition (C) and a wax (W2), and pulverizing the melt-kneaded material obtained in the above step. And classifying.
Examples of the wax (W2) used in the method (2) include the same preferable examples as the above-mentioned wax (W2).

In the step of melt-kneading, it is preferable to further melt-knead the colorant, and it is also preferable to melt-knead together other additives such as other wax and charge control agent.

The melt kneading can be performed using a known kneader such as a closed kneader, a single-screw extruder, a twin-screw extruder, or an open roll kneader.

It is preferable that the resin, the colorant, the charge control agent, and the toner raw material such as wax are mixed in advance with a mixer such as a Henschel mixer or a ball mill and then supplied to the kneader.

The set temperature (barrel set temperature) of the twin-screw extruder is appropriately set so that the temperature K _t falls within a predetermined range, but is preferably 50° C. or higher, more preferably 60° C. or higher, and It is preferably 160°C or lower, more preferably 140°C or lower.

The rotation speed is the same-direction rotating biaxial from the viewpoint of improving the dispersibility of additives such as colorants, charge control agents and waxes in the toner, and reducing mechanical force during melt kneading and suppressing heat generation. In the case of an extruder, it is preferably 100 r/min or more, more preferably 130 r/min or more, more preferably 150 r/min or more, and preferably 300 r/min or less, more preferably 280 r/min or less, more preferably It is 250 r/min or less.

The melt-kneaded product obtained in the above step is cooled to such an extent that it can be ground, and then subjected to the subsequent step.
The crushing process may be performed in multiple stages. For example, the resin kneaded product obtained by curing the melt kneaded product may be roughly crushed to a size of 1 mm or more and 5 mm or less, and then further pulverized to a desired particle size. The crusher used in the crushing step is not particularly limited, but examples of the crusher preferably used for coarse crushing include a hammer mill, an atomizer, and a rotoplex. Further, as a pulverizer preferably used for fine pulverization, a fluidized bed type jet mill, a collision plate type jet mill, a rotary type mechanical mill and the like can be mentioned. From the viewpoint of pulverization efficiency, it is preferable to use a fluidized bed type jet mill and a collision plate type jet mill, and more preferable to use a fluidized bed type jet mill.

Examples of the classifier used in the classifying process include a rotor classifier, an airflow classifier, an inertial classifier, and a sieve classifier. In the classification step, the pulverized product removed due to insufficient pulverization may be subjected to the pulverization step again, or the pulverization step and the classification step may be repeated if necessary.
By this step, toner base particles can be obtained.

[Toner for developing electrostatic image]
<Toner mother particles>
The toner mother particles obtained by the above-mentioned method can be used as they are as the toner for developing an electrostatic charge image, but it is preferable that the toner mother particles whose surface is treated as described below are used as the toner for developing an electrostatic charge image. preferable.

In the toner mother particles, the total content of the crystalline resin (A) with respect to the total content of the crystalline resin (A) and the amorphous resin (B) is the low temperature fixability and the low temperature fixability after high temperature and high humidity storage. From the viewpoint of obtaining a toner excellent in charging stability and further excellent in charging stability, it is preferably 5% by mass or more, more preferably 10% by mass or more, further preferably 15% by mass or more, and preferably 45% by mass or less, It is more preferably 40% by mass or less, still more preferably 35% by mass or less.
The total content of the crystalline resin (A) is based on the total amount of resin components in the toner from the viewpoint of obtaining a toner having excellent low-temperature fixability and low-temperature fixability after high-temperature and high-humidity storage and also excellent charge stability. It is preferably 5% by mass or more, more preferably 10% by mass or more, further preferably 15% by mass or more, and preferably 45% by mass or less, more preferably 40% by mass or less, further preferably 35% by mass. It is as follows.
The "total content of the crystalline resin (A)" means the crystalline resin (A) added as a raw material of the resin composition (C) and the crystalline resin (A) added in another step. Means the total amount of.

The volume median particle diameter (D ₅₀ ) of the toner mother particles is preferably 2 μm or more, from the viewpoint of obtaining a toner having excellent low-temperature fixability and low-temperature fixability after storage at high temperature and high humidity, and also excellent charging stability. It is preferably 3 μm or more, more preferably 4 μm or more, and preferably 10 μm or less, more preferably 8 μm or less, still more preferably 6 μm or less.
The CV value of the toner mother particles is preferably 12% or more, more preferably 14% or more, still more preferably 16% or more, from the viewpoint of improving toner productivity, and from the viewpoint of obtaining a high-quality image. , Preferably 30% or less, more preferably 26% or less

The circularity of the toner base particles is preferably 0.955 or more, and more preferably 0.960, from the viewpoint of obtaining a toner having excellent low-temperature fixability and low-temperature fixability after high-temperature and high-humidity storage and also excellent charge stability. The above is more preferably 0.965 or more, and preferably 0.990 or less, more preferably 0.985 or less, still more preferably 0.980 or less.

The toner for developing an electrostatic image is preferably one obtained by adding a fluidizing agent or the like as an external additive to the surface of toner mother particles.
Examples of the external additive include hydrophobic silica, titanium oxide fine particles, alumina fine particles, cerium oxide fine particles, inorganic fine particles such as carbon black, and polymer fine particles such as polycarbonate, polymethylmethacrylate, and silicone resin. , Hydrophobic silica is preferred.
When an external additive is used, the addition amount of the external additive is preferably 1 part by mass or more, more preferably 2 parts by mass or more, still more preferably 3 parts by mass or more, relative to 100 parts by mass of the toner mother particles. And it is preferably 5 parts by mass or less, more preferably 4.5 parts by mass or less, and further preferably 4 parts by mass or less.

The toner for developing an electrostatic image can be used as a one-component developer or a two-component developer mixed with a carrier.

With respect to the above-described embodiments, the present invention further discloses the following electrostatic charge image developing toner and a method for producing the electrostatic charge image developing toner.
<1> At least one of the crystalline resin (A) and the amorphous resin (B) having a constituent component (b1) derived from a hydrocarbon wax (W1) having a hydroxyl group or a carboxy group and a polyester portion (b2). A toner for developing an electrostatic charge image, which comprises a resin composition (C) containing a reaction product obtained by a reaction of chemically bonding parts.
<2> The crystalline resin (A) and the amorphous resin (B) having a constituent component (b1) derived from a hydrocarbon wax (W1) having a hydroxyl group or a carboxy group and a polyester portion (b2) are prepared by the above-mentioned crystal For developing an electrostatic charge image, containing a resin composition (C) containing a reaction product obtained by a reaction of chemically bonding at least a part of the crystalline resin (A) terminal and the amorphous resin (B) terminal toner.
<3> The electrostatic image developing toner according to <1> or <2>, wherein the crystalline resin (A) is a crystalline polyester.
<4> The crystalline polyester is obtained by polycondensing a polyhydric alcohol component (a-al) and a polyvalent carboxylic acid component (a-ac), and the electrostatic charge according to <3> above. Toner for image development.
<5> The polyhydric alcohol component (a-al) contains an α,ω-aliphatic diol, and the content of the α,ω-aliphatic diol in the polyhydric alcohol component (a-al) is preferably Is 80 mol% or more, more preferably 85 mol% or more, even more preferably 90 mol% or more, even more preferably 95 mol% or more, and 100 mol% or less, even more preferably 100 mol%. The toner for developing an electrostatic charge image according to the item <4>.
<6> The α,ω-aliphatic diol is preferably selected from ethylene glycol, 1,6-hexanediol, 1,9-nonanediol, 1,10-decanediol and 1,12-dodecanediol. <1> or more, more preferably one or more selected from 1,6-hexanediol, 1,10-decanediol, and 1,12-dodecanediol, and further preferably 1,10-decanediol. <5> The toner for developing an electrostatic image as described in 1.
<7> The polyvalent carboxylic acid component (a-ac) contains an aliphatic dicarboxylic acid, and the content of the aliphatic dicarboxylic acid in the polyvalent carboxylic acid component (a-ac) is preferably 80 mol% or more. More preferably 85 mol% or more, still more preferably 90 mol% or more, even more preferably 95 mol% or more, and 100 mol% or less, still more preferably 100 mol%, the above <4. > To <6>, the toner for developing an electrostatic charge image according to any one of <> to <6>.
<8> The polyvalent carboxylic acid component (a-ac) is preferably one or more selected from sebacic acid, dodecanedioic acid, and tetradecanedioic acid, more preferably sebacic acid. 7> The toner for developing an electrostatic charge image according to any one of 7>.
<9> The softening point of the crystalline resin (A) is preferably 60° C. or higher, more preferably 70° C. or higher, further preferably 80° C. or higher, and preferably 150° C. or lower, more preferably 120° C. The toner for developing an electrostatic charge image according to any one of the items <1> to <8>, which is more preferably 100° C. or less.
<10> The crystalline resin (A) has a melting point of preferably 50° C. or higher, more preferably 60° C. or higher, even more preferably 70° C. or higher, and preferably 100° C. or lower, more preferably 90° C. or lower. The toner for developing an electrostatic charge image according to any one of the items <1> to <9>, which is more preferably 80° C. or lower.
<11> The hydroxyl value of the crystalline resin (A) is preferably 3 mgKOH/g or more, more preferably 5 mgKOH/g or more, and preferably 35 mgKOH/g or less, more preferably 25 mgKOH/g or less, The toner for developing an electrostatic charge image according to any one of <1> to <10>, which is preferably 20 mgKOH/g or less.

