JP6849277B2 - Manufacturing method of toner for static charge image development - Google Patents

Description

The present invention relates to a toner for developing an electrostatic charge image, a resin composition, and a method for producing the same.

In the field of electrophotographic, with the development of electrophotographic systems, there is a demand for the development of toner for static charge image development corresponding to high image quality and high speed. In particular, as a method for obtaining a toner having excellent fixability at a low temperature, it is known to use a crystalline resin in addition to the amorphous resin conventionally used as a binder resin. Further, in order to improve the basic characteristics of the toner such as storage stability, it is being studied to give the resin a specific structure.

For example, Patent Document 1 describes a toner binder containing a non-crystalline polyester resin, a crystalline polyester resin composed of only a crystalline portion, and a block resin composed of a crystalline portion and a non-crystalline portion. It is described that both low temperature fixability and hot offset resistance can be achieved, and that it is excellent in storage stability and charge stability.
Further, Patent Document 2 contains at least an amorphous polyester resin, a crystalline polyester resin, a mold release agent, a graft-modified polymer, and a colorant, and the graft-modified polymer is a hydrocarbon wax and a crystalline polyester resin. The polymer is grafted with an acrylic resin, and the glass transition temperature is more than 40 ° C. and less than 80 ° C., the SP value of the amorphous polyester resin is SP1, and the SP value of the crystalline polyester resin is SP1. Is SP2, the SP value of the release agent is SP3, and the SP value of the graft-modified polymer is SP4. It is described as a toner having no mming and having excellent low temperature fixability, high temperature offset resistance, and heat storage resistance.
Further, Patent Document 3 describes a binder resin composition for toner containing an amorphous composite resin having a polyester resin portion and a vinyl resin portion and a crystalline polyester, and the composite resin has a melting point. The crystalline polyester is obtained by using a raw material monomer containing an aliphatic diol having 6 to 12 carbon atoms and containing 0.5 to 10% by mass of a structural portion derived from a hydrocarbon wax having a hydroxyl group at 60 to 110 ° C. , A binder resin composition for toner, a binder resin composition for toner capable of achieving both low-temperature fixability and heat-resistant storage stability of the obtained toner, a method for producing the same, and an electrostatic charge containing the binder resin composition. The image development toner is described.

Japanese Unexamined Patent Publication No. 2015-42737 Japanese Unexamined Patent Publication No. 2012-53196 Japanese Unexamined Patent Publication No. 2015-7765

However, it has been found that even if a crystalline resin is mixed with a binder resin to improve the low temperature fixability of the toner, there is a problem that the low temperature fixability is lowered with time. Further, conventional techniques such as giving a specific structure to a resin, which has been studied to improve basic properties of toner such as storage stability, are insufficient to suppress a decrease in low temperature fixability over time. I've come to understand.
Therefore, the present invention provides a toner for electrostatic charge image development, a resin composition, and a method for producing the same, which are excellent in low-temperature fixability, can suppress a decrease in low-temperature fixability over time, and are also excellent in heat-resistant storage stability. That is the issue.

The present inventors considered that the factor affecting the characteristics of the toner using the crystalline resin is the dispersed state of the crystalline resin in the toner particles. As a result, the toner contains a multimer of a crystalline resin (A) having at least a part of the addition-polymerizable group and an amorphous resin (B) having at least a part of the addition-polymerizable group. It has been found that a toner for electrostatic charge image development, which is excellent in low-temperature fixability, can suppress a decrease in low-temperature fixability over time, and is also excellent in heat-resistant storage stability, can be obtained.

That is, the present invention relates to the following [1] to [3].
[1] A resin composition (C) containing a multimer of a crystalline resin (A) having at least a part of an addition-polymerizable group and an amorphous resin (B) having at least a part of an addition-polymerizable group. Toner for static charge image development.
[2] A resin composition containing a multimer of a crystalline resin (A) having at least a part having an addition-polymerizable group and an amorphous resin (B) having at least a part having an addition-polymerizable group.
[3] A method for producing a toner for static charge image development, which comprises the following step (1).
Step (1): A resin composition (C) containing a multimer of a crystalline resin (A) having at least a part of an addition-polymerizable group and an amorphous resin (B) having at least a part of an addition-polymerizable group. ) Is obtained

According to the present invention, there are provided a toner for electrostatic charge image development, a resin composition, and a method for producing the same, which are excellent in low-temperature fixability, can suppress a decrease in low-temperature fixability over time, and are also excellent in heat-resistant storage stability. be able to.

[Toner for static charge image development]
The static charge image developing toner of the present invention (hereinafter, also simply referred to as “toner”) is a crystalline resin (A) having at least a part having an addition-polymerizable group and an amorphous resin having at least a part having an addition-polymerizable group. An electrostatic charge containing a resin composition (C) (hereinafter, also simply referred to as "resin composition (C)") containing a multimer (hereinafter, also simply referred to as "multimer") with the sex resin (B). Image development toner.

The reason why the toner for static charge image development of the present invention is excellent in low-temperature fixability, can suppress a decrease in low-temperature fixability over time, and is also excellent in heat-resistant storage stability is not clear, but it is considered as follows. ..
Since the crystalline resin in the toner does not necessarily have good compatibility with the resin components constituting other binder resins, even if the crystalline resin is sufficiently finely dispersed in the toner particles during the production of the toner, the toner is produced. It has been found that the size of the crystal domain cannot be fixed during later storage, and the size of the crystal domain tends to gradually increase as the crystallization progresses. As a result, the interface between the crystalline resin and the other binder resin is relatively reduced, and it becomes difficult for the surrounding amorphous resin to melt as the crystalline resin melts when the toner is fixed, so that the low temperature fixability is deteriorated over time. It is thought that it will decrease.

The resin composition (C) contains a multimer of a crystalline resin (A) having at least a part having an addition-polymerizable group and an amorphous resin (B) having at least a part having an addition-polymerizable group. .. In this multimer, the segment derived from the crystalline resin (A) of the multimer bound to the segment derived from the amorphous resin (B) enters the domain of the crystalline resin, and the crystalline resin domain is substantially the same as the amorphous resin. It is considered that the crystalline resin domain is finely dispersed in the toner and stabilized because the bonded state can be maintained. As a result, it is considered that the low-temperature fixability and the heat-resistant storage property are excellent, the expansion of the crystalline resin domain during storage is suppressed, and the low-temperature fixability after storage is also good.

Definitions of various terms in the present specification are shown below.
Whether the resin is crystalline or amorphous is determined by the crystallinity index. The crystallinity index is defined by the ratio of the softening point of the resin to the maximum endothermic peak temperature (softening point (° C.) / maximum endothermic peak temperature (° C.)) in the measurement method described in Examples described later. The crystalline resin has a crystallinity index of 0.6 or more and 1.4 or less. Amorphous resins have a crystallinity index of less than 0.6 or more than 1.4. The crystallinity index can be appropriately adjusted depending on the type and ratio of the raw material monomers, and the production conditions such as reaction temperature, reaction time, and cooling rate.
The term "multimer" means a compound having a dimerization or a trimerization or more of a large amount due to an addition-polymerizable group, a polymer (graft polymer) obtained by polymerizing an addition-polymerizable group, and the like.
The resin "having an addition-polymerizable group at least partially" means a resin in which an addition-polymerizable group is introduced into a part or all of the polymer structure in the components of the resin.
In the specification, the carboxylic acid component of polyester includes not only the compound but also an anhydride that decomposes during the reaction to generate an acid, and an alkyl ester of each carboxylic acid (alkyl group having 1 or more and 3 or less carbon atoms). included.

<Resin composition (C)>
The resin composition (C) is at least one with the crystalline resin (A) having an addition-polymerizable group at least in part from the viewpoints of low-temperature fixability, suppression of deterioration of low-temperature fixability over time, and heat-resistant storage stability. The portion contains a multimer with an amorphous resin (B) having an addition-polymerizable group.
The above-mentioned resin composition (C) includes, for example, a crystalline resin (A) having at least a part of an addition-polymerizable group and an amorphous resin (B) having at least a part of an addition-polymerizable group. It is a resin composition (C) containing a multimer obtained by reacting with a polymerization initiator.

[Crystalline resin (A)]
The crystalline resin (A) is preferably a crystalline polyester resin such as a crystalline polyester, a crystalline composite resin having a polyester segment and a vinyl resin segment, and more preferably a crystalline polyester.
The crystalline polyester is a polycondensate of an alcohol component (a-al) and a carboxylic acid component (a-ac).

(Alcohol component (a-al))
As the alcohol component (a-al), α, ω-aliphatic diols are preferable.
The number of carbon atoms of the α, ω-aliphatic diol is preferably 2 or more, more preferably 4 or more, further preferably 6 or more, and preferably 16 or less, more preferably 14 or less, still more preferably 12 or less. is there.
Examples of the α, ω-aliphatic diol include ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, and 1,7-heptanediol. 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,11-undecanediol, 1,12-dodecanediol, 1,13-tridecanediol, 1,14-tetradecanediol, etc. Can be mentioned. Among these, ethylene glycol, 1,6-hexanediol, 1,9-nonanediol, 1,10-decanediol and 1,12-dodecanediol are preferable, and 1,6-hexanediol and 1,10-decanediol are preferable. , 1,12-Dodecanediol is more preferable, and 1,6-hexanediol and 1,10-decanediol are even more preferable.

The amount of α, ω-aliphatic diol is preferably 80 mol% or more, more preferably 85 mol% or more, still more preferably 90 mol% or more, still more preferably 95 mol% or more in the alcohol component (a-al). It is more and less than 100 mol%, and even more preferably 100 mol%.

The alcohol component (a-al) may contain another alcohol component different from the α, ω-aliphatic diol. Other alcohol components include, for example, aliphatic diols other than α, ω-aliphatic diols such as 1,2-propylene glycol and neopentyl glycol; aromatic diols such as alkylene oxide adducts of bisphenol A; glycerin and penta. Examples thereof include trihydric or higher alcohols such as erythritol and trimethylol propane. These alcohol components can be used alone or in combination of two or more.

(Carboxylic acid component (a-ac))
Examples of the carboxylic acid component (a-ac) include aliphatic dicarboxylic acids.
The aliphatic dicarboxylic acid has preferably 4 or more, more preferably 8 or more, still more preferably 10 or more, and preferably 14 or less, more preferably 12 or less.
Examples of the aliphatic dicarboxylic acid include fumaric acid, sebacic acid, dodecanedioic acid, and tetradecanedioic acid. Among these, sebacic acid, dodecanedioic acid, and tetradecanedioic acid are preferable, and sebacic acid is more preferable. These carboxylic acid components can be used alone or in combination of two or more.

The amount of the aliphatic dicarboxylic acid is preferably 80 mol% or more, more preferably 85 mol% or more, still more preferably 90 mol% or more, still more preferably 95 mol% or more in the carboxylic acid component (a-ac). Yes, and less than 100 mol%, even more preferably 100 mol%.

The carboxylic acid component (a-ac) may contain another carboxylic acid component different from the aliphatic dicarboxylic acid. Examples of other carboxylic acid components include aromatic dicarboxylic acids such as terephthalic acid and isophthalic acid; and polyvalent carboxylic acids having a trivalent or higher valence. These carboxylic acid components can be used alone or in combination of two or more.

(Additionally polymerizable group)
As the "additionally polymerizable group", a group having an unsaturated bond at the molecular terminal is preferable from the viewpoint of reactivity. More specifically, a (meth) acrylate group, a vinyl group, a (meth) acrylamide group, a vinyl ester group, a halovinyl group, an N-vinylacetamide group, an N-vinylamino group and the like can be mentioned.
The addition-polymerizable group may be introduced into the crystalline resin (A) in any form, but from the viewpoint of introducing the addition-polymerizable group at the resin terminal, the carboxylic acid component of the crystalline resin (A) (A-ac) preferably contains a monocarboxylic acid having an addition-polymerizable group. By containing a monocarboxylic acid having an addition-polymerizable group as the carboxylic acid component (a-ac), a crystalline resin (A) having at least a part of the addition-polymerizable group can be obtained.
Examples of the monocarboxylic acid having an addition-polymerizable group include acrylic acid and methacrylic acid.
The amount of the monocarboxylic acid having an addition-polymerizable group is preferably 1 mol% or more, more preferably 3 mol% or more, still more preferably 5 mol% or more, and more preferably 5 mol% or more in the carboxylic acid component (a-ac). It is preferably 20 mol% or less, more preferably 15 mol% or less.

The ratio of the carboxy group of the carboxylic acid component (a-ac) to the hydroxyl group of the alcohol component (a-al) [COOH group / OH group] is preferably 0.7 or more, more preferably 0.8 or more, and It is preferably 1.3 or less, more preferably 1.2 or less.

(Physical properties of crystalline resin (A))
The softening point of the crystalline resin (A) is preferably 60 ° C. or higher, more preferably 70 ° C. or higher, still more preferably 80 ° C. or higher, and further improving the low-temperature fixability, from the viewpoint of further improving the heat-resistant storage stability. From the viewpoint of improvement, it is preferably 150 ° C. or lower, more preferably 120 ° C. or lower, and further preferably 100 ° C. or lower.

The melting point of the crystalline resin (A) is preferably 50 ° C. or higher, more preferably 60 ° C. or higher, still more preferably 70 ° C. or higher, and further improves low-temperature fixability, from the viewpoint of further improving heat-resistant storage stability. From the viewpoint of making the temperature, it is preferably 100 ° C. or lower, more preferably 90 ° C. or lower, and further preferably 80 ° C. or lower.

The acid value of the crystalline resin (A) is preferably 5 mgKOH / g or more, more preferably 10 mgKOH / g or more, and preferably 35 mgKOH / g or less from the viewpoint of further improving heat storage stability and low temperature fixability. , More preferably 25 mgKOH / g or less, still more preferably 20 mgKOH / g or less.

The hydroxyl value of the crystalline resin (A) is preferably 1 mgKOH / g or more, more preferably 2 mgKOH / g or more, still more preferably 3 mgKOH / g or more, from the viewpoint of further improving heat storage stability and low temperature fixability. Then, it is preferably 35 mgKOH / g or less, more preferably 20 mgKOH / g or less, and further preferably 10 mgKOH / g or less.

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

(Manufacturing of crystalline resin (A))
When the crystalline resin (A) is a crystalline polyester, for example, the alcohol component (a-al) and the carboxylic acid component (a-ac) are polycondensed. In addition, if necessary, an esterification catalyst such as di (2-ethylhexanoic acid) tin (II) or titanium diisopropyrate bistriethanolaminate is added to the total amount of 100 parts by mass of the alcohol component and the carboxylic acid component. 01 parts by mass or more and 5 parts by mass or less; 0.001 parts by mass of an esterification co-catalyst such as gallic acid (same as 3,4,5-trihydroxybenzoic acid) with respect to 100 parts by mass of the total amount of the alcohol component and the carboxylic acid component. 0.001 part by mass or more and 0.5 part by mass or less; and if necessary, 0.001 part by mass or more with respect to 100 parts by mass of the total amount of the alcohol component and the carboxylic acid component. Polycondensation may be carried out using 5 parts by mass or less.
The polycondensation temperature is preferably 120 ° C. or higher, more preferably 160 ° C. or higher, further preferably 180 ° C. or higher, and preferably 250 ° C. or lower, more preferably 230 ° C. or lower, still more preferably 220 ° C. or lower. is there.
The polycondensation may be carried out in an inert gas atmosphere.
In the case of crystalline polyester, the crystalline resin (A) having an addition-polymerizable group at least in part has an alcohol component and a carboxylic acid component containing a monocarboxylic acid having an addition-polymerizable group. Obtained by condensation.

[Amorphous resin (B)]
The amorphous resin (B) is preferably an amorphous polyester resin such as an amorphous composite resin having an amorphous polyester, a polyester segment and a vinyl resin segment from the viewpoint of improving low temperature fixability. ..

(Amorphous polyester)
Amorphous polyester is, for example, a polycondensate of an alcohol component (bal) and a carboxylic acid component (b-ac).

(Alcohol component (b-al))
The alcohol component (b-al) preferably contains an alkylene oxide adduct of bisphenol A or an aliphatic diol having a hydroxyl group bonded to a secondary carbon atom from the viewpoint of improving heat-resistant storage stability.
The alkylene oxide adduct of bisphenol A is preferably at least one selected from the ethylene adduct adduct of bisphenol A (2,2-bis (4-hydroxyphenyl) propane) and the propylene oxide adduct of bisphenol A. More preferably, it is a propylene oxide adduct of bisphenol A.

The average number of moles of alkylene oxide added as the alkylene oxide adduct of bisphenol A is preferably 1 or more, more preferably 1 or more, from the viewpoints of further improving low temperature fixability, suppression of decrease in low temperature fixability over time, and heat storage stability. It is 1.2 or more, more preferably 1.5 or more, and preferably 16 or less, more preferably 12 or less, still more preferably 8 or less, still more preferably 4 or less.
The amount of the alkylene oxide adduct of bisphenol A is preferably 80 mol% or more, more preferably 90 mol% or more, still more preferably 95 mol% or more, still more preferably 98 mol% or more in the alcohol component (bal). The above, and 100 mol% or less, and even more preferably 100 mol%.

