JP2016173405A - Production method of toner for electrostatic charge image development - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a production method of a toner for electrostatic charge image development, by which a toner excellent in low-temperature fixability and capable of suppressing reduction in the low-temperature fixability with time can be obtained.SOLUTION: The production method of a toner for electrostatic charge image development includes the following steps (1) to (3): a step (1) of mixing wax and an aqueous dispersion of resin particles (A) to obtain an aqueous dispersion of wax particles; a step (2) of mixing and coagulating the aqueous dispersion of wax particles obtained in the step (1) with an aqueous dispersion of resin particles (B) and an aqueous dispersion of resin particles (C) to obtain coagulated particles; and a step (3) of fusing the coagulated particles obtained in the step (2) to obtain fused particles. The resin constituting the resin particles (A) comprises a polyester-based resin containing a polyester segment (a1); the resin constituting the resin particles (B) comprises a crystalline polyester (b); and the resin constituting the resin particles (C) comprises a composite resin (c) containing a polyester segment (c1) and a vinyl-based resin segment (c2) having a structural unit derived from a styrene compound.SELECTED DRAWING: None

Description

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

  In recent years, in the field of toner for electrophotography, with the development of an electrophotographic system, development of a toner corresponding to high image quality and high speed has been demanded. From the viewpoint of high image quality, it is necessary to reduce the particle size of the toner. Instead of the conventional melt-kneading method, a chemical method such as a suspension polymerization method, an emulsion polymerization method, or a dissolution suspension method is used. A method of obtaining is disclosed. Furthermore, from the standpoint of speeding up, chemical toners with internal addition of crystalline polyester or wax have been reported to improve low-temperature fixability.

  For example, Patent Document 1 discloses that an amorphous composite resin (a) in which the core of core-shell particles has a segment (A1) made of a polyester resin and a segment (A2) made of an addition polymer containing styrene as a structural unit. And a shell containing an amorphous resin (B) obtained by condensation polymerization of an alcohol component containing an aliphatic diol having 2 to 6 carbon atoms and a carboxylic acid component. However, there is a disclosure that it is excellent in low-temperature fixability and hot offset resistance.

  Patent Document 2 melts a crystalline polyester (a) and an amorphous polyester (b) obtained by polycondensation of an alcohol component containing 80 mol% or more of a propylene oxide adduct of bisphenol A and a carboxylic acid component. Step of mixing and emulsifying in an aqueous medium to obtain resin particles (A), step of aggregating resin particles (A) to obtain aggregated particles, addition of ethylene oxide of bisphenol A to the dispersion of the aggregated particles Adding a resin particle (C) containing an amorphous polyester (d) obtained by polycondensation of an alcohol component containing 80 mol% or more of a product and a carboxylic acid component to obtain a core-shell particle, and a core-shell particle Holding the temperature of the system containing 5 at a temperature of 5 ° C. lower than the glass transition point of the amorphous polyester (d) to obtain coalesced core-shell particles. Method for producing a toner is disclosed that. As an effect of the toner obtained by the production method, it is described that the particle size distribution is sharp, the low-temperature fixability and the storage stability are compatible, and the toner scattering can be improved.

  Patent Document 3 discloses that in the step of obtaining fused particles at the time of toner preparation, the release of wax from the binder resin can be suppressed, and the exposure of the wax to the surface of the toner particles can be suppressed. As a method for producing an electrophotographic toner having the characteristics of being able to reduce fine powder and having excellent low temperature fixability and high temperature offset resistance, a wax, an emulsion of a resin having a specific acid value, and an oxazoline group-containing The polymer is mixed and emulsified to obtain an aqueous dispersion of wax particles, and then the aqueous dispersion and an aqueous dispersion of resin particles containing a binder resin having a carboxy group are mixed to agglomerate and melt. An electrophotographic toner manufacturing method for obtaining fused particles by adhesion is disclosed.

JP 2014-13384 A JP 2012-118236 A JP 2014-89442 A

However, when a toner is manufactured by a chemical method, there is a problem that the low-temperature fixability deteriorates with time even if the low-temperature fixability of the toner is improved by mixing crystalline polyester with the binder resin.
The present invention provides an electrostatic charge capable of obtaining a toner having excellent low-temperature fixability and capable of suppressing a decrease in low-temperature fixability with time even when a toner is produced by a chemical method using crystalline polyester. It is an object of the present invention to provide a method for producing an image developing toner.

  The present inventors use, as a binder resin, a composite resin including a segment made of polyester and a vinyl resin segment containing a structural unit derived from a styrene compound in addition to crystalline polyester, and a wax to be aggregated By using particles obtained by dispersing wax in the presence of specific resin particles, it is possible to obtain a toner that is excellent in low-temperature fixability and that can suppress a decrease in low-temperature fixability over time. I found.

That is, the present invention includes the following steps (1) to (3).
Step (1): A step of mixing a wax and an aqueous dispersion of resin particles (A) to obtain an aqueous dispersion of wax particles Step (2): An aqueous dispersion of the wax particles obtained in Step (1) Step of mixing the liquid, the aqueous dispersion of the resin particles (B), and the aqueous dispersion of the resin particles (C) and aggregating them to obtain aggregated particles Step (3): Aggregated particles obtained in Step (2) A method for producing a toner for developing an electrostatic image, comprising the step of fusing a toner to obtain fused particles,
The resin constituting the resin particles (A) contains a polyester resin containing a segment (a1) made of polyester,
The resin constituting the resin particles (B) contains the crystalline polyester (b),
The resin constituting the resin particles (C) contains a composite resin (c) including a segment (c1) made of polyester and a vinyl resin segment (c2) having a structural unit derived from a styrene compound,
A method for producing a toner for developing an electrostatic image is provided.

  According to the present invention, it is possible to provide a method for producing an electrostatic charge image developing toner capable of obtaining a toner having excellent low-temperature fixability and capable of suppressing a decrease in low-temperature fixability with time.

[Method for producing toner for developing electrostatic image]
The method for producing the toner for developing an electrostatic image of the present invention includes
Next steps (1) to (3)
Step (1): A step of mixing a wax and an aqueous dispersion of resin particles (A) to obtain an aqueous dispersion of wax particles Step (2): An aqueous dispersion of the wax particles obtained in Step (1) Step of mixing the liquid, the aqueous dispersion of the resin particles (B), and the aqueous dispersion of the resin particles (C) and aggregating them to obtain aggregated particles Step (3): Aggregated particles obtained in Step (2) A method for producing a toner for developing an electrostatic image, comprising the step of fusing a toner to obtain fused particles,
The resin constituting the resin particles (A) contains a polyester resin containing a segment (a1) made of polyester, the resin constituting the resin particles (B) contains a crystalline polyester (b), and resin particles The resin constituting (C) contains a composite resin (c) including a segment (c1) made of polyester and a vinyl resin segment (c2) having a structural unit derived from a styrene compound, for developing an electrostatic charge image A toner manufacturing method.

The detailed mechanism by which the toner of the present invention is excellent in low-temperature fixability and can provide a toner capable of suppressing a decrease in low-temperature fixability over time is not clear, but is considered as follows.
In the production of toner by chemical method, when crystalline polyester is mixed with the binder resin to improve low-temperature fixability, if the wax is further added, the crystalline polyester is compatible with low polarity wax. There is a tendency to gather at the interface. Therefore, when the dispersibility of the wax in the toner particles is not good, that is, when the size of the wax domain is large and the interface of the wax is small, the crystalline polyester is more densely packed. The size gradually increases. As a result, the interface between the crystalline polyester and the other binder resin is relatively reduced, so it becomes difficult to melt the surrounding resin with the melting of the crystalline polyester during toner fixing, and the low-temperature fixability gradually decreases. It was considered.

In order to solve this problem, the present invention pays attention to the dispersion state of the wax in the toner particles. That is, in the present invention, the step of dispersing the wax particles in the presence of the resin particles (A) containing a polyester-based resin containing a segment made of polyester (hereinafter also referred to as “polyester segment”) (a1) (1 ). In the step (1), it is possible to disperse the wax in the aqueous medium using the resin particles (A) as a substitute for the surfactant via the polyester segment (a1) having an appropriate polarity. Become. The resulting aqueous dispersion of wax particles is considered to have a structure in which a large number of resin particles (A) are adsorbed around the wax particles.
In the present invention, in addition to the crystalline polyester, the binder resin that is the base material of the toner is a composite resin that includes a polyester segment (c1) and a vinyl resin segment (c2) that contains a structural unit derived from a styrene compound. c). The composite resin (c) having the polyester segment (c1) is easily compatible with not only the crystalline polyester but also the resin particles (A) in which the wax is dispersed, and the resin particles containing the composite resin (c) in the aggregation process ( The wax particles are easily taken into the aggregate of (C). Further, in the fusing step, the composite resin (c) constituting the resin particles (C) and the polyester segments of the polyester resin constituting the resin particles (A) are easily integrated with each other. Since the vinyl-based resin segment (c2) containing the unit is compatible with the wax having a low polarity, the wax is finely dispersed in the fused particles and the toner particles.
Thus, as described above, even if crystal domains derived from low-polarity crystalline polyester exist in the vicinity of the wax, the crystalline polyester does not concentrate locally in the toner particles because there are many wax interfaces. It becomes easy to keep a fine dispersion state. For this reason, it is considered that the toner melts quickly at the time of toner fixing, the low temperature fixability is improved, the finely dispersed state of the crystalline polyester is kept long, and the low temperature fixability is prevented from aging.

<Step (1)>
Step (1) in the method for producing a toner of the present invention is a step of obtaining an aqueous dispersion of wax particles by mixing a wax and an aqueous dispersion of resin particles (A) containing a polyester resin.

(wax)
Examples of the wax include mineral or petroleum waxes; synthetic waxes; low molecular weight polyolefins; silicone waxes; fatty acid amides; plant waxes;
Examples of the mineral or petroleum-based wax include montan wax, paraffin wax, and Fischer-Tropsch wax. Paraffin wax is preferable from the viewpoint of improving toner releasability and low-temperature fixability.
As the synthetic wax, ester wax is preferable.
As the low molecular weight polyolefin, polyethylene, polypropylene, polybutene and the like are preferable.
As the fatty acid amide, oleic acid amide, stearic acid amide and the like are preferable.
As the plant wax, carnauba wax, rice wax, candelilla wax and the like are preferable.
The animal wax is preferably beeswax or the like.
Among these, from the viewpoint of improving the releasability and low-temperature fixability of the toner, mineral or petroleum wax and synthetic wax are preferable, one or more selected from ester wax and paraffin wax are more preferable, and paraffin wax is more preferable. .
From the viewpoint of improving the releasability and low-temperature fixability of the toner, the wax preferably contains 95% by mass or more of paraffin wax, more preferably 97% by mass or more, and 99% by mass or more. Further preferred.

The melting point of the wax is preferably 60 ° C. or higher, more preferably 65 ° C. or higher, and further preferably 70 ° C. or higher from the viewpoint of improving the releasability of the toner. From the viewpoint of improving the temporal stability, it is preferably 100 ° C. or lower, more preferably 95 ° C. or lower, still more preferably 90 ° C. or lower, and still more preferably 85 ° C. or lower. When two or more kinds of waxes are used in combination, any melting point is preferably 60 ° C. or more and 100 ° C. or less, and any melting point is more preferably 60 ° C. or more and 90 ° C. or less.
In the present invention, the melting point of the wax is determined by the method described in the examples. When two or more kinds of waxes are used in combination, the melting point of the wax in the present invention is the melting point of the wax having the largest mass ratio among the waxes contained in the obtained toner. When all have the same ratio, the lowest melting point is the melting point of the wax in the present invention.

  The amount of the wax used is preferably 1 part by mass or more with respect to 100 parts by mass of the total amount of resin in the toner, from the viewpoint of improving the releasability of the toner, low-temperature fixability, and low-temperature fixability over time. The amount is preferably 2 parts by mass or more, more preferably 3 parts by mass or more, and preferably 30 parts by mass or less, more preferably 20 parts by mass or less, and further preferably 15 parts by mass or less.

(Resin particles (A))
The resin constituting the resin particle (A) is a polyester resin containing a segment (a1) made of polyester (hereinafter simply referred to as “polyester resin” from the viewpoint of improving low temperature fixability of toner and stability with time of low temperature fixability. "). The resin particles (A) are considered to function as a wax dispersant.
In the present invention, one of the major features is that the wax particles contain the resin particles (A). In the aqueous dispersion of wax particles, since the wax is dispersed through the resin particles (A) having an appropriate polarity, a stable dispersion of wax particles can be obtained without adding a surfactant, In addition, it is considered that the wax particles are easily taken into the aggregate of the (binding) resin particles (B) and the resin particles (C) by stirring and mixing in the aggregation step.

[Resin constituting resin particles (A)]
The resin constituting the resin particles (A) contains a polyester-based resin containing the polyester segment (a1) from the viewpoint of improving the low-temperature fixability of the toner and the temporal stability of the low-temperature fixability.
The content of the polyester resin in the resin constituting the resin particles (A) is preferably 50% by mass or more, more preferably in the resin from the viewpoint of improving low-temperature fixability and low-temperature fixability of the toner over time. Is 70% by mass or more, more preferably 90% by mass or more, still more preferably 95% by mass or more, still more preferably substantially 100% by mass, and still more preferably 100% by mass.

The resin constituting the resin particles (A) is preferably an amorphous resin from the viewpoint of improving the low-temperature fixability of the toner and the temporal stability of the low-temperature fixability.
Here, in the present invention, whether the resin is crystalline or amorphous is determined by the crystallinity index. The crystallinity index is defined by the ratio between the softening point of the resin and the maximum endothermic peak temperature (softening point (° C.) / Maximum endothermic peak temperature (° C.)) in the measurement methods described in the examples described later. The crystalline resin has a crystallinity index of 0.6 or more and 1.4 or less, and the amorphous resin has a crystallinity index of more than 1.4 or less than 0.6.
The crystallinity index can be appropriately adjusted according to the production conditions such as the type and ratio of the raw material monomers, the reaction temperature, the reaction time, and the cooling rate, and the value is determined by the method described in the examples below. It is done.

The content of the polyester segment (a1) in the polyester resin contained in the resin constituting the resin particles (A) is preferably in the resin from the viewpoint of improving the low temperature fixability of the toner and the stability over time of the low temperature fixability. Is 50% by mass or more, more preferably 55% by mass or more, further preferably 58% by mass or more, still more preferably 60% by mass or more, and preferably 100% by mass or less, more preferably 80% by mass or less, More preferably, it is 70 mass% or less.
That is, the resin constituting the resin particles (A) may contain not only a polyester resin but also a composite resin having a polyester segment (a1) as a polyester resin, and the resin constituting the resin particles (A). As above, it is preferable to contain the above-mentioned amount corresponding to the polyester.

≪Polyester segment (a1) ≫
The polyester segment (a1) is a polycondensation of a polyhydric alcohol component (a-al) and a polyvalent carboxylic acid component (a-ac) from the viewpoint of improving low-temperature fixability and low-temperature fixability of the toner over time. It is a segment made of a polyester resin.

The polyhydric alcohol component (a-al) preferably contains 80 mol% or more of an alkylene oxide adduct of bisphenol A from the viewpoint of improving low-temperature fixability and low-temperature fixability of the toner over time. From the same viewpoint, the content of the alkylene oxide adduct of bisphenol A in the polyhydric alcohol component (a-al) is preferably 80 mol% or more, more preferably 90 mol% or more, and still more preferably 95 mol% or more. More preferably, it is 98 mol% or more, and still more preferably 100 mol%.
The alkylene oxide adduct of bisphenol A is preferably an ethylene oxide adduct of bisphenol A (polyoxyethylene-2,2-bis (4-hydroxyphenyl) propane) and a propylene oxide adduct of bisphenol A (polyoxypropylene- 1,2-bis (4-hydroxyphenyl) propane), more preferably a propylene oxide adduct of bisphenol A.
The average addition mole number of alkylene oxide of the alkylene oxide adduct of bisphenol A is preferably 1 or more, more preferably 1.2 or more, further from the viewpoint of improving the low-temperature fixability and low-temperature fixability of the toner over time. It is preferably 1.5 or more, and preferably 16 or less, more preferably 12 or less, still more preferably 8 or less, and still more preferably 4 or less.

The polyhydric alcohol component (a-al) may contain other polyhydric alcohols other than the bisphenol A alkylene oxide adduct. Other polyhydric alcohol components that the polyhydric alcohol component (a-al) may contain include aliphatic diols, aromatic diols, alicyclic diols, trihydric or higher polyhydric alcohols, or those having 2 or more carbon atoms. The following alkylene oxide (average addition mole number 1-16) addition products etc. are mentioned. Specific examples thereof include ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, and 2,3-butanediol. Neopentyl glycol, 1,4-butenediol, 1,5-pentanediol, 1,6-hexanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,12 Aliphatic diols such as dodecanediol; aromatic diols such as bisphenol A (2,2-bis (4-hydroxyphenyl) propane); hydrogenated bisphenol A (2,2-bis (4-hydroxycyclohexyl) propane), etc. Of these alicyclic diols, or alkylene oxides having 2 or more and 4 or less carbon atoms (average added mole number 2) Top 12 or less) Adducts: Trivalent or higher polyhydric alcohols such as glycerin, pentaerythritol, trimethylolpropane, sorbitol, or their alkylene oxides having 2 to 4 carbon atoms (average added mole number of 1 to 16) Thing etc. are mentioned.
These polyhydric alcohol components (a-al) can be used alone or in combination of two or more.

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

Examples of the dicarboxylic acid include aromatic dicarboxylic acid, aliphatic dicarboxylic acid, and alicyclic dicarboxylic acid, and aromatic dicarboxylic acid and aliphatic dicarboxylic acid are preferable.
The polyvalent carboxylic acid component (a-ac) includes not only a free acid but also an anhydride that decomposes to generate an acid during the reaction and an alkyl ester having 1 to 3 carbon atoms of each carboxylic acid.
Examples of the aromatic dicarboxylic acid include phthalic acid, isophthalic acid, terephthalic acid and the like. From the viewpoint of improving low-temperature fixability and low-temperature fixability of the toner over time, isophthalic acid and terephthalic acid are preferable, and terephthalic acid is preferable. More preferred.
From the same viewpoint, the aliphatic dicarboxylic acid preferably has 2 to 30 carbon atoms, and more preferably 3 to 20 carbon atoms.
Examples of the aliphatic dicarboxylic acid having 2 to 30 carbon atoms include oxalic acid, malonic acid, maleic acid, fumaric acid, citraconic acid, itaconic acid, glutaconic acid, succinic acid, adipic acid, sebacic acid, 1,12-dodecanedioic acid. Examples include acid, 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, and improve the low-temperature fixability and low-temperature fixability of toner with time. From the viewpoint of making it succinic acid, it is preferable. Specific examples of the succinic acid substituted with an alkyl group having 1 to 20 carbon atoms or an alkenyl group having 2 to 20 carbon atoms include dodecyl succinic acid, dodecenyl succinic acid, octenyl succinic acid, and the like.
Among these, terephthalic acid, succinic acid, and dodecenyl succinic acid are preferable, and from the viewpoint of improving low-temperature fixability and low-temperature fixability of the toner over time, it is more preferable to use them in combination.