<12> The component (b1) derived from the hydrocarbon wax (W1) of the amorphous resin (B) is a component derived from a hydrocarbon wax having both a hydroxyl group and a carboxy group. <11> The toner for developing an electrostatic charge image according to any one of <11>.
The acid value of the <13> hydrocarbon wax (W1) is preferably 1 mgKOH/g or more, more preferably 5 mgKOH/g or more, even more preferably 8 mgKOH/g or more, even more preferably 15 mgKOH/g or more, and The toner for developing an electrostatic charge image according to any one of <1> to <12>, which is preferably 30 mgKOH/g or less, more preferably 25 mgKOH/g or less, further preferably 20 mgKOH/g or less.
<14> The hydrocarbon wax (W1) has a hydroxyl value of preferably 40 mgKOH/g or more, more preferably 50 mgKOH/g or more, still more preferably 70 mgKOH/g or more, still more preferably 90 mgKOH/g or more, and , Preferably 180 mgKOH/g or less, more preferably 150 mgKOH/g or less, still more preferably 120 mgKOH/g or less, still more preferably 100 mgKOH/g or less, and the static amount according to any one of <1> to <13> above. Toner for charge image development.
<15> The total of the hydroxyl value and the acid value of the hydrocarbon wax (W1) is preferably 41 mgKOH/g or more, more preferably 55 mgKOH/g or more, even more preferably 80 mgKOH/g or more, even more preferably 90 mgKOH/g. Or more, more preferably 110 mgKOH/g or more, and preferably 210 mgKOH/g or less, more preferably 175 mgKOH/g or less, even more preferably 140 mgKOH/g or less, even more preferably 120 mgKOH/g or less, The toner for developing an electrostatic charge image according to any one of <1> to <14>.
<16> The melting point of the hydrocarbon wax (W1) is preferably 50° C. or higher, more preferably 60° C. or higher, even more preferably 70° C. or higher, even more preferably 75° C. or higher, and preferably 120° C. Or less, more preferably 110° C. or lower, further preferably 100° C. or lower, still more preferably 95° C. or lower, still more preferably 80° C. or lower, and the electrostatic charge according to any one of the above items <1> to <15>. Toner for image development.
The number average molecular weight of the <17> hydrocarbon wax (W1) is preferably 500 or more, from the viewpoint of obtaining a toner having excellent low-temperature fixability and low-temperature fixability after high-temperature and high-humidity storage, and also excellent charge stability. It is preferably 600 or more, more preferably 700 or more, and preferably 2000 or less, more preferably 1700 or less, still more preferably 1500 or less, even more preferably 1200 or less, still more preferably 900 or less, 1> to <16>, the toner for developing an electrostatic charge image.

<18> The content of the constituent component derived from the hydrocarbon wax (W1) contained in the amorphous resin (B) in the amorphous resin (B) is preferably 1% by mass or more, more preferably 3% by mass. Or more, and preferably 20% by mass or less, more preferably 15% by mass or less, still more preferably 12% by mass or less, for electrostatic image development according to any one of <1> to <17> above. toner.
<19> The polyester portion (b2) is a polyester portion (b2) obtained by polycondensing a polyhydric alcohol component (b-al) and a polyvalent carboxylic acid component (b-ac), <1. > To <18>, the toner for developing an electrostatic charge image according to any one of <> to <18>.
<20> The polyhydric alcohol component (b-al) contains an alkylene oxide adduct of bisphenol A, and the content of the alkylene oxide adduct of bisphenol A in the polyhydric alcohol component (b-al) is preferably 80 mol% or more, more preferably 90 mol% or more, even more preferably 95 mol% or more, even more preferably 98 mol% or more, and 100 mol% or less, even more preferably 100 mol%. The electrostatic image developing toner according to <19>.
<21> The electrostatic image developing toner according to <20>, wherein the alkylene oxide adduct of bisphenol A is a propylene oxide adduct of bisphenol A.
<22> The hydroxyl value of the amorphous resin (B) is preferably 4 mgKOH/g or more, more preferably 7 mgKOH/g or more, further preferably 10 mgKOH/g or more, and preferably 40 mgKOH/g or less, The toner for developing an electrostatic charge image according to any one of <1> to <21>, which is more preferably 30 mgKOH/g or less, further preferably 20 mgKOH/g or less.
<23> The mass ratio [(A)/(B)] of the crystalline resin (A) and the amorphous resin (B) is preferably 2/98 or more, more preferably 5/95 or more, and further preferably 10/90 or more, and preferably 45/55 or less, more preferably 40/60 or less, further preferably 35/65 or less, still more preferably 30/70 or less, <1> to <22 > The toner for developing an electrostatic charge image according to any one of <1>.
<24> The total amount of the crystalline resin (A) and the amorphous resin (B) used is preferably 70% by mass or more, more preferably 90% by mass or more, in the resin components constituting the resin composition (C). Any of the above <1> to <23>, further preferably 95 mass% or more, further preferably 98 mass% or more, and preferably 100 mass% or less, still more preferably 100 mass%. The toner for developing an electrostatic image as described in 1.

<25> The toner for developing an electrostatic charge image according to any one of <1> to <24>, wherein a polyfunctional compound (S) is used in the reaction.
<26> The electrostatic charge image developing toner according to any one of <1> to <25>, wherein the resin composition (C) is obtained by the following steps (1-1) and (1-2).
Step (1-1): Introduce a functional group with a polyfunctional compound (S) into one resin (i) selected from the group X consisting of the crystalline resin (A) and the amorphous resin (B). Step (1-2): reacting the reaction intermediate with a resin (ii) selected from the group X and different from the resin (i) <27> The polyfunctional compound The toner for developing an electrostatic charge image according to <26>, wherein the compound (S) is a diisocyanate compound.
<28> The toner for developing an electrostatic charge image according to <26> or <27>, wherein the crystalline resin (A) is selected as the resin (i) and the amorphous resin (B) is selected as the resin (ii). ..
The molar ratio (OH/NCO) of the hydroxyl group of the <29> resin (i) to the isocyanate group of the diisocyanate compound is preferably 1.0 or less, more preferably less than 1.0, and preferably 0.1. The toner for developing an electrostatic charge image according to <27> or <28> above, more preferably 0.25 or more, and further preferably 0.3 or more.
<30> The equivalent ratio of the diisocyanate compound used in the reaction with the hydroxyl group of the resin (i) is preferably 0.70 or more, more preferably 0.80 or more, still more preferably 0.90 or more, still more preferably Is 1.00 or more, and is preferably 1.20 or less, more preferably 1.10 or less, and still more preferably 1.05 or less, according to any one of the items <27> to <29>. Toner for charge image development.
Equivalent ratio of diisocyanate compound={mass of diisocyanate compound (g)/molecular weight of diisocyanate compound}/[{hydroxyl value of resin (i) (mgKOH/g) x blending amount of resin (i)}/ (56×1000)]
<31> The electrostatic image development according to any one of <1> to <30>, wherein the resin composition (C) is obtained by the following steps (1-1′) and (1-2′). toner.
Step (1-1'): Step of Obtaining Reaction Intermediate by Introducing Isocyanate Group with Diisocyanate Compound at Terminal of Crystalline Polyester Step (1-2'): Said Reaction Intermediate and Amorphous Resin (B <32> The total content of the crystalline resin (A) is preferably 5% by mass or more, more preferably 10% by mass or more, based on the total amount of the resin components in the toner. More preferably 15% by mass or more, and preferably 45% by mass or less, more preferably 40% by mass or less, further preferably 35% by mass or less, in any one of the above <1> to <31>. Toner for developing electrostatic images.

