JP6095500B2 - Method for producing toner particles - Google Patents

Description

  The present invention relates to a method for producing toner particles that reveals an electrostatic latent image.

In recent years, there has been a demand for means for outputting further high-definition full-color images, and in particular, there has been an increase in demand for added value (hereinafter referred to as energy saving) that reduces energy consumption, and energy saving is one of the important quality of toner. It is recognized as one. One means for achieving the energy saving performance of the toner is how to fix the toner at a low temperature, and various approaches have been taken from the toner material. Among them, there is a technique for incorporating a crystalline material into the toner, which is an effective means for achieving low-temperature fixing of the toner.
For example, Patent Document 1 provides a toner having excellent low-temperature fixability, image glossiness, and filming resistance by incorporating a composite resin containing a styrene resin component and a condensation polymerization resin component in the toner. Technology is disclosed.
Further, for example, in Patent Document 2, excellent low-temperature fixability and resistance are obtained by using a binder resin for toner including a hybrid resin of a crystalline resin (X) and an amorphous resin (Y) and an amorphous resin (Z). A technique for achieving both offset properties is disclosed.
Further, for example, in Patent Document 3, the flowability of toner, blocking resistance, and the like by using as a binder a block copolymer or graft copolymer obtained by chemically bonding a crystalline polyester and an amorphous vinyl polymer, It is disclosed that a toner having good low-temperature fixability and offset resistance and further excellent durability can be provided.
Furthermore, Patent Document 4 discloses a technique related to a toner produced by polymerization using a peroxide polymerization initiator in the presence of a polymerizable monomer and a crystalline polyester resin in an aqueous medium. Yes. It is described that a toner, an image forming method, and an image forming apparatus excellent in development durability, low-temperature fixability and offset resistance can be obtained thereby.
However, in response to these problem-solving proposals, on the other hand, in addition to energy saving of the toner, the user can make further improvements on a wide range of items such as high image quality, high durability, and storage stability as the toner coloring power increases. Seeking improvement. However, such a requirement has a technical relationship that is a trade-off with each other in terms of toner characteristics, and it must be said that the hurdles for achieving both are extremely high. Nevertheless, this trend is expected to accelerate further in the future, and the toner has various technologies such as low-temperature fixability and high coloring power / high image quality that can achieve energy savings, as well as improved durability and storage stability. There is a need for further balance between issues, and further technical improvements are required.

JP 2010-139659 A International Publication No. 06/135041 Japanese Patent Laid-Open No. 02-294659 JP 2009-63969 A

  It is an object of the present invention to provide a method for producing toner particles that is excellent in low-temperature fixability and colorant dispersibility, has good tinting strength, and has excellent development durability and storage stability.

The improvement in low-temperature fixability by incorporating a crystalline resin in the toner particles is due to the crystalline resin quickly melting in the fixing temperature region. However, if only the crystalline resin is melted, it does not contribute to the low-temperature fixing of the toner, and the entire binder resin of the toner (hereinafter also simply referred to as the binder resin) is melted simultaneously with the melting of the crystalline resin at the time of fixing. It is necessary to plasticize and melt. For this purpose, the affinity between the crystalline resin and the polymerizable monomer constituting the binder resin is considered important.
On the other hand, a polymerizable monomer composition containing a polymerizable monomer, a colorant, and a crystalline resin is added to an aqueous medium, and the polymerizable monomer composition is granulated in the aqueous medium. In order to obtain good colorant dispersibility in a method for producing toner particles in which particles of a polymerizable monomer composition are formed and the polymerizable monomer contained in the particles is polymerized, a crystalline resin It is considered that the affinity of the monomer with the polymerizable monomer is a particularly important factor. This is because the colorant causes pigment shock and aggregates in the toner due to the low solubility of the crystalline resin in the polymerizable monomer. In particular, when the polymerizable monomer composition is granulated in an aqueous medium to form particles of the polymerizable monomer composition, a large number of repeated contact at the liquid-liquid interface having a large polarity difference is performed. It is thought that the effect becomes remarkable.
Based on the above, the present inventors have considered these phenomena, that is, the plasticizing effect of the crystalline resin contained in the toner particles upon fixing to the binder resin, and the polymerizable monomer containing the crystalline resin. The inventors studied diligently by paying attention to the dispersion of the colorant during granulation in an aqueous medium. As a result, the polymerizable monomer composition is added to the aqueous medium, the polymerizable monomer composition is granulated in the aqueous medium to form particles of the polymerizable monomer composition, and the polymerization is performed. In a toner particle production method for obtaining toner particles by polymerizing the polymerizable monomer contained in the particles of a polymerizable monomer composition, a vinyl-based monomer, and a crystalline polyester site and an amorphous property as a crystalline resin The inventors have found that it is optimal to use a polymerizable monomer composition containing a specific hybrid resin having a vinyl moiety, and have reached the present invention.

