JP6711314B2 - Method for producing toner for developing electrostatic image - Google Patents

Description

The present invention relates to a method of manufacturing a toner for developing an electrostatic image.

In the field of electrophotography, along with the development of electrophotographic systems, development of toners for electrostatic image development that are compatible with higher image quality and higher speed is required. As a method of obtaining a toner excellent in fixability at low temperature, in addition to an amorphous resin which has been conventionally used as a binder resin, a crystalline resin is used, and fine resin particles are aggregated in an aqueous medium, A toner is manufactured by a cohesive fusion method (emulsion aggregation method, aggregation coalescence method) in which a toner is obtained by fusing.

For example, in Patent Document 1, a crystal obtained by polycondensing an alcohol component containing an α,ω-alkanediol having 10 to 12 carbon atoms and an average carbon number of 10 to 12 and an acid component containing succinic acid. Core-shell particles having a hydrophilic polyester and an amorphous polyester in the core portion and an amorphous polyester in the shell portion are obtained by a cohesive fusion method, and the dispersion liquid of the core-shell particles is 25° C. or more and 50° C. or less per minute. The method for producing a toner for developing an electrostatic charge image is characterized in that the toner is cooled at a cooling rate of 1, and it is described that a toner for developing an electrostatic charge image having excellent OHP transparency of a printed matter can be obtained.

Further, in Patent Document 2, 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, a polyester segment and an addition polymerization resin segment are described. Aggregate X containing resin particles containing amorphous composite resin (B) containing 3% by mass or more and 15% by mass or less of both reactive monomer-derived components in the addition polymerization resin segment. , A step I of obtaining in an aqueous medium, and a step II of fusing the agglomerates X, and a mass ratio of the crystalline polyester (A) and 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 developing an electrostatic image is described, which has both low-temperature fixability and heat-resistant storability. It is described that the toner for developing an electrostatic charge image having excellent bending resistance can be obtained.

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

JP, 2014-130254, A JP, 2014-235409, A JP, 2005-7765, A

However, when the toner particles are produced by a chemical method such as a cohesive fusion method, even if the crystalline resin is mixed with the binder resin to improve the low-temperature fixability of the toner, the low-temperature fixability decreases with time. I've learned that there are challenges.
Therefore, the present invention is excellent in low-temperature fixability and can suppress deterioration of low-temperature fixability over time even when a toner is produced by a chemical method such as a cohesive fusion method using a crystalline resin. It is an object of the present invention to provide a method for producing a toner for developing an electrostatic charge image capable of obtaining a toner.

The inventors of the present invention considered that the factor that affects the characteristics of the toner using the crystalline resin is the dispersed state of the crystalline resin in the toner particles. As a result, by performing a specific cooling method on the dispersion liquid of toner particles, even when the toner is manufactured by a chemical method such as a cohesive fusion method, the low-temperature fixability is excellent and the low-temperature fixability over time is obtained. It has been found that a toner which can suppress the deterioration of the toner and has excellent heat-resistant storage stability can be obtained.

That is, the present invention is a method for producing an electrostatic charge image developing toner, which comprises a step of cooling a dispersion liquid of toner particles containing an amorphous resin (A) and a crystalline resin (B),
The cooling step includes an operation of adding a dispersion liquid of toner particles having a temperature T _u (° C.) to an aqueous medium (W) and cooling to a temperature T _d (° C.),
The temperature T _u , the temperature T _d, and the melting point T _m (° C.) of the crystalline resin (B) satisfy the following relational expressions (a) and (b),
_{T u - T m ≧ -15 (} a)
T _d −T _m ≦−20 (b)
The present invention relates to a method for producing a toner for developing an electrostatic charge image, wherein a temperature T _{w of} an aqueous medium (W) at the start of adding a dispersion liquid of toner particles is a temperature T _d or lower.

According to the present invention, even when a toner is produced by a chemical method such as a cohesive fusion method using a crystalline resin, excellent low-temperature fixability can be obtained, and deterioration of the low-temperature fixability over time can be suppressed. Further, it is possible to provide a method for producing a toner for developing an electrostatic charge image, which makes it possible to obtain a toner having excellent heat resistant storage stability.

[Method for producing toner for developing electrostatic image]
The method for producing the toner for developing an electrostatic image (also simply referred to as “toner” in the present specification) of the present invention is a dispersion of toner particles containing an amorphous resin (A) and a crystalline resin (B). Including the step of cooling
The cooling step includes an operation of adding a dispersion liquid of toner particles having a temperature T _u (° C.) to an aqueous medium (W) and cooling to a temperature T _d (° C.),
The temperature T _u , the temperature T _d, and the melting point T _m (° C.) of the crystalline resin (B) satisfy the following relational expressions (a) and (b),
_{T u - T m ≧ -15 (} a)
T _d −T _m ≦−20 (b)
The temperature T _w of the aqueous medium (W) at the start of adding the dispersion liquid of toner particles is equal to or lower than the temperature T _d .
The reason why the toner obtained by the production method of the present invention is excellent in low-temperature fixability, can suppress deterioration of low-temperature fixability over time, and can provide a toner which is also excellent in heat resistant storage stability is not clear, but Thought to be.
Since the crystalline resin does not necessarily have good compatibility with the resin components constituting the other binder resin, the size of the crystal domain derived from the crystalline resin is likely to gradually expand. As a result, the interface between the crystalline resin and other binder resin is relatively reduced, and it becomes difficult to melt the surrounding amorphous resin together with the melting of the crystalline resin during toner fixing, which lowers the low temperature fixability. To do. In particular, in the production of toner by a chemical method such as a cohesive fusion method without a kneading step, the crystalline resin cannot be sufficiently dispersed in the amorphous resin, and the crystalline resin is finely dispersed and crystallized. It seems that it is becoming difficult to make it into a product.

Conventionally, the rate of crystal growth is represented by a relational expression consisting of a diffusion rate term of a crystalline segment and a production rate term of crystal nuclei, and the production of crystal nuclei becomes more dominant as the temperature during crystal growth becomes lower. It is known that the higher the temperature during crystal growth, the more the crystal growth due to the increased diffusion rate. However, as a result of the investigation, since the compatibility of the crystalline resin (B) and the amorphous resin (A) in the toner particles is increased immediately after the fusion, it is difficult to crystallize the crystalline resin (B). In addition, it was found that the crystallization proceeded rapidly when the temperature fell below 15° C. lower than the melting point of the crystalline resin (B). On the other hand, since the generation of crystal nuclei becomes more dominant than the crystal growth at lower temperatures, it becomes easier to keep the finely dispersed crystal region in a temperature range lower than a certain temperature. It was found that by keeping the temperature below the melting point by 20° C. or less, a large amount of crystal nuclei derived from the crystalline resin (B) can be generated before the crystal domains grow large in the toner particles. ..
Therefore, it is necessary to pass through the temperature range where crystallization rapidly progresses as quickly as possible to cool. In the method of the present invention, by adding the dispersion liquid of toner particles to the separately prepared low-temperature water for cooling, it is possible to cool at once to a temperature range where crystal nucleation is dominant. Moreover, in this method, the temperature after cooling can be controlled from the temperature and the amount of low-temperature water used, so that the crystallization temperature of the crystalline resin (B) can be substantially controlled, resulting in toner particles. It is considered that the crystal size of the crystalline resin (B) and the crystallinity of the resulting crystal domain can be controlled.
Then, after a large amount of crystal nuclei have been generated, even if the temperature is raised to a temperature at which crystal growth becomes more dominant than crystal nucleation, a large amount of crystal nuclei are already present in the amorphous resin (A). Since it is finely dispersed in the above, it is considered that the enlargement of the crystal domain derived from the crystalline resin (B) can be suppressed. For these reasons, even when the crystalline resin (B) is used to produce a toner by a chemical method such as a cohesive fusion method, the crystalline resin (B) is added to the amorphous resin in the toner. It is considered that the toner can be finely dispersed, and as a result, it becomes possible to obtain a toner which is excellent in low-temperature fixability and heat-resistant storage stability and can suppress deterioration of low-temperature fixability over time.

The toner particles may be toner particles obtained by any conventionally known method such as a melt-kneading method, an emulsion phase inversion method, a polymerization method, and an aggregation and fusion method. Particles are preferred.
In the case of the aggregation and fusion method, the toner manufacturing method is, for example,
Step (1): a step of aggregating the amorphous resin (A) and the crystalline resin (B) in an aqueous medium to obtain a dispersion liquid of aggregated particles (hereinafter, also simply referred to as “step (1)”),
Step (2): a step of fusing the obtained aggregated particles to obtain a dispersion liquid of toner particles (hereinafter, also simply referred to as “step (2)”),
Step (3): including a step of cooling the obtained dispersion liquid of toner particles containing the amorphous resin (A) and the crystalline resin (B) (hereinafter, also simply referred to as “step (3)”) ..
Hereinafter, each step will be described in detail.

<Step (1)>
The step (1) is, for example, a step of aggregating the amorphous resin (A) and the crystalline resin (B) in an aqueous medium to obtain a dispersion liquid of agglomerated particles.
[Amorphous resin (A)]
The amorphous resin (A) is preferably a resin containing a polyester 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. Examples of the resin containing the polyester resin segment include polyester resins, but from the same viewpoint, an amorphous composite resin in which the polyester resin segment contains a hydrophobic constituent component is more preferable.
Examples of the amorphous composite resin include an amorphous composite resin containing a polyester resin segment and a vinyl resin segment, a polyester resin segment, and an amorphous composite resin containing a component derived from a hydrocarbon wax having a hydroxyl group or a carboxy group. Although it may be any amorphous composite resin, it is preferably a polyester resin segment from the viewpoint of excellent low-temperature fixability, and suppression of deterioration of low-temperature fixability over time, and excellent heat resistance storage stability. , A vinyl-based resin segment, and a component derived from a hydrocarbon wax having a hydroxyl group or a carboxy group.

In the present invention, whether the resin is crystalline or amorphous is determined by the crystallinity index. The crystallinity index is defined as the ratio (softening point (° C.)/maximum endothermic peak temperature (° C.)) between the softening point of the resin and the maximum endothermic peak temperature in the measuring method described in the examples. The 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 the examples. The crystallinity index can be appropriately adjusted depending on the types and ratios of the raw material monomers, and the production conditions such as reaction temperature, reaction time, and cooling rate.

(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 composed 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 more preferably Is of formula (I):

[Wherein 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 showing the average number of moles of alkylene oxide added. 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]. 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, further preferably 95 mol% or more, further preferably 98 mol% or more, and preferably 100 mol% or less, and more preferably 100 mol% Is.

The alkylene oxide adduct of bisphenol A is preferably an ethylene oxide adduct of bisphenol A (polyoxyethylene-2,2-bis(4-hydroxyphenyl)propane) and a propylene oxide adduct of bisphenol A (polyoxypropylene-). 2,2-bis(4-hydroxyphenyl)propane), and more preferably a propylene oxide adduct of bisphenol A.
The average number of moles of alkylene oxide added to the alkylene oxide adduct of bisphenol A is preferably 1 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 preferably 1.2 or more, more preferably 1.5 or more, and preferably 16 or less, more preferably 12 or less, further preferably 8 or less, further preferably 4 or less.

The alcohol component (A-al) is preferably 80 mol% or more of a 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 is contained, more preferably 90 mol% or more, further preferably 95 mol% or more, further preferably 98 mol% or more, and preferably 100 mol% or less, and further preferably 100 mol%.

The alcohol component (A-al) may contain a polyhydric alcohol other than the alkylene oxide adduct of bisphenol A. As the other alcohol component that the alcohol component (A-al) may contain, an aliphatic diol, an aromatic diol, an alicyclic diol, a trivalent or higher polyhydric alcohol, or an alkylene oxide having 2 or more and 4 or less carbon atoms thereof. (For example, the average number of added moles is 1 or more and 16 or less) and the like.
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, Aliphatic diols such as 12-dodecanediol; aromatic diols such as bisphenol A (2,2-bis(4-hydroxyphenyl)propane) or their alkylene oxides having 4 carbon atoms (for example, the average number of moles added is 1 or more). 16 or less) adduct; alicyclic diol such as hydrogenated bisphenol A (2,2-bis(4-hydroxycyclohexyl)propane), or their alkylene oxide having 2 to 4 carbon atoms (for example, the average number of moles added). 2 or more and 12 or less) adduct; trihydric or higher polyhydric alcohol such as glycerin, pentaerythritol, trimethylolpropane, and sorbitol, or alkylene oxides having 2 or more and 4 or less carbon atoms (for example, 1 to 16 on the average added mole number). The following) include adducts and the like.
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 their alkyl esters having 1 to 3 carbon atoms. Among them, dicarboxylic acid is preferable, and it is more preferable to use dicarboxylic acid and polyvalent carboxylic acid having a valence of 3 or more in combination.

Examples of the dicarboxylic acid include aromatic dicarboxylic acid, aliphatic dicarboxylic acid, and alicyclic dicarboxylic acid, and aromatic dicarboxylic acid and aliphatic dicarboxylic acid are preferable.
The carboxylic acid component (A-ac) includes not only a free acid, but also an anhydride that decomposes to form an acid during the reaction, and an alkyl ester having 1 to 3 carbon atoms of each carboxylic acid.
Examples of the aromatic dicarboxylic acid include phthalic acid, isophthalic acid, terephthalic acid and the like. Among these, isophthalic acid and terephthalic acid are preferable, and terephthalic acid is more preferable, from the 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 aromatic dicarboxylic acid is preferably 97 mols in the 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. % Or less, more preferably 90 mol% or less, further preferably 80 mol% or less, further preferably 75 mol% or less, further preferably 70 mol% or less, and preferably 30 mol% or more, more preferably 40 mol% or less. It is at least mol%, more preferably at least 50 mol%, further preferably at least 55 mol%, further preferably at least 60 mol%.

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 preferably 30 or less, more preferably 20 or less.
Examples of the aliphatic dicarboxylic acid having 2 to 30 carbon atoms include oxalic acid, malonic acid, maleic acid, fumaric acid, citraconic acid, itaconic acid, glutaconic acid, succinic acid, adipic acid, sebacic acid, dodecanedioic acid, azelaic acid. And succinic acid substituted with an alkyl group having 1 to 20 carbon atoms or an alkenyl group having 2 to 20 carbon atoms. Examples of the succinic acid substituted with an alkyl group having 1 to 20 carbon atoms or an alkenyl group having 2 to 20 carbon atoms include dodecyl succinic acid, dodecenyl succinic acid, octenyl succinic acid and the like.
Among these, at least one selected from terephthalic acid, fumaric acid, and sebacic acid is preferable, and 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 more preferred to use in combination.

The trivalent or higher polyvalent carboxylic acid is preferably a trivalent carboxylic acid, and more preferably a trivalent carboxylic acid, 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 anhydride, and more preferably trimellitic anhydride.
In the case of containing a polyvalent carboxylic acid having a valence of 3 or more, the content of the carboxylic acid component (A-ac ), preferably 3 mol% or more, more preferably 5 mol% or more, still more preferably 8 mol% or more, and preferably 30 mol% or less, more preferably 20 mol% or less, further 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) is excellent in low-temperature fixability and aging. From the viewpoint of suppression of deterioration of low temperature fixing property 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 preferably contains a constituent unit derived from a vinyl monomer having a hydrocarbon group, from the viewpoints of excellent low-temperature fixability, suppression of deterioration of low-temperature fixability over time, and excellent heat-resistant storage stability.
The vinyl monomer having a hydrocarbon group is preferably a (meth)acrylic acid ester from the viewpoint of availability and reactivity. Here, "(meth)acrylic acid ester" refers to acrylic acid ester or methacrylic acid ester.
In the case of (meth)acrylic acid ester, 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, more preferably a saturated aliphatic hydrocarbon group.
The carbon number of the hydrocarbon group of the vinyl monomer is preferably 6 or more, 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 preferably 10 or more, more preferably 12 or more, still more preferably 14 or more, and preferably 22 or less, more preferably 20 or less, still more preferably 18 or less.

Examples of the vinyl monomer having a hydrocarbon group include (iso)butyl (meth)acrylate, (iso)hexyl (meth)acrylate, cyclohexyl (meth)acrylate, (iso)octyl (meth)acrylate (hereinafter (( (Meth)acrylic acid 2-ethylhexyl), (meth)acrylic acid (iso)decyl, (meth)acrylic acid (iso)dodecyl (hereinafter, also referred to as (meth)acrylic acid (iso)lauryl), (meth)acrylic Examples thereof include acid (iso)palmityl, (meth)acrylic acid (iso)stearyl, and (meth)acrylic acid (iso)behenyl. Among these, 2-ethylhexyl (meth)acrylate, (iso)lauryl (meth)acrylate, and stearyl (meth)acrylate are preferable, and (iso)lauryl (meth)acrylate and stearyl (meth)acrylate are more preferable. Stearyl methacrylate is more preferable.
In addition, "(iso)" means normal or iso.