The aliphatic diol having a hydroxyl group bonded to a secondary carbon atom preferably has 3 or more carbon atoms, and preferably 6 or less, more preferably 5 or less, and further preferably 4 or less.
Examples of the aliphatic diol having a hydroxy group bonded to a secondary carbon atom include 1,2-propanediol, 1,2-butanediol, 1,3-butanediol, 2,3-butanediol, and 1, 2-Pentanediol, 1,4-Pentanediol, 2,4-Pentanediol, 1,2-hexanediol, 1,5-hexanediol, 2,5-hexanediol, 3,3-dimethyl-1,2- Butanediol can be mentioned. Among these, 1,2-propanediol and 2,3-butanediol are preferable, and 1,2-propanediol is more preferable.
The amount of the aliphatic diol having a hydroxy group bonded to the secondary carbon atom is preferably 60% by mass or more, more preferably 70% by mass or more, still more preferably 80% by mass or more in the alcohol component (bal). It is more preferably 90% by mass or more, further preferably 95% by mass or more, further preferably 99% by mass or more, and 100% by mass, preferably 100% by mass or less.

The alcohol component (b-al) may contain an alkylene oxide adduct of bisphenol A or another alcohol component different from the aliphatic diol having a hydroxy group bonded to a secondary carbon atom. Examples of other alcohol components include other aliphatic diols, other aromatic diols, alicyclic diols, and trihydric or higher polyhydric alcohols.
Examples of the alicyclic diol include hydrogenated bisphenol A (2,2-bis (4-hydroxycyclohexyl) propane) and alkylene oxide having 2 or more and 4 or less carbon atoms (average number of added moles 2 or more and 12). The following) Additives can be mentioned.
Examples of the trihydric or higher polyhydric alcohol include trihydric alcohols, and examples thereof include glycerin, pentaerythritol, trimethylolpropane, and sorbitol.
These alcohol components can be used alone or in combination of two or more.

(Carboxylic acid component (b-ac))
Examples of the carboxylic acid component (b-ac) include a dicarboxylic acid and a trivalent or higher valent carboxylic acid.
Examples of the dicarboxylic acid include aromatic dicarboxylic acid, aliphatic dicarboxylic acid, and alicyclic dicarboxylic acid. Among these, at least one selected from aromatic dicarboxylic acids and aliphatic dicarboxylic acids is preferable.
The aromatic dicarboxylic acid has preferably 8 or more carbon atoms, and preferably 30 or less, more preferably 20 or less, and further preferably 10 or less.
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.
The amount of the aromatic dicarboxylic acid is preferably 40 mol% or more, more preferably 50 mol% or more, more preferably 60 mol% or more, and preferably 95 mol% or more in the carboxylic acid component (b-ac). Below, it is more preferably 90 mol% or less, still more preferably 85 mol% or less, still more preferably 80 mol% or less.

The aliphatic dicarboxylic acid has preferably 2 or more carbon atoms, more preferably 3 or more carbon atoms, and preferably 30 or less, more preferably 20 or less carbon atoms.
Examples of aliphatic dicarboxylic acids having 2 to 30 carbon atoms include oxalic acid, malonic acid, maleic acid, fumaric acid, citraconic acid, itaconic acid, glutaconic acid, succinic acid, adipic acid, sebacic acid, and dodecanedioic acid. Examples thereof include azelaic acid, succinic acid substituted with an alkyl group having 1 to 20 carbon atoms or an alkenyl group having 2 to 20 carbon atoms. Examples of the succinic acid substituted with an alkyl group having 1 to 20 carbon atoms or an alkenyl group having 2 to 20 carbon atoms include dodecyl succinic acid, dodecenyl succinic acid, and octenyl succinic acid.
Among these, terephthalic acid, sebacic acid, and fumaric acid are preferable, and it is more preferable to use them in combination.

The carboxylic acid component (b-ac) of the amorphous resin (B) has an addition-polymerizable group introduced at the terminal, and a multimer having an amorphous resin (B) segment as a side chain can be easily obtained from the viewpoint. Preferably, it contains a monocarboxylic acid having an addition-polymerizable group. By containing a monocarboxylic acid having an addition-polymerizable group as the carboxylic acid component (b-ac), an amorphous resin (B) having at least a part of the addition-polymerizable group can be obtained.
The monocarboxylic acid having an addition-polymerizable group is the same as described above.
The amount of the monocarboxylic acid having an addition-polymerizable group is preferably 1 mol% or more, more preferably 3 mol% or more, still more preferably 4 mol% or more, and more preferably 4 mol% or more in the carboxylic acid component (b-ac). It is preferably 20 mol% or less, more preferably 15 mol% or less.
Here, when the amorphous resin (B) is a composite resin, the carboxylic acid component (b-ac) does not contain the bireactive monomers described later. The component added before the addition polymerization reaction for obtaining the vinyl-based resin segment described later is a bireactive monomer, and the monocarboxylic acid having an addition-polymerizable group to be condensed after the addition-polymerization reaction is a monocarboxylic acid having an addition-polymerizable group. Calculated by including in the amount of carboxylic acid. The "condensation" may be a condensation reaction with a terminal OH group or a polycondensation reaction between an alcohol component and a carboxylic acid component.

The trivalent or higher valent carboxylic acid is preferably a trivalent carboxylic acid, and examples thereof include trimellitic acid.
When a trivalent or higher polyvalent carboxylic acid is contained, the amount of the trivalent or higher polyvalent carboxylic acid is preferably 3 mol% or more, more preferably 5 mol% or more in the carboxylic acid component (b-ac). , And preferably 20 mol% or less, more preferably 15 mol% or less, still more preferably 12 mol% or less.
These carboxylic acid components can be used alone or in combination of two or more.

The ratio of the carboxy group of the carboxylic acid component (b-ac) to the hydroxyl group of the alcohol component (b-al) [COOH group / OH group] is preferably 0.7 or more, more preferably 0.8 or more, and It is preferably 1.3 or less, more preferably 1.2 or less.

[Amorphous composite resin]
The amorphous composite resin is preferably a graft polymer type resin having a vinyl resin segment in the main chain and a polyester segment in the side chain. Here, the "main chain" means the main chain of the graft polymer. The "side chain" means a polymer chain branched from the main chain of the graft polymer.

(Polyester segment)
The polyester segment is a segment made of polyester obtained by polycondensing an alcohol component (bal) and a carboxylic acid component (b-ac). Examples and suitable ranges of the alcohol component (b-al) and the carboxylic acid component (b-ac) are as described above.

(Vinyl resin segment)
The vinyl-based resin segment is preferably a vinyl-based compound having a styrene-based compound and an aliphatic hydrocarbon group having 4 to 22 carbon atoms from the viewpoint of further improving low-temperature fixability and suppression of deterioration of low-temperature fixability over time. It is an addition polymer of a raw material monomer containing a monomer.

Examples of the styrene-based compound include substituted or unsubstituted styrene. Examples of the substituent include an alkyl group having 1 to 5 carbon atoms, a halogen atom, an alkoxy group having 1 to 5 carbon atoms, a sulfonic acid group or a salt thereof and the like.
Examples of the styrene-based compound include styrenes such as styrene, methylstyrene, α-methylstyrene, β-methylstyrene, t-butylstyrene, chlorostyrene, chloromethylstyrene, methoxystyrene, styrenesulfonic acid or a salt thereof. Be done.
Of these, styrene is preferable.
The amount of the styrene-based compound is preferably 50% by mass or more, more preferably 55% by mass or more, still more preferably 60% by mass or more, and preferably 95% by mass or less, in the raw material monomer of the vinyl-based resin segment. It is more preferably 90% by mass or less, still more preferably 85% by mass or less.

The number of carbon atoms of the hydrocarbon group of the vinyl-based monomer having an aliphatic hydrocarbon group is preferably 4 or more, from the viewpoint of further improving low-temperature fixability, suppression of decrease in low-temperature fixability over time, and heat-resistant storage stability. It is preferably 6 or more, more preferably 8 or more, even more preferably 10 or more, even more preferably 12 or more, even more preferably 14 or more, and preferably 22 or less, more preferably 20 or less, even more preferably. It is 18 or less. When the vinyl-based resin segment has a hydrophobic hydrocarbon group, it is considered that the highly hydrophobic crystalline resin is easily dispersed in the toner.

Examples of the aliphatic hydrocarbon group include an alkyl group, an alkynyl group and an alkenyl group, preferably an alkyl group and an alkenyl group, and more preferably an alkyl group. The hydrocarbon group may be branched or linear.
The vinyl-based monomer having an aliphatic hydrocarbon group is preferably an alkyl ester of (meth) acrylic acid. In the case of alkyl esters of (meth) acrylic acid, the hydrocarbon group is the alcohol-side residue of the ester.
Examples of the alkyl ester of (meth) acrylic acid include (meth) acrylic acid (iso) butyl, (meth) acrylic acid (iso) hexyl, (meth) acrylic acid cyclohexyl, and (meth) acrylic acid (iso) octyl (. Hereinafter, (meth) acrylic acid (also referred to as 2-ethylhexyl), (meth) acrylic acid (iso) decyl, (meth) acrylic acid (iso) dodecyl (hereinafter, also referred to as (meth) acrylic acid (iso) lauryl), ( Examples thereof include (meth) acrylic acid (iso) palmityl, (meth) acrylic acid (iso) stearyl, and (meth) acrylic acid (iso) behenyl.
Among these, the alkyl ester of (meth) acrylic acid is preferably 2-ethylhexyl (meth) acrylic acid, (meth) acrylic acid (iso) decyl, (meth) acrylic acid (iso) lauryl, (meth) acrylic acid. (Iso) stearyl, (meth) acrylic acid (iso) behenyl, more preferably (meth) acrylic acid (iso) decyl, (meth) acrylic acid (iso) lauryl, (meth) acrylic acid (iso) stearyl, more preferably Is (meth) acrylic acid (iso) lauryl, (meth) acrylic acid (iso) stearyl, and even more preferably (meth) acrylic acid (iso) stearyl.
Here, "alkyl (meth) acrylate" means alkyl acrylate or alkyl methacrylate. Further, with respect to the alkyl moiety, "(iso)" means normal alkyl or isoalkyl.

The amount of the vinyl-based monomer having an aliphatic hydrocarbon group having 4 to 22 carbon atoms is a vinyl-based resin segment from the viewpoint of further improving low-temperature fixability, suppression of deterioration of low-temperature fixability over time, and heat-resistant storage stability. Of the raw material monomers of, preferably 5% by mass 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 45% by mass or less, still more preferably. It is 40% by mass or less.

Examples of other raw material monomers include ethylenically unsaturated monoolefins such as ethylene and propylene; conjugated dienes such as butadiene; halovinyls such as vinyl chloride; vinyl esters such as vinyl acetate and vinyl propionate; (meth). ) (Meta) acrylic acid aminoalkyl esters such as dimethylaminoethyl acrylate; vinyl ethers such as methyl vinyl ether; vinylidene halides such as vinylidene chloride; N-vinyl compounds such as N-vinylpyrrolidone.

Among the raw material monomers of the vinyl resin segment, the mass ratio of the styrene compound to the vinyl monomer having an aliphatic hydrocarbon group having 4 to 22 carbon atoms [styrene compound / vinyl monomer having an aliphatic hydrocarbon group] ] Is preferably 50/50 or more, more preferably 55/45 or more, still more preferably 60/40 or more, from the viewpoint of further improving low-temperature fixability, suppression of decrease in low-temperature fixability over time, and heat-resistant storage stability. And preferably 95/5 or less, more preferably 90/10 or less, still more preferably 85/15 or less.

Among the raw material monomers in the vinyl-based resin segment, the total amount of the styrene-based compound and the vinyl-based monomer having an aliphatic hydrocarbon group having 4 to 22 carbon atoms is low-temperature fixability and suppression of deterioration of low-temperature fixability over time. From the viewpoint of further improving the heat-resistant storage property, 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, still more preferably 100. It is mass%.

(Bi-reactive monomer)
The amorphous composite resin preferably has a structural unit derived from both reactive monomers. When a bireactive monomer is used as the raw material monomer of the amorphous composite resin, the bireactive monomer reacts with the polyester segment, the vinyl resin segment, or each of these raw material monomers, and the polyester segment and the vinyl resin segment It becomes the connection point of.
Examples of the bireactive monomer include vinyl-based 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 the molecule. Among these, from the viewpoint of reactivity, a vinyl-based monomer having a hydroxyl group or a carboxy group is preferable, and a vinyl-based 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, acrylic acid and methacrylic acid are preferable, and acrylic acid is more preferable, from the viewpoint of reactivity of both the polycondensation reaction and the addition polymerization reaction.

The amount of both reactive monomers used is preferably relative to 100 mol parts of the alcohol component of the polyester segment of the amorphous composite resin from the viewpoint of further improving low temperature fixability and suppression of deterioration of low temperature fixability over time. It is 1 mol part or more, more preferably 5 mol parts or more, further preferably 10 mol parts or more, and preferably 30 mol parts or less, more preferably 25 mol parts or less, still more preferably 20 mol parts or less. When both reactive monomers are used and the amount of each segment in the amorphous composite resin is calculated, the structural units derived from the bireactive monomers are calculated as being contained in the polyester segment. ..

The amount of the polyester segment in the amorphous composite resin is preferably 40% by mass or more, more preferably 50% by mass, from the viewpoints of improving low-temperature fixability, suppressing deterioration of low-temperature fixability over time, and heat-resistant storage stability. % Or more, more preferably 60% by mass or more, and preferably 90% by mass or less, more preferably 80% by mass or less, still more preferably 70% by mass or less.
The amount of the vinyl-based resin segment in the amorphous composite resin is preferably 10% by mass or more, more preferably 10% by mass or more, from the viewpoint of further improving low-temperature fixability, suppression of deterioration of low-temperature fixability over time, and heat-resistant storage stability. It is 20% by mass or more, more preferably 30% by mass or less, and preferably 60% by mass or less, more preferably 50% by mass or less, still more preferably 40% by mass or less.
The total amount of the polyester segment and the vinyl-based resin segment in the amorphous composite resin is preferably 80% by mass from the viewpoint of further improving low-temperature fixability, suppression of deterioration of low-temperature fixability over time, and heat-resistant storage stability. The above is more preferably 90% by mass or more, further preferably 93% by mass or more, still more preferably 95% by mass or more, and 100% by mass or less, preferably 99% by mass or less, more preferably 97% by mass. % Or less, more preferably 96% by mass or less.

[Components derived from hydrocarbon wax (W1)]
The amorphous resin (B) is a hydrocarbon wax (W1) having a hydroxyl group or a carboxy group (hereinafter, simply referred to as simply) from the viewpoint of further improving low temperature fixability, suppression of deterioration of low temperature fixability over time, and heat storage stability. It is preferable to have a constituent component derived from (also referred to as "hydrocarbon wax (W1)").
The hydrocarbon wax (W1) may have either one or both of a hydroxyl group and a carboxy group, but is polycondensed with an alcohol component (bal) or a carboxylic acid component (b-ac) of the polyester segment. Hydrocarbon waxes having both hydroxyl and carboxy groups are preferred from the perspective of reacting over time and covalently forming bonds with the polyester segment through this.
The constituent component of the hydrocarbon wax-derived (W1) having a hydroxyl group or a carboxy group contained in the amorphous resin (B) is a site where the hydrocarbon wax is bonded to a part of the polyester segment via an ester. is there.
Examples of commercially available hydrocarbon waxes having a hydroxyl group and a carboxy group include "Paracol 6420", "Paracol 6470", and "Paracol 6490" (all manufactured by Nippon Seiro Co., Ltd.).

The hydroxyl value of the hydrocarbon wax (W1) is preferably 40 mgKOH / g or more, more preferably 50 mgKOH / g or more, still more preferably 70 mgKOH / g or more, and preferably 180 mgKOH / g or more from the viewpoint of reactivity with polyester. / G or less, more preferably 150 mgKOH / g or less, still more preferably 120 mgKOH / g or less.
The acid value of the hydrocarbon wax (W1) is preferably 1 mgKOH / g or more, more preferably 5 mgKOH / g or more, still more preferably 8 mgKOH / g or more, and preferably 30 mgKOH / g or more from the viewpoint of reactivity with polyester. / G or less, more preferably 25 mgKOH / g or less, still more preferably 20 mgKOH / g or less.

The total hydroxyl value and acid value of the hydrocarbon wax (W1) is preferably 41 mgKOH / g or more, more preferably 55 mgKOH / g or more, still more preferably 80 mgKOH / g or more, from the viewpoint of reactivity with polyester. Then, it is preferably 210 mgKOH / g or less, more preferably 175 mgKOH / g or less, and further preferably 140 mgKOH / g or less.
The hydroxyl value and acid value of the hydrocarbon wax (W1) are determined by the method described in Examples.

The melting point of the hydrocarbon wax (W1) is preferably 60 ° C. or higher, more preferably 65 ° C. or higher, still more preferably 70 ° C. or higher, and preferably 120 ° C. from the viewpoint of further improving the low temperature fixability of the toner. Below, it is more preferably 110 ° C. or lower, still more preferably 100 ° C. or lower.

