JP6763512B2 - Manufacturing method of toner for static charge image development - Google Patents

Description

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

In the field of electrophotographic, with the development of electrophotographic systems, there is a demand for the development of toner for static charge image development corresponding to high image quality and high speed. As a method of obtaining a toner having excellent fixability at a low temperature, a crystalline resin is used in addition to the amorphous resin conventionally used as a binder resin, and fine resin particles and the like are aggregated in an aqueous medium. Toners are manufactured by a coagulation fusion method (emulsification coagulation method, coagulation coalescence method) in which toner is obtained by fusion.

For example, Patent Document 1 describes a crystal obtained by polycondensing an alcohol component containing α, ω-alcandiol having 10 or more and 12 or less carbon atoms and having an average carbon number of 10 or more and 12 or less and an acid component containing succinic acid. After the core-shell particles having the property polyester and the amorphous polyester in the core portion and the amorphous polyester in the shell portion are obtained by the coagulation fusion method, the dispersion liquid of the core-shell particles is 25 ° C. or higher and 50 ° C. or lower per minute. A method for producing a toner for static charge image development, which comprises cooling at the cooling rate of the above, is described, and it is described that a toner for static charge image development having excellent OHP permeability of a printed matter can be obtained.

Further, Patent Document 2 describes resin particles containing a crystalline polyester (A) having a polyester portion obtained by using a monomer having a molar average carbon number of 8 to 12, and a polyester segment and an addition polymerization resin segment. An aggregate X containing resin particles containing an amorphous composite resin (B) containing 3% by mass or more and 15% by mass or less of a constituent component derived from a bireactive monomer in the addition polymerization resin segment. The step I obtained in an aqueous medium and the step II of fusing the aggregate X, and the mass ratio of the crystalline polyester (A) to the amorphous composite resin (B) (crystalline polyester (A). ) / Amorphous composite resin (B)) is 1/99 to 40/60, and a method for producing a toner for static charge image development is described, and a printed matter obtained by achieving both low-temperature fixability and heat-resistant storage stability. It is described that a toner for static charge image development having excellent bending resistance can be obtained.

Further, Patent Document 3 describes a binder resin composition for toner containing an amorphous composite resin having a polyester resin portion and a vinyl resin portion and a crystalline polyester, and the composite resin has a melting point. The crystalline polyester is obtained by using a raw material monomer containing an aliphatic diol having 6 to 12 carbon atoms and containing 0.5 to 10% by mass of a structural portion derived from a hydrocarbon wax having a hydroxyl group at 60 to 110 ° C. , A binder resin composition for toner is described, and it is described that a toner containing the binder resin composition can achieve both low temperature fixability and storage stability.

JP-A-2014-130254 Japanese Unexamined Patent Publication No. 2014-235409 Japanese Unexamined Patent Publication No. 2015-7765

However, when toner particles are produced by the coagulation fusion method, there is a problem that the low temperature fixability is lowered over time even if the low temperature fixability of the toner is improved by mixing the crystalline resin with the binder resin. I have come to understand.
Therefore, the present invention is excellent in low-temperature fixability, can suppress deterioration of low-temperature fixability over time, and is further heat-resistant storage even when toner is produced by the coagulation fusion method using a crystalline resin. An object of the present invention is to provide a method for producing a toner for static charge image development, which can obtain a toner having excellent properties.

The present inventors have considered that the factor affecting the characteristics of the toner using the crystalline resin is the dispersed state of the crystalline resin in the toner particles. As a result, the crystalline resin and the amorphous composite resin having a specific component are combined and rapidly cooled after the fusion step, so that the toner can be fixed at a low temperature even when the toner is produced by the coagulation fusion method. It has been found that a toner that is excellent in quality, can suppress a decrease in low temperature fixability over time, and is also excellent in heat storage stability can be obtained.

That is, the present invention
Step (1): A step of aggregating the amorphous composite resin and the crystalline resin in an aqueous medium to obtain a dispersion of agglomerated particles.
Step (2): A step of fusing the obtained agglomerated particles to obtain a dispersion liquid of the fused particles.
Step (3): A step of cooling the obtained dispersion of fused particles at a rate of 10 ° C./min or more, and
Is a method for producing a toner for developing an electrostatic charge image, which has
A method for producing a toner for static charge image development, wherein the amorphous composite resin contains a polyester resin segment and a vinyl resin segment containing a structural unit derived from a vinyl monomer having a hydrocarbon group having 6 or more and 22 or less carbon atoms. Regarding.

According to the present invention, even when toner is produced by the coagulation fusion method using a crystalline resin, it is excellent in low-temperature fixability, can suppress a decrease in low-temperature fixability over time, and is further heat-resistant storage. It is possible to provide a method for producing a toner for static charge image development, which can obtain a toner having excellent properties.

[Manufacturing method of toner for static charge image development]
The method for producing a hydrocarbon for developing an electrostatic charge image of the present invention (also simply referred to as “toner” in the present specification) includes the above-mentioned steps (1) to (3), and the amorphous composite resin is a polyester resin. The segment and a vinyl resin segment containing a structural unit derived from a vinyl monomer having a hydrocarbon group having 6 or more and 22 or less carbon atoms are included. The reason why the toner obtained by the production method of the present invention can provide a toner having excellent low-temperature fixability, suppressing a decrease in low-temperature fixability over time, and further having excellent heat-resistant storage stability is not clear, but the following Can be thought of as.
Since the crystalline resin does not necessarily have good compatibility with the resin components constituting other binding resins, the size of the crystal domain derived from the crystalline resin tends to gradually increase. As a result, the interface between the crystalline resin and the other binder resin is relatively reduced, and the crystalline resin is melted at the time of toner fixing, and the surrounding amorphous resin is less likely to be melted, so that the low temperature fixability is lowered. To do. In addition, the expansion of the crystal domain also reduces the heat-resistant storage stability at high temperatures. In particular, in the production of toner by the coagulation fusion method without a kneading step, the crystalline resin cannot be sufficiently dispersed in the amorphous resin, and the crystalline resin may be finely dispersed and crystallized. It seems to be difficult.

In the production method of the present invention, as a method for finely dispersing the crystalline resin in the toner particles, a crystalline resin, a polyester resin segment, and a vinyl monomer having a hydrocarbon group having 6 or more and 22 or less carbon atoms are used. A non-crystalline composite resin containing a vinyl-based resin segment containing a constituent unit of origin is used.
By providing the amorphous composite resin with a vinyl-based resin segment containing a structural unit derived from a vinyl monomer having a hydrocarbon group having 6 or more and 22 or less carbon atoms, these constituent components form a hydrophobic field in an aqueous medium. It is considered that the particles are formed so as to be surrounded by a relatively hydrophilic polyester resin segment. Further, since the vinyl-based resin segment containing a structural unit derived from a vinyl monomer having a hydrocarbon group having 6 or more and 22 or less carbon atoms acts as a crystal nucleating agent for the crystalline resin, the crystalline resin becomes the toner particles when the toner particles are formed. It can be rapidly crystallized in a finely dispersed state to form a fine crystal domain. Then, crystallization proceeds from each crystal nucleus, but since a large amount of crystal nuclei are already finely dispersed in the amorphous composite resin, the enlargement of the crystal domain derived from the crystalline resin is suppressed. It is thought that it can be done.

Further, in the production method of the present invention, the dispersion liquid of the fused particles is rapidly cooled (step (3)). It is considered that this operation makes the nucleation term of the crystal dominant, and it becomes possible to generate a large amount of crystal nuclei derived from the crystalline resin before the crystal domain grows large in the toner particles.
For these reasons, even when the toner is produced by the coagulation fusion method using the crystalline resin, the crystalline resin can be finely dispersed in the amorphous composite resin in the toner, and as a result. It is considered that a toner having excellent low-temperature fixability and heat-resistant storage property and capable of suppressing a decrease in low-temperature fixability over time can be obtained.

<Process (1)>
[Amorphous composite resin (A)]
The amorphous composite resin (hereinafter, also referred to as “acrystalline composite resin (A)”) has excellent low-temperature fixability, suppresses deterioration of low-temperature fixability over time, and has excellent heat-resistant storage stability. It includes a polyester resin segment and a vinyl resin segment containing a structural unit derived from a vinyl monomer having a hydrocarbon group having 6 or more and 22 or less carbon atoms.
In the present invention, whether the resin is crystalline or amorphous is determined by the crystallinity index. The crystallinity index is defined by the ratio of the softening point to the maximum endothermic peak temperature (softening point (° C.) / maximum endothermic peak temperature (° C.)) in the measuring method described in the examples. Amorphous resin means a resin having a crystallinity index of more than 1.4 or less than 0.6.
The crystallinity index is determined by the method described in Examples. The crystallinity index can be appropriately adjusted depending on the type and ratio of the raw material monomers, and the production conditions such as reaction temperature, reaction time, and cooling rate.

(Polyester resin segment)
The polyester resin segment contains an alcohol component (A-al) and a carboxylic acid component (A-ac) from the viewpoints of excellent low-temperature fixability, suppression of deterioration of low-temperature fixability over time, and excellent heat-resistant storage stability. It is a segment made of a polyester resin obtained by polycondensation.

The alcohol component (A-al) preferably contains an alkylene oxide adduct of bisphenol A from the viewpoints of excellent low-temperature fixability, suppression of deterioration of low-temperature fixability over time, and excellent heat-resistant storage stability, and is more preferable. Is equation (I):

[In the formula, OR ¹ and R ¹ O are alkylene oxides, R ¹ is an alkylene group having 2 or 3 carbon atoms, preferably a propylene group, and x and y are positive numbers indicating the average number of moles of alkylene oxide added. The alkylene oxide adduct of bisphenol A represented by [shown, the sum of x and y is 1 or more, preferably 1.5 or more, and 16 or less, preferably 8 or less, more preferably 4 or less] is used. Including.

The content of the alkylene oxide adduct of bisphenol A in the alcohol component (A-al) is preferably from the viewpoint of excellent low-temperature fixability, suppression of deterioration of low-temperature fixability over time, and excellent heat-resistant storage stability. 80 mol% or more, more preferably 90 mol% or more, still more preferably 95 mol% or more, still more preferably 98 mol% or more, and 100 mol% or less, and 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-). It is at least one selected from 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 as the alkylene oxide adduct of bisphenol A is preferably 1 or more from the viewpoint of excellent low temperature fixability, suppression of decrease in low temperature fixability over time, and excellent heat storage stability. It is preferably 1.2 or more, more preferably 1.5 or more, and preferably 16 or less, more preferably 12 or less, still more preferably 8 or less, still more preferably 4 or less.

The alcohol component (A-al) preferably contains 80 mol% or more of the propylene oxide adduct of bisphenol A from the viewpoints of excellent low-temperature fixability, suppression of deterioration of low-temperature fixability over time, and excellent heat-resistant storage stability. It contains 90 mol% or more, more preferably 95 mol% or more, further preferably 98 mol% or more, preferably 100 mol% or less, and further preferably 100 mol% or more.

The alcohol component (A-al) may contain a polyhydric alcohol other than the alkylene oxide adduct of bisphenol A. Other alcohol components that can be contained in the alcohol component (A-al) include aliphatic diols, aromatic diols, alicyclic diols, trihydric or higher polyhydric alcohols, and alkylene oxides having 2 or more and 4 or less carbon atoms thereof. (Average number of added moles 1 or more and 16 or less) Additives and the like can be mentioned.
Other alcohol components include ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, and 2,3-butane. Diol, neopentyl glycol, 1,4-butenediol, 1,5-pentanediol, 1,6-hexanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1, An aliphatic diol such as 12-dodecanediol; an aromatic diol such as bisphenol A (2,2-bis (4-hydroxyphenyl) propane), or an alkylene oxide having 4 carbon atoms (average addition molar number 1 or more and 16 or less). ) Additives: Alicyclic diols such as hydrogenated bisphenol A (2,2-bis (4-hydroxycyclohexyl) propane) or alkylene oxides having 2 or more and 4 or less carbon atoms (average addition molars of 2 or more and 12 or less). ) Additives: Polyhydric alcohols of trivalent or higher such as glycerin, pentaerythritol, trimethylolpropane, sorbitol, etc., or alkylene oxides having 2 or more and 4 or less carbon atoms (average addition molars of 1 to 16). Can be mentioned.
These alcohol components (A-al) can be used alone or in combination of two or more.

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

Examples of the dicarboxylic acid include aromatic dicarboxylic acid, aliphatic dicarboxylic acid, and alicyclic dicarboxylic acid, and aromatic dicarboxylic acid and aliphatic dicarboxylic acid are preferable.
The carboxylic acid component (A-ac) includes not only free acids, but also anhydrouss that decompose during the reaction to produce acids, and alkyl esters 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 viewpoints of excellent low-temperature fixability, suppression of deterioration of low-temperature fixability over time, and excellent heat-resistant storage stability.
The aliphatic dicarboxylic acid preferably has 2 or more carbon atoms, more preferably 3 or more carbon atoms, from the viewpoints of excellent low-temperature fixability, suppression of deterioration of low-temperature fixability over time, and excellent heat-resistant storage stability. , And preferably 30 or less, more preferably 20 or less.
Examples of aliphatic dicarboxylic acids 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, and azelaic acid. Examples thereof include succinic acid substituted with an alkyl group having 1 to 20 carbon atoms or an alkenyl group having 2 to 20 carbon atoms. Examples of the succinic acid substituted with an alkyl group having 1 to 20 carbon atoms or an alkenyl group having 2 to 20 carbon atoms include dodecyl succinic acid, dodecenyl succinic acid, and octenyl succinic acid.
Among these, at least one selected from terephthalic acid, fumaric acid, and sebacic acid is preferable, and these are selected from the viewpoints of excellent low-temperature fixability, suppression of deterioration of low-temperature fixability over time, and excellent heat-resistant storage stability. It is more preferable to use them in combination.

The trivalent or higher valent carboxylic acid is preferably a trivalent carboxylic acid, more preferably, from the viewpoints of excellent low-temperature fixability, suppression of deterioration of low-temperature fixability over time, and excellent heat-resistant storage stability. Trimellitic acid and its anhydrides, more preferably trimellitic acid anhydrides.
The content of a polyvalent carboxylic acid having a trivalent or higher value is a carboxylic acid component (A-ac) from the viewpoints of excellent low-temperature fixability, suppression of deterioration of low-temperature fixability over time, and excellent heat-resistant storage stability. ), It is preferably 3 mol% or more, more preferably 5 mol% or more, and preferably 30 mol% or less, more preferably 20 mol% or less, still more preferably 15 mol% or less.
These carboxylic acid components (A-ac) can be used alone or in combination of two or more.

The molar equivalent ratio (COOH group / OH group) of the carboxy group (COOH group) of the carboxylic acid component (A-ac) to the hydroxyl group (OH group) of the alcohol component (A-al) has excellent low-temperature fixability and aging. From the viewpoint of suppressing the decrease in low-temperature fixability and excellent heat-resistant storage stability, it is preferably 0.7 or more, more preferably 0.8 or more, and preferably 1.3 or less, more preferably 1. It is 2 or less.

(Vinyl resin segment)
The vinyl resin segment is composed of a vinyl monomer having a hydrocarbon group having 6 to 22 carbon atoms from the viewpoint of excellent low temperature fixability, suppression of deterioration of low temperature fixability over time, and excellent heat storage stability. Contains units.
The vinyl monomer having a hydrocarbon group is preferably a (meth) acrylic acid ester. Here, the "(meth) acrylic acid ester" refers to an acrylic acid ester or a methacrylic acid ester.
In the case of (meth) acrylic acid esters, the hydrocarbon group is the alcohol-side residue of the ester.
The hydrocarbon group of the vinyl monomer is preferably a saturated or unsaturated aliphatic hydrocarbon group, preferably a saturated aliphatic hydrocarbon group.
The number of carbon atoms of the hydrocarbon group of the vinyl monomer is preferably 8 or more, more preferably 10 or more, and further, from the viewpoint of excellent low-temperature fixability, suppression of deterioration of low-temperature fixability over time, and excellent heat-resistant storage stability. It is preferably 12 or more, more preferably 14 or more, and preferably 20 or less, more preferably 18 or less.
Examples of the vinyl monomer include (meth) acrylic acid (iso) hexyl, (meth) acrylic acid cyclohexyl, (meth) acrylic acid (iso) octyl (hereinafter, also referred to as (meth) acrylic acid 2-ethylhexyl), and (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 , (Meta) acrylic acid (iso) behenyl and the like. Among these, 2-ethylhexyl (meth) acrylate, (iso) lauryl (meth) acrylate, and stearyl (meth) acrylate are preferable, and (meth) lauryl acrylate (iso) lauryl and stearyl (meth) acrylate are more preferable. Preferably, stearyl methacrylate is more preferred.
In addition, "(iso)" means normal or iso.
The content of the structural unit derived from a vinyl monomer having a hydrocarbon group having 6 to 22 carbon atoms is from the viewpoint of excellent low-temperature fixability, suppression of deterioration of low-temperature fixability over time, and excellent heat-resistant storage stability. In the vinyl resin segment, it is preferably 5% by mass or more, more preferably 10% by mass or more, further preferably 15% by mass or more, still more preferably 20% by mass or more, and preferably 60% by mass or less, more preferably. Is 40% by mass or less, more preferably 30% by mass or less.