<33> The volume median particle diameter (D ₅₀ ) of the toner mother particles is preferably 2 μm or more, more preferably 3 μm or more, still more preferably 4 μm or more, and preferably 10 μm or less, more preferably 8 μm or less, The toner for developing an electrostatic charge image according to any one of <1> to <32>, which is more preferably 6 μm or less.
<34> The circularity of the toner mother particles is preferably 0.955 or more, more preferably 0.960 or more, still more preferably 0.965 or more, and preferably 0.990 or less, more preferably 0. The toner for developing an electrostatic charge image according to any one of <1> to <33>, which is 985 or less, more preferably 0.980 or less.
<35> At least one of the crystalline resin (A) and the amorphous resin (B) having a constituent component (b1) derived from a hydrocarbon wax (W1) having a hydroxyl group or a carboxy group and a polyester portion (b2) A resin composition containing a reaction product obtained by a reaction of chemically bonding parts.

<36> A method for producing a toner for developing an electrostatic charge image, which comprises the following steps (1) to (4).
Step (1): a crystalline resin (A) and an amorphous resin (B) having a constituent component (b1) derived from a hydrocarbon wax (W1) having a hydroxyl group or a carboxy group and a polyester portion (b2), Step of Obtaining Resin Composition (C) Containing Reaction Product Obtained by Reaction of Chemically Bonding At Least Part Step (2): Resin composition (C) obtained in step (1) in an aqueous medium To obtain a dispersion liquid of the resin particles (D) Step (3): A step of aggregating the resin particles (D) obtained in the Step (2) in an aqueous medium to obtain agglomerated particles Step (4 ): Step of fusing the aggregated particles obtained in step (3) <37> The electrostatic image development according to <36>, wherein the polyfunctional compound (S) is used in the reaction of step (1). For manufacturing toner for toner.
<38> The method for producing an electrostatic charge image developing toner according to <36> or <37>, wherein the step (1) is the following steps (1-1) and (1-2).
Step (1-1): Introduce a functional group with a polyfunctional compound (S) into one resin (i) selected from the group X consisting of the crystalline resin (A) and the amorphous resin (B). Step (1-2) of reacting the reaction intermediate with a resin (ii) of the group X selected from the group X and different from the resin (i)<39> In the step (3), the resin particles (D) obtained in the step (2) are aggregated in an aqueous medium in the presence of the wax (W2) to obtain aggregated particles (1). The method for producing an electrostatic charge image developing toner according to any one of <36> to <38>.
<40> The electrostatic charge according to any one of <36> to <39>, wherein the step (3) includes the following step (3A) and the step (3B) may be continuously performed. Method for producing toner for image development.
Step (3A): A step of aggregating the resin particles (D) obtained in the step (2) in an aqueous medium, preferably in the presence of a wax (W2), to obtain agglomerated particles (1) Step (3B) : Agglomerated particles (2) obtained by adding resin particles (E) containing an amorphous resin to the agglomerated particles (1) obtained in the step (3A) and adhering the resin particles (E). Process to obtain

Each property value was measured and evaluated by the following methods.
[Hydroxyl value and acid value]
The hydroxyl value and acid value of the resin and wax were measured according to the neutralization titration method described in JIS K 0070-1992. However, the measurement solvent was chloroform.

[Softening point, crystallinity index, melting point and glass transition temperature of resin]
(1) Using a softening point flow tester “CFT-500D” (manufactured by Shimadzu Corp.), a load of 1.96 MPa was applied by a plunger while heating 1 g of a sample at a heating rate of 6° C./min, and the diameter was increased. It was extruded from a nozzle having a length of 1 mm and a length of 1 mm. The plunger drop of the flow tester was plotted against the temperature, and the temperature at which half the sample flowed out was taken as the softening point.
(2) Crystallinity index Using a differential scanning calorimeter "Q100" (manufactured by TA Instruments Japan Co., Ltd.), 0.02 g of a sample was weighed in an aluminum pan, and the temperature decreasing rate from room temperature (25°C) to 10°C/ It was cooled to 0° C. in min. Then, the sample was allowed to stand for 1 minute as it was, and then the temperature was raised to 180° C. at a heating rate of 10° C./min to measure the amount of heat. Of the observed endothermic peaks, the temperature of the peak having the largest peak area is defined as the maximum endothermic peak temperature (1), and (softening point (°C))/(maximum endothermic peak temperature (1) (°C)) The crystallinity index was determined.
(3) Melting point and glass transition temperature Using a differential scanning calorimeter “Q100” (manufactured by TA Instruments Japan Co., Ltd.), 0.02 g of a sample was weighed in an aluminum pan and heated to 200° C., and the temperature was measured. To 0° C. at a temperature decrease rate of 10° C./min. Then, the sample was heated at a heating rate of 10° C./min to measure the amount of heat. Of the observed endothermic peaks, the temperature of the peak having the largest peak area was defined as the maximum endothermic peak temperature (2). In the case of crystalline resin, the peak temperature was taken as the melting point.
In the case of an amorphous resin, when a peak is observed, the temperature of the peak is measured. When a peak is not observed and a step is observed, the tangent line showing the maximum slope of the curve of the step and the step The temperature at the intersection with the extension line of the base line on the low temperature side was defined as the glass transition temperature.

[Wax melting point]
Using a differential scanning calorimeter "Q100" (manufactured by TA Instruments Japan Co., Ltd.), 0.02 g of the sample was weighed in an aluminum pan and heated to 200°C, and then the temperature lowering rate from 200°C was 10°C/min. It was cooled to 0°C. Then, the sample was heated at a heating rate of 10° C./min, the amount of heat was measured, and the maximum endothermic peak temperature was taken as the melting point.
[Hydroxyl value and acid value of wax]
It was measured according to JIS K 0070. However, the measurement solvent was a mixed solvent of xylene and ethanol (mass ratio; xylene:ethanol=3:5).
[Number average molecular weight (Mn) of wax]
The number average molecular weight (Mn) was measured by the gel permeation chromatography (GPC) method shown below.
(1) Preparation of Sample Solution The sample was dissolved in chloroform at 25° C. so that the concentration was 0.5 g/100 mL, and this solution was then mixed with a fluororesin filter having a pore size of 0.2 μm (product name: “DISMIC”, A sample solution was obtained by removing insoluble components by filtration using a model "25JP", manufactured by ADVANTEC.
(2) Measurement Chloroform as an eluent was caused to flow at a flow rate of 1 mL/min, the column was stabilized in a constant temperature bath at 40° C., and 100 μL of the sample solution was injected therein by using the following measuring device and analytical column. The molecular weight was measured. The molecular weight (number average molecular weight Mn) of the sample is several kinds of monodisperse polystyrene (product name: “TSKgel standard polystyrene”; type name (Mw): “A-500 (5.0×10 ² )”, “A1000(1 .01×10 ³ )”, “A2500 (2.63×10 ³ )”, “A-5000 (5.97×10 ³ )”, “F-1 (1.02×10 ⁴ )”, “F -2 (1.81 x 10 ⁴ )", "F-4 (3.97 x 10 ⁴ )", "F-10 (9.64 x 10 ⁴ )", "F-20 (1.90 x 10 ⁴ )" ⁵ )”, “F-40(4.27×10 ⁵ )”, “F-80(7.06×10 ⁵ )”, “F-128(1.09×10 ⁶ )”; (Manufactured by the company) was used as a standard sample and calculated based on a calibration curve prepared in advance.
・Measuring device: "HLC-8220GPC" (manufactured by Tosoh Corporation)
-Analytical column: "GMHXL" and "G3000HXL" (manufactured by Tosoh Corporation)