As the trivalent or higher polyvalent carboxylic acid, trimellitic acid and acid anhydride thereof are preferable, and trimellitic acid anhydride is more preferable from the viewpoint of improving low-temperature fixability and low-temperature fixability of the toner over time.
In addition, the content in the case of containing a trivalent or higher polyvalent carboxylic acid is preferably in the polyvalent carboxylic acid component (a-ac) from the viewpoint of improving low-temperature fixability and low-temperature fixability of the toner over time. Is 3 mol% or more, more preferably 5 mol% or more, and preferably 20 mol% or less, more preferably 10 mol% or less.
These polyvalent carboxylic acid components (a-ac) can be used alone or in combination of two or more.

  The equivalent ratio (COOH group / OH group) of the polycarboxylic acid component (a-ac) to the polyhydric alcohol component (a-al) is from the viewpoint of improving the low-temperature fixability and low-temperature fixability of the toner over time. , Preferably 0.7 or more, more preferably 0.8 or more, and preferably 1.3 or less, more preferably 1.2 or less.

  The polyester resin may be a polyester resin composed only of the polyester segment (a1). From the viewpoint of improving the low temperature fixability of the toner and the stability over time of the low temperature fixability, the polyester segment (a1) and the vinyl resin are used. The composite resin (a) containing the segment (a2) is preferable.

≪Vinyl resin segment (a2) ≫
The vinyl resin segment (a2) preferably contains a structural unit derived from a styrene compound from the viewpoint of improving the low temperature fixability of the toner and the stability over time of the low temperature fixability.

Examples of the styrenic 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. Specifically, styrenes such as styrene, methyl styrene, α-methyl styrene, β-methyl styrene, t-butyl styrene, chlorostyrene, chloromethyl styrene, methoxy styrene, styrene sulfonic acid or a salt thereof are preferable. More preferably, styrene is more preferable.
The content of the styrene compound in the raw material vinyl monomer which is the component derived from the vinyl resin segment (a2) is preferably 50% by mass or more from the viewpoint of improving the low-temperature fixability and low-temperature fixability of the toner over time. More preferably, it is 60% by mass or more, further preferably 70% by mass or more, and preferably 95% by mass or less, more preferably 90% by mass or less, and further preferably 85% by mass or less.

As raw material vinyl monomers other than styrene compounds, (meth) acrylic acid such as alkyl (meth) acrylate (alkyl group having 1 to 24 carbon atoms), benzyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, etc. Acid esters; olefins such as ethylene, propylene and butadiene; halovinyls such as vinyl chloride; vinyl esters such as vinyl acetate and vinyl propionate; vinyl ethers such as vinyl methyl ether; vinylidene halides such as vinylidene chloride; Examples thereof include N-vinyl compounds such as vinyl pyrrolidone. Among these, from the viewpoint of improving low-temperature fixability of toner and stability over time of low-temperature fixability, (meth) acrylic acid esters are preferable, and alkyl (meth) acrylate (alkyl group having 1 to 22 carbon atoms) is preferable. More preferred.
Here, “(meth) acrylic acid ester” refers to acrylic acid ester or methacrylic acid ester.
The number of carbon atoms of the alkyl group in the alkyl (meth) acrylate is preferably 1 or more, more preferably 4 or more, and still more preferably 6 or more, from the viewpoint of improving low-temperature fixability and low-temperature fixability of the toner over time. From the viewpoint of availability of the monomer, it is preferably 24 or less, more preferably 22 or less, and still more preferably 20 or less.
Specifically, methyl (meth) acrylate, ethyl (meth) acrylate, (iso) propyl (meth) acrylate, (meth) acrylic acid (iso or tertiary) butyl, (meth) acrylic acid (iso) Amyl, cyclohexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, (meth) acrylic acid (iso) octyl, (meth) acrylic acid (iso) decyl, (meth) acrylic acid (iso) dodecyl, (meta ) (Iso) palmityl acrylate, (meth) acrylic acid (iso) stearyl, (meth) acrylic acid (iso) behenyl, etc., and (meth) acrylic acid 2-ethylhexyl or stearyl methacrylate is preferred, stearyl methacrylate Is more preferable.
In addition, “(iso or tertiary)” means normal, iso or tertiary, and “(iso)” means normal or iso.

Among these, the raw material vinyl monomer that is a component derived from the vinyl resin segment (a2) is styrene alone or from the viewpoint of improving the availability of the monomer and the low temperature fixability and low temperature fixability of the toner over time. The combined use of styrene and (meth) acrylic acid ester is preferable, the combined use of styrene and (meth) acrylic acid ester is more preferable, and the combined use of styrene and alkyl (meth) acrylate having 6 to 20 carbon atoms in the alkyl group. Is more preferable.
When the styrene compound and the (meth) acrylic acid ester are used in combination, the content of the (meth) acrylic acid ester in the raw material vinyl monomer that is a component derived from the vinyl resin segment (a2) is determined by the low-temperature fixability of the toner and From the viewpoint of improving the temporal stability of the low-temperature fixability, it is preferably 5% by mass or more, more preferably 10% by mass or more, still more preferably 15% by mass or more, and preferably 50% by mass or less, more preferably It is 40 mass% or less, More preferably, it is 30 mass% or less.
In addition, the total amount of styrene compound and (meth) acrylic acid ester in the starting vinyl monomer, which is the component derived from the vinyl resin segment (a2), improves the low temperature fixability and low temperature fixability of the toner over time. From the viewpoint of achieving the above, it is preferably 80% by mass or more, more preferably 90% by mass or more, still more preferably 95% by mass or more, and still more preferably 100% by mass.

≪Amotropic monomer≫
When the polyester resin is a composite resin (a), by using an amphoteric monomer as a raw material monomer, the amphoteric monomer reacts with both the polyester segment (a1) and the vinyl resin segment (a2). This makes it easier to produce the composite resin (a). That is, the composite resin (a) preferably includes a structural unit derived from the both reactive monomers, and the structural unit derived from the both reactive monomers includes the vinyl resin segment (a2) and the polyester segment (a1). It is preferable that it becomes a coupling | bonding point with.
Examples of the both reactive monomers include vinyl monomers having one or more functional groups selected from a hydroxyl group, a carboxy group, an epoxy group, a primary amino group, and a secondary amino group in the molecule. Among these, from the viewpoint of reactivity, a vinyl monomer having a hydroxyl group and / or a carboxy group is preferable, and a vinyl monomer having a carboxy group is more preferable. Specific examples include acrylic acid, methacrylic acid, fumaric acid, maleic acid and the like. Among these, 1 selected from acrylic acid and methacrylic acid from the viewpoint of both the polycondensation reaction and the addition polymerization reaction. More than seeds are preferred, and acrylic acid is more preferred.

  The amount of both reactive monomers used is the raw material of the polyester segment (a1) from the viewpoint of dispersibility of the addition polymer containing a styrene compound as a structural unit in the polyester resin and reaction control of the addition polymerization reaction and the polycondensation reaction. Preferably, it is 1 mol part or more, more preferably 5 mol parts or more, still more preferably 10 mol parts or more, and preferably 30 mol parts, relative to 100 mol parts of the total amount of the polyhydric alcohol component (a-al). Hereinafter, it is more preferably 25 parts by mole or less, and still more preferably 20 parts by mole or less.

  The content of the polyester resin or the composite resin (a) in the resin constituting the resin particles (A) is preferably 80% by mass or more from the viewpoint of improving the low-temperature fixability and low-temperature fixability of the toner over time. More preferably, it is 90 mass% or more, More preferably, it is 95 mass% or more, More preferably, it is substantially 100 mass%, More preferably, it is 100 mass%.

When the resin constituting the resin particle (A) is the composite resin (a), the content of the polyester segment (a1) in the composite resin (a) is to improve the low temperature fixability and low temperature fixability of the toner over time. From the viewpoint of improvement, it is preferably 50% by mass or more, more preferably 55% by mass or more, still more preferably 58% by mass or more, and preferably 90% by mass or less, more preferably 85% by mass or less.
The content of the vinyl resin segment (a2) in the composite resin (a) is preferably 10% by mass or more, more preferably from the viewpoint of improving the low-temperature fixability and low-temperature fixability of the toner over time. It is 15% by mass or more, and preferably 50% by mass or less, more preferably 45% by mass or less, and still more preferably 42% by mass or less.
Further, the total content of the polyester segment (a1) and the vinyl resin segment (a2) in the composite resin (a) is preferably from the viewpoint of improving the low-temperature fixability and low-temperature fixability of the toner over time. It is 80 mass% or more, More preferably, it is 90 mass% or more, More preferably, it is 95 mass% or more, More preferably, it is 100 mass%.

[Manufacture of polyester resin]
Specifically, the polyester resin is preferably produced by the following method (i) from the viewpoint of a high degree of freedom in the reaction temperature of the polycondensation reaction.
(I) Used as necessary after a polycondensation reaction step (hereinafter also referred to as “step (X)”) with a polyhydric alcohol component (a-al) and a polycarboxylic acid component (a-ac). A method of performing a step of addition polymerization reaction (hereinafter also referred to as “step (Y)”) using a raw material monomer and an amphoteric monomer of the vinyl resin segment (a2).
In addition, when a polyester-type resin is a composite resin (a), it is preferable from a reactive viewpoint that both reactive monomers are supplied to a reaction system with the raw material monomer of a vinyl-type resin segment (a2). Further, from the viewpoint of reactivity, a catalyst such as an esterification catalyst or an esterification cocatalyst may be used, and a radical polymerization initiator and a radical polymerization inhibitor may be further used.
In addition, the polycarboxylic acid component (a-ac) may be subjected to polycondensation by partially subjecting it to a polycondensation reaction, then performing an addition polymerization reaction and then increasing the reaction temperature again and adding the remainder to the reaction system. This is more preferable because the reaction and, if necessary, the reaction with both reactive monomers can be further advanced.

In addition, when the polyester resin is the composite resin (a), it can be produced by the following method (ii) or (iii).
(Ii) Method of performing the step (X) of the polycondensation reaction with the raw material monomer of the polyester segment (a1) after the step (Y) of the addition polymerization reaction with the raw material monomer of the vinyl resin segment (a2) and the both reactive monomers (Iii) Step (X) of polycondensation reaction with polyhydric alcohol component (a-al) and polyhydric carboxylic acid component (a-ac) and addition of vinyl resin segment (a2) with raw material monomers and both reactive monomers Method of performing the step (Y) of the polymerization reaction in parallel The polycondensation reaction and the addition polymerization reaction of the methods (i) to (iii) are preferably performed in the same vessel.

From the viewpoint of resin productivity, the polycondensation reaction temperature is preferably 180 ° C. or higher, more preferably 200 ° C. or higher, and preferably 260 ° C. or lower, more preferably 250 ° C. or lower.
Moreover, it is preferable to accelerate the reaction by reducing the pressure of the reaction system in the latter half of the polycondensation reaction.

Examples of the esterification catalyst suitably used for the polycondensation reaction include tin compounds such as dibutyltin oxide and di (2-ethylhexanoic acid) tin (II), and titanium compounds such as titanium diisopropylate bistriethanolamate. Can be mentioned. Among these, a tin compound is preferable, and di (2-ethylhexanoic acid) tin (II) is more preferable.
The use amount of the esterification catalyst is preferably 0.01 mass with respect to the total amount of 100 mass parts of the polyhydric alcohol component (a-al) and the polyvalent carboxylic acid component (a-ac) from the viewpoint of reactivity. Part or more, more preferably 0.1 part by weight or more, and preferably 5 parts by weight or less, more preferably 2 parts by weight or less.

Examples of esterification promoters include pyrogallol compounds such as pyrogallol, gallic acid, and gallic acid esters; benzophenone derivatives such as 2,3,4-trihydroxybenzophenone and 2,2 ′, 3,4-tetrahydroxybenzophenone; epigallocatechin And catechin derivatives such as epigallocatechin gallate, etc., and gallic acid is preferred from the viewpoint of reactivity.
The use amount of the esterification cocatalyst is preferably 0.001 with respect to the total amount of 100 parts by mass of the polyhydric alcohol component (a-al) and the polyvalent carboxylic acid component (a-ac) from the viewpoint of reactivity. It is not less than 0.01 part by mass, more preferably not less than 0.01 part by mass, and preferably not more than 0.5 part by mass, more preferably not more than 0.2 part by mass.

As a radical polymerization inhibitor in the polycondensation reaction, 4-tert-butylcatechol or the like can be used.
The amount of the radical polymerization inhibitor used is preferably 0.001 part by mass or more, more preferably 100 parts by mass or more, more preferably 100 parts by mass of the total amount of the polyhydric alcohol component (a-al) and the polyvalent carboxylic acid component (a-ac). Is 0.005 parts by mass or more, and preferably 0.5 parts by mass or less, more preferably 0.2 parts by mass or less.

  The temperature of the addition polymerization reaction varies depending on the type of radical polymerization initiator used, but is preferably 110 ° C. or higher, more preferably 130 ° C. or higher, and preferably from the viewpoint of the productivity of the composite resin (a). Is 220 ° C. or lower, more preferably 210 ° C. or lower.

Known polymerization initiators for 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). These radical polymerization initiators 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 with respect to 100 parts by mass of the raw material monomer of the vinyl resin segment (a2). Hereinafter, it is more preferably 15 parts by mass or less.

  The softening point of the polyester resin is preferably 70 ° C. or higher, more preferably 80 ° C. or higher, and still more preferably 85 ° C. or higher, from the viewpoint of improving low-temperature fixability and low-temperature fixability of the toner over time. The temperature is preferably 140 ° C. or lower, more preferably 120 ° C. or lower, and still more preferably 110 ° C. or lower.

  The glass transition temperature of the polyester-based resin is preferably 30 ° C. or higher, more preferably 35 ° C. or higher, and further preferably 40 ° C. or higher, from the viewpoint of improving the low-temperature fixability and low-temperature fixability of the toner over time. And preferably it is 70 degrees C or less, More preferably, it is 60 degrees C or less, More preferably, it is 55 degrees C or less.

  The acid value of the polyester-based resin is preferably 5 mgKOH / g or more from the viewpoint of improving the dispersion stability of the resin particles (A), which will be described later, and from the viewpoint of improving the low-temperature fixability and low-temperature fixability of the toner over time. More preferably, it is 10 mgKOH / g or more, More preferably, it is 15 mgKOH / g or more, Preferably it is 40 mgKOH / g or less, More preferably, it is 35 mgKOH / g or less, More preferably, it is 30 mgKOH / g or less.

The softening point, glass transition temperature and acid value of the polyester-based resin can be appropriately adjusted according to the production conditions such as the type and ratio of the raw material monomers, the reaction temperature, the reaction time, and the cooling rate. It is calculated | required by the method of the below-mentioned Example.
In addition, when using 2 or more types of polyester resin in mixture, it is preferable that the value of the softening point, glass transition temperature, and acid value which were obtained as those mixtures is in the above-mentioned range, respectively.

As the resin constituting the resin particles (A), in addition to the polyester resin and the composite resin (a), a known resin used for toner, for example, a styrene-acrylic copolymer, epoxy, polycarbonate, polyurethane, or the like is contained. be able to.
The content of the resin in the resin particles (A) is preferably 80% by mass or more, more preferably 90% by mass or more, and still more preferably, from the viewpoint of improving the low-temperature fixability and low-temperature fixability of the toner over time. It is 95 mass% or more.

(Production of resin particles (A))
The resin particle (A) is obtained as an aqueous dispersion by dispersing a resin component constituting the resin particle (A) and an optional component such as a colorant, if necessary, in an aqueous medium.
As a method for obtaining an aqueous dispersion of the resin particles (A), a method of adding a resin or the like to an aqueous medium and performing a dispersion treatment with a disperser or the like, or a method of gradually adding an aqueous medium to a resin or the like and performing phase inversion emulsification From the viewpoint of improving the low-temperature fixability and low-temperature fixability of the obtained toner over time, a method using phase inversion emulsification is preferable.

The aqueous medium used for the production of the resin particles (A) is preferably one containing water as a main component, from the viewpoint of improving the dispersion stability of the aqueous dispersion of the resin particles (A), and from the viewpoint of environmental properties. The content of water in the aqueous medium is preferably 80% by mass or more, more preferably 90% by mass or more, still more preferably 95% by mass or more, still more preferably 98% by mass or more, and still more preferably 100% by mass. is there. As water, deionized water or distilled water is preferred.
Components other than water that can form an aqueous medium with water include alkyl alcohols having 1 to 5 carbon atoms; dialkyl ketones having 3 to 5 carbon atoms such as acetone and methyl ethyl ketone; dissolved in water such as cyclic ethers such as tetrahydrofuran An organic solvent is used. Among these, from the viewpoint of preventing the organic solvent from being mixed into the toner, an alkyl alcohol having 1 to 5 carbon atoms that does not dissolve the polyester is preferable, and methanol, ethanol, isopropanol, and butanol are more preferable.

As a phase inversion emulsification method, a resin and other optional components are dissolved in an organic solvent, an aqueous medium is added to the obtained solution to carry out phase inversion emulsification, and the resin and others. There is a method (1-2) in which an aqueous medium is added to a resin mixture obtained by melting and mixing the optional components and phase-inverted and emulsified. From the viewpoint of obtaining an aqueous dispersion of homogeneous resin particles (A), the method (1-1) is preferred.
In the method (1-1), first, the resin and other optional components are dissolved in an organic solvent to obtain an organic solvent solution of a mixture containing the resin and other optional components, and then the aqueous solution is added to the obtained solution. The method of adding phase and emulsifying phase inversion is preferred.