The vinyl-based resin segment preferably contains a structural unit derived from a styrene-based compound from the viewpoints of excellent low-temperature fixability, suppression of deterioration of low-temperature fixability over time, and excellent heat-resistant storage stability.
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 and the like.
Examples of the styrene-based compound include styrene, methylstyrene, α-methylstyrene, β-methylstyrene, tert-butylstyrene, chlorostyrene, chloromethylstyrene, methoxystyrene, styrenesulfonic acid or a salt thereof. Of these, styrene is preferable.
The content of the structural unit derived from the styrene-based compound is preferably 40% by mass in the vinyl-based resin segment from the viewpoints of excellent low-temperature fixability, suppression of deterioration of low-temperature fixability over time, and excellent heat-resistant storage stability. The above is more preferably 60% by mass or more, further preferably 70% by mass or more, and preferably 95% by mass or less, more preferably 90% by mass or less, still more preferably 85% by mass or less, still more preferably 80% by mass. % Or less.

Examples of the raw material vinyl monomer other than the vinyl monomer having a hydrocarbon group having 6 or more and 22 carbon atoms and the styrene compound include alkyl (meth) acrylate (alkyl group having 1 to 5 carbon atoms) and dimethyl (meth) acrylate. (Meta) acrylic acid aminoalkyl esters such as aminoethyl; olefins such as ethylene, propylene and butadiene; halovinyls such as vinyl chloride; vinyl esters such as vinyl acetate and vinyl propionate; vinyl ethers such as methyl vinyl ether; Examples thereof include vinylidene halides such as vinylidene chloride; and N-vinyl compounds such as N-vinylpyrrolidone.

The vinyl-based resin segment preferably has an aliphatic hydrocarbon group having 6 to 22 carbon atoms from the viewpoint of excellent low-temperature fixability, suppression of deterioration of low-temperature fixability over time, and excellent heat-resistant storage stability. It contains a structural unit derived from (meth) acrylic acid ester and a structural unit derived from styrene.
The total amount of the structural unit derived from the vinyl monomer having a hydrocarbon group having 6 or more and 22 or less carbon atoms and the structural unit derived from the styrene compound in the vinyl resin segment is excellent in low temperature fixability and low temperature fixability with time. It is preferably 80% by mass or more, more preferably 90% by mass or more, further preferably 95% by mass or more, and 100% by mass or less, and from the viewpoint of suppressing the decrease in heat resistance and excellent heat storage stability. More preferably, it is 100% by mass.

The amorphous composite resin (A) preferably contains a structural unit derived from both reactive monomers, and the structural unit derived from both reactive monomers is a bond between the above-mentioned vinyl resin segment and the above-mentioned polyester resin segment. It is preferable to be a point.
Examples of the bireactive monomer include a vinyl monomer having at least one functional group selected from a hydroxyl group, a carboxy group, an epoxy group, a primary amino group and a secondary amino group in one 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 bireactive monomer include acrylic acid, methacrylic acid, fumaric acid, maleic acid and the like. Among these, at least one selected from acrylic acid and methacrylic acid is preferable, and acrylic acid is more preferable, from the viewpoints of excellent low-temperature fixability, suppression of deterioration of low-temperature fixability over time, and excellent heat-resistant storage stability. ..

The content of the structural unit derived from both reactive monomers is from the viewpoint of improving the dispersibility of the crystalline resin (B) in the amorphous composite resin (A) and from the viewpoint of controlling the reaction of the addition polymerization reaction and the polycondensation reaction. Therefore, with respect to 100 mol parts of the total amount of the alcohol component (A-al) which is the raw material of the polyester resin segment, preferably 1 mol part or more, more preferably 5 mol parts or more, still more preferably 10 mol parts or more, still more preferably. It is 15 mol parts or more, and preferably 30 mol parts or less, more preferably 25 mol parts or less, still more preferably 20 mol parts or less. When both reactive monomers are used and the content of each segment in the amorphous composite resin (A) is calculated, the structural unit derived from the bireactive monomer is in the constituent unit of the polyester resin segment. Calculated as included in.

The content of the polyester resin segment in the amorphous composite resin (A) is preferably 40% by mass from the viewpoint of excellent low-temperature fixability, suppression of deterioration of low-temperature fixability over time, and excellent heat-resistant storage stability. The above is more preferably 45% by mass or more, still more preferably 50% by mass or more, and is preferable from the viewpoint of excellent low-temperature fixability, suppression of deterioration of low-temperature fixability over time, and excellent heat-resistant storage stability. Is 90% by mass or less, more preferably 80% by mass or less, still more preferably 70% by mass or less.
The content of the polyester resin segment in the amorphous composite resin (A) is the polyester resin segment and vinyl from the viewpoints of excellent low-temperature fixability, suppression of deterioration of low-temperature fixability over time, and excellent heat-resistant storage stability. It is preferably 40% by mass or more, more preferably 45% by mass or more, further preferably 50% by mass or more, and preferably 90% by mass or less, more preferably 85% by mass, based on the total content of the based resin segment. % Or less, more preferably 80% by mass or less.

The content of the vinyl resin segment in the amorphous composite resin (A) is preferably 10% by mass from the viewpoints of excellent low-temperature fixability, suppression of deterioration of low-temperature fixability over time, and excellent heat-resistant storage stability. % Or more, more preferably 20% by mass or more, and preferably 60% by mass or less, more preferably 50% by mass or less, still more preferably 45% by mass or less.
The content of the vinyl resin segment in the amorphous composite resin (A) is the polyester resin segment and the polyester resin segment from the viewpoint of excellent low temperature fixability, suppression of deterioration of low temperature fixability over time, and excellent heat storage stability. With respect to the total content of the vinyl resin segment, it is preferably 10% by mass or more, more preferably 15% by mass or more, and preferably 60% by mass or less, more preferably 40% by mass or less, still more preferably 30% by mass or less. It is mass% or less.
The total content of the polyester resin segment and the vinyl-based resin segment in the amorphous composite resin (A) is from the viewpoint of excellent low-temperature fixability, suppression of deterioration of low-temperature fixability over time, and excellent heat-resistant storage stability. Therefore, it is preferably 80% by mass or more, more preferably 90% by mass or more, further preferably 93% by mass or more, further preferably 95% by mass or more, and 100% by mass or less, preferably 99% by mass or less. , More preferably 98% by mass or less, still more preferably 97% by mass or less.

(Components derived from hydrocarbon wax)
The amorphous composite resin (A) is a hydrocarbon wax having a hydroxyl group or a carboxy group (hereinafter, "" from the viewpoints of excellent low-temperature fixability, suppression of deterioration of low-temperature fixability over time, and excellent heat-resistant storage stability. It is preferable to contain a constituent component derived from "hydrocarbon wax (W1)"). In the amorphous composite resin (A), the constituent component derived from the hydrocarbon wax (W1) is preferably bonded to the polyester resin segment.
The hydrocarbon wax (W1) is a hydrocarbon wax having a hydroxyl group or a carboxy group from the viewpoints of excellent low-temperature fixability, suppression of deterioration of low-temperature fixability over time, and excellent heat-resistant storage stability, and the hydroxyl group and carboxy group. It may have either one or both of the groups, but from the viewpoint of reactivity with polyester, excellent low-temperature fixability, suppression of deterioration of low-temperature fixability over time, and excellent heat-resistant storage stability. From the viewpoint of the above, a hydrocarbon wax having both a hydroxyl group and a carboxy group is preferable.
The hydrocarbon wax (W1) is obtained by modifying the hydrocarbon wax by a known method. Examples of the raw material of the hydrocarbon wax (W1) include paraffin wax, Fischer-Tropsch wax, microcrystalline wax, polyethylene wax and the like. Among these, paraffin wax and Fischer-Tropsch wax are preferable. Commercially available paraffin wax and Fischer-Tropsch wax as raw materials include "HNP-11", "HNP-9", "HNP-10", "FT-0070", "HNP-51", and "FNP-0090". (The above is manufactured by Nippon Seiro Co., Ltd.) and the like.

The hydrocarbon wax having a hydroxyl group is obtained by modifying a hydrocarbon wax such as paraffin wax or Fischer-Tropsch wax by an oxidation treatment. Examples of the method of oxidation treatment include the methods described in JP-A-62-79267 and JP-A-2010-1979979. Specifically, there is a method of liquid-phase oxidation of a hydrocarbon wax with a gas containing oxygen in the presence of boric acid.
Examples of commercially available products of hydrocarbon wax having a hydroxyl group include "Unirin 700", "Unirin 425", and "Unirin 550" (all manufactured by Baker Petrolite).

Examples of the hydrocarbon wax having a carboxy group include acid-modified wax, which can be obtained by introducing a carboxy group into the above-mentioned hydrocarbon wax such as paraffin wax and Fischer-Tropsch wax. Examples of the acid denaturation method include the methods described in JP-A-2006-328388 and JP-A-2007-84787. 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. Can be done.
Examples of commercially available products of hydrocarbon wax having a carboxy group include high wax 1105A (maleic anhydride-modified ethylene-propylene copolymer, manufactured by Mitsui Chemicals, Inc.) and the like.

The hydrocarbon wax having a hydroxyl group and a carboxy group can be obtained, for example, by the same method as the above-mentioned 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 "Paracol 6420", "Paracol 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, suppression of deterioration of low-temperature fixability over time, and excellent heat-resistant storage stability. 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 preferable. Is 120 mgKOH / g or less, more preferably 100 mgKOH / g or less.

The acid value of the hydrocarbon wax (W1) is preferably 1 mgKOH / g or more, more preferably 5 mgKOH / g, from the viewpoints of excellent low-temperature fixability, suppression of deterioration of low-temperature fixability over time, and excellent heat-resistant storage stability. It is g or more, more preferably 8 mgKOH / g or more, and preferably 30 mgKOH / g or less, more preferably 25 mgKOH / g or less, still more preferably 20 mgKOH / g or less.

The total hydroxyl value and acid value of the hydrocarbon wax (W1) is preferably 41 mgKOH / g or more from the viewpoints of excellent low-temperature fixability, suppression of deterioration of low-temperature fixability over time, and excellent heat-resistant storage stability. More preferably 55 mgKOH / g or more, still more preferably 80 mgKOH / g or more, still more preferably 90 mgKOH / g or more, and preferably 210 mgKOH / g or less, more preferably 175 mgKOH / g or less, still more preferably 140 mgKOH / g or less. More preferably, it is 120 mgKOH / g or less.
The hydroxyl value and acid value of the hydrocarbon wax (W1) are determined by the method described in Examples.

The melting point of the hydrocarbon wax (W1) is preferably 60 ° C. or higher, more preferably 70 ° C. or higher, from the viewpoints of excellent low-temperature fixability, suppression of deterioration of low-temperature fixability over time, and excellent heat-resistant storage stability. It is more preferably 73 ° C. or higher, and preferably 120 ° C. or lower, more preferably 110 ° C. or lower, still more preferably 100 ° C. or lower, still more preferably 95 ° C. or lower, still more preferably 80 ° C. or lower.

The number average molecular weight of the hydrocarbon wax (W1) is preferably 500 or more, more preferably 600 or more, from the viewpoints of excellent low-temperature fixability, suppression of deterioration of low-temperature fixability over time, and excellent heat-resistant storage stability. It is more preferably 700 or more, and preferably 2000 or less, more preferably 1700 or less, still more preferably 1500 or less.

The content of the component derived from the hydrocarbon wax (W1) in the amorphous composite resin (A) is from the viewpoint of excellent low-temperature fixability, suppression of deterioration of low-temperature fixability over time, and excellent heat-resistant storage stability. Therefore, it is preferably 1% by mass or more, more preferably 2% by mass or more, further 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. Hereinafter, it is more preferably 8% by mass or less.

(Physical properties of amorphous composite resin (A))
The softening point of the amorphous composite resin (A) is preferably 70 ° C. or higher, more preferably 90, from the viewpoints of excellent low-temperature fixability, suppression of deterioration of low-temperature fixability over time, and excellent heat-resistant storage stability. ° C. or higher, more preferably 100 ° C. or higher, and preferably 140 ° C. or lower, more preferably 130 ° C. or lower.

The glass transition temperature of the amorphous composite resin (A) is preferably 30 ° C. or higher, more preferably 30 ° C. or higher, from the viewpoints of excellent low-temperature fixability, suppression of deterioration of low-temperature fixability over time, and excellent heat-resistant storage stability. It is 35 ° C. or higher, more preferably 40 ° C. or higher, and preferably 70 ° C. or lower, more preferably 60 ° C. or lower, still more preferably 55 ° C. or lower.

The acid value of the amorphous composite resin (A) is excellent in terms of improving the dispersion stability of the resin particles (X) described later, excellent low-temperature fixability, and suppression of deterioration of low-temperature fixability over time. From the viewpoint of heat-resistant storage, it is preferably 5 mgKOH / g or more, more preferably 10 mgKOH / g or more, further preferably 15 mgKOH / g or more, and preferably 40 mgKOH / g or less, more preferably 35 mgKOH / g or less. More preferably, it is 30 mgKOH / g or less.

The above-mentioned softening point, glass transition temperature and acid value are determined by the method described in Examples. The softening point, glass transition temperature, and acid value of the amorphous composite resin (A) can be appropriately adjusted depending on the type and ratio of the raw material monomers, and the production conditions such as reaction temperature, reaction time, and cooling rate.
When two or more amorphous composite resins (A) are used in combination, it is preferable that the softening point, the glass transition temperature, and the acid value obtained as a mixture thereof are within the above ranges. ..

(Manufacturing of amorphous composite resin (A))
The amorphous composite resin (A) can be produced, for example, by any of the following methods (i) to (iii), but the polycondensation reaction can be produced by the following method (i). It is preferable because it has a high degree of freedom in the reaction temperature of.
(I) A method of performing a condensation reaction with an alcohol component (A-al) and a carboxylic acid component (A-ac) followed by an addition polymerization reaction with a vinyl monomer as a raw material for a vinyl resin segment and a bireactive monomer. When the sex composite resin (A) is desired to contain a constituent component derived from a hydrocarbon wax (W1) having a hydroxyl group or a carboxy group, a polycondensation reaction with an alcohol component and a carboxylic acid component is carried out by the presence of the hydrocarbon wax (W1). Good to do below.
From the viewpoint of reactivity, it is preferable that both reactive monomers are supplied to the reaction system together with the raw material vinyl monomer of the vinyl resin segment. Further, from the viewpoint of reactivity, catalysts such as an esterification catalyst and an esterification co-catalyst may be used, and a radical polymerization initiator and a radical polymerization inhibitor may be used.
Further, a part of the carboxylic acid component (A-ac) is subjected to a polycondensation reaction, then an addition polymerization reaction is carried out, the reaction temperature is raised again, and the rest is added to the reaction system. It is more preferable because the reaction with the bireactive monomer can be further advanced if necessary.

(Ii) Method of performing a polycondensation reaction with a raw material monomer of a polyester resin segment after an addition polymerization reaction with a raw material vinyl monomer and a bireactive monomer of a vinyl resin segment (iii) Alcohol component (A-al) and a carboxylic acid component Method of performing the polycondensation reaction by (A-ac) and the addition polymerization reaction of the raw material vinyl monomer of the vinyl resin segment and the bireactive monomer in parallel. The polycondensation reaction of the methods (i) to (iii) described above and It is preferable that all the addition polymerization reactions are carried out in the same container.