[Volume median particle diameter (D ₅₀ ) and CV value of resin particles, colorant particles, and wax particles]
(1) Measuring device: Laser diffraction type particle size measuring device "LA-920" (manufactured by Horiba Ltd.)
(2) Measurement conditions: Distilled water was added to the measurement cell, and the volume median particle diameter (D ₅₀ ) and the volume average particle diameter were measured at a concentration such that the absorbance was in an appropriate range. The CV value was calculated according to the following formula.
CV value (%)=(standard deviation of particle size distribution/volume average particle size)×100

[Solid content concentration of resin particle dispersion liquid, colorant dispersion liquid, and wax particle dispersion liquid]
Using an infrared moisture meter "FD-230" (manufactured by Ketsuto Scientific Laboratory Co., Ltd.), a measurement sample of 5 g was dried at a temperature of 150° C., measurement mode 96 (monitoring time 2.5 minutes, moisture content fluctuation range 0.05%). ), water content (mass %) was measured. The solid content concentration was calculated according to the following formula.
Solid content concentration (mass %)=100−water content (mass %)

[Amount of coarse particles in resin particle dispersion]
Using a centrifuge “Sigma 3-30KS” (manufactured by Sigma), 20 g of the resin particle dispersion liquid (solid content concentration 20 mass %) was centrifuged at 2500 rpm for 1 hour, and the mass of the precipitate was measured. The amount of coarse particles was calculated according to the following formula.
Amount of coarse particles (mass %) in resin particle dispersion = (mass of precipitate (g)/20) x 100

[Volume median particle diameter (D ₅₀ )]
The volume median particle diameter (D ₅₀ ) of the agglomerated particles was measured as follows.
・Measuring machine: "Coulter Multisizer (registered trademark) III" (manufactured by Beckman Coulter, Inc.)
・Aperture diameter: 50 μm
-Analysis software: "Multisizer (registered trademark) III version 3.51" (manufactured by Beckman Coulter, Inc.)
Electrolyte: "Isoton (registered trademark) II" (manufactured by Beckman Coulter, Inc.)
-Measurement conditions: The sample dispersion was added to 100 mL of the electrolytic solution to adjust the particle size of 30,000 particles to a concentration at which measurement was possible in 20 seconds, and then 30,000 particles were measured again, and the particle size was measured. The volume median particle size (D ₅₀ ) was determined from the distribution.

[Circularity of fused particles]
The circularity of the fused particles was measured under the following conditions.
・Measuring device: Flow-type particle image analyzer "FPIA-3000" (manufactured by Sysmex Corporation)
-Preparation of dispersion liquid: A dispersion liquid of fused particles (Ma) was diluted with deionized water so as to have a solid content concentration of 0.001 to 0.05 mass%.
・Measurement mode: HPF measurement mode

[Volume median particle diameter (D ₅₀ ) and CV value of toner mother particles]
The volume median particle diameter (D ₅₀ ) of the toner mother particles was measured as follows.
The measuring device, aperture diameter, analysis software, and electrolytic solution used were the same as those used in the measurement of the volume median particle diameter (D ₅₀ ) of the aggregated particles.
Dispersion: Polyoxyethylene lauryl ether "Emulgen (registered trademark) 109P" [manufactured by Kao Corporation, HLB (Hydrophile-Lipophile Balance) = 13.6] is dissolved in the electrolyte to obtain a dispersion having a concentration of 5% by mass. Got
Dispersion condition: 10 mg of the toner mother particle measurement sample after drying was added to 5 mL of the above dispersion liquid, dispersed for 1 minute with an ultrasonic disperser, and then 25 mL of the electrolytic solution was added, and further to the ultrasonic disperser. For 1 minute to prepare a sample dispersion liquid.
-Measurement conditions: The sample dispersion was added to 100 mL of the electrolytic solution to adjust the particle size of 30,000 particles to a concentration at which measurement was possible in 20 seconds, and then 30,000 particles were measured, and the particle size was measured. The volume median particle diameter (D ₅₀ ) and the volume average particle diameter were determined from the distribution.
The CV value (%) was calculated according to the following formula.
CV value (%)=(standard deviation of particle size distribution/volume average particle size)×100

[Low temperature fixability of toner and low temperature fixability after high temperature and high humidity storage]
<Low temperature fixability>
The commercially available printer "Microline (registered trademark) 5400" (manufactured by Oki Data Co., Ltd.) was used for the high-quality paper "J paper A4 size" (manufactured by Fuji Xerox Co., Ltd.), and the toner adhesion amount on the paper was 1.45 to 1 A solid image of 0.55 mg/cm ² was output at a length of 50 mm without fixing, leaving a blank portion of 5 mm from the upper end of the A4 paper.
Next, the printer in which the fixing device was modified to have a variable temperature was prepared, the temperature of the fixing device was set to 90° C., and the toner was fixed at a speed of 1.2 seconds per sheet in the A4 vertical direction to obtain a printed matter.
In the same manner, the temperature of the fixing device was increased by 5° C., the toner was fixed, and a printed matter was obtained.
A 50 mm long piece of mending tape "Scotch (registered trademark) Mending Tape 810" (Sumitomo 3M Co., Ltd., width 18 mm) was lightly applied from the blank area at the top edge of the printed matter to the solid image. After that, a weight of 500 g was placed and pressed back and forth once at a speed of 10 mm/s. Then, the attached tape was peeled from the lower end side at a peeling angle of 180° and a speed of 10 mm/s to obtain a printed matter after peeling the tape. 30 sheets of high-quality paper "Excellent White Paper A4 Size" (Okidata Co., Ltd.) are laid under the printed matter before and after the tape application, and the reflection image density of the fixed image part before and after the tape application of each printed matter is measured. , A spectrophotometer “SpectroEye” (manufactured by GretagMacbeth, irradiation conditions; standard light source D50, observation field of view 2°, density standard DINNB, absolute white standard), and the fixing ratio from each reflection image density according to the following formula: Was calculated.
Fixing rate (%)=(reflection image density after tape peeling/reflection image density before tape attachment)×100
The lowest temperature at which the fixing rate is 90% or more was defined as the lowest fixing temperature (T ₁ ). The lower the minimum fixing temperature is, the better the low-temperature fixing property is.
<Low temperature fixability after high temperature and high humidity storage>
After the toner was held in a constant temperature bath having a temperature of 40° C. and a humidity of 80% for 200 hours, the minimum fixing temperature (T ₂ ) after high temperature and high humidity storage was evaluated by the same method as the evaluation of the low temperature fixing property. The lower the minimum fixing temperature is, the better the low-temperature fixing property after high temperature and high humidity storage is.