In the present invention, a polymerizable monomer composition containing a polymerizable monomer, a colorant, and a crystalline resin is added to an aqueous medium, and the polymerizable monomer composition is granulated in the aqueous medium. Toner particles comprising a step of forming particles of the polymerizable monomer composition, and a step of obtaining toner particles by polymerizing the polymerizable monomer contained in the particles of the polymerizable monomer composition A manufacturing method comprising:
The polymerizable monomer is a vinyl monomer,
The crystalline resin is a hybrid resin having a crystalline polyester portion and an amorphous vinyl portion,
Mass ratio of the crystalline polyester part and the amorphous vinyl part of the crystalline resin (crystal part /
The present invention relates to a method for producing toner particles, wherein the amorphous part is 70/30 to 98/2.

  According to the method of the present invention, toner particles having excellent low-temperature fixability and colorant dispersibility, good coloring power, and excellent development durability and storage stability can be obtained.

A system incorporating a mixing device comprising a rotor and a stator. It is a main body side view of a mixing apparatus. FIG. 3 is a cross-sectional view of the main body of the mixing device taken along the line B-B ′ in FIG. It is a main body sectional drawing of the mixing apparatus in the A-A 'cross section in FIG. It is a perspective view of the stator of a mixing device. It is a perspective view of the rotor of a mixing apparatus.

Hereinafter, the present invention will be described in detail.
In the present invention, toner particles having excellent coloring power and excellent low-temperature fixability and colorant dispersibility can be obtained by using a method for producing toner particles that satisfies the above conditions. Furthermore, toner particles having excellent development durability and storage stability can be obtained.
Although the detailed reason why the effect of the present invention can be obtained by the method that satisfies the above conditions is not clear, the present inventors consider as follows. That is, from the viewpoint of the low-temperature fixability described above, it is preferable that the affinity between the crystalline resin when the binder resin is melted and the polymerizable monomer constituting the binder resin is high. Therefore, it is considered essential to include an amorphous vinyl moiety in the crystalline resin in order to increase the affinity.
Still further, since the crystalline resin is difficult to precipitate in the polymerizable monomer, the resin precipitates in the polymerizable monomer composition or during granulation of the composition in an aqueous medium. Even in easy-to-understand conditions, it can exist stably in a solution state, and as a result, it is considered that there is no deterioration of the dispersion state due to the aggregation of the colorant due to pigment shock.

Here, when the mass ratio (crystalline part / amorphous part) of the crystalline polyester part and the amorphous vinyl part of the crystalline resin of the present invention is 70/30 to 98/2, the crystalline resin is melted. Sometimes the affinity with the polymerizable monomer constituting the binder resin is good, the entire toner can be melted quickly, and the low-temperature fixability is improved. Further, in the method for producing toner particles as in the present invention, not only the coloring agent does not aggregate due to pigment shock, the dispersion state of the coloring agent in the toner is good, and the coloring power of the toner is improved. Storage stability and development durability are improved. The mass ratio (crystal part / amorphous part) is preferably 70/30 or more, 95
/ 5 or less.
On the other hand, when the mass ratio of the present invention is greater than 98/2, the affinity between the crystalline resin and the polymerizable monomer is insufficient due to the small number of amorphous vinyl sites, and low temperature fixability and coloration are achieved. The dispersibility of the agent tends to decrease.
Moreover, when the said mass ratio of this invention is smaller than 70/30, storage stability and image development durability will fall easily. The reason why the storage stability is lowered is that when the mass ratio is smaller than 70/30, the amount of low molecular components of the crystalline resin increases, and the toner during storage is plasticized. Further, the reason why the development durability is lowered is that the fluidity of the toner is deteriorated due to the presence of such low molecular weight components in the toner surface layer. These adverse effects are caused by adding a polymerizable monomer composition to an aqueous medium as in the present invention, granulating the polymerizable monomer composition in the aqueous medium, and It is a problem that is manifested in a toner particle manufacturing method including a step of forming particles and a step of obtaining toner particles by polymerizing the polymerizable monomer contained in the particles of the polymerizable monomer composition. . This is because the low molecular weight component of the crystalline resin has high polarity and tends to be unevenly distributed in the vicinity of the toner surface layer.
The crystalline polyester portion in the crystalline resin used in the present invention can be obtained by a reaction between a divalent or higher polyvalent carboxylic acid and a diol. Among these, a polyester mainly composed of an aliphatic diol and an aliphatic dicarboxylic acid is preferable because of high crystallinity. Only one type of crystalline polyester may be used, or a plurality of types may be used in combination.