From the viewpoint of the productivity of the amorphous composite resin (A), 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. or higher. It is as follows.
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 the esterification catalyst preferably used for the polycondensation reaction include tin compounds such as dibutyltin oxide and tin (II) di (2-ethylhexanoic acid), and titanium compounds such as titanium diisopropyrate bistriethanolamine. Can be mentioned.
From the viewpoint of reactivity, the amount of the esterification catalyst used is preferably 0.01 part by mass or more, based on 100 parts by mass of the total amount of the alcohol component (A-al) and the carboxylic acid component (A-ac). It is preferably 0.1 part by mass or more, preferably 5 parts by mass or less, and more preferably 2 parts by mass or less.

Examples of the esterification co-catalyst include pyrogallol compounds such as pyrogallol, 3,4,5-trihydroxybenzoic acid, and 3,4,5-trihydroxybenzoic acid ester; 2,3,4-trihydroxybenzophenone, 2,2'. , 3,4-Benzophenone derivatives such as tetrahydroxybenzophenone; catechin derivatives such as epigalocatechin and epigalocatechin gallate are mentioned, and gallic acid is preferable from the viewpoint of reactivity.
The amount of the esterification cocatalyst used in the polycondensation reaction is preferably 0.001 with respect to 100 parts by mass of the total amount of the alcohol component (A-al) and the carboxylic acid component (A-ac) from the viewpoint of reactivity. It is more than parts by mass, more preferably 0.01 parts by mass or more, and preferably 0.5 parts by mass or less, more preferably 0.2 parts by mass or less.

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 part by mass or more, more preferably 0.005 with respect to 100 parts by mass of the total amount of the alcohol component (A-al) and the carboxylic acid component (A-ac). It is more than parts by mass, and 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 productivity of the amorphous composite resin (A), it is preferably 110 ° C. or higher, more preferably 130 ° C. or higher, still more preferable. Is 150 ° C. or higher, and preferably 220 ° C. or lower, more preferably 200 ° C. or lower, still more preferably 180 ° 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 the above 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 vinyl monomer of the vinyl resin segment. More preferably, it is 15 parts by mass or less.

The amount of the hydrocarbon wax (W1) used is a raw material constituting the amorphous composite resin (A) from the viewpoints of excellent low-temperature fixability, suppression of deterioration of low-temperature fixability over time, and excellent heat-resistant storage stability. The content of the hydrocarbon wax (W1) in the mixture is preferably 1% by mass or more, more preferably 2% by mass or more, further preferably 3% by mass or more, and preferably 20% by mass or less, more preferably 20% by mass or less. The amount is 15% by mass or less, more preferably 12% by mass or less, still more preferably 8% by mass or less.
The component derived from the hydrocarbon wax (W1) contained in the amorphous composite resin (A) is a portion where the hydrocarbon wax (W1) is ester-bonded.

[Crystallinity resin (B)]
The crystalline resin (B) is preferably a crystalline polyester resin from the viewpoints of excellent low-temperature fixability, suppression of deterioration of low-temperature fixability over time, and excellent heat-resistant storage stability.
In the present invention, the crystalline resin has the above-mentioned crystallinity index of 0.6 or more and 1.4 or less.
The crystallinity index of the crystalline resin is preferably 0.8 or more, more preferably 0.9 or more, from the viewpoints of excellent low-temperature fixability, suppression of deterioration of low-temperature fixability over time, and excellent heat-resistant storage stability. And preferably 1.3 or less, more preferably 1.2 or less.
The crystallinity index can be appropriately adjusted according to the type and ratio of the raw material monomer, and the production conditions such as reaction temperature, reaction time, and cooling rate, and the value thereof is determined by the method described in Examples.

The crystalline polyester resin is a polycondensate of an alcohol component (B-al) and a carboxylic acid component (B-ac).
The alcohol component (B-al) preferably contains 80 mol% of α, ω-aliphatic diol from the viewpoint of excellent low-temperature fixability, suppression of deterioration of low-temperature fixability over time, and excellent heat-resistant storage stability. Including the above.
The content of α, ω-aliphatic diol is preferably in the alcohol component (B-al) from the viewpoint of excellent low-temperature fixability, suppression of deterioration of low-temperature fixability over time, and excellent heat-resistant storage stability. It is 80 mol% or more, more preferably 85 mol% or more, further preferably 90 mol% or more, further preferably 95 mol% or more, and 100 mol% or less, still more preferably 100 mol%.
The carbon number of the α, ω-aliphatic diol is preferably 4 or more, more preferably 6 or more, from the viewpoints of excellent low-temperature fixability, suppression of deterioration of low-temperature fixability over time, and excellent heat-resistant storage stability. It is more preferably 8 or more, and preferably 16 or less, more preferably 14 or less, still more preferably 12 or less, still more preferably 10 or less.
Specific examples of the α, ω-aliphatic diol include ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, and 1,7-. Heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,11-undecanediol, 1,12-dodecanediol, 1,13-tridecanediol, 1,14- Examples thereof include tetradecanediol. Among these, 1,6-hexanediol and 1,10-decanediol are preferable, 1,10, from the viewpoints of excellent low-temperature fixability, suppression of deterioration of low-temperature fixability over time, and excellent heat-resistant storage stability. -Decandiol is more preferred.

The alcohol component (B-al) may contain an alcohol component other than α and ω-aliphatic diols. 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 and the like. Examples thereof include alcohols having a trivalent value or higher.
These alcohol components (B-al) can be used alone or in combination of two or more.

The carboxylic acid component (B-ac) preferably contains 80 mol% or more of an aliphatic dicarboxylic acid from the viewpoints of excellent low-temperature fixability, suppression of deterioration of low-temperature fixability over time, and excellent heat-resistant storage stability. ..
The content of the aliphatic dicarboxylic acid is preferably 80 mol in the carboxylic acid component (B-ac) from the viewpoint of excellent low-temperature fixability, suppression of deterioration of low-temperature fixability over time, and excellent heat-resistant storage stability. % Or more, more preferably 85 mol% or more, still more preferably 90 mol% or more, still more preferably 95 mol% or more, and 100 mol% or less, and even more preferably 100 mol%.
The carbon number of the aliphatic dicarboxylic acid is preferably 4 or more, more preferably 8 or more, still more preferably 8 or more, from the viewpoints of excellent low-temperature fixability, suppression of deterioration of low-temperature fixability over time, and excellent heat-resistant storage stability. It is 10 or more, and preferably 16 or less, more preferably 14 or less, still more preferably 12 or less.
Examples of the aliphatic dicarboxylic acid include succinic acid, adipic acid, sebacic acid, dodecanedioic acid, tetradecanedioic acid and the like. Among these, sebacic acid and tetradecanedioic acid are preferable, and sebacic acid is more preferable.
The carboxylic acid component (B-ac) includes not only free acids, but also anhydrouss that decompose during the reaction to produce acids, and alkyl esters having 1 to 3 carbon atoms of each carboxylic acid.
These carboxylic acid components (B-ac) can be used alone or in combination of two or more.

The molar equivalent ratio (COOH group / OH group) of the carboxy group (COOH group) of the carboxylic acid component (B-ac) to the hydroxyl group (OH group) of the alcohol component (B-al) has excellent low-temperature fixability and aging. From the viewpoint of suppressing the decrease in low-temperature fixability and excellent heat-resistant storage stability, it is preferably 0.7 or more, more preferably 0.8 or more, still more preferably 0.9 or more, still more preferably 1.0 or more. Yes, and preferably 1.3 or less, more preferably 1.2 or less, still more preferably 1.1 or less.

The softening point of the crystalline resin (B) is preferably 60 ° C. or higher, more preferably 70 ° C. or higher, from the viewpoints of excellent low-temperature fixability, suppression of deterioration of low-temperature fixability over time, and excellent heat-resistant storage stability. It is more preferably 80 ° C. or higher, and preferably 150 ° C. or lower, more preferably 120 ° C. or lower, still more preferably 100 ° C. or lower.

The melting point of the crystalline resin (B) is preferably 50 ° C. or higher, more preferably 60 ° C. or higher, from the viewpoints of excellent low-temperature fixability, suppression of deterioration of low-temperature fixability over time, and excellent heat-resistant storage stability. It is more preferably 65 ° C. or higher, and preferably 100 ° C. or lower, more preferably 90 ° C. or lower, still more preferably 80 ° C. or lower.

The acid value of the crystalline resin (B) is preferably 5 mgKOH / g or more, more preferably 10 mgKOH / g, from the viewpoints of excellent low-temperature fixability, suppression of deterioration of low-temperature fixability over time, and excellent heat-resistant storage stability. It is g or more, more preferably 15 mgKOH / g or more, and preferably 35 mgKOH / g or less, more preferably 30 mgKOH / g or less, still more preferably 25 mgKOH / g or less.

The softening point, melting point, and acid value described above are determined by the method described in Examples. The softening point, melting point, and acid value of the crystalline resin (B) can be appropriately adjusted depending on the type and ratio of the raw material monomers, and the production conditions such as reaction temperature, reaction time, and cooling rate.
When two or more kinds of crystalline resin (B) are used in combination, it is preferable that the values of the softening point, the melting point, and the acid value obtained as a mixture thereof are within the above ranges.

(Manufacturing of crystalline resin (B))
The crystalline resin (B) can be produced by a known method. For example, in the case of a crystalline polyester resin, an alcohol component (B-al) and a carboxylic acid component (B-ac) are contained in an inert gas atmosphere. If necessary, it can be produced by polycondensation using an esterification catalyst, an esterification co-catalyst, a radical polymerization prohibiting agent, or the like.
As the esterification catalyst, the esterification co-catalyst, and the radical polymerization inhibitor, the same ones as in the case of producing the amorphous composite resin (A) described above can be used.
The amount of the esterification catalyst used is preferably 0.01 parts by mass or more, more preferably 0.1 parts by mass, based on 100 parts by mass of the total amount of the alcohol component (B-al) and the carboxylic acid component (B-ac). It is 5 parts by mass or less, and more preferably 2 parts by mass or less.
The temperature of the polycondensation reaction is preferably 120 ° C. or higher, more preferably 160 ° C. or higher, further 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.

[Aqueous medium]
The water-based medium preferably contains water as a main component, and the content of water in the water-based medium is preferably 70% by mass or more from the viewpoint of improving the dispersion stability of the water-based dispersion and from the viewpoint of environmental friendliness. , More preferably 80% by mass or more, further preferably 90% by mass or more, and 100% by mass or less. As the water, deionized water, ion-exchanged water, or distilled water is preferable.
As a component other than water that can form an aqueous medium together with water, an alkyl alcohol having 1 to 5 carbon atoms; a dialkyl ketone having 3 to 5 carbon atoms such as acetone and methyl ethyl ketone; and a cyclic ether such as tetrahydrofuran is dissolved in water. An organic solvent is used.
Among these, methyl ethyl ketone is preferable.

[Conditions of step (1)]
The step (1) preferably includes the following step (1-1), and may subsequently include the step (1-2) in order to obtain toner particles having a core-shell structure.
Step (1-1): A step of aggregating the resin particles (X) containing the amorphous composite resin (A) in the presence of the crystalline resin (B) in an aqueous medium to obtain the agglomerated particles (1). Step (1-2): Resin particles (Z) containing an amorphous resin (C) are added to the agglomerated particles (1) obtained in the step (1-1) to make the agglomerated particles (1). Step of obtaining aggregated particles (2) formed by adhering resin particles (Z) In addition, when step (1) includes step (1-1) and step (1-2), in step (2) The "obtained agglomerated particles" mean "aggregated particles (2) obtained in the step (1-2)". When the step (1) includes only the step (1-1), the "obtained agglomerated particles" in the step (2) are "aggregated particles obtained in the step (1-1)". 1) ”.

[Step (1-1)]
The step (1-1) is preferably any of the following steps (1-1A) to (1-1C).
Step (1-1A): Resin particles (X) containing an amorphous composite resin (A), resin particles (Y) containing a crystalline resin (B), wax, a colorant, and agglomeration, if necessary. Step of aggregating arbitrary components such as an agent and a surfactant in an aqueous medium to obtain aggregated particles Step (1-1B): Resin particles (X) containing an amorphous composite resin (A) and a crystalline resin (B). ), If necessary, a step of aggregating arbitrary components such as wax, colorant, flocculant, and surfactant in an aqueous medium to obtain agglomerated particles Step (1-1C): Amorphous composite resin (A) , Crystalline resin (B) and resin particles (X) containing wax, and if necessary, any component such as wax, colorant, flocculant, surfactant, etc. are aggregated in an aqueous medium to obtain aggregated particles. Steps Among these, from the viewpoint of improving the production stability of the toner, the step (1-1A) or the step (1-1B) is preferable, and the step (1-1A) is more preferable.

[Resin particles (X)]
The resin particles (X) include a resin component containing an amorphous composite resin (A) and, if necessary, an optional component such as a colorant (hereinafter, the resin component and the optional component are collectively referred to as "resin component and the like". ) Is dispersed in an aqueous medium to obtain an aqueous dispersion.
As a method for obtaining an aqueous dispersion of the resin particles (X), a method of adding a resin component or the like to an aqueous medium and performing a dispersion treatment with a disperser or the like, or a method of adding an aqueous medium to a melt of the resin component or the like or an organic solvent solution. Examples thereof include a method of gradually adding and emulsifying the phase (phase emulsification). Among these, the method by phase inversion emulsification is preferable from the viewpoints of excellent low-temperature fixability, suppression of deterioration of low-temperature fixability over time, and excellent heat-resistant storage stability.

The phase inversion emulsification method includes a method (A) in which a resin component or the like is dissolved in an organic solvent and an aqueous medium is added to the obtained solution for phase inversion emulsification, and a resin component or the like is melted and mixed. A method (B) of adding an aqueous medium to the obtained resin mixture for phase inversion emulsification can be mentioned. The method (A) is preferable from the viewpoint of obtaining an aqueous dispersion of homogeneous resin particles (X).
In the method (A), first, a resin component or the like is dissolved in an organic solvent to obtain an organic solvent solution such as the resin component, and then an aqueous medium is added to the solution for phase inversion emulsification.

As the organic solvent used in the phase inversion emulsification method, the solubility parameter (SP value: POLYMER HANDBOOK THIRD EDITION 1989 by John Wiley & Sons, Inc) is preferably 15.0 MPa ^1/2 or more, more preferably 16.0 MPa. ^{It is 1/2} or more, more preferably 17.0 MPa ^1/2 or more, and preferably 26.0 MPa ^1/2 or less, more preferably 24.0 MPa ^1/2 or less, still more preferably 22.0 MPa ^1/2. It is as follows.
Examples of the organic solvent include alcohol solvents such as ethanol (26.0), isopropanol (23.5) and isobutanol (21.5); acetone (20.3), methyl ethyl ketone (19.0) and methyl isobutyl ketone (19.0). 17.2), Ketone solvents such as diethyl ketone (18.0); ether solvents such as dibutyl ether (16.5), tetrahydrofuran (18.6), dioxane (20.5); ethyl acetate (18. 6), acetate-based solvents such as isopropyl acetate (17.4) and the like can be mentioned. The numerical value in parentheses after each solvent is each SP value (unit: MPa ^1/2 ). Among these, at least one selected from a ketone solvent and an acetic acid ester solvent is preferable, and more preferably methyl ethyl ketone, ethyl acetate and isopropyl acetate from the viewpoint of easy removal from the mixed solution after addition of the aqueous medium. At least one selected, more preferably methyl ethyl ketone.

The mass ratio of the organic solvent to the resin constituting the resin particles (X) (the resin constituting the organic solvent / resin particles (X)) is from the viewpoint of dissolving the resin and facilitating the phase inversion to the aqueous medium, and the resin. From the viewpoint of improving the dispersion stability of the particles (X), 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. Below, it is more preferably 1.5 or less.
Further, from the viewpoint of obtaining homogeneous resin particles, excellent low-temperature fixability, suppression of deterioration of low-temperature fixability over time, and excellent heat-resistant storage stability, when obtaining an organic solvent solution such as a resin component, It is preferable to mix 30% by mass or less of water with respect to the organic solvent together with the above-mentioned organic solvent. When water is mixed with an organic solvent, the mixed mass ratio of the organic solvent and water (organic solvent / water) has excellent low-temperature fixability, suppresses deterioration of low-temperature fixability over time, and has excellent heat-resistant storage stability. From the viewpoint of, preferably 70/30 or more, more preferably 80/20 or more, further preferably 85/15 or more, and preferably 98/2 or less, more preferably 95/5 or less, still more preferably 90. It is less than / 10.