The organic solvent is preferably 15 when expressed by a solubility parameter (SP value: POLYMER HANDBOOK THIRD EDITION 1989 by John Wiley & Sons, Inc.) from the viewpoint of facilitating phase inversion to an aqueous medium by dissolving the resin. 1.0 MPa ^1/2 or more, more preferably 16.0 MPa ^1/2 or more, still more preferably 17.0 MPa ^1/2 or more, and preferably 26.0 MPa ^1/2 or less, more preferably 24.0 MPa ^{1 / 2} or less, more preferably 22.0 MPa ^1/2 or less.
Specific examples include alcohol solvents such as ethanol (26.0), isopropanol (23.5), isobutanol (21.5); acetone (20.3), methyl ethyl ketone (19.0), methyl isobutyl ketone ( 17.2), ketone solvents such as diethyl ketone (18.0); ether solvents such as dibutyl ether (16.5), tetrahydrofuran (18.6), dioxane (20.5); ethyl acetate (18. 6), and acetate solvents such as isopropyl acetate (17.4). In addition, the numerical value in the parenthesis after each solvent is each SP value (unit: MPa < ^1/2 >). Among these, from the viewpoint of easy removal from the mixed solution after addition of the aqueous medium, preferably one or more selected from ketone solvents and acetate solvents, more preferably from methyl ethyl ketone, ethyl acetate and isopropyl acetate. One or more selected, more preferably methyl ethyl ketone is used.

  The mass ratio between the organic solvent and the resin constituting the resin particles (A) (organic solvent / resin constituting the resin particles (A)) is a viewpoint that dissolves the resin and facilitates phase inversion to an aqueous medium, and the resin. From the viewpoint of improving the dispersion stability of the particles (A), it is preferably 0.1 or more, more preferably 0.2 or more, still more preferably 0.4 or more, and preferably 4 or less, more preferably 2 Hereinafter, it is more preferably 1.5 or less.

In the method (1-1), it is preferable to add a neutralizing agent to the solution. Examples of the neutralizing agent include basic substances. For example, alkali metal hydroxides such as lithium hydroxide, sodium hydroxide and potassium hydroxide; nitrogen-containing basic substances such as ammonia, trimethylamine, ethylamine, diethylamine, triethylamine, diethanolamine, triethanolamine and tributylamine Among these, from the viewpoint of improving the dispersion stability and aggregation of the resin particles (A), an alkali metal hydroxide is preferable, and sodium hydroxide is more preferable.
The neutralization degree (mol%) of the resin with the neutralizing agent is preferably 10 mol% or more, more preferably 30 mol% or more, and preferably 150 mol% or less, more preferably 120 mol% or less, Preferably it is 100 mol% or less.
In addition, the neutralization degree (mol%) of resin can be calculated | required by a following formula.
Degree of neutralization = [{addition mass of neutralizing agent (g) / equivalent of neutralizing agent} / [{resin acid value (mgKOH / g) × resin mass (g)} / (56 × 1000)]] × 100

The amount of the aqueous medium to be added is 100 mass of the resin constituting the resin particles (A) from the viewpoint of improving the dispersion stability of the resin particles (A) and obtaining uniform aggregated particles in the subsequent step (2). The amount 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.
From the viewpoint of improving the dispersion stability of the resin particles (A), the mass ratio of the aqueous medium to the organic solvent (aqueous medium / organic solvent) is preferably 20/80 or more, more preferably 50/50 or more. More preferably, it is 80/20 or more, and preferably 97/3 or less, more preferably 93/7 or less, and still more preferably 90/10 or less.

From the viewpoint of improving the dispersion stability of the resin particles (A), 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 (A). Specifically, it is preferably 50 ° C. or higher, more preferably 60 ° C. or higher, still more preferably 70 ° C. or higher, and preferably 85 ° C. or lower, more preferably 80 ° C. or lower, still more preferably 75 ° C. or lower. .
From the viewpoint of obtaining resin particles (A) having a small particle size, the addition rate of the aqueous medium is preferably 0.1 with respect to 100 parts by mass of the resin constituting the resin particles (A) until the phase inversion is completed. Parts by weight / minute or more, more preferably 0.5 parts by weight / minute or more, further preferably 1 part by weight / minute or more, still more preferably 3 parts by weight / minute or more, and preferably 50 parts by weight / minute. Hereinafter, it is more preferably 30 parts by mass / min or less, and further preferably 25 parts by mass / min or less. There is no restriction | limiting in the addition rate of the aqueous medium after phase inversion.

You may have the process of removing an organic solvent from the obtained dispersion liquid as needed after phase inversion emulsification. The method for removing the organic solvent is preferably distilled because it dissolves in water. In this case, it is preferable to raise the temperature to a temperature equal to or higher than the boiling point of the organic solvent to be distilled off while stirring. Further, from the viewpoint of maintaining the dispersion stability of the resin particles (A), it is more preferable to perform distillation under reduced pressure, and it is preferable to perform distillation at a constant temperature and pressure. Note that the temperature may be increased after the pressure is reduced, or the pressure may be decreased after the temperature is increased.
Further, the organic solvent may not be completely removed and may remain in the aqueous dispersion. In this case, the remaining amount of the organic solvent is preferably 1% by mass or less, more preferably 0.5% by mass or less, and still more preferably substantially 0% in the aqueous dispersion.

  The solid content concentration of the obtained aqueous dispersion of the resin particles (A) is preferably 5% from the viewpoint of improving the productivity of the toner and the dispersion stability of the aqueous dispersion of the resin particles (A). % Or more, more preferably 10% by weight or more, still more preferably 15% by weight or more, and preferably 50% by weight or less, more preferably 40% by weight or less, still more preferably 30% by weight or less, and still more preferably. 25% by mass or less. In addition, solid content is the total amount of non-volatile components, such as resin, a coloring agent, and surfactant.

The volume average particle diameter (D _V ) of the resin particles (A) in the aqueous dispersion is preferably 0.01 μm or more, more preferably 0.02 μm or more, further from the viewpoint of obtaining a toner capable of obtaining a high-quality image. The thickness is preferably 0.03 μm or more, and preferably 0.30 μm or less, more preferably 0.20 μm or less, and still more preferably 0.10 μm or less.
Here, the volume average particle diameter is a particle diameter obtained by multiplying the particle diameter measured on a volume basis by the ratio of particles having the particle diameter value and dividing the value obtained by the number of particles. Yes, it is determined by the method described in the examples below.

The coefficient of variation (CV value) (%) of the particle size distribution of the resin particles (A) is preferably 5% or more, more preferably from the viewpoint of improving the productivity of the aqueous dispersion of the resin particles (A). From the viewpoint of obtaining a toner capable of obtaining a high-quality image, it is preferably 50% or less, more preferably 40% or less, and still more preferably 30% or less.
The CV value is a value represented by the following formula.
CV value (%) = [standard deviation of particle size distribution (nm) / volume average particle size (nm)] × 100

(Production of aqueous dispersion of wax particles)
The aqueous dispersion of wax particles can be obtained by mixing the above wax, the above aqueous dispersion of the resin particles (A) and, if necessary, an aqueous medium.
In the step (1), since the polyester segment (a1) has an appropriate polarity by preparing wax particles using the wax and the resin particles (A), a surfactant is not particularly used. It becomes possible to disperse the wax in the aqueous medium.
That is, the wax particles contain wax and resin particles (A). In the aqueous dispersion of wax particles, it is considered that the wax is dispersed through the resin particles (A) having an appropriate polarity, and a large number of resin particles (A) are adsorbed around the wax particles. . Thereby, it is considered that the wax particles are easily taken into the aggregate of the (binding) resin particles (B) and the resin particles (C) in the subsequent aggregation step.

The aqueous dispersion of wax particles is preferably obtained by dispersing the aqueous dispersion of wax and resin particles (A) and, if necessary, an aqueous medium using a disperser at a temperature equal to or higher than the melting point of the wax. . As the disperser to be used, a homogenizer, a high-pressure disperser, an ultrasonic disperser and the like are preferable, and an ultrasonic disperser is more preferable, from the viewpoint of widening the fixable temperature range of the obtained toner and improving durability. What is necessary is just to set dispersion | distribution time suitably with the disperser to be used.
Examples of the ultrasonic disperser include an ultrasonic homogenizer. The commercially available products include “US-150T”, “US-300T”, “US-600T” (manufactured by Nippon Seiki Seisakusho Co., Ltd.), “SONIFIER (registered trademark) 4020-400”, “SONIFIER (registered trademark) 4020. -800 "(manufactured by Branson).
Further, before using the disperser, an aqueous dispersion of wax and resin particles (A), and if necessary, an aqueous medium may be preliminarily dispersed in a mixer such as a homomixer or a ball mill in advance. .

  The preferred embodiment of the aqueous medium used in the production is the same as that used when obtaining the resin particles (A).

  From the viewpoint of improving the dispersion stability of the wax particles, from the viewpoint of obtaining uniform aggregated particles in the subsequent aggregation process, and from the viewpoint of containing the wax in the toner even after heating in the fusing process, the wax and the resin particles (A) The mass ratio [wax / resin particles (A)] is preferably 100/5 to 100/100, more preferably 100/10 to 100/70, still more preferably 100/20 to 100/60, and still more preferably. 100/30 to 100/50.

From the viewpoint of obtaining a toner having excellent stability over time at low temperature fixability, the aqueous dispersion of wax particles preferably contains no surfactant, but contains a surfactant as long as the effect of the present invention is not impaired. May be.
From this viewpoint, when a surfactant is contained, the amount of the surfactant is preferably 1 part by mass or less, more preferably 0.5 part by mass or less, and still more preferably 0. When used for improving the dispersion stability of wax particles, it is preferably 0.01 parts by weight or more, more preferably 0.02 parts by weight or more, and still more preferably 0.001 part by weight or less. 05 parts by mass or more.

In step (1), it is preferable to add a wax and an aqueous dispersion of resin particles (A) to an aqueous medium and disperse the mixture while heating at a temperature equal to or higher than the melting point of the wax.
Specifically, the heating temperature at the time of dispersion is preferably not less than the melting point of the wax and not less than 80 ° C., more preferably not less than 85 ° C., and still more preferably 90, from the viewpoint of improving the productivity of the aqueous dispersion of wax particles. It is 100 degreeC or less, More preferably, it is 98 degreeC or less, More preferably, it is 95 degreeC or less.
The heating time during dispersion is preferably 5 minutes or more, more preferably 10 minutes or more, still more preferably 15 minutes or more, and preferably 3 from the viewpoint of improving the productivity of the aqueous dispersion of wax particles. It is not more than time, more preferably not more than 2 hours, still more preferably not more than 1 hour.

  The solid content concentration of the aqueous dispersion of wax particles is preferably 5% by mass or more, more preferably from the viewpoints of improving the dispersion stability of the wax particles, facilitating handling, and improving the productivity of the toner. Is 10% by mass or more, more preferably 15% by mass or more, and preferably 40% by mass or less, more preferably 30% by mass or less, and further preferably 25% by mass or less.

The volume median particle size (D ₅₀ ) of the wax particles is preferably 0 from the viewpoint of obtaining uniform agglomerated particles in the subsequent agglomeration step and improving the low-temperature fixability and low-temperature fixability of the toner over time. 0.05 μm or more, more preferably 0.20 μm or more, still more preferably 0.30 μm or more, still more preferably 0.40 μm or more, and preferably 1.00 μm or less, more preferably 0.80 μm or less, even more preferably. Is 0.70 μm or less, more preferably 0.65 μm or less, and still more preferably 0.60 μm or less.
Here, the volume-median particle size is a particle size at which the cumulative volume frequency calculated by the volume fraction is 50% when calculated from the smaller particle size, and is determined by the method described in the examples described later. .

The volume of the volume-median particle size volume average particle diameter _{(D V)} of the ratio (wax particles having a volume median particle size of the wax particles _{(D 50)} and the resin particles (A) _{(D 50)} / resin particles (A) The average particle diameter (D _V ) is preferably 1.0 or more, more preferably from the viewpoint of improving the dispersion stability of the wax particles and improving the low-temperature fixability and low-temperature fixability of the toner over time. Is 3.0 or more, more preferably 5.0 or more, and preferably 50 or less, more preferably 30 or less, still more preferably 15 or less, still more preferably 12 or less, and still more preferably 10 or less. .

<Step (2)>
Step (2) contains an aqueous dispersion of wax particles obtained in step (1), an aqueous dispersion of resin particles (B) containing crystalline polyester (b), and a composite resin (c). In this step, the resin particles (C) are mixed with an aqueous dispersion and aggregated to obtain aggregated particles.
The amount of wax particles relative to 100 parts by mass of the total amount of resin particles (B) and resin particles (C) used in step (2) is from the viewpoint of improving low-temperature fixability of toner and stability over time of low-temperature fixability. Preferably it is 1 part by mass or more, more preferably 3 parts by mass or more, more preferably 5 parts by mass or more, still more preferably 10 parts by mass or more, and preferably 40 parts by mass or less, more preferably 30 parts by mass or less. More preferably, it is 28 parts by mass or less.

Step (2) includes the next step (2A), and may further perform step (2B).
Step (2A): The aqueous dispersion of wax particles obtained in Step (1), the aqueous dispersion of resin particles (B), the aqueous dispersion of resin particles (C) and the flocculant are mixed in an aqueous medium. Step of obtaining aggregated particles (1) Step (2B): Resin particles (D) containing amorphous polyester (d) are added to the aggregated particles (1) obtained in step (2A) at once or a plurality of times. Step of obtaining the aggregated particles (2) obtained by attaching the resin particles (D) to the aggregated particles (1) by adding in a divided manner. When the step (2A) and the step (2B) are performed, the step “Aggregated particles obtained in step (2)” in (3) refers to “aggregated particles (2) obtained in step (2B)”. In addition, when step (2A) is performed and step (2B) is not performed, “aggregated particles obtained in step (2)” in step (3) is “obtained in step (2A)”. It means “aggregated particles (1)”.
Further, a colorant may be added in the step (2), particularly in the step (2A).

<Process (2A)>
In step (2A), the aqueous dispersion of wax particles obtained in step (1), the aqueous dispersion of resin particles (B), the aqueous dispersion of resin particles (C) and the flocculant are mixed in an aqueous medium. To obtain aggregated particles (1).

(Resin particles (B))
The resin particles (B) contain the crystalline polyester (b) from the viewpoint of improving the low temperature fixability of the toner and the stability over time of the low temperature fixability.

[Resin constituting resin particles (B)]
The content of the crystalline polyester (b) in the resin constituting the resin particles (B) is preferably 50% by mass or more in the resin from the viewpoint of improving the low temperature fixability of the toner and the stability over time of the low temperature fixability. More preferably, it is 70 mass% or more, More preferably, it is 90 mass% or more, More preferably, it is 95 mass% or more, More preferably, it is substantially 100 mass%, More preferably, it is 100 mass%.

In the present invention, the crystalline polyester (b) has a crystallinity index of 0.6 to 1.4.
The crystallinity index of the crystalline polyester (b) is preferably 0.8 or more, more preferably 0.9 or more, from the viewpoint of improving the low-temperature fixability and low-temperature fixability of the toner over time. Preferably it is 1.3 or less, More preferably, it is 1.2 or less.
The crystallinity index can be appropriately adjusted according to the production conditions such as the type and ratio of the raw material monomers, the reaction temperature, the reaction time, and the cooling rate, and the value is determined by the method described in the examples below. It is done.

  The crystalline polyester (b) is obtained by polycondensation of a polyhydric alcohol component (b-al) and a polyvalent carboxylic acid component (b-ac).

The polyhydric alcohol component (b-al) contains 80 mol% or more of an α, ω-aliphatic diol having 4 to 16 carbon atoms from the viewpoint of improving low-temperature fixability and low-temperature fixability of the toner over time. Those are preferred. The content of the α, ω-aliphatic diol is preferably 80 mol% or more, more preferably 85 mol% or more, still more preferably 90 mol% or more, and still more preferably in the polyhydric alcohol component (b-al). Is 95 mol% or more, more preferably 100 mol%.
From the same viewpoint, the α, ω-aliphatic diol has a carbon number of preferably 6 or more, more preferably 8 or more, and more preferably 14 or less, still more preferably 12 or less. Specifically, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10 -Decanediol, 1,11-undecanediol, 1,12-dodecanediol, 1,13-tridecanediol, 1,14-tetradecanediol and the like. Among these, 1,9-nonanediol, 1,10-decanediol, and 1,12-dodecanediol are preferable from the viewpoint of improving low-temperature fixability and low-temperature fixability of toner over time, and 1,10- Decanediol and 1,12-dodecanediol are more preferable, and 1,10-decanediol is more preferable.

The polyhydric alcohol component (b-al) may contain a polyhydric alcohol component other than an α, ω-aliphatic diol having 4 to 16 carbon atoms. For example, aliphatic diols having 2 to 7 carbon atoms such as ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, neopentyl glycol; aromatic diols such as alkylene oxide adducts of bisphenol A; glycerin, Examples thereof include trihydric or higher alcohols such as pentaerythritol and trimethylolpropane.
These polyhydric alcohol components (b-al) can be used alone or in combination of two or more.

The polyvalent carboxylic acid component (b-ac) preferably contains 80 mol% or more of an aliphatic dicarboxylic acid from the viewpoint of improving the low temperature fixability of the toner and the stability over time of the low temperature fixability. The content of the aliphatic dicarboxylic acid is preferably 80 mol% or more, more preferably 85 mol% or more, still more preferably 90 mol% or more, and still more preferably 95 mol in the polyvalent carboxylic acid component (b-ac). % Or more, more preferably 100 mol%.
The number of carbon atoms of the aliphatic dicarboxylic acid is preferably 4 or more, more preferably 8 or more, still more preferably 10 or more, from the viewpoint of improving the low-temperature fixability and low-temperature fixability of the toner over time. Preferably it is 14 or less, More preferably, it is 12 or less. Specifically, fumaric acid, sebacic acid and dodecanedioic acid are preferable, sebacic acid and dodecanedioic acid are more preferable, and sebacic acid is more preferable.
The polyvalent carboxylic acid component (b-ac) includes not only a free acid but also an anhydride that decomposes to generate an acid during the reaction, and an alkyl ester having 1 to 3 carbon atoms of each carboxylic acid.
These polyvalent carboxylic acid components (b-ac) can be used alone or in combination of two or more.

  The equivalent ratio (COOH group / OH group) of the polyvalent carboxylic acid component (b-ac) to the polyhydric alcohol component (b-al) is from the viewpoint of improving the low-temperature fixability and low-temperature fixability of the toner over time. , Preferably 0.7 or more, more preferably 0.8 or more, still more preferably 0.9 or more, and preferably 1.3 or less, more preferably 1.2 or less, still more preferably 1.1 or less. It is.

  The softening point of the crystalline polyester (b) is preferably 60 ° C. or higher, more preferably 70 ° C. or higher, and still more preferably 80 ° C. or higher, from the viewpoint of improving low-temperature fixability and low-temperature fixability of the toner over time. Yes, and preferably 150 ° C. or lower, more preferably 120 ° C. or lower, and still more preferably 100 ° C. or lower.