The number average molecular weight of the hydrocarbon wax (W1) is preferably 500 or more, more preferably 600 or more, still more preferably 700 or more, and preferably 2000 or less, from the viewpoint of improving the low temperature fixability of the toner. It is preferably 1700 or less, more preferably 1500 or less.
When the amorphous resin (B) contains a component derived from the hydrocarbon wax (W1), the amount of the component derived from the hydrocarbon wax (W1) contained in the amorphous resin (B) is low temperature fixability. From the viewpoint of suppressing a decrease in low-temperature fixability over time and further improving heat-resistant storage stability, the amount is preferably 1% by mass or more, more preferably 3% by mass or more, and preferably 3% by mass or more in the amorphous resin (B). Is 20% by mass or less, more preferably 15% by mass or less, still more preferably 12% by mass or less.

[Manufacturing of amorphous resin (B)]
In the case of an amorphous polyester, the method for producing the amorphous resin (B) is exemplified by the same method as the above-mentioned method for producing the crystalline polyester of the crystalline resin (A).
The method for producing the amorphous resin (B) is not particularly limited when it is an amorphous composite resin, and examples thereof include the following methods (i) to (iii).
(I) Method of performing an addition polymerization reaction with a raw material monomer and a bireactive monomer of a vinyl resin segment after a polycondensation reaction with an alcohol component (bal) and a carboxylic acid component (b-ac). When it is desired to include a component derived from a hydrocarbon wax having a hydroxyl group or a carboxy group in the composite resin, a polycondensation reaction with an alcohol component and a carboxylic acid component is carried out in the presence of the hydrocarbon wax (W1) having a hydroxyl group or a carboxy group. It is good to do it at. Further, from the viewpoint of reactivity, it is preferable that both reactive monomers are supplied to the reaction system together with the raw material monomer of the vinyl resin segment. From the viewpoint of reactivity, catalysts such as an esterification catalyst and an esterification co-catalyst may be used, and a radical polymerization initiator and a radical polymerization inhibitor may be used.
From the viewpoint of further advancing the polycondensation reaction and, if necessary, the reaction with the bireactive monomers, the carboxylic acid component is partially subjected to the polycondensation reaction, then the addition polymerization reaction is carried out, and then the reaction temperature is raised again. It is preferable to add the balance to the reaction system.

It can also be produced by the following method (ii) or (iii).
(Ii) Method of performing polycondensation reaction with raw material monomer of polyester segment after addition polymerization reaction with raw material monomer and bireactive monomer of vinyl resin segment (iii) Polycondensation reaction with alcohol component and carboxylic acid component and vinyl type Method of performing addition polymerization reaction with raw material monomer of resin segment and bireactive monomer in parallel Both of the polycondensation reaction and addition polymerization reaction of the methods (i) to (iii) above shall be carried out in the same container. Is preferable.
The amorphous composite resin is preferably produced by the method (i) above because it has a high degree of freedom in the reaction temperature of the polycondensation reaction.

From the viewpoint of obtaining an amorphous composite resin having an addition-polymerizable group at least in part, the above addition is made when the amorphous composite resin contains a monocarboxylic acid having an addition-polymerizable group as a carboxylic acid component. After completion of the polymerization reaction, a monocarboxylic acid having an addition-polymerizable group may be condensed.

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, from the viewpoint of productivity of the amorphous composite resin. ..
Other examples of polycondensation conditions such as an esterification catalyst, an esterification co-catalyst, and a radical polymerization inhibitor are the same as those of the crystalline resin (A).

The temperature of the addition polymerization reaction is preferably 110 ° C. or higher, more preferably 130 ° C. or higher, and preferably 220 ° C. or lower, more preferably 200 ° C. or lower, from the viewpoint of productivity of the amorphous composite resin. .. Further, it is preferable to accelerate the reaction by reducing the pressure of the reaction system in the latter half of the polymerization.

Examples of the polymerization initiator 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). Known radical polymerization initiators of the above can be used.

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

[Physical characteristics of amorphous resin (B)]
The softening point of the amorphous resin (B) is preferably 70 ° C. or higher, more preferably 90 ° C. or higher, further preferably 100 ° C. or higher, and low-temperature fixability, from the viewpoint of further improving heat-resistant storage stability. From the viewpoint of further improvement, it is preferably 140 ° C. or lower, more preferably 130 ° C. or lower.

The glass transition temperature of the amorphous resin (B) is preferably 30 ° C. or higher, more preferably 35 ° C. or higher, further preferably 40 ° C. or higher, and low-temperature fixability, from the viewpoint of further improving heat-resistant storage stability. From the viewpoint of further improving the temperature, the temperature is preferably 70 ° C. or lower, more preferably 60 ° C. or lower, still more preferably 55 ° C. or lower.

The acid value of the amorphous resin (B) is preferably 5 mgKOH / g or more, more preferably 10 mgKOH / g or more, still more preferably 15 mgKOH / g or more, from the viewpoint of further improving heat storage stability and low temperature fixability. And, preferably 40 mgKOH / g or less, more preferably 35 mgKOH / g or less, still more preferably 30 mgKOH / g or less.

The hydroxyl value of the amorphous resin (B) is preferably 1 mgKOH / g or more, more preferably 3 mgKOH / g or more, still more preferably 5 mgKOH / g or more, from the viewpoint of further improving heat storage stability and low temperature fixability. And, preferably 40 mgKOH / g or less, more preferably 25 mgKOH / g or less, still more preferably 15 mgKOH / g or less.

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

[Multiple]
The multimer is a multimer of a crystalline resin (A) having at least a part having an addition-polymerizable group and an amorphous resin (B) having at least a part having an addition-polymerizable group, and is a crystalline resin (A). ) And the structure of the amorphous resin (B) are included in the molecular structure, so that the crystalline resin (A) can be easily finely dispersed in the amorphous resin (B), and low-temperature fixability and heat-resistant storage. It is considered that a toner having excellent properties and excellent low-temperature fixability after storage can be obtained by suppressing the expansion of the crystalline resin domain during storage.
Examples of the multimer include a graft polymer having a crystalline resin (A) and an amorphous resin (B) in a side chain, a crystalline resin (A) having an addition-polymerizable group, and a non-polymerized resin having an addition-polymerizable group. Examples thereof include a dimer or a trimer with a crystallinity resin (B).

[Method for producing resin composition (C); step (1)]
The method for producing the resin composition (C) has the following step (1).
Step (1): A resin composition (C) containing a multimer of a crystalline resin (A) having at least a part of an addition-polymerizable group and an amorphous resin (B) having at least a part of an addition-polymerizable group. The method for producing the resin composition (C) preferably has the following step (1').
Step (1'): A crystalline resin (A) having at least a part of an addition-polymerizable group and an amorphous resin (B) having at least a part of an addition-polymerizable group are reacted with a polymerization initiator. To obtain the resin composition (C) containing a multimer

The crystalline resin (A) having at least a part having an addition-polymerizable group preferably contains an alcohol component and a carboxylic acid component containing a monocarboxylic acid having an addition-polymerizable group of 1 mol% or more and 20 mol% or less. It is a crystalline polyester which is a polycondensate of. When the carboxylic acid component contains a monocarboxylic acid in the above range, a crystalline resin (A) having an addition-polymerizable group at least in part can be obtained.
The amorphous resin (B) having at least a part of the addition polymerizable group is preferably an amorphous composite resin having a polyester segment which is a polycondensate of an alcohol component and a carboxylic acid component and a vinyl resin segment. It is an amorphous composite resin obtained by condensing a monocarboxylic acid having an addition polymerizable group after addition polymerization of a vinyl resin segment. The amount of the monocarboxylic acid having an addition-polymerizable group is preferably 1 mol% or more and 20 mol% or less with respect to the carboxylic acid component. By condensing the monocarboxylic acid in this way, an amorphous composite resin having at least a part of it having an addition-polymerizable group can be obtained.

In the resin composition (C), the blending amount of the crystalline resin (A) having at least a part of the addition polymerizable group and the blending amount of the amorphous resin (B) having at least a part of the addition polymerizable group The mass ratio [the crystalline resin (A) / the amorphous resin (B)] is preferably 5 from the viewpoints of improving low-temperature fixability, suppressing deterioration of low-temperature fixability over time, and further improving heat-resistant storage stability. It is / 95 or more, more preferably 15/85 or more, still more preferably 25/75 or more, and preferably 90/10 or less, more preferably 80/20 or less, still more preferably 70/30 or less.
When the synthesis of the amorphous resin (B) and the quantification reaction with the crystalline resin (A) are continuously carried out, the mass of the amorphous resin (B) is dehydrated from the amount of the monomer charged. It shall be calculated in consideration of the amount.

Reacting with a polymerization initiator in the presence of the above-mentioned crystalline resin (A) having an addition-polymerizable group in at least a part and an amorphous resin (B) having an addition-polymerizable group in at least a part. Then, a multimer of a crystalline resin (A) having an addition-polymerizable group and an amorphous resin (B) having an addition-polymerizable group, an unreacted crystalline resin (A), and an unreacted non-crystal. It is considered that the resin composition (C) containing the sex resin (B) can be obtained. However, the resin composition actually obtained contains various resin structures, and the reality is that the structure and characteristics cannot be simply specified and specified. Further, if the structure is to be specified by a known analysis method, extremely complicated analysis such as isolation and purification, establishment of a polymer structure definition method, etc. is required. That is, there are circumstances in which it is practically impractical to directly specify the resin composition (C) by its structure or properties.

The polymerization initiator is preferably a radical polymerization initiator, and more specifically, an azo-based or diazo-based polymerization initiator, a peroxide-based polymerization initiator and the like can be mentioned.
Examples of the azo-based or diazo-based polymerization initiator include 2,2'-azobis (2,4-dimethylvaleronitrile), 2,2'-azobisisobutyronitrile, and 1,1'-azobis (cyclohexane-). 1-Carbonitrile), 2,2'-azobis-4-methoxy-2,4-dimethylvaleronitrile. Examples of the peroxide-based polymerization initiator include dibutyl peroxide, benzoyl peroxide, methyl ethyl ketone peroxide, isopropyl peroxy carbonate, cumene hydroperoxide, 2,4-dichlorobenzoyl peroxide, lauroyl peroxide, and dichloromethane. Oxides can be mentioned. Among these, an azo-based polymerization initiator and a peroxide-based polymerization initiator are preferable, and 2,2'-azobis (2,4-dimethylvaleronitrile) and dibutyl peroxide are more preferable.
The amount of the polymerization initiator added is a crystalline resin (A) having an addition-polymerizable group at least in part from the viewpoint of low-temperature fixability, suppression of deterioration of low-temperature fixability over time, and further improvement of heat-resistant storage stability. With respect to 100 parts by mass of the total amount of the amorphous resin (B) having an addition polymerizable group at least in part, preferably 0.1 part by mass or more, more preferably 0.5 part by mass or more, still more preferable. Is 1 part by mass or more, and preferably 30 parts by mass or less, more preferably 25 parts by mass or less, still more preferably 20 parts by mass or less.

From the viewpoint of suppressing side reactions, the reaction temperature is preferably 50 ° C. or higher, more preferably 60 ° C. or higher, further preferably 70 ° C. or higher, and preferably 250 ° C. or lower, more preferably 230 ° C. or lower, further. It is preferably 200 ° C. or lower.
The above reaction may be carried out in either an organic solvent or a solvent-free condition. Each condition such as the type and amount of the polymerization initiator, the reaction temperature, and the presence or absence of the solvent is appropriately selected after comprehensively judging them.

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

When an organic solvent is used, the amount of the organic solvent used is as follows: from the viewpoint of reactivity, the crystalline resin (A) having at least a part having an addition-polymerizable group and the amorphous resin having at least a part having an addition-polymerizable group. With respect to 100 parts by mass of the total amount of the resin (B), it is preferably 30 parts by mass or more, more preferably 50 parts by mass or more, and preferably 500 parts by mass or less, more preferably 300 parts by mass or less, further. It is preferably 150 parts by mass or less.
After the reaction, the organic solvent is preferably removed by means such as distillation under reduced pressure. Further, the organic solvent solution can be used as it is for the phase inversion emulsification in the step (2A).
From the viewpoint of suppressing side reactions, the reaction temperature is preferably 50 ° C. or higher, more preferably 60 ° C. or higher, further preferably 70 ° C. or higher, and preferably 120 ° C. or lower, more preferably 100 ° C. or lower, further. It is preferably 90 ° C. or lower.
The polymerization initiator is preferably an azo-based polymerization initiator, more preferably 2,2'-azobis (2,4-dimethylvaleronitrile) from the viewpoint of reacting at the above reaction temperature.
The amount of the polymerization initiator added is a crystalline resin (A) having at least a part of an addition-polymerizable group from the viewpoint of low-temperature fixability, suppression of deterioration of low-temperature fixability over time, and further improvement of heat-resistant storage stability. With respect to 100 parts by mass of the total amount of the amorphous resin (B) having an addition-polymerizable group at least in part, preferably 1 part by mass or more, more preferably 3 parts by mass or more, still more preferably 5 parts by mass. The above, and preferably 30 parts by mass or less, more preferably 25 parts by mass or less, still more preferably 20 parts by mass or less.

When the reaction is carried out without a solvent, the reaction temperature is preferably 120 ° C. or higher, more preferably 150 ° C. or higher, still more preferably 160 ° C. or higher, and suppresses side reactions, from the viewpoint of carrying out the reaction with the resin in a molten state. From the viewpoint, it is preferably 250 ° C. or lower, more preferably 230 ° C. or lower, still more preferably 200 ° C. or lower.
The polymerization initiator is preferably a peroxide-based polymerization initiator, more preferably dibutyl peroxide, from the viewpoint of reacting at the above reaction temperature.
The amount of the polymerization initiator added is a crystalline resin (A) having at least a part of an addition-polymerizable group from the viewpoint of low-temperature fixability, suppression of deterioration of low-temperature fixability over time, and further improvement of heat-resistant storage stability. With respect to 100 parts by mass of the total amount of the amorphous resin (B) having an addition polymerizable group at least in part, preferably 0.1 part by mass or more, more preferably 0.5 part by mass or more, still more preferable. Is 1 part by mass or more, and preferably 20 parts by mass or less, more preferably 10 parts by mass or less, still more preferably 5 parts by mass or less.

When the toner is produced by the coagulation fusion method, the crystalline resin (A) and the amorphous resin (B) are preferably reacted in an organic solvent from the viewpoint of ease of reaction control.
When the toner is produced by the melt-kneading method, the crystalline resin (A) and the amorphous resin (B) are preferably reacted without a solvent from the viewpoint of not mixing an organic solvent during the subsequent melt-kneading. More specifically, from the viewpoint of production efficiency, an amorphous resin (B) in which an alcohol component (b-al) and a carboxylic acid component (b-ac) are polycondensed and have at least a part of an addition-polymerizable group. ) After obtaining, a crystalline resin (A) having an addition-polymerizable group and a polymerization initiator are added to at least a part thereof, and at least a part of the crystalline resin (A) having an addition-polymerizable group is added. It is preferable that the amorphous resin (B) having an addition-polymerizable group is reacted with a polymerization initiator to obtain a resin composition (C) containing a multimer.

[Physical characteristics of resin composition (C)]
The physical property value of the resin composition (C) described below means a value obtained by measuring various physical properties of the entire resin composition (C).
The softening point of the resin composition (C) is preferably 55 ° C. or higher, more preferably 60 ° C. or higher, still more preferably 65 ° C. or higher, and further improves the low-temperature fixability, from the viewpoint of further improving the heat-resistant storage stability. From the viewpoint of improvement, it is preferably 120 ° C. or lower, more preferably 110 ° C. or lower, and further preferably 100 ° C. or lower.
When the toner is obtained by the coagulation fusion method, the softening point of the resin composition (C) is preferably 55 ° C. or higher, more preferably 60 ° C. or higher, still more preferably 65 ° C. or higher from the viewpoint of further improving the heat-resistant storage stability. From the viewpoint of further improving the low temperature fixability, the temperature is preferably 120 ° C. or lower, more preferably 100 ° C. or lower, and further preferably 80 ° C. or lower.
When the toner is obtained by the melt-kneading method, the softening point of the resin composition (C) is preferably 70 ° C. or higher, more preferably 75 ° C. or higher, and further preferably 80 ° C. from the viewpoint of further improving grindability and heat-resistant storage stability. The temperature is preferably 120 ° C. or lower, more preferably 110 ° C. or lower, still more preferably 100 ° C. or lower, from the viewpoint of further improving the low temperature fixability.

The melting point of the resin composition (C) is preferably 55 ° C. or higher, more preferably 60 ° C. or higher, still more preferably 65 ° C. or higher, and further improves low-temperature fixability, from the viewpoint of further improving heat-resistant storage stability. From the viewpoint of the temperature, it is preferably 120 ° C. or lower, more preferably 100 ° C. or lower, and further preferably 80 ° C. or lower.

The softening point and melting point of the resin composition (C) can be appropriately adjusted according to the type and ratio of the raw material monomers, and the production conditions such as reaction temperature, reaction time, cooling rate, etc., and their values are set. Obtained by the method described in the example.