In the phase inversion emulsification method, it is preferable to treat the resin with a neutralizing agent.
Examples of the neutralizing agent include basic substances. As basic substances, hydroxides of alkali metals such as lithium hydroxide, sodium hydroxide and potassium hydroxide; nitrogen-containing basic substances such as ammonia, trimethylamine, ethylamine, diethylamine, triethylamine, diethanolamine, triethanolamine and tributylamine. Examples thereof include substances, and among these, alkali metal hydroxides are preferable, and sodium hydroxide is more preferable, from the viewpoint of improving the dispersion stability and cohesiveness of the resin particles (X).

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. , More preferably 100 mol% or less.
The equivalent amount (mol%) of the neutralizing agent used can be calculated by the following formula. When the equivalent amount of the neutralizing agent is 100 mol% or less, it is synonymous with the degree of neutralization, and when the equivalent amount of the neutralizing agent used exceeds 100 mol% by the following formula, the neutralizing agent is the acid group of the resin. The neutralization degree of the resin at this time is considered to be 100 mol%.
Equivalent to use of neutralizer (mol%) = [{Equivalent mass of neutralizer (g) / Equivalent of neutralizer} / [{Weighted average acid value of resin (mgKOH / g) x mass of resin (g) } / (56 x 1000)]] x 100

The amount of the aqueous medium added by the phase inversion emulsification method is preferably 100 parts by mass with respect to 100 parts by mass of the resin component constituting the resin particles (X) from the viewpoint of improving the dispersion stability of the resin particles (X). The above is 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, still more preferably 400 parts by mass or less.
Further, from the viewpoint of improving the dispersion stability of the resin particles (X), the mass ratio of the aqueous medium to the organic solvent (aqueous medium / organic solvent) is preferably 20/80 or more, more preferably 50/50 or more. It is more preferably 80/20 or more, and preferably 97/3 or less, more preferably 93/7 or less, still more preferably 90/10 or less.

The temperature at which the aqueous medium is added is preferably equal to or higher than the glass transition temperature of the amorphous composite resin (A) from the viewpoint of improving the dispersion stability of the resin particles (X), and specifically, preferably 50 ° C. As described above, it is more preferably 60 ° C. or higher, further preferably 70 ° C. or higher, and preferably 85 ° C. or lower, more preferably 80 ° C. or lower, still more preferably 75 ° C. or lower.
From the viewpoint of obtaining resin particles (X) having a small particle size, the addition rate of the aqueous medium is based on 100 parts by mass of the amorphous composite resin (A) constituting the resin particles (X) until the phase inversion is completed. It is preferably 0.1 part by mass or more, more preferably 0.5 part by mass or more, still more preferably 1 part by mass / min or more, still more preferably 3 parts by mass / min or more, and preferably. Is 50 parts by mass / min or less, more preferably 30 parts by mass / min or less, still more preferably 20 parts by mass / min or less. There is no limit to the rate of addition of the aqueous medium after phase inversion.

After the phase inversion emulsification, if necessary, it may have a step of removing the organic solvent from the obtained dispersion.
The method for removing the organic solvent is preferably distillation because it is dissolved in water. In this case, it is preferable to raise the temperature to a temperature equal to or higher than the boiling point of the organic solvent to be used and distill off while stirring. Further, from the viewpoint of maintaining the dispersion stability of the resin particles (X), it is more preferable to distill under reduced pressure, and it is preferable to distill at a constant temperature and pressure. The temperature may be increased after the pressure is reduced, or the temperature may be reduced after the temperature is increased.
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 is preferably 1% by mass or less, more preferably 0.5% by mass or less, still more preferably substantially 0% in the aqueous dispersion.

The solid content concentration of the aqueous dispersion of the resin particles (X) is preferably 5% by mass or more from the viewpoint of improving the productivity of the toner and improving the dispersion stability of the aqueous dispersion of the resin particles (X). , 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, still more preferably 30% by mass or less, still more preferably 25% by mass. It is as follows. 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 (X) in the aqueous dispersion is preferable from the viewpoints of excellent low-temperature fixability, suppression of deterioration of low-temperature fixability over time, and excellent heat-resistant storage stability. Is 0.05 μm or more, more preferably 0.10 μm or more, still more preferably 0.12 μm or more, 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 in which the cumulative volume frequency calculated by the volume fraction is 50% 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 (X) is preferably 5% or more, more preferably 5% or more, from the viewpoint of improving the productivity of the aqueous dispersion of the resin particles (X). It is 15% or more, more preferably 20% or more, and preferably 50% or less, more preferably 40% or less, still more preferably 30% or less, from the viewpoint of obtaining toner for a high-quality image.
The CV value is a value represented by the following formula. The volume average particle size in the following formula is the particle size obtained by multiplying the particle size measured on a volume basis by the ratio of particles having that particle size value and dividing the value obtained thereby by the number of particles. Yes, it is obtained by the method described in Examples described later.
CV value (%) = [standard deviation of particle size distribution (nm) / volume average particle size (nm)] x 100

[Resin particles (Y)]
The resin particles (Y) are preferably obtained as an aqueous dispersion by dispersing a resin component containing the crystalline resin (B) and, if necessary, an optional component such as a wax or a colorant in an aqueous medium.
As in the case of the resin particles (X), the method for obtaining the aqueous dispersion is a method in which the crystalline resin (B) or the like is added to the aqueous medium and dispersed using a disperser, or the aqueous system is added to the crystalline resin (B) or the like. Examples include a method of gradually adding a medium to emulsify the phase inversion. From the viewpoints of excellent low temperature fixability, suppression of deterioration of low temperature fixability over time, and excellent heat storage stability, the method of phase inversion emulsification is used. preferable.
In the phase inversion emulsification method as well, as in the case of the resin particles (X), an aqueous medium is added to a solution obtained by dissolving the resin and other optional components described above in an organic solvent for phase inversion emulsification. The method of The preferred embodiments of the aqueous medium and the organic solvent that can be used are the same as those for producing the resin particles (X) described above.

The mass ratio of the organic solvent to the resin constituting the resin particles (Y) (the resin constituting the organic solvent / resin particles (Y)) is from the viewpoint of dissolving the resin and facilitating the phase inversion to the aqueous medium, and the resin. From the viewpoint of improving the dispersion stability of the particles (Y), 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. Hereinafter, it is more preferably 1 or less.

Further, from the viewpoint of improving the dispersion stability of the resin particles (Y), it is preferable to add a neutralizing agent to the solution. A preferred embodiment of the neutralizer is the same as in the production of the resin particles (X).
The equivalent amount (mol%) of the neutralizing agent to the acid group of the crystalline resin (B) is preferably 10 mol% or more, more preferably 30 mol% or more, and preferably 150 mol% or less, more preferably. Is 120 mol% or less, more preferably 100 mol% or less.

The amount of the aqueous medium to be added is preferably 100 parts by mass or more, more preferably 150 parts by mass, based on 100 parts by mass of the resin constituting the resin particles (Y) from the viewpoint of improving the dispersion stability of the resin particles (Y). It is more than parts by mass, more preferably 200 parts by mass or more, and preferably 900 parts by mass or less, more preferably 600 parts by mass or less, still more preferably 400 parts by mass or less.
The mass ratio of the aqueous medium to the organic solvent (aqueous medium / organic solvent) is preferably 20/80 or more, more preferably 50/50 or more, still more preferably, from the viewpoint of improving the dispersion stability of the resin particles (Y). Is 80/20 or more, and preferably 97/3 or less, more preferably 93/7 or less, still more preferably 90/10 or less.

The temperature at which the aqueous medium is added is preferably 10 ° C. or higher than the melting point of the crystalline resin (B) from the viewpoint of improving the dispersion stability of the resin particles (Y), and specifically, preferably 50. ° C. or higher, more preferably 60 ° C. or higher, still more preferably 70 ° C. or higher, and preferably 85 ° C. or lower, more preferably 80 ° C. or lower, still more preferably 75 ° C. or lower.
From the viewpoint of obtaining resin particles (Y) having a small particle size, the addition rate of the aqueous medium is preferably 0.1 with respect to 100 parts by mass of the resin constituting the resin particles (Y) until the phase inversion is completed. By mass / min or more, more preferably 0.5 parts by mass 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 or less. , More preferably 30 parts by mass / min or less, still more preferably 20 parts by mass / min or less, still more preferably 10 parts by mass / min or less. There is no limit to the rate of addition of the aqueous medium after phase inversion.

After the phase inversion emulsification, if necessary, it may have a step of removing the organic solvent from the obtained dispersion.
The method for removing the organic solvent and the preferred embodiment of the residual amount of the organic solvent in the aqueous dispersion are the same as those for producing the resin particles (X) described above.

The solid content concentration of the obtained aqueous dispersion of the resin particles (Y) is preferably 5 mass from the viewpoint of improving the productivity of the toner and improving the dispersion stability of the aqueous dispersion of the resin particles (Y). % Or more, more preferably 10% by mass or more, still more preferably 15% by mass or more, and preferably 50% by mass or less, more preferably 40% by mass or less, still more preferably 30% by mass or less, still more preferably 25. It is mass% or less. 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 (Y) in the aqueous dispersion is preferable from the viewpoints of excellent low-temperature fixability, suppression of deterioration of low-temperature fixability over time, and excellent heat-resistant storage stability. Is 0.05 μm or more, more preferably 0.10 μm or more, still more preferably 0.12 μm or more, and preferably 0.80 μm or less, more preferably 0.40 μm or less, still more preferably 0.20 μm or less. ..

The coefficient of variation (CV value) (%) of the particle size distribution of the resin particles (Y) is preferably 5% or more, more preferably 5% or more, from the viewpoint of improving the productivity of the aqueous dispersion of the resin particles (Y). It is 15% or more, more preferably 20% or more, and preferably 50% or less, more preferably 40% or less, still more preferably 30% or less, from the viewpoint of obtaining toner for a high-quality image.

The mass ratio of the amorphous composite resin (A) and the crystalline resin (B) in the step (1) [amorphous composite resin / crystalline resin] has excellent low-temperature fixability and low-temperature fixability over time. From the viewpoint of suppressing the decrease in the amount of the resin, the amount is preferably 50/50 or more, more preferably 55/45 or more, still more preferably 60/40 or more, and preferably 95/5 or less, more preferably 90/10 or less, further. It is preferably 85/15 or less, more preferably 80/20 or less, still more preferably 75/25 or less. The mass ratio [amorphous composite resin / crystalline resin] is preferably 50/50 or more, more preferably 60/40 or more, still more preferably 70/30 or more, from the viewpoint of excellent heat-resistant storage stability. It is more preferably 75/25 or more, and preferably 95/5 or less, more preferably 90/10 or less, still more preferably 85/15 or less.
The total content of the amorphous composite resin (A) and the crystalline resin (B) is preferably 80% by mass or more, more preferably 90% by mass or more, still more preferably 90% by mass or more, among the resin components contained in the aggregated particles (1). Is 95% by mass or more, and is 100% by mass or less, and more preferably 100% by mass.

[Wax particles]
In the step (1), the wax may be further agglomerated in an aqueous medium to obtain a dispersion of agglomerated particles.
When the step (1) is a step (1-1A) or a step (1-1B), it is preferable to use a dispersion liquid of wax particles in which wax is dispersed in an aqueous medium.
The wax used in the step (1) includes low molecular weight polyolefins such as polyethylene, polypropylene and polybutene; silicone wax; fatty acid amides such as oleic acid amide and stearic acid amide; and plants such as carnauba wax, rice wax and candelilla wax. Examples include animal waxes such as honey wax; mineral waxes such as Montan wax, paraffin wax and Fishertropsh wax; and synthetic waxes such as ester wax. These waxes can be used alone or in combination of two or more. Among these, at least one selected from carnauba wax and paraffin wax is preferable, and paraffin is more preferable, from the viewpoints of excellent low-temperature fixability, suppression of deterioration of low-temperature fixability over time, and excellent heat-resistant storage stability. It is wax.

The melting point of the wax is preferably 60 ° C. or higher, more preferably 65 ° C. or higher, still more preferably 70 ° C., from the viewpoints of excellent low-temperature fixability, suppression of deterioration of low-temperature fixability over time, and excellent heat-resistant storage stability. As described above, it is more preferably 73 ° C. or higher, and preferably 100 ° C. or lower, more preferably 95 ° C. or lower, still more preferably 90 ° C. or lower, still more preferably 85 ° C. or lower.
In the present invention, the melting point of wax is determined by the method described in Examples. When two or more kinds of waxes are used in combination, the melting point of the wax having the largest mass ratio among the waxes contained in the toner is defined as the melting point of the wax in the present invention. If all the ratios are the same, the lowest value is used.

The wax particles are preferably obtained as a dispersion liquid in which the wax is dispersed in an aqueous medium, and more preferably obtained as an aqueous dispersion of the wax particles by mixing and dispersing the wax with the resin particles (P) in the aqueous medium.
The resin particles (P) used for dispersing the wax are not particularly limited, but from the viewpoint of dispersion stability in the toner particles, a preferable example is the same as the above-mentioned resin particles (X).

The dispersion liquid of the wax particles is preferably obtained by dispersing the aqueous dispersion of the wax and the resin particles (P) and, if necessary, the aqueous medium at a temperature equal to or higher than the melting point of the wax using a disperser.
Examples of the disperser include a homogenizer, an ultrasonic disperser, a high-pressure disperser, and the like.
Examples of the ultrasonic disperser include an ultrasonic homogenizer. The commercially available products include "US-150T", "US-300T", "US-600T" (manufactured by Nissei Tokyo Office Co., Ltd.), "SONIFIER (registered trademark) 4020-400", and "SONIFIER (registered trademark) 4020". -800 "(manufactured by Branson) and the like.
Examples of the device commercially available as a high-pressure disperser include a high-pressure wet atomizing device "Nanomizer (registered trademark) NM2-L200-D08" (manufactured by Yoshida Kikai Kogyo Co., Ltd.).
Further, before using the disperser, the wax, the resin particles (P), and the aqueous medium may be pre-dispersed in advance with a mixer such as a homomixer or a ball mill.
A preferred embodiment of the aqueous medium of the dispersion liquid of the wax particles is the same as the aqueous medium used for obtaining the aqueous dispersion of the resin particles (X).

For the dispersion of the wax particles in the aqueous medium, a surfactant may be used from the viewpoint of improving the dispersion stability of the wax particles and from the viewpoint of obtaining uniform aggregated particles.
Examples of the surfactant include nonionic surfactants, anionic surfactants, cationic surfactants, etc., from the viewpoint of improving the dispersion stability of the wax particles, and the cohesiveness of the wax particles and the resin particles. From the viewpoint of improvement, an anionic surfactant is preferable.
Examples of the surfactant include sodium dodecylbenzene sulfonate, sodium dodecyl sulfate, sodium lauryl ether sulfate, dipotassium alkenylsuccinate and the like. Among these, dipotassium alkenyl succinate is preferable.

The content of the surfactant in the wax particle dispersion is preferably 5% by mass or less, more preferably 2% by mass or less, and more preferably 1% by mass or less from the viewpoint of preventing the release of the wax particles during toner production. , More preferably 0.5% by mass or less, and 0% by mass or more.

The solid content concentration of the wax particle dispersion is preferably 5% by mass or more, more preferably 10% by mass or more, and further, from the viewpoint of improving the productivity of the toner and the dispersion stability of the wax particle dispersion. It is preferably 15% by mass or more, and preferably 50% by mass or less, more preferably 30% by mass or less, still more preferably 25% by mass or less.

The volume median particle diameter (D ₅₀ ) of the wax particles is preferably 0.10 μm or more, more preferably 0.20 μm or more, still more preferably 0.30 μm or more, and from the viewpoint of obtaining uniform aggregated particles. It is preferably 1.0 μm or less, more preferably 0.80 μm or less, still more preferably 0.60 μm or less.

The coefficient of variation (CV value) of the particle size distribution of the wax particles is preferably 10% or more, more preferably 25% or more from the viewpoint of improving the productivity of the toner, and from the viewpoint of obtaining uniform aggregated particles. It is preferably 50% or less, more preferably 45% or less, still more preferably 40% or less.
The volume median particle diameter and CV value of the wax particles are specifically determined by the methods described in Examples described later.