  The melting point of the crystalline polyester (b) is preferably 50 ° C. or higher, more preferably 60 ° C. or higher, and still more preferably 70 ° C. or higher, from the viewpoint of improving low-temperature fixability and low-temperature fixability of the toner. And, it is preferably 100 ° C. or lower, more preferably 90 ° C. or lower, still more preferably 80 ° C. or lower.

  The acid value of the crystalline polyester (b) is preferably 5 mg KOH from the viewpoint of improving low-temperature fixability and low-temperature fixability of the toner over time and improving the dispersion stability of the resin particles (B) described later. / G or more, more preferably 10 mgKOH / g or more, still more preferably 15 mgKOH / g or more, and preferably 35 mgKOH / g or less, more preferably 30 mgKOH / g or less, still more preferably 25 mgKOH / g or less.

The softening point, melting point, and acid value of the crystalline polyester (b) can be appropriately adjusted according to the production conditions such as the type and ratio of the raw material monomers, the reaction temperature, the reaction time, and the cooling rate. A value is calculated | required by the method as described in the below-mentioned Example.
In addition, when using 2 or more types of crystalline polyester (b) in mixture, it is preferable that the value of the softening point, melting | fusing point, and acid value which were obtained as those mixtures is in the said range, respectively.

[Production of crystalline polyester (b)]
For example, the crystalline polyester (b) may be prepared by mixing a polyhydric alcohol component (b-al) and a polyvalent carboxylic acid component (b-ac) in an inert gas atmosphere as necessary. It can be produced by polycondensation using a catalyst, a radical polymerization inhibitor or the like.
As the esterification catalyst, esterification co-catalyst, and radical polymerization inhibitor, the same ones as in the production of the polyester-based resin described above can be used. The preferable use amount is also the same.
The temperature of the polycondensation reaction is preferably 120 ° C. or higher, more preferably 160 ° C. or higher, still more preferably 180 ° C. or higher, and preferably 250 ° C. or lower, more preferably 230 ° C. or lower, more preferably 220 ° C. or lower. It is.

The resin constituting the resin particles (B) can contain, in addition to the crystalline polyester (b), known resins used for toners, such as styrene-acrylic copolymers, epoxies, polycarbonates, polyurethanes, and the like. .
The resin content in the resin particles (B) is preferably 80% by mass or more, more preferably 90% by mass or more, and still more preferably from the viewpoint of improving low-temperature fixability and low-temperature fixability of the toner over time. It is 95 mass% or more.

(Production of resin particles (B))
The resin particles (B) are preferably obtained as an aqueous dispersion by dispersing a resin component containing the crystalline polyester (b) and optional components such as a colorant, if necessary, in an aqueous medium.
The method for obtaining an aqueous dispersion is the same as in the case of the resin particles (A), in which the crystalline polyester (b) is added to an aqueous medium and dispersed using a disperser, and the crystalline polyester (b) is aqueous. Examples thereof include a method of gradually adding a medium for phase inversion emulsification, and the method by phase inversion emulsification is preferred from the viewpoint of improving the low-temperature fixability and low-temperature fixability of the resulting toner over time.
Also in the phase inversion emulsification method, in the same manner as in the case of the resin particles (A), a phase inversion emulsification is performed by adding an aqueous medium to a solution obtained by dissolving the resin and other optional components in an organic solvent. Is preferred. Preferred embodiments of the aqueous medium and the organic solvent that can be used are the same as in the production of the resin particles (A).

  The mass ratio of the organic solvent and the resin constituting the resin particles (B) (organic solvent / resin constituting the resin particles (B)) is a viewpoint that dissolves the resin and facilitates phase inversion to an aqueous medium, and the resin. From the viewpoint of improving the dispersion stability of the particles (B), it is preferably 0.1 or more, more preferably 0.2 or more, still more preferably 0.4 or more, and preferably 4 or less, more preferably 2 Hereinafter, it is more preferably 1 or less.

Moreover, it is preferable to add a neutralizing agent to a solution from a viewpoint of improving the dispersion stability of a resin particle (B). A preferred embodiment of the neutralizing agent is the same as in the production of the resin particles (A).
The degree of neutralization (mol%) of the crystalline polyester (b) by the neutralizer is preferably 10 mol% or more, more preferably 30 mol% or more, and preferably 150 mol% or less, more preferably 120 mol%. The mol% or less, more preferably 100 mol% or less.

The amount of the aqueous medium to be added is preferably 100 parts by mass or more, more preferably 150 parts by mass with respect to 100 parts by mass of the resin constituting the resin particles (B) from the viewpoint of improving the dispersion stability of the resin particles (B). It is at least 200 parts by mass, more preferably at least 200 parts by mass, and preferably at most 900 parts by mass, more preferably at most 600 parts by mass, and even more preferably at most 400 parts by mass.
From the same viewpoint, the mass ratio of the aqueous medium to the organic solvent (aqueous medium / organic solvent) is preferably 20/80 or more, more preferably 50/50 or more, still more preferably 80/20 or more, and , Preferably 97/3 or less, more preferably 93/7 or less, and still more preferably 90/10 or less.

From the viewpoint of improving the dispersion stability of the resin particles (B), the temperature at which the aqueous medium is added is preferably 30 ° C. or higher, more preferably 50 ° C. or higher, further preferably 60 ° C. or higher, and preferably Is 85 ° C. or lower, more preferably 80 ° C. or lower, and still more preferably 75 ° C. or lower.
From the viewpoint of stably obtaining an aqueous dispersion of the resin particles (B), the addition rate of the aqueous medium is preferably 0 with respect to 100 parts by mass of the resin constituting the resin particles (B) until the phase inversion is completed. 1 part by weight / minute or more, more preferably 0.5 part by weight / minute or more, further preferably 1 part by weight / minute or more, still more preferably 5 parts by weight / minute or more, and preferably 50 parts by weight. / Min or less, more preferably 30 parts by mass or less, still more preferably 20 parts by mass or less, and even more preferably 10 parts by mass or less. There is no restriction | limiting in the addition rate of the aqueous medium after phase inversion.

You may have the process of removing an organic solvent from the obtained dispersion as needed after phase inversion emulsification.
A preferred embodiment of the method for removing the organic solvent and the remaining amount of the organic solvent in the aqueous dispersion is the same as in the production of the resin particles (A).

  The solid content concentration of the obtained aqueous dispersion of the resin particles (B) is preferably 5% from the viewpoint of improving the productivity of the toner and improving the dispersion stability of the aqueous dispersion of the resin particles (B). % Or more, more preferably 10% by weight or more, still more preferably 15% by weight or more, and preferably 50% by weight or less, more preferably 40% by weight or less, still more preferably 30% by weight or less, and still more preferably. 25% by mass or less. In addition, solid content is the total amount of non-volatile components, such as resin, a coloring agent, and surfactant.

The volume median particle size (D ₅₀ ) of the resin particles (B) in the aqueous dispersion is preferably 0.05 μm or more, more preferably from the viewpoint of improving the low-temperature fixability and low-temperature fixability of the toner over time. Is 0.10 μm or more, more preferably 0.12 μm or more, and preferably 0.80 μm or less, more preferably 0.40 μm or less, still more preferably 0.20 μm or less.
Here, the volume-median particle size is a particle size at which the cumulative volume frequency calculated by the volume fraction is 50% when calculated from the smaller particle size, and is determined by the method described in the examples described later. .

  The coefficient of variation (CV value) (%) of the particle size distribution of the resin particles (B) is preferably 5% or more, more preferably from the viewpoint of improving the productivity of the aqueous dispersion of the resin particles (B). From the viewpoint of obtaining a toner capable of obtaining a high-quality image, it is preferably 50% or less, more preferably 40% or less, and even more preferably 30% or less.

(Resin particles (C))
The resin particles (C) are composed of a polyester resin segment (c1) and a vinyl resin segment containing a structural unit derived from a styrenic compound from the viewpoint of improving low temperature fixability of toner and stability over time of low temperature fixability. A composite resin (c) containing (c2). The resin particles (C) function as a binder resin for the toner.

[Resin constituting resin particles (C)]
The composite resin (c) having the polyester segment (c1) is easily compatible with not only the crystalline polyester (b) but also the resin particles (A) in which wax is dispersed, and an aggregate of the resin particles (C) in the aggregation process Wax particles are easily taken into the inside. Furthermore, in the fusing step, the polyester segments of the composite resin (c) constituting the resin particles (C) and the polyester resin constituting the resin particles (A) existing on the surface of the wax particles are easily integrated. In addition, since the vinyl resin segment (c2) containing a structural unit derived from a styrene compound is compatible with a wax having a low polarity, the wax is finely dispersed in the fused particles and the toner particles.
The content of the composite resin (c) in the resin constituting the resin particles (C) is preferably from 50% by mass or more in the resin from the viewpoint of improving the low temperature fixability of the toner and the stability over time of the low temperature fixability. More preferably, it is 70 mass% or more, More preferably, it is 90 mass% or more, More preferably, it is 95 mass% or more, More preferably, it is substantially 100 mass%.

The composite resin (c) is preferably an amorphous resin from the viewpoint of improving the low temperature fixability of the toner and the stability over time of the low temperature fixability.
In the present invention, the amorphous resin is one having a crystallinity index exceeding 1.4 or less than 0.6.
The crystallinity index can be appropriately adjusted according to the production conditions such as the type and ratio of the raw material monomers, the reaction temperature, the reaction time, and the cooling rate, and the value is determined by the method described in the examples below. It is done.

≪Polyester segment (c1) ≫
The polyester segment (c1) is a polycondensation of a polyhydric alcohol component (c-al) and a polyvalent carboxylic acid component (c-ac) from the viewpoint of improving low-temperature fixability and low-temperature fixability of the toner over time. It is a segment made of a polyester resin.

The polyhydric alcohol component (c-al) preferably contains 80 mol% or more of an alkylene oxide adduct of bisphenol A from the viewpoint of improving low-temperature fixability and low-temperature fixability of the toner over time. From the same viewpoint, the content of the alkylene oxide adduct of bisphenol A in the polyhydric alcohol component (c-al) is preferably 80 mol% or more, more preferably 90 mol% or more, and still more preferably 95 mol% or more. More preferably, it is 98 mol% or more, and still more preferably 100 mol%.
The alkylene oxide adduct of bisphenol A is preferably an ethylene oxide adduct of bisphenol A (polyoxyethylene-2,2-bis (4-hydroxyphenyl) propane) and a propylene oxide adduct of bisphenol A (polyoxypropylene- 1,2-bis (4-hydroxyphenyl) propane), more preferably a propylene oxide adduct of bisphenol A.
The average addition mole number of alkylene oxide of the alkylene oxide adduct of bisphenol A is preferably 1 or more, more preferably 1.2 or more, further from the viewpoint of improving the low-temperature fixability and low-temperature fixability of the toner over time. It is preferably 1.5 or more, and preferably 16 or less, more preferably 12 or less, still more preferably 8 or less, and still more preferably 4 or less.

The polyhydric alcohol component (c-al) may contain other polyhydric alcohols other than the bisphenol A alkylene oxide adduct. Other polyhydric alcohol components that the polyhydric alcohol component (c-al) may contain include aliphatic diols, aromatic diols, alicyclic diols, trivalent or higher polyhydric alcohols, or those having 2 or more carbon atoms. The following alkylene oxide (average addition mole number 1-16) addition products etc. are mentioned. Specific examples thereof include ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, and 2,3-butanediol. Neopentyl glycol, 1,4-butenediol, 1,5-pentanediol, 1,6-hexanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,12 Aliphatic diols such as dodecanediol; aromatic diols such as bisphenol A (2,2-bis (4-hydroxyphenyl) propane); hydrogenated bisphenol A (2,2-bis (4-hydroxycyclohexyl) propane), etc. Of these alicyclic diols, or alkylene oxides having 2 or more and 4 or less carbon atoms (average added mole number 2) Top 12 or less) Adducts: Trivalent or higher polyhydric alcohols such as glycerin, pentaerythritol, trimethylolpropane, sorbitol, or their alkylene oxides having 2 to 4 carbon atoms (average added mole number of 1 to 16) Thing etc. are mentioned.
These polyhydric alcohol components (c-al) can be used alone or in combination of two or more.

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

Examples of the dicarboxylic acid include aromatic dicarboxylic acid, aliphatic dicarboxylic acid, and alicyclic dicarboxylic acid, and aromatic dicarboxylic acid and aliphatic dicarboxylic acid are preferable.
The polyvalent carboxylic acid component (c-ac) includes not only a free acid but also an anhydride that decomposes to generate an acid during the reaction, and an alkyl ester having 1 to 3 carbon atoms of each carboxylic acid.
Examples of the aromatic dicarboxylic acid include phthalic acid, isophthalic acid, terephthalic acid and the like. From the viewpoint of improving low-temperature fixability and low-temperature fixability of the toner over time, isophthalic acid and terephthalic acid are preferable, and terephthalic acid is preferable. More preferred.
From the same viewpoint, the aliphatic dicarboxylic acid preferably has 2 to 30 carbon atoms, and more preferably 3 to 20 carbon atoms.
Examples of the aliphatic dicarboxylic acid having 2 to 30 carbon atoms include oxalic acid, malonic acid, maleic acid, fumaric acid, citraconic acid, itaconic acid, glutaconic acid, succinic acid, adipic acid, sebacic acid, 1,12-dodecanedioic acid. Acid, 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, and fumaric acid and sebacic acid from the viewpoint of improving the charging characteristics of the toner. Adipic acid is preferable, and fumaric acid and sebacic acid are more preferable. Specific examples of the succinic acid substituted with an alkyl group having 1 to 20 carbon atoms or an alkenyl group having 2 to 20 carbon atoms include dodecyl succinic acid, dodecenyl succinic acid, octenyl succinic acid, and the like.
Among these, terephthalic acid, fumaric acid, sebacic acid, and adipic acid are preferable. From the viewpoint of improving low-temperature fixability and low-temperature fixability of the toner over time, it is more preferable to use these in combination. And fumaric acid are more preferably used in combination.

As the trivalent or higher polyvalent carboxylic acid, trimellitic acid and acid anhydride thereof are preferable, and trimellitic acid anhydride is more preferable from the viewpoint of improving low-temperature fixability and low-temperature fixability of the toner over time.
In addition, the content in the case of containing a trivalent or higher polyvalent carboxylic acid is preferable in the polyvalent carboxylic acid component (c-ac) from the viewpoint of improving low-temperature fixability and low-temperature fixability of the toner over time. Is 3 mol% or more, more preferably 5 mol% or more, and preferably 30 mol% or less, more preferably 20 mol% or less.
These polyvalent carboxylic acid components (c-ac) can be used alone or in combination of two or more.

  The equivalent ratio (COOH group / OH group) of the polycarboxylic acid component (c-ac) to the polyhydric alcohol component (c-al) is from the viewpoint of improving the low-temperature fixability and low-temperature fixability of the toner over time. , Preferably 0.7 or more, more preferably 0.8 or more, and preferably 1.3 or less, more preferably 1.2 or less.

≪Vinyl resin segment (c2) ≫
The vinyl resin segment (c2) preferably contains a structural unit derived from a styrene compound from the viewpoint of improving the low-temperature fixability and low-temperature fixability of the toner over time.

Examples of the styrenic 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. Specifically, styrenes such as styrene, methyl styrene, α-methyl styrene, β-methyl styrene, t-butyl styrene, chlorostyrene, chloromethyl styrene, methoxy styrene, styrene sulfonic acid or a salt thereof are preferable. More preferably, styrene is more preferable.
The content of the styrene compound in the raw material vinyl monomer that is a component derived from the vinyl resin segment (c2) is preferably 50% by mass or more from the viewpoint of improving the low temperature fixability of the toner and the temporal stability of the low temperature fixability. More preferably, it is 60 mass% or more, More preferably, it is 70 mass% or more, And it is preferably 95 mass% or less, More preferably, it is 90 mass% or less, More preferably, it is 85 mass% or less.

As raw material vinyl monomers other than styrene compounds, (meth) acrylic acid such as alkyl (meth) acrylate (alkyl group having 1 to 24 carbon atoms), benzyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, etc. Acid esters; olefins such as ethylene, propylene and butadiene; halovinyls such as vinyl chloride; vinyl esters such as vinyl acetate and vinyl propionate; vinyl ethers such as vinyl methyl ether; vinylidene halides such as vinylidene chloride; Examples thereof include N-vinyl compounds such as vinyl pyrrolidone. Among these, from the viewpoint of improving low-temperature fixability of toner and stability over time of low-temperature fixability, (meth) acrylic acid esters are preferable, and alkyl (meth) acrylate (alkyl group having 1 to 22 carbon atoms) is preferable. More preferred.
The number of carbon atoms of the alkyl group in the alkyl (meth) acrylate is preferably 1 or more, more preferably 4 or more, and still more preferably 6 or more, from the viewpoint of improving low-temperature fixability and low-temperature fixability of the toner over time. From the viewpoint of availability of the monomer, it is preferably 24 or less, more preferably 22 or less, and still more preferably 20 or less.
Specifically, methyl (meth) acrylate, ethyl (meth) acrylate, (iso) propyl (meth) acrylate, (meth) acrylic acid (iso or tertiary) butyl, (meth) acrylic acid (iso) Amyl, cyclohexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, (meth) acrylic acid (iso) octyl, (meth) acrylic acid (iso) decyl, (meth) acrylic acid (iso) dodecyl, (meta ) (Iso) palmityl acrylate, (meth) acrylic acid (iso) stearyl, (meth) acrylic acid (iso) behenyl, etc., and (meth) acrylic acid 2-ethylhexyl or stearyl methacrylate is preferred, stearyl methacrylate Is more preferable.

Among these, the vinyl resin segment (c2) is styrene alone or styrene and (meth) acrylic acid ester from the viewpoint of improving the availability of the monomer and the low-temperature fixability and low-temperature fixability of the toner over time. In combination, styrene and a (meth) acrylic acid ester are more preferable, and a combination of styrene and an alkyl (meth) acrylate having an alkyl group having 6 to 20 carbon atoms is more preferable.
When a styrene compound and a (meth) acrylic acid ester are used in combination, the content of the (meth) acrylic acid ester in the raw material vinyl monomer that is a component derived from the vinyl resin segment (c2) depends on the low-temperature fixability of the toner and From the viewpoint of improving the temporal stability of the low-temperature fixability, it is preferably 5% by mass or more, more preferably 10% by mass or more, still more preferably 15% by mass or more, and preferably 50% by mass or less, more preferably It is 40 mass% or less, More preferably, it is 30 mass% or less.
In addition, the total amount of styrene compound and (meth) acrylate in the raw material vinyl monomer, which is the component derived from the vinyl resin segment (c2), improves the low-temperature fixability and low-temperature fixability of the toner over time. From the viewpoint of making it, it is preferably 80% by mass or more, more preferably 90% by mass or more, still more preferably 95% by mass or more, and still more preferably 100% by mass.