The content of the constituent unit derived from a vinyl monomer having a hydrocarbon group is preferably in the vinyl resin segment from the viewpoint of excellent low-temperature fixability, and suppression of deterioration of low-temperature fixability over time, and excellent heat-resistant storage stability. Is 5% by mass or more, more preferably 10% by mass or more, further preferably 15% by mass or more, further preferably 20% by mass or more, and preferably 60% by mass or less, more preferably 40% by mass or less, and It is preferably 30% by mass or less.

The vinyl resin segment preferably contains a structural unit derived from a styrene 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.
Examples of the styrene-based compound include styrene, methylstyrene, α-methylstyrene, β-methylstyrene, tert-butylstyrene, chlorostyrene, chloromethylstyrene, methoxystyrene, styrenesulfonic acid and salts 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 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 60 mass% or more, further preferably 70 mass% or more, and preferably 95 mass% or less, more preferably 90 mass% or less, further preferably 85 mass% or less, further preferably 80 mass% % Or less.

Raw material vinyl monomers other than hydrocarbon group-containing vinyl monomers and styrene compounds include (meth)acrylic acid aminoalkyl esters such as dimethylaminoethyl (meth)acrylate; olefins such as ethylene, propylene and butadiene; Examples thereof include halovinyls such as vinyl; vinyl esters such as vinyl acetate and vinyl propionate; vinyl ethers such as methyl vinyl ether; vinylidene halides such as vinylidene chloride; N-vinyl compounds such as N-vinylpyrrolidone.

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

When the amorphous composite resin contains a polyester resin segment and a vinyl resin segment, it is preferable that the amorphous composite resin further contains a structural unit derived from both reactive monomers, and the structural unit derived from both reactive monomers is It is preferable that it serves as a bonding point between the resin segment and the above polyester resin segment.
Examples of the bireactive monomer include vinyl monomers 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 constitutional unit derived from the both-reactive monomer, the viewpoint of improving the dispersibility of the crystalline resin to the amorphous composite resin, and from the viewpoint of reaction control of the addition polymerization reaction and polycondensation reaction of the polyester resin segment It is preferably 1 part by mole or more, more preferably 5 parts by mole or more, still more preferably 10 parts by mole or more, still more preferably 15 parts by mole or more based on 100 parts by weight of the total amount of the alcohol component (A-al) as a raw material. , And preferably 30 parts by mole or less, more preferably 25 parts by mole or less, and further preferably 20 parts by mole or less. In the case of using a bireactive monomer, when calculating the content of each segment in the amorphous composite resin, the constitutional unit derived from the bireactive monomer is contained in the constitutional unit of the polyester resin segment. Calculate as

When the amorphous composite resin contains a polyester resin segment and a vinyl resin segment, the content of the polyester resin segment in the amorphous composite resin is excellent in low-temperature fixability and suppresses deterioration of low-temperature fixability over time. From the viewpoint of 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 80% by mass. % Or less, more preferably 70% by mass or less.
When the amorphous composite resin contains a polyester resin segment and a vinyl-based resin segment, the content of the polyester resin segment in the amorphous composite resin is excellent low temperature fixing property, suppression of deterioration of low temperature fixing property over time, From the viewpoint of excellent heat-resistant storage stability, the content is preferably 40% by mass or more, more preferably 45% by mass or more, and further preferably 50% by mass or more, based on the total content of the polyester resin segment and the vinyl resin segment. , And preferably 90% by mass or less, more preferably 85% by mass or less, still more preferably 80% by mass or less.

When the amorphous composite resin contains a polyester resin segment and a vinyl resin segment, the content of the vinyl resin segment in the amorphous composite resin is excellent in low-temperature fixability and deterioration in low-temperature fixability over time. From the viewpoint of suppression and excellent heat resistant storage stability, it is preferably 10% by mass or more, more preferably 20% by mass or more, and preferably 60% by mass or less, more preferably 50% by mass or less, further preferably 45% by mass. It is not more than mass %.
When the amorphous composite resin contains a polyester resin segment and a vinyl-based resin segment, the content of the vinyl-based resin segment in the amorphous composite resin is excellent in low-temperature fixability and suppression of deterioration of low-temperature fixability over time. From the viewpoint of excellent heat resistant storage stability, the content is preferably 10% by mass or more, more preferably 15% by mass or more, and further preferably 20% by mass or more, based on the total content of the polyester resin segment and the vinyl resin segment. And preferably 60% by mass or less, more preferably 55% by mass or less, and further preferably 50% by mass or less.
When the amorphous composite resin contains a polyester resin segment and a vinyl resin segment, the total content of the polyester resin segment and the vinyl resin segment in the amorphous composite resin is excellent at low temperature fixability and From the viewpoint of suppressing the deterioration of low temperature fixability and excellent heat resistant storage stability, it is preferably 80% by mass or more, more preferably 90% by mass or more, further preferably 93% by mass or more, and further preferably 95% by mass or more. , And 100% by mass or less.

(Constituents derived from hydrocarbon wax)
When the amorphous resin (A) is an amorphous composite resin containing a polyester resin segment and a constituent component derived from a hydrocarbon wax having a hydroxyl group or a carboxy group, a hydrocarbon wax having a hydroxyl group or a carboxy group ( Hereinafter, the constituent component derived from "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. It may have either one or both of the groups, but from the viewpoint of reactivity with polyester, and excellent low temperature fixing property, and suppression of deterioration of low temperature fixing property over time, and excellent heat resistance storage stability. From the viewpoint of, 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 products of paraffin wax and Fischer-Tropsch wax as raw materials are "HNP-11", "HNP-9", "HNP-10", "FT-0070", "HNP-51", "FNP-0090". (Above, manufactured by Nippon Seiro Co., Ltd.) and the like.

Hydrocarbon wax having a hydroxyl group is obtained by modifying hydrocarbon wax such as paraffin wax and Fischer-Tropsch wax by oxidation treatment. Examples of the oxidation treatment method include the methods described in JP-A-62-79267 and JP-A-2010-197979. Specifically, there is a method of liquid-phase oxidizing a hydrocarbon wax with a gas containing oxygen in the presence of boric acid.
Examples of commercially available hydrocarbon waxes having a hydroxyl group include "Unilin 700", "Unilin 425", and "Unilin 550" (all manufactured by Baker Petrolite Co., Ltd.).

Examples of the hydrocarbon wax having a carboxy group include acid-modified wax, which can be obtained by introducing a carboxy group into the above hydrocarbon wax such as paraffin wax and Fischer-Tropsch wax. Examples of the acid modification method include the methods described in JP 2006-328388 A, JP 2007-84787 A, and the like. Specifically, a carboxyl group is introduced by adding an organic peroxide compound (reaction initiator) such as DCP (dicumyl peroxide) and a carboxylic acid compound to a melt of a hydrocarbon wax and reacting them. You can
Examples of commercially available hydrocarbon waxes having a carboxy group include Hiwax 1105A (maleic anhydride-modified ethylene-propylene copolymer, manufactured by Mitsui Chemicals, Inc.).

The hydrocarbon wax having a hydroxyl group and a carboxy group can be obtained, for example, by the same method as the 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 "Parachol 6420", "Paracoll 6470", and "Paracol 6490" (all manufactured by Nippon Seiro Co., Ltd.).

The hydroxyl value of the hydrocarbon wax (W1) is preferably 40 mgKOH/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. g or more, more preferably 50 mgKOH/g or more, further preferably 70 mgKOH/g or more, further preferably 90 mgKOH/g or more, and preferably 180 mgKOH/g or less, more preferably 150 mgKOH/g or less, further preferably 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, and 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. g or more, more preferably 8 mgKOH/g or more, and preferably 30 mgKOH/g or less, more preferably 25 mgKOH/g or less, further preferably 20 mgKOH/g or less.

The total of the hydroxyl value and the 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, further preferably 90 mgKOH/g or more, and preferably 210 mgKOH/g or less, more preferably 175 mgKOH/g or less, further preferably 140 mgKOH/g or less. , And more preferably 120 mgKOH/g or less.
The hydroxyl value and acid value of the hydrocarbon wax (W1) are determined by the method described in the examples.

The melting point of the hydrocarbon wax (W1) is preferably 60° C. or higher, more preferably 70° C. or higher, 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 more preferably 73°C or higher, and preferably 120°C or lower, more preferably 110°C or lower, further preferably 100°C or lower, further preferably 95°C or lower, further 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.

Hydrocarbon wax in the amorphous composite resin when the amorphous resin (A) is an amorphous composite resin containing a polyester resin segment and a constituent component derived from a hydrocarbon wax having a hydroxyl group or a carboxy group. The content of the constituent component derived from (W1) is preferably 1% by mass or more, more preferably 2 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 at least mass%, more preferably at least 3 mass%, and preferably at most 20 mass%, more preferably at most 15 mass%, even more preferably at most 12 mass%.

(Physical properties of amorphous resin (A))
The softening point of the amorphous resin (A) is preferably 70° C. or higher, more preferably 90° 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, the temperature is 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 resin (A) is preferably 30° C. or higher, and more preferably 35, 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 40.degree. C. or higher, and preferably 70.degree. C. or lower, more preferably 65.degree. C. or lower, still more preferably 60.degree. C. or lower, still more preferably 55.degree. C. or lower.

The acid value of the amorphous resin (A) is, from the viewpoint of improving the dispersion stability of the resin particles (X) described later, excellent low-temperature fixability, suppression of deterioration of low-temperature fixability over time, and excellent heat-resistant storage. From the viewpoint of sex, 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, further preferably It is 30 mgKOH/g or less.

The above-mentioned softening point, glass transition temperature and acid value are determined by the methods described in Examples. The softening point, glass transition temperature and acid value of the amorphous 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 kinds of amorphous resins (A) are used in combination, the softening point, glass transition temperature and acid value obtained as a mixture thereof are preferably within the above-mentioned ranges.

(Production of amorphous resin (A))
The amorphous resin (A) can be produced by a known method. For example, when the polyester resin segment is included, the alcohol component (A-al) and the carboxylic acid component (A-ac) are placed in an inert gas atmosphere. Then, it can be produced by polycondensation using an esterification catalyst, an esterification co-catalyst, a radical polymerization inhibitor, etc., if necessary.
The amorphous composite resin containing a polyester resin segment can be produced, for example, by any of the following methods (i) to (iii). It is preferable because the degree of freedom in the reaction temperature of the condensation reaction is high.
(I) A method of performing an addition polymerization reaction with a vinyl monomer as a raw material of a vinyl-based resin segment and a bireactive monomer after a polycondensation reaction with an alcohol component (A-al) and a carboxylic acid component (A-ac). When it is desired to include the constituent component derived from the hydrocarbon wax (W1) having a hydroxyl group or a carboxy group in the organic composite resin, the polycondensation reaction with the alcohol component and the carboxylic acid component is performed in the presence of the hydrocarbon wax (W1). Good.
Further, from the viewpoint of reactivity, it is preferable that both the reactive monomers are supplied to the reaction system together with the raw material vinyl monomer of the vinyl resin segment. From the viewpoint of reactivity, a catalyst such as an esterification catalyst or an esterification promoter may be used, and a radical polymerization initiator and a radical polymerization inhibitor may be used.
In addition, a part of the carboxylic acid component (A-ac) is subjected to a polycondensation reaction, then an addition polymerization reaction is performed, and then 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 promoted if necessary.

(Ii) A method of carrying out 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) An alcohol component (A-al) and a carboxylic acid component. A method in which the polycondensation reaction by (A-ac) and the addition polymerization reaction by the raw material vinyl monomer of the vinyl-based resin segment and the bireactive monomer are performed in parallel, and the polycondensation reaction by the above-mentioned methods (i) to (iii) and Both addition polymerization reactions are preferably carried out in the same container.

From the viewpoint of the productivity of the amorphous 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 lower. Is.
Further, it is preferable to accelerate the reaction by reducing the pressure of the reaction system in the latter half of the polymerization.

Examples of esterification catalysts preferably used in the polycondensation reaction include tin compounds such as dibutyltin oxide and tin(II) di(2-ethylhexanoate), and titanium compounds such as titanium diisopropylate bistriethanolaminate. Can be mentioned.
From the viewpoint of reactivity, the amount of the esterification catalyst used is preferably 0.01 parts by mass or more, and more preferably 100 parts by mass or more 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 preferably 0.1 part by mass or more, and preferably 5 parts by mass or less, more preferably 2 parts by mass or less.

As the esterification promoter, pyrogallol, 3,4,5-trihydroxybenzoic acid, pyrogallol compounds such as 3,4,5-trihydroxybenzoic acid ester; 2,3,4-trihydroxybenzophenone, 2,2' Examples thereof include benzophenone derivatives such as 3,3,4-tetrahydroxybenzophenone; catechin derivatives such as epigallocatechin and epigallocatechin gallate, and 3,4,5-trihydroxybenzoic acid is preferable from the viewpoint of reactivity.
From the viewpoint of reactivity, the amount of the esterification promoter 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). The amount is at least parts by mass, more preferably at least 0.01 parts by mass, and preferably at most 0.5 parts by mass, more preferably at most 0.2 parts by mass.
4-tert-butylcatechol etc. can be used as a radical polymerization inhibitor in a polycondensation reaction.
The use amount of the radical polymerization inhibitor is preferably 0.001 part by mass or more, more preferably 0.005 part by mass 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 more than 1 part by mass, and preferably less than 0.5 part by mass, more preferably less than 0.2 part by mass.

The temperature of the addition polymerization reaction varies depending on the type of radical polymerization initiator used and the like, but from the viewpoint of the productivity of the amorphous composite resin, it is preferably 110° C. or higher, more preferably 130° C. or higher, further preferably 150° C. It is above, 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 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, with respect to 100 parts by mass of the raw material vinyl monomer of the vinyl resin segment. It is more preferably 15 parts by mass or less.

The amount of the hydrocarbon wax (W1) used is determined 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 hydrogen wax (W1) 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. Hereafter, the amount is more preferably 12% by mass or less.
The constituent component derived from the hydrocarbon wax (W1) contained in the amorphous composite resin is a site where the hydrocarbon wax (W1) is ester-bonded.

[Crystalline 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 a 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 viewpoint of excellent low-temperature fixability, suppression of deterioration of low-temperature fixability over time, and excellent heat-resistant storage stability. And is preferably 1.3 or less, more preferably 1.2 or less.
The crystallinity index can be appropriately adjusted according to the types and ratios of the raw material monomers, and the production conditions such as reaction temperature, reaction time, and cooling rate, and the value can be obtained 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) is preferably 80 mol% of α,ω-aliphatic diol, from the viewpoints 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 the α,ω-aliphatic diol is preferably from the viewpoint of excellent low-temperature fixability in the alcohol component (B-al), 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, still more preferably 90 mol% or more, still more preferably 95 mol% or more, and 100 mol% or less, further 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.
Examples of the α,ω-aliphatic diol include ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,11-undecanediol, 1,12-dodecanediol, 1,13-tridecanediol, 1,14-tetradecanediol, etc. Is mentioned. Among these, 1,6-hexanediol and 1,10-decanediol are preferable and 1,10-hexanediol 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 the α,ω-aliphatic diol. Examples of alcohol components other than α,ω-aliphatic diols include aliphatic diols other than α,ω-aliphatic diols such as 1,2-propylene glycol and neopentyl glycol; alkylene oxide adducts of bisphenol A and the like. Aromatic diols; trivalent or higher alcohols such as glycerin, pentaerythritol, and trimethylolpropane, and the like.
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 in the carboxylic acid component (B-ac) is preferably 80 mol 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, further preferably 90 mol% or more, further preferably 95 mol% or more, and 100 mol% or less, and further preferably 100 mol%.
The carbon number of the aliphatic dicarboxylic acid is preferably 4 or more, more preferably 8 or more, still more preferably 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 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 and tetradecanedioic acid. Among these, sebacic acid and tetradecanedioic acid are preferable, and sebacic acid is more preferable.
The carboxylic acid component (B-ac) includes not only a free acid but also an anhydride that decomposes to form an acid during the reaction, and an alkyl ester having 1 to 3 carbon atoms of each carboxylic acid.
These 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) is excellent in low-temperature fixability and aging. From the viewpoint of suppressing deterioration of low-temperature fixing property 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. 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 viewpoint of excellent low-temperature fixability, suppression of deterioration of low-temperature fixability over time, and excellent heat-resistant storage stability. , 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. g or more, more preferably 15 mgKOH/g or more, and preferably 35 mgKOH/g or less, more preferably 30 mgKOH/g or less, further preferably 25 mgKOH/g or less.

The above-mentioned softening point, melting point, and acid value are determined by the methods described in the 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 raw material monomers, and the production conditions such as reaction temperature, reaction time, and cooling rate.
When two or more crystalline resins (B) are used in combination, the softening point, melting point, and acid value obtained as a mixture thereof are preferably within the above ranges.