[Toner charge stability]
0.6 g of the toner and 19.4 g of a ferrite carrier (ferrite core, silicone coat, saturation magnetization: 71 Am ^{2 /} kg) were put into a polypropylene bottle “PP sampler bottle wide mouth” (manufactured by Sanplatec Co., Ltd.) having a capacity of 50 mL, and the mixture was placed on a ball mill. After stirring for 20 minutes, 5 g was sampled and measured with a charge amount measuring device "q-test" (manufactured by Epping Co.) under the following measurement conditions.
・Toner Flow (ml/min): 160
・Electrode Voltage(V): 4000
・Deposition Time(s): 2
The median q/d was defined as the toner charge amount Q/d (fC/10 μm). At that time, the Specific Density (specific gravity) was 1.2 g/cm ^3, and the value of the volume median particle diameter (D ₅₀ ) of the toner was used as the Median Diameter. The obtained Q/d was connected by a straight line in the range of −0.4 to 0.4 (fC/10 μm), and a graph of the charge amount distribution was created.
The half-value width of the maximum peak of this charge amount distribution (the cut width when the distribution was cut at a value of half the maximum peak height in the distribution) was evaluated. The smaller the value, the narrower the distribution of charge amount, and the better the charge stability.

[Production of resin]
Production Example A1
(Production of crystalline resin A-1)
The inside of a four-necked flask having an internal volume of 10 L equipped with a nitrogen introduction tube, a dehydration tube, a stirrer, and a thermocouple was replaced with nitrogen, and 3471 g of 1,10-decanediol and 4029 g of sebacic acid were put therein. While stirring, the temperature was raised to 135° C., the temperature was kept at 135° C. for 3 hours, and then the temperature was raised from 135° C. to 200° C. over 10 hours. After that, 15 g of di(2-ethylhexanoic acid)tin(II) was added, and the mixture was further held at 200° C. for 1 hour, then the pressure in the flask was lowered, and the desired acid value was obtained at −8.3 kPa(G). The reaction was carried out to obtain crystalline resin A-1. The physical properties are shown in Table 1.

Production Examples A2 to A6
(Production of Crystalline Resins A-2 to A-6)
Crystalline resins A-2 to A-6 were obtained in the same manner as in Production Example A1 except that the raw material composition was changed as shown in Table 1. The physical properties are shown in Table 1.

Production Example B1
(Production of Amorphous Resin B-1)
The interior of a four-necked flask with an internal volume of 10 L equipped with a nitrogen introduction tube, a dehydration tube, a stirrer, and a thermocouple was replaced with nitrogen to give polyoxypropylene (2.2)-2,2-bis(4-hydroxyphenyl). ) Propane 4756 g, terephthalic acid 1805 g, Paracor 6490 (hydrocarbon wax manufactured by Nippon Seiro Co., Ltd.) 325 g, di(2-ethylhexanoic acid)tin (II) 35 g, and 3,4,5-trihydroxybenzoic acid 3 0.5 g was added, the temperature was raised to 235° C. with stirring under a nitrogen atmosphere, and the temperature was maintained at 235° C. for 5 hours, then the pressure in the flask was reduced, and the pressure was maintained at −8 kPa(G) for 1 hour. Then, after returning to atmospheric pressure, it cooled to 190 degreeC, 79 g of fumaric acid, 99 g of adipic acid, 261 g of trimellitic acid anhydride, and 3.5 g of 4-tert-butyl catechol were added, and it was 10 degreeC/hr to 210 degreeC. Then, the pressure in the flask was lowered, and the reaction was carried out at -4 kPa (G) to a desired softening point to obtain an amorphous resin B-1. The physical properties are shown in Table 2.

Production Example B2
(Production of Amorphous Resin B-2)
The interior of a four-necked flask with an internal volume of 10 L equipped with a nitrogen introduction tube, a dehydration tube, a stirrer, and a thermocouple was replaced with nitrogen to give polyoxypropylene (2.2)-2,2-bis(4-hydroxyphenyl). ) Propane 4724 g, terephthalic acid 2017 g, Paracor 6490 (manufactured by Nippon Seiro Co., Ltd.) 649 g, di(2-ethylhexanoic acid)tin (II) 35 g, and 3,4,5-trihydroxybenzoic acid 3.5 g The temperature was raised to 235° C. with stirring under a nitrogen atmosphere, and the temperature was maintained at 235° C. for 5 hours, then the pressure in the flask was reduced, and the pressure was maintained at −8 kPa (G) for 1 hour. Then, after returning to atmospheric pressure, it was cooled to 200° C., 259 g of trimellitic anhydride was added, the temperature was raised to 210° C. at 10° C./hr, and then the pressure in the flask was lowered to −4 kPa(G). The reaction was performed up to the desired softening point to obtain an amorphous resin B-2. The physical properties are shown in Table 2.

Production Example B3
(Production of Amorphous Resin B-3)
The interior of a four-necked flask with an internal volume of 10 L equipped with a nitrogen introduction tube, a dehydration tube, a stirrer, and a thermocouple was replaced with nitrogen to give polyoxypropylene (2.2)-2,2-bis(4-hydroxyphenyl). ) Propane 4752 g, terephthalic acid 1690 g, Paracor 6490 (manufactured by Nippon Seiro Co., Ltd.) 130 g, di(2-ethylhexanoic acid)tin (II) 35 g, and 3,4,5-trihydroxybenzoic acid 3.5 g are put. The temperature was raised to 235° C. with stirring under a nitrogen atmosphere, and the temperature was maintained at 235° C. for 5 hours, then the pressure in the flask was reduced, and the pressure was maintained at −8 kPa (G) for 1 hour. Then, after returning to atmospheric pressure, it was cooled to 190° C., 297 g of adipic acid and 261 g of trimellitic anhydride were added, the temperature was raised to 210° C. at 10° C./hr, and then the pressure in the flask was lowered, − The reaction was performed at 4 kPa (G) up to the desired softening point to obtain amorphous resin B-3. The physical properties are shown in Table 2.

Production Examples B4 to B6
(Production of Amorphous Resins B-4 to B-6)
Amorphous resins B-4 to B-6 were obtained in the same manner as in Production Example B1 except that the raw material composition was changed as shown in Table 2. The physical properties are shown in Table 2.

Production Example B7
(Production of Amorphous Resin B-7)
The interior of a four-necked flask with an internal volume of 10 L equipped with a nitrogen introduction tube, a dehydration tube, a stirrer, and a thermocouple was replaced with nitrogen to give polyoxypropylene (2.2)-2,2-bis(4-hydroxyphenyl). ) 4940 g of propane, 1523 g of terephthalic acid, 35 g of di(2-ethylhexanoic acid)tin(II), and 3.5 g of 3,4,5-trihydroxybenzoic acid were added, and the mixture was heated to 235° C. under stirring in a nitrogen atmosphere. After the temperature was raised and the temperature was maintained at 235° C. for 8 hours, the pressure in the flask was reduced and the pressure was maintained at −8 kPa(G) for 1 hour. Then, after returning to atmospheric pressure, it cooled to 190 degreeC, fumaric acid 164g, adipic acid 103g, trimellitic acid anhydride 271g, and 4-tert-butyl catechol 3.5g were added, and it was 10 degreeC/hr to 210 degreeC. Then, the pressure in the flask was lowered, and the reaction was performed at -10 kPa (G) to a desired softening point to obtain an amorphous resin B-7. The physical properties are shown in Table 2.

Production Example B8
(Production of Amorphous Resin Bs-1)
The interior of a four-necked flask with an internal volume of 10 L equipped with a nitrogen introduction tube, a dehydration tube, a stirrer, and a thermocouple was replaced with nitrogen to give polyoxyethylene (2.2)-2,2-bis(4-hydroxyphenyl). ) 5001 g of propane, 1788 g of terephthalic acid, 30 g of tin(II) di(2-ethylhexanoate), and 3.0 g of 3,4,5-trihydroxybenzoic acid were added, and the mixture was heated to 235° C. with stirring under a nitrogen atmosphere. After the temperature was raised and the temperature was maintained at 235° C. for 8 hours, the pressure in the flask was reduced and the pressure was maintained at −8 kPa(G) for 1 hour. Then, after returning to atmospheric pressure, it was cooled to 180° C., 179 g of fumaric acid, 206 g of dodecenylsuccinic anhydride, 325 g of trimellitic acid anhydride, and 3.8 g of 4-tert-butylcatechol were added, and 10° C. to 220° C. Then, the pressure in the flask was lowered, and the reaction was carried out at -10 kPa (G) to a desired softening point to obtain an amorphous resin Bs-1. The physical properties are shown in Table 2.