[Manufacturing method of toner for static charge image development]
As a method for producing the static charge image developing toner of the present invention, for example, the above-mentioned step (1): a crystalline resin (A) having at least a part of an addition-polymerizable group and at least a part of an addition-polymerizable group The step of obtaining a resin composition (C) containing a multimer with the amorphous resin (B) having the resin composition (B) is included. The manufacturing method then includes, for example, the following method (A) or (B).
(A) A method for producing toner by aggregating and fusing resin particles in a mixture containing a dispersion liquid in which the resin composition (C) is dispersed in a water-soluble medium to obtain toner particles (hereinafter, "" Also called "coagulation fusion method"),
(B) A method of melt-kneading a mixture containing the resin composition (C) and pulverizing the obtained melt-kneaded product to produce a toner (hereinafter, also referred to as "melt-kneading method").
And so on.
Among these, the coagulation fusion method (A) is preferable. Further, the toner may be obtained by the melt-kneading method of (B).

In either method, the blending amount of each component in the resin component in the toner is as follows.
The blending amount of the resin composition (C) is preferably 10% by mass or more in the resin component of the toner from the viewpoints of low-temperature fixability, suppression of deterioration of low-temperature fixability over time, and further improvement of heat-resistant storage stability. More preferably 30% by mass or more, further preferably 40% by mass or more, more preferably 50% by mass or more, and 100% by mass or less, preferably 90% by mass or less, more preferably 80% by mass or less, still more preferable. Is 70% by mass or less.

In addition to the resin composition (C), a crystalline resin and an amorphous resin may be further blended.
The crystalline resin to be blended separately may not have a polymerizable group, and is preferably a crystalline polyester-based resin, and more preferably a crystalline polyester. The crystalline polyester is the crystalline polyester exemplified in the above-mentioned crystalline resin (A) (however, it does not have to have a polymerizable group).
The amorphous resin to be blended separately may not have a polymerizable group, and is preferably an amorphous polyester resin, and more preferably an amorphous composite resin. Examples of the amorphous resin include the amorphous resin exemplified in the above-mentioned amorphous resin (B) (however, it does not have to have a polymerizable group).

When the crystalline resin is further blended, the blending amount of the crystalline resin is preferably 1% by mass or more, more preferably 3% by mass or more, still more preferably 5% by mass or more in the resin component of the toner, and It is preferably 25% by mass or less, more preferably 20% by mass or less, still more preferably 15% by mass or less.

When the amorphous resin is further blended, the blending amount of the amorphous resin is preferably 10% by mass or more, more preferably 20% by mass or more, still more preferably 30% by mass or more in the resin component of the toner. Then, it is preferably 90% by mass or less, more preferably 80% by mass or less, still more preferably 70% by mass or less, still more preferably 60% by mass or less.

The total amount of the crystalline resin is preferably 5% by mass or more, more preferably 5% by mass or more, in the resin component of the toner, from the viewpoints of low-temperature fixability, suppression of deterioration of low-temperature fixability over time, and further improvement of heat-resistant storage stability. Is 10% by mass or more, more preferably 15% by mass or more, and preferably 45% by mass or less, more preferably 40% by mass or less, still more preferably 35% by mass or less.
The total amount of the amorphous resin is preferably 55% by mass or more in the resin component of the toner from the viewpoint of low-temperature fixability, suppression of deterioration of low-temperature fixability over time, and further improvement of heat-resistant storage stability. It is preferably 60% by mass or more, more preferably 65% by mass or more, and preferably 95% by mass or less, more preferably 90% by mass or less, still more preferably 85% by mass or less.

The total blending amount of the crystalline resin is preferable with respect to the total blending amount of the crystalline resin and the amorphous resin from the viewpoint of further improving the low-temperature fixability, the suppression of the decrease in the low-temperature fixability over time, and the heat-resistant storage stability. Is 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, still more preferably 35% by mass or less. ..
The "total blending amount" means the total amount of the resin blended as the raw material of the resin composition (C) and the resin blended in other steps.

(A) Coagulation and Fusion Method The method for producing a toner of the present invention preferably has the following steps (1) and steps (2A) to (4A).
Step (1): A resin composition (C) containing a multimer of a crystalline resin (A) having at least a part of an addition-polymerizable group and an amorphous resin (B) having at least a part of an addition-polymerizable group. Step (2A): A step of dispersing the resin composition (C) obtained in the step (1) in an aqueous medium to obtain a dispersion liquid of the resin particles (P1) Step (3A): Step ( Step of aggregating the resin particles (P1) obtained in 2A) in an aqueous medium to obtain agglomerated particles Step (4A): A step of fusing the agglomerated particles obtained in step (3A).

The step (1) is as described in the method for producing the resin composition (C) described above.

<Process (2A)>
The step (2A) is a step of dispersing the resin composition (C) obtained in the step (1) in an aqueous medium to obtain a dispersion liquid of the resin particles (P1).
Here, in addition to the resin composition (C), a crystalline resin or an amorphous resin may be further added. The types of the crystalline resin and the amorphous resin, and the blending ratios of the crystalline resin, the amorphous resin, and the resin composition (C) are as described above.
As a method for obtaining a dispersion liquid of the resin particles (P1), for example, a method in which the resin composition (C) is added to an aqueous medium and a dispersion treatment is performed by a disperser or the like, and an aqueous medium is gradually added to the resin composition (C). A method of inversion emulsification by adding to the above can be mentioned, but a method of inversion emulsification is preferable.

≪Aqueous medium≫
The aqueous medium preferably contains water as a main component, and the content of water in the aqueous medium is preferably 80% by mass from the viewpoint of improving the dispersion stability of the dispersion liquid of the resin particles and from the viewpoint of environmental friendliness. % Or more, more preferably 90% by mass or more, still more preferably 95% by mass or more, even more preferably 98% by mass or more, and 100% by mass or less, still more preferably 100% by mass. As the water, deionized water or distilled water is preferable.
Examples of components other than water that can be contained in the aqueous medium include alkyl alcohols having 1 to 5 carbon atoms; dialkyl ketones having 3 to 5 carbon atoms such as acetone and methyl ethyl ketone; and soluble in water such as cyclic ethers such as tetrahydrofuran. Examples of organic solvents are used.
Among these, from the viewpoint of preventing the organic solvent from being mixed into the toner, an alkyl alcohol having 1 or more and 5 or less carbon atoms that does not dissolve polyester is preferable, and methanol, ethanol, isopropanol, and butanol are more preferable.

[Phase inversion emulsification]
Examples of the phase inversion emulsification method include a method of preparing an organic solvent solution of the resin composition (C) and then adding an aqueous medium to the obtained solution for phase inversion emulsification, and a molten resin composition (C). ) Is added with an aqueous medium for phase inversion emulsification. The former method is preferable from the viewpoint of obtaining a dispersion liquid of homogeneous resin particles (P1).

The concentration of the resin in the organic solvent solution is preferably 20% by mass or more, more preferably 50% by mass or more, and preferably 90% by mass or less, more preferably 80% by mass or less. In addition to the resin composition (C), other resin components such as a crystalline resin and an amorphous resin may be further added to the organic solvent solution of the resin. A preferred embodiment of the organic solvent is the same as the organic solvent that can be used for producing the resin composition (C) in the step (1). The resin composition (C) may be produced in the organic solvent in the step (1) and subjected to the step (2A) as it is in the organic solvent solution.

It is preferable to add a neutralizing agent to the organic solvent solution of the resin. Examples of the neutralizing agent include basic substances. Examples of the basic substance include hydroxides of alkali metals such as lithium hydroxide, sodium hydroxide and potassium hydroxide; and nitrogen-containing substances such as ammonia, trimethylamine, ethylamine, diethylamine, triethylamine, diethanolamine, triethanolamine and tributylamine. Examples include basic substances. Among these, from the viewpoint of improving the dispersion stability and cohesiveness of the resin particles (P1), alkali metal hydroxide is preferable, and sodium hydroxide is more preferable.

The equivalent equivalent (mol%) of the neutralizing agent to the acid group of the resin is preferably 10 mol% or more, more preferably 30 mol% or more, and preferably 150 mol% or less, more preferably 120 mol% or less. , More preferably 100 mol% or less.
The equivalent amount (mol%) of the neutralizing agent used can be calculated by the following formula. When the equivalent amount of the neutralizing agent is 100 mol% or less, it is synonymous with the degree of neutralization. When the equivalent amount of the neutralizing agent used exceeds 100 mol% by the following formula, the neutralizing agent is the acid group of the resin. The degree of neutralization of the resin at this time is considered to be 100 mol%.
Equivalent to use of neutralizer (mol%) = [{Equivalent mass of neutralizer (g) / Equivalent of neutralizer} / [{Weighted average acid value (mgKOH / g) of the resin constituting the resin particles (P1) ) × Mass of resin constituting resin particles (P1) (g)} / (56 × 1000)]] × 100

The amount of the aqueous medium to be added is 100 mass of the resin constituting the resin particles (P1) from the viewpoint of improving the dispersion stability of the resin particles (P1) and obtaining uniform aggregated particles in the subsequent step (3A). It is preferably 100 parts by mass or more, more preferably 150 parts by mass or more, still more preferably 200 parts by mass or more, and preferably 900 parts by mass or less, more preferably 600 parts by mass or less.

Further, from the viewpoint of improving the dispersion stability of the resin particles (P1), the mass ratio (aqueous medium / organic solvent) of the aqueous medium to the organic solvent is preferably 20/80 or more, more preferably 50/50 or more. , More preferably 60/40 or more, and preferably 97/3 or less, more preferably 93/7 or less, still more preferably 90/10 or less.

The temperature at which the aqueous medium is added is preferably equal to or higher than the glass transition temperature of the resin constituting the resin particles (P1) from the viewpoint of improving the dispersion stability of the resin particles (P1). Specifically, the temperature is preferably 50 ° C. or higher, 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 higher. It is below ° C.

From the viewpoint of obtaining resin particles having a small particle size, the addition rate of the aqueous medium is preferably 0.1 part by mass or more with respect to 100 parts by mass of the resin constituting the resin particles until the phase inversion is completed. More preferably 0.5 parts by mass or more, further preferably 1 part by mass or more, and preferably 50 parts by mass or less, more preferably 30 parts by mass or less, still more preferably 20 parts by mass. It is less than a part / minute. There is no limit to the rate of addition of the aqueous medium after phase inversion.

After the phase inversion emulsification, if necessary, it may have a step of removing the organic solvent from the obtained dispersion liquid by distillation or the like. In this case, the residual amount of the organic solvent is preferably 1% by mass or less, more preferably 0.5% by mass or less, still more preferably substantially 0% in the aqueous dispersion.

The solid content concentration of the dispersion liquid of the resin particles (P1) is preferably 5% by mass or more, more preferably 10% by mass or more, further preferably 15% by mass or more, and preferably 50% by mass or less, more preferably. Is 40% by mass or less, more preferably 30% by mass or less, still more preferably 25% by mass or less. The solid content is the total amount of non-volatile components such as resin, colorant, and surfactant.

_{The volume median particle diameter (D 50} ) of the resin particles (P1) in the 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. And, preferably 0.80 μm or less, more preferably 0.40 μm or less, still more preferably 0.20 μm or less, still more preferably 0.15 μm or less.
Here, the volume median particle size (D ₅₀ ) is a particle size in which the cumulative volume frequency calculated by the volume fraction is 50% calculated from the smaller particle size, and is described in Examples described later. Required by the method.
The coefficient of variation (CV value) (%) of the particle size distribution of the resin particles (P1) is preferably 5% or more, more preferably 10% or more from the viewpoint of improving the productivity of the dispersion liquid of the resin particles (P1). It is more preferably 15% or more, and from the viewpoint of obtaining a toner that can obtain a high-quality image, it is preferably 50% or less, more preferably 40% or less, still more preferably 30% or less.
The CV value is a value represented by the following formula. The volume average particle size in the following formula is the particle size obtained by multiplying the particle size measured on a volume basis by the ratio of particles having that particle size value and dividing the value obtained by that by the number of particles. is there. The CV value is determined by the method described in Examples.
CV value (%) = [standard deviation of particle size distribution (nm) / volume average particle size (nm)] x 100

The resin particles (P1) may contain a colorant and a charge control agent, if necessary. Further, an additive such as a reinforcing filler such as a fibrous substance, an antioxidant, and an antiaging agent may be contained as long as the effect of the present invention is not impaired.

<Process (3A)>
The step (3A) is a step of aggregating the resin particles (P1) obtained in the step (2A) in an aqueous medium to obtain agglomerated particles. The step (3A) is, for example, an optional dispersion of resin particles (P1), and if necessary, a wax (W2) particle dispersion containing wax (W2), a flocculant, a surfactant, a colorant, and the like. A method in which the components are mixed in the aqueous medium and the resin particles (P1) and other components are aggregated to obtain aggregated particles is preferable.
The step (3A) may include the next step (3A-1), followed by the step (3A-2).
Step (3A-1): A step of aggregating the resin particles (P1) obtained in the step (2A) in an aqueous medium preferably in the presence of wax (W2) to obtain agglomerated particles (1). 3A-2): Resin particles (P2) containing an amorphous resin (Bs) are added to the agglomerated particles (1) obtained in the step (3A-1), and the resin particles (P2) are attached. Step to obtain agglomerated particles (2)

<Process (3A-1)>
The step (3A-1) is a step of aggregating the resin particles (P1) obtained in the step (2A) in an aqueous medium to obtain agglomerated particles (1), preferably in the step (2A). This is a step of aggregating the obtained resin particles (P1) in an aqueous medium in the presence of wax (W2) to obtain agglomerated particles (1).

[Aggregated particles (1)]
The agglomerated particles (1) are a wax particle dispersion containing wax (W2), if necessary, in the dispersion of the resin particles (P1) obtained in the step (2A), an aggregating agent, a surfactant, and a coloring agent. It is obtained by mixing arbitrary components such as and agglomerating.
A dispersion of resin particles (P1), a dispersion of wax (W2) particles, and, if necessary, an optional component such as a flocculant, a surfactant, and a colorant are mixed in an aqueous medium to obtain a mixed dispersion. Is preferable. Then, when the components in the mixed dispersion liquid are agglomerated to obtain the dispersion liquid of the agglomerated particles (1), it is preferable to add a coagulant from the viewpoint of efficiently performing the agglomeration.
When the colorant is not mixed with the resin particles (P1), it is preferable to mix the colorant in the mixed dispersion.
The mixing order of each component is not particularly limited, and each component may be added in any order, or each component may be added at the same time.

≪Wax (W2) particle dispersion ≫
The wax (W2) particle dispersion can be obtained by using a surfactant, but the wax (W2) and the resin particles (F) described later can be mixed and obtained at the time of aggregation and fusion. It is preferable from the viewpoint of suppressing desorption and exposure of wax.

(Wax (W2))
Examples of the wax (W2) include hydrocarbon waxes, ester waxes, silicone waxes, and fatty acid amide waxes.
Examples of the hydrocarbon wax include minerals such as paraffin wax and Fishertropsh wax or petroleum-based hydrocarbon wax; synthetic hydrocarbon wax such as polyolefin wax such as polyethylene wax, polypropylene wax and polybutene wax.
Examples of the ester wax include mineral or petroleum-based ester waxes such as Montan wax; plant-based ester waxes such as carnauba wax, rice wax and candelilla wax; and animal-based ester waxes such as beeswax.
Examples of the fatty acid amide wax include oleic acid amide and stearic acid amide.
Among these, from the viewpoint of toner releasability, hydrocarbon wax or ester wax is preferable, hydrocarbon wax is more preferable, and at least one selected from paraffin wax, Fishertroph wax, and polyolefin wax is more preferable, and paraffin is more preferable. Wax is even more preferred.

The melting point of the wax is preferably 60 ° C. or higher, more preferably 65 ° C. or higher, still more preferably 70 ° C. or higher from the viewpoint of toner releasability, and preferably from the viewpoint of improving the low temperature fixability of the toner. Is 100 ° C. or lower, more preferably 95 ° C. or lower, still more preferably 90 ° C. or lower, still more preferably 85 ° C. or lower.
The melting point of the wax is determined by the method described in the examples.

From the viewpoint of toner releasability, the amount of wax used is preferably 1 part by mass or more, more preferably 2 parts by mass or more, and further preferably 3 parts by mass or more with respect to 100 parts by mass of the resin component in the toner. Yes, and from the viewpoint of suppressing desorption and exposure of the wax at the time of aggregation and fusion, it is preferably 25 parts by mass or less, more preferably 20 parts by mass or less, and further preferably 15 parts by mass or less.

(Resin particles (F))
The resin constituting the resin particles (F) is not particularly limited, but is preferably a polyester-based resin, and the polyester segment and the vinyl-based resin segment are selected from the viewpoint of improving the dispersibility of the wax (W2) in the aqueous medium. It is more preferable to use the composite resin (Bw) having. The composite resin (Bw) is preferably an amorphous resin.
As the composite resin (Bw), the composite resin described in the above-mentioned amorphous resin (B) may be used as it is, but from the viewpoint of obtaining resin particles having a small particle size and the wax (W2) in an aqueous medium. From the viewpoint of improving dispersibility, the softening point of the composite resin (Bw) is preferably 70 ° C. or higher, more preferably 80 ° C. or higher, and preferably 140 ° C. or lower, more preferably 120 ° C. or lower, still more preferable. Is 100 ° C. or lower.