The amount of wax used is based on 100 parts by mass of the total amount of the resin component of the toner from the viewpoints of toner releasability, excellent low-temperature fixability, suppression of deterioration of low-temperature fixability over time, and excellent heat-resistant storage stability. It is preferably 1 part by mass or more, more preferably 3 parts by mass or more, further preferably 5 parts by mass or more, and preferably 20 parts by mass or less, more preferably 15 parts by mass or less, still more preferably 10 parts by mass. It is as follows.

[Colorant particles]
In the step (1), the colorant may be further agglomerated in an aqueous medium to obtain a dispersion of agglomerated particles.
Examples of the colorant used in the step (1) include pigments and dyes, and pigments are preferable from the viewpoint of improving the image density of printed matter.
Examples of the pigment include a cyan pigment, a yellow pigment, a magenta pigment, and a black pigment. As the cyan pigment, a phthalocyanine pigment is preferable, and copper phthalocyanine is more preferable. The yellow pigment is preferably a monoazo pigment, an isoindoline pigment, or a benzimidazolone pigment. The magenta pigment is preferably a soluble azo pigment such as a quinacridone pigment or a BONA lake pigment, or an insoluble azo pigment such as a naphthol AS pigment. The black pigment is preferably carbon black.
Examples of the dye include acrydin dye, azo dye, benzoquinone dye, azine dye, anthraquinone dye, indigo dye, phthalocyanine dye, aniline black dye and the like.
The colorants can be used alone or in combination of two or more.

When the colorant is mixed in the step (1), it is preferable to use a dispersion of colorant particles in which the colorant is dispersed in an aqueous medium.
The dispersion liquid of the colorant particles is preferably obtained by dispersing the colorant and the aqueous medium in the presence of a surfactant or the like using a disperser. As the disperser, a homogenizer, an ultrasonic disperser, or the like is preferable.
A preferred embodiment of the aqueous medium is the same as the aqueous medium used for the aqueous dispersion of the resin particles (X) described above.

When the colorant particles are dispersed in an aqueous medium, it is preferable to disperse the colorant particles in the presence of a surfactant from the viewpoint of improving the dispersion stability of the colorant particles.
Examples of the surfactant include nonionic surfactants, anionic surfactants, cationic surfactants, etc., from the viewpoint of improving the dispersion stability of the colorant particles, and the colorant particles and the resin particles (X). ) And the resin particles (Y) are preferably anionic surfactants from the viewpoint of improving the cohesiveness. Specific examples thereof include sodium dodecylbenzene sulfonate, sodium dodecyl sulfate, sodium lauryl ether sulfate, dipotassium alkenylsuccinate and the like, and sodium dodecylbenzene sulfonate is preferable.

The content of the surfactant in the colorant particle dispersion is preferable from the viewpoint of improving the dispersion stability of the colorant particles and improving the cohesiveness of the colorant particles at the time of preparing the toner to prevent the release. Is 0.1% by mass or more, more preferably 0.5% by mass or more, still more preferably 1.0% by mass or more, and preferably 5.0% by mass or less, more preferably 4.5% by mass or less. Is.

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

The volume median particle diameter (D ₅₀ ) of the colorant particles is preferably 0.050 μm or more, more preferably 0.080 μm or more, still more preferably 0.10 μm or more, from the viewpoint of obtaining toner for a high-quality image. And, preferably 0.50 μm or less, more preferably 0.30 μm or less, still more preferably 0.15 μm or less.
From the viewpoint of improving the image density of the printed matter, the amount of the colorant is preferably 2 parts by mass or more, more preferably 3 parts by mass or more, and further preferably 5 parts by mass with respect to 100 parts by mass of the total amount of the resin component of the toner. The above, and preferably 30 parts by mass or less, more preferably 20 parts by mass or less, still more preferably 15 parts by mass or less.

[Aggregated particles (1)]
The agglomerated particles (1) are obtained by mixing an arbitrary component such as a wax particle dispersion containing wax, a coagulant, a surfactant, and a colorant with a dispersion of resin particles, if necessary, and aggregating them.
Specifically, first, an aqueous dispersion of resin particles and, if necessary, an arbitrary component such as a wax particle dispersion, a surfactant, and a colorant are mixed in an aqueous medium to obtain a mixed dispersion. Is preferable. Then, when the components in the mixed dispersion are agglomerated to obtain the dispersion of the agglomerated particles (1), it is preferable to add a coagulant from the viewpoint of efficiently agglomerating.
The mixing order of each component is not particularly limited, and each component may be added in any order, or each component may be added at the same time.
The mixing temperature in the step (1-1) is preferably 0 ° C. or higher, more preferably 10 ° C. or higher, still more preferably 20 ° C. or higher, from the viewpoint of controlling aggregation to obtain agglomerated particles having a desired particle size. Then, it is preferably 40 ° C. or lower, more preferably 30 ° C. or lower.

When preparing the mixed dispersion, it may be carried out in the presence of a surfactant from the viewpoint of improving the dispersion stability of arbitrary components such as resin particles and wax particles added as needed.
Surfactants include, for example, anionic surfactants such as sulfate ester-based, sulfonate-based, phosphoric acid ester-based and soap-based (for example, alkyl ether carboxylate, etc.); amine salt type and quaternary ammonium salt. Cationic surfactants such as molds; polyoxyethylene alkylaryl ethers such as polyoxyethylene nonylphenyl ether, polyoxyethylene alkyl ethers such as polyoxyethylene oleyl ether and polyoxyethylene lauryl ether, and polyoxyethylene alkenyl ethers. , Polyoxyethylene sorbitan esters such as polyoxyethylene sorbitan monolaurate and polyoxyethylene sorbitan monostearate, polyoxyethylene fatty acid esters such as polyethylene glycol monolaurate, polyethylene glycol monostearate and polyethylene glycol monooleate. , Nonionic surfactants such as oxyethylene / oxypropylene block copolymers and the like. Among these, nonionic surfactants are preferable, polyoxyethylene alkyl ethers and polyoxyethylene alkenyl ethers are preferable, and polyoxyethylene lauryl ethers are more preferable.
When a surfactant is used, the amount used is preferably 0.1 part by mass or more, more preferably 0.5 part by mass or more, and preferably 10 parts by mass with respect to 100 parts by mass of the resin particles. Hereinafter, it is more preferably 5 parts by mass or less, still more preferably 3 parts by mass or less.

[Coagulant]
From the viewpoint of efficient aggregation, it is preferable to add a flocculant.
The coagulant is preferably an electrolyte and more preferably a salt from the viewpoint of obtaining a toner having a desired particle size while preventing excessive agglomeration.
Examples of the flocculant include a cationic surfactant of a quaternary salt, an organic flocculant such as polyethyleneimine; an inorganic metal salt, an inorganic ammonium salt, and an inorganic flocculant such as a divalent or higher metal complex. Among these, an inorganic flocculant is preferable, an inorganic metal salt and an inorganic ammonium salt are more preferable, and an inorganic ammonium salt is more preferable, from the viewpoint of improving the cohesiveness and obtaining uniform agglomerated particles.
The valence of the cation of the inorganic flocculant is preferably pentavalent or less, more preferably divalent or less, and further preferably monovalent 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. Ammonium ions are preferable from the viewpoint of improving cohesiveness and obtaining uniform agglomerated particles.
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.
The flocculant is more preferably ammonium sulfate.

The amount of the aggregating agent used is preferably 5 parts by mass or more with respect to 100 parts by mass of the resin constituting the resin particles (X) and the resin particles (Y) from the viewpoint of controlling aggregation to obtain a desired particle size. More preferably 10 parts by mass or more, further preferably 20 parts by mass or more, and from the viewpoint of improving the low-temperature fixability and heat-resistant storage stability of the toner, preferably 50 parts by mass or less, more preferably 45 parts by mass or less. More preferably, it is 40 parts by mass or less.

The flocculant is preferably added as an aqueous solution by dropping into the mixed dispersion. The flocculant may be added at one time, intermittently or continuously. Sufficient stirring is preferable at the time of addition and after the addition is completed.
Further, from the viewpoint of controlling aggregation to obtain aggregated particles having a desired particle size and particle size distribution, it is preferable to use the aqueous solution of the flocculant by adjusting the pH to 7.0 or more and 9.0 or less.
The temperature at which the flocculant is dropped is preferably 0 ° C. or higher, more preferably 10 ° C. or higher, still more preferably 20 ° C. or higher, and preferably 45 ° C. or lower, more preferably 45 ° C. or lower, from the viewpoint of improving the productivity of the toner. Is 40 ° C. or lower, more preferably 35 ° C. or lower, still more preferably 30 ° C. or lower.

Further, from the viewpoint of promoting aggregation and obtaining aggregated particles having a desired particle size and particle size distribution, it is preferable to 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, further preferably 55 ° C. or higher, and preferably 70 ° C. or lower, more preferably 65 ° C. or lower, still more preferably 63 ° C. or lower. is there.
It is preferable to confirm the progress of aggregation by monitoring the volume median particle diameter of the aggregated particles in the above-mentioned temperature range.

The volume median particle diameter (D ₅₀ ) of the agglomerated particles (1) is preferably 2 μm or more, from the viewpoint of excellent low temperature fixability, suppression of deterioration of low temperature fixability over time, and excellent heat storage 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 volume median particle diameter of the agglomerated particles (1) is determined by the method described in Examples described later.

[Step (1-2)]
[Amorphous resin (C)]
When the step (1-2) is included, the amorphous resin (C) is a resin having a crystallinity index of more than 1.4 or less than 0.6. The crystallinity index can be adjusted according to the type and ratio of the raw material monomers, production conditions (for example, reaction temperature, reaction time, cooling rate, etc.), and the values thereof will be described in Examples described later. Obtained by the method.

The amorphous resin (C) is preferably an alcohol component (C-al) and a carboxylic acid component (C-al) from the viewpoint of excellent low-temperature fixability, suppression of deterioration of low-temperature fixability over time, and excellent heat-resistant storage stability. It is an amorphous polyester resin obtained by polycondensing with C-ac).

[Alcohol component (C-al)]
The alcohol component (C-al) preferably contains an alkylene oxide adduct of bisphenol A from the viewpoints of excellent low-temperature fixability, suppression of deterioration of low-temperature fixability over time, and excellent heat-resistant storage stability, and is more preferable. Is equation (I):

[In the formula, OR ¹ and R ¹ O are alkylene oxides, R ¹ is an alkylene group having 2 or 3 carbon atoms, preferably an ethylene group, and x and y are positive numbers indicating the average number of moles of alkylene oxide added. The alkylene oxide adduct of bisphenol A represented by [shown, the sum of x and y is 1 or more, preferably 1.5 or more, and 16 or less, preferably 8 or less, more preferably 4 or less] is used. Including.

The alcohol component (C-al) contains 80 mol% or more of the alkylene oxide adduct of bisphenol A. The content of the alkylene oxide adduct of bisphenol A in the alcohol component (C-al) is preferably from the viewpoint of excellent low-temperature fixability, suppression of deterioration of low-temperature fixability over time, and excellent heat-resistant storage stability. 80 mol% or more, more preferably 90 mol% or more, still more preferably 95 mol% or more, still more preferably 98 mol% or more, and 100 mol% or less, and even more preferably 100 mol%. ..
The alkylene oxide adduct of bisphenol A is preferably an ethylene oxide adduct of bisphenol A from the viewpoints of excellent low temperature fixability, suppression of deterioration of low temperature fixability over time, and excellent heat storage stability.
The average number of moles of alkylene oxide added as the alkylene oxide adduct of bisphenol A is preferably 1 or more from the viewpoint of excellent low temperature fixability, suppression of decrease in low temperature fixability over time, and excellent heat storage stability. It is preferably 1.2 or more, more preferably 1.5 or more, and preferably 16 or less, more preferably 12 or less, still more preferably 8 or less, still more preferably 4 or less.

The alcohol component (C-al) may contain a polyhydric alcohol other than the alkylene oxide adduct of bisphenol A. Other alcohol components that can be contained in the alcohol component (C-al) are the same as those of the alcohol component (A-al) constituting the polyester resin segment of the amorphous composite resin (A) described above.

[Carboxylic acid component (C-ac)]
Examples of the carboxylic acid component (C-ac) include dicarboxylic acids and trivalent or higher valent carboxylic acids. Of these, a dicarboxylic acid is preferable, and it is more preferable to use a dicarboxylic acid in combination with a trivalent or higher valent carboxylic acid.

Examples of the dicarboxylic acid include aromatic dicarboxylic acid, aliphatic dicarboxylic acid, and alicyclic dicarboxylic acid, and preferably at least one selected from aromatic dicarboxylic acid and aliphatic dicarboxylic acid, more preferably aromatic dicarboxylic acid. Is.
The carboxylic acid component (C-ac) includes not only free acids, but also anhydrouss that decompose during the reaction to produce acids, and alkyl esters having 1 to 3 carbon atoms of each carboxylic acid.
Examples of the aromatic dicarboxylic acid include phthalic acid, isophthalic acid, terephthalic acid, etc., and isophthalic acid is preferable from the viewpoint of excellent low-temperature fixability, suppression of deterioration of low-temperature fixability over time, and excellent heat-resistant storage stability. It is an acid or terephthalic acid, more preferably terephthalic acid.
The aliphatic dicarboxylic acid has a carbon number of preferably 2 or more, more preferably 3 or more, from the viewpoints of excellent low-temperature fixability, suppression of deterioration of low-temperature fixability over time, and excellent heat-resistant storage stability. And it is preferably 30 or less, more preferably 20 or less.
Examples of aliphatic dicarboxylic acids 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, and azelaic acid. Examples thereof include succinic acid substituted with an alkyl group having 1 to 20 carbon atoms or an alkenyl group having 2 to 20 carbon atoms. Examples of the succinic acid substituted with an alkyl group having 1 to 20 carbon atoms or an alkenyl group having 2 to 20 carbon atoms include dodecyl succinic acid, dodecenyl succinic acid, and octenyl succinic acid.
Among these, succinic acid substituted with an alkyl group having 1 to 20 carbon atoms or an alkenyl group having 2 to 20 carbon atoms is preferable, and dodecenyl succinic acid is more preferable. Further, from the viewpoint of excellent low-temperature fixability, suppression of deterioration of low-temperature fixability over time, and excellent heat-resistant storage stability, it is replaced with an alkyl group having 1 to 20 carbon atoms or an alkenyl group having 2 to 20 carbon atoms. It is more preferable to use the obtained succinic acid in combination with terephthalic acid, fumaric acid, adipic acid, sebacic acid and the like, and it is further preferable to use terephthalic acid, fumaric acid, and dodecenyl succinic acid in combination.

The trivalent or higher valent carboxylic acid is preferably a trivalent carboxylic acid, more preferably, from the viewpoints of excellent low-temperature fixability, suppression of deterioration of low-temperature fixability over time, and excellent heat-resistant storage stability. , Trimellitic acid and at least one selected from the acid anhydride thereof, more preferably trimellitic acid anhydride.
Further, the content when a polyvalent carboxylic acid having a trivalent value or higher is contained is a carboxylic acid component (C) from the viewpoint of excellent low-temperature fixability, suppression of deterioration of low-temperature fixability over time, and excellent heat-resistant storage stability. -Ac), preferably 3 mol% or more, more preferably 5 mol% or more, and preferably 30 mol% or less, more preferably 20 mol% or less.
These carboxylic acid components (C-ac) can be used alone or in combination of two or more.

The molar equivalent ratio (COOH group / OH group) of the carboxy group (COOH group) of the carboxylic acid component (C-ac) to the hydroxyl group (OH group) of the alcohol component (C-al) is a viewpoint for obtaining a resin having preferable thermophysical properties. Therefore, it is preferably 0.7 or more, more preferably 0.8 or more, and preferably 1.2 or less, more preferably 1.1 or less, still more preferably 1.05 or less.

The softening point of the amorphous resin (C) is preferably 90 ° C. or higher, more preferably 100 ° C., from the viewpoints of excellent low-temperature fixability, suppression of deterioration of low-temperature fixability over time, and excellent heat-resistant storage stability. As mentioned above, it is 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.

The glass transition temperature of the amorphous resin (C) is preferably 40 ° C. or higher, more preferably 50, from the viewpoints of excellent low-temperature fixability, suppression of deterioration of low-temperature fixability over time, and excellent heat-resistant storage stability. ° C. or higher, more preferably 60 ° C. or higher, and preferably 90 ° C. or lower, more preferably 80 ° C. or lower, still more preferably 70 ° C. or lower.