In the present invention, the crystalline resin refers to a resin having an endothermic peak at the time of temperature rise in differential scanning calorimetry (DSC) and an exothermic peak at the time of temperature fall, and the measurement is performed according to “ASTM D 3417-99”.
Examples of alcohol monomers for obtaining a crystalline polyester portion in such a crystalline resin include ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, dipropylene glycol, Examples include trimethylene glycol, tetramethylene glycol, pentamethylene glycol, hexamethylene glycol, octamethylene glycol, nonamethylene glycol, decamethylene glycol, dodecamethylene glycol, neopentyl glycol, 1,4-butadiene glycol and the like.
Examples of the carboxylic acid monomer for obtaining the crystalline polyester moiety include oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, peric acid, glutaconic acid, azelaic acid, sebacic acid, and nonanedicarboxylic acid. , Decanedicarboxylic acid, undecanedicarboxylic acid, dodecanedicarboxylic acid, maleic acid, fumaric acid, mesaconic acid, citraconic acid, itaconic acid, isophthalic acid, terephthalic acid, n-dodecyl succinic acid, n-dedecenyl succinic acid, cyclohexanedicarboxylic acid, these An acid anhydride or lower alkyl ester of
A particularly preferable crystalline polyester moiety is more preferably a saturated polyester.

The crystalline polyester moiety used in the present invention can be produced by a normal polyester synthesis method. For example, it can be obtained by subjecting a dicarboxylic acid component and a dial alcohol component to an esterification reaction or a transesterification reaction, and then performing a polycondensation reaction under reduced pressure or by introducing nitrogen gas according to a conventional method.
In the esterification or transesterification reaction, a normal esterification catalyst or a transesterification catalyst such as sulfuric acid, tertiary butyl titanium butoxide, dibutyl tin oxide, manganese acetate, magnesium acetate can be used as necessary. For polymerization, it is possible to use conventional polymerization catalysts such as tertiary butyl titanium butoxide, dibutyl tin oxide, tin acetate, zinc acetate, tin disulfide, antimony trioxide, germanium dioxide and the like. it can. The polymerization temperature and the amount of catalyst are not particularly limited, and may be arbitrarily selected as necessary.

  As the catalyst, a titanium catalyst is preferable, and a chelate-type titanium catalyst is more preferable. This is because the reactivity of the titanium catalyst is appropriate, and a polyester having a desirable molecular weight distribution can be obtained in the present invention. In addition, the crystalline polyester produced using a titanium catalyst is superior in terms of toner chargeability from the titanium or titanium catalyst incorporated into the polyester during production. A chelate-type titanium catalyst is desirable because these effects increase.

The crystalline resin preferably has an endothermic peak top (hereinafter also simply referred to as an endothermic peak top) in a range of 60 ° C. or higher and 110 ° C. or lower in differential scanning calorimetry (DSC). When the peak top of the endothermic end of the crystalline resin is lower than 60 ° C., the toner is likely to be blocked and the storage stability may be lowered. On the other hand, if the peak endotherm of the crystalline resin is higher than 110 ° C., the low-temperature fixability tends to decrease. In the case where toner particles are obtained by suspension polymerization, which is a preferred method for producing toner particles in the present invention, the solubility of the crystalline resin in the polymerizable monomer is lowered, and the colorant or crystalline resin is reduced. As a result, the dispersibility of the toner particle constituting material tends to decrease.
When the endothermic peak top of the crystalline resin is 60 to 110 ° C., it is possible to maintain storability and fixability, and when the toner particles are produced by a polymerization method, the solubility in the polymerizable monomer is increased. ,preferable. The peak top of the endotherm of the crystalline resin can be measured using differential scanning calorimetry (DSC). The peak endotherm of the crystalline resin can be adjusted by the type of alcohol monomer or carboxylic acid monomer used, the degree of polymerization, and the like.