≪Amotropic monomer≫
By using an amphoteric monomer as a raw material monomer, the amphoteric monomer reacts with both the polyester segment (c1) and the vinyl resin segment (c2), thereby making it easy to produce a composite resin (c). Become. That is, it is preferable that the composite resin (c) includes a structural unit derived from the both reactive monomers, and the structural unit derived from the both reactive monomers includes the vinyl resin segment (c2) and the polyester segment (c1). It is preferable that it becomes a coupling | bonding point with.
Examples of the both reactive monomers include vinyl monomers having one or more functional groups selected from a hydroxyl group, a carboxy group, an epoxy group, a primary amino group, and a secondary amino group in the molecule. Among these, from the viewpoint of reactivity, a vinyl monomer having a hydroxyl group and / or a carboxy group is preferable, and a vinyl monomer having a carboxy group is more preferable. Specific examples include acrylic acid, methacrylic acid, fumaric acid, maleic acid and the like. Among these, 1 selected from acrylic acid and methacrylic acid from the viewpoint of both the polycondensation reaction and the addition polymerization reaction. More than seeds are preferred, and acrylic acid is more preferred.

  The amount of the both reactive monomers used is the raw material for the polyester segment (c1) from the viewpoint of dispersibility of the addition polymer containing the structural unit derived from the styrene compound in the polyester resin and reaction control of the addition polymerization reaction and the polycondensation reaction. Is preferably 1 mol part or more, more preferably 5 mol part or more, still more preferably 10 mol part or more, and preferably 30 mol with respect to 100 mol part of the total amount of the polyhydric alcohol component (c-al). Part or less, more preferably 25 parts by mole or less, still more preferably 20 parts by mole or less.

The content of the polyester segment (c1) in the composite resin (c) is preferably 40% by mass or more, more preferably 50% by mass or more, from the viewpoint of improving low-temperature fixability and low-temperature fixability of the toner over time. More preferably, it is 55% by mass or more, and preferably 90% by mass or less, more preferably 85% by mass or less.
Further, the content of the vinyl resin segment (c2) in the composite resin (c) is preferably 10% by mass or more, more preferably from the viewpoint of improving the low-temperature fixability and low-temperature fixability of the toner over time. It is 15% by mass or more, and preferably 60% by mass or less, more preferably 50% by mass or less, and still more preferably 45% by mass or less.
Further, the total content of the polyester segment (c1) and the vinyl resin segment (c2) in the composite resin (c) is preferably from the viewpoint of improving the low-temperature fixability and low-temperature fixability of the toner over time. It is 80 mass% or more, More preferably, it is 90 mass% or more, More preferably, it is 95 mass% or more, More preferably, it is 100 mass%.

[Production of composite resin (c)]
The composite resin (c) can be produced by the same method as in the production of the composite resin (a) described above. The temperature and procedure of the polycondensation reaction and the addition polymerization reaction can be produced by the same method as in the production of the composite resin (a) described above, and can be used as an esterification catalyst, esterification cocatalyst, radical polymerization inhibitor. As the radical polymerization initiator and the like, those similar to those used in the production of the composite resin (a) can be used. The preferable use amount is also the same.

  The softening point of the composite resin (c) is preferably 70 ° C. or higher, more preferably 80 ° C. or higher, and still more preferably 85 ° C. or higher, from the viewpoint of improving the low-temperature fixability and low-temperature fixability of the toner over time. And, it is preferably 140 ° C. or lower, more preferably 120 ° C. or lower, still more preferably 110 ° C. or lower.

  From the same viewpoint, the glass transition temperature of the composite resin (c) is preferably 30 ° C. or higher, more preferably 33 ° C. or higher, still more preferably 35 ° C. or higher, and preferably 70 ° C. or lower, more preferably 60 ° C. ° C or lower, more preferably 50 ° C or lower, and still more preferably 40 ° C or lower.

  The acid value of the composite resin (c) is preferably 5 mgKOH / g from the viewpoint of improving the dispersion stability of the resin particles (C), which will be described later, and improving the low-temperature fixability and low-temperature fixability of the toner over time. Above, more preferably 10 mgKOH / g or more, still more preferably 15 mgKOH / g or more, and preferably 40 mgKOH / g or less, more preferably 35 mgKOH / g or less, still more preferably 30 mgKOH / g or less.

The softening point, glass transition temperature, and acid value of the composite resin (c) can be appropriately adjusted according to the production conditions such as the type and ratio of the raw material monomers, the reaction temperature, the reaction time, and the cooling rate. A value is calculated | required by the method as described in the below-mentioned Example.
In addition, when using 2 or more types of resin which comprises resin particle (C) in mixture, the softening point, glass transition temperature, and acid value which were obtained as those mixtures are in the above-mentioned range, respectively. Is preferred.

As the resin constituting the resin particles (C), in addition to the composite resin (c), known resins used for toner, for example, polyester, styrene-acrylic copolymer, epoxy, polycarbonate, polyurethane and the like are contained. Can do.
The content of the resin in the resin particles (C) is preferably 80% by mass or more, more preferably 90% by mass or more, and still more preferably, from the viewpoint of improving low-temperature fixability and low-temperature fixability of the toner over time. It is 95 mass% or more.

(Production of resin particles (C))
The resin particles (C) are preferably obtained as an aqueous dispersion by dispersing a resin component constituting the resin particles (C) and optional components such as a colorant, if necessary, in an aqueous medium.
As in the case of the resin particles (A), the aqueous dispersion is obtained by adding the composite resin (c) or the like to the aqueous medium and dispersing it using a disperser, or by adding the aqueous medium to the composite resin (c) or the like. Examples include a method of gradually adding and phase inversion emulsification, and the method by phase inversion emulsification is preferable from the viewpoint of improving the low-temperature fixability and low-temperature fixability of the resulting toner over time.
Also in the phase inversion emulsification method, in the same manner as in the case of the resin particles (A), a phase inversion emulsification is performed by adding an aqueous medium to a solution obtained by dissolving the resin and other optional components in an organic solvent. Is preferred. Preferred embodiments of the aqueous medium and the organic solvent that can be used are the same as in the production of the resin particles (A).

  The mass ratio between the organic solvent and the resin constituting the resin particles (C) (organic solvent / resin constituting the resin particles (C)) is a viewpoint that dissolves the resin and facilitates phase inversion to an aqueous medium, and the resin. From the viewpoint of improving the dispersion stability of the particles (C), it is preferably 0.1 or more, more preferably 0.2 or more, still more preferably 0.4 or more, and preferably 4 or less, more preferably 2 Hereinafter, it is more preferably 1 or less.

Moreover, it is preferable to add a neutralizing agent to a solution from a viewpoint of improving the dispersion stability of the resin particle (C). A preferred embodiment of the neutralizing agent is the same as in the production of the resin particles (A).
The degree of neutralization (mol%) of the composite resin (c) with the neutralizing agent 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 amount of the aqueous medium to be added is preferably 100 parts by mass or more, more preferably 150 parts by mass with respect to 100 parts by mass of the resin constituting the resin particles (C) from the viewpoint of improving the dispersion stability of the resin particles (C). It is at least 200 parts by mass, more preferably at least 200 parts by mass, and preferably at most 900 parts by mass, more preferably at most 600 parts by mass, and even more preferably at most 400 parts by mass.
From the same viewpoint, the mass ratio of the aqueous medium to the organic solvent (aqueous medium / organic solvent) is preferably 20/80 or more, more preferably 50/50 or more, still more preferably 80/20 or more, and , Preferably 97/3 or less, more preferably 93/7 or less, and still more preferably 90/10 or less.

From the viewpoint of improving the dispersion stability of the resin particles (C), the temperature at which the aqueous medium is added is preferably 30 ° C. or higher, more preferably 50 ° C. or higher, still more preferably 60 ° C. or higher, and preferably Is 85 ° C. or lower, more preferably 80 ° C. or lower, and still more preferably 75 ° C. or lower.
From the viewpoint of stably obtaining an aqueous dispersion of the resin particles (C), the addition rate of the aqueous medium is preferably 0 with respect to 100 parts by mass of the resin constituting the resin particles (C) until the phase inversion is completed. 1 part by weight / minute or more, more preferably 0.5 part by weight / minute or more, further preferably 1 part by weight / minute or more, still more preferably 5 parts by weight / minute or more, and preferably 50 parts by weight. / Min or less, more preferably 30 parts by mass or less, still more preferably 20 parts by mass or less, and even more preferably 10 parts by mass or less. There is no restriction | limiting in the addition rate of the aqueous medium after phase inversion.

You may have the process of removing an organic solvent from the obtained dispersion as needed after phase inversion emulsification.
A preferred embodiment of the method for removing the organic solvent and the remaining amount of the organic solvent in the aqueous dispersion is the same as in the production of the resin particles (A).

  The solid content concentration of the aqueous dispersion of the resin particles (C) obtained is preferably 5% from the viewpoint of improving the productivity of the toner and the dispersion stability of the aqueous dispersion of the resin particles (C). % Or more, more preferably 10% by weight or more, still more preferably 15% by weight or more, and preferably 50% by weight or less, more preferably 40% by weight or less, still more preferably 30% by weight or less, and still more preferably. 25% by mass or less. In addition, solid content is the total amount of non-volatile components, such as resin, a coloring agent, and surfactant.

The volume median particle size (D ₅₀ ) of the resin particles (C) in the aqueous dispersion is preferably 0.05 μm or more, more preferably from the viewpoint of improving the low temperature fixability and low temperature fixability of the toner over time. Is 0.10 μm or more, more preferably 0.12 μm or more, and preferably 0.80 μm or less, more preferably 0.40 μm or less, still more preferably 0.20 μm or less.

  Further, the coefficient of variation (CV value) (%) of the particle size distribution of the resin particles (C) is preferably 5% or more, more preferably from the viewpoint of improving the productivity of the aqueous dispersion of the resin particles (C). From the viewpoint of obtaining a toner capable of obtaining a high-quality image, it is preferably 50% or less, more preferably 40% or less, and even more preferably 30% or less.

(Optional component)
The toner produced according to the present invention may contain a colorant and a charge control agent as necessary. Moreover, additives such as reinforcing fillers such as fibrous substances, antioxidants, and anti-aging agents may be included as long as the effects of the present invention are not impaired.

(Agglomerated particles (1))
In the step (2A), the aqueous dispersion of the wax particles, the aqueous dispersion of the resin particles (B), the aqueous dispersion of the resin particles (C), and a flocculant as necessary are mixed and aggregated. Aggregated particles (1) are obtained. At this time, the above-mentioned aqueous dispersion of wax particles, aqueous dispersion of resin particles (B), aqueous dispersion of resin particles (C), and optional components such as an aggregating agent, a surfactant, and a colorant as necessary. Are preferably mixed in an aqueous medium to obtain a mixed dispersion. Then, the particles in the mixed dispersion are aggregated to obtain a dispersion of aggregated particles (1). From the viewpoint of efficiently performing the aggregation, it is preferable to add an aggregating agent.

In addition, when a colorant is not mixed in the resin particle (B) and the resin particle (C), it is preferable to mix the colorant in the present mixed dispersion. When adding a colorant, it may be added in one or both of step (2A) and step (2B), but it is preferably added in step (2A) and not in step (2B). This further suppresses the colorant from being detached from the toner.
Moreover, you may mix resin particles other than the resin particle (B) and resin particle (C) in the mixed dispersion liquid in the range which does not inhibit the effect of this invention.
The total content of the resin particles (B) and the resin particles (C) is preferably 80% by mass or more, more preferably 90% by mass or more, in all the resin particles in the mixed dispersion excluding the resin particles (A). More preferably, it is 95 mass% or more, More preferably, it is 98 mass% or more, More preferably, it is 100 mass%.
There is no restriction | limiting in order of mixing, You may add any in order and may add simultaneously.

[Colorant]
When the colorant is mixed in the mixed dispersion, it is preferable to use a dispersion of colorant particles in which the colorant is dispersed in an aqueous medium.
As the colorant, pigments and dyes are used, and pigments are preferable from the viewpoint of improving the image density of the toner.
Specific examples of the pigment include carbon black, inorganic composite oxide, benzidine yellow, brilliantamine 3B, brilliantamine 6B, bengal, aniline blue, ultramarine blue, copper phthalocyanine, and phthalocyanine green. Among these, copper Phthalocyanine is preferred.
Specific examples of the dye include acridine series, azo series, benzoquinone series, azine series, anthraquinone series, indigo series, phthalocyanine series, and aniline black series.
A coloring agent can be used individually or in combination of 2 or more types.
The amount of the colorant used is preferably 2 masses per 100 mass parts of the total amount of the resin particles (B) and the resin particles (C) from the viewpoint of improving the image density of the printed material and obtaining a high-quality image. Part or more, more preferably 5 parts by weight or more, still more preferably 7 parts by weight or more, and preferably 30 parts by weight or less, more preferably 20 parts by weight or less, still more preferably 15 parts by weight or less.

The colorant dispersion is preferably obtained by dispersing a colorant and an aqueous medium using a disperser. As the disperser, a homogenizer, an ultrasonic disperser or the like is preferable.
As an aqueous medium, what was mentioned by manufacture of the aqueous dispersion of the above-mentioned resin particle (A) is preferable.
The dispersion of the colorant in the 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 include nonionic surfactants, anionic surfactants, and cationic surfactants, and the viewpoint of improving the dispersion stability of the colorant particles, and From the viewpoint of improving the cohesiveness between the colorant particles, the resin particles (B), and the resin particles (C), an anionic surfactant is preferable. Specific examples include sodium dodecylbenzenesulfonate, sodium dodecylsulfate, sodium lauryl ether sulfate, dipotassium alkenyl succinate, and preferably sodium dodecylbenzenesulfonate.
From the viewpoint of improving the dispersion stability of the colorant, the content of the surfactant in the colorant dispersion is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, and still more preferably 1. It is 0 mass% or more, and preferably 5.0 mass% or less, more preferably 4.5 mass% or less.
The solid content concentration of the colorant dispersion is preferably 5% by mass or more, more preferably 10% by mass or more, and still more preferably, from the viewpoint of improving the productivity of the toner and improving the dispersion stability of the colorant. It is 15% by mass or more, and preferably 50% by mass or less, more preferably 40% by mass or less, and further preferably 30% by mass or less.
The volume median particle size (D ₅₀ ) of the colorant particles in the colorant dispersion is preferably 0.050 μm or more, more preferably 0.080 μm or more, still more preferably 0.10 μm or more, and preferably It is 0.30 μm or less, more preferably 0.20 μm or less, and still more preferably 0.15 μm or less.

The total content of the resin particles (B) and the resin particles (C) in the mixed dispersion is preferably 5% by mass or more from the viewpoint of improving low-temperature fixability and low-temperature fixability of the resulting toner over time. More preferably 10% by mass or more, and still more preferably 12% by mass or more, and preferably 40% by mass or less, more preferably 30% by mass from the viewpoint of controlling aggregation and obtaining aggregated particles having a desired particle size. % Or less, more preferably 20% by mass or less.
The mass ratio [resin particles (B) / resin particles (C)] of the resin particles (B) and the resin particles (C) in the mixed dispersion improves the low-temperature fixability and low-temperature fixability of the toner over time. In view of the above, it is preferably 1/99 or more, more preferably 3/97 or more, still more preferably 5/95 or more, still more preferably 8/92 or more, and preferably 30/70 or less, more preferably 25/75 or less, more preferably 18/82 or less, and still more preferably 12/88 or less.

  The content of the wax particles in the mixed dispersion is such that the total amount of the resin particles (B) and the resin particles (C) is 100 from the viewpoint of improving the releasability, low-temperature fixability, and low-temperature fixability of the toner over time. The amount is preferably 1 part by weight or more, more preferably 3 parts by weight or more, still more preferably 5 parts by weight or more, and still more preferably 10 parts by weight or more with respect to parts by weight. From the viewpoint of improving the stability over time, the amount is preferably 40 parts by mass or less, more preferably 30 parts by mass or less, and still more preferably 28 parts by mass or less.

The mass ratio [resin particles (B) / wax particles] of the resin particles (B) and wax particles in the mixed dispersion is preferably from the viewpoint of improving the low-temperature fixability and low-temperature fixability of the toner over time. Is 0.10 or more, more preferably 0.20 or more, further preferably 0.30 or more, and preferably 5.0 or less, more preferably 3.0 or less, still more preferably 2.0 or less, more More preferably, it is 1.4 or less.
The content of the colorant in the case of mixing the colorant in the mixed dispersion is 100 parts by mass in total of the resin particles (B) and the resin particles (C) from the viewpoint of obtaining a toner capable of obtaining a high-quality image. On the other hand, it is preferably 2 parts by mass or more, more preferably 5 parts by mass or more, still more preferably 7 parts by mass or more, 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 mixing temperature is preferably 0 ° C. or higher, more preferably 10 ° C. or higher, further preferably 20 ° C. or higher, and preferably 40 ° C. or lower, from the viewpoint of controlling aggregation and obtaining aggregated particles having a target particle size. More preferably, it is 30 ° C. or lower.

[Flocculant]
Next, particles in the mixed dispersion can be aggregated to suitably obtain an aqueous dispersion of aggregated particles (1). It is preferable to add a flocculant for efficient aggregation.
The flocculant is preferably an electrolyte, and more preferably a salt, from the viewpoint of obtaining a toner having a desired particle size while preventing excessive aggregation. Specific examples of the flocculant include quaternary salt cationic surfactants, organic flocculants such as polyethyleneimine; inorganic flocculants such as inorganic metal salts, inorganic ammonium salts, and bivalent metal complexes. It is done. From the viewpoint of improving cohesion and obtaining uniform aggregated particles, inorganic coagulants are preferred, inorganic metal salts and inorganic ammonium salts are more preferred, and inorganic ammonium salts are even more preferred.
The valence of the cation of the inorganic flocculant is preferably 5 or less, more preferably 2 or less, and even more preferably 1 from the viewpoint of obtaining a toner having a desired particle size while preventing excessive aggregation. Examples of the monovalent cation of the inorganic flocculant include sodium ion, potassium ion, ammonium ion, and the like. From the viewpoint of improving low-temperature fixability and low-temperature fixability of the resulting toner over time, ammonium ions are preferable. .
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 inorganic ammonium salts include ammonium sulfate, ammonium chloride, and ammonium nitrate.
As the flocculant, ammonium sulfate is more preferable.