Production Example B9
(Production of Amorphous Composite Resin Bw-1)
The interior of a four-necked flask with an internal volume of 10 L equipped with a nitrogen introduction tube, a dehydration tube, a stirrer, and a thermocouple was replaced with nitrogen to give polyoxypropylene (2.2)-2,2-bis(4-hydroxyphenyl). ) 4313 g of propane, 818 g of terephthalic acid, 727 g of succinic acid, 30 g of tin(II) di(2-ethylhexanoate), and 3.0 g of 3,4,5-trihydroxybenzoic acid were added and stirred under a nitrogen atmosphere. The temperature in the flask was raised to 235° C., and the temperature in the flask was maintained at 235° C. for 5 hours. Then, after returning to atmospheric pressure, the mixture was cooled to 160° C., and while being kept at 160° C., a mixture of 2756 g of styrene, 689 g of stearyl methacrylate, 142 g of acrylic acid, and 413 g of dibutyl peroxide was added dropwise over 1 hour. Then, after holding at 160° C. for 30 minutes, the temperature is raised to 200° C., the pressure in the flask is further lowered, and the reaction is carried out up to a desired softening point at −8 kPa(G) to obtain an amorphous composite resin Bw−. Got 1. The physical properties are shown in Table 2.

[Production of resin composition]
Production Example C1
(Production of Resin Composition C-1)
In a container having an internal volume of 3 L equipped with a stirrer, a reflux condenser, a thermometer and a nitrogen introduction tube, under a nitrogen atmosphere, 60 g of the crystalline resin A-1, 60 g of methyl ethyl ketone dehydrated with molecular sieves, and di 0.3 g of (2-ethylhexanoic acid) tin (II) was added, the temperature was raised to 73° C. with stirring, and the resin was dissolved at 73° C. over 30 minutes. 2.4 g of isophorone diisocyanate was added to the obtained solution as a polyfunctional compound (S), and it hold|maintained at 73 degreeC for 1 hour.
Next, a solution prepared by dissolving 60 g of the amorphous resin B-1 in 60 g of methyl ethyl ketone was added to the solution and kept at 73° C. for 2 hours to obtain a methyl ethyl ketone solution of the resin composition C-1.

Production Example C2
(Production of Resin Composition C-2)
In Production Example C1, except that the solution obtained by dissolving 60 g of the amorphous resin B-1 in 60 g of methyl ethyl ketone was changed to the solution obtained by dissolving 140 g of the amorphous resin B-1 in 140 g of methyl ethyl ketone, respectively. Similarly, a methyl ethyl ketone solution of the resin composition C-2 was obtained.

Production Example C3
(Production of Resin Composition C-3)
A resin composition C-3 was prepared in the same manner as in Production Example C1 except that in Production Example C1, the crystalline resin A-1 was changed to the crystalline resin A-2, and the isophorone diisocyanate 2.4 g was changed to 4.0 g. A methyl ethyl ketone solution was obtained.

Production Example C4
(Production of Resin Composition C-4)
A resin composition C-4 was prepared in the same manner as in Production Example C1 except that in Production Example C1, the crystalline resin A-1 was changed to the crystalline resin A-3 and the isophorone diisocyanate 2.4 g was changed to 1.0 g. A methyl ethyl ketone solution was obtained.

Production Examples C5 to C13
(Production of Resin Compositions C-5 to C-13)
Methyl ethyl ketone solutions of resin compositions C-5 to C-13 were obtained in the same manner as in Production Example C1 except that the types of crystalline resin and amorphous resin used were changed as shown in Table 3.

[Production of resin particle dispersion]
Production Example D1
(Production of Resin Particle Dispersion D-1)
A solution prepared by dissolving 80 g of the amorphous resin B-1 in 80 g of methyl ethyl ketone was added to the total amount of the methyl ethyl ketone solution of the resin composition C-1 obtained in Production Example C1, and the mixture was stirred at 73° C. for 1 hour, and further 5 26 g of a mass% sodium hydroxide aqueous solution was added, and the mixture was stirred for 30 minutes.
Next, while maintaining the temperature at 73° C., 700 g of deionized water was added over 60 minutes while stirring at 200 r/min (circumferential speed of 63 m/min) to carry out phase inversion emulsification. While maintaining the temperature at 73° C. continuously, methyl ethyl ketone was distilled off under reduced pressure to obtain an aqueous dispersion. Then, the aqueous dispersion was cooled to 30° C. with stirring at 280 r/min (peripheral speed 88 m/min), and deionized water was added so that the solid content concentration became 20% by mass to disperse the resin particles. Liquid D-1 was obtained. Physical properties are shown in Table 4-1.

Production Example D2
(Production of Resin Particle Dispersion D-2)
A solution prepared by dissolving 280 g of the amorphous resin B-1 in 280 g of methyl ethyl ketone was added to the total amount of the methyl ethyl ketone solution of the resin composition C-1 obtained in Production Example C1, and the mixture was stirred at 73° C. for 1 hour, and further 5 52 g of a mass% sodium hydroxide aqueous solution was added and stirred for 30 minutes.
Next, while maintaining the temperature at 73° C., 700 g of deionized water was added over 60 minutes while stirring at 200 r/min (circumferential speed of 63 m/min) to carry out phase inversion emulsification. While maintaining the temperature at 73° C. continuously, methyl ethyl ketone was distilled off under reduced pressure to obtain an aqueous dispersion. Then, the aqueous dispersion was cooled to 30° C. with stirring at 280 r/min (peripheral speed 88 m/min), and deionized water was added so that the solid content concentration became 20% by mass to disperse the resin particles. Liquid D-2 was obtained. Physical properties are shown in Table 4-1.

Production Example D3
(Production of Resin Particle Dispersion D-3)
27 g of 5 mass% sodium hydroxide aqueous solution was added to the total amount of the methyl ethyl ketone solution of the resin composition C-2 obtained in Production Example C2, and the mixture was stirred at 73° C. for 30 minutes.
Next, while maintaining the temperature at 73° C., 700 g of deionized water was added over 60 minutes while stirring at 200 r/min (circumferential speed of 63 m/min) to carry out phase inversion emulsification. While maintaining the temperature at 73° C. continuously, methyl ethyl ketone was distilled off under reduced pressure to obtain an aqueous dispersion. Then, the aqueous dispersion was cooled to 30° C. with stirring at 280 r/min (peripheral speed 88 m/min), and deionized water was added so that the solid content concentration became 20% by mass to disperse the resin particles. Liquid D-3 was obtained. The physical properties are shown in Table 4.

Production Examples D4 to D13 and D16
(Production of Resin Particle Dispersions D-4 to D-13 and D16)
Resin particle dispersions D-4 to D-13 and D16 were obtained in the same manner as in Production Example D1 except that the types of resin compositions were changed as shown in Table 4. The physical properties are shown in Table 4.
Production Example D14
(Production of Resin Particle Dispersion D-14)
A solution prepared by dissolving 60 g of the crystalline resin A-1 and 220 g of the amorphous resin B-1 in 280 g of methyl ethyl ketone was added to the total amount of the methyl ethyl ketone solution of the resin composition C-1 obtained in Production Example C1, and the mixture was heated to 73°C. The mixture was stirred for 1 hour, 49 g of a 5 mass% sodium hydroxide aqueous solution was further added, and the mixture was stirred for 30 minutes.
Next, while maintaining the temperature at 73° C., 700 g of deionized water was added over 60 minutes while stirring at 200 r/min (circumferential speed of 63 m/min) to carry out phase inversion emulsification. While maintaining the temperature at 73° C. continuously, methyl ethyl ketone was distilled off under reduced pressure to obtain an aqueous dispersion. Then, the aqueous dispersion was cooled to 30° C. with stirring at 280 r/min (peripheral speed 88 m/min), and deionized water was added so that the solid content concentration became 20% by mass to disperse the resin particles. Liquid D-14 was obtained. The physical properties are shown in Table 4.
Production Example D15
(Production of Resin Particle Dispersion D-15)
In a container with an internal volume of 3 L equipped with a stirrer, a reflux condenser, a thermometer and a nitrogen introduction tube, under a nitrogen atmosphere, 60 g of crystalline resin A-1, 140 g of amorphous resin B-1, and 200 g of methyl ethyl ketone. The resin was dissolved at 73° C. for 2 hours while being put and stirred. 27 g of 5 mass% sodium hydroxide aqueous solution was added to the obtained solution, and the mixture was stirred for 30 minutes.
Next, while maintaining the temperature at 73° C., 600 g of deionized water was added over 60 minutes while stirring at 200 r/min (circumferential speed of 63 m/min) to carry out phase inversion emulsification. While maintaining the temperature at 73° C. continuously, methyl ethyl ketone was distilled off under reduced pressure to obtain an aqueous dispersion. Then, the aqueous dispersion was cooled to 30° C. with stirring at 280 r/min (peripheral speed 88 m/min), and deionized water was added so that the solid content concentration became 20% by mass to disperse the resin particles. Liquid D-15 was obtained. The physical properties are shown in Table 4.