(Production 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, the alcohol component (B-al) and the carboxylic acid component (B-ac) are placed in an inert gas atmosphere. Then, it can be produced by polycondensation using an esterification catalyst, an esterification co-catalyst, a radical polymerization inhibitor, etc., if necessary.
As the esterification catalyst, the esterification co-catalyst, and the radical polymerization inhibitor, the same ones as in the case of producing the above-mentioned amorphous composite resin 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 at least 5 parts by mass, and is preferably at most 5 parts by mass, more preferably at most 2 parts by mass.
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, further 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 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 water, deionized water, ion-exchanged water, or distilled water is preferable.
As components other than water that can form an aqueous medium together with water, alkyl alcohols having 1 to 5 carbon atoms; dialkyl ketones having 3 to 5 carbon atoms such as acetone and methyl ethyl ketone; dissolved in water such as cyclic ethers such as tetrahydrofuran An organic solvent is used.
Of these, methyl ethyl ketone is preferable.

[Conditions of Step (1)]
The step (1) preferably includes the following step (1-1), and may further 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 resin (A) in the presence of the crystalline resin (B) in an aqueous medium to obtain agglomerated particles (1) (1-2): The resin particles (Z) containing the amorphous resin (C) are added to the agglomerated particles (1) obtained in the step (1-1) to obtain a resin for the agglomerated particles (1). Step of Obtaining Aggregated Particles (2) Adhering Particles (Z) When step (1) includes step (1-1) and step (1-2), “in step (2)” The term "aggregated particles obtained" means "aggregated particles (2) obtained in step (1-2)". Moreover, when the step (1) includes only the step (1-1), the “aggregated particles obtained in the step (2)” means the “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 resin (A), and resin particles (Y) containing a crystalline resin (B), if necessary, a wax, a colorant, and an aggregating agent. A step of aggregating arbitrary components such as a surfactant in an aqueous medium to obtain agglomerated particles Step (1-1B): resin particles (X) containing an amorphous resin (A) and a crystalline resin (B), A step of aggregating optional components such as a wax, a colorant, a coagulant, and a surfactant in an aqueous medium to obtain agglomerated particles, if necessary Step (1-1C): Amorphous resin (A), crystalline Resin particles (X) containing resin (B) and wax, and optionally a step of aggregating optional components such as wax, colorant, aggregating agent and surfactant in an aqueous medium to obtain aggregating particles Among them, the step (1-1A) or the step (1-1B) is preferable, and the step (1-1A) is more preferable, from the viewpoint of improving the production stability of the toner.

[Resin particles (X)]
The resin particles (X) include a resin component containing the amorphous resin (A) and, if necessary, an optional component such as a coloring agent (hereinafter, the resin component and the optional component are collectively referred to as “resin component, etc.”). ) Is dispersed in an aqueous medium to obtain an aqueous dispersion.
As a method for obtaining an aqueous dispersion of resin particles (X), a resin component or the like is added to an aqueous medium and a dispersion treatment is performed by a disperser or the like. Examples thereof include a method of gradually adding and performing phase inversion emulsification (phase inversion 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 resulting solution to perform phase inversion emulsification, or a resin component or the like is melted and mixed to obtain a solution. A method (B) in which an aqueous medium is added to the obtained resin mixture to carry out phase inversion emulsification. Method (A) is preferable from the viewpoint of obtaining an aqueous dispersion of homogeneous resin particles (X).
In the method (A), it is preferable that first, a resin component or the like is dissolved in an organic solvent to obtain an organic solvent solution of the resin component or the like, and then an aqueous medium is added to the solution to carry out phase inversion emulsification.

As the organic solvent used in the phase inversion emulsification method, a 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. ^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, further preferably 22.0 MPa ^1/2. It is the following.
As the organic solvent, alcohol solvents such as ethanol (26.0), isopropanol (23.5), isobutanol (21.5); acetone (20.3), methyl ethyl ketone (19.0), methyl isobutyl ketone ( 17.2), a ketone solvent such as diethyl ketone (18.0); an ether solvent such as dibutyl ether (16.5), tetrahydrofuran (18.6), dioxane (20.5); ethyl acetate (18. 6), acetic acid ester solvents such as isopropyl acetate (17.4), and the like. The numerical value in parentheses after each solvent is the SP value (unit: MPa ^1/2 ) of each. Among these, from the viewpoint of easy removal from the mixed solution after addition of the aqueous medium, preferably at least one selected from a ketone solvent and an acetate ester solvent, more preferably from methyl ethyl ketone, ethyl acetate and isopropyl acetate. At least one selected, and more preferably methyl ethyl ketone.

The mass ratio of the organic solvent and the resin forming the resin particles (X) (organic solvent/resin forming the resin particles (X)) is such that the resin is dissolved and the phase inversion into the aqueous medium is facilitated, 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 Or less, more preferably 1.5 or less.
Further, from the viewpoint of obtaining uniform resin particles, and excellent low-temperature fixability, and 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 mixing mass ratio of the organic solvent and water (organic solvent/water) has excellent low-temperature fixability, suppression of deterioration of low-temperature fixability over time, and excellent heat-resistant storage stability. From the viewpoint, it is preferably 70/30 or more, more preferably 80/20 or more, still more preferably 85/15 or more, and preferably 98/2 or less, more preferably 95/5 or less, further preferably 90. /10 or less.

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. Basic substances include alkali metal hydroxides 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 of these, from the viewpoint of improving the dispersion stability and the cohesiveness of the resin particles (X), a hydroxide of an alkali metal is preferable, and sodium hydroxide is more preferable.

The equivalent amount (mol %) of the neutralizing agent to the acid group of the resin is preferably 10 mol% or more, more preferably 30 mol% or more, and preferably 150 mol% or less, more preferably 120 mol% or less. , And more preferably 100 mol% or less.
The equivalent amount (mol %) of the neutralizing agent can be calculated by the following formula. When the use equivalent of the neutralizing agent is 100 mol% or less, it is synonymous with the degree of neutralization, and when the use equivalent of the neutralizing agent exceeds 100 mol% in the following formula, the neutralizing agent is an acid group of the resin. Is excessive, and the degree of neutralization of the resin at this time is considered to be 100 mol %.
Equivalent amount of the neutralizing agent (mol %)=[{added mass of neutralizing agent (g)/equivalent amount of neutralizing agent}/[{weighted average acid value of resin (mgKOH/g)×mass of resin (g) }/(56×1000)]]×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 forming 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.
From the viewpoint of improving the dispersion stability of the resin particles (X), the mass ratio of the aqueous medium and the organic solvent (aqueous medium/organic solvent) is preferably 20/80 or more, more preferably 50/50 or more, 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.

From the viewpoint of improving the dispersion stability of the resin particles (X), the temperature at which the aqueous medium is added is preferably not less than the glass transition temperature of the amorphous resin (A), specifically, preferably not less than 50°C. , 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 diameter, the addition rate of the aqueous medium is preferably 100 parts by mass of the amorphous resin constituting the resin particles (X) until the phase inversion is completed. 0.1 parts by mass/min or more, more preferably 0.5 parts by mass/min or more, further preferably 1 part by mass/min or more, further preferably 3 parts by mass/min or more, and preferably 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 limitation on the addition rate of the aqueous medium after the phase inversion.

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

The solid content concentration of the 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, further preferably 30% by mass or less, further preferably 25% by mass. It is below. The solid content is the total amount of non-volatile components such as resins, colorants and surfactants.

The volume median particle diameter (D ₅₀ ) of the resin particles (X) in the aqueous dispersion is preferably 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, further preferably 0.12 μm or more, and preferably 0.80 μm or less, more preferably 0.40 μm or less, further preferably 0.30 μm or less, and It is preferably 0.20 μm or less.
Here, the volume median particle diameter (D ₅₀ ) is a particle diameter at which the cumulative volume frequency calculated by the volume fraction becomes 50% when calculated from the smaller particle diameter, 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 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, and further preferably 30% or less from the viewpoint of obtaining a high quality image as a toner.
The CV value is a value represented by the following formula. The volume average particle diameter in the following formula is the particle diameter obtained by multiplying the particle diameter measured on a volume basis by the proportion of particles having that particle diameter value and dividing the value obtained by the number of particles. Yes, and can be obtained by the method described in Examples below.
CV value (%)=[standard deviation of particle size distribution (nm)/volume average particle size (nm)]×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, optional components such as wax and colorant in an aqueous medium.
As in the case of the resin particles (X), the aqueous dispersion is obtained by adding the crystalline resin (B) or the like to an aqueous medium and dispersing using a disperser, or by adding the crystalline resin (B) or the like to the aqueous system. Examples include a method of gradually adding a medium to perform phase inversion emulsification, excellent low-temperature fixability, and suppression of deterioration of low-temperature fixability over time, and from the viewpoint of excellent heat-resistant storage stability, a method by phase inversion emulsification is preferable.
Also in the phase inversion emulsification method, as in the case of the resin particles (X), the aqueous medium is added to the solution obtained by dissolving the resin and the other optional components described above in the organic solvent to perform the phase inversion emulsification. The method of doing is preferable. The preferred embodiments of the aqueous medium and organic solvent that can be used are the same as in the production of the resin particles (X) described above.

The mass ratio of the organic solvent and the resin constituting the resin particles (Y) (organic solvent/resin constituting the resin particles (Y)) is a 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 or more. It is preferably 1 or less, 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 neutralizing agent 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.

From the viewpoint of improving the dispersion stability of the resin particles (Y), the amount of the aqueous medium to be added is preferably 100 parts by mass or more, and more preferably 150 parts by mass with respect to 100 parts by mass of the resin constituting the resin particles (Y). The amount is not less than 200 parts by mass, more preferably not less than 200 parts by mass, and preferably not more than 900 parts by mass, more preferably not more than 600 parts by mass, further preferably not more than 400 parts by mass.
The mass ratio of the aqueous medium and the organic solvent (aqueous medium/organic solvent) is preferably 20/80 or more, more preferably 50/50 or more, further 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, and further preferably 90/10 or less.

From the viewpoint of improving the dispersion stability of the resin particles (Y), the temperature at which the aqueous medium is added is preferably 10° C. or more lower than the melting point of the crystalline resin (B), specifically, preferably 50. C. or higher, more preferably 60.degree. C. or higher, even more preferably 70.degree. C. or higher, and preferably 85.degree. C. or lower, more preferably 80.degree. C. or lower, still more preferably 75.degree. C. or lower.
From the viewpoint of obtaining resin particles (Y) having a small particle diameter, 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. Mass part/min or more, more preferably 0.5 mass part/min or more, further preferably 1 mass part/min or more, further preferably 3 mass part/min or more, and preferably 50 mass part/min 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 limitation on the addition rate of the aqueous medium after the phase inversion.

After the phase inversion emulsification, it may have a step of removing the organic solvent from the obtained dispersion, if necessary.
A preferred embodiment of the method for removing the organic solvent and the remaining amount of the organic solvent in the aqueous dispersion is the same as in the production of 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, further preferably 30% by mass or less, further preferably 25% by mass. It is not more than mass %. The solid content is the total amount of non-volatile components such as resins, colorants and surfactants.

The volume median particle diameter (D ₅₀ ) of the resin particles (Y) in the aqueous dispersion is preferably 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, further preferably 0.12 μm or more, and preferably 0.80 μm or less, more preferably 0.40 μm or less, further 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 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 from the viewpoint of obtaining a high quality image toner, it is preferably 50% or less, more preferably 40% or less, and further preferably 30% or less.

The mass ratio [amorphous resin (A)/crystalline resin (B)] of the amorphous resin (A) and the crystalline resin (B) in the step (1) is excellent in low-temperature fixability and with time. From the viewpoint of suppressing deterioration of low-temperature fixability, it 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/. It is 10 or less, more preferably 85/15 or less, further preferably 80/20 or less, further preferably 75/25 or less. Further, the mass ratio [amorphous resin (A)/crystalline resin (B)] is preferably 50/50 or more, more preferably 60/40 or more, further preferably from the viewpoint of excellent heat resistant storage stability. Is 70/30 or more, 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 resin (A) and the crystalline resin (B) is preferably 80% by mass or more, more preferably 90% by mass or more, still more preferably in the resin component contained in the aggregated particles (1). It is 95% by mass or more and 100% by mass or less, and more preferably 100% by mass.

[Wax particles]
In the step (1), the wax may be further aggregated in an aqueous medium to obtain a dispersion liquid of aggregated particles.
When the step (1) is the step (1-1A) or the step (1-1B), it is preferable to use a dispersion liquid of wax particles in which a wax is dispersed in an aqueous medium.
Examples of the wax used in the step (1) include low molecular weight polyolefins such as polyethylene, polypropylene and polybutene; silicone waxes; fatty acid amides such as oleic acid amide and stearic acid amide; plants such as carnauba wax, rice wax and candelilla wax. Waxes; animal waxes such as beeswax; mineral waxes such as montan wax, paraffin wax, Fischer-Tropsch wax; petroleum waxes; synthetic waxes such as ester waxes. 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, more preferably paraffin, 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, and further 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, the temperature is more preferably 73° C. or higher, and preferably 100° C. or lower, more preferably 95° C. or lower, further preferably 90° C. or lower, further 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 waxes are used in combination, the wax having the highest mass ratio among the waxes contained in the toner is the melting point of the wax in the invention. When all have the same ratio, the lowest value is used.

Wax particles are preferably obtained as a dispersion liquid in which wax is dispersed in an aqueous medium, and more preferably obtained as an aqueous dispersion of wax particles by mixing and dispersing wax with resin particles (P) in an aqueous medium.
The resin particles (P) used to disperse the wax are not particularly limited, and from the viewpoint of dispersion stability in the toner particles, suitable examples are the same as the resin particles (X) described above, but they have excellent low-temperature fixability. It is more preferable to use an amorphous composite resin containing a polyester resin segment and a vinyl resin segment from the viewpoints of suppressing deterioration of low-temperature fixing property over time and excellent heat-resistant storage stability.
As the amorphous composite resin used for the resin particles (P), the above-mentioned amorphous composite resin may be used as it is, but the viewpoint of obtaining resin particles having a small particle diameter and the dispersibility of wax in an aqueous medium. From the viewpoint of improving the softening point, the softening point of the amorphous composite resin used for the resin particles (P) is preferably 70° C. or higher, more preferably 80° C. or higher, and preferably 140° C. or lower, more preferably The temperature is 120°C or lower, and more preferably 100°C or lower. Other preferable ranges of resin characteristics, preferable examples of raw material monomers constituting the resin, and the like are the same as those of the above-mentioned amorphous composite resin.

The dispersion liquid of wax particles is preferably obtained by dispersing the wax, the aqueous dispersion of 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, and a high pressure disperser.
Examples of the ultrasonic disperser include an ultrasonic homogenizer. Examples of the commercially available product include "US-150T", "US-300T", "US-600T" (manufactured by Nippon Seiki Co., Ltd.), "SONIFIER (registered trademark) 4020-400", "SONIFIER (registered trademark) 4020. -800" (manufactured by Branson).
As a commercially available device as a high-pressure disperser, a high-pressure wet atomization device "Nanomizer (registered trademark) NM2-L200-D08" (manufactured by Yoshida Kikai Co., Ltd.) can be mentioned.
Further, before using the disperser, the wax, the resin particles (P), and the aqueous medium may be preliminarily dispersed by a mixer such as a homomixer or a ball mill.
A preferred embodiment of the aqueous medium of the wax particle dispersion is the same as the aqueous medium used for obtaining the aqueous dispersion of the resin particles (X).

A surfactant may be used to disperse the wax particles in the aqueous medium, from the viewpoint of improving the dispersion stability of the wax particles and obtaining uniform agglomerated particles.
Examples of the surfactant include nonionic surfactants, anionic surfactants, cationic surfactants, etc., from the viewpoint of improving the dispersion stability of wax particles and the cohesiveness of wax particles and resin particles. From the viewpoint of improvement, it is preferably an anionic surfactant.
Examples of the surfactant include sodium dodecylbenzene sulfonate, sodium dodecyl sulfate, sodium lauryl ether sulfate, dipotassium alkenyl succinate 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 further preferably 1% by mass or less, from the viewpoint of preventing the release of wax particles during toner preparation. , More preferably 0.5 mass% or less, and 0 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, from the viewpoint of improving the productivity of the toner and improving 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, and further 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, from the viewpoint of obtaining uniform agglomerated particles, and It is preferably 1.0 μm or less, more preferably 0.80 μm or less, still more preferably 0.60 μm or less.

The variation coefficient (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 agglomerated particles. It is preferably 50% or less, more preferably 45% or less, still more preferably 40% or less.
The volume median particle size and CV value of the wax particles are specifically determined by the methods described in Examples below.