  The use amount of the flocculant is preferably 100 parts by mass with respect to the total amount of the resin constituting the resin particles (B) and the resin particles (C) from the viewpoint of obtaining the desired particle size by controlling the aggregation of the resin particles. 5 parts by mass or more, more preferably 10 parts by mass or more, and further preferably 20 parts by mass or more. From the viewpoint of improving the low-temperature fixability and low-temperature fixability of the resulting toner over time, preferably 50 parts by mass or less. More preferably, it is 45 mass parts or less, More preferably, it is 40 mass parts or less.

The flocculant is preferably added dropwise to the mixed dispersion. The flocculant may be added at once, or may be added intermittently or continuously. It is preferable to perform sufficient stirring during and after the addition.
The flocculant is preferably added dropwise as an aqueous solution from the viewpoint of controlling aggregation and obtaining aggregated particles having a desired particle diameter. The concentration of the aqueous flocculant solution is preferably 2% by mass or more, more preferably 4% by mass. More preferably, it is 6% 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, and still more preferably 10% by mass or less.
From the viewpoint of controlling aggregation and obtaining aggregated particles having a desired particle diameter and particle size distribution, the aqueous solution of the aggregating agent is preferably used by adjusting the pH to 7.0 or more and 9.0 or less.
The dropping time of the aggregating agent is preferably 1 minute or more, more preferably 3 minutes or more from the viewpoint of controlling aggregation and obtaining aggregated particles having a desired particle diameter, and from the viewpoint of improving toner productivity. , Preferably 120 minutes or less, more preferably 30 minutes or less, still more preferably 10 minutes or less.
Further, the temperature at which the flocculant is dropped is preferably 0 ° C. or higher, more preferably 10 ° C. or higher, further preferably 20 ° C. or higher, and preferably 40 ° C. or lower, from the viewpoint of improving toner productivity. More preferably, it is 35 degrees C or less, More preferably, it is 30 degrees C or less.
Further, from the viewpoint of promoting aggregation and obtaining aggregated particles having a desired particle size and particle size distribution, it is preferable to increase the temperature of the dispersion after adding the flocculant. The holding temperature is preferably 45 ° C. or higher, more preferably 50 ° C. or higher, further preferably 55 ° C. or higher, from the viewpoint of improving the low-temperature fixability and low-temperature fixability of the resulting toner over time. The temperature is preferably 70 ° C. or lower, more preferably 65 ° C. or lower, and still more preferably 60 ° C. or lower.
It is preferable to confirm the progress of aggregation by monitoring the volume-median particle size of the aggregated particles in the temperature range.

The volume-median particle size (D ₅₀ ) of the obtained aggregated particles (1) is preferably 2 μm or more, more preferably 3 μm or more from the viewpoint of improving the low-temperature fixability and low-temperature fixability of the obtained toner over time. More preferably, it is 4 μm or more, and preferably 10 μm or less, more preferably 8 μm or less, and still more preferably 6 μm or less. The volume-median particle size of the aggregated particles (1) is determined by the method described in Examples described later.

<Process (2B)>
In step (2B), resin particles (D) containing amorphous polyester (d) are added to the aggregated particles (1) obtained in step (2A), and the resin particles are added to the aggregated particles (1). This is a step of obtaining aggregated particles (2) formed by adhering (D).
In the step (2), the low temperature fixability and low temperature fixability of the toner, which is the effect of the present invention, can be improved only by the step (2A). The wax finely dispersed in the particles (1) becomes more difficult to be detached when the particles in the aggregated particles are fused in the next step (3), and the finely dispersed state in the toner particles is maintained. It will be easier.

(Resin particles (D))
The resin particles (D) are produced by a method in which a resin component containing the amorphous polyester (d) is dispersed in an aqueous medium to obtain an aqueous dispersion of the resin particles (D).

[Amorphous polyester (d)]
In the present invention, the amorphous resin has a crystallinity index greater than 1.4 or less than 0.6, and the amorphous polyester (d) has a crystallinity index of 1 .4 or less than 0.6 polyester.
The crystallinity index can be adjusted depending on the type and ratio of the raw material monomer and the production conditions (for example, reaction temperature, reaction time, cooling rate, etc.), and the value is described in the examples described later. It is required by the method.
The amorphous polyester (d) contains a polyhydric alcohol component (d-al) and a polyhydric carboxylic acid component (d-ac) from the viewpoint of improving the low-temperature fixability and low-temperature fixability of the toner over time. It is a polyester resin obtained by polycondensation.

The polyhydric alcohol component (d-al) preferably contains 80 mol% or more of an alkylene oxide adduct of bisphenol A from the viewpoint of improving low-temperature fixability of toner and stability over time of low-temperature fixability. The content of the alkylene oxide adduct of bisphenol A in the polyhydric alcohol component (d-al) is preferably 80 mol% or more from the viewpoint of improving the low temperature fixability and low temperature fixability of the toner over time. Preferably it is 90 mol% or more, More preferably, it is 95 mol% or more, More preferably, it is 98 mol% or more, More preferably, it is 100 mol%.
The alkylene oxide adduct of bisphenol A is preferably an ethylene oxide adduct of bisphenol A (polyoxyethylene-2,2-bis (4-hydroxyphenyl) propane) and a propylene oxide adduct of bisphenol A (polyoxypropylene- 1,2-bis (4-hydroxyphenyl) propane), more preferably an ethylene oxide adduct of bisphenol A.
The average addition mole number of alkylene oxide of the alkylene oxide adduct of bisphenol A is preferably 1 or more, more preferably 1.2 or more, further from the viewpoint of improving the low-temperature fixability and low-temperature fixability of the toner over time. It is preferably 1.5 or more, and preferably 16 or less, more preferably 12 or less, still more preferably 8 or less, and still more preferably 4 or less.

The polyhydric alcohol component (d-al) may contain other polyhydric alcohols other than the bisphenol A alkylene oxide adduct. The other polyhydric alcohol component that the polyhydric alcohol component (d-al) can contain is the same as the polyhydric alcohol component (c-al) constituting the polyester segment (c1) of the composite resin (c) described above, Specifically, aliphatic diols, aromatic diols, alicyclic diols, trihydric or higher polyhydric alcohols, or alkylene oxides having 2 to 4 carbon atoms (average addition mole number of 1 to 16) addition products. Etc.
These polyhydric alcohol components (d-al) can be used alone or in combination of two or more.

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

Examples of the dicarboxylic acid include aromatic dicarboxylic acids, aliphatic dicarboxylic acids, and alicyclic dicarboxylic acids. Aromatic dicarboxylic acids and aliphatic dicarboxylic acids are preferable, and aromatic dicarboxylic acids are more preferable.
The polyvalent carboxylic acid component (d-ac) includes not only a free acid but also an anhydride that decomposes to produce an acid during the reaction, and an alkyl ester having 1 to 3 carbon atoms of each carboxylic acid.
Examples of the aromatic dicarboxylic acid include phthalic acid, isophthalic acid, terephthalic acid and the like. From the viewpoint of improving low-temperature fixability and low-temperature fixability of the toner over time, isophthalic acid and terephthalic acid are preferable, and terephthalic acid is preferable. More preferred.
From the same viewpoint, the aliphatic dicarboxylic acid preferably has 2 to 30 carbon atoms, and more preferably 3 to 20 carbon atoms.
Examples of the aliphatic dicarboxylic acid having 2 to 30 carbon atoms include oxalic acid, malonic acid, maleic acid, fumaric acid, citraconic acid, itaconic acid, glutaconic acid, succinic acid, adipic acid, sebacic acid, 1,12-dodecanedioic acid. Examples thereof include acid, 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, and fumaric acid is preferable from the viewpoint of improving the charging characteristics of the toner. Specific examples of the succinic acid substituted with an alkyl group having 1 to 20 carbon atoms or an alkenyl group having 2 to 20 carbon atoms include dodecyl succinic acid, dodecenyl succinic acid, octenyl succinic acid, and the like.
Among these, terephthalic acid, fumaric acid, and dodecenyl succinic acid are preferable. From the viewpoint of improving low-temperature fixability of toner and stability over time of low-temperature fixability, these are more preferably used in combination, and these three types are used in combination. More preferably.

As the trivalent or higher polyvalent carboxylic acid, trimellitic acid and acid anhydride thereof are preferable, and trimellitic acid anhydride is more preferable from the viewpoint of improving low-temperature fixability and low-temperature fixability of the toner over time.
In addition, the content in the case of containing a trivalent or higher polyvalent carboxylic acid is preferably in the polyvalent carboxylic acid component (d-ac) from the viewpoint of improving low-temperature fixability and low-temperature fixability of the toner over time. Is 3 mol% or more, more preferably 5 mol% or more, and preferably 30 mol% or less, more preferably 20 mol% or less.
These polyvalent carboxylic acid components (d-ac) can be used alone or in combination of two or more.

  The equivalent ratio (COOH group / OH group) of the polyvalent carboxylic acid component (d-ac) to the polyhydric alcohol component (d-al) is from the viewpoint of improving the low-temperature fixability and low-temperature fixability of the toner over time. , Preferably 0.7 or more, more preferably 0.8 or more, and preferably 1.2 or less, more preferably 1.1 or less, and still more preferably 1.05 or less.

  The softening point of the amorphous polyester (d) is preferably 90 ° C. or higher, more preferably 100 ° C. or higher, and still more preferably 110 ° C. or higher, from the viewpoint of improving low-temperature fixability and low-temperature fixability of the toner over time. And preferably 160 ° C. or lower, more preferably 140 ° C. or lower, and still more preferably 130 ° C. or lower.

  From the viewpoint of improving the low temperature fixability of the toner and the stability over time of the low temperature fixability, the glass transition temperature of the amorphous polyester (d) is preferably 40 ° C. or higher, more preferably 50 ° C. or higher, still more preferably 60 ° C. The temperature is preferably 90 ° C. or lower, more preferably 80 ° C. or lower, and still more preferably 70 ° C. or lower.

  The acid value of the amorphous polyester (d) is preferably 5 mgKOH / g from the viewpoint of improving the dispersion stability of the resin particles (D) and improving the low-temperature fixability of the toner and the temporal stability of the low-temperature fixability. More preferably, it is 10 mgKOH / g or more, more preferably 15 mgKOH / g or more, and preferably 35 mgKOH / g or less, more preferably 30 mgKOH / g or less, still more preferably 25 mgKOH / g or less.

The softening point, glass transition temperature, and acid value of the amorphous polyester (d) can be appropriately adjusted according to the production conditions such as the type and ratio of the raw material monomers, the reaction temperature, the reaction time, and the cooling rate. These values are obtained by the method described in the examples below.
In addition, when using 2 or more types of amorphous polyester (d) in mixture, it is preferable that the value of the softening point, glass transition temperature, and acid value which were obtained as those mixtures is in the said range, respectively.

[Production of amorphous polyester (d)]
Amorphous polyester (d) is, for example, an esterification catalyst, if necessary, in an inert gas atmosphere, the polyhydric alcohol component (d-al) and the polyhydric carboxylic acid component (d-ac), It can be produced by polycondensation using an esterification cocatalyst, a radical polymerization inhibitor or the like.
Examples of the esterification catalyst, esterification co-catalyst, and radical polymerization inhibitor are the same as those used for the synthesis of the polyester segment (c1), and the preferred use amounts are also the same.

The temperature of the polycondensation reaction is preferably 140 ° C. or higher, more preferably 180 ° C. or higher, more preferably 200 ° C. or higher, and preferably 260 ° C. or lower, from the viewpoint of productivity of the amorphous polyester (d). More preferably, it is 250 degrees C or less, More preferably, it is 245 degrees C or less.
Moreover, it is preferable to accelerate the reaction by reducing the pressure of the reaction system in the latter half of the polymerization.

(Manufacture of resin particles (D))
The resin particles (D) are obtained as an aqueous dispersion of the resin particles (D) by dispersing the resin component containing the amorphous polyester (d) and, if necessary, the optional components in an aqueous medium. Is preferred.
The method for obtaining the aqueous dispersion is the same as that for the resin particles (A).

  The mass ratio of the organic solvent and the resin constituting the resin particles (D) (organic solvent / resin constituting the resin particles (D)) is a viewpoint that dissolves the resin and facilitates phase inversion to an aqueous medium, and the resin. From the viewpoint of improving the dispersion stability of the particles (D), it is preferably 0.1 or more, more preferably 0.2 or more, still more preferably 0.4 or more, and preferably 4 or less, more preferably 3 Hereinafter, it is more preferably 1 or less.

Moreover, it is preferable to add a neutralizing agent to a solution from a viewpoint of improving the dispersion stability of a resin particle (D). A preferred embodiment of the neutralizing agent is the same as in the production of the resin particles (A).
The neutralization degree (mol%) of the amorphous polyester (d) with the neutralizing agent is preferably 10 mol% or more, more preferably 30 mol% or more, and preferably 150 mol% or less, more preferably It is 120 mol% or less, More preferably, it is 100 mol% or less.

The amount of the aqueous medium to be added is preferably 100 parts by mass or more, more preferably 150 parts by mass with respect to 100 parts by mass of the resin constituting the resin particles (D) from the viewpoint of improving the dispersion stability of the resin particles (D). It is at least 200 parts by mass, more preferably at least 200 parts by mass, and preferably at most 900 parts by mass, more preferably at most 600 parts by mass, and even more preferably at most 400 parts by mass.
From the same viewpoint, the mass ratio of the aqueous medium to the organic solvent (aqueous medium / organic solvent) is preferably 20/80 or more, more preferably 50/50 or more, still more preferably 80/20 or more, and , Preferably 97/3 or less, more preferably 93/7 or less, and still more preferably 90/10 or less.

The temperature at which the aqueous medium is added is preferably 60 ° C. or higher, more preferably 65 ° C. or higher, and preferably 85 ° C. or lower, more preferably, from the viewpoint of improving the dispersion stability of the resin particles (D). Is 80 ° C. or lower, more preferably 75 ° C. or lower.
From the viewpoint of stably obtaining an aqueous dispersion of the resin particles (D), the addition rate of the aqueous medium is preferably 0 with respect to 100 parts by mass of the resin constituting the resin particles (D) until the phase inversion is completed. .1 part by weight / minute or more, more preferably 0.5 part by weight / minute or more, further preferably 1 part by weight / minute or more, still more preferably 3 parts by weight / minute or more, and preferably 50 parts by weight. / Min or less, more preferably 30 parts by mass or less, still more preferably 20 parts by mass or less, and even more preferably 10 parts by mass or less. There is no restriction | limiting in the addition rate of the aqueous medium after phase inversion.

You may have the process of removing an organic solvent from the obtained dispersion as needed after phase inversion emulsification.
A preferred embodiment of the method for removing the organic solvent and the remaining amount of the organic solvent in the aqueous dispersion is the same as in the production of the resin particles (A).

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

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

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

As the resin constituting the resin particles (D), in addition to the amorphous polyester (d), a known resin used for the toner, for example, a styrene-acrylic copolymer, epoxy, polycarbonate, polyurethane or the like may be contained. it can.
The content of the resin in the resin particles (D) is preferably 80% by mass or more, more preferably 90% by mass or more, and still more preferably from the viewpoint of improving the low-temperature fixability and low-temperature fixability of the toner over time. It is 95 mass% or more.
The content of the amorphous polyester (d) in the resin constituting the resin particles (D) is preferably 80% by mass or more from the viewpoint of improving low-temperature fixability and low-temperature fixability of the toner over time. Preferably it is 90 mass% or more, More preferably, it is 95 mass% or more, More preferably, it is 100 mass%.

(Agglomerated particles (2))
The step (2B) is a step of adding the resin particles (D) to the aggregated particles (1) obtained in the step (2A) to obtain aggregated particles (2) formed by adhering the resin particles (D). Yes, the resin particles (D) are further adhered to the aggregated particles (1) by adding the aqueous dispersion of the resin particles (D) to the dispersion of the aggregated particles (1) described above. It is preferable to obtain a dispersion liquid.

  Before adding the aqueous dispersion of resin particles (D) to the dispersion of aggregated particles (1), an aqueous medium may be added to the dispersion of aggregated particles (1) for dilution. Further, when the aqueous dispersion of the resin particles (D) is added to the dispersion of the aggregated particles (1), the aggregating agent is used to efficiently attach the resin particles (D) to the aggregated particles (1). May be used in step (2B).

  The temperature at which the aqueous dispersion of the resin particles (D) is added is preferably 40 ° C. or higher, more preferably 45 ° C. or higher, from the viewpoint of improving low-temperature fixability and low-temperature fixability of the resulting toner over time. Further, it is preferably 50 ° C. or higher, and preferably 80 ° C. or lower, more preferably 70 ° C. or lower, still more preferably 65 ° C. or lower.

The aqueous dispersion of the resin particles (D) may be added continuously over a certain period of time, or may be added at once, or may be added in multiple portions. It is preferable to add them continuously or in several divided portions. By adding in this way, the resin particles (D) are likely to selectively adhere to the aggregated particles (1). Among these, from the viewpoint of promoting selective adhesion and improving the productivity of toner, it is preferable to add continuously over a certain period of time.
When the aqueous dispersion of the resin particles (D) is continuously added, the addition speed is 100 masses of the aggregated particles (1) from the viewpoint of obtaining uniform aggregated particles (2) and improving the productivity of the toner. Part of the resin particles (D) is preferably 0.03 parts by mass / min or more, more preferably 0.07 parts by mass / min or more, and preferably 1.0 parts by mass / min or less. More preferably, it is 0.5 mass part / min or less, More preferably, it is 0.3 mass part / min or less.

  The addition amount of the resin particles (D) is the sum of the resin particles (D), the resin particles (B), and the resin particles (C) from the viewpoint of improving the low temperature fixability of the toner and the stability over time of the low temperature fixability. The mass ratio [(D) / ((B) + (C))] is preferably 0.1 or more, more preferably 0.15 or more, still more preferably 0.2 or more, and even more preferably 0.25 or more. The amount is preferably 0.9 or less, more preferably 0.6 or less, and still more preferably 0.4 or less.