The preferred range of other resin properties of the composite resin (Bw), the preferred examples of the raw material monomers constituting the resin, and the like are the same as those shown in the amorphous composite resin of the amorphous resin (B) (however, however). It does not have to have a polymerizable group).
The dispersion liquid of the resin particles (F) can be obtained, for example, by the phase inversion emulsification method in the above-mentioned step (2A). The specific conditions and procedures for phase inversion emulsification, that is, the aqueous medium to be used, the components other than water that can constitute the aqueous medium, the amount of the aqueous medium, the addition temperature, and the addition rate are also applied to the items described in step (2A). Can be done.

The solid content concentration of the dispersion liquid of the resin particles (F) is preferably 5% by mass or more, more preferably 10% by mass or more, and preferably 50% by mass or less, more preferably 40% by mass or less.
The volume median particle diameter (D ₅₀ ) of the resin particles (F) is preferably 0.01 μm or more, more preferably 0.03 μm or more, and preferably 0. It is 30 μm or less, more preferably 0.15 μm or less.
The coefficient of variation (CV value) (%) of the particle size distribution of the resin particles (F) is preferably 5% or more, more preferably 10% or more, still more preferably 15% or more, and preferably 50% or less. , More preferably 40% or less, still more preferably 30% or less.

(Manufacturing of wax particle dispersion)
The wax particle dispersion liquid is obtained by mixing the wax (W2) and the dispersion liquid of the resin particles (F).
By preparing the wax particles using the wax (W2) and the resin particles (F), the wax particles are stabilized by the resin particles (F), and the wax can be put into the aqueous medium without using a surfactant. It becomes possible to disperse. It is considered that the dispersion liquid of the wax particles has a structure in which a large number of resin particles (F) are adsorbed around the wax particles. As a result, the wax particles are easily incorporated into the aggregate of the (binding) resin particles (P1) in the subsequent agglutination step.

The wax particle dispersion liquid is prepared by, for example, dispersing the wax (W2), the resin particle (F) dispersion liquid, and an aqueous medium, if necessary, at a temperature equal to or higher than the melting point of the wax (W2) using a disperser. can get. The disperser is preferably a homogenizer, a high-pressure disperser, an ultrasonic disperser, or the like, and more preferably an ultrasonic disperser, from the viewpoint of the stability of the wax particles. The dispersion time may be appropriately set depending on the disperser used. Examples of the ultrasonic disperser include an ultrasonic homogenizer. Examples of commercially available products include "US-150T", "US-300T", "US-600T" (manufactured by Nissei Tokyo Office Co., Ltd.), "SONIFIER (registered trademark) 4020-400", and "SONIFIER (registered trademark)". ) 4020-800 ”(manufactured by Branson).
Further, before using the disperser, the wax (W2), the resin particle (F) dispersion liquid, and if necessary, the aqueous medium may be pre-dispersed in advance with a mixer such as a homomixer or a ball mill. .. A preferred embodiment of the aqueous medium is the same as that used for obtaining the resin particles (P1).

From the viewpoint of improving the dispersion stability of the wax particles, the amount of the resin particles (F) with respect to 100 parts by mass of the wax (W2) is preferably 5 parts by mass or more, more preferably 10 parts by mass or more, still more preferably 20 parts by mass. Above, it is more preferably 30 parts by mass or more, and preferably 100 parts by mass or less, more preferably 70 parts by mass or less, still more preferably 60 parts by mass or less, still more preferably 50 parts by mass or less.
The wax particle dispersion may contain a surfactant, but it is preferable that the wax particle dispersion does not contain a surfactant from the viewpoint of further improving the stability over time of low temperature fixability. When a surfactant is contained, the amount of the surfactant in the wax particles is preferably 1 part by mass or less, more preferably 0.5 part by mass or less, still more preferably 0.1 part by mass with respect to 100 parts by mass of the wax. It is less than or equal to parts, and is preferably 0.01 parts by mass or more, more preferably 0.02 parts by mass or more, and further preferably 0.05 parts by mass or more.

It is preferable to add the dispersion liquid of the wax (W2) and the resin particles (F) to the aqueous medium and disperse the wax (W2) while heating at a temperature equal to or higher than the melting point of the wax (W2).
The heating temperature at the time of dispersion is preferably equal to or higher than the melting point of the wax (W2) and 80 ° C. or higher, more preferably 85 ° C. or higher, still more preferably 90 ° C. or higher, from the viewpoint of improving the productivity of the wax particle dispersion liquid. Then, it is preferably less than the softening point of the resin contained in the resin particles (F) and 100 ° C. or lower, more preferably 98 ° C. or lower, still more preferably 95 ° C. or lower.

The solid content concentration of the wax (W2) particle dispersion is preferably 5% by mass or more, more preferably 10% by mass or more, still more preferably 15% by mass or more, from the viewpoint of improving the dispersion stability of the wax particles. Then, it is preferably 40% 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 (W2) particles is preferably 0.05 μm or more, more preferably 0.20 μm or more, still more preferably 0, from the viewpoint of obtaining uniform agglutinated particles in the subsequent agglutination step. It is .40 μm or more, and preferably 1.00 μm or less, more preferably 0.80 μm or less, still more preferably 0.60 μm or less.
The coefficient of variation (CV value) (%) of the particle size distribution of the wax (W2) particles is preferably 5% or more, more preferably 10% or more, still more preferably 15% or more, and preferably 50% or less. , More preferably 40% or less, still more preferably 30% or less.

Wax (W2) ratio of the volume median particle size of a volume-median particle size of the particles _{(D 50)} and the resin particles _{(F) (D 50)} (Wax (W2) a volume-median particle size of the particles _(D 50) / The volume median particle diameter (D ₅₀ )) of the resin particles (F) is preferably 2.0 or more, more preferably 3.0 or more, and preferably 3.0 or more, from the viewpoint of improving the dispersion stability of the wax particles. Is 50 or less, more preferably 30 or less, still more preferably 10 or less.

≪Colorant≫
When the colorant is mixed in the mixed dispersion containing the resin particles (P1), it is preferable to use a dispersion of the colorant particles in which the colorant is dispersed in an aqueous medium.
Pigments and dyes are used as the colorant, and pigments are preferable from the viewpoint of improving the image density of the toner.
Examples of the pigment include carbon black, inorganic composite oxide, benzidine yellow, brilliantamine 3B, brilliantamine 6B, Bengal, aniline blue, ultramarine blue, copper phthalocyanine, and phthalocyanine green. Of these, copper phthalocyanine is preferable.

Examples of the dye include acridine-based, azo-based, benzoquinone-based, azine-based, anthraquinone-based, indigo-based, phthalocyanine-based, and aniline black-based dyes.
The colorants can be used alone or in combination of two or more.
From the viewpoint of improving the image density of the printed matter, the amount of the colorant used is preferably 2 parts by mass or more, more preferably 5 parts by mass or more, and further preferably 7 parts by mass with respect to 100 parts by mass of the total amount of the resin in the toner. It is more than parts, and preferably 30 parts by mass or less, more preferably 20 parts by mass or less, still more preferably 15 parts by mass or less.

The colorant dispersion is preferably obtained by dispersing the colorant and an aqueous medium using a disperser such as a homogenizer or an ultrasonic disperser.
Dispersion of the colorant in an aqueous medium is preferably performed in the presence of a surfactant from the viewpoint of improving the dispersion stability of the colorant.
Examples of the surfactant used in the production of the colorant dispersion liquid include a nonionic surfactant, an anionic surfactant, and a cationic surfactant, from the viewpoint of improving the dispersion stability of the colorant particles. , Preferably an anionic surfactant. Examples of the anionic surfactant include sodium dodecylbenzenesulfonate, sodium dodecylsulfate, sodium lauryl ether sulfate, and dipotassium alkenylsuccinate, and sodium dodecylbenzenesulfonate is preferable.

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

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

_{The volume median particle diameter (D 50} ) of the colorant particles in the colorant dispersion is preferably 0.05 μm or more, more preferably 0.08 μm or more, still more preferably 0.10 μm or more, and preferably 0.10 μm or more. It is 0.30 μm or less, more preferably 0.20 μm or less, still more preferably 0.15 μm or less.

The content of the resin particles (P1) in the mixed dispersion is preferably 5% by mass or more, more preferably 5% by mass or more, from the viewpoint of further improving low-temperature fixability, suppression of deterioration of low-temperature fixability over time, and heat-resistant storage stability. It is 10% by mass or more, more preferably 12% by mass or more, and preferably 40% by mass or less, more preferably 30% by mass or less, still more preferably 20% by mass or less.
The mass ratio of wax (W2) particles to resin particles (P1) in the mixed dispersion [wax (W2) particles / resin particles (P1)] has low-temperature fixability, suppression of deterioration of low-temperature fixability over time, and heat resistance. From the viewpoint of further improving the storage stability, it is preferably 0.05 or more, more preferably 0.1 or more, and preferably 1.0 or less, more preferably 0.5 or less, still more preferably 0.2 or less. Is.
The mixing temperature is preferably 0 ° C. or higher, more preferably 10 ° C. or higher, still more preferably 20 ° C. or higher, and preferably 40 ° C. or lower, from the viewpoint of controlling aggregation to obtain agglomerated particles having a desired particle size. , More preferably 30 ° C. or lower.

When preparing the mixed dispersion, even if it is performed in the presence of a surfactant from the viewpoint of improving the dispersion stability of arbitrary components such as resin particles (P1) and wax (W2) particles added as needed. Good. Examples of the surfactant include anionic surfactants such as alkylbenzene sulfonates and alkyl ether sulfates; and nonionic surfactants such as polyoxyethylene alkyl ethers and polyoxyethylene alkenyl ethers.
When a surfactant is used, the amount used is preferably 0.1 part by mass or more, more preferably 0.5 part by mass or more, and preferably 0.5 part by mass or more, based on 100 parts by mass of the resin particles (P1). It is 10 parts by mass or less, more preferably 5 parts by mass or less, still more preferably 3 parts by mass or less.

≪Coagulant≫
Next, the particles in the mixed dispersion can be agglomerated to preferably obtain the dispersion of the agglomerated particles (1). It is preferable to add a flocculant for efficient agglomeration.

Examples of the flocculant include a cationic surfactant for a quaternary salt, an organic flocculant such as polyethyleneimine; and an inorganic flocculant such as an inorganic metal salt, an inorganic ammonium salt, and a divalent or higher metal complex. .. From the viewpoint of improving the cohesiveness and obtaining uniform agglomerated particles, an inorganic flocculant having a valence of 1 or more and 5 or less is preferable, an inorganic metal salt having a valence or more and a divalent value or less, an inorganic ammonium salt is more preferable, and an inorganic ammonium salt is preferable. More 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, and ammonium nitrate.
Among these, ammonium sulfate is more preferable as the flocculant.
The coagulant is preferably added dropwise as an aqueous coagulant solution of 2% by mass or more and 40% by mass or less from the viewpoint of controlling agglomeration to obtain agglomerated particles having a desired particle size. The aqueous solution of the flocculant preferably has a pH of 7.0 or more and 9.0 or less.

Using a coagulant, for example, a coagulant of 5 parts by mass or more and 50 parts by mass or less is added to a mixed dispersion containing resin particles (P1) of 0 ° C. or higher and 40 ° C. or lower with respect to 100 parts by mass of the total amount of resin. The resin particles (P1) are agglomerated in an aqueous medium to obtain agglomerated particles (1).
Further, from the viewpoint of promoting agglutination and obtaining agglomerated particles having a desired particle size and particle size distribution, it is preferable to raise the temperature of the dispersion liquid after adding the agglutinating agent. The holding temperature is preferably 45 ° C. or higher, more preferably 50 ° C. or higher, further preferably 55 ° C. or higher, and preferably 70 ° C. or lower, more preferably 65 ° C. or lower, still more preferably 60 ° C. or lower. is there.

The volume median particle diameter (D ₅₀ ) of the agglomerated particles (1) 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. It is preferably 6 μm or less. The volume median particle size of the agglomerated particles is determined by the method described in Examples described later.

<Process (3A-2)>
In the step (3A-2), the resin particles (P2) containing the resin (Bs) are added to the agglomerated particles (1) obtained in the step (3A-1), and the resin particles are added to the agglomerated particles (1). This is a step of obtaining agglomerated particles (2) formed by adhering (P2).

[Aggregated particles (2)]
By passing through the agglomerated particles (2), a toner particle having a core-shell structure containing the component of the agglomerated particles (1) in the core portion and the resin (Bs) in the shell portion can be obtained.

≪Resin particles (P2) ≫
The resin particles (P2) are preferably obtained as a dispersion liquid of the resin particles (P2) by dispersing a resin component containing polyester as the resin (Bs) in an aqueous medium.

(Resin (Bs))
As the resin (Bs), polyester which is a polycondensate of an alcohol component (bs-al) and a carboxylic acid component (bs-ac) is preferable. The resin (Bs) is preferably an amorphous resin.
Examples of the alcohol component (bs-al) and the carboxylic acid component (bs-ac) are common to the amorphous polyester of the amorphous resin (B), and thus the description thereof will be omitted, but as the amorphous resin (Bs). Prefers the following aspects.

The alcohol component (bs-al) preferably contains an alkylene oxide adduct of bisphenol A, and more preferably an ethylene adduct adduct of bisphenol A.

The softening point of the resin (Bs) is preferably 90 ° C. or higher, more preferably 100 ° C. or higher, still more preferably 110 ° C. or higher from the viewpoint of further improving heat-resistant storage stability, and from the viewpoint of low-temperature fixability. It is preferably 160 ° C. or lower, more preferably 140 ° C. or lower, and even more preferably 130 ° C. or lower.

The glass transition temperature of the resin (Bs) is preferably 40 ° C. or higher, more preferably 50 ° C. or higher, further preferably 60 ° C. or higher, and from the viewpoint of low-temperature fixability, from the viewpoint of further improving heat-resistant storage stability. It is preferably 90 ° C. or lower, more preferably 80 ° C. or lower, and even more preferably 70 ° C. or lower.

The acid value of the resin (Bs) is preferably 5 mgKOH / g or more, more preferably 10 mgKOH / g or more, still more preferably 15 mgKOH / g or more, and more preferably 15 mgKOH / g or more, from the viewpoint of further improving heat storage stability and low temperature fixability. It is preferably 35 mgKOH / g or less, more preferably 30 mgKOH / g or less, still more preferably 25 mgKOH / g or less.

As for the method of obtaining the dispersion liquid, as in the case of the resin particles (P1), a method of gradually adding an aqueous medium to an organic solvent solution of the resin or the like and emulsifying the phase inversion is preferable.
As a phase inversion emulsification method, as in the case of resin particles (P1), a method of adding an aqueous medium to a solution obtained by dissolving the resin and other optional components in an organic solvent to invert phase emulsification preferable. Preferred embodiments of the aqueous medium and the organic solvent that can be used are also the same as those of the aqueous medium and the organic solvent used in the method for producing the resin particles (P1). Further, the mass ratio of the aqueous medium to the organic solvent, the temperature at which the aqueous medium is added, and the addition rate of the aqueous medium are the same as the method for producing the resin particles (P1).

In the step (3A-2), for example, the dispersion liquid of the resin particles (P2) is added to the dispersion liquid of the agglomerated particles (1) at a temperature of 40 ° C. or higher and 80 ° C. or lower with respect to 100 parts by mass of the agglomerated particles (1). By adding the resin particles (P2) at a rate of 0.03 parts by mass / min or more and 1.0 parts by mass / min or less, the resin particles (P2) are further attached to the agglomerated particles (1), and the agglomerated particles are further attached. It is preferable to obtain the dispersion liquid of (2).
An aqueous medium may be added to the dispersion of the agglomerated particles (1) to dilute the dispersion of the agglomerated particles (1) before adding the dispersion of the resin particles (P2) to the dispersion of the agglomerated particles (1). Further, in order to efficiently attach the resin particles (P2) to the agglomerated particles (1), the aggregating agent may be used in the step (3A-2).

The amount of the resin particles (P2) added is preferably 0 from the viewpoint that the mass ratio [(P2) / (P1)] of the resin particles (P2) and the resin particles (P1) further improves the heat-resistant storage stability. 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. It is an amount that becomes 0.2 or less.

The volume median particle diameter (D ₅₀ ) of the agglomerated particles (2) is preferably 2 μm or more, more preferably 3 μm or more, still more preferably 4 μm or more, and more preferably 4 μm or more, from the viewpoint of obtaining a toner for obtaining a high-quality image. It is preferably 10 μm or less, more preferably 9 μm or less, and further preferably 8 μm or less.

In the step (3A), the agglomeration may be stopped when the agglomerated particles have grown to an appropriate particle size as a toner.
Examples of the method for stopping the aggregation include a method of cooling the dispersion, a method of adding an aggregation inhibitor, a method of diluting the dispersion, and the like. From the viewpoint of surely preventing unnecessary aggregation, a method of adding an aggregation terminator to stop aggregation is preferable.

≪Coagulation terminator≫
As the aggregation terminator, a surfactant is preferable, and an anionic surfactant is more preferable. Examples of the anionic surfactant include alkylbenzene sulfonate, alkyl sulfate, alkyl ether sulfate, polyoxyalkylene alkyl ether sulfate and the like.