From the viewpoint of toner releasability, excellent low-temperature fixability, suppression of deterioration of low-temperature fixability over time, and excellent heat-resistant storage stability, the amount of wax used is 100 parts by mass of the total amount of resin components of the toner. 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, further preferably 10 parts by mass. It is below.

[Colorant particles]
In the step (1), the colorant may be further aggregated in an aqueous medium to obtain a dispersion liquid of aggregated particles.
Examples of the colorant used in the step (1) include a pigment and a dye, and the pigment is preferable from the viewpoint of improving the image density of the printed matter.
Examples of pigments include cyan pigments, yellow pigments, magenta pigments, and black pigments. The cyan pigment is preferably a phthalocyanine pigment, more preferably copper phthalocyanine. 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 acridine dye, azo dye, benzoquinone dye, azine dye, anthraquinone dye, indigo dye, phthalocyanine dye and aniline black dye.
The colorants may 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 liquid 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 using a disperser in the presence of a surfactant and the like. As the disperser, a homogenizer, an ultrasonic disperser and the like are preferable.
A preferred embodiment of the aqueous medium is the same as the aqueous medium used in the aqueous dispersion of the resin particles (X).

When the colorant particles are dispersed in the aqueous medium, it is preferable to perform the dispersion 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, and cationic surfactants, and from the viewpoint of improving the dispersion stability of the colorant particles, the colorant particles and the resin particles (X ) And from the viewpoint of improving the cohesiveness with the resin particles (Y), an anionic surfactant is preferable. Specific examples thereof include sodium dodecylbenzene sulfonate, sodium dodecyl sulfate, sodium lauryl ether sulfate, and dipotassium alkenyl succinate, with sodium dodecylbenzene sulfonate being preferred.

The content of the surfactant in the colorant particle dispersion is preferably from the viewpoint of improving the dispersion stability of the colorant particles, and the viewpoint of improving the cohesiveness of the colorant particles during toner production and preventing the release. Is 0.1% by mass or more, more preferably 0.5% by mass or more, further 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 improving the dispersion stability of the colorant particle dispersion. , More preferably 15% by mass or more, and preferably 50% by mass or less, more preferably 40% by mass or less, further preferably 30% by mass or less.

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 a high quality image toner. , 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. It is above, and preferably 30 parts by mass or less, more preferably 20 parts by mass or less, and further preferably 15 parts by mass or less.

[Agglomerated particles (1)]
Aggregated particles (1) are obtained by mixing a dispersion liquid of resin particles with optional components such as a wax particle dispersion liquid containing a wax as necessary, an aggregating agent, a surfactant, and a coloring agent, and aggregating them.
Specifically, first, an aqueous dispersion of resin particles and, if necessary, optional components such as a wax particle dispersion, a surfactant, and a colorant are mixed in an aqueous medium to obtain a mixed dispersion. Is preferred. Then, when the components in the mixed dispersion liquid are aggregated to obtain a dispersion liquid of aggregated particles (1), it is preferable to add an aggregating agent from the viewpoint of efficiently performing aggregation.
The mixing order of each component is not particularly limited, and each component may be added in any order, or all the components may be added simultaneously.
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 aggregated particles having a desired particle size. And it is preferably 40° C. or lower, and more preferably 30° C. or lower.

The mixed dispersion may be prepared in the presence of a surfactant from the viewpoint of improving the dispersion stability of the resin particles and optional components such as wax particles added as necessary.
Examples of the surfactant include anionic surfactants such as sulfuric acid ester-based, sulfonate-based, phosphoric acid ester-based, and soap-based (for example, alkyl ether carboxylate); amine salt-type and quaternary ammonium Cationic surfactants such as salt type; polyoxyethylene alkylaryl ethers such as polyoxyethylene nonylphenyl ether; polyoxyethylene alkyl ethers and polyoxyethylene alkenyl ethers such as polyoxyethylene oleyl ether and polyoxyethylene lauryl ether; , Polyoxyethylene sorbitan monolaurate and polyoxyethylene sorbitan monostearate and other polyoxyethylene sorbitan esters, polyethylene glycol monolaurate, polyethylene glycol monostearate and polyethylene glycol monooleate and other polyoxyethylene fatty acid esters And nonionic surfactants such as oxyethylene/oxypropylene block copolymers. Among these, nonionic surfactants are preferable, polyoxyethylene alkyl ethers and polyoxyethylene alkenyl ethers are preferable, and polyoxyethylene lauryl ether is more preferable.
When a surfactant is used, its amount 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. The amount is preferably 5 parts by mass or less, more preferably 3 parts by mass or less.

(Flocculant)
From the viewpoint of efficiently performing aggregation, it is preferable to add an aggregating agent.
The aggregating agent is preferably an electrolyte, and more preferably a salt, from the viewpoint of obtaining a toner having a desired particle size while preventing excessive aggregation.
Examples of the aggregating agent include a cationic surfactant of a quaternary salt, an organic aggregating agent such as polyethyleneimine; an inorganic aggregating agent such as an inorganic metal salt, an inorganic ammonium salt and a divalent or higher metal complex. Among these, from the viewpoint of improving the cohesiveness and obtaining uniform coagulated particles, an inorganic coagulant is preferable, an inorganic metal salt or an inorganic ammonium salt is more preferable, and an inorganic ammonium salt is still more preferable.
The valence of the cation of the inorganic coagulant is preferably 5 or less, more preferably 2 or less, and further preferably 1 from the viewpoint of obtaining a toner having a desired particle size while preventing excessive aggregation. Examples of the monovalent cation of the inorganic flocculant include sodium ion, potassium ion, ammonium ion and the like. From the viewpoint of improving the aggregability and obtaining uniform agglomerated particles, ammonium ions are preferred.
Examples of the inorganic metal salt include metal salts such as sodium sulfate, sodium nitrate, sodium chloride, calcium chloride and calcium nitrate, and inorganic metal salt polymers such as polyaluminum chloride and polyaluminum hydroxide.
Examples of the inorganic ammonium salt include ammonium sulfate, ammonium chloride, ammonium nitrate and the like.
The coagulant 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. The amount is more preferably 10 parts by mass or more, further preferably 20 parts by mass or more, and preferably 50 parts by mass or less, more preferably 45 parts by mass or less, from the viewpoint of improving the low temperature fixing property and heat resistant storage stability of the toner. More preferably, it is 40 parts by mass or less.

The aggregating agent is preferably added dropwise to the mixed dispersion as an aqueous solution. The aggregating agent may be added at once, or may be added intermittently or continuously. It is preferable to perform sufficient stirring at the time of addition and after the completion of addition.
Further, from the viewpoint of controlling aggregation to obtain aggregated particles having a desired particle size and particle size distribution, it is preferable to adjust the pH of the aqueous solution of the aggregating agent to 7.0 or more and 9.0 or less before use.
The temperature at which the aggregating agent is dropped is preferably 0° C. or higher, more preferably 10° C. or higher, even more preferably 20° C. or higher, and preferably 45° C. or lower, more preferably from the viewpoint of improving toner productivity. Is 40° C. or lower, more preferably 35° C. or lower, further preferably 30° C. or lower.

Furthermore, from the viewpoint of promoting aggregation and obtaining aggregated particles having a desired particle size and particle size distribution, it is preferable to raise the temperature of the dispersion after adding the aggregating agent. The holding temperature is preferably 45°C or higher, more preferably 50°C or higher, further preferably 55°C or higher, and preferably 70°C or lower, more preferably 65°C or lower, further 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 temperature range.

The volume median particle diameter (D ₅₀ ) of the agglomerated particles (1) is preferably 2 μm 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 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 obtained by the method described in Examples below.

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

The amorphous resin (C) is preferably an alcohol component (C-al) and a carboxylic acid component (C-al) 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 polyester resin obtained by polycondensing 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 more preferably Is of formula (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 showing the average number of moles of alkylene oxide added. 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]. Including.

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

The alcohol component (C-al) may contain a polyhydric alcohol other than the alkylene oxide adduct of bisphenol A. The other alcohol component that may be contained in the alcohol component (C-al) is the same as the alcohol component (A-al) that constitutes the polyester resin segment of the amorphous resin (A) described above.

(Carboxylic acid component (C-ac))
Examples of the carboxylic acid component (C-ac) include dicarboxylic acid and trivalent or higher polyvalent carboxylic acid. Among them, dicarboxylic acid is preferable, and it is more preferable to use dicarboxylic acid and polyvalent carboxylic acid having a valence of 3 or more in combination.

Examples of dicarboxylic acids include aromatic dicarboxylic acids, aliphatic dicarboxylic acids, and alicyclic dicarboxylic acids, preferably at least one selected from aromatic dicarboxylic acids and aliphatic dicarboxylic acids, and more preferably aromatic dicarboxylic acids. Is.
The carboxylic acid component (C-ac) includes not only a free acid but also an anhydride that decomposes to produce an acid during the reaction, and an alkyl ester having 1 to 3 carbon atoms of each carboxylic acid.
Examples of the aromatic dicarboxylic acid include phthalic acid, isophthalic acid, and terephthalic acid. From the viewpoint of excellent low-temperature fixing property, suppression of deterioration of low-temperature fixing property over time, and excellent heat-resistant storage stability, isophthalic acid is preferable. Acid or terephthalic acid, and 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 preferably 30 or less, more preferably 20 or less.
Examples of the aliphatic dicarboxylic acid having 2 to 30 carbon atoms include oxalic acid, malonic acid, maleic acid, fumaric acid, citraconic acid, itaconic acid, glutaconic acid, succinic acid, adipic acid, sebacic acid, dodecanedioic acid, azelaic acid. And succinic acid substituted with an alkyl group having 1 to 20 carbon atoms or an alkenyl group having 2 to 20 carbon atoms. Examples of the succinic acid substituted with an alkyl group having 1 to 20 carbon atoms or an alkenyl group having 2 to 20 carbon atoms include dodecyl succinic acid, dodecenyl succinic acid, octenyl succinic acid and the like.
Among these, 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 viewpoints of excellent low-temperature fixability, suppression of deterioration of low-temperature fixability over time, and excellent heat-resistant storage stability, substitution with an alkyl group having 1 to 20 carbon atoms or an alkenyl group having 2 to 20 carbon atoms is performed. The succinic acid thus obtained is more preferably used 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 dodecenylsuccinic acid in combination.

The trivalent or higher polyvalent carboxylic acid is preferably a trivalent carboxylic acid from the viewpoints of excellent low-temperature fixability, suppression of deterioration of low-temperature fixability over time, and excellent heat-resistant storage stability, and more preferably, It is at least one selected from trimellitic acid and its acid anhydride, and more preferably trimellitic acid anhydride.
In addition, the content of the polyvalent carboxylic acid having a valency of 3 or more is determined from the viewpoint of excellent carboxylic acid component (C -Ac), 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.
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 the viewpoint of 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 described above, the temperature is more preferably 110°C or higher, and preferably 160°C or lower, more preferably 140°C or lower, and further 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 viewpoint 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.degree. C. or higher, and preferably 90.degree. C. or lower, more preferably 80.degree. C. or lower, still more preferably 70.degree. 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, further preferably 15 mgKOH/g, from the viewpoint of improving the dispersion stability of the resin particles (Z) described later. It is above, and preferably 35 mgKOH/g or less, more preferably 30 mgKOH/g or less, further 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 below. The softening point, glass transition temperature and acid value of the amorphous resin (C) can be appropriately adjusted depending on the types and ratios of the raw material monomers and the production conditions such as reaction temperature, reaction time and cooling rate.
When two or more kinds of the amorphous resin (C) are used in combination, the softening point, glass transition temperature and acid value of the mixture thereof are preferably within the above-mentioned ranges. ..

(Production 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, as an esterification catalyst, an esterification promoter, a radical. It can be produced by polycondensation using a polymerization inhibitor or the like.
As the esterification catalyst, the esterification promoter, and the radical polymerization inhibitor, the same ones as those used in the production of the polyester resin segment of the above-mentioned amorphous composite resin can be mentioned. The conditions shown in the production of the polyester resin segment of the above-mentioned amorphous composite resin can be similarly applied to these suitable amounts and conditions such as 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 the amorphous resin (C) is dispersed in an aqueous medium to obtain an aqueous dispersion of the resin particles (Z).
The resin particles (Z) are obtained as an aqueous dispersion of the resin particles (Z) by dispersing a resin component containing the amorphous resin (C) and, if necessary, the above-mentioned optional components in an aqueous medium. Is preferred.
The method for obtaining the aqueous dispersion and its preferable conditions are the same as those for the resin particles (X).

The solid content concentration of the aqueous dispersion of the resin particles (Z) is preferably 5% by mass or more, and more preferably 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 capable of obtaining 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 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, and further preferably 30% or less from the viewpoint of obtaining a toner capable of obtaining a high-quality image.

The resin particles (Z) include, in addition to the amorphous resin (C), known resins used for toner, for example, polyesters other than the amorphous resin (C), styrene-acryl copolymer, epoxy, polycarbonate, Polyurethane and the like can be contained.
The content of the amorphous resin (C) in all the resin components contained in the resin particles (Z) is excellent in low temperature fixability, suppression of deterioration of low temperature fixability over time, and excellent heat resistance storage stability. Therefore, it is preferably 80% by mass or more, more preferably 90% by mass or more, further preferably 95% by mass or more, and further preferably 100% by mass.
Further, the resin particles (Z) may contain the above-mentioned colorant and charge control agent, if necessary. In addition, a reinforcing filler such as a fibrous substance, an additive such as an antioxidant and an anti-aging agent, and the like may be contained as long as the effects of the present invention are not impaired.

[Agglomerated particles (2)]
In the step (1-2), the resin particles (Z) are added to the aggregated particles (1) obtained in the step (1-1), and the resin particles (Z) are attached to the aggregated particles (1). In the step of obtaining the agglomerated particles (2), the aqueous dispersion of the resin particles (Z) is added to the dispersion liquid of the agglomerated particles (1) described above to further add the resin particles (Z) to the agglomerated particles (Z). ) Is attached to obtain a dispersion liquid of aggregated particles (2).

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

The temperature at which the aqueous dispersion of the resin particles (Z) is added is from the viewpoint of obtaining uniform agglomerated particles, excellent low-temperature fixability, suppression of deterioration of low-temperature fixability over time, and excellent heat-resistant storage stability. Therefore, the temperature 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, further preferably 65° C. or lower.

The aqueous dispersion of resin particles (Z) may be added continuously over a certain period of time, added at one time, or added in a plurality of divided portions, but it may take a certain period of time. Is preferably added continuously or divided into a plurality of times. By adding in this way, the resin particles (Z) are likely to selectively adhere to the aggregated particles (1). Among them, from the viewpoint of promoting selective adhesion and improving the productivity of the toner, it is preferable to continuously add them over a certain period of time.
When the aqueous dispersion of the resin particles (Z) is continuously added, the addition speed is 100 mass% of the aggregated particles (1) from the viewpoint of obtaining uniform aggregated particles (2) and improving the productivity of the toner. With respect to parts, 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 , Preferably 1.0 part by mass/min or less, more preferably 0.5 part by mass/min or less, still more preferably 0.3 part by mass/min or less.

The addition amount of the resin particles (Z) is such that the resin particles (Z), the resin particles (X), and the resin are excellent in terms of excellent low-temperature fixability, suppression of deterioration of the low-temperature fixability over time, and excellent heat-resistant storage stability. The mass ratio [(Z)/((X)+(Y))] of 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, and further preferably 0.2 or less.

In addition, in the manufacturing method of the present invention, other than the amorphous resin (A), the crystalline resin (B), and the amorphous resin (C), the toner is used in a toner within a range that does not impair the effects of the present invention. Known resins such as styrene-acrylic copolymers, epoxies, polycarbonates and polyurethanes can be contained.
When performing the step (1-2), the total content of the amorphous resin (A), the crystalline resin (B), and the amorphous resin (C) is excellent in low-temperature fixability and low temperature over time. From the viewpoint of suppressing deterioration of fixing property and excellent heat-resistant storage stability, it is preferably 80% by mass or more, more preferably 90% by mass or more, still more preferably 95% by mass or more, based on the total amount of resin components of the toner. It is preferably 98% by mass or more, and more preferably 100% by mass.
Further, the mass ratio [(C)/((A)+(B))] of the amorphous resin (C) and the total amount of the amorphous resin (A) and the crystalline resin (B) is the low temperature of the toner. From the viewpoint of improving 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 or less, more preferably 0.3 or less, and further preferably 0.2 or less.

The volume median particle diameter (D ₅₀ ) of the agglomerated particles (2) is excellent from the viewpoint of obtaining a toner capable of obtaining a high quality image, and is excellent in low-temperature fixability and suppression of deterioration of low-temperature fixability over time, and excellent. Further, from the viewpoint of heat resistant storage stability, 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, further preferably 6 μm or less.