  In the method for producing toner particles of the present invention, it is preferable to contain 3.0 to 30.0 parts by mass of a crystalline resin with respect to 100 parts by mass of the polymerizable monomer used for the toner particles, and 3.0 to 25 is preferable. The content is more preferably 0.0 parts by mass, and particularly preferably 3.0 to 20.0 parts by mass. A crystalline resin content of 3.0 parts by mass or more is desirable because the above-described effects of the present invention are great. In addition, since the crystalline resin is easy to absorb moisture, if the content is more than 30.0 parts by mass with respect to the polymerizable monomer, the uniformity of charging of the toner tends to be impaired, and fogging increases. May invite. In particular, it is desirable for the chargeability of the toner to be 20.0 parts by mass or less.

  The crystalline resin used in the method for producing toner particles of the present invention is a hybrid resin having a crystalline polyester portion and an amorphous vinyl portion. Such a resin can be obtained by the following method. For example, a method in which a vinyl monomer is radically polymerized in the presence of a crystalline polyester having an unsaturated bond. Another example is a method in which condensation polymerization is performed with a crystalline polyester or a condensation polymerization monomer constituting the crystalline polyester in the presence of a vinyl polymer having an acid value or a hydroxyl value. The mass ratio of the crystalline polyester portion and the amorphous vinyl portion of the crystalline resin can be controlled by adjusting the amount of each monomer charged.

  A monofunctional polymerizable monomer or a polyfunctional polymerizable monomer can be used as the vinyl polymerizable monomer used when the amorphous vinyl moiety in the hybrid resin is produced. Examples of the monofunctional polymerizable monomer include styrene; styrene derivatives such as α-methylstyrene, o-methylstyrene, m-methylstyrene, and p-methylstyrene; methyl acrylate, ethyl acrylate, n-propyl acrylate, iso- Acrylic materials such as propyl acrylate, n-butyl acrylate, iso-butyl acrylate, tert-butyl acrylate, n-amyl acrylate, n-hexyl acrylate, 2-ethylhexyl acrylate, n-octyl acrylate, n-nonyl acrylate, cyclohexyl acrylate Polymerizable monomer; Methacrylic polymerizable monomer in which the acrylic polymerizable monomer is changed to methacrylate.

As polyfunctional polymerizable monomers, diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, polyethylene glycol diacrylate, 1,6-hexanediol diacrylate, neopentyl glycol diacrylate, tripropylene glycol Acrylic polyfunctional polymerizable monomers such as diacrylate, polypropylene glycol diacrylate, 2,2′-bis (4- (acryloxy-diethoxy) phenyl) propane, trimethylolpropane triacrylate, tetramethylolmethane tetraacrylate; Methacrylic polyfunctional polymerizable monomer obtained by replacing the acrylic polyfunctional polymerizable monomer with methacrylate; divinylbenzene, divinylnaphthalene, divinylacetate Tell.
As the vinyl monomer, those having a carboxyl group or a hydroxyl group and those containing (meth) acrylic acid esters are preferable. This is because when a functional group having a strong polarity such as a carboxyl group is present in the amorphous vinyl portion of the hybrid resin, the amorphous vinyl portion has an appropriate polarity, and toner particles in an aqueous medium This is preferable because the toner particles are stabilized during the production.
In addition, if the amorphous vinyl portion of the hybrid resin is a copolymer of a vinyl-based polymerizable monomer and acrylic acid, the hydrogen surface due to the carboxyl group of acrylic acid will make the toner surface stronger and more durable. It is preferable because it is excellent. However, when the content of acrylic acid in the hybrid resin exceeds 3.0% by mass, the hygroscopicity tends to increase in a high-temperature and high-humidity environment, and the triboelectric chargeability of the toner tends to decrease.