Production Example E1
(Production of Resin Particle Dispersion E-1)
In a container with an internal volume of 3 L equipped with a stirrer, a reflux condenser, a dropping funnel, a thermometer and a nitrogen introducing tube, 300 g of the amorphous resin Bs-1 and 180 g of methyl ethyl ketone and a mixed solvent of 25 g of deionized water were put, The resin was dissolved at 73° C. for 2 hours. 46 g of 5 mass% sodium hydroxide aqueous solution was added to the obtained solution, and the mixture was stirred for 30 minutes.
Next, while maintaining the temperature at 73° C., 600 g of deionized water was added over 60 minutes while stirring at 200 r/min (circumferential speed of 63 m/min) to carry out phase inversion emulsification. While maintaining the temperature at 73° C. continuously, methyl ethyl ketone was distilled off under reduced pressure to obtain an aqueous dispersion. Then, the aqueous dispersion was cooled to 30° C. with stirring at 280 r/min (peripheral speed 88 m/min), and deionized water was added so that the solid content concentration became 20% by mass to disperse the resin particles. Liquid E-1 was obtained. The physical properties are shown in Table 5.
Production Example F1
(Production of Resin Particle Dispersion Liquid F-1)
200 g of amorphous composite resin Bw-1 and 200 g of methyl ethyl ketone were placed in a container having an internal volume of 3 L equipped with a stirrer, a reflux condenser, a dropping funnel, a thermometer and a nitrogen introducing tube, and the resin was added at 73° C. for 2 hours. Was dissolved. 41 g of a 5 mass% sodium hydroxide aqueous solution was added to the obtained solution, and the mixture was stirred for 30 minutes.
Next, while maintaining the temperature at 73° C., 700 g of deionized water was added over 50 minutes while stirring at 200 r/min (peripheral speed 88 m/min) to carry out phase inversion emulsification. While maintaining the temperature at 73° C. continuously, methyl ethyl ketone was distilled off under reduced pressure to obtain an aqueous dispersion. Then, the aqueous dispersion was cooled to 30° C. with stirring at 280 r/min (peripheral speed 88 m/min), and deionized water was added so that the solid content concentration became 20% by mass to disperse the resin particles. Liquid F-1 was obtained. The physical properties are shown in Table 5.

[Production of wax particle dispersion]
Production Example G1
(Production of Wax Particle Dispersion G-1)
To a beaker having an internal volume of 1 L, 120 g of deionized water, 86 g of a resin particle dispersion F-1 and 40 g of paraffin wax "HNP-9" (manufactured by Nippon Seiro Co., Ltd., melting point 75°C) were added, and the temperature was 90 to 95°C. The temperature was maintained at 1, the mixture was melted, and the mixture was stirred to obtain a molten mixture.
While maintaining the temperature of the obtained melted mixture at 90 to 95° C., using an ultrasonic homogenizer “US-600T” (manufactured by Nippon Seiki Seisakusho Co., Ltd.), a dispersion treatment was performed for 20 minutes and then up to room temperature (25° C.). Cooled. Deionized water was added to adjust the solid content concentration to 20 mass% to obtain a wax particle dispersion G-1. The wax particles in the dispersion had a volume median particle diameter (D ₅₀ ) of 0.47 μm and a CV value of 27%.

[Production of colorant particle dispersion]
Production Example H1
(Production of Colorant Particle Dispersion Liquid H-1)
In a beaker having an internal volume of 1 L, 150 g of a copper phthalocyanine pigment "ECB-301" (manufactured by Dainichiseika Kogyo Co., Ltd.) and an anionic surfactant "Neoperex (registered trademark) G-15" (manufactured by Kao Corporation, 15 mass) % Dodecylbenzenesulfonate aqueous solution) (200 g) and deionized water (257 g) were mixed and dispersed at room temperature for 10 hours using an ultrasonic homogenizer "US-600T" (manufactured by Nippon Seiki Seisakusho Co., Ltd.), and then the solid content. Colorant dispersion liquid H-1 was obtained by adding deionized water to a concentration of 24% by mass. The volume median particle diameter (D ₅₀ ) of the colorant particles in the dispersion was 0.10 μm.

[Manufacture of toner]
Example 1
(Preparation of Toner 1)
300 g of resin particle dispersion D-1, 30 g of wax particle dispersion G-1 and 30 g of colorant particle dispersion H-1 were placed in a four-necked flask having an internal volume of 3 L equipped with a dehydration tube, a stirrer and a thermocouple. 30 g and 9 g of a 10 mass% aqueous solution of a nonionic surfactant "Emulgen (registered trademark) 150" (manufactured by Kao Corporation, polyoxyethylene (average addition mole number: 50) lauryl ether) were mixed at a temperature of 25°C. Next, while stirring the mixture, a solution in which 19 g of ammonium sulfate was dissolved in 187 g of deionized water and 20 g of a 4.8 mass% potassium hydroxide aqueous solution was added to adjust the pH to 8.6 was added to the solution at 25° C. for 5 minutes. Then, the temperature was raised to 60° C. over 2 hours, and the mixture was kept at 60° C. until the volume median particle diameter (D ₅₀ ) of the aggregated particles became 5.5 μm to disperse the aggregated particles (1). A liquid was obtained.
In the dispersion liquid of the agglomerated particles (1), 10 g of anionic surfactant "Emar (registered trademark) E-27C" (manufactured by Kao Corporation, sodium polyoxyethylene lauryl ether sulfate, effective concentration 27% by mass), deionized An aqueous solution obtained by mixing 900 g of water and 40 g of 0.1 mol/L sulfuric acid was added. Then, the temperature was raised to 83° C. over 1 hour, and then the temperature was maintained at 83° C. until the circularity reached 0.975 to obtain a dispersion liquid of fused particles in which agglomerated particles were fused.
The obtained fused particle dispersion liquid was cooled to 30° C., the dispersion liquid was suction-filtered to separate solids, washed with deionized water at 25° C., and suction-filtered at 25° C. for 2 hours. Then, using a vacuum constant temperature dryer (DRV622DA manufactured by ADVANTEC), vacuum drying was performed at 33° C. for 48 hours to obtain toner mother particles. Table 5 shows the physical properties of the obtained toner mother particles.
100 parts by mass of the toner mother particles, 2.5 parts by mass of hydrophobic silica “RY50” (manufactured by Nippon Aerosil Co., Ltd., number average particle size: 0.04 μm), and hydrophobic silica “Cabosil® TS720” (Cabot) Toner 1 was obtained by putting 1.0 part by mass of a number average particle diameter (0.012 μm, manufactured by Japan Ltd.) in a Henschel mixer, stirring and passing through a 150-mesh sieve. The evaluation results of Toner 1 thus obtained are shown in Table 6.