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

(Flocculating agent)
As the aggregation 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, and more preferably sodium polyoxyethylene lauryl ether sulfate.
The aggregation terminator may be used alone or in combination of two or more kinds.
The addition amount of the aggregation terminator is preferably 0.1 parts by mass or more, more preferably 1 part by mass or more, based on 100 parts by mass of the total amount of the resin in the toner, from the viewpoint of reliably preventing unnecessary aggregation. The amount is more preferably 2 parts by mass or more, and is preferably 25 parts by mass or less, more preferably 15 parts by mass or less, and further preferably 10 parts by mass or less, from the viewpoint of reducing the residue on the toner. The aggregation stopper is preferably added as an aqueous solution from the viewpoint of improving the productivity of the toner.

The temperature at which the aggregation stopper is added is preferably the same as the temperature at which the dispersion liquid of the aggregated particles (2) is held, from the viewpoint of improving the productivity of the toner. The temperature at which the aggregation stopper is added is preferably 40° C. or higher, more preferably 45° C. or higher, even more preferably 50° C. or higher, and preferably 80° C. or lower, more preferably 70° C. or lower, further preferably 65. It is below ℃.
Further, from the viewpoint of stabilizing the aggregated particles and preventing the particles that have once aggregated from being dispersed before fusion, it is preferable to add an acid together with stopping the aggregation to make the dispersion liquid of the aggregated particles from neutral to acidic. ..
The acid to be added is not limited and, for example, sulfuric acid, hydrochloric acid, nitric acid, phosphoric acid, acetic acid and the like are preferably mentioned, but from the viewpoint of rapid pH change with respect to addition, preferably hydrochloric acid, sulfuric acid, nitric acid and acetic acid are used. At least one selected from the above, more preferably at least one selected from hydrochloric acid, sulfuric acid, and nitric acid, and further preferably sulfuric acid.
The acid is preferably added as an aqueous solution. Further, it may be added together with the aggregation stopper.

<Step (2)>
The step (2) is, for example, a step of fusing the aggregated particles obtained in the step (1) to obtain a dispersion liquid of toner particles.
The particles in the agglomerated particles, which were mainly in the state of being physically attached to each other, are fused and integrated to form toner particles (also referred to as “fused particles”).

In the step (2), the crystalline resin is used from the viewpoints of improving the fusion property of aggregated particles, excellent low-temperature fixability, suppression of deterioration of low-temperature fixability over time, and excellent heat-resistant storage stability. It is preferable to maintain at a temperature not lower than 15° C. lower than the melting point of (B).
The holding temperature is more preferably at least 10° C. lower than the melting point of the crystalline resin (B) from the viewpoint of improving the fusion property of the aggregated particles and the productivity of the toner, and further preferably the crystalline resin. It is at least 8°C lower than the melting point of (B), more preferably at least 5°C lower than the melting point of crystalline resin (B), more preferably at least the melting point of crystalline resin (B), and preferably crystalline. At a temperature not higher than 30° C. higher than the melting point of the crystalline resin (B), more preferably not higher than 20° C. higher than the melting point of the crystalline resin (B), further preferably not higher than 12° C. higher than the melting point of the crystalline resin (B). is there.
At that time, the time of holding at a temperature 15° C. or lower lower than the melting point of the crystalline resin (B) is preferably 1 minute from the viewpoint of improving the fusion property of the aggregated particles and 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, further preferably 120 minutes or less, further preferably 90 minutes or less.

The volume median particle diameter (D ₅₀ ) of the toner particles in the dispersion liquid obtained in the step (2) is excellent in low-temperature fixability, suppression of deterioration of low-temperature fixability over time, and excellent heat-resistant storage stability. Therefore, 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, further preferably 6 μm or less.
The circularity of the toner particles in the dispersion liquid obtained in the step (2) is excellent in low-temperature fixability, suppression of deterioration of low-temperature fixability over time, and excellent heat-resistant storage stability, and high-quality images. From the viewpoint of obtaining, it is preferably 0.955 or more, more preferably 0.960 or more, still more preferably 0.965 or more, and preferably 0.990 or less, more preferably 0.985 or less, further preferably It is 0.980 or less.

<Step (3)>
The step (3) (cooling step) includes the amorphous resin (A) and the crystalline resin (A) and the crystalline resin (from the viewpoint of excellent low-temperature fixability, suppression of deterioration of the low-temperature fixability over time, and excellent heat-resistant storage stability. In the step of cooling the dispersion liquid of toner particles containing B), the dispersion liquid of toner particles having a temperature T _u (° C.) is added to an aqueous medium (W) and cooled to a temperature T _d (° C.). Including the operation, the temperature T _u , the temperature T _d, and the melting point T _m (° C.) of the crystalline resin satisfy the following relational expressions (a) and (b), and the aqueous medium at the start of addition of the dispersion liquid of toner particles The temperature T _w of (W) is equal to or lower than the temperature T _d .
_{T u - T m ≧ -15 (} a)
T _d −T _m ≦−20 (b)

The toner particles are preferably the toner particles obtained in step (2).
The toner particles may be core-shell type toner particles having a core part and a shell part existing on the surface of the core part. When the toner particles are core-shell type toner particles, the core part contains the amorphous resin (A) and the crystalline resin (B), and the shell part contains the amorphous resin (C).
In the toner particles to be cooled, the mass ratio of the amorphous resin (A) and the crystalline resin (B) [amorphous resin (A)/crystalline resin (B)] is excellent in low-temperature fixability and aging. From the viewpoint of suppressing reduction in low-temperature fixing property, it 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, more preferably 85/15 or less, further preferably 80/20 or less, further preferably 75/25 or less. Further, the mass ratio [amorphous resin (A)/crystalline resin (B)] is preferably 50/50 or more, more preferably 60/40 or more, further preferably from the viewpoint of excellent heat resistant storage stability. Is 70/30 or more, 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.
In the toner particles to be cooled, the content of the crystalline resin (B) depends on the content of the resin component in the toner from the viewpoint of excellent low-temperature fixability, suppression of deterioration of low-temperature fixability over time, and excellent heat-resistant storage stability. The total amount is preferably 5% by mass or more, more preferably 10% by mass or more, further preferably 15% by mass or more, and preferably 45% by mass or less, more preferably 40% by mass or less, further preferably It is 35 mass% or less.
In the case of core-shell type toner particles, the mass ratio [(C)/((A)+(B)) of the amorphous resin (C) to the total of the amorphous resin (A) and the crystalline resin (B) ] 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, from the viewpoint of improving the low temperature fixing property and durability of the toner. And, it is preferably 0.5 or less, more preferably 0.3 or less, and further preferably 0.2 or less.

The temperature T _u (° C.) means the temperature of the dispersion liquid of toner particles when it is added to the aqueous medium (W).
The temperature T _d (° C.) means the temperature when the temperature in the mixed liquid becomes constant after the addition of the dispersion liquid of toner particles is completed.
The temperature T _w (° C.) means the temperature of the aqueous medium (W) immediately before the dispersion liquid of toner particles is added.
A preferred embodiment of the aqueous medium (W) used for cooling in the step (3) is the same as the aqueous medium used for obtaining the aqueous dispersion of the resin particles (X).

With respect to the relational expression (a), (T _u −T _m ) is −15 or more, from the viewpoint of excellent low-temperature fixability, suppression of deterioration of low-temperature fixability over time, and excellent heat-resistant storage stability, and is preferable. Is -12 or more, more preferably -10 or more, and from the viewpoint of excellent heat-resistant storage stability and work efficiency, preferably 30 or less, more preferably 20 or less, still more preferably 12 or less, From the viewpoint of excellent low-temperature fixability and suppression of deterioration of the low-temperature fixability over time, it is more preferably 3 or less, further preferably 0 or less, and further preferably -5 or less.

With respect to the relational expression (b), (T _d −T _m ) is −20 or less from the viewpoint of excellent low-temperature fixing property, suppression of deterioration of low-temperature fixing property over time, and excellent heat-resistant storage stability, and is preferable. Is -30 or less, more preferably -40 or less, and from the viewpoint of work efficiency, it is preferably -80 or more, more preferably -65 or more, still more preferably -50 or more.

Temperature T _u and the temperature T _d is excellent low temperature fixing property, and over time the low-temperature fixability of suppressing reduction, and excellent in view of heat storage stability, preferably relationship _{(c): T u - T} d ≧ 10 (c) is further satisfied.
With respect to the relational expression (c), (T _u − T _d ) is preferably 15 or more, more preferably from the viewpoint of excellent low-temperature fixability, suppression of deterioration of low-temperature fixability over time, and excellent heat-resistant storage stability. Is 20 or more, more preferably 30 or more, still more preferably 40 or more, and from the viewpoint of work efficiency, preferably 80 or less, more preferably 70 or less, still more preferably 60 or less.

The temperature T _d and the temperature T _w are preferably the relational expression (d): T _d −T _w ≦ from the viewpoint of excellent low-temperature fixability, suppression of deterioration of low-temperature fixability over time, and excellent heat-resistant storage stability. 40 (d) is further satisfied.
With regard to the relational expression (d), (T _d −T _w ) is preferably 30 or less, more preferably 25 or less, and preferably 0 or more, more preferably 0 or more, further preferably 5 or more, further preferably Is 10 or more.

The temperature T _w of the aqueous medium (W) is preferably (T _m −20)° C. or lower, from the viewpoint of excellent low-temperature fixability, suppression of deterioration of low-temperature fixability over time, and excellent heat-resistant storage stability. preferably _(T m -30) ℃ or less, still more preferably less ℃ _(T m -40), and, from the viewpoint of work efficiency, preferably _(T m -90) ℃ or higher, more preferably _{(T m} The temperature is −80)° C. or higher, more preferably (T _m −70)° C. or higher.

From the viewpoint of stabilizing the shape of the toner particles, a basic substance may be added to the dispersion liquid of the toner particles before addition to the aqueous medium. As the basic substance, the same substances as those exemplified above can be mentioned.
The method of adding the dispersion liquid of toner particles to the aqueous medium is not particularly limited, and the entire amount of the dispersion liquid may be added at once, or may be added gradually over time. The toner particle dispersion liquid may be cooled while being added and mixed with the aqueous medium via a mixer or the like. The aqueous medium to be added may be further cooled by a cooling device such as a cooling jacket if the desired relational expression is satisfied.

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

Next, it is preferable to perform drying. The drying temperature is preferably set so that the temperature of the toner particles themselves is lower than the glass transition temperature of the resin forming the resin particles (Z), and the minimum glass transition temperature of the resin forming the toner particles. It is more preferable that it is lower. As a drying method, it is preferable to use a vacuum low temperature drying method, a vibration type fluidized drying method, a spray drying method, a freeze drying method, a flash jet method or the like. The water content after drying is adjusted to preferably 1.5% by mass or less, more preferably 1.0% by mass or less, from the viewpoint of improving the charging characteristics of the toner.

[Toner for developing electrostatic image]
[Toner particles]
The toner particles obtained by performing drying or the like can be used as they are as a toner for developing an electrostatic image, but it is preferable to use toner particles whose surface is treated as described below as a toner for developing an electrostatic image. 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 resin (A) is excellent in low-temperature fixability and deterioration in low-temperature fixability over time. From the viewpoint of suppression and excellent heat resistant storage stability, it is preferably 5% by mass or more, more preferably 10% by mass or more, still more preferably 15% by mass or more, and preferably 45% by mass or less, more preferably 40% by mass or less. It is not more than 35% by mass, more preferably not more than 35% by mass.

In addition, the content of the crystalline resin (B) is based on the total amount of resin components in the toner from the viewpoint of excellent low-temperature fixability, suppression of deterioration of low-temperature fixability over time, and excellent heat-resistant storage stability. , Preferably 5% by mass or more, more preferably 10% by mass or more, further preferably 15% by mass or more, and preferably 45% by mass or less, more preferably 40% by mass or less, further preferably 35% by mass or less. Is.

The volume median particle diameter (D ₅₀ ) of the toner particles is to improve the productivity of the toner, to improve the image density of the printed matter, to have excellent low-temperature fixability, and to suppress deterioration of the low-temperature fixability over time. From the viewpoint of excellent heat resistant storage stability, 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, further 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 toner productivity, 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 from the viewpoint of improving the low temperature fixing property and the charging property 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, as the toner, those 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, polymethylmethacrylate, and silicone resin. , Hydrophobic silica is preferred.

When the surface treatment of the toner particles is performed using the external additive, the addition amount of the external additive is preferably 1 part by mass or more, more preferably 2 parts by mass or more, and further preferably, 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 electrostatic image developing toner obtained by the present invention can be used as a one-component developer or a two-component developer by mixing with a carrier.

Regarding the above-described embodiment, the present invention further discloses the following method for producing a toner for developing an electrostatic charge image.
<1> A method for producing an electrostatic charge image developing toner, comprising a step (step (3)) of cooling a dispersion of toner particles containing an amorphous resin (A) and a crystalline resin (B),
The cooling step includes an operation of adding a dispersion liquid of toner particles having a temperature T _u (° C.) to an aqueous medium (W) and cooling to a temperature T _d (° C.),
The temperature T _u , the temperature T _d, and the melting point T _m (° C.) of the crystalline resin (B) satisfy the following relational expressions (a) and (b),
_{T u - T m ≧ -15 (} a)
T _d −T _m ≦−20 (b)
A method for producing an electrostatic charge image developing toner, wherein a temperature T _{w of} an aqueous medium (W) at the start of addition of a dispersion liquid of toner particles is a temperature T _d or less.
<2> A step of aggregating the amorphous resin (A) and the crystalline resin (B) in an aqueous medium to obtain a dispersion liquid of aggregated particles (step (1)), and fusing the obtained aggregated particles The method for producing an electrostatic charge image developing toner according to <1>, further including a step (step (2)) of obtaining a dispersion liquid of toner particles.

<3> The amorphous resin (A) is preferably a resin containing a polyester resin segment, more preferably an amorphous composite resin in which a polyester resin segment contains a hydrophobic constituent component, <1> Alternatively, the method for producing the toner for developing an electrostatic charge image according to <2>.
<4> The amorphous composite resin preferably contains an amorphous composite resin containing a polyester resin segment and a vinyl resin segment, or a polyester resin segment and a constituent component derived from a hydrocarbon wax having a hydroxyl group or a carboxy group. <3>, which is an amorphous composite resin, more preferably an amorphous composite resin containing a polyester resin segment, a vinyl resin segment, and a component derived from a hydrocarbon wax having a hydroxyl group or a carboxy group. 1. A method for producing a toner for developing an electrostatic image as described in 1.
<5> The alcohol component (A-al) of the polyester resin segment of the amorphous resin (A) preferably contains 80 mol% or more of a propylene oxide adduct of bisphenol A, more preferably 90 mol% or more, and further preferably Is 95 mol% or more, more preferably 98 mol% or more, and preferably 100 mol% or less, and more preferably 100 mol%. <3> or <4> Method for producing toner for image development.
<6> The electrostatic image development according to any one of <3> to <5>, in which the amorphous composite resin preferably contains a vinyl-based resin segment containing a constitutional unit derived from a vinyl monomer having a hydrocarbon group. For manufacturing toner for toner.
<7> The hydrocarbon group of the vinyl monomer of the amorphous composite resin is preferably a saturated or unsaturated aliphatic hydrocarbon group, more preferably a saturated aliphatic hydrocarbon group, according to <6>. Method for producing toner for developing electrostatic image.
<8> The carbon number of the hydrocarbon group of the vinyl monomer of the amorphous composite resin is preferably 6 or more, more preferably 8 or more, further preferably 10 or more, further preferably 12 or more, further preferably 14 or more. And preferably 22 or less, more preferably 20 or less, still more preferably 18 or less, the method for producing an electrostatic image developing toner according to <6> or <7>.
<9> The content of the constituent unit derived from the vinyl monomer having a hydrocarbon group of the amorphous composite resin is preferably 5% by mass or more, more preferably 10% by mass or more, still more preferably 15% by mass in the vinyl resin segment. Any of <6> to <8>, which is at least mass%, more preferably at least 20 mass%, and preferably at most 60 mass%, more preferably at most 40 mass%, further preferably at most 30 mass%. A method for producing a toner for developing an electrostatic image as described in 1.
<10> The vinyl resin segment of the amorphous composite resin preferably contains a structural unit derived from a (meth)acrylic acid ester having an aliphatic hydrocarbon group having 6 to 22 carbon atoms and a structural unit derived from styrene. The method for producing the toner for developing an electrostatic charge image according to any one of <6> to <9>.