In the production method of the present invention, in addition to the polyester resin and composite resin (a) constituting the resin particles (A), the crystalline polyester (b), the composite resin (c), and the amorphous polyester (d) As long as the effects of the present invention are not impaired, a known resin used for the toner, for example, a styrene-acrylic copolymer, epoxy, polycarbonate, polyurethane or the like can be used.
The total content of the polyester resin, the crystalline polyester (b), the composite resin (c), and the amorphous polyester (d) constituting the resin particles (A) depends on the low temperature fixability and low temperature fixability of the toner over time. From the viewpoint of improving the stability, the total resin component constituting the toner is preferably 80% by mass or more, more preferably 90% by mass or more, still more preferably 95% by mass or more, and still more preferably 98% by mass or more. More preferably, it is 100 mass%.
Further, the mass ratio [(d) / ((b) + (c))] of the amorphous polyester (d) and the total of the crystalline polyester (b) and the composite resin (c) is a low temperature fixability of the toner. From the viewpoint of improving the temporal stability of the low-temperature fixability, it is preferably 0.1 or more, more preferably 0.15 or more, still more preferably 0.2 or more, still more preferably 0.25 or more, and Preferably it is 0.9 or less, More preferably, it is 0.6 or less, More preferably, it is 0.4 or less.

The volume-median particle size (D ₅₀ ) of the agglomerated particles (2) is from the viewpoint of obtaining a toner capable of obtaining a high-quality image, and from the viewpoint of improving the low-temperature fixability and low-temperature fixability of the obtained toner over time. The thickness is preferably 2 μm or more, more preferably 3 μm or more, still more preferably 4 μm or more, and preferably 10 μm or less, more preferably 9 μm or less, still more preferably 8 μm or less.

In step (3), the aggregation may be stopped when the aggregated 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 stopper, and a method of diluting the dispersion. From the viewpoint of reliably preventing unnecessary aggregation, a method of stopping aggregation by adding an aggregation stopper is preferable.

(Aggregation stop agent)
As the aggregation terminator, a surfactant is preferable, and an anionic surfactant is more preferable. Examples of the anionic surfactant include alkylbenzene sulfonates, alkyl sulfates, alkyl ether sulfates, polyoxyalkylene alkyl ether sulfates, preferably polyoxyalkylene alkyl ether sulfates, more preferably polyoxyethylene. Lauryl ether sulfate, more preferably sodium polyoxyethylene lauryl ether sulfate.
An aggregation terminator can be used individually or in combination of 2 or more types.
The addition amount of the aggregation terminator is preferably 0 with respect to 100 parts by mass of the total amount of the resin particles (B), the resin particles (C), and the resin particles (D) from the viewpoint of surely preventing unnecessary aggregation. 1 part by mass or more, more preferably 1 part by mass or more, further preferably 2 parts by mass or more, and preferably 15 parts by mass or less, more preferably 10 parts by mass or less, from the viewpoint of reducing residual toner. More preferably, it is 7 parts by mass or less. The aggregation terminator is preferably added as an aqueous solution from the viewpoint of improving toner productivity.

  The temperature at which the aggregation terminator is added is preferably the same as the temperature at which the dispersion liquid of the aggregated particles (2) is retained from the viewpoint of improving toner productivity. Preferably it is 40 degreeC or more, More preferably, it is 50 degreeC or more, Preferably it is 80 degrees C or less, More preferably, it is 70 degrees C or less.

<Step (3)>
Step (3) is a step of obtaining fused particles by fusing the particles in the aggregated particles obtained in step (2).
Here, the “aggregated particles obtained in the step (2)” means the aggregated particles (1) obtained in the step (2A) when the step (2B) is not performed, and the step (2B). In the case of carrying out the step, it means the aggregated particles (2) obtained in the step (2B).
At the time of fusing, the resin particles and wax particles in the agglomerated particles obtained in the step (2) are mainly physically adhered, but are fused and integrated into It is estimated that

In this step, the resin or resin particles constituting the resin particles (C) from the viewpoint of improving the fusing property of the aggregated particles and improving the low-temperature fixability and low-temperature fixability of the resulting toner over time. It is preferable to hold | maintain at the temperature more than the maximum value of the glass transition temperature of resin which comprises (D).
The holding temperature is the glass transition temperature of the resin constituting the resin particle (C) or the resin constituting the resin particle (D) from the viewpoint of improving the fusing property of the aggregated particles and improving the productivity of the toner. More than the maximum value, preferably 2 ° C. higher temperature or more, more preferably 4 ° C. higher temperature or higher, more preferably 6 ° C. higher temperature or higher, and the resin or resin particles (D) constituting the resin particles (C) The temperature is preferably 30 ° C. or higher, more preferably 20 ° C. or lower, and further preferably 12 ° C. higher or lower than the maximum value of the glass transition temperature of the constituent resin.
At that time, the time for holding the resin particles (C) or the resin constituting the resin particles (D) at a temperature equal to or higher than the maximum value of the glass transition temperature of the obtained toner is low temperature fixability and low temperature fixability. From the viewpoint of improving the stability over time, it is preferably 1 minute or more, more preferably 10 minutes or more, still more preferably 30 minutes or more, and preferably 240 minutes or less, more preferably 180 minutes or less, and still more preferably 120 minutes. Minutes or less, more preferably 90 minutes or less.

The volume median particle size (D ₅₀ ) of the fused particles in the dispersion obtained in the step (3) is preferably 2 μm from the viewpoint of improving the low-temperature fixability and low-temperature fixability of the resulting toner over time. More preferably, it is 3 μm or more, more preferably 4 μm or more, and preferably 10 μm or less, more preferably 8 μm or less, still more preferably 6 μm or less.

  The circularity of the fused particles in the dispersion obtained in the step (3) is preferably 0.900 or more, more preferably from the viewpoint of improving the low temperature fixability of the toner and the stability over time of the low temperature fixability. 950 or more, more preferably 0.970 or more, and preferably 0.990 or less, more preferably 0.985 or less, and further preferably 0.980 or less. The circularity of the fused particles is determined by the method described in the examples described later.

<Post-processing process>
In the present invention, a post-treatment step may be performed after step (3), and it is preferable to obtain toner particles by isolating the fused particles.
Since the fused particles obtained in the step (3) are present in the aqueous medium, it is preferable to first perform solid-liquid separation. For solid-liquid separation, a suction filtration method or the like is preferably used.
It is preferable to perform washing after the solid-liquid separation. At this time, since it is preferable to remove the added surfactant, it is preferable to wash with an aqueous medium below the cloud point of the surfactant. The washing is preferably performed a plurality of times.
Next, drying is preferably performed, but the temperature during 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 fused particles. As a drying method, it is preferable to use a vacuum low temperature drying method, a vibration type fluidized drying method, a spray drying method, a freeze drying method, a flash jet method, or the like. The water content after drying is preferably adjusted to 1.5% by mass or less, more preferably 1.0% by mass or less, from the viewpoint of improving the chargeability of the toner.

[Toner for electrostatic image development]
The toner particles obtained by drying or the like can be used as they are as the toner for developing an electrostatic image, but it is preferable to use toner particles whose surface has been treated as described later as toner for developing an electrostatic image. .

The volume-median particle size (D ₅₀ ) of the toner particles is preferably 2 μm or more, more preferably from the viewpoint of obtaining a high-quality image and improving the low-temperature fixability and low-temperature fixability of the toner over time. It is 3 μm or more, more preferably 4 μm or more, and preferably 20 μm or less, more preferably 15 μm or less, still more preferably 10 μm or less, and even more preferably 8 μm or less.
The CV value of the toner particles is preferably 12% or more, more preferably 14% or more, and further preferably 16% or more from the viewpoint of improving the productivity of the toner, and from the viewpoint of obtaining a high-quality image. Preferably it is 30% or less, More preferably, it is 26% or less.

  The circularity of the toner particles is preferably 0.900 or more, more preferably 0.950 or more, and still more preferably 0.970 or more, from the viewpoint of improving the low-temperature fixability and low-temperature fixability of the toner over time. And preferably 0.990 or less, more preferably 0.985 or less, and still more preferably 0.980 or less.

<External additive>
As the toner particles, it is preferable to use a toner obtained by adding a fluidizing agent or the like to the toner particle surface as an external additive.
Examples of the external additive include hydrophobic silica, titanium oxide fine particles, alumina fine particles, cerium oxide fine particles, inorganic fine particles such as carbon black, and polymer fine particles such as polycarbonate, polymethyl methacrylate, and silicone resin. Among these, Hydrophobic silica is preferred.
When surface treatment of toner particles is performed using an external additive, the amount of the external additive added is preferably 1 part by mass or more, more preferably 2 parts by mass or more, and still more preferably with respect to 100 parts by mass of the toner particles. It is 3 parts by mass or more, and preferably 5 parts by mass or less, more preferably 4.5 parts by mass or less.
The electrostatic image developing toner obtained by the present invention can be used as a one-component developer or mixed with a carrier and used as a two-component developer.

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

[Compound resin, polyester acid value]
It measured according to JIS K0070. However, the measurement solvent was chloroform.

[Composite resin, polyester softening point, crystallinity index, melting point and glass transition temperature]
(1) Softening point Using a flow tester “CFT-500D” (manufactured by Shimadzu Corporation), a 1 g sample was heated at a heating rate of 6 ° C./min, and a load of 1.96 MPa was applied by a plunger. The nozzle was extruded from a nozzle having a length of 1 mm and a length of 1 mm. The amount of plunger drop of the flow tester was plotted against the temperature, and the temperature at which half of the sample flowed out was taken as the softening point.
(2) Crystallinity Index Using a differential scanning calorimeter “Q100” (manufactured by TA Instruments Japan Co., Ltd.), 0.01 to 0.02 g of a sample was weighed into an aluminum pan and room temperature (20 ° C. ) To 0 ° C. at a temperature drop rate of 10 ° C./min. Next, the sample was allowed to stand still for 1 minute, and then heated to 180 ° C. at a heating rate of 10 ° C./min, and the amount of heat was measured. Of the observed endothermic peaks, the peak temperature with the maximum peak area is defined as the endothermic maximum peak temperature (1), and (softening point (° C.)) / (Maximum endothermic peak temperature (1) (° C.)) The crystallinity index was determined.
(3) Melting point and glass transition temperature Using a differential scanning calorimeter “Q100” (manufactured by TA Instruments Japan Co., Ltd.), 0.01 to 0.02 g of a sample was weighed into an aluminum pan, and 200 ° C. The temperature was raised to 0 ° C. from the temperature at a temperature drop rate of 10 ° C./min. Next, the sample was heated at a temperature rising rate of 10 ° C./min, and the heat quantity was measured. Among the observed endothermic peaks, the temperature of the peak having the maximum peak area was defined as the maximum endothermic temperature (2).
In the case of crystalline polyester (b), the peak temperature was taken as the melting point. In the case of amorphous polyester, when a peak is observed, the temperature of the peak is measured. When a step is observed without a peak being observed, the tangent line indicating the maximum slope of the step portion and the step The temperature of the intersection with the extended line of the base line on the high temperature side was taken as the glass transition temperature.

[Melting point of wax]
Using a differential scanning calorimeter “Q100” (manufactured by TA Instruments Japan Co., Ltd.), 0.01 to 0.02 g of a sample was weighed into an aluminum pan, heated to 200 ° C., and from that temperature It cooled to 0 degreeC with the temperature-fall rate 10 degreeC / min. Next, the sample was heated at a temperature rising rate of 10 ° C./min, the amount of heat was measured, and the maximum peak temperature of endotherm was taken as the melting point.

[Volume Average Particle Size (D _V ) of Resin Particles (A)]
・ Measurement device: Zeta potential / particle size measurement system “ELSZ-2” (manufactured by Otsuka Electronics Co., Ltd.)
Measurement conditions: Distilled water was added to the measurement cell, and the volume average particle diameter was measured at a concentration at which the absorbance was in an appropriate range.

[Volume Median Particle Size (D ₅₀ ) and CV Value of Resin Particle (B), Resin Particle (C), Resin Particle (D), Colorant Particle, and Wax Particle]
・ Measuring device: Laser diffraction particle size measuring instrument “LA-920” (manufactured by Horiba, Ltd.)
Measurement conditions: Distilled water was added to the measurement cell, and the volume-median particle size (D ₅₀ ) and the volume average particle size were measured at a concentration where the absorbance was in an appropriate range. The CV value was calculated according to the following formula.
CV value (%) = (standard deviation of particle size distribution / volume average particle size) × 100

[Solid Concentration of Resin Particle Water Dispersion, Colorant Dispersion, and Wax Particle Dispersion]
・ Measuring device: Infrared moisture meter “FD-230” (manufactured by Ketsu Scientific Research Institute)
Measurement conditions: 5 g of a measurement sample was measured for moisture (mass%) at a drying temperature of 150 ° C. and in a measurement mode 96 (monitoring time 2.5 min / variation width 0.05%). The solid content concentration was calculated according to the following formula.
Solid content concentration (% by mass) = 100-water content (% by mass)

[Volume Median Particle Size (D ₅₀ ) of Aggregated Particles (1)]
The volume-median particle size (D ₅₀ ) of the aggregated particles was measured as follows.
Measuring device: “Coulter Multisizer (registered trademark) III” (manufactured by Beckman Coulter, Inc.)
・ Aperture diameter: 50μm
Analysis software: “Multisizer (registered trademark) III version 3.51” (manufactured by Beckman Coulter, Inc.)
Electrolyte: “Isoton (registered trademark) II” (manufactured by Beckman Coulter, Inc.)
-Measurement conditions: After adjusting the particle size of 30,000 particles to a concentration that can be measured in 20 seconds by adding the sample dispersion to 100 mL of the electrolyte solution, 30,000 particles are measured and the particle size distribution From this, the volume median particle size (D ₅₀ ) was determined.

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

[Volume Median Particle Size (D ₅₀ ) and CV Value of Toner Particles]
The volume median particle size of the toner particles was measured as follows.
As the measuring device, aperture diameter, analysis software, and electrolyte, the same volume median particle size as the aggregated particles was used.
-Dispersion: Polyoxyethylene lauryl ether "Emulgen (registered trademark) 109P" (manufactured by Kao Corporation, HLB: 13.6) was dissolved in the electrolytic solution to obtain a dispersion having a concentration of 5% by mass.
Dispersion condition: 10 mg of a measurement sample of toner particles after drying is added to 5 mL of the dispersion, and dispersed for 1 minute with an ultrasonic disperser, and then 25 mL of electrolyte is added, and further with an ultrasonic disperser. A sample dispersion was prepared by dispersing for 1 minute.
Measurement conditions: After adding the sample dispersion to 100 mL of the electrolyte 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. 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) × 100

[Minimum fixing temperature of toner]
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 toner adhesion amount on the paper is 0.42 to 0. A solid image of .48 mg / cm ² was output without being fixed at a length of 50 mm, leaving a margin of 5 mm from the top edge of the A4 paper.
Next, the same printer with a variable temperature fixing device was prepared, the fixing device temperature was set to 90 ° C., and fixing was performed at a speed of 1.0 second per sheet in the A4 lengthwise direction to obtain a printed matter.
In the same manner, the temperature of the fixing device was increased by 5 ° C., and the fixing was performed to obtain a printed matter.
From the margin at the top edge of the printed image to the solid image, lightly paste a 50 mm long mending tape “Scotch (registered trademark) mending tape 810” (manufactured by Sumitomo 3M Limited, width 18 mm). After that, a weight of 500 g was placed and pressed once back and forth at a speed of 10 mm / sec. Thereafter, the affixed tape was peeled off from the lower end side at a peeling angle of 180 degrees and at a speed of 10 mm / sec to obtain a printed matter after the tape was peeled off. 30 sheets of high quality paper “Excellent White Paper A4 Size” (made by Oki Data Co., Ltd.) is laid under the printed material before and after the tape is applied, and the reflected image density of the fixed image portion before and after the tape is applied to each printed material. , A colorimeter “SpectroEye” (manufactured by GretagMacbeth, Inc., light emission conditions: standard light source D50, observation field of view 2 °, density standard DINNB, absolute white standard), and from these values, the fixing rate is calculated by the following formula: Calculated.
Fixing rate (%) = (Reflected image density after peeling tape / Reflected image density before applying tape) × 100
The lowest temperature at which the fixing rate was 90% or higher was defined as the lowest fixing temperature (1). The lower the minimum fixing temperature (1), the better the low temperature fixing property.

(Low-temperature fixability over time)
After keeping the toner in a constant temperature bath at 40 ° C. for 24 hours, the minimum fixing temperature (2) was measured by the same method as described above. Next, the difference between the lowest fixing temperature (1) and the lowest fixing temperature (2) was calculated, and the stability over time 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.

[Production of resin]
Production Example 1
(Production of resin a-1)
The inside of a four-necked flask equipped with a nitrogen introduction tube, a dehydration tube, a stirrer, and a thermocouple was replaced with nitrogen, and 4313 g of polyoxypropylene (2.2) -2,2-bis (4-hydroxyphenyl) propane, 818 g of terephthalic acid, 727 g of succinic acid, 30 g of di (2-ethylhexanoic acid) tin (II) and 3 g of gallic acid were added, and the temperature was raised to 235 ° C. with stirring in a nitrogen atmosphere and held at 235 ° C. for 5 hours. Thereafter, the pressure in the flask was lowered and held at 8 kPa for 1 hour. Then, in the state which cooled to 160 degreeC and hold | maintained at 160 degreeC, the mixture of styrene 2756g, stearyl methacrylate 689g, acrylic acid 142g, and dibutyl peroxide 413g was dripped over 1 hour. Then, after maintaining at 160 ° C. for 30 minutes, the temperature was raised to 200 ° C., the pressure in the flask was further lowered, and the reaction was carried out at 8 kPa to the desired softening point to obtain resin a-1. The physical properties are shown in Table 1.

Production Example 2
(Production of resin a-2)
The inside of a four-necked flask equipped with a nitrogen introduction tube, a dehydration tube, a stirrer, and a thermocouple was replaced with nitrogen, and 6364 g of polyoxypropylene (2.2) -2,2-bis (4-hydroxyphenyl) propane, 1509 g of terephthalic acid, 30 g of di (2-ethylhexanoic acid) tin (II) and 3 g of gallic acid were added, and the temperature was raised to 235 ° C. with stirring in a nitrogen atmosphere and held at 235 ° C. for 9 hours. Thereafter, the mixture was cooled to 200 ° C., 1949 g of dodecenyl succinic anhydride and 244 g of trimellitic anhydride were added, the temperature was raised to 210 ° C. at 10 ° C./hr, and then held at 210 ° C. for 2 hours to obtain resin a-2. Obtained. The physical properties are shown in Table 1.