Examples 2-14, Comparative Examples 1, 2
(Preparation of Toners 2-14, 17, 18)
A toner was prepared in the same manner as in Example 1 except that the type of the resin particle dispersion liquid used was changed as shown in Table 6. Table 6 shows the physical properties of the obtained toner base particles and the evaluation results of the toner.

Example 15
(Preparation of Toner 15)
300 g of resin particle dispersion D-1, 30 g of wax particle dispersion G-1 and 30 g of colorant particle dispersion H-1 were placed in a four-necked flask having an internal volume of 3 L equipped with a dehydration tube, a stirrer and a thermocouple. 30 g and 6 g of a 10 mass% aqueous solution of a nonionic surfactant "Emulgen (registered trademark) 150" (manufactured by Kao Corporation, polyoxyethylene (average addition mole number: 50) lauryl ether) were mixed at a temperature of 25°C. Next, while stirring the mixture, a solution in which 19 g of ammonium sulfate was dissolved in 187 g of deionized water and 20 g of a 4.8 mass% potassium hydroxide aqueous solution was added to adjust the pH to 8.6 was added to the solution at 25° C. for 5 minutes. Then, the temperature was raised to 59° C. over 2 hours, and the mixture was kept at 59° C. until the volume median particle diameter (D ₅₀ ) of the aggregated particles became 5.2 μm, to disperse the aggregated particles (1). A liquid was obtained.
While maintaining the temperature of the dispersion liquid of the aggregated particles (1) at 59° C., 46 g of the resin particle dispersion liquid E-1 was dropped at a rate of 0.3 ml/min to obtain a dispersion liquid of the aggregated particles (2). It was
To the dispersion liquid of the agglomerated particles (2), 11 g of anionic surfactant "Emar (registered trademark) E-27C" (manufactured by Kao Corporation, sodium polyoxyethylene lauryl ether sulfate, effective concentration 27 mass%), deionized An aqueous solution obtained by mixing 1050 g of water and 45 g of 0.1 mol/L sulfuric acid was added. Then, the temperature was raised to 83° C. over 1 hour, and then the temperature was maintained at 83° C. until the circularity reached 0.975 to obtain a dispersion liquid of fused particles in which agglomerated particles were fused.
The obtained fused particle dispersion liquid was cooled to 30° C., the dispersion liquid was suction-filtered to separate solids, washed with deionized water at 25° C., and suction-filtered at 25° C. for 2 hours. Then, using a vacuum constant temperature dryer (DRV622DA manufactured by ADVANTEC), vacuum drying was performed at 33° C. for 48 hours to obtain toner mother particles. Table 5 shows the physical properties of the obtained toner mother particles.
100 parts by mass of the toner mother particles, 2.5 parts by mass of hydrophobic silica “RY50” (manufactured by Nippon Aerosil Co., Ltd., number average particle diameter: 0.04 μm), and hydrophobic silica “Cabosil® TS720” (Cabot) 1.0 part by mass of Japan Co., Ltd. (number average particle diameter: 0.012 μm) was put in a Henschel mixer, stirred, and passed through a 150-mesh sieve to obtain Toner 16. Table 6 shows the evaluation results of the obtained toner 15.

Example 16
(Preparation of Toner 16)
The methyl ethyl ketone solution of resin composition C-1 was kept at 80° C., and methyl ethyl ketone was distilled off under reduced pressure to obtain resin composition C-1.
In a Henschel mixer, 60 parts by mass of the resin composition C-1, 40 parts by mass of the amorphous resin B-1, 10 parts by mass of copper phthalocyanine pigment “ECB-301” (manufactured by Dainichiseika Kogyo Co., Ltd.), paraffin wax. After adding 6 parts by mass of "HNP-9" (manufactured by Nippon Seiro Co., Ltd., melting point 75°C) and mixing for 5 minutes, a co-rotating twin-screw extruder PCM-30 (manufactured by Ikegai Co., Ltd., shaft diameter 2) 1.9 cm, axial cross-sectional area 7.06 cm ² ) was used, and the melt was kneaded at a roll rotation speed of 200 r/min, a heating temperature in the roll of 70° C., and a mixture supply temperature of 10 kg/h. The obtained melt-kneaded product was cooled and roughly pulverized, then pulverized by a jet mill and classified to obtain toner mother particles. Table 6 shows the physical properties of the obtained toner mother particles.
100 parts by mass of the toner mother particles, 2.5 parts by mass of hydrophobic silica “RY50” (manufactured by Nippon Aerosil Co., Ltd., number average particle diameter: 0.04 μm), and hydrophobic silica “Cabosil® TS720” (Cabot) Toner 16 was obtained by putting 1.0 part by mass of a number average particle size (0.012 μm, manufactured by Japan Ltd.) in a Henschel mixer, stirring and passing through a 150-mesh screen. Table 6 shows the toner evaluation results.

It can be seen from Table 6 that the toners of Examples 1 to 16 are superior to the toners of Comparative Examples 1 and 2 in low-temperature fixability and low-temperature fixability after storage at high temperature and high humidity.
Further, the resin particle dispersions D-1 to D-14 of Production Examples 1 to 14 containing the resin composition (C) of the present invention are resin particle dispersion D-15 containing no resin composition (C), Coarse particles in the resin particle dispersion liquid, as compared with the resin particle dispersion liquid D-16 containing the resin composition using the amorphous resin having no constituent component (b1) derived from the hydrocarbon wax (W1). Small quantity. Then, among Examples 1 to 16, Examples 1 to 15 which are toners manufactured by an emulsion aggregation method using the resin particle dispersions D-1 to D-14 in which the amount of coarse particles in the resin particle dispersion is small Shows that the toner has excellent charge stability.

Claims (6)

At least a part of the crystalline resin (A) and the amorphous resin (B) having a constituent component (b1) derived from a hydrocarbon wax (W1) having a hydroxyl group or a carboxy group and a polyester portion (b2) are chemically synthesized. Is a toner for developing an electrostatic charge image, which contains a resin composition (C) containing a reaction product obtained by a reaction for chemically bonding.
A polyfunctional compound (S) is used in the reaction,
The polyfunctional compound (S) is a polyisocyanate compound,
A toner for developing an electrostatic charge image, wherein the crystalline resin (A) is a crystalline polyester having a hydroxyl value of 3 mgKOH/g or more and 20 mgKOH/g or less. The electrostatic image developing toner according to claim 1, wherein the amorphous resin (B) has a hydroxyl value of 4 mgKOH/g or more and 40 mgKOH/g or less. The total content of the crystalline resin (A) is 5% by mass or more and 45% by mass or less with respect to the total amount of the crystalline resin (A) and the amorphous resin (B) in the toner. Or the toner for developing an electrostatic charge image according to item 2. The content of the component (b1) derived from the hydrocarbon wax (W1) in the amorphous resin (B) is 1% by mass or more and 20% by mass or less. Toner for developing electrostatic images. At least a part of the crystalline resin (A) and the amorphous resin (B) having a constituent component (b1) derived from a hydrocarbon wax (W1) having a hydroxyl group or a carboxy group and a polyester portion (b2) are chemically synthesized. A resin composition containing a reaction product obtained by a reaction of chemically binding,
A polyfunctional compound (S) is used in the reaction,
The polyfunctional compound (S) is a polyisocyanate compound,
The resin composition, wherein the crystalline resin (A) is a crystalline polyester having a hydroxyl value of 3 mgKOH/g or more and 20 mgKOH/g or less. At least a part of the crystalline resin (A) and the amorphous resin (B) having a constituent component (b1) derived from a hydrocarbon wax (W1) having a hydroxyl group or a carboxy group and a polyester portion (b2) are chemically synthesized. And a step of obtaining a resin composition (C) containing a reaction product obtained by a reaction of physically binding, and a method for producing a toner for developing an electrostatic charge image,
A polyfunctional compound (S) is used in the reaction,
The polyfunctional compound (S) is a polyisocyanate compound,
A method for producing a toner for developing an electrostatic charge image, wherein the crystalline resin (A) is a crystalline polyester having a hydroxyl value of 3 mgKOH/g or more and 20 mgKOH/g or less.