<11> The amorphous composite resin preferably further contains a constitutional unit derived from a bireactive monomer, more preferably the constitutional unit derived from a bireactive monomer is the vinyl resin segment and the polyester resin segment described above. <6> The method for producing a toner for developing an electrostatic image according to any one of <6> to <10>, which serves as a bonding point with.
<12> The method for producing an electrostatic charge image developing toner according to <11>, wherein the bireactive monomer is preferably at least one selected from acrylic acid and methacrylic acid, and more preferably acrylic acid.
<13> The content of the constitutional unit derived from the bireactive monomer is preferably 1 part by mole or more, more preferably 5 parts by mole, relative to 100 parts by mole of the total amount of the alcohol component (A-al) as a raw material of the polyester resin segment. Parts or more, more preferably 10 parts by mole or more, further preferably 15 parts by mole or more, and preferably 30 parts by mole or less, more preferably 25 parts by mole or less, still more preferably 20 parts by mole or less, <11. > Or <12>, the method for producing the toner for developing an electrostatic charge image as described above.

<14> The content of the polyester resin segment in the amorphous composite resin 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. The method for producing a toner for developing an electrostatic charge image according to any one of <3> to <13>, which is more preferably 80% by mass or less, and further preferably 70% by mass or less.
<15> The content of the vinyl resin segment in the amorphous composite resin is preferably 10% by mass or more, more preferably 20% by mass or more, and preferably 60% by mass or less, more preferably 50% by mass. % Or less, more preferably 45% by mass or less, the method for producing an electrostatic charge image developing toner according to any one of <6> to <14>.
<16> Amorphous resin (A) is an amorphous composite resin containing a polyester resin segment and a constituent component derived from a hydrocarbon wax having a hydroxyl group or a carboxy group, and derived from a hydrocarbon wax having a hydroxyl group or a carboxy group. The method for producing a toner for developing an electrostatic charge image according to any one of <3> to <15>, wherein the constituent component (1) is bound to a polyester resin segment.
<17> The content of the hydrocarbon wax-derived constituent in the amorphous composite resin is preferably 1% by mass or more, more preferably 2% by mass or more, further preferably 3% by mass or more, and preferably Is 20% by mass or less, more preferably 15% by mass or less, still more preferably 12% by mass or less, and the method for producing an electrostatic charge image developing toner according to <16>.

<18> The amorphous resin (A) has a softening point of preferably 70° C. or higher, more preferably 90° C. or higher, further preferably 100° C. or higher, and preferably 140° C. or lower, more preferably 130° C. The method for producing a toner for developing an electrostatic charge image according to any one of <1> to <17>, which is described below.
The glass transition temperature of the <19> amorphous resin (A) is preferably 30° C. or higher, more preferably 35° C. or higher, even more preferably 40° C. or higher, and preferably 70° C. or lower, more preferably 65. C. or less, more preferably 60.degree. C. or less, and further preferably 55.degree. C. or less, <1> to <18>.

<20> The method for producing an electrostatic charge image developing toner according to any one of <1> to <19>, wherein the crystalline resin (B) is preferably a crystalline polyester resin.
<21> The crystalline polyester resin is the method for producing a toner for developing an electrostatic charge image according to <20>, which is a polycondensation product of an alcohol component (B-al) and a carboxylic acid component (B-ac).
<22> The alcohol component (B-al) of the crystalline polyester resin preferably contains the α,ω-aliphatic diol in an amount of 80 mol% or more, and the electrostatic image developing toner according to <20> or <21>. Manufacturing method.
The content of the <23> α,ω-aliphatic diol in the alcohol component (B-al) is preferably 80 mol% or more, more preferably 85 mol% or more, further preferably 90 mol% or more, further preferably The method for producing a toner for developing an electrostatic charge image according to <22>, wherein the content is 95 mol% or more and 100 mol% or less, more preferably 100 mol%.
<24> The toner for developing an electrostatic charge image according to any one of <20> to <23>, wherein the carboxylic acid component (B-ac) of the crystalline polyester resin preferably contains 80 mol% or more of an aliphatic dicarboxylic acid. Manufacturing method.
<25> The content of the aliphatic dicarboxylic acid in the crystalline polyester resin in the carboxylic acid component (B-ac) is preferably 80 mol% or more, more preferably 85 mol% or more, still more preferably 90 mol% or more, The toner for developing an electrostatic charge image according to any one of <20> to <24>, which is more preferably 95 mol% or more, 100 mol% or less, and further preferably 100 mol%. Production method.
<26> The number of carbon atoms of the aliphatic dicarboxylic acid of the crystalline polyester resin is preferably 4 or more, more preferably 8 or more, still more preferably 10 or more, and preferably 16 or less, more preferably 14 or less, further The method for producing an electrostatic image developing toner according to any one of <20> to <25>, which is preferably 12 or less.
The melting point of the <27> crystalline resin is preferably 50° C. or higher, more preferably 60° C. or higher, even more preferably 65° C. or higher, and preferably 100° C. or lower, more preferably 90° C. or lower, further preferably The method for producing a toner for developing an electrostatic charge image according to any one of <20> to <26>, which is 80° C. or lower.

<28> Step (1) preferably includes the following step (1-1), and may further include step (1-2). <2> to <27> 1. A method for producing a toner for developing an electrostatic image according to 1.
Step (1-1): A step of aggregating the resin particles (X) containing the amorphous resin (A) in the presence of the crystalline resin (B) in an aqueous medium to obtain agglomerated particles (1) (1-2): The resin particles (Z) containing the amorphous resin (C) are added to the agglomerated particles (1) obtained in the step (1-1) to obtain a resin for the agglomerated particles (1). Step of obtaining aggregated particles (2) formed by adhering particles (Z)

<29> The mass ratio [amorphous resin (A)/crystalline resin (B)] of the amorphous resin (A) and the crystalline resin (B) in the step (1) 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 preferably 85/15 or less, further preferably 80/20. The method for producing a toner for developing an electrostatic charge image according to any one of <2> to <28>, which is more preferably 75/25 or less.
<30> The mass ratio [amorphous resin (A)/crystalline resin (B)] of the amorphous resin (A) and the crystalline resin (B) in the step (1) is preferably 50/50 or more. , More preferably 60/40 or more, still more preferably 70/30 or more, still more preferably 75/25 or more, and preferably 95/5 or less, more preferably 90/10 or less, further preferably 85/15. The following is a method for producing a toner for developing an electrostatic charge image according to any one of <2> to <28>.

<31> The method for producing an electrostatic charge image developing toner according to any one of <2> to <30>, wherein in the step (1), the wax is further aggregated in an aqueous medium to obtain a dispersion liquid of aggregated particles.
<32> The method for producing an electrostatic charge image developing toner according to <31>, wherein the wax is used as a dispersion liquid of wax particles.
<33> The wax particles are obtained by mixing and dispersing the wax and the resin particles (P) in an aqueous medium to obtain an aqueous dispersion of the wax particles. <31> or <32> A method for producing the toner for developing an electrostatic image as described above.

<34> The method for producing a toner for developing an electrostatic charge image according to any one of <28> to <33>, wherein the step (1) includes the step (1-2).
<35> The amorphous resin (C) is preferably a polyester resin obtained by polycondensation of an alcohol component (C-al) and a carboxylic acid component (C-ac), and the static resin according to <34>. A method for producing a toner for developing a charge image.
<36> The electrostatic image developing toner according to <34> or <35>, wherein the alcohol component (C-al) of the amorphous resin (C) contains 80 mol% or more of an ethylene oxide adduct of bisphenol A. Manufacturing method.
<37> The alcohol component (C-al) of the amorphous resin (C) preferably contains succinic acid substituted with an alkyl group having 1 to 20 carbon atoms or an alkenyl group having 2 to 20 carbon atoms, More preferably, the method for producing a toner for developing an electrostatic charge image according to any one of <34> to <36>, which contains dodecenylsuccinic acid.
The softening point of the <38> amorphous resin (C) is preferably 90° C. or higher, more preferably 100° C. or higher, further preferably 110° C. or higher, and preferably 160° C. or lower, more preferably 140° C. The method for producing a toner for developing an electrostatic charge image according to any one of <34> to <37>, which is more preferably 130° C. or less.
The glass transition temperature of the <39> amorphous resin (C) is preferably 40° C. or higher, more preferably 50° C. or higher, even more preferably 60° C. or higher, and preferably 90° C. or lower, more preferably 80. The method for producing a toner for developing an electrostatic charge image according to any one of <34> to <38>, which is not higher than 70°C, more preferably not higher than 70°C.
The mass ratio [(C)/((A)+(B))] of the <40> amorphous resin (C) and the total of the amorphous resin (A) and the crystalline resin (B) is preferably Is 0.05 or more, more preferably 0.10 or more, further preferably 0.13 or more, more preferably 0.15 or more, and preferably 0.5 or less, more preferably 0.3 or less, The method for producing an electrostatic charge image developing toner according to any one of <34> to <39>, which is preferably 0.2 or less.

<41> In the step (2), the toner for developing an electrostatic charge image according to any one of <1> to <40>, which is preferably maintained at a temperature of 15° C. lower than the melting point of the crystalline resin (B). Manufacturing method.
<42> The holding temperature is preferably 10° C. or more lower than the melting point of the crystalline resin (B), more preferably 8° C. or more lower than the melting point of the crystalline resin (B), further preferably crystalline resin (B ) 5°C lower than the melting point of the crystalline resin (B), more preferably 30°C higher than the melting point of the crystalline resin (B), and more preferably 30°C higher than the melting point of the crystalline resin (B), more preferably crystalline resin. The method for producing a toner for developing an electrostatic charge image according to <41>, wherein the temperature is 20° C. or higher higher than the melting point of (B), and more preferably 12° C. or lower higher than the melting point of the crystalline resin (B).

<43> The toner particles are core-shell type toner particles having a core part and a shell part existing on the surface of the core part, and the core part contains the amorphous resin (A) and the crystalline resin (B). The method for producing a toner for developing an electrostatic charge image according to any one of <1> to <42>, in which the shell portion contains an amorphous resin (C).
The mass ratio [(C)/((A)+(B))] of the <44> amorphous resin (C) to the total of the amorphous resin (A) and the crystalline resin (B) 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 0.5 or less, more preferably 0.3 or less, still more preferably Is 0.2 or less, The method for producing a toner for developing an electrostatic image according to any one of <43>.
<45> The mass ratio [amorphous resin (A)/crystalline resin (B)] of the amorphous resin (A) and the crystalline resin (B) is preferably 50/50 or more, more preferably 55. /45 or more, more preferably 60/40 or more, and preferably 95/5 or less, more preferably 90/10 or less, further preferably 85/15 or less, further preferably 80/20 or less, further preferably 75/25 or less, The manufacturing method of the toner for electrostatic image development in any one of <1>-<44>.
<46> The mass ratio [amorphous resin (A)/crystalline resin (B)] of the amorphous resin (A) and the crystalline resin (B) is preferably 50/50 or more, more preferably 60. /40 or more, more preferably 70/30 or more, further preferably 75/25 or more, and preferably 95/5 or less, more preferably 90/10 or less, further preferably 85/15 or less, <1> to <45>, a method for producing a toner for developing an electrostatic charge image.
<47>(T _u −T _m ) is −15 or more, preferably −12 or more, more preferably −10 or more, and preferably 30 or less, more preferably 20 or less, further preferably 12 The method for producing a toner for developing an electrostatic charge image according to any one of <1> to <46>, which is preferably 3 or less, more preferably 0 or less, still more preferably -5 or less.
<48> (T _d − T _m ) is −20 or less, preferably −30 or less, more preferably −40 or less, and preferably −80 or more, more preferably −65 or more, and further preferably. Is -50 or more, The manufacturing method of the toner for electrostatic image development in any one of <1>-<47>.
<49> The method for producing an electrostatic charge image developing toner according to any one of <1> to <48>, which further satisfies the following relational expression (c).
_{Tu− Td} ≧10 (c)
<50>(T _u −T _d ) is preferably 15 or more, more preferably 20 or more, further preferably 30 or more, further preferably 40 or more, and preferably 80 or less, more preferably 70 or less, The method for producing a toner for developing an electrostatic charge image according to <49>, which is more preferably 60 or less.
<51> The method for producing an electrostatic charge image developing toner according to any one of <1> to <50>, further satisfying the following relational expression (d).
T _d −T _w ≦40 (d)
<52>(T _d −T _w ) is preferably 30 or less, more preferably 25 or less, and preferably 0 or more, more preferably 0 or more, still more preferably 5 or more, still more preferably 10 or more. <51> The method for producing a toner for developing an electrostatic charge image according to <51>.
<53> temperature _{T w} of the aqueous medium (W) _is, (T m -90) is ° C. or higher _(T m -20) ℃ or less, <1> to <52> developing an electrostatic charge image according to any one of For manufacturing toner for toner.
<54> temperature _{T w} of the aqueous medium (W) is preferably _(T m -20) ℃ or less, more preferably _(T m -30) ℃ or less, more preferably be a _(T m -40) ℃ or less And preferably ( _Tm- 90)°C or higher, more preferably ( _Tm- 80)°C or higher, still more preferably ( _Tm- 70)°C or higher, according to <53>. For manufacturing toner for toner.

Each property value of each resin, wax, each particle, toner and the like 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.

[Softening point, crystallinity index, melting point and glass transition temperature of resin]
(1) Using a softening point flow tester “CFT-500D” (manufactured by Shimadzu Corp.), a load of 1.96 MPa was applied by a plunger while heating 1 g of a sample at a heating rate of 6° C./min, and the diameter was increased. It was extruded from a nozzle having a length of 1 mm and a length of 1 mm. The amount of plunger drop of the flow tester was plotted against the temperature, and the temperature at which half the sample flowed out was taken as the softening point.
(2) Crystallinity index Using a differential scanning calorimeter "Q100" (manufactured by TA Instruments Japan Co., Ltd.), 0.02 g of a sample was weighed in an aluminum pan and cooled from room temperature (20°C) to 10°C/ It was cooled to 0° C. in min. Then, the sample was allowed to stand for 1 minute as it was, and then the temperature was raised to 180° C. at a heating rate of 10° C./min to measure the amount of heat. Of the observed endothermic peaks, the temperature of the peak having the largest peak area is defined as the maximum endothermic peak temperature (1), and (softening point (°C))/(maximum endothermic peak temperature (1) (°C)) The crystallinity index was determined.
(3) Melting point and glass transition temperature Using a differential scanning calorimeter “Q100” (manufactured by TA Instruments Japan Co., Ltd.), 0.02 g of a sample was weighed in an aluminum pan and heated to 200° C., and the temperature was measured. To 10° C. at a cooling rate of 10° C./min. Then, the sample was heated at a heating rate of 10° C./min and the amount of heat was measured. Of the observed endothermic peaks, the temperature of the peak having the largest peak area was defined as the maximum endothermic peak temperature (2). In the case of crystalline resin, the peak temperature was taken as the melting point.
In the case of an amorphous resin, when a peak is observed, the temperature of the peak is measured. When a peak is not observed and a step is observed, the tangent line showing the maximum inclination of the curve of the step and the step The temperature at the intersection with the extension of the low temperature side baseline was defined as the glass transition temperature.

[Wax melting point]
Using a differential scanning calorimeter "Q100" (manufactured by TA Instruments Japan Co., Ltd.), 0.02 g of the sample was weighed in an aluminum pan and heated to 200°C, and then the temperature decreasing rate from 200°C was 10°C/min. It 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 endotherm was taken as the melting point.