As a polymerization initiator used for polymerizing the above-mentioned vinyl-based polymerizable monomer when producing the hybrid resin, as long as it does not inhibit the effects of the present invention other than those used in the present invention, Oil-soluble initiators and / or water-soluble initiators can be used as appropriate. For example, as an oil-soluble initiator, azo compounds such as 2,2′-azobisisobutyronitrile; t-butylperoxyneodecanoate, t-hexylperoxypivalate, lauroyl peroxide, t- Examples thereof include peroxides such as butyl peroxy 2-ethylhexanoate, t-butyl peroxyisobutyrate, di-t-butyl peroxyisophthalate, and di-t-butyl peroxide.
Water-soluble initiators include ammonium persulfate, potassium persulfate, 2,2′-azobis (N, N′-dimethyleneisobutyroamidine) hydrochloride, 2,2′-azobis (2-aminodinopropane) hydrochloric acid Salt, azobis (isobutylamidine) hydrochloride, sodium 2,2′-azobisisobutyronitrile sulfonate, 2,2′-azobis {2-methyl-N- [1,1-bis (hydroxymethyl) -2 -Hydroxyethyl] propionamide}, 2,2′-azobis {2-methyl-N- [2- (1-hydroxybutyl)]-propionamide}, hydrochloride ferrous sulfate or hydrogen peroxide.
In particular, it is preferably a peroxide, and when the polyester resin is vinyl-modified by a hydrogen abstraction reaction, the 10-hour half-life temperature is preferably 70 ° C. or higher and 170 ° C. or lower, and 75 ° C. or higher and 130 ° C. or lower. When used, it is more preferable because it has an appropriate reactivity.

Hereinafter, further preferred embodiments of the method of the present invention will be described.
The crystalline resin of the present invention preferably has a content ratio of a molecular weight of 3000 or less in a GPC molecular weight distribution of tetrahydrofuran-soluble content of 3 area% or more and 10 area% or less.
It is presumed that the low molecular weight component of the crystalline resin tends to be a harmful factor with respect to the development durability and storage stability of the toner. That is, it is considered that the low molecular weight component may lower the toner performance by plasticizing the binder resin at the time of development durability or storage of the toner and reducing its strength. On the other hand, from the viewpoint of the low temperature fixability described above, it is considered that the low molecular weight component of the crystalline resin may act as a good plasticizer at the time of fixing and contribute to the low temperature fixing of the toner.
Here, particularly when a polymerizable monomer composition containing a crystalline resin is granulated in an aqueous medium, the crystalline resin is unevenly distributed on the surface of the toner particles due to the high hydrophilicity of the low molecular weight component. It becomes easy to do. As a result, effects such as a decrease in development durability and storage stability or a contribution to low-temperature fixing are easily manifested, and it is considered preferable to control the component to a certain amount.
Here, when the content ratio of the molecular weight of 3000 or less in the GPC molecular weight distribution of the tetrahydrofuran-soluble component of the crystalline resin of the present invention is 3 area% or more, the low-temperature fixability of the toner tends to be sufficient. In the case of 10% by area or less, the development durability and storage stability of the toner tend to be improved. The content ratio of the molecular weight of 3000 or less in the GPC molecular weight distribution of the tetrahydrofuran-soluble component of the crystalline resin can be controlled by the ratio of charged monomers at the time of producing the crystalline resin and the reaction conditions at the time of production.

The polymerizable monomer composition of the present invention contains an amorphous polyester, and the interfacial tension between water and the amorphous polyester dissolved in styrene by the hanging drop method is XSt (mN / m), When XaP (mN / m), it is preferable to satisfy the following formula (1).
10 ≦ XSt−XaP ≦ 15 (1)
The value of the interfacial tension by the hanging drop method means that the lower the value, the higher the hydrophilicity. When suspension polymerization is performed using a resin in the above range, it means that the amorphous polyester is more unevenly distributed on the toner particle surface. By setting the interfacial tension between styrene and the amorphous polyester dissolved in styrene in such a relationship, the amorphous polyester has sufficient hydrophilicity, so that the amorphous polyester is unevenly distributed in the toner particle surface layer. It becomes possible.
Thereby, the toner particles can have a core-shell structure, and the development durability and storage stability of the toner can be further improved.
The interfacial tension of amorphous polyester dissolved in styrene with water by the hanging drop method can be controlled by adjusting the polarity of the amorphous polyester such as monomer composition, acid value and hydroxyl value.