The acid value of the amorphous resin (C) is preferably 5 mgKOH / g or more, more preferably 10 mgKOH / g or more, still more preferably 15 mgKOH / g, from the viewpoint of improving the dispersion stability of the resin particles (Z) described later. The above, and preferably 35 mgKOH / g or less, more preferably 30 mgKOH / g or less, still more preferably 25 mgKOH / g or less.

The above-mentioned softening point, glass transition temperature and acid value are determined by the methods described in Examples described later. The softening point, glass transition temperature, and acid value of the amorphous resin (C) can be appropriately adjusted depending on the type and ratio of the raw material monomers, and the production conditions such as reaction temperature, reaction time, and cooling rate.
When two or more types of amorphous resin (C) are used in combination, it is preferable that the softening point, the glass transition temperature, and the acid value obtained as a mixture thereof are within the above ranges. ..

[Manufacturing of amorphous resin (C)]
The amorphous resin (C) contains, for example, an alcohol component (C-al) and a carboxylic acid component (C-ac) in an inert gas atmosphere, if necessary, an esterification catalyst, an esterification cocatalyst, and a radical. It can be produced by polycondensation using a polymerization inhibitor or the like.
Examples of the esterification catalyst, the esterification cocatalyst, and the radical polymerization inhibitor include the same as those used for producing the polyester resin segment of the amorphous composite resin (A) described above. Similarly, the conditions shown in the production of the polyester resin segment of the amorphous composite resin (A) described above can be applied to the conditions such as these suitable amounts and the reaction temperature of the polycondensation reaction.

[Resin particles (Z)]
The resin particles (Z) are produced by a method in which a resin component containing an amorphous resin (C) is dispersed in an aqueous medium to obtain the resin particles (Z) as an aqueous dispersion.
The resin particles (Z) can be obtained as an aqueous dispersion of the resin particles (Z) by dispersing a resin component containing an amorphous resin (C) and, if necessary, the above-mentioned optional component in an aqueous medium. Is preferable.
The method for obtaining the aqueous dispersion and suitable conditions thereof are the same as in the case of the resin particles (X).

The solid content concentration of the aqueous dispersion of the resin particles (Z) is preferably 5% by mass or more, more preferably 5% by mass or more, from the viewpoint of improving the productivity of the toner and the dispersion stability of the resin particles (Z). It is 10% by mass or more, more preferably 15% by mass or more, and preferably 50% by mass or less, more preferably 40% by mass or less, still more preferably 30% by mass or less. The solid content is the total amount of non-volatile components such as resin and surfactant.

The volume median particle diameter (D ₅₀ ) of the resin particles (Z) in the aqueous dispersion is preferably 0.05 μm or more, more preferably 0.08 μm or more, from the viewpoint of obtaining a toner that can obtain a high-quality image. It is more preferably 0.10 μm or more, and preferably 0.50 μm or less, more preferably 0.40 μm or less, still more preferably 0.30 μm or less.

The coefficient of variation (CV value) (%) of the particle size distribution of the resin particles (Z) is preferably 5% or more, more preferably 5% or more, from the viewpoint of improving the productivity of the aqueous dispersion of the resin particles (Z). It is 10% or more, more preferably 15% or more, and preferably 50% or less, more preferably 40% or less, still more preferably 30% or less, from the viewpoint of obtaining a toner that can obtain a high-quality image.

In addition to the amorphous resin (C), the resin particles (Z) include known resins used for toner, such as polyesters other than the amorphous resin (C), styrene-acrylic copolymers, epoxies, and polycarbonates. It can contain polyurethane and the like.
The content of the amorphous resin (C) in all the resin components contained in the resin particles (Z) is from the viewpoint of excellent low-temperature fixability, suppression of deterioration of low-temperature fixability over time, and excellent heat-resistant storage stability. Therefore, it is preferably 80% by mass or more, more preferably 90% by mass or more, still more preferably 95% by mass or more, still more preferably 100% by mass.
Further, the resin particles (Z) may contain the above-mentioned colorant and charge control agent, if necessary. Further, an additive such as a reinforcing filler such as a fibrous substance, an antioxidant, and an antiaging agent may be contained as long as the effect of the present invention is not impaired.

[Aggregated particles (2)]
In the step (1-2), the resin particles (Z) are added to the agglomerated particles (1) obtained in the step (1-1), and the resin particles (Z) are attached to the agglomerated particles (1). This is a step of obtaining agglomerated particles (2), which is obtained by adding an aqueous dispersion of resin particles (Z) to the above-mentioned dispersion of agglomerated particles (1) to further add resin particles (Z) to the agglomerated particles (1). ) Is adhered to obtain a dispersion of agglomerated particles (2).

Before adding the aqueous dispersion of the resin particles (Z) to the dispersion of the agglomerated particles (1), an aqueous medium may be added to the dispersion of the agglomerated particles (1) to dilute it. Further, when the aqueous dispersion of the resin particles (Z) is added to the dispersion liquid of the agglomerated particles (1), the agglomeration described above is performed in order to efficiently attach the resin particles (Z) to the agglomerated particles (1). The agent may be used in step (1-2).

The temperature at which the aqueous dispersion of the resin particles (Z) is added is from the viewpoint of obtaining uniform aggregated particles, excellent low-temperature fixability, suppression of deterioration of low-temperature fixability over time, and excellent heat-resistant storage stability. Therefore, it is preferably 40 ° C. or higher, more preferably 45 ° C. or higher, further 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 aqueous dispersion of the resin particles (Z) may be added continuously over a certain period of time, at one time, or in multiple portions, but over a certain period of time. It is preferable to add them continuously or in a plurality of times. By adding in this way, the resin particles (Z) are likely to selectively adhere to the agglomerated particles (1). Above all, from the viewpoint of promoting selective adhesion and improving the productivity of toner, it is preferable to add the toner continuously over a certain period of time.
The addition rate when the aqueous dispersion of the resin particles (Z) is continuously added is 100 mass of the agglomerated particles (1) from the viewpoint of obtaining uniform agglomerated particles (2) and improving the productivity of the toner. The resin particles (Z) are preferably 0.03 parts by mass / min or more, more preferably 0.05 parts by mass / min or more, still more preferably 0.07 parts by mass / min or more, and based on parts. It is preferably 1.0 part by mass or less, more preferably 0.5 part by mass or less, and further preferably 0.3 part by mass or less.

The amount of the resin particles (Z) added is the resin particles (Z), the resin particles (X), and the resin from the viewpoints of excellent low-temperature fixability, suppression of deterioration of low-temperature fixability over time, and excellent heat-resistant storage stability. The mass ratio [(Z) / ((X) + (Y))] with the total of the particles (Y) is preferably 0.05 or more, more preferably 0.10 or more, still more preferably 0.13 or more. The amount is more preferably 0.15 or more, and preferably 0.5 or less, more preferably 0.3 or less, still more preferably 0.2 or less.

In the production method of the present invention, in addition to the amorphous composite resin (A), the crystalline resin (B), and the amorphous resin (C), the toner is used as long as the effects of the present invention are not impaired. Known resins such as styrene-acrylic copolymer, epoxy, polycarbonate, polyurethane and the like can be contained.
When the step (1-2) is performed, the total content of the amorphous composite resin (A), the crystalline resin (B), and the amorphous resin (C) is excellent in low temperature fixability and over time. From the viewpoint of suppressing the decrease in low-temperature fixability and excellent heat-resistant storage stability, the resin component of the toner is preferably 80% by mass or more, more preferably 90% by mass or more, still more preferably 95% by mass or more, still more preferably 98. It is 100% by mass or more, more preferably 100% by mass.
Further, the mass ratio [(C) / ((A) + (B))] of the total of the amorphous resin (C), the amorphous composite resin (A) and the crystalline resin (B) is the toner. From the viewpoint of improving low temperature fixability and durability, it is preferably 0.05 or more, more preferably 0.10 or more, still more preferably 0.13 or more, still more preferably 0.15 or more, and preferably 0. It is 5.5 or less, more preferably 0.3 or less, still more preferably 0.2 or less.

The volume median particle diameter (D ₅₀ ) of the agglomerated particles (2) is excellent in terms of obtaining a toner that can obtain a high-quality image, excellent low-temperature fixability, and suppression of deterioration of low-temperature fixability over time. From the viewpoint of heat-resistant storage, 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.

In the step (1-2), the agglomeration may be stopped when the agglomerated particles have grown to an appropriate particle size as a toner.
Examples of the method for stopping the aggregation include a method of cooling the dispersion, a method of adding an aggregation inhibitor, a method of diluting the dispersion, and the like. From the viewpoint of surely preventing unnecessary aggregation, a method of adding an aggregation terminator to stop aggregation is preferable.

[Coagulation terminator]
As the aggregation terminator, a surfactant is preferable, and an anionic surfactant is more preferable. Examples of the anionic surfactant include alkylbenzene sulfonate, alkyl sulfate, alkyl ether sulfate, polyoxyalkylene alkyl ether sulfate and the like, preferably polyoxyalkylene alkyl ether sulfate, and more preferably polyoxyethylene. Lauryl ether sulfate, more preferably sodium polyoxyethylene lauryl ether sulfate.
The aggregation terminator can be used alone or in combination of two or more.
The amount of the aggregation terminator added is preferably 0.1 part by mass or more, 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 surely preventing unnecessary aggregation. It is more preferably 2 parts by mass or more, and from the viewpoint of reducing the residue on the toner, it is preferably 25 parts by mass or less, more preferably 15 parts by mass or less, still more preferably 10 parts by mass or less. The aggregation terminator is preferably added in an aqueous solution from the viewpoint of improving the productivity of the toner.

The temperature at which the aggregation terminator is added is preferably the same as the temperature at which the dispersion liquid of the agglomerated particles (2) is held from the viewpoint of improving the productivity of the toner. It is preferably 40 ° C. or higher, 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.

Further, from the viewpoint of stabilizing the agglomerated particles and preventing the once agglomerated particles from being dispersed before fusion, it is preferable to stop the agglomeration and add an acid to make the dispersion liquid of the agglomerated particles neutral to acidic. ..
The acid to be added is not limited, and examples thereof include sulfuric acid, hydrochloric acid, nitric acid, phosphoric acid, and acetic acid. However, from the viewpoint of rapid pH change with respect to addition, hydrochloric acid, hydrochloric acid, nitric acid, and acetic acid are preferable. At least one selected from, more preferably at least one selected from hydrochloric acid, sulfuric acid, and nitric acid, still more preferably sulfuric acid.
The acid is preferably added in the form of an aqueous solution. Further, it may be added together with the aggregation terminator.

<Process (2)>
The step (2) is a step of fusing the agglomerated particles obtained in the step (1) to obtain a dispersion liquid of the fused particles.
The particles in the agglomerated particles, which were mainly physically attached to each other, are fused and integrated to form fused particles (toner particles).

In the step (2), the crystalline resin is obtained from the viewpoint of improving the fusion property of the agglomerated particles, excellent low temperature fixability, suppression of deterioration of low temperature fixability over time, and excellent heat storage stability. It is preferable to keep the temperature at a temperature equal to or higher than the melting point of (B) by 15 ° C.
The holding temperature is more preferably a temperature 10 ° C. lower than the melting point of the crystalline resin (B), more preferably a crystalline resin, from the viewpoint of improving the fusion property of the aggregated particles and improving the productivity of the toner. A temperature 5 ° C. lower than the melting point of (B), more preferably a temperature equal to or higher than the melting point of the crystalline resin (B), and preferably a temperature 30 ° C. higher than the melting point of the crystalline resin (B), more preferably crystals. The temperature is 20 ° C. higher than the melting point of the sex resin (B), more preferably 12 ° C. or lower than the melting point of the crystalline resin (B).
At that time, the time for holding at a temperature equal to or higher than the melting point of the crystalline resin (B) by 15 ° C. is preferably 1 minute from the viewpoint of improving the fusion property of the aggregated particles and improving the productivity of the toner. The above is 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, still more preferably 90 minutes or less.

The volume median particle diameter (D ₅₀ ) of the fused particles in the dispersion obtained in the step (2) has excellent low-temperature fixability, suppresses deterioration of low-temperature fixability over time, and has excellent heat-resistant storage stability. 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 8 μm or less, still more preferably 6 μm or less.
The circularity of the fused particles in the dispersion obtained in the step (2) provides a high-quality image from the viewpoint of excellent low-temperature fixability, suppression of deterioration of low-temperature fixability over time, and excellent heat-resistant storage stability. From the viewpoint of obtaining, it is preferably 0.955 or more, more preferably 0.960 or more, further preferably 0.965 or more, and preferably 0.990 or less, more preferably 0.985 or less, still more preferably 0. It is .980 or less.

<Process (3)>
The step (3) is a step of cooling the dispersion liquid of the fused particles obtained in the step (2) at a speed of 10 ° C./min or more.

The cooling rate is preferably 10 ° C./min or higher, more preferably 20 ° C./min or higher, and further, from the viewpoint of excellent low-temperature fixability, suppression of deterioration of low-temperature fixability over time, and excellent heat-resistant storage stability. It is preferably 30 ° C./min or higher.
The cooling rate refers to the rate of temperature decrease per minute between the temperature ( _Tm- 15) ° C. and ( _Tm- 20) ° C. in the cooling process after the fusion process is completed.
However, T _m is the melting point of the crystalline resin (B).

In the step (3), it is preferable to cool the obtained dispersion of the fused particles from the temperature T _u of the dispersion of the fused particles to the temperature T _d at a rate of 10 ° C./min or more.
The starting point of speed of the cooling, the temperature T _u of the dispersion of the fused particles, excellent low temperature fixing property, and over time the low-temperature fixability of suppressing reduction, and excellent in view of heat storage stability, preferably It is ( _Tm- 15) ° C. or higher, more preferably ( _Tm- 10) ° C. or higher, and even more preferably ( _Tm + 5) ° C. or higher. The temperature _Tu is preferably ( _Tm +30) ° C. or lower, more preferably ( _Tm +20) ° C. or lower, still more preferably ( _Tm +10) ° C. or lower, still more preferably, in order to reduce the load of the cooling work. (T _m + 5) ° C. or lower, more preferably T _m ° C. or lower.

The temperature T _d of the dispersion liquid of the fused particles, which is the end point of the cooling rate, is preferably set from the viewpoints of excellent low-temperature fixability, suppression of deterioration of low-temperature fixability over time, and excellent heat-resistant storage stability. It is ( _Tm- 20) ° C. or lower, more preferably ( _Tm- 35) ° C. or lower, still more preferably ( _Tm- 45) ° C. or lower, and preferably ( _Tm- 70) from the viewpoint of work efficiency. ) ° C. or higher, more preferably ( _Tm- 60) ° C. or higher, and even more preferably ( _Tm- 50) ° C. or higher.

The cooling method is not particularly limited, and examples thereof include a method of cooling the dispersion in a tank containing a dispersion of fused particles, and more specifically, a dispersion of fused particles is added. A method of attaching a cooling jacket to the tank for cooling and the like can be mentioned, but from the viewpoint of cooling efficiency, a method of adding an aqueous medium having a temperature of less than T _{d to} the dispersion liquid of the fused particles is preferable. The aqueous medium having a temperature lower than T _d may be added at the cooling rate described above, and for example, the aqueous medium may be added in portions at predetermined time intervals.

<Post-treatment process>
A post-treatment step may be performed after the step (3), and it is preferable to obtain toner particles by isolation.
Since the fused particles in the dispersion liquid obtained in the step (3) 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 cleaning after solid-liquid separation. At this time, since it is preferable to remove the added surfactant as well, it is preferable to wash with an aqueous medium below the cloud point of the surfactant. The washing is preferably performed a plurality of times.

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

[Toner for static charge image development]
<Toner particles>
The toner particles obtained by drying or the like can be used as they are as the toner for static charge image development, but the toner particles whose surface is treated as described later can be used as the toner for static charge image development. preferable.
In the toner particles, the content of the crystalline resin (B) with respect to the total content of the crystalline resin (B) and the amorphous composite resin (A) has excellent low-temperature fixability and low-temperature fixability over time. From the viewpoint of suppressing the decrease and excellent heat storage 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 45% by mass or less. It is 40% by mass or less, more preferably 35% by mass or less.
Further, the content of the crystalline resin (B) is based on the total amount of the resin components in the toner from the viewpoints of excellent low-temperature fixability, suppression of deterioration of low-temperature fixability over time, and excellent heat-resistant storage 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, still more preferably 35% by mass or less. Is.