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

[Number average molecular weight of wax (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 was dissolved in chloroform at 25° C. so that the concentration was 0.5 g/100 mL, and this solution was then mixed with a fluororesin filter having a pore size of 0.2 μm (product name: “DISMIC”, Insoluble components were removed by filtration using a model “25JP”, manufactured by ADVANTEC) to obtain a sample solution.
(2) Measurement Chloroform was used 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 by using the following measuring device and analytical column. The molecular weight was measured. The molecular weight (number average molecular weight Mn) of the sample is several kinds of monodisperse polystyrene (product name: “TSKgel standard polystyrene”; type name (Mw): “A-500 (5.0×10 ² )”, “A1000(1 .01×10 ³ )”, “A2500 (2.63×10 ³ )”, “A-5000 (5.97×10 ³ )”, “F-1 (1.02×10 ⁴ )”, “F -2 (1.81 x 10 ⁴ )", "F-4 (3.97 x 10 ⁴ )", "F-10 (9.64 x 10 ⁴ )", "F-20 (1.90 x 10 ⁴ )" ⁵ )”, “F-40(4.27×10 ⁵ )”, “F-80(7.06×10 ⁵ )”, “F-128(1.09×10 ⁶ )”; (Manufactured by the company) was used as a standard sample and was calculated based on a calibration curve prepared in advance.
・Measuring device: "HLC-8220GPC" (manufactured by Tosoh Corporation)
-Analytical column: "GMHXL" and "G3000HXL" (manufactured by Tosoh Corporation)

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

[Solid Concentration of Aqueous Dispersion of Resin Particles (X), Aqueous Dispersion of Resin Particles (Y), Colorant Particle Dispersion Liquid, and Wax Particle Dispersion Liquid]
Using an infrared moisture meter "FD-230" (manufactured by Ketsuto Scientific Laboratory Co., Ltd.), a measurement sample of 5 g was dried at a temperature of 150° C., a measurement mode 96 (monitoring time 2.5 minutes, moisture content fluctuation range 0.05%). ), the water content (mass %) was measured. The solid content concentration was calculated according to the following formula.
Solid content concentration (mass %)=100−water content (mass %)

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

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

[Volume median particle diameter (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 "Emulgen (registered trademark) 109P" [Kao Corporation, HLB (Hydrophile-Lipophile Balance) = 13.6] was dissolved in the electrolyte solution to obtain a dispersion having a concentration of 5 mass%. Obtained.
-Dispersion condition: To the dispersion liquid (5 mL), 10 mg of a dried toner particle measurement sample was added and 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: The sample dispersion was added to 100 mL of the electrolytic solution to adjust the particle size of 30,000 particles to a concentration at which measurement was possible in 20 seconds, then 30,000 particles were measured, and the particle size was measured. The volume median particle diameter (D ₅₀ ) and the volume average particle diameter were determined from the distribution.
The CV value (%) was calculated according to the following formula.
CV value (%)=(standard deviation of particle size distribution/volume average particle size)×100

[Low temperature fixability of toner and stability over time of low temperature fixability]
<Low temperature fixability>
The commercially available printer "Microline (registered trademark) 5400" (manufactured by Oki Data Co., Ltd.) was used for the high-quality paper "J paper A4 size" (manufactured by Fuji Xerox Co., Ltd.), and the toner adhesion amount on the paper was 1.3 to 1 A solid image of 0.5 mg/cm ² was output at a length of 50 mm without fixing, leaving a blank portion of 5 mm from the upper end of the A4 paper.
Next, the printer in which the fixing device was modified to have a variable temperature was prepared, the temperature of the fixing device was set to 90° C., and the toner was fixed at a speed of 1.2 seconds per sheet in the A4 vertical direction to obtain a printed matter.
In the same manner, the temperature of the fixing device was increased by 5° C., the toner was fixed, and a printed matter was obtained.
A 50 mm long mending tape "Scotch (registered trademark) Mending Tape 810" (Sumitomo 3M Co., Ltd., width 18 mm) was lightly applied from the blank area at the top of the printed image to the solid image. After that, a weight of 500 g was placed and pressed back and forth once at a speed of 10 mm/s. Then, the attached tape was peeled from the lower end side at a peeling angle of 180° and a speed of 10 mm/s to obtain a printed matter after peeling the tape. 30 sheets of high-quality paper "Excellent white paper A4 size" (Okidata Co., Ltd.) is laid under the printed matter before and after the tape application, and the reflection image density of the fixed image part before and after the tape application of the printed matter is measured. , A spectrophotometer “SpectroEye” (manufactured by GretagMacbeth, light irradiation condition; standard light source D50, observation field of view 2°, density standard DINNB, absolute white standard) and measured from each reflection image density according to the following formula. Was calculated.
Fixing rate (%)=(reflection image density after tape peeling/reflection image density before tape attachment)×100
The lowest temperature at which the fixing rate is 90% or more was defined as the lowest fixing temperature (T1). The lower the minimum fixing temperature is, the better the low temperature fixing property is.
<Stability of low-temperature fixability over time>
After holding the toner in a constant temperature bath of 45° C. for 200 hours, the minimum fixing temperature (T2) was measured by the same method as in the evaluation of the low temperature fixing property. 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 more excellent the stability over time of the low temperature fixability.

[Heat-resistant storage stability of toner]
20 g of toner was put into 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 left standing still for 12 hours or more and cooled while being hermetically sealed at a temperature of 25°C. Next, a sieve with a mesh opening of 250 μm was set on a vibrating table of “Powder Tester (registered trademark)” (manufactured by Hosokawa Micron Co., Ltd.), 20 g of the toner was placed on the sieve and vibrated for 30 seconds to leave the toner on the sieve. Whether or not to do so was visually determined, and the maximum value of the storage temperature that did not remain was defined as the maximum temperature at which aggregation did not occur. The higher the temperature, the better the heat resistant storage stability of the toner.

[Production of resin]
Production Example A1
(Production of Amorphous Resin A-1)
The inside of a four-necked flask having an internal volume of 10 L equipped with a nitrogen introduction tube, a dehydration tube, a stirrer, and a thermocouple was replaced with nitrogen, and polyoxypropylene (2.2-bis(4-hydroxyphenyl)propane) (2. 2) Adduct 3356 g, terephthalic acid 955 g, Paracor 6490 (manufactured by Nippon Seiro Co., Ltd.) 385 g, di(2-ethylhexanoic acid)tin (II) 25 g, and 3,4,5-trihydroxybenzoic acid 2.5 g Was charged, the temperature was raised to 235° C. with stirring under a nitrogen atmosphere, the temperature was maintained at 235° C. for 5 hours, the pressure in the flask was reduced, and the pressure was maintained at −8 kPa (G) for 1 hour. Then, after returning to atmospheric pressure, the mixture was cooled to 160° C., and while being maintained at 160° C., 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, after holding at 160 degreeC for 30 minutes, it heated up to 200 degreeC, pressure in the flask was further reduced, and it hold|maintained at -8 kPa (G) for 1 hour. Then, after returning to atmospheric pressure, it 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 10° C./hr to 210° C. After that, the temperature was raised, and then the reaction was carried out at -4 kPa (G) to a desired softening point to obtain an amorphous resin A-1. The physical properties are shown in Table 1.

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

Production Example C1
(Production of Amorphous Resin C-1)
The interior of a four-necked flask having an internal volume of 10 L equipped with a nitrogen introduction tube, a dehydration tube, a stirrer, and a thermocouple was replaced with nitrogen, and 2,2-bis(4-hydroxyphenyl)propane polyoxyethylene (2. 2) Add 5001 g of an adduct, 1788 g of terephthalic acid, 30 g of tin(II) di(2-ethylhexanoate), and 3.0 g of 3,4,5-trihydroxybenzoic acid, and stir 235 under a nitrogen atmosphere while stirring. After raising the temperature to ℃ and holding it at 235 ℃ for 8 hours, the pressure in the flask was lowered and it was maintained at -8 kPa (G) for 1 hour. Then, after returning to atmospheric pressure, it cooled to 180 degreeC, 179 g of fumaric acid, 206 g of dodecenyl succinic anhydride, 325 g of trimellitic acid anhydride, and 3.8 g of 4-tert-butyl catechol were added, and it was 10 degreeC to 220 degreeC. The temperature inside the flask was lowered, and the pressure inside the flask was lowered, and the reaction was carried out at -10 kPa (G) up to the desired softening point to obtain amorphous resin C-1. The physical properties are shown in Table 1.

Production Example A11
(Production of Amorphous Resin A-11)
The inside of a four-necked flask having an internal volume of 10 L equipped with a nitrogen introduction tube, a dehydration tube, a stirrer, and a thermocouple was replaced with nitrogen, and polyoxypropylene (2.2-bis(4-hydroxyphenyl)propane) (2. 2) Addition product 4313 g, terephthalic acid 818 g, succinic acid 727 g, di(2-ethylhexanoic acid)tin(II) 30 g, and 3,4,5-trihydroxybenzoic acid 3.0 g were added and stirred under a nitrogen atmosphere. However, the temperature in the flask was raised to 235° C., and the temperature in the flask was maintained at 235° C. for 5 hours. Then, after returning to atmospheric pressure, the mixture was cooled to 160° C., and while being kept at 160° C., a mixture of 2756 g of styrene, 689 g of stearyl methacrylate, 142 g of acrylic acid, and 413 g of dibutyl peroxide was added dropwise over 1 hour. Then, after holding at 160° C. for 30 minutes, the temperature was raised to 200° C., the pressure in the flask was further lowered, and the reaction was carried out to a desired softening point at −8 kPa (G) to obtain the amorphous resin A-11. Got The physical properties are shown in Table 1.

Production Example B1
(Production of crystalline resin B-1)
The interior of a four-necked flask having an internal volume of 10 L equipped with a nitrogen introduction tube, a dehydration tube, a stirrer, and a thermocouple was replaced with nitrogen, and 3416 g of 1,10-decanediol and 4084 g of sebacic acid were put therein. While stirring, the temperature was raised to 135° C., the temperature was maintained at 135° C. for 3 hours, and then the temperature was raised from 135° C. to 200° C. over 10 hours. After that, 23 g of di(2-ethylhexanoic acid)tin (II) was added, and the mixture was further held at 200° C. for 1 hour, then the pressure inside the flask was lowered, and the mixture was kept 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
(Production 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.

[Production of Aqueous Dispersion of Resin Particles]
Production Example X1
(Production of Aqueous Dispersion X-1 of Resin Particles)
In a container having an internal volume of 3 L equipped with a stirrer, a reflux condenser, a dropping funnel, a thermometer and a nitrogen introducing tube, 300 g of the amorphous resin A-1 and 300 g of methyl ethyl ketone and 41 g of deionized water were added as a mixed solvent, The resin was dissolved at 73° C. for 2 hours. A 5% by mass aqueous solution of sodium hydroxide was added to the obtained solution so that the degree of neutralization was 60 mol% with respect to the acid value of the resin, and the mixture was stirred for 30 minutes.
Next, while maintaining the temperature at 73° C., 600 g of deionized water was added over 60 minutes while stirring at 200 r/min (peripheral speed 63 m/min) to carry out phase inversion emulsification. While maintaining the temperature at 73° C. continuously, methyl ethyl ketone was distilled off under reduced pressure to obtain an aqueous dispersion. After that, the aqueous dispersion was cooled to 30° C. with stirring at 280 r/min (peripheral speed 88 m/min), and deionized water was added so that the solid content concentration became 20% by mass. An aqueous dispersion X-1 was obtained. The physical properties are shown in Table 3.

Production Examples X2 to X6
(Production of Aqueous Dispersions X-2 to X-6 of Resin Particles)
Aqueous dispersions X-2 to X-6 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.

Production Example Z1
(Production of Aqueous Dispersion Z-1 of Resin Particles)
In a container having an internal volume of 3 L equipped with a stirrer, a reflux condenser, a dropping funnel, a thermometer and a nitrogen introducing pipe, 300 g of the amorphous resin C-1 and 180 g of methyl ethyl ketone and a mixed solvent of 25 g of deionized water were put, The resin was dissolved at 73° C. for 2 hours. A 5% by mass aqueous solution of sodium hydroxide was added to the obtained solution so that the degree of neutralization was 60 mol% with respect to the acid value of the resin, and the mixture was stirred for 30 minutes.
Next, while maintaining the temperature at 73° C., 600 g of deionized water was added over 60 minutes while stirring at 200 r/min (peripheral speed 63 m/min) to carry out phase inversion emulsification. While maintaining the temperature at 73° C. continuously, methyl ethyl ketone was distilled off under reduced pressure to obtain an aqueous dispersion. After that, the aqueous dispersion was cooled to 30° C. with stirring at 280 r/min (peripheral speed 88 m/min), and deionized water was added so that the solid content concentration became 20% by mass. An aqueous dispersion C-1 was obtained. The physical properties are shown in Table 3.

Production Example P1
(Production of Aqueous Dispersion P-1 of Resin Particles)
200 g of the amorphous 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 introducing tube, and the mixture was placed at 73° C. for 2 hours. The resin was allowed to dissolve. A 5% by mass aqueous solution of sodium hydroxide was added to the obtained solution so that the degree of neutralization was 60 mol% with respect to the acid value of the resin, and the mixture was stirred for 30 minutes.
Next, while maintaining the temperature at 73° C., 700 g of deionized water was added over 50 minutes while stirring at 280 r/min (circumferential speed of 88 m/min) to carry out phase inversion emulsification. While maintaining the temperature at 73° C. continuously, methyl ethyl ketone was distilled off under reduced pressure to obtain an aqueous dispersion. After that, the aqueous dispersion was cooled to 30° C. with stirring at 280 r/min (peripheral speed 88 m/min), and deionized water was added so that the solid content concentration became 20% by mass. Aqueous dispersion P-1 was obtained. The physical properties are shown in Table 3.

Production Example Y1
(Production of Aqueous Dispersion Y-1 of Resin Particles)
In a container having an internal volume of 3 L equipped with a stirrer, a reflux condenser, a dropping funnel, a thermometer and a nitrogen introducing tube, 300 g of the crystalline resin B-1 and 300 g of methyl ethyl ketone and 41 g of deionized water were put, and 73 The resin was dissolved at 0° C. for 2 hours. A 5 mass% sodium hydroxide aqueous solution was added to the obtained solution so that the neutralization degree was 60 mol% with respect to the acid value of the crystalline resin B-1, and the mixture was stirred for 30 minutes.
Next, while maintaining the temperature at 73° C., 600 g of deionized water was added over 60 minutes while stirring at 200 r/min (peripheral speed 63 m/min) to carry out phase inversion emulsification. While maintaining the temperature at 73° C. continuously, methyl ethyl ketone was distilled off under reduced pressure to obtain an aqueous dispersion. After that, the aqueous dispersion was cooled to 30° C. with stirring at 280 r/min (peripheral speed 88 m/min), and deionized water was added so that the solid content concentration became 20% by mass. An aqueous dispersion Y-1 was obtained. The physical properties are shown in Table 4.

Production Example Y2
(Production of Aqueous Dispersion of Resin Particles Y-2)
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.

Production Example X21
(Production of Aqueous Dispersion of Resin Particles X-21)
In a container having an internal volume of 3 L equipped with a stirrer, a reflux condenser, a dropping funnel, a thermometer and a nitrogen introducing tube, 210 g of amorphous resin A-1 (mixing ratio 70) and 90 g of crystalline resin B-1 ( A mixing ratio of 30) and 300 g of methyl ethyl ketone were added, and the resin was dissolved at 73° C. for 2 hours. A 5% by mass aqueous solution of sodium hydroxide was added to the resulting solution to obtain a neutralization degree with respect to the acid value of the mixed resin obtained from the weighted average of the acid values of the amorphous resin A-1 and the crystalline resin B-1. It was added so as to be 60 mol% and stirred for 30 minutes.
Next, while maintaining the temperature at 73° C., 630 g of deionized water was added over 60 minutes while stirring at 200 r/min (circumferential speed of 63 m/min) to carry out phase inversion emulsification. While maintaining the temperature at 73° C. continuously, methyl ethyl ketone was distilled off under reduced pressure to obtain an aqueous dispersion. After that, the aqueous dispersion was cooled to 30° C. with stirring at 280 r/min (peripheral speed 88 m/min), and deionized water was added so that the solid content concentration became 20% by mass. Aqueous dispersion X-21 was obtained. The physical properties are shown in Table 5.

[Production of wax particle dispersion]
Production Example D1
(Production of Wax Particle Dispersion D-1)
To a beaker having an internal volume of 1 L, 120 g of deionized water, 186 g of an aqueous dispersion P-1 of resin particles, and 40 g of paraffin wax "HNP-9" (manufactured by Nippon Seiro Co., Ltd., melting point 75° C.) were added, and 90- The temperature was kept at 95° C., the mixture was melted and stirred to obtain a molten mixture.
While maintaining the temperature of the obtained melted mixture at 90 to 95° C., an ultrasonic homogenizer “US-600T” (manufactured by Nippon Seiki Seisakusho Co., Ltd.) was used for dispersion treatment for 20 minutes, and then up to room temperature (25° C.). Cooled. Deionized water was added to adjust the solid content concentration to 20 mass% to obtain a wax particle dispersion D-1. The wax particles in the dispersion had a volume median particle diameter (D ₅₀ ) of 0.47 μm and a CV value of 27%.

[Production of colorant particle dispersion]
Production Example E1
(Production of Colorant Particle Dispersion E-1)
In a beaker with an internal volume of 1 L, 150 g of copper phthalocyanine pigment "ECB-301" (manufactured by Dainichiseika Kogyo Co., Ltd.) and anionic surfactant "NeoPerex (registered trademark) G-15" (manufactured by Kao Corporation, 15 mass) % Sodium dodecylbenzene sulfonate 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 solid content. Colorant particle dispersion E-1 was obtained by adding deionized water to a concentration of 24% by mass. The volume median particle diameter (D ₅₀ ) of the colorant particles in the dispersion was 0.12 μm.