The aggregation terminator can be used alone or in combination of two or more.
The amount of the aggregation terminator added is preferably 0.1 part by mass or more, more preferably 1 part by mass or more, based on 100 parts by mass of the total amount of the resin in the toner, from the viewpoint of surely preventing unnecessary aggregation. It is more preferably 2 parts by mass or more, and from the viewpoint of reducing the residue on the toner, it is preferably 15 parts by mass or less, more preferably 10 parts by mass or less, still more preferably 7 parts by mass or less. The aggregation terminator may be added in an aqueous solution.

The temperature at which the aggregation terminator is added is preferably the same as the temperature at which the dispersion liquid of the agglomerated particles is held from the viewpoint of improving the productivity of the toner. The temperature is preferably 40 ° C. or higher, more preferably 45 ° C. or higher, still more preferably 50 ° C. or higher, and preferably 80 ° C. or lower, more preferably 70 ° C. or lower, still more preferably 65 ° C. or lower.
Further, from the viewpoint of stabilizing the agglomerated particles and preventing the once agglomerated particles from being dispersed before fusion, it is preferable to add an acid at the same time as stopping the agglomeration to make the dispersion liquid of the agglomerated particles neutral to acidic. ..
The acid to be added is not limited, and examples thereof include sulfuric acid, hydrochloric acid, nitric acid, phosphoric acid, and acetic acid. However, from the viewpoint of rapid pH change with respect to addition, hydrochloric acid, hydrochloric acid, nitric acid, and acetic acid are preferable. At least one selected from, more preferably at least one selected from hydrochloric acid, sulfuric acid, and nitric acid, still more preferably sulfuric acid.
The acid is preferably added in the form of an aqueous solution. It may also be added together with an aggregation terminator.

<Process (4A)>
The step (4A) is a step of fusing the agglomerated particles obtained in the step (3A).
Here, the "aggregated particles obtained in the step (3A)" refer to the agglomerated particles (1) obtained in the step (3A-1) when the step (3A-2) is not performed. When the step (3A-2) is carried out, it means the agglomerated particles (2) obtained in the step (3A-2).
In this step, among the agglomerated particles obtained in step (3A), the particles that were mainly physically attached to each other are fused and integrated to form fused particles.
When the agglomerated particles (2) are fused, toner particles having a core-shell structure can be obtained.

In this step, from the viewpoint of improving the fusion property of the agglomerated particles, it is preferable to keep the temperature at a temperature equal to or higher than 10 ° C. lower than the melting point of the crystalline resin (A). The holding temperature is more preferably 5 ° C. lower than the melting point of the crystalline resin (A) and more preferably equal to or higher than the melting point of the crystalline resin (A). The holding time is not particularly limited, and the circularity of the fused particles may be monitored, and the fusion may be terminated when the fusion particles reach an appropriate range.

The volume median particle diameter (D ₅₀ ) of the fused particles is preferably 2 μm or more, more preferably 3 μm or more, still more preferably 4 μm or more, and preferably 10 μm or less, more preferably 8 μm or less, still more preferably. It is 6 μm or less.
The circularity of the fused particles is preferably 0.955 or more, more preferably 0.960 or more, still more preferably 0.965 or more, and preferably 0.990 or less, more preferably 0.985 or less. More preferably, it is 0.980 or less.

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

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

(B) Melt-kneading method The method for producing a toner of the present invention preferably has the following steps (1) and steps (2B) to (3B).
Step (1): A resin composition (C) containing a multimer of a crystalline resin (A) having at least a part of an addition-polymerizable group and an amorphous resin (B) having at least a part of an addition-polymerizable group. Step (2B): A step of melt-kneading the mixture containing the resin composition (C) obtained in the step (1) Step (3B): The melt-kneaded product obtained in the step (2B) is crushed. , Classification process

The step (1) is as described in the method for producing the resin composition (C) described above.

<Step 2B>
Here, in addition to the resin composition (C), a crystalline resin or an amorphous resin may be further added. The types of the crystalline resin and the amorphous resin, and the blending ratios of the crystalline resin, the amorphous resin, and the resin composition (C) are as described above.
The mixture of step (2B) preferably further comprises wax (W2).
Examples of the wax (W2) used in the step (2B) include the same preferred examples as the wax (W2) described above.
In the step of melt-kneading, it is preferable to further melt-knead the colorant, and it is preferable to melt-knead the other additives such as wax and charge control agent together.
The melt kneading can be performed by using a known kneader such as a closed kneader, a single-screw extruder or a twin-screw extruder, or an open roll type kneader.

It is preferable that the toner raw materials such as the resin, the above-mentioned colorant, and wax are mixed in advance with a mixer such as a Henschel mixer or a ball mill, and then supplied to the kneader.

When a twin-screw extruder is used for melt-kneading, the set temperature (barrel set temperature) of the twin-screw extruder is preferably 50 ° C. or higher, more preferably 60 ° C. or higher, and preferably 160 ° C. or lower, more preferably. Is 140 ° C. or lower. The rotation speed is the same direction from the viewpoint of improving the dispersibility of additives such as colorants, charge control agents, and waxes in the toner, reducing the mechanical force during melt-kneading, and suppressing heat generation. In the case of a twin-screw extruder, it is preferably 100 r / min or more, more preferably 130 r / min or more, more preferably 150 r / min or more, and preferably 300 r / min or less, more preferably 280 r / min or less, and more. It is preferably 250 r / min or less.
The melt-kneaded product obtained in the above step is cooled to a extent that it can be pulverized, and then subjected to the subsequent step.

<Process 3B>
The pulverization may be performed in multiple stages. For example, the resin kneaded product obtained by curing the melt-kneaded product may be roughly pulverized to about 1 mm or more and 5 mm or less, and then finely pulverized to a desired particle size. The crusher used in the crushing step is not particularly limited, and examples of the crusher preferably used for coarse crushing include a hammer mill, an atomizer, and a rotoplex. Further, examples of the pulverizer preferably used for fine pulverization include a fluidized bed type jet mill, a collision plate type jet mill, and a rotary mechanical type mill. From the viewpoint of pulverization efficiency, it is preferable to use a fluidized bed type jet mill and a collision plate type jet mill, and it is more preferable to use a fluidized bed type jet mill.

Examples of the classifier used for classification include a rotor type classifier, an air flow type classifier, an inertial type classifier, and a sieve type classifier. In the classification step, the pulverized product removed due to insufficient pulverization may be subjected to the pulverization step again, or the pulverization step and the classification step may be repeated as necessary.
Toner particles can be obtained by this step.

<Toner particles>
The toner particles obtained by the above method can be used as they are as a toner for developing an electrostatic charge image, but it is preferable to use a toner whose surface is treated as described later.

The volume median particle diameter (D ₅₀ ) of the toner particles is preferably 2 μm or more, more preferably 3 μm or more, still more preferably 4 μm or more, and preferably 10 μm or less, from the viewpoint of obtaining a high-quality image. It is preferably 8 μm or less, more preferably 6 μm or less.
The CV value of the toner particles is preferably 12% or more, more preferably 14% or more, further preferably 16% or more, and preferably 30% or less, more preferably 26, from the viewpoint of obtaining a high-quality image. % Or less.
The circularity of the toner particles is preferably 0.955 or more, more preferably 0.960 or more, still more preferably 0.965 or more, and preferably 0.990 or less, from the viewpoint of obtaining a high-quality image. It is more preferably 0.985 or less, still more preferably 0.980 or less.

The toner is preferably treated 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 fine particles, titanium oxide fine particles, alumina fine particles, cerium oxide fine particles, inorganic fine particles such as carbon black, and polymer fine particles such as polycarbonate, polymethyl methacrylate, and silicone resin. Among these, hydrophobic silica is preferable.
When an external additive is used, the amount of the external additive added is preferably 1 part by mass or more, more preferably 2 parts by mass or more, still more preferably 3 parts by mass or more, and more preferably 3 parts by mass or more, based on 100 parts by mass of the toner particles. It is preferably 5 parts by mass or less, more preferably 4.5 parts by mass or less, and further preferably 4 parts by mass or less.

Toner is used for developing a latent image formed by an electrophotographic method, an electrostatic recording method, an electrostatic printing method, or the like. The toner can be used as a one-component developer or mixed with a carrier as a two-component developer.

Each property value was measured and evaluated by the following method.

[Hydroxy group value and acid value of resin]
The hydroxyl value and acid value of the resin were measured according to the neutralization titration method described in JIS K 0070-1992. However, the measurement solvent was chloroform.

[Resin, softening point of resin composition, crystallinity index, melting point and glass transition temperature]
(1) Softening point Using a flow tester "CFT-500D" (manufactured by Shimadzu Corporation), a 1 g sample is heated at a heating rate of 6 ° C./min while a load of 1.96 MPa is applied by a plunger to give a diameter of 1.96 MPa. Extruded from a 1 mm, 1 mm long nozzle. The amount of plunger drop of the flow tester was plotted against the temperature, and the temperature at which half of the sample flowed out was used as the softening point.
(2) Crystallinity index Using a differential scanning calorimeter "Q100" (manufactured by TA Instruments Japan Co., Ltd.), weigh 0.02 g of a sample into an aluminum pan, and cool from room temperature (25 ° C) to a temperature lowering rate of 10 ° C / It was cooled to 0 ° C. in min. Then, the sample was allowed to stand still for 1 minute, and then the temperature was raised to 180 ° C. at a heating rate of 10 ° C./min to measure the amount of heat. Of the observed endothermic peaks, the temperature of the peak with the largest endothermic area is set as the maximum endothermic temperature (1), and is determined by (softening point (° C.)) / (maximum endothermic peak temperature (1) (° C.)). The crystallinity index was calculated.
(3) Melting point and glass transition temperature Using a differential scanning calorimeter "Q100" (manufactured by TA Instruments Japan Co., Ltd.), 0.02 g of the sample is weighed in an aluminum pan, heated to 200 ° C, and the temperature thereof. The temperature was lowered to 0 ° C. at a temperature lowering rate of 10 ° C./min. Next, the temperature of the sample was raised at a heating rate of 10 ° C./min, and the amount of heat was measured. Among the observed endothermic peaks, the temperature of the peak having the largest peak area was defined as the maximum endothermic peak temperature (2). In the case of crystalline resin, the peak temperature was taken as the melting point.
In the case of amorphous resin, when a peak is observed, the temperature of the peak is observed, and when a step is observed without a peak, a tangent line indicating the maximum inclination of the curve of the step portion and the step The temperature at the intersection with the extension line of the baseline on the low temperature side was defined as the glass transition temperature.

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

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

[Wax number average molecular weight (Mn)]
The number average molecular weight (Mn) was measured by the gel permeation chromatography (GPC) method shown below.
(1) Preparation of sample solution The sample is dissolved in chloroform at 25 ° C. so that the concentration becomes 0.5 g / 100 mL, and then this solution is dissolved in a fluororesin filter "DISMIC 25JP" (manufactured by ADVANTEC) having a pore size of 0.2 μm. ) Was used to remove insoluble components to prepare a sample solution.
(2) Measurement Using the following measuring device and analytical column, chloroform was flowed as an eluent at a flow rate of 1 mL / min, the column was stabilized in a constant temperature bath at 40 ° C., and 100 μL of the sample solution was injected therein. The molecular weight was measured. Molecular weight of the sample (number average molecular weight Mn) of several kinds of monodisperse polystyrene "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 × 10 ⁴ ) ”,“ F-4 (3.97 × 10 ⁴ ) ”,“ F-10 (9.64 × 10 ⁴ ) ”,“ F-20 (1.90 × 10 ⁵ ) ” , ^{"F-40 (4.27 × 10 5} ) ", ^{"F-80 (7.06 × 10 5} ) ", ^{"F-128 (1.09 × 10 6} ) " (both manufactured by Tosoh Corporation) Was used as a standard sample and calculated based on a calibration line prepared in advance.
-Measuring device: "HLC-8220GPC" (manufactured by Tosoh Corporation)
-Analytical columns: "GMHXL" and "G3000HXL" (manufactured by Tosoh Corporation)

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

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

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

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

[Volume medium particle size (D50) and CV value of toner particles]
The volume median particle diameter (D ₅₀ ) of the toner particles was measured as follows.
Measuring device, aperture diameter, analysis software, the electrolytic solution used was the same as that used in the measurement of the volume-median particle size of the aggregated particles described above (D _50).
Dispersion: Polyoxyethylene lauryl ether "Emargen (registered trademark) 109P" (manufactured by Kao Corporation, HLB (Hydrophile-Lipopfile Balance) = 13.6) is dissolved in the electrolytic solution to prepare a dispersion having a concentration of 5% by mass. Obtained.
Dispersion conditions: 10 mg of a sample to be measured of dried toner particles is added to 5 mL of the dispersion liquid, dispersed for 1 minute with an ultrasonic disperser, then 25 mL of an electrolytic solution is added, and further, with an ultrasonic disperser. A sample dispersion was prepared by dispersing for 1 minute.
-Measurement conditions: By adding the sample dispersion to 100 mL of the electrolytic solution, the particle size of 30,000 particles is adjusted to a concentration that can be measured in 20 seconds, and then 30,000 particles are measured and the particle size is measured. The volume median particle size (D ₅₀ ) and the volume average particle size were determined from the distribution.
The CV value (%) was calculated according to the following formula.
CV value (%) = (standard deviation of particle size distribution / volume average particle size) x 100

[Low-temperature fixability and low-temperature fixability of toner over time]
<Low temperature fixability>
The low-temperature fixability was evaluated by the method of condition 1 for the toner produced by the coagulation fusion method, and by the method of condition 2 for the toner produced by the melt-kneading method.
(Condition 1)
Using a commercially available printer "Microline (registered trademark) 5400" (manufactured by Oki Data Corporation) on high-quality paper "J paper A4 size" (manufactured by Fuji Xerox Co., Ltd.), the amount of toner adhered to the paper is 1.45 to 1. A solid image of .55 mg / cm ² was output with a length of 50 mm without fixing, leaving a margin of 5 mm from the upper end of the A4 paper.
Next, the same printer in which the fixing device was modified to have a variable temperature was prepared, the temperature of the fixing device was set to 90 ° C., and toner was fixed at a speed of 1.2 seconds per sheet in the A4 vertical direction to obtain a printed matter.
In the same manner, the temperature of the fuser was raised by 1 ° C. to fix the toner, and a printed matter was obtained.
From the top margin of the printed matter to the solid image, lightly paste the mending tape "Scotch (registered trademark) Mending Tape 810" (manufactured by Sumitomo 3M Ltd., width 18 mm) cut to a length of 50 mm. After that, a weight of 500 g was placed and pressed back and forth at a speed of 10 mm / s. Then, the attached tape was peeled off from the lower end side at a peeling angle of 180 ° and a speed of 10 mm / s to obtain a printed matter after the tape was peeled off. 30 sheets of high-quality paper "Excellent White Paper A4 size" (manufactured by Oki Data Co., Ltd.) are laid under the printed matter before and after the tape is applied, and the reflected image density of the fixed image part before and after the tape is applied to each printed matter is measured. , Colorimeter "SpectroEye" (manufactured by GretagMacbeth, light emission conditions; standard light source D50, observation field of view 2 °, density standard DINNB, absolute white standard), and the fixation rate from each reflected image density according to the following formula. Was calculated.
Fixing rate (%) = (Reflected image density after tape peeling / Reflected image density before tape application) x 100
The lowest temperature at which the fixing rate was 90% or more was defined as the lowest fixing temperature (T1). The lower the minimum fixing temperature, the better the low temperature fixing property.

(Condition 2)
The fixing machine of the copying machine "AR-505" (manufactured by Sharp Corporation) is equipped with toner on an improved device so that it can be fixed outside the device, and the high-quality paper "CopyBondo SF-70NA" (manufactured by Sharp Corporation) , 75 g / m ² ), a solid image with an adhesion amount of 1.45 to 1.55 mg / cm ² was output with a length of 50 mm without fixing, leaving a margin of 5 mm from the top edge of A4 paper. ..
Using a fixing machine (fixing speed 390 mm / sec) adjusted so that the total fixing pressure is 40 kgf, the temperature of the fixing roller is gradually increased by 1 ° C. from 100 ° C. to 240 ° C., and the unfixed state is obtained at each temperature. A fixing test was conducted on the printed matter.
"UNICEF cellophane" (Mitsubishi Pencil Co., Ltd., width: 18 mm, JIS Z1522) was attached to the fixed image, passed through a fixing roller set at 30 ° C., and then the tape was peeled off. The optical reflection density before and after the tape was applied was measured using a reflection densitometer "RD-915" (manufactured by GretagMacbeth), and the ratio of the two (after peeling / before applying x 100) was initially 90%. The temperature of the fixing roller that exceeds the temperature is defined as the minimum fixing temperature (T1). The lower the minimum fixing temperature, the better the low temperature fixing property.

<Castability over time for low temperature fixing>
After holding the toner in a constant temperature bath at a temperature of 45 ° C. for 200 hours, the minimum fixing temperature (T2) was measured by the same method as in the evaluation of low temperature fixability. Next, the difference between the minimum fixing temperature (T2) and the minimum fixing temperature (T1) was calculated, and the temporal stability of the low temperature fixing property was evaluated. The smaller the absolute value of the numerical value, the better the low temperature fixability over time.