As the amorphous polyester, either one or both of a saturated polyester resin and an unsaturated polyester resin can be appropriately selected and used. The alcohol component and acid component which comprise an amorphous polyester resin are illustrated below.
Examples of the alcohol component include ethylene glycol, propylene glycol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, diethylene glycol, triethylene glycol, cyclohexanedimethanol, hydrogenated bisphenol A, and the following general A bisphenol derivative represented by the formula (I),

（式中、Ｒはエチレンまたはプロピレン基であり、ｘ、ｙはそれぞれ１以上の整数であり、かつｘ＋ｙの平均値は２乃至１０である。）

(In the formula, R is an ethylene or propylene group, x and y are each an integer of 1 or more, and the average value of x + y is 2 to 10.)

Alternatively, a hydrogenated compound of the compound of the general formula (I), a diol represented by the following general formula (II),

  Or the diol of the hydrogenated compound of the compound of Formula (II), and also polyhydric alcohols such as glycerin, pentaerythritol, sorbit, sorbitan, oxyalkylene ethers of novolac type phenol resins.

  Examples of the divalent carboxylic acid include the following. Benzene dicarboxylic acid or its anhydride such as phthalic acid, terephthalic acid, isophthalic acid, phthalic anhydride, unsaturated dicarboxylic acid such as fumaric acid, maleic acid, citraconic acid, itaconic acid or its anhydride, and trimellit Polyvalent carboxylic acids such as acid, pyromellitic acid, 1,2,3,4-butanetetracarboxylic acid and benzophenonetetracarboxylic acid and their anhydrides;

In the present invention, the interfacial tension between the amorphous polyester dissolved in styrene and the crystalline resin dissolved in styrene having a molecular weight of 3000 or less with water by the hanging drop method is XaP (mN / m ), XcP ₃₀₀₀ (mN / m), the following formula (2) is preferably satisfied.
−5 ≦ XaP-XcP ₃₀₀₀ ≦ 5 (2)
A component having a molecular weight of 3000 or less in the crystalline resin also acts to improve low-temperature fixability, and adversely affects development durability and storage stability. When the interfacial tension between the amorphous polyester and the crystalline resin having a molecular weight of 3000 or less is in the above relationship, the hydrophilicity of the amorphous polyester and the crystalline resin having a molecular weight of 3000 or less is at the same level. Therefore, it means that the low molecular weight component of the crystalline resin is appropriately present in the vicinity of the amorphous polyester.
By satisfying this relationship, it is easy to achieve a more favorable balance between fixability, durability, and storage stability.
The interfacial tension between the crystalline resin dissolved in styrene and water having a molecular weight of 3000 or less by the hanging drop method can be controlled by adjusting the polarity of the crystalline resin such as monomer composition, acid value, and hydroxyl value.

The crystalline resin used in the present invention preferably has a peak molecular weight of 1.0 × 10 ⁴ or more and 2.0 × 10 ⁴ or less in the GPC molecular weight distribution of the tetrahydrofuran-soluble component. By setting the peak molecular weight within this range, the low-temperature fixability tends to be good, and the storage stability of the toner tends to be improved.
The peak molecular weight of the crystalline resin can be adjusted by the type of alcohol monomer or carboxylic acid monomer used, the polymerization time, the polymerization temperature, and the like.
The peak molecular weight of the crystalline resin can be measured using gel permeation chromatography (GPC) as described below.

It is also a preferred embodiment of the present invention that the particles of the polymerizable monomer composition contain an aromatic solvent. When the polymerizable monomer composition is granulated in an aqueous medium such as the present invention and the polymerizable monomer contained in the particles is polymerized to obtain toner particles, each material in the toner particles Although it is arranged from the center of the toner to the surface layer according to the polarity, such movement is hindered by an increase in the viscosity of the particles as the polymerization proceeds. However, when the polymerizable monomer composition particles contain an aromatic solvent such as toluene, the increase in viscosity is suppressed even when the polymerization proceeds, and the optimal arrangement of each material can be further promoted. It becomes possible, and the effect expression of the present invention becomes more remarkable. The aromatic solvent in the toner particles can be removed by a distillation step after polymerization or a toner drying step.
Moreover, the aromatic solvent shown here is an aromatic solvent which does not have a reactive double bond, and any conventionally known one can be used. For example, toluene and xylene are mentioned, and toluene is particularly preferable.

The toner particle production method of the present invention includes a plurality of slits in the step of granulating the polymerizable monomer composition in an aqueous medium to form particles of the polymerizable monomer composition. Using a stirrer installed coaxially so that a rotor having ring-shaped protrusions formed in multiple stages on concentric circles and a stator having similar-shaped protrusions are maintained at regular intervals and meshed with each other, polymerization is