[Production of toner]
Example 1 (Preparation of Toner 1)
(Cohesive fusion process)
210 g of an aqueous dispersion X-1 of resin particles, 90 g of an aqueous dispersion Y-1 of resin particles, and a wax particle dispersion D are placed in a four-necked flask having an internal volume of 3 L equipped with a dehydration tube, a stirrer and a thermocouple. -1 for 30 g, colorant particle dispersion E-1 for 20 g, and a nonionic surfactant "Emulgen (registered trademark) 150" (manufactured by Kao Corporation, polyoxyethylene (average addition mole number 50) lauryl ether). 6 g of a 10 mass% aqueous solution of was mixed at a temperature of 25°C. Next, while stirring the mixture, a solution of 19 g of ammonium sulfate dissolved in 187 g of deionized water was added with 19 g of a 4.8 mass% potassium hydroxide aqueous solution to adjust the pH to 8.6. Then, the temperature was raised to 59° C. over 2 hours, and the mixture was kept at 59° C. until the volume median particle size (D ₅₀ ) of the aggregated particles became 5.2 μm, and the aggregated particles (1) were dispersed. A liquid was obtained.
While maintaining the temperature of the dispersion liquid of the aggregated particles (1) at 59° C., 46 g of the resin particle dispersion liquid Z-1 was dropped at a rate of 0.3 ml/min to obtain a dispersion liquid of the aggregated particles (2). It was
In the dispersion liquid of the agglomerated particles (2), 15 g of anionic surfactant "Emar (registered trademark) E-27C" (manufactured by Kao Corporation, sodium polyoxyethylene lauryl ether sulfate, effective concentration 27 mass%), deionized An aqueous solution obtained by mixing 1050 g of water and 20 g of 0.1 mol/L sulfuric acid was added. After that, the temperature was raised to 83° C. over 1 hour, 20 g of 0.1 mol/L sulfuric acid was added, and the mixture was kept at 83° C. until the circularity reached 0.970, whereby the toner particles fused with the aggregated particles A dispersion liquid of was obtained.

(Cooling process)
3980 g of deionized water was placed in a 4-necked flask having an internal volume of 10 L equipped with a stirrer and a thermocouple, and cooled to 10°C. While stirring the cooled deionized water, 1500 g of the toner particle dispersion at 83° C. was added all at once to the cooled deionized water to cool the toner particle dispersion to 30° C.±2° C. A cooled dispersion of particles was obtained.
The amount of deionized water used for cooling was calculated and estimated as follows.
Required amount of deionized water used for cooling (g)=[amount of dispersion liquid of toner particles (g)×(temperature _Tu (° C.)−temperature T _d (° C.))]/(temperature T _d (° C.)− Temperature T _w (°C))
However, the specific heat of the dispersion liquid of the toner particles was made equal to the specific heat of the deionized water used for cooling.
In the case of the cooling step, the necessary amount of deionized water used for cooling (g)=[1500×(83-30)]/(30-10)=3975(g), so deionized water at 10° C. 3980 g was prepared and this cooling process was performed.

(Filtration and drying process)
The cooled dispersion liquid of the obtained toner particles was suction-filtered to separate solids, washed with deionized water at 25° C., and suction-filtered at 25° C. for 2 hours. Then, using a vacuum constant temperature dryer (DRV622DA manufactured by ADVANTEC), vacuum drying was performed at 33° C. for 48 hours to obtain toner particles. Table 6 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 diameter: 0.04 μm), and hydrophobic silica “Cabosil® TS720” (Cabot Japan Toner 1 was obtained by placing 1.0 part by mass of a number average particle size (0.012 μm, manufactured by Co., Ltd.) in a Henschel mixer, stirring and passing through a 150 mesh screen. Table 6 shows the evaluation results of Toner 1 thus obtained.

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 6 shows the evaluation results of the obtained toner 2.
(Cooling process)
3980 g of deionized water was placed in a 4-necked flask having an internal volume of 10 L equipped with a stirrer and a thermocouple, and cooled to 10°C. After adding 20 g of a 4.8 mass% potassium hydroxide aqueous solution to the dispersion liquid of the toner particles at 83° C. obtained in the previous step, 1500 g of the dispersion liquid was kept at a temperature of 83° C., and at a rate of 60 mL/min. Then, the dispersion liquid of toner particles was cooled to 30° C.±2° C. by adding it to cooled deionized water to obtain a cooled dispersion liquid of toner particles.
The amount of deionized water used for cooling was calculated and estimated in the same manner as in Example 1.

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 6 shows the evaluation results of Toner 3 thus obtained.
(Cooling process)
The 83° C. toner particle dispersion obtained in the previous step was cooled to 68° C. at room temperature (25° C.) with stirring. Separately, 2850 g of deionized water was placed in a four-necked flask having an internal volume of 10 L equipped with a stirrer and a thermocouple, and cooled to 10°C. While stirring the cooled deionized water, 1500 g of the toner particle dispersion liquid of 68° C. was added all at once to the cooled deionized water, and the toner particle dispersion liquid was cooled to 30° C.±2° C. A cooled dispersion of was obtained.
The amount of deionized water used for cooling was calculated and estimated in the same manner as in Example 1.
That is, since the required amount of deionized water used for cooling (g)=[1500×(68-30)]/(30-10)=2850(g), 2850 g of deionized water at 10° C. is prepared. This cooling process was performed.

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 6 shows the evaluation results of Toner 4 thus obtained.
(Cooling process)
1980 g of deionized water was placed in a 4-necked flask having an internal volume of 10 L equipped with a stirrer and a thermocouple and cooled to 25°C. While stirring the cooled deionized water, 1500 g of the toner particle dispersion liquid at 83° C. was added all at once to the cooled deionized water, and the toner particle dispersion liquid was cooled to 50° C.±2° C. A cooled dispersion of was obtained. The dispersion was allowed to stand at room temperature (25°C), further cooled to 30°C, and then subjected to the next filtration step.
The amount of deionized water used for cooling was calculated and estimated in the same manner as in Example 1.
That is, the required amount of deionized water used for cooling (g)=[1500×(83-50)]/(50-25)=1980(g), so 1980 g of deionized water at 25° C. is prepared. This cooling process was performed.

Example 5 (Preparation of Toner 5)
In the cohesive fusion process of Example 1, except that the aqueous dispersion X-1 of resin particles and the aqueous dispersion Y-1 of resin particles were not used, and 300 g of the aqueous dispersion X-21 of resin particles was used. Toner 5 was obtained in the same manner as in Example 1. Table 6 shows the evaluation results of the obtained toner 5.

Example 6 (Preparation of Toner 6)
In the cohesive fusion process 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 changed to 60 g, respectively. Toner 6 was obtained in the same manner as in. Table 6 shows the evaluation results of Toner 6 thus obtained.

Example 7 (Preparation of Toner 7)
In the cohesive fusion process 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 changed to 120 g, respectively. Toner 7 was obtained in the same manner as in. Table 6 shows the evaluation results of Toner 7 thus obtained.

Examples 8 to 12, 15 (Preparation of Toners 8 to 12, 15)
Toners 8 to 12 and 15 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 6 in the aggregation and fusion step of Example 1. Table 6 shows the evaluation results of the obtained toner.

Example 13 (Preparation of Toner 13)
Toner 13 was obtained in the same manner as in Example 1 except that the cooling step was changed as follows. The evaluation results of Toner 13 thus obtained are shown in Table 6.
(Cooling process)
The 83° C. toner particle dispersion obtained in the previous step was cooled to 68° C. at room temperature (25° C.) with stirring. Separately, 1080 g of deionized water was placed in a four-necked flask having an internal volume of 10 L equipped with a stirrer and a thermocouple, and cooled to 25°C. While stirring the cooled deionized water, 1500 g of the 68° C. toner particle dispersion was added all at once to 25° C. deionized water to cool the toner particle dispersion to 50° C.±2° C. A cooled dispersion of particles was obtained. The dispersion was allowed to stand at room temperature (25°C), further cooled to 30°C, and then subjected to the next filtration step.
The amount of deionized water used for cooling was calculated and estimated in the same manner as in Example 1.
That is, since the required amount of deionized water used for cooling (g)=[1500×(68−50)]/(50−25)=1080(g), 1080 g of deionized water at 25° C. is prepared. This cooling process was performed.

Example 14 (Preparation of Toner 14)
(Cohesive fusion process)
210 g of an aqueous dispersion X-1 of resin particles, 90 g of an aqueous dispersion Y-1 of resin particles, and a wax particle dispersion D are placed in a four-necked flask having an internal volume of 3 L equipped with a dehydration tube, a stirrer and a thermocouple. -1 for 30 g, colorant particle dispersion E-1 for 20 g, and a nonionic surfactant "Emulgen (registered trademark) 150" (manufactured by Kao Corporation, polyoxyethylene (average addition mole number 50) lauryl ether). 6 g of a 10 mass% aqueous solution of was mixed at a temperature of 25°C. Next, while stirring the mixture, a solution of 19 g of ammonium sulfate dissolved in 187 g of deionized water was added with 19 g of a 4.8 mass% potassium hydroxide aqueous solution to adjust the pH to 8.6. Then, the temperature was raised to 59° C. over 2 hours, and the mixture was kept at 59° C. until the volume median particle size (D ₅₀ ) of the aggregated particles became 5.2 μm, and the aggregated particles (1) were dispersed. A liquid was obtained.
While maintaining the temperature of the dispersion liquid of the aggregated particles (1) at 59° C., 46 g of the resin particle dispersion liquid Z-1 was dropped at a rate of 0.3 ml/min to obtain a dispersion liquid of the aggregated particles (2). It was
In the dispersion liquid of the agglomerated particles (2), 15 g of anionic surfactant "Emar (registered trademark) E-27C" (manufactured by Kao Corporation, sodium polyoxyethylene lauryl ether sulfate, effective concentration 27 mass%), deionized An aqueous solution obtained by mixing 1050 g of water and 30 g of 0.1 mol/L sulfuric acid was added, and then the temperature was raised to 75° C. over 50 minutes, and then 20 g of 0.1 mol/L sulfuric acid was added, and the circularity was 0.970. By holding the mixture at 75° C. until the temperature becomes, a dispersion liquid of toner particles in which the aggregated particles are fused is obtained.

(Cooling process)
3380 g of deionized water was placed in a four-necked flask having an internal volume of 10 L equipped with a stirrer and a thermocouple and cooled to 10°C. While stirring the cooled deionized water, 1500 g of the toner particle dispersion at 75° C. was added all at once to the cooled deionized water to cool the toner particle dispersion to 30° C.±2° C. A cooled dispersion of particles was obtained.
The amount of deionized water used for cooling was calculated and estimated in the same manner as in Example 1.
That is, since the required amount of deionized water used for cooling (g)=[1500×(75-30)]/(30-10)=3375(g), 3375 g of deionized water at 10° C. is prepared. This cooling process was performed.

Comparative Example 1 (Preparation of Toner 16)
Toner 16 was obtained in the same manner as in Example 1 except that the cooling step was changed as follows. Table 6 shows the evaluation results of the obtained toner.
(Cooling process)
The 83° C. toner particle dispersion obtained in the previous step was cooled to 30° C. with stirring at room temperature (25° C.) to obtain a cooled toner particle dispersion.

Comparative Example 2 (Preparation of Toner 17)
Toner 17 was obtained in the same manner as in Example 1 except that the cooling step was changed as follows. Table 6 shows the evaluation results of the obtained toner.
(Cooling process)
The 83° C. toner particle dispersion obtained in the previous step was cooled to 60° C. with stirring at room temperature (25° C.). Separately, 2250 g of deionized water was placed in a four-necked flask having an internal volume of 10 L equipped with a stirrer and a thermocouple, and cooled to 10°C. While stirring the cooled deionized water, 1500 g of the toner particle dispersion liquid at 60° C. was added all at once to the cooled deionized water, and the toner particle dispersion liquid was cooled to 30° C.±2° C. A cooled dispersion of was obtained.
The amount of deionized water used for cooling was calculated and estimated in the same manner as in Example 1.
That is, since the required amount of deionized water used for cooling (g)=[1500×(60-30)]/(30-10)=2250(g), 2250 g of deionized water at 10° C. is prepared. This cooling process was performed.

Comparative Example 3 (Preparation of Toner 18)
Toner 18 was obtained in the same manner as in Example 1 except that the cooling step was changed as follows. Table 6 shows the evaluation results of the obtained toner.
(Cooling process)
690 g of deionized water was placed in a four-necked flask having an internal volume of 10 L equipped with a stirrer and a thermocouple and cooled to 10°C. While stirring the cooled deionized water, 1500 g of the toner particle dispersion liquid at 83° C. was added all at once to the cooled deionized water, and the toner particle dispersion liquid was cooled to 60° C.±2° C. A cooled dispersion of was obtained. The dispersion was allowed to stand at room temperature (25°C), further cooled to 30°C, and then subjected to the next filtration step.
The amount of deionized water used for cooling was calculated and estimated in the same manner as in Example 1.
That is, the required amount of deionized water used for cooling (g)=[1500×(83-60)]/(60-10)=690(g), so 690 g of deionized water at 10° C. is prepared. This cooling process was performed.

The various cooling conditions in Table 6 are as follows.
Cooling 1: A dispersion of toner particles at 83° C. was added all at once to deionized water at 10° C. and cooled to 30° C.
Cooling 2: A dispersion of toner particles at 83° C. was added to deionized water at 10° C. at a rate of 60 mL/min and cooled to 30° C.
Cooling: The dispersion of toner particles at 3:83° C. was cooled to 68° C. with stirring in an environment of 25° C. and then added to deionized water at 10° C. to cool to 30° C.
Cooling: The dispersion liquid of toner particles at 4:83° C. was added all at once to deionized water at 25° C. to cool to 50° C.
Cooling: The dispersion of toner particles at 5:83° C. was cooled to 68° C. with stirring in an environment of 25° C., and then added to deionized water at 25° C. to cool to 50° C.
Cooling 6:75° C. dispersion of toner particles was added to deionized water at 10° C. to cool to 30° C.
Cooling: The dispersion of toner particles at 7:83° C. was cooled to 60° C. with stirring in an environment of 25° C. and then added to deionized water at 10° C. to cool to 30° C.
Cooling 8: The toner particle dispersion liquid at 83°C was added to deionized water at 10°C to cool it to 60°C.
Slow cooling: The dispersion liquid of toner particles at 83° C. was cooled to 30° C. while stirring in an environment of 25° C.

From Table 6, the toners obtained by the production methods of Examples 1 to 15 are superior in low-temperature fixability to the toners obtained by the production methods of Comparative Examples 1 to 3 and exhibit low temperature fixability over time. It can be seen that the decrease can be suppressed and the heat-resistant storage stability is excellent.

Claims (9)

A method for producing a toner for developing an electrostatic charge image, which comprises the step of cooling a dispersion of toner particles containing an amorphous resin (A) and a crystalline resin (B),
The amorphous resin (A) is an amorphous composite resin containing a polyester resin segment and a vinyl resin segment, and the mass ratio of the amorphous resin (A) and the crystalline resin (B) [amorphous resin (A)/crystalline resin (B)] is 50/50 or more and 95/5 or less,
The cooling step includes an operation of adding a dispersion liquid of toner particles having a temperature T _u (° C.) to an aqueous medium (W) and cooling to a temperature T _d (° C.),
The temperature T _u , the temperature T _d, and the melting point T _m (° C.) of the crystalline resin (B) satisfy the following relational expressions (a) and (b),
_{T u - T m ≧ -15 (} a)
T _d −T _m ≦−20 (b)
A method for producing an electrostatic charge image developing toner, wherein a temperature T _{w of} an aqueous medium (W) at the start of addition of a dispersion liquid of toner particles is a temperature T _d or less. A step of aggregating the amorphous resin (A) and the crystalline resin (B) in an aqueous medium to obtain a dispersion liquid of aggregated particles, and fusion of the obtained aggregated particles to obtain a dispersion liquid of toner particles. The method for producing an electrostatic charge image developing toner according to claim 1, further comprising a step. The method for producing an electrostatic charge image developing toner according to claim 1, further satisfying the following relational expression (c).
_{Tu− Td} ≧10 (c) The method for producing a toner for developing an electrostatic charge image according to claim 1, further satisfying the following relational expression (d).
T _d −T _w ≦40 (d) The method for producing a toner for developing an electrostatic charge image according to claim 1, wherein the temperature T _w of the aqueous medium (W) is (T _m −90)° C. or higher and (T _m −20)° C. or lower. .. The crystalline resin (B) is a polycondensate of an alcohol component containing 80 mol% or more of α,ω-aliphatic diol and a carboxylic acid component containing 80 mol% or more of aliphatic dicarboxylic acid having 4 to 14 carbon atoms. The method for producing an electrostatic charge image developing toner according to claim 1, which is a polyester. Amorphous resin (A) is a polyester resin segments, and amorphous composite resin containing a hydrocarbon wax derived constituents of having a hydroxyl group or a carboxyl group, an electrostatic charge according to any one of claims 1 to 6 Method for producing toner for image development. The amorphous resin (A) contains a polyester resin segment, and the alcohol component of the polyester resin segment contains 80 mol% or more of a propylene oxide adduct of 2,2-bis(4-hydroxyphenyl)propane. 8. The method for producing a toner for developing an electrostatic charge image according to any one of 7 . The content of the crystalline resin (B) is, the toner based on the total amount of the resin component, is not more than 5 wt% or more 45 wt%, of the toner according to any one of claims 1-8 Production method.