[Heat-resistant storage of toner]
20 g of toner was placed in a wide-mouthed polybin having an internal volume of 100 mL, sealed, and allowed to stand for 2 hours in an environment of an arbitrary temperature. Then, it was allowed to stand for 12 hours or more while being sealed at a temperature of 25 ° C. and cooled. Next, set a flue with a mesh opening of 250 μm on the shaking table of "Powder Tester (registered trademark)" (manufactured by Hosokawa Micron Co., Ltd.), place 20 g of the toner on it, and vibrate for 30 seconds to leave the toner on the flue. The maximum value of the arbitrary temperature of the non-aggregated product (non-aggregated product) was set as the maximum temperature at which it did not aggregate, and was used as an index of heat-resistant storage stability. The larger the value, the better the heat-resistant storage stability of the toner.

[Manufacturing of resin]
Manufacturing example A1
(Manufacturing of crystalline resin A-1)
Nitrogen was substituted inside a four-necked flask with an internal volume of 10 L equipped with a nitrogen introduction tube, a dehydration tube, a stirrer, and a thermocouple, and 1,10-decanediol 3200 g, sebacic acid 3744 g, acrylic acid 66 g, and 4- 3.5 g of tert-butylcatechol was added. The temperature was raised to 135 ° C. with stirring, held at 135 ° C. for 1 hour, and then raised from 135 ° C. to 200 ° C. at 10 ° C./hr. Then, 14 g of di (2-ethylhexanoic acid) tin (II) was added and held at 200 ° C. for 1 hour, then the pressure in the flask was lowered and held at 8.3 kPa for 1 hour to obtain crystalline resin A. I got -1. The physical characteristics are shown in Table 1.

Manufacturing examples A2, A3
(Manufacture of crystalline resins A-2 and A-3)
Crystalline resins A-2 and A-3 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 characteristics are shown in Table 1.

Manufacturing example A4
(Manufacturing of crystalline resin A-4)
The inside of a four-necked flask with an internal volume of 10 L equipped with a nitrogen introduction tube, a dehydration tube, a stirrer, and a thermocouple was replaced with nitrogen, and 3188 g of 1,10-decanediol and 3812 g of sebacic acid were added. The temperature was raised to 135 ° C. with stirring, held at 135 ° C. for 2 hours, and then raised from 135 ° C. to 200 ° C. at 10 ° C./hr. Then, 14 g of di (2-ethylhexanoic acid) tin (II) was added and held at 200 ° C. for 1 hour, then the pressure in the flask was lowered and held at 8.3 kPa for 1 hour to obtain crystalline resin A. I got -4. The physical characteristics are shown in Table 1.

Production example B1
(Manufacturing of amorphous resin B-1)
The inside of a four-necked flask with an internal volume of 10 L equipped with a nitrogen introduction tube, a dehydration tube, a stirrer, and a thermocouple was replaced with nitrogen, and 3287 g of a polyoxypropylene (2.2) adduct of bisphenol A, 1107 g of terephthalic acid, Add 385 g of Paracol 6490 (hydrocarbon wax manufactured by Nippon Seikan Co., Ltd.), 25 g of di (2-ethylhexanoic acid) tin (II), and 2.5 g of 3,4,5-trihydroxybenzoic acid under a nitrogen atmosphere. The temperature was raised to 235 ° C. while stirring, and the temperature was maintained at 235 ° C. for 5 hours, then the pressure inside the flask was lowered, and the temperature was maintained at 8 kPa for 1 hour. Then, after returning to atmospheric pressure, the mixture was cooled to 160 ° C. and kept at 160 ° C., and a mixture of 2201 g of styrene, 550 g of stearyl methacrylate, 110 g of acrylic acid, and 330 g of dibutyl peroxide was added dropwise over 1 hour. Then, the temperature was maintained at 160 ° C. for 30 minutes, the temperature was raised to 200 ° C., the pressure in the flask was further reduced, and the temperature was maintained at 8 kPa for 1 hour. Then, after returning to atmospheric pressure, the mixture was cooled to 190 ° C., 285 g of sebacic acid, 180 g of trimellitic anhydride, 32 g of acrylic acid, and 2.5 g of 4-tert-butylcatechol were added, and the temperature was 10 ° C./hr to 210 ° C. Then, the reaction was carried out at 4 kPa to a desired softening point to obtain an amorphous resin B-1. The physical characteristics are shown in Table 2.

Production example B2
(Manufacturing of amorphous resin B-2)
Amorphous 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 characteristics are shown in Table 2.

Production example B3
(Manufacturing of amorphous resin B-3)
The inside of a four-necked flask with an internal volume of 10 L equipped with a nitrogen introduction tube, a dehydration tube, a stirrer, and a thermocouple was replaced with nitrogen, and 4711 g of a polyoxypropylene (2.2) adduct of bisphenol A, 1519 g of terephthalic acid, 35 g of di (2-ethylhexanoic acid) tin (II) and 3.5 g of 3,4,5-trihydroxybenzoic acid were added, and the temperature was raised to 235 ° C. with stirring under a nitrogen atmosphere, and 5 at 235 ° C. After holding for a time, the pressure in the flask was lowered and held at 8 kPa for 1 hour. Then, after returning to atmospheric pressure, the mixture was cooled to 190 ° C., 462 g of sebacic acid, 258 g of trimellitic anhydride, 48 g of acrylic acid, and 3.5 g of 4-tert-butylcatechol were added, and the temperature was 10 ° C./hr to 210 ° C. Then, the reaction was carried out at 4 kPa to a desired softening point to obtain an amorphous resin B-3. The physical characteristics are shown in Table 2.

Production example B4
(Manufacturing of amorphous resin B-4)
Amorphous resin B-4 was obtained in the same manner as in Production Example B3 except that the raw material composition was changed as shown in Table 2. The physical characteristics are shown in Table 2.

Production example B5
(Manufacturing of amorphous resin B-5)
The inside of a four-necked flask with an internal volume of 10 L equipped with a nitrogen introduction tube, a dehydration tube, a stirrer, and a thermocouple was replaced with nitrogen, and 1,269 g of 1,2-propanediol, 3316 g of terephthalic acid, and di (2-ethylhexane) were replaced. 35 g of (acid) tin (II) was added, the temperature was raised to 185 ° C. with stirring under a nitrogen atmosphere, the temperature was maintained at 185 ° C. for 5 hours, and then the temperature was raised to 220 ° C. at 5 ° C./hr. It was confirmed that the reaction rate reached 95% or more at 220 ° C., the pressure in the flask was lowered, and the temperature was maintained at 8 kPa for 1 hour. Then, after returning to atmospheric pressure, the mixture was cooled to 190 ° C., 865 g of sebacic acid, 548 g of trimellitic anhydride, 103 g of acrylic acid, and 3.5 g of 4-tert-butylcatechol were added, and the temperature was 10 ° C./hr to 210 ° C. Then, the reaction was carried out at 4 kPa to a desired softening point to obtain an amorphous resin B-5. The physical characteristics are shown in Table 2. The reaction rate means a value of the amount of produced reaction water / the theoretical amount of produced water × 100.

Production example B6
(Manufacturing of amorphous resin B-6)
The inside of a four-necked flask with an internal volume of 10 L equipped with a nitrogen introduction tube, a dehydration tube, a stirrer, and a thermocouple was replaced with nitrogen, and 3356 g of a polyoxypropylene (2.2) adduct of bisphenol A, 955 g of terephthalic acid, Add 385 g of Paracol 6490 (hydrocarbon wax manufactured by Nippon Seikan Co., Ltd.), 25 g of di (2-ethylhexanoic acid) tin (II), and 2.5 g of 3,4,5-trihydroxybenzoic acid under a nitrogen atmosphere. The temperature was raised to 235 ° C. while stirring, and the temperature was maintained at 235 ° C. for 5 hours, then the pressure inside the flask was lowered, and the temperature was maintained at 8 kPa for 1 hour. Then, after returning to atmospheric pressure, the mixture was cooled to 160 ° C. and kept at 160 ° C., and a mixture of 2198 g of styrene, 550 g of stearyl methacrylate, 110 g of acrylic acid, and 330 g of dibutyl peroxide was added dropwise over 1 hour. Then, the temperature was maintained at 160 ° C. for 30 minutes, the temperature was raised to 200 ° C., the pressure in the flask was further reduced, and the temperature was maintained at 8 kPa for 1 hour. Then, after returning to atmospheric pressure, the mixture was cooled to 190 ° C., 200 g of fumaric acid, 194 g of sebacic acid, 184 g of trimellitic acid anhydride, and 2.5 g of 4-tert-butylcatechol were added, and the temperature was 10 ° C./hr to 210 ° C. Then, the reaction was carried out at 4 kPa to a desired softening point to obtain an amorphous resin B-6. The physical characteristics are shown in Table 2.

Production example B7
(Manufacturing of amorphous resin Bw-1)
The inside of a four-necked flask with an internal volume of 10 L equipped with a nitrogen introduction tube, a dehydration tube, a stirrer, and a thermocouple was replaced with nitrogen, and 3594 g of a polyoxypropylene (2.2) adduct of bisphenol A, 682 g of terephthalic acid, 25 g of di (2-ethylhexanoic acid) tin (II) and 2.5 g of 3,4,5-trihydroxybenzoic acid were added, and the temperature was raised to 235 ° C. with stirring under a nitrogen atmosphere, and 5 at 235 ° C. After holding for a time, the pressure in the flask was lowered and held at 8 kPa for 1 hour. Then, after returning to atmospheric pressure, the mixture was cooled to 160 ° C. and kept at 160 ° C., and a mixture of 2208 g of styrene, 552 g of stearyl methacrylate, 118 g of acrylic acid, and 330 g of dibutyl peroxide was added dropwise over 1 hour. Then, the temperature was maintained at 160 ° C. for 30 minutes, the temperature was raised to 200 ° C., the pressure in the flask was further reduced, and the temperature was maintained at 8 kPa for 1 hour. Then, after returning to atmospheric pressure, the mixture was cooled to 180 ° C., 602 g of succinic acid was added, the temperature was raised to 200 ° C. at 10 ° C./hr, and then the reaction was carried out at 4 kPa to a desired softening point to form an amorphous substance. The sex resin Bw-1 was obtained. The physical characteristics are shown in Table 2.

The notes in Table 2 are as follows.
* 1: BPA-PO means a polyoxypropylene (2.2) adduct of bisphenol A. BPA-EO means a polyoxyethylene (2.2) adduct of bisphenol A.
* 2: When the alcohol component of the raw material monomer (P) is 100 parts by mole, it means the molar part of each monomer constituting the raw material monomer (P) and the bireactive monomer.
* 3: It means the content (mass%) of each monomer constituting the raw material monomer (V) in the total amount of the raw material monomer (V).
* 4: Paracol 6490; manufactured by Nippon Seiro Co., Ltd., Mn 800, melting point 76 ° C., acid value 18 mgKOH / g, hydroxyl value 97 mgKOH / g
* 5: The amount of the polyester portion was calculated as the theoretical yield excluding the amount of reaction water, and the amount of the vinyl resin segment was calculated as including the amount of the radical polymerization initiator.
* 6: Content in resin.

[Manufacturing of resin composition]
Production example C1
(Production of Resin Composition C-1)
In a container with an internal volume of 3 L equipped with a stirrer, a reflux condenser, a thermometer, and a nitrogen introduction tube, 200 g of crystalline resin A-1, 200 g of amorphous resin B-1, and molecular sieves under a nitrogen atmosphere. 300 g of the dehydrated methyl ethyl ketone was added, and the temperature was raised to 83 ° C. with stirring to dissolve the resin at 83 ° C. for 1 hour. A solution prepared by dissolving 40 g of 2,2'-azobis (2,4-dimethylvaleronitrile) in 100 g of methyl ethyl ketone dehydrated with molecular sieves was added dropwise to the obtained solution at 83 ° C. over 2 hours. .. Then, it was held at 83 ° C. for 2 hours. While continuously maintaining the temperature at 83 ° C., methyl ethyl ketone was distilled off under reduced pressure to obtain a resin composition C-1. The physical characteristics are shown in Table 3.

Production Examples C2 to C9
(Production of Resin Compositions C-2 to C-9)
Resin compositions C-2 to C-9 were obtained in the same manner as in Production Example C1 except that the types of crystalline resin and amorphous resin used were changed as shown in Table 3. The physical characteristics are shown in Table 3.

Production example C10
(Manufacture of Resin Composition C-10)
In a container with an internal volume of 3 L equipped with a stirrer, a reflux condenser, a thermometer, and a nitrogen introduction tube, 200 g of crystalline resin A-1, 200 g of amorphous resin B-1, and molecular sieves under a nitrogen atmosphere. 300 g of the dehydrated methyl ethyl ketone was added, and the temperature was raised to 83 ° C. with stirring to dissolve the resin at 83 ° C. for 1 hour. Then, it was held at 83 ° C. for 4 hours. While continuously maintaining the temperature at 83 ° C., methyl ethyl ketone was distilled off under reduced pressure to obtain a resin composition C-10. The physical characteristics are shown in Table 3.

[Manufacturing of resin particle dispersion]
Production example D1
(Manufacture of Resin Particle Dispersion Liquid D-1)
A solution prepared by dissolving 120 g of the resin composition C-1 and 80 g of the amorphous resin B-6 obtained in Production Example C1 in 200 g of methyl ethyl ketone was stirred at 73 ° C. for 1 hour, and further, a 5 mass% sodium hydroxide aqueous solution was added. 28 g was added, and the mixture was stirred for 30 minutes.
Then, while maintaining the temperature at 73 ° C., 700 g of deionized water was added over 60 minutes while stirring at 200 r / min (peripheral speed 63 m / min) for phase inversion emulsification. While continuously maintaining the temperature at 73 ° C., methyl ethyl ketone was distilled off under reduced pressure to obtain an aqueous dispersion. After that, the aqueous dispersion was cooled to 30 ° C. while stirring at 280 r / min (peripheral speed 88 m / min), and then deionized water was added so that the solid content concentration became 20% by mass to disperse the resin particles. Liquid D-1 was obtained. The physical characteristics are shown in Table 4.

Production example D2
(Manufacture of Resin Particle Dispersion Liquid D-2)
A solution prepared by dissolving 80 g of the resin composition C-1 and 120 g of the amorphous resin B-6 obtained in Production Example C1 in 200 g of methyl ethyl ketone was stirred at 73 ° C. for 1 hour, and further, a 5 mass% sodium hydroxide aqueous solution was added. 28 g was added, and the mixture was stirred for 30 minutes. After that, the resin particle dispersion liquid D-2 was obtained in the same manner as in Production Example D1. The physical characteristics are shown in Table 4.

Production example D3
(Manufacture of Resin Particle Dispersion Liquid D-3)
A solution prepared by dissolving 40 g of the resin composition C-1 and 160 g of the amorphous resin B-6 obtained in Production Example C1 in 200 g of methyl ethyl ketone was stirred at 73 ° C. for 1 hour, and further, a 5 mass% sodium hydroxide aqueous solution was added. 28 g was added, and the mixture was stirred for 30 minutes. After that, the resin particle dispersion liquid D-3 was obtained in the same manner as in Production Example D1. The physical characteristics are shown in Table 4.

Manufacturing Examples D4 to D11, D16
(Manufacturing of resin particle dispersions D-4 to D-11 and D-16)
Resin particle dispersions D-4 to D-11 and D-16 were obtained in the same manner as in Production Example D1, except that the types of the resin composition and the amorphous resin were changed as shown in Table 4, respectively. The physical characteristics are shown in Table 4.

Production example D12
(Manufacture of Resin Particle Dispersion Liquid D-12)
A solution prepared by dissolving 200 g of the resin composition C-1 obtained in Production Example C1 in 200 g of methyl ethyl ketone is stirred at 73 ° C. for 1 hour, and 28 g of a 5 mass% sodium hydroxide aqueous solution is further added and stirred for 30 minutes. did. After that, the resin particle dispersion liquid D-12 was obtained in the same manner as in Production Example D1. The physical characteristics are shown in Table 4.

Production example D13
(Manufacture of Resin Particle Dispersion Liquid D-13)
A solution prepared by dissolving 200 g of amorphous resin B-6 in 200 g of methyl ethyl ketone was stirred at 73 ° C. for 1 hour, and 28 g of a 5 mass% sodium hydroxide aqueous solution was further added and stirred for 30 minutes. After that, the resin particle dispersion liquid D-13 was obtained in the same manner as in Production Example D1. The physical characteristics are shown in Table 4.

Production example D14
(Manufacture of Resin Particle Dispersion Liquid D-14)
A solution prepared by dissolving 80 g of the resin composition C-1 obtained in Production Example C1, 20 g of the crystalline resin A-4, and 100 g of the amorphous resin B-6 in 200 g of methyl ethyl ketone was stirred at 73 ° C. for 1 hour. Further, 28 g of a 5 mass% sodium hydroxide aqueous solution was added, and the mixture was stirred for 30 minutes. After that, a resin particle dispersion liquid D-14 was obtained in the same manner as in Production Example D1. The physical characteristics are shown in Table 4.