Production Example 3
(Production of resin b-1)
The inside of a four-necked flask equipped with a nitrogen introduction tube, a dehydration tube, a stirrer, and a thermocouple was purged with nitrogen, and 3,416 g of 1,10-decanediol and 4084 g of sebacic acid were added. While stirring, the temperature was raised to 135 ° C., maintained at 135 ° C. for 3 hours, and then heated from 135 ° C. to 200 ° C. over 10 hours. Thereafter, 16 g of di (2-ethylhexanoic acid) tin (II) was added, and the mixture was further maintained at 200 ° C. for 1 hour, and then the pressure in the flask was lowered and maintained at 8.3 kPa for 1 hour. Got. The physical properties are shown in Table 2.

Production Example 4
(Production of resin b-2)
Resin b-2 was obtained in the same manner as in Production Example 3 except that the types and amounts of the raw material monomers were changed as shown in Table 2. The physical properties are shown in Table 2.

Production Example 5
(Production of resin b-3)
The inside of a four-necked flask equipped with a nitrogen introduction tube, a dehydration tube, a stirrer, and a thermocouple was purged with nitrogen, and 4294 g of 1,9-nonanediol, 3206 g of fumaric acid and 5 g of 4-tert-butylcatechol were added. While stirring, the temperature was raised to 140 ° C., maintained at 140 ° C. for 6 hours, and then heated from 135 ° C. to 200 ° C. over 10 hours. Thereafter, 16 g of di (2-ethylhexanoic acid) tin (II) was added, and the mixture was further maintained at 200 ° C. for 1 hour, then the pressure in the flask was lowered, and the reaction mixture was maintained at 8.3 kPa for 1 hour, and resin b-3 Got. The physical properties are shown in Table 2.

Production Example 6
(Production of resin c-1)
The inside of a four-necked flask equipped with a nitrogen introduction tube, a dehydration tube, a stirrer, and a thermocouple was replaced with nitrogen, and 2991 g of polyoxypropylene (2.2) -2,2-bis (4-hydroxyphenyl) propane, 397 g of terephthalic acid, 30 g of di (2-ethylhexanoic acid) tin (II) and 3 g of gallic acid were added, heated to 235 ° C. with stirring in a nitrogen atmosphere, and held at 235 ° C. for 5 hours. The pressure was reduced and held at 8 kPa for 1 hour. Thereafter, a mixture of 1961 g of styrene, 490 g of stearyl methacrylate, 99 g of acrylic acid and 294 g of dibutyl peroxide was added dropwise over 1 hour while cooling to 160 ° C. and maintaining at 160 ° C. Then, after maintaining at 160 ° C. for 30 minutes, the temperature was raised to 200 ° C., and the pressure in the flask was further lowered and maintained at 8 kPa for 1 hour. Then, after returning to atmospheric pressure, it cooled to 180 degreeC, fumaric acid 159g, sebacic acid 691g, trimellitic anhydride 164g, and 4-tert- butyl catechol 3.8g were added, and 10 degreeC / hr to 220 degreeC. The temperature was raised, and then the reaction was carried out at 10 kPa to the desired softening point to obtain Resin c-1. Table 3 shows the physical properties.

Production Example 7
(Production of resin c-2)
Resin c-2 was obtained in the same manner as in Production Example 6 except that the types and amounts of the raw material monomers were changed as shown in Table 3. Table 3 shows the physical properties.

Production Example 8
(Production of resin c-3)
Resin c-3 was obtained in the same manner as in Production Example 6 except that the types and amounts of the raw material monomer and the radical polymerization initiator were changed as shown in Table 3 and no radical polymerization inhibitor was used. Table 3 shows the physical properties.

Production Example 9
(Production of resin c-4)
The inside of a four-necked flask equipped with a nitrogen introduction tube, a dehydration tube, a stirrer, and a thermocouple was replaced with nitrogen, and 5001 g of polyoxypropylene (2.2) -2,2-bis (4-hydroxyphenyl) propane, 1186 g of terephthalic acid, 30 g of di (2-ethylhexanoic acid) tin (II) and 3 g of gallic acid were added, the temperature was raised to 230 ° C. with stirring in a nitrogen atmosphere, and the temperature was maintained at 230 ° C. for 8 hours. Then, 1149 g of dodecenyl succinic anhydride and 165 g of trimellitic anhydride are added, the temperature is raised to 220 ° C. at 10 ° C./hr, and then the reaction is carried out at 10 kPa to the desired softening point to obtain resin c-4. Got. Table 3 shows the physical properties.

Production Example 10
(Production of resin d-1)
The inside of a four-necked flask equipped with a nitrogen introduction tube, a dehydration tube, a stirrer, and a thermocouple was replaced with nitrogen, and 5001 g of polyoxyethylene (2.2) -2,2-bis (4-hydroxyphenyl) propane, 1788 g of terephthalic acid, 30 g of di (2-ethylhexanoic acid) tin (II) and 3 g of gallic acid were added, heated to 235 ° C. with stirring in a nitrogen atmosphere, held at 235 ° C. for 8 hours, and then 180 ° C. The mixture was cooled to 179 g of fumaric acid, 206 g of dodecenyl succinic anhydride, 325 g of trimellitic anhydride and 3.8 g of 4-tert-butylcatechol, heated to 220 ° C. at 10 ° C./hr, and then at 10 kPa. Reaction was performed to the desired softening point, and resin d-1 was obtained. Table 3 shows the physical properties.

Production Example 11
(Production of resin d-2)
Resin d-2 was obtained in the same manner as in Production Example 10 except that the type and amount of the raw material monomer were changed as shown in Table 3. Table 3 shows the physical properties.

[Production of aqueous dispersion of resin particles]
Production Example 12
(Production of aqueous dispersion A-1 of resin particles)
In a 3 L container equipped with a stirrer, reflux condenser, dropping funnel, thermometer and nitrogen inlet tube, 200 g of resin a-1 and 200 g of methyl ethyl ketone were placed and dissolved at 73 ° C. over 2 hours. 5 mass% sodium hydroxide aqueous solution was added to the obtained solution so that the neutralization degree might be 60 mol% with respect to the acid value of resin a-1, and it stirred for 30 minutes.
Next, while maintaining at 73 ° C., 1000 g of deionized water was added over 50 minutes while stirring at 280 r / min (peripheral speed 88 m / min), and phase inversion emulsification was performed. While maintaining the temperature at 73 ° C., methyl ethyl ketone was distilled off under reduced pressure to obtain an aqueous dispersion. Thereafter, 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 was 20% by mass. An aqueous dispersion A-1 was obtained. Physical properties are shown in Table 4-1.

Production Example 13
(Production of aqueous dispersion A-2 of resin particles)
An aqueous dispersion A-2 of resin particles was obtained in the same manner as in Production Example 12 except that the resin type was changed to a-2.

Production Example 14
(Production of aqueous dispersion B-1 of resin particles)
300 g of resin b-1 and 180 g of methyl ethyl ketone were placed in a 3 L container equipped with a stirrer, a reflux condenser, a dropping funnel, a thermometer, and a nitrogen introduction tube, and dissolved at 73 ° C. for 2 hours. To the obtained solution, a 5 mass% sodium hydroxide aqueous solution was added so that the neutralization degree was 60 mol% with respect to the acid value of the resin b-1, and the mixture was stirred for 30 minutes.
Next, while maintaining at 73 ° C., 1000 g of deionized water was added over 60 minutes while stirring at 280 r / min (peripheral speed 88 m / min), and phase inversion emulsification was performed. While maintaining the temperature at 73 ° C., methyl ethyl ketone was distilled off under reduced pressure to obtain an aqueous dispersion. Thereafter, 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 was 20% by mass. An aqueous dispersion B-1 was obtained. The physical properties are shown in Table 4-2.

Production Examples 15-22
(Production of aqueous dispersions B-2, B-3, C-1 to C-4, D-1, and D-2 of resin particles)
Except having changed the kind of resin as shown in Table 4-2, it is the same as that of manufacture example 14, and is the aqueous dispersion B-2, B-3, C-1 to C-4, D-1, of the resin particle, D-2 was obtained. The physical properties are shown in Table 4-2.

[Production of aqueous dispersion of wax particles]
Production Example 23
(Production of aqueous dispersion W-1 of wax particles)
120 g of deionized water, 86 g of an aqueous dispersion A-1 of resin particles, and 40 g of paraffin wax “HNP-9” (manufactured by Nippon Seiwa Co., Ltd., melting point 75 ° C.) are added to a 1 L beaker, and 90 to 95 ° C. The mixture was melted while maintaining the temperature to obtain a molten mixture. While maintaining the temperature at 90 to 95 ° C., a dispersion treatment was performed for 20 minutes using an ultrasonic homogenizer “US-600T” (manufactured by Nippon Seiki Seisakusho Co., Ltd.), and then cooled to room temperature. Deionized water was added to the resulting dispersion to adjust the solid content concentration to 20% by mass to obtain an aqueous dispersion W-1 of wax particles. Table 5 shows the physical properties.

Production Examples 24 and 25
(Production of aqueous dispersions W-2 and W-3 of wax particles)
Aqueous dispersions W-2 and W-3 of wax particles were obtained in the same manner as in Production Example 23, except that the type of the aqueous dispersion of wax and resin particles was changed as shown in Table 5. Table 5 shows the physical properties.

Production Example 26
(Production of aqueous dispersion W-4 of wax particles)
After mixing 213 g of deionized water and 5.36 g of anionic surfactant “Latemul (registered trademark) ASK” (manufactured by Kao Corporation, dipotassium alkenyl succinate, effective concentration: 28% by mass) into a beaker having an internal volume of 1 L To this, 50 g of paraffin wax “HNP-9” (manufactured by Nippon Seiki Co., Ltd., melting point 75 ° C.) is added, and an ultrasonic homogenizer “US-600T” (Japan Co., Ltd.) is maintained while maintaining the temperature at 95 to 98 ° C. A dispersion process was performed for 20 minutes using Seiki Seisakusho. Then, it cooled to 25 degreeC, deionized water was added, solid content concentration was adjusted to 20 mass%, and the aqueous dispersion W-4 of the wax particle was obtained. Table 5 shows the physical properties.

[Production of colorant dispersion]
Production Example 27
(Production of Colorant Dispersion E-1)
In a 1 liter beaker, 116.2 g of a copper phthalocyanine pigment “ECB-301” (manufactured by Dainichi Seika Kogyo Co., Ltd.), an anionic surfactant “Neopelex (registered trademark) G-15” (manufactured by Kao Corporation, 154.9% sodium dodecylbenzenesulfonate aqueous solution) and 340 g of deionized water were mixed and dispersed for 3 hours at room temperature using a homogenizer, and then deionized water so that the solid concentration was 24% by mass. Was added to obtain a colorant dispersion E-1. The volume median particle size (D ₅₀ ) of the colorant particles in the dispersion was 0.118 μm.

[Production of toner]
Example 1
(Manufacture of toner 1)
In a four-necked flask with an internal volume of 3 liters equipped with a dehydrating tube, a stirrer and a thermocouple, 30 g of resin particle aqueous dispersion B-1, 270 g of resin particle aqueous dispersion C-1 and aqueous dispersion of wax particles W-1 39 g, colorant dispersion E-1 23 g, and nonionic surfactant “Emulgen (registered trademark) 150” (manufactured by Kao Corporation, polyoxyethylene (50 mol) lauryl ether) 10 mass% aqueous solution 6 g Were mixed at a temperature of 25 ° C. Next, while stirring the mixture, a solution adjusted to pH 8.1 by adding 4.8 mass% aqueous potassium hydroxide solution to an aqueous solution in which 17 g of ammonium sulfate was dissolved in 178 g of deionized water was added at 25 ° C. over 5 minutes. Then, the temperature was raised to 56 ° C. over 2 hours, and maintained at 56 ° C. until the volume-median particle size of the aggregated particles became 4.3 μm to obtain a dispersion of aggregated particles (1).
While maintaining the temperature of the dispersion of the obtained aggregated particles (1) at 56 ° C., 79 g of an aqueous dispersion D-1 of resin particles was dropped at a rate of 0.3 ml / min to disperse the aggregated particles (2). A liquid was obtained.
12. To the dispersion of the obtained aggregated particles (2), an anionic surfactant “Emar (registered trademark) E-27C” (manufactured by Kao Corporation, sodium polyoxyethylene lauryl ether sulfate, effective concentration: 27 mass%) An aqueous solution in which 5 g and 1200 g of deionized water were mixed was added. Thereafter, the temperature was raised to 73 ° C. over 1 hour, and maintained at 73 ° C. until the circularity reached 0.970, thereby obtaining a dispersion of fused particles.
The obtained fused particle dispersion was cooled to 30 ° C., the solid content of the dispersion was separated by suction filtration, washed with deionized water, and dried at 33 ° C. to obtain toner particles. . Table 6 shows the physical properties of the obtained toner particles. 100 parts by mass of the toner particles, 2.5 parts by mass of hydrophobic silica “RY50” (manufactured by Nippon Aerosil Co., Ltd., number average particle size; 0.04 μm), and hydrophobic silica “Cabosil (registered trademark) TS720” (Cabot Japan) 1.0 part by mass (manufactured by Co., Ltd., number average particle size; 0.012 μm) was placed in a Henschel mixer, stirred, and passed through a 150 mesh sieve to obtain toner 1. Table 6 shows the evaluation of the toner.

Example 2
(Manufacture of toner 2)
In Example 1, a toner 2 was obtained in the same manner as in Example 1 except that the amount of the aqueous dispersion W-1 of wax particles used was changed to 78 g. Table 6 shows the physical properties and evaluation.

Example 3
(Manufacture of toner 3)
In Example 1, a toner 3 was obtained in the same manner as in Example 1 except that the amount of the aqueous dispersion W-1 of wax particles used was changed to 20 g. Table 6 shows the physical properties and evaluation.

Example 4
(Manufacture of toner 4)
In Example 1, except that the amount of resin particle aqueous dispersion B-1 used was changed to 60 g and the amount of resin particle aqueous dispersion C-1 used was changed to 240 g, the same as in Example 1, Toner 4 was obtained. Table 6 shows the physical properties and evaluation.

Example 5
(Manufacture of toner 5)
In Example 1, except that the usage amount of the aqueous dispersion B-1 of the resin particles used was changed to 15 g and the usage amount of the aqueous dispersion C-1 of the resin particles was changed to 285 g, Toner 5 was obtained. Table 6 shows the physical properties and evaluation.

Examples 6-12
(Manufacture of toners 6 to 12)
In Example 1, toners 6 to 12 were obtained in the same manner as in Example 1 except that the types of the aqueous dispersion of resin particles and the aqueous dispersion of wax particles used were changed as shown in Table 6, respectively. It was. Table 6 shows the physical properties and evaluation.

Comparative Example 1
(Manufacture of toner 13)
In Example 1, the toner 13 was prepared in the same manner as in Example 1 except that the type of the aqueous dispersion of wax particles used was changed to the aqueous dispersion W-4 of wax particles and the usage amount was changed to 28 g. Got. Table 6 shows the physical properties and evaluation.

Comparative Example 2
(Manufacture of toner 14)
A toner 14 was obtained in the same manner as in Example 1 except that the aqueous dispersion C-1 of resin particles was changed to the aqueous dispersion C-4 of resin particles in Example 1. Table 6 shows the physical properties and evaluation.

  From Table 6, it can be seen that the toners of Examples 1 to 12 are both superior in low-temperature fixability and stability over time as compared with the toners of Comparative Examples 1 and 2.

Claims (11)

Next steps (1) to (3)
Step (1): A step of mixing a wax and an aqueous dispersion of resin particles (A) to obtain an aqueous dispersion of wax particles Step (2): An aqueous dispersion of the wax particles obtained in Step (1) Step of mixing the liquid, the aqueous dispersion of the resin particles (B), and the aqueous dispersion of the resin particles (C) and aggregating them to obtain aggregated particles Step (3): Aggregated particles obtained in Step (2) A method for producing a toner for developing an electrostatic image, comprising the step of fusing a toner to obtain fused particles,
The resin constituting the resin particles (A) contains a polyester resin containing a segment (a1) made of polyester,
The resin constituting the resin particles (B) contains the crystalline polyester (b),
The resin constituting the resin particles (C) contains a composite resin (c) including a segment (c1) made of polyester and a vinyl resin segment (c2) having a structural unit derived from a styrene compound,
A method for producing a toner for developing an electrostatic image.   The method for producing a toner for developing an electrostatic charge image according to claim 1, wherein the composite resin (c) contains a structural unit derived from both reactive monomers. The volume of the volume-median particle size volume average particle diameter _{(D V)} of the ratio (wax particles having a volume median particle size of the wax particles _{(D 50)} and the resin particles (A) _{(D 50)} / resin particles (A) The method for producing a toner for developing an electrostatic charge image according to claim 1, wherein the average particle diameter (D _V ) is 1.0 or more and 50 or less. The method for producing a toner for developing an electrostatic charge image according to claim 1, wherein the resin particles (A) have a volume average particle diameter (D _V ) of 0.01 μm or more and 0.30 μm or less. The method for producing a toner for developing an electrostatic charge image according to any one of claims 1 to 4, wherein the wax particles have a volume-median particle size (D ₅₀ ) of 0.05 µm or more and 1.00 µm or less.   The mass ratio [resin particles (B) / resin particles (C)] of the resin particles (B) and the resin particles (C) is 1/99 or more and 30/70 or less. A method for producing a toner for developing electrostatic images.   The electrostatic charge image development in any one of Claims 1-6 whose mass ratio [resin particle (B) / wax particle] of resin particle (B) and the said wax particle is 0.10 or more and 5.0 or less. Of manufacturing toner.   The method for producing a toner for developing an electrostatic charge image according to claim 1, wherein the wax contains 95% by mass or more of paraffin wax.   The resin particle (A) contains 90% by mass or more of a composite resin (a) including a segment (a1) made of polyester and a vinyl resin segment (a2) having a structural unit derived from a styrene compound. A method for producing a toner for developing an electrostatic charge image according to any one of -8.   The electrostatic image developing toner according to claim 1, wherein the content of the surfactant in the aqueous dispersion of the wax particles is 0.5 parts by mass or less with respect to 100 parts by mass of the wax. Manufacturing method. The step (2) includes the following steps (2A) and (2B), and the fused particles to be aggregated in the step (3) are aggregated particles (2) obtained in the following step (2B). 10. A method for producing a toner for developing an electrostatic charge image according to any one of 10 to 10.
Step (2A): The aqueous dispersion of wax particles obtained in Step (1), the aqueous dispersion of resin particles (B), and the aqueous dispersion of resin particles (C) are mixed and aggregated in an aqueous medium. Step of obtaining particles (1) Step (2B): The resin particles (D) containing amorphous polyester (d) are added to the aggregated particles (1) obtained in step (2A), and aggregated particles ( Step of obtaining aggregated particles (2) obtained by attaching resin particles (D) to 1)