The volume median particle diameter (D ₅₀ ) of the toner particles is from the viewpoint of improving the productivity of the toner, improving the image density of the printed matter, and excellent low temperature fixability and suppressing the decrease of the low temperature fixability over time. From the viewpoint of excellent heat storage stability, it is preferably 2 μm or more, more preferably 3 μm or more, further preferably 4 μm or more, and preferably 10 μm or less, more preferably 8 μm or less, still more preferably 6 μm or less.
The CV value of the toner particles is preferably 12% or more, more preferably 14% or more, still more preferably 16% or more from the viewpoint of improving the productivity of the toner, and from the viewpoint of obtaining a high-quality image. It is preferably 30% or less, more preferably 26% or less.

The circularity of the toner particles is preferably 0.955 or more, more preferably 0.960 or more, still more preferably 0.965 or more, and preferably 0.965 or more, from the viewpoint of improving the low temperature fixability and charging characteristics of the toner. It is 0.990 or less, more preferably 0.985 or less, still more preferably 0.980 or less.

As the toner particles, it is preferable to use the toner particles obtained by adding a fluidizing agent or the like as an external additive to the surface of the toner particles.
Examples of the external additive include hydrophobic silica, titanium oxide fine particles, alumina fine particles, cerium oxide fine particles, inorganic fine particles such as carbon black, and polymer fine particles such as polycarbonate, polymethyl methacrylate, and silicone resin, among these. , Hydrophobic silica is preferred.
When the surface treatment of the toner particles is performed using an external additive, the amount of the external additive added is preferably 1 part by mass or more, more preferably 2 parts by mass or more, still more preferably 2 parts by mass or more with respect to 100 parts by mass of the toner particles. It is 3 parts by mass or more, and 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 static charge image developing obtained by the present invention can be used as a one-component developer or mixed with a carrier as a two-component developer.

Each property value of each resin, wax, each particle, toner, etc. was measured and evaluated by the following method.

[Acid value of resin]
It was measured according to the neutralization titration method described in JIS K 0070-1992. However, the measurement solvent was chloroform.

[Resin softening point, crystallinity index, melting point and glass transition temperature]
(1) Softening point Using a flow tester "CFT-500D" (manufactured by Shimadzu Corporation), a 1 g sample is heated at a heating rate of 6 ° C./min while a load of 1.96 MPa is applied by a plunger to give a diameter of 1.96 MPa. Extruded from a 1 mm, 1 mm long nozzle. The amount of plunger drop of the flow tester was plotted against the temperature, and the temperature at which half of the sample flowed out was used as the softening point.
(2) Crystallinity index 0.02 g of a sample is weighed on an aluminum pan using a differential scanning calorimeter "Q100" (manufactured by TA Instruments Japan Co., Ltd.), and the temperature drops from room temperature (20 ° C) to 10 ° C / It was cooled to 0 ° C. in min. Next, the sample was allowed to stand still for 1 minute, 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 with the largest peak area is set as the maximum endothermic peak temperature (1), and (softening point (° C.)) / (maximum endothermic peak temperature (1) (° C.)). The crystallinity index was calculated.
(3) Melting point and glass transition temperature Using a differential scanning calorimeter "Q100" (manufactured by TA Instruments Japan Co., Ltd.), 0.02 g of the sample is weighed in an aluminum pan, heated to 200 ° C, and the temperature thereof. The temperature was lowered to 0 ° C. at a temperature lowering rate of 10 ° C./min. Next, the temperature of the sample was raised at a heating rate of 10 ° C./min, and the amount of heat was measured. Among the observed endothermic peaks, the temperature of the peak having the 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 amorphous resin, when a peak is observed, the temperature of the peak is observed, and when a step is observed without a peak, a tangent line indicating the maximum inclination of the curve of the step portion and the step The temperature at the intersection with the extension of the baseline on the low temperature side was defined as the glass transition temperature.

[Melting point of wax]
Using a differential scanning calorimeter "Q100" (manufactured by TA Instruments Japan Co., Ltd.), weigh 0.02 g of a sample into an aluminum pan, raise the temperature to 200 ° C, and then lower the temperature from 200 ° C to 10 ° C / min. Was cooled to 0 ° C. Next, the sample was heated at a heating rate of 10 ° C./min, the amount of heat was measured, and the maximum peak temperature of endothermic reaction was taken as the melting point.

[Hydroxy group value and acid value of wax]
Measured according to JIS K 0070-1992. However, the measurement solvent was a mixed solvent of xylene and ethanol (mass ratio; xylene: ethanol = 3: 5).

[Wax number average molecular weight (Mn)]
The number average molecular weight (Mn) was measured by the gel permeation chromatography (GPC) method shown below.
(1) Preparation of sample solution The sample is dissolved in chloroform at 25 ° C. so that the concentration becomes 0.5 g / 100 mL, and then this solution is dissolved in a fluororesin filter having a pore size of 0.2 μm (product name: “DISMIC”, It was filtered using a model "25JP" (manufactured by ADVANTEC) to remove insoluble components, and used as a sample solution.
(2) Measurement Using the following measuring device and analytical column, chloroform was flowed as an eluent 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. The molecular weight was measured. Molecular weight of the sample (number average molecular weight Mn) of 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) " ⁵ ) ”,“ F-40 (4.27 × 10 ⁵ ) ”,“ F-80 (7.06 × 10 ⁵ ) ”,“ F-128 (1.09 × 10 ⁶ ) ”; all of Tosoh shares It was calculated based on a calibration line prepared in advance using (manufactured by the company) as a standard sample.
-Measuring device: "HLC-8220GPC" (manufactured by Tosoh Corporation)
-Analytical columns: "GMHXL" and "G3000HXL" (manufactured by Tosoh Corporation)

[Volume medium particle size (D ₅₀ ) and CV value of resin particles, colorant particles, and wax particles]
(1) Measuring device: Laser diffraction type particle size measuring machine "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 at which the absorbance was within 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) x 100

[Solid content concentration of aqueous dispersion of resin particles (X), aqueous dispersion of resin particles (Y), colorant particle dispersion, and wax particle dispersion]
Using an infrared moisture meter "FD-230" (manufactured by Ketsuto Scientific Research Institute Co., Ltd.), a measurement sample of 5 g was dried at a drying temperature of 150 ° C. ), The water content (% by mass) was measured. The solid content concentration was calculated according to the following formula.
Solid content concentration (mass%) = 100-moisture (mass%)

[Volume medium particle size of aggregated particles (D ₅₀ )]
The volume median particle size (D ₅₀ ) of the agglomerated particles was measured as follows.
-Measuring machine: "Coulter Multi-Sizar (registered trademark) III" (manufactured by Beckman Coulter Co., Ltd.)
・ Aperture diameter: 50 μm
-Analysis software: "Multisizer (registered trademark) III version 3.51" (manufactured by Beckman Coulter Co., Ltd.)
-Electrolytic solution: "Isoton (registered trademark) II" (manufactured by Beckman Coulter Co., Ltd.)
-Measurement conditions: By adding the sample dispersion to 100 mL of the electrolytic solution, the particle size of 30,000 particles is adjusted to a concentration that can be measured in 20 seconds, and then 30,000 particles are measured again and the particle size is 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: The dispersion of fused particles (Ma) was adjusted by diluting with deionized water so that the solid content concentration was 0.001 to 0.05% by mass.
-Measurement mode: HPF measurement mode

[Volume medium particle size (D ₅₀ ) and CV value of toner particles]
The volume median particle diameter (D ₅₀ ) of the toner 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 "Emargen (registered trademark) 109P" [manufactured by Kao Corporation, HLB (Hydrophile-Lipopfile Balance) = 13.6] is dissolved in the electrolytic solution to prepare a dispersion having a concentration of 5% by mass. Obtained.
-Dispersion condition: 10 mg of a sample to be measured of dried toner particles was added to 5 mL of the dispersion liquid, dispersed for 1 minute with an ultrasonic disperser, then 25 mL of an electrolytic solution was added, and further, with an ultrasonic disperser. A sample dispersion was prepared by dispersing for 1 minute.
-Measurement conditions: By adding the sample dispersion to 100 mL of the electrolytic solution, the particle size of 30,000 particles is adjusted to a concentration that can be measured in 20 seconds, and then 30,000 particles are measured and the particle size is measured. The volume median particle size (D ₅₀ ) and volume average particle size were determined from the distribution.
The CV value (%) was calculated according to the following formula.
CV value (%) = (standard deviation of particle size distribution / volume average particle size) x 100

[Low-temperature fixability and low-temperature fixability of toner over time]
<Low temperature fixability>
Using a commercially available printer "Microline (registered trademark) 5400" (manufactured by Oki Data Corporation) on high-quality paper "J paper A4 size" (manufactured by Fuji Xerox Co., Ltd.), the amount of toner adhered to the paper is 1.3 to 1. A solid image of .5 mg / cm ² was output with a length of 50 mm without fixing, leaving a margin of 5 mm from the upper end of the A4 paper.
Next, the same printer in which the fuser was modified to have a variable temperature was prepared, the temperature of the fuser was set to 90 ° C., and 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 fuser was raised by 5 ° C. to fix the toner, and a printed matter was obtained.
Lightly paste the mending tape "Scotch (registered trademark) Mending Tape 810" (manufactured by Sumitomo 3M Ltd., width 18 mm) cut to a length of 50 mm from the top margin on the printed image to the solid image. After that, a weight of 500 g was placed and pressed back and forth at a speed of 10 mm / s. Then, the attached tape was peeled off from the lower end side at a peeling angle of 180 ° and a speed of 10 mm / s to obtain a printed matter after the tape was peeled off. 30 sheets of high-quality paper "Excellent White Paper A4 size" (manufactured by Oki Data Co., Ltd.) are laid under the printed matter before and after the tape is attached, and the reflected image density of the fixed image part before and after the tape is attached to each printed matter is measured. , Colorimeter "SpectroEye" (manufactured by GretagMacbeth, light irradiation conditions; standard light source D50, observation field of view 2 °, density standard DINNB, absolute white standard), and the fixation rate from each reflected image density according to the following formula. Was calculated.
Fixing rate (%) = (reflection image density after tape peeling / reflection image density before tape application) x 100
The lowest temperature at which the fixing rate was 90% or more was defined as the lowest fixing temperature (T1). The lower the minimum fixing temperature, the better the low temperature fixing property.
<Castability over time of low temperature fixability>
After holding the toner in a constant temperature bath at 45 ° C. for 200 hours, the minimum fixing temperature (T2) was measured by the same method as in the evaluation of low temperature fixability. Next, the difference between the minimum fixing temperature (T1) and the minimum fixing temperature (T2) was calculated, and the temporal stability of the low temperature fixing property was evaluated. The smaller the absolute value of the numerical value, the better the low temperature fixability over time.

[Heat-resistant storage of toner]
20 g of toner was placed in a wide-mouthed polybin having an internal volume of 100 mL, sealed, and allowed to stand at an arbitrary temperature for 12 hours. Then, it was allowed to stand for 12 hours or more while being sealed at a temperature of 25 ° C. to cool. Next, set a flue with a mesh opening of 250 μm on the shaking table of "Powder Tester (registered trademark)" (manufactured by Hosokawa Micron Co., Ltd.), place 20 g of the toner on it, and vibrate for 30 seconds to leave the toner on the flue. It was visually determined whether or not to do so, and the maximum value of the storage temperature that did not remain was set as the maximum temperature at which aggregation did not occur. The higher the temperature, the better the heat-resistant storage stability of the toner.

[Manufacturing of resin]
Manufacturing example A1
(Manufacture of Amorphous Composite Resin A-1)
The inside 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, and 2,2-bis (4-hydroxyphenyl) propane polyoxypropylene (2. 2) Additives 3356 g, terephthalic acid 955 g, Paracol 6490 (manufactured by Nippon Seikan Co., Ltd.) 385 g, di (2-ethylhexanoic acid) tin (II) 25 g, and 3,4,5-trihydroxybenzoic acid 2.5 g. The temperature was raised to 235 ° C. while stirring under a nitrogen atmosphere, and the temperature was maintained at 235 ° C. for 5 hours. Then, after returning to atmospheric pressure, the mixture was cooled to 160 ° C. and kept at 160 ° C., and a mixture of 2198 g of styrene, 550 g of stearyl methacrylate, 110 g of acrylic acid, and 330 g of dibutyl peroxide was added dropwise over 1 hour. Then, the temperature was maintained at 160 ° C. for 30 minutes, the temperature was raised to 200 ° C., the pressure in the flask was further reduced, and the temperature was maintained at −8 kPa (G) for 1 hour. Then, after returning to atmospheric pressure, the mixture was cooled to 190 ° C., 200 g of fumaric acid, 194 g of sebacic acid, 184 g of trimellitic anhydride, and 2.5 g of 4-tert-butylcatechol were added, and the temperature was 10 ° C./hr to 210 ° C. After that, the reaction was carried out at -4 kPa (G) to a desired softening point to obtain an amorphous composite resin A-1. The physical properties are shown in Table 1.

Production Examples A2 to A6
(Manufacture of Amorphous Composite Resins A-2 to A-6)
Amorphous composite 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.

Manufacturing example A7
(Manufacture of Amorphous Composite Resin A-7)
The inside 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, and 2,2-bis (4-hydroxyphenyl) propane polyoxypropylene (2. 2) Add 5405 g of adduct, 769 g of terephthalic acid, 30 g of di (2-ethylhexanoic acid) tin (II), and 3.0 g of 3,4,5-trihydroxybenzoic acid, and 235 with stirring under a nitrogen atmosphere. After raising the temperature to ° C. and holding at 235 ° C. for 8 hours, the pressure in the flask was lowered and the mixture was held at −8 kPa (G) for 1 hour. Then, after returning to atmospheric pressure, the mixture was cooled to 190 ° C., 197 g of fumaric acid, 1404 g of sebacic acid, 296 g of trimellitic anhydride, and 3.8 g of 4-tert-butylcatechol were added, and the temperature was 10 ° C./hr to 220 ° C. After that, 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 composite resin A-7. The physical properties are shown in Table 1.

Production example C1
(Manufacturing of amorphous resin C-1)
The inside 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, and 2,2-bis (4-hydroxyphenyl) propane polyoxyethylene (2. 2) Add 5001 g of adduct, 1788 g of terephthalic acid, 30 g of di (2-ethylhexanoic acid) tin (II), and 3.0 g of 3,4,5-trihydroxybenzoic acid, and 235 with stirring under a nitrogen atmosphere. After raising the temperature to ° C. and holding at 235 ° C. for 8 hours, the pressure in the flask was lowered and held 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 dodecenyl succinic anhydride, 325 g of trimellitic anhydride, and 3.8 g of 4-tert-butylcatechol were added, and 10 ° C. was added to 220 ° C. The temperature was raised at / hr, 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 C-1. The physical properties are shown in Table 1.

Production example A11
(Manufacture of Amorphous Composite Resin A-11)
The inside 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, and 2,2-bis (4-hydroxyphenyl) propane polyoxypropylene (2. 2) Add 4313 g of adduct, 818 g of terephthalic acid, 727 g of succinic acid, 30 g of di (2-ethylhexanoic acid) tin (II), and 3.0 g of 3,4,5-trihydroxybenzoic acid, and stir in a nitrogen atmosphere. While the temperature was raised to 235 ° C. and the temperature was maintained at 235 ° C. for 5 hours, the pressure inside the flask was lowered and the temperature was maintained at −8 kPa (G) for 1 hour. Then, after returning to atmospheric pressure, the mixture was cooled to 160 ° C. and kept at 160 ° C., and 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 the temperature at 160 ° C. for 30 minutes, the temperature was raised to 200 ° C., the pressure in the flask was further lowered, and the reaction was carried out at -8 kPa (G) to a desired softening point, whereby the amorphous composite resin A-. I got 11. The physical properties are shown in Table 1.

Production example B1
(Manufacturing of crystalline resin B-1)
The inside 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, and 3,416 g of 1,10-decanediol and 4084 g of sebacic acid were added. The temperature was raised to 135 ° C. with stirring, held at 135 ° C. for 3 hours, and then raised from 135 ° C. to 200 ° C. over 10 hours. Then, 23 g of di (2-ethylhexanoic acid) tin (II) was added and held at 200 ° C. for 1 hour, the pressure in the flask was lowered, and the mixture was held at −8.3 kPa (G) for 1 hour. Crystalline resin B-1 was obtained. The physical properties are shown in Table 2.