Production example D15
(Manufacture of Resin Particle Dispersion Liquid D-15)
A solution prepared by dissolving 60 g of crystalline resin A-4 and 140 g of amorphous resin B-6 in 200 g of methyl ethyl ketone was stirred at 73 ° C. for 1 hour, and 28 g of a 5 mass% sodium hydroxide aqueous solution was further added to 30. Stir for minutes. After that, the resin particle dispersion liquid D-15 was obtained in the same manner as in Production Example D1. The physical characteristics are shown in Table 4.

Production example F1
(Manufacturing of resin particle dispersion liquid F-1)
200 g of amorphous composite resin Bw-1 and 200 g of methyl ethyl ketone were placed in a container having an internal volume of 3 L equipped with a stirrer, a reflux condenser, a dropping funnel, a thermometer and a nitrogen introduction tube, and the resin was placed at 73 ° C. for 2 hours. Was dissolved. To the obtained solution, 41 g of a 5 mass% sodium hydroxide aqueous solution was added, and the mixture was stirred for 30 minutes.
Then, while maintaining the temperature at 73 ° C., 700 g of deionized water was added over 50 minutes while stirring at 200 r / min (peripheral speed 63 m / min) for phase inversion emulsification. While continuously maintaining the temperature at 73 ° C., methyl ethyl ketone was distilled off under reduced pressure to obtain a dispersion. After that, the dispersion was cooled to 30 ° C. while stirring at 280 r / min (peripheral speed 88 m / min), and then deionized water was added so that the solid content concentration became 20% by mass, whereby the resin particle dispersion was F-1 was obtained. The volume median particle diameter (D ₅₀ ) of the resin particles in the dispersion was 0.09 μm, and the CV value was 23%.

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

[Manufacturing of colorant particle dispersion]
Production example H1
(Manufacture of Colorant Particle Dispersion Solution H-1)
In a beaker with an internal volume of 1 L, 150 g of copper phthalocyanine pigment "ECB-301" (manufactured by Dainichi Seika Kogyo Co., Ltd.) and anionic surfactant "Neoperex (registered trademark) G-15" (manufactured by Kao Co., Ltd., 15 mass) 200 g of% dodecylbenzene benzene sulfonate aqueous solution) and 257 g of deionized water were mixed and dispersed at room temperature (25 ° C.) for 3 hours using an ultrasonic homogenizer "US-600T" (manufactured by Nippon Seiki Seisakusho Co., Ltd.). The colorant dispersion H-1 was obtained by adding deionized water so that the solid content concentration was 24% by mass. The volume median particle diameter (D ₅₀ ) of the colorant particles in the dispersion was 0.12 μm.

[Manufacturing by coagulation and fusion method of toner]
Example 1
(Preparation of toner 1)
300 g of resin particle dispersion D-1, 30 g of wax particle dispersion G-1, and colorant particle dispersion H-1 are placed in a 4-necked flask having an internal volume of 3 L equipped with a dehydration tube, a stirrer, and a thermocouple. 30 g and 6 g of a 10 mass% aqueous solution of the nonionic surfactant "Emargen (registered trademark) 150" (manufactured by Kao Co., Ltd., polyoxyethylene (average number of added moles 50) lauryl ether) were mixed at a temperature of 25 ° C. Next, while stirring the mixture, a solution prepared by adding 20 g of a 4.8 mass% potassium hydroxide aqueous solution to an aqueous solution prepared by dissolving 19 g of ammonium sulfate in 187 g of deionized water to adjust the pH to 8.6 was prepared at 25 ° C. for 5 minutes. The temperature is raised to 60 ° C. over 2 hours, and the temperature _{is maintained at 60 ° C. until the volume median particle diameter (D 50} ) of the agglomerated particles reaches 5.5 μm, and the agglomerated particles (1) are dispersed. I got the liquid.
Anionic surfactant "Emar (registered trademark) E-27C" (manufactured by Kao Corporation, sodium polyoxyethylene lauryl ether sulfate, effective concentration 27% by mass), 10 g, deionized water in a dispersion of agglomerated particles (1). An aqueous solution containing 900 g and 20 g of 0.1 mol / L sulfuric acid was added. Then, the temperature was raised to 83 ° C. over 1 hour, and then the temperature was maintained at 83 ° C. until the circularity became 0.970 to obtain a dispersion of fused particles in which aggregated particles were fused.
The obtained fused particle dispersion was cooled to 30 ° C., the dispersion 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 5 shows the physical characteristics of the obtained toner particles.
100 parts by mass of toner particles, 2.5 parts by mass of hydrophobic silica "RY50" (manufactured by Nippon Aerosil Co., Ltd., number average particle size; 0.04 μm), and hydrophobic silica "Cabosil (registered trademark) TS720" (Cabot Japan Co., Ltd.) Company-made, number average particle size; 0.012 μm) 1.0 part by mass was placed in a Henschel mixer and stirred, and passed through a 150 mesh sieve to obtain toner 1. The evaluation results of the obtained toner 1 are shown in Table 5.

Examples 2-11, 13, Comparative Examples 1, 2
(Preparation of toners 2-11 and 13-15)
Toners were produced in the same manner as in Example 1 except that the type of resin particle dispersion used was changed as shown in Table 5. Table 5 shows the physical characteristics of the obtained toner particles and the evaluation results of the toner.

Example 12
(Preparation of toner 12)
180 g of resin particle dispersion D-12, 120 g of resin particle dispersion D-13, and 30 g of wax particle dispersion G-1 in a four-necked flask with an internal volume of 3 L equipped with a dehydration tube, agitator, and thermocouple. , 30 g of colorant particle dispersion H-1, and 10% by mass of nonionic surfactant "Emargen (registered trademark) 150" (manufactured by Kao Co., Ltd., polyoxyethylene (average addition molar number 50) lauryl ether). 6 g of the aqueous solution was mixed at a temperature of 25 ° C. Next, while stirring the mixture, a solution prepared by adding 20 g of a 4.8 mass% potassium hydroxide aqueous solution to an aqueous solution prepared by dissolving 19 g of ammonium sulfate in 187 g of deionized water to adjust the pH to 8.6 was prepared at 25 ° C. for 5 minutes. The temperature is raised to 60 ° C. over 2 hours, and the temperature _{is maintained at 60 ° C. until the volume median particle diameter (D 50} ) of the agglomerated particles reaches 5.5 μm, and the agglomerated particles (1) are dispersed. I got the liquid.
10 g of anionic surfactant "Emar (registered trademark) E-27C" (manufactured by Kao Corporation, sodium polyoxyethylene lauryl ether sulfate, effective concentration 27% by mass), deionized in the dispersion liquid of the aggregated particles (1). An aqueous solution containing 900 g of water and 20 g of 0.1 mol / L sulfuric acid was added. Then, the temperature was raised to 83 ° C. over 1 hour, and then the temperature was maintained at 83 ° C. until the circularity became 0.970 to obtain a dispersion of fused particles in which aggregated particles were fused.
The obtained fused particle dispersion was cooled to 30 ° C., the dispersion 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 5 shows the physical characteristics of the obtained toner particles.
100 parts by mass of toner particles, 2.5 parts by mass of hydrophobic silica "RY50" (manufactured by Nippon Aerosil Co., Ltd., number average particle size; 0.04 μm), and hydrophobic silica "Cabosil (registered trademark) TS720" (Cabot Japan Co., Ltd.) Company-made, number average particle size; 0.012 μm) 1.0 part by mass was placed in a Henshell mixer and stirred, and passed through a 150 mesh sieve to obtain toner 12. The evaluation results of the obtained toner 12 are shown in Table 5.

From Table 5, the toners of Examples 1 to 13 have excellent low-temperature fixability as compared with the toners of Comparative Examples 1 and 2, can suppress a decrease in low-temperature fixability over time, and are also excellent in heat-resistant storage stability. You can see that.

[Manufacturing of resin composition]
Production example C101
(Manufacture of Resin Composition C-101)
Nitrogen was substituted inside a four-necked flask with an internal volume of 10 L equipped with a nitrogen introduction tube, a dehydration tube, a stirrer, and a thermocouple. 35 g of di (2-ethylhexanoic acid) tin (II) and 3.5 g of 3,4,5-trihydroxybenzoic acid were added, and the temperature was raised to 235 ° C. with stirring under a nitrogen atmosphere, and 5 at 235 ° C. After holding for a time, the pressure in the flask was reduced and the flask was held at 8 kPa for 1 hour. Then, after returning to atmospheric pressure, the mixture was cooled to 180 ° C., 105 g of adipic acid, 138 g of trimellitic anhydride, 52 g of acrylic acid, and 3.5 g of 4-tert-butylcatechol were added, and the temperature was 10 ° C./hr up to 200 ° C. The temperature was raised in 1 and the pressure in the flask was lowered, and the temperature was maintained at 8 kPa for 30 minutes.
Then, after returning to atmospheric pressure, it cooled to 170 degreeC, 1949 g of crystalline resin A-1 was added, and it held at 170 degreeC for 30 minutes. 70 g of dibutyl peroxide was added dropwise over 1 hour and kept at 170 ° C. for 30 minutes, then the pressure in the flask was lowered and the reaction was carried out at 8 kPa to a desired softening point to obtain a resin composition C-101. .. The physical characteristics are shown in Table 6.

Production Examples C102 to C108
(Manufacture of Resin Compositions C-102 to C-108)
Resin compositions C-102 to C-108 were obtained in the same manner as in Production Example C101 except that the raw material composition was changed as shown in Table 6. The physical characteristics are shown in Table 6.

Production example C109
(Manufacture of Resin Composition C-109)
The inside of a four-necked flask with an internal volume of 10 L equipped with a nitrogen introduction tube, a dehydration tube, a stirrer, and a thermocouple was replaced with nitrogen, and 1,2-propanediol (2239 g), terephthalic acid (4157 g), and di (2-ethylhexane) were replaced. Add 35 g of (acid) tin (II), raise the temperature to 185 ° C while stirring in a nitrogen atmosphere, hold at 185 ° C for 3 hours, then raise the temperature to 220 ° C at 5 ° C / hr and at 220 ° C. Retained. After confirming that the reaction rate reached 95% or more, the mixture was cooled to 180 ° C. and returned to atmospheric pressure to 215 g of adipic acid, 283 g of trimellitic anhydride, 106 g of acrylic acid, and 4-tert-butylcatechol. 5 g was added, the temperature was raised to 220 ° C. at 5 ° C./hr, the pressure in the flask was lowered, and the temperature was maintained at 8 kPa for 30 minutes. Then, after returning to atmospheric pressure, it cooled to 170 degreeC, 1790 g of crystalline resin A-1 was added, and it held at 170 degreeC for 30 minutes. While maintaining the temperature at 170 ° C., 70 g of dibutyl peroxide was added dropwise over 1 hour, the temperature was maintained at 170 ° C. for 30 minutes, the pressure inside the flask was lowered, and the reaction was carried out at 8 kPa to a desired softening point to obtain a resin composition. Object C-109 was obtained. The physical characteristics are shown in Table 6. The reaction rate means a value of the amount of produced reaction water / the theoretical amount of produced water × 100.

Manufacturing example C110
(Manufacture of Resin Composition C-110)
The inside of a four-necked flask with an internal volume of 10 L equipped with a nitrogen introduction tube, a dehydration tube, a stirrer, and a thermocouple was replaced with nitrogen, and 4670 g of a polyoxyethylene (2.2) adduct of bisphenol A, 2087 g of terephthalic acid, 35 g of di (2-ethylhexanoic acid) tin (II) and 3.5 g of 3,4,5-trihydroxybenzoic acid were added, and the temperature was raised to 235 ° C. with stirring under a nitrogen atmosphere, and 5 at 235 ° C. After holding for a time, the pressure in the flask was reduced and the flask was held at 8 kPa for 1 hour. Then, after returning to atmospheric pressure, the mixture was cooled to 180 ° C., 105 g of adipic acid and 138 g of trimellitic acid anhydride were added, the temperature was raised to 200 ° C. at 10 ° C./hr, the pressure in the flask was lowered, and the pressure in the flask was reduced to 8 kPa. It was held for 30 minutes. Then, after returning to atmospheric pressure, it cooled to 170 degreeC, 1949 g of crystalline resin A-4 was added, and it kept at 170 degreeC for 2 hours. While maintaining the temperature at 170 ° C., 70 g of dibutyl peroxide was added dropwise over 1 hour to reduce the pressure in the flask, and the reaction was carried out at 8 kPa to a desired softening point to obtain a resin composition C-110. The physical characteristics are shown in Table 6.

[Manufacturing by melt-kneading toner]
Example 101
(Preparation of Toner 101)
100 parts by mass of resin composition C-101, 5 parts by mass of carbon black "Regal 330R" (manufactured by Cabot Japan Co., Ltd.), polypropylene wax "Mitsui High Wax NP055" (manufactured by Mitsui Chemicals Co., Ltd., melting point 125 ° C.) ) Add 2 parts by mass, mix for 5 minutes, and then roll using a PCM-30 rotary twin-screw extruder (manufactured by Ikegai Co., Ltd., shaft diameter 2.9 cm, shaft cross-sectional area 7.06 cm ^2). The mixture was melt-kneaded at a rotation speed of 200 r / min, a heating temperature in the roll of 80 ° C., and a mixture supply speed of 10 kg / h. The obtained melt-kneaded product was cooled and roughly pulverized, then pulverized by a jet mill and classified to obtain toner particles having _{a volume medium particle size (D 50) of 8 μm.}
100 parts by mass of toner particles and 1.0 part by mass of hydrophobic silica "NAX-50" (manufactured by Nippon Aerosil Co., Ltd., number average particle size; 0.03 μm) were placed in a Henshell mixer and stirred to obtain toner 101. The evaluation results of the toner are shown in Table 7.

Examples 102 to 109, Comparative Example 101
(Preparation of toners 102 to 110)
Toners were produced in the same manner as in Example 101, except that the type of resin composition used was changed as shown in Table 7. The evaluation results of the obtained toner are shown in Table 7.

From Table 7, the toners of Examples 101 to 109 are superior to the toners of Comparative Example 101 in low-temperature fixability, can suppress a decrease in low-temperature fixability over time, and are also excellent in heat-resistant storage stability. Understand.

Claims (9)

Contains a resin composition (C) containing a multimer of a crystalline resin (A) having at least a part having an addition-polymerizable group and an amorphous resin (B) having at least a part having an addition-polymerizable group. , A method for producing a toner for static charge image development , wherein the crystalline resin (A) is a crystalline polyester resin and the amorphous resin (B) is an amorphous polyester resin.
A method for producing a toner for developing an electrostatic charge image, which comprises the following step (1') .
Step (1'): A crystalline resin (A) having at least a part of an addition-polymerizable group and an amorphous resin (B) having at least a part of an addition-polymerizable group are reacted with a polymerization initiator. To obtain the resin composition (C) containing a multimer Mass ratio of the amount of the crystalline resin (A) having an addition-polymerizable group at least in part to the amount of the amorphous resin (B) having at least part of the addition-polymerizable group [The crystalline resin (the above-mentioned crystalline resin ( The method for producing an electrostatic charge image developing toner according to claim 1, wherein A) / the amorphous resin (B)] is 5/95 or more and 90/10 or less. The method for producing an electrostatic charge image developing toner according to claim 1 or 2 , wherein the blending amount of the resin composition (C) is 10% by mass or more in the resin component of the toner. The method for producing an electrostatic charge image developing toner according to any one of claims 1 to 3 , wherein the total amount of the crystalline resin is 5% by mass or more and 45% by mass or less in the resin component of the toner. The method for producing an electrostatic charge image developing toner according to any one of claims 1 to 4 , wherein the total amount of the amorphous resin is 55% by mass or more and 95% by mass or less in the resin component of the toner. The method for producing a toner for static charge image development according to any one of claims 1 to 5, further comprising the following steps (2A) to (4A).
Step (2A): Step of dispersing the resin composition (C) obtained in step (1' ) in an aqueous medium to obtain a dispersion liquid of resin particles (P1) Step (3A): In step (2A) Step of aggregating the obtained resin particles (P1) in an aqueous medium to obtain agglomerated particles Step (4A): A step of fusing the agglomerated particles obtained in the step (3A). Step (1 ' ) is carried out in an organic solvent.
The static charge image developing toner according to claim 6 , wherein the step (2A) is a step of adding an aqueous medium and inverting emulsification to obtain a dispersion liquid of resin particles (P1) after the step (1'). Production method. The method for producing a toner for static charge image development according to any one of claims 1 to 5, further comprising the following steps (2B) to (3B).
Step (2B): A step of melt-kneading the mixture containing the resin composition (C) obtained in the step (1' ) Step (3B): The melt-kneaded product obtained in the step (2B) is crushed and classified. Process Resin composition for toner for static charge image development, which comprises a multimer of a crystalline resin (A) having at least a part having an addition-polymerizable group and an amorphous resin (B) having at least a part having an addition-polymerizable group. A method for producing a product (C), wherein the crystalline resin (A) is a crystalline polyester resin, and the amorphous resin (B) is an amorphous polyester resin.
A method for producing a resin composition for a toner for developing an electrostatic charge image, which comprises the following step (1').
Step (1'): A crystalline resin (A) having at least a part of an addition-polymerizable group and an amorphous resin (B) having at least a part of an addition-polymerizable group are reacted with a polymerization initiator. To obtain the resin composition (C) containing a multimer