Production example B2
(Manufacturing of crystalline resin B-2)
A crystalline resin B-2 was 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.

[Manufacturing of aqueous dispersion of resin particles]
Manufacturing example X1
(Manufacture of water-based dispersion X-1 of resin particles)
300 g of amorphous composite resin A-1 and a mixed solvent of 300 g of methyl ethyl ketone and 41 g of deionized water are 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 introduction tube. , The resin was dissolved at 73 ° C. for 2 hours. A 5 mass% sodium hydroxide aqueous solution was added to the obtained solution so as to have a neutralization degree of 60 mol% with respect to the acid value of the resin, and the mixture was stirred for 30 minutes.
Then, while maintaining the temperature at 73 ° C., 600 g of deionized water was added over 60 minutes while stirring at 200 r / min (peripheral speed 63 m / min) for phase inversion emulsification. Methyl ethyl ketone was distilled off under reduced pressure while the temperature was continuously maintained at 73 ° C. to obtain an aqueous dispersion. Then, the aqueous dispersion was cooled to 30 ° C. while stirring at 280 r / min (peripheral speed 88 m / min), and then deionized water was added so that the solid content concentration became 20% by mass to obtain the resin particles. An aqueous dispersion X-1 was obtained. The physical properties are shown in Table 3.

Production example X2 to X7
(Manufacture of aqueous dispersions X-2 to X-7 of resin particles)
Aqueous dispersions X-2 to X-7 of resin particles were obtained in the same manner as in Production Example X1 except that the type of resin was changed as shown in Table 3. The physical properties are shown in Table 3.

Manufacturing example Z1
(Manufacture of aqueous dispersion Z-1 of resin particles)
300 g of amorphous resin C-1 and a mixed solvent of 180 g of methyl ethyl ketone and 25 g of deionized water 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 introduction tube. The resin was dissolved at 73 ° C. for 2 hours. A 5 mass% sodium hydroxide aqueous solution was added to the obtained solution so as to have a neutralization degree of 60 mol% with respect to the acid value of the resin, and the mixture was stirred for 30 minutes.
Then, while maintaining the temperature at 73 ° C., 600 g of deionized water was added over 60 minutes while stirring at 200 r / min (peripheral speed 63 m / min) for phase inversion emulsification. Methyl ethyl ketone was distilled off under reduced pressure while the temperature was continuously maintained at 73 ° C. to obtain an aqueous dispersion. Then, the aqueous dispersion was cooled to 30 ° C. while stirring at 280 r / min (peripheral speed 88 m / min), and then deionized water was added so that the solid content concentration became 20% by mass to obtain the resin particles. An aqueous dispersion Z-1 was obtained. The physical properties are shown in Table 3.

Production example P1
(Manufacture of aqueous dispersion P-1 of resin particles)
200 g of amorphous composite resin A-11 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 introduction tube, and placed at 73 ° C. for 2 hours. The resin was dissolved. A 5 mass% sodium hydroxide aqueous solution was added to the obtained solution so as to have a neutralization degree of 60 mol% with respect to the acid value of the resin, and the mixture was stirred for 30 minutes.
Then, while maintaining the temperature at 73 ° C., while stirring at 280 r / min (peripheral speed 88 m / min), 700 g of deionized water was added over 50 minutes for phase inversion emulsification. Methyl ethyl ketone was distilled off under reduced pressure while the temperature was continuously maintained at 73 ° C. to obtain an aqueous dispersion. Then, the aqueous dispersion was cooled to 30 ° C. while stirring at 280 r / min (peripheral speed 88 m / min), and then deionized water was added so that the solid content concentration became 20% by mass to obtain the resin particles. An aqueous dispersion P-1 was obtained. The physical properties are shown in Table 3.

Production example Y1
(Manufacture of water-based dispersion Y-1 of resin particles)
300 g of crystalline resin B-1 and a mixed solvent of 300 g of methyl ethyl ketone and 41 g of deionized water 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 introduction tube. The resin was dissolved at ° C. for 2 hours. A 5 mass% aqueous sodium hydroxide solution was added to the obtained solution so as to have a neutralization degree of 60 mol% with respect to the acid value of the crystalline resin B-1, and the mixture was stirred for 30 minutes.
Then, while maintaining the temperature at 73 ° C., 600 g of deionized water was added over 60 minutes while stirring at 200 r / min (peripheral speed 63 m / min) for phase inversion emulsification. Methyl ethyl ketone was distilled off under reduced pressure while the temperature was continuously maintained at 73 ° C. to obtain an aqueous dispersion. Then, the aqueous dispersion was cooled to 30 ° C. while stirring at 280 r / min (peripheral speed 88 m / min), and then deionized water was added so that the solid content concentration became 20% by mass to obtain the resin particles. An aqueous dispersion Y-1 was obtained. The physical properties are shown in Table 4.

Production example Y2
(Manufacture of water-based dispersion Y-2 of resin particles)
An aqueous dispersion Y-2 of resin particles was obtained in the same manner as in Production Example Y1 except that the crystalline resin B-1 was changed to the crystalline resin B-2. The physical properties are shown in Table 4.

[Manufacturing of wax particle dispersion]
Production example D1
(Manufacture of Wax Particle Dispersion Liquid D-1)
To a beaker with an internal volume of 1 L, 120 g of deionized water, 86 g of an aqueous dispersion of resin particles P-1, and 40 g of paraffin wax "HNP-9" (manufactured by Nippon Seikan Co., Ltd., melting point 75 ° C.) were added, and 90 to The temperature was maintained at 95 ° C., and the mixture was melted and stirred to obtain a molten mixture.
The obtained molten mixture was further dispersed at 90 to 95 ° C. using an ultrasonic homogenizer "US-600T" (manufactured by Nissei Tokyo Office Co., Ltd.) for 20 minutes and then up to room temperature (25 ° C.). Cooled. Deionized water was added to adjust the solid content concentration to 20% by mass to obtain a wax particle dispersion D-1. The volume median particle diameter (D ₅₀ ) of the wax particles in the dispersion was 0.47 μm, and the CV value was 27%.

[Manufacturing of colorant particle dispersion]
Production example E1
(Manufacture of Colorant Particle Dispersion Liquid E-1)
In a beaker with an internal volume of 1 L, 150 g of copper phthalocyanine pigment "ECB-301" (manufactured by Dainichi Seika Kogyo Co., Ltd.) and anionic surfactant "Neoperex (registered trademark) G-15" (manufactured by Kao Co., Ltd., 15 mass) 200 g of% dodecylbenzene benzene sulfonate aqueous solution) and 257 g of deionized water were mixed and dispersed at room temperature for 3 hours using an ultrasonic homogenizer "US-600T" (manufactured by Nippon Seiki Seisakusho Co., Ltd.), and then the solid content. Deionized water was added so as to have a concentration of 24% by mass to obtain a colorant particle dispersion E-1. The volume median particle diameter (D ₅₀ ) of the colorant particles in the dispersion was 0.12 μm.

[Manufacturing of toner]
Example 1 (Preparation of Toner 1)
(Coagulation fusion process)
210 g of aqueous dispersion X-1 of resin particles, 90 g of aqueous dispersion Y-1 of resin particles, wax particle dispersion D in a four-necked flask with an internal volume of 5 L equipped with a dehydration tube, agitator and thermocouple. 30 g of -1, 20 g of colorant particle dispersion E-1, and nonionic surfactant "Emargen (registered trademark) 150" (manufactured by Kao Co., Ltd., polyoxyethylene (average addition molar number 50) lauryl ether) 6 g of the 10 mass% aqueous solution of the above was mixed at a temperature of 25 ° C. Next, while stirring the mixture, a solution prepared by adding 19 g of a 4.8 mass% potassium hydroxide aqueous solution to an aqueous solution prepared by dissolving 19 g of ammonium sulfate in 187 g of deionized water to adjust the pH to 8.6 was prepared at 25 ° C. for 5 minutes. After dropping the solution, the temperature was raised to 59 ° C. over 2 hours, and the temperature was maintained at 59 ° C. until the volume median particle diameter (D ₅₀ ) of the agglomerated particles reached 5.2 μm, and the agglomerated particles (1) were dispersed. I got the liquid.
While maintaining the temperature of the dispersion liquid of the agglomerated particles (1) at 59 ° C., 46 g of the resin particle dispersion liquid Z-1 was added dropwise at a rate of 0.3 ml / min to obtain a dispersion liquid of the agglomerated particles (2). It was.
15 g of anionic surfactant "Emar (registered trademark) E-27C" (manufactured by Kao Corporation, sodium polyoxyethylene lauryl ether sulfate, effective concentration 27% by mass), deionized in the dispersion of the aggregated particles (2). An aqueous solution containing 1050 g of water and 20 g of 0.1 mol / L sulfuric acid was added. Then, after raising the temperature to 83 ° C. over 1 hour, 20 g of 0.1 mol / L sulfuric acid was added and kept at 83 ° C. until the circularity became 0.970, whereby the aggregated particles were fused. A dispersion of particles was obtained.

(Cooling process)
Deionized water at 10 ° C. prepared separately was added to the dispersion liquid every 10 seconds while checking the temperature so that the temperature of the dispersion liquid of the fused particles at 83 ° C. would drop at a rate of 30 ° C./min. The dispersion of the fused particles was cooled to 30 ° C. ± 2 ° C. to obtain a cooled dispersion of the fused particles.

(Filtration / drying process)
The obtained cooled dispersion of the fused particles was suction-filtered to separate the solid content, 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 particles. Table 5 shows the physical properties of the obtained toner particles.
(External process)
100 parts by mass of the toner particles, 2.5 parts by mass of hydrophobic silica "RY50" (manufactured by Nippon Aerosil Co., Ltd., number average particle size; 0.04 μm), and hydrophobic silica "Cabosil (registered trademark) TS720" (Cabot Japan) Manufactured by Co., Ltd., number average particle size; 0.012 μm) 1.0 part by mass was placed in a Henshell mixer and stirred, and passed through a 150 mesh sieve to obtain toner 1. Table 5 shows the evaluation results of the obtained toner.

Example 2 (Preparation of Toner 2)
Toner 2 was obtained in the same manner as in Example 1 except that the cooling step was changed as follows. Table 5 shows the evaluation results of the obtained toner.
(Cooling process)
The dispersion of fused particles at 83 ° C. was allowed to cool at room temperature (25 ° C.) and cooled to 67 ° C. After that, deionized water at 10 ° C. prepared separately was added to the dispersion liquid while checking the temperature every 10 seconds so that the temperature of the fused particle dispersion liquid at 67 ° C. would decrease at a rate of 30 ° C./min. The dispersion of the fused particles was cooled to 30 ° C. to obtain a cooled dispersion of the fused particles.

Example 3 (Preparation of Toner 3)
Toner 3 was obtained in the same manner as in Example 1 except that the cooling step was changed as follows. Table 5 shows the evaluation results of the obtained toner.
(Cooling process)
Deionized water at 10 ° C. prepared separately was added to the dispersion liquid every 10 seconds while checking the temperature so that the temperature of the dispersion liquid of the fused particles at 83 ° C. would drop at a rate of 30 ° C./min. The dispersion of the fused particles was cooled to 50 ° C. Then, the mixture was stirred at room temperature (25 ° C.), and the fused particle dispersion was cooled to 30 ° C. to obtain a cooled dispersion of fused particles.

Example 4 (Preparation of Toner 4)
Toner 4 was obtained in the same manner as in Example 1 except that the cooling step was changed as follows. Table 5 shows the evaluation results of the obtained toner.
(Cooling process)
Deionized water at 10 ° C. prepared separately was added to the dispersion liquid while checking the temperature every 10 seconds so that the temperature of the dispersion liquid of the fused particles at 83 ° C. would drop at a rate of 10 ° C./min. The dispersion of the fused particles was cooled to 30 ° C. to obtain a cooled dispersion of the fused particles.

Example 5 (Preparation of Toner 5)
In the coagulation and fusion step of Example 1, the amount of the aqueous dispersion X-1 of the resin particles used was changed to 240 g, and the amount of the aqueous dispersion Y-1 of the resin particles used was changed to 60 g. Toner 5 was obtained in the same manner as above. Table 5 shows the evaluation results of the obtained toner.

Example 6 (Preparation of Toner 6)
In the coagulation-fusion step of Example 1, the amount of the aqueous dispersion X-1 of the resin particles used was changed to 180 g, and the amount of the aqueous dispersion Y-1 of the resin particles used was changed to 120 g. Toner 6 was obtained in the same manner as above. Table 5 shows the evaluation results of the obtained toner.

Examples 7 to 11, Comparative Examples 2 and 3 (Preparation of toners 7 to 11, 13 and 14)
Toners 7 to 11, 13, and 14 were obtained in the same manner as in Example 1 except that the aqueous dispersion of the resin particles used was changed as shown in Table 4 in the coagulation and fusion step of Example 1. Table 5 shows the evaluation results of the obtained toner.

Comparative Example 1
(Preparation of toner 12)
Toner 12 was obtained in the same manner as in Example 1 except that the cooling step was changed as follows. Table 5 shows the evaluation results of the obtained toner.
(Cooling process)
Deionized water at 10 ° C. prepared separately was added to the dispersion liquid every 10 seconds while checking the temperature so that the temperature of the dispersion liquid of the fused particles at 83 ° C. would drop at a rate of 5 ° C./min. The dispersion of the fused particles was cooled to 30 ° C. ± 2 ° C. to obtain a cooled dispersion of the fused particles.

From Table 5, the toners obtained by the production methods of Examples 1 to 11 are superior in low temperature fixability and have low temperature fixability over time as compared with the toners obtained by the production methods of Comparative Examples 1 to 3. It can be seen that the decrease can be suppressed and the heat-resistant storage property is excellent.

Claims (7)

Step (1): A step of aggregating the amorphous composite resin and the crystalline resin in an aqueous medium to obtain a dispersion of agglomerated particles.
Step (2): A step of fusing the obtained agglomerated particles to obtain a dispersion liquid of the fused particles.
Step (3): A step of cooling the obtained dispersion of fused particles at a rate of 10 ° C./min or more, and
Is a method for producing a toner for developing an electrostatic charge image, which has
Amorphous composite resin, a polyester resin segments, and, seen containing a vinyl resin segment having a unit derived from a vinyl monomer having a hydrocarbon group having 6 to 22 carbon atoms,
A method for producing a toner for developing an electrostatic charge image, wherein the amorphous composite resin contains a component derived from a hydrocarbon wax having a hydroxyl group or a carboxy group . The crystalline resin comprises an alcohol component containing 80 mol% or more of α, ω-aliphatic diol having 4 or more and 16 or less carbon atoms and a carboxylic acid component containing 80 mol% or more of an aliphatic dicarboxylic acid having 4 or more and 16 or less carbon atoms. The method for producing a toner for static charge image development according to claim 1, which is a crystalline polyester resin which is a polycondensate. The method for producing an electrostatic charge image developing toner according to claim 1 or 2, wherein the hydrocarbon group in the structural unit derived from the vinyl monomer of the amorphous composite resin has 10 or more and 20 or less carbon atoms. The static charge according to any one of claims 1 to 3, wherein the alcohol component of the polyester resin segment of the amorphous composite resin contains 80 mol% or more of a propylene oxide adduct of 2,2-bis (4-hydroxyphenyl) propane. A method for manufacturing a toner for image development. The electrostatic charge image according to any one of claims 1 to 4 , wherein the content of the component derived from the hydrocarbon wax having a hydroxyl group or a carboxy group in the amorphous composite resin is 1% by mass or more and 20% by mass or less. A method for manufacturing a developing toner. Any of claims 1 to 5 , wherein the mass ratio [amorphous composite resin / crystalline resin] of the amorphous composite resin to the crystalline resin in the step (1) is 50/50 or more and 95/5 or less. The method for producing a toner for developing an electrostatic charge image according to. The method for producing a toner for static charge image development according to any one of claims 1 to 6 , wherein the step (1) is the following step (1-1) and step (1-2).
Step (1-1): A step of aggregating resin particles (X) containing an amorphous composite resin in the presence of a crystalline resin in an aqueous medium to obtain agglomerated particles (1) Step (1-2) ): Resin particles (Z) containing an amorphous resin are added to the agglomerated particles (1) obtained in the step (1-1), and the resin particles (Z) are attached to the agglomerated particles (1). Step to obtain agglomerated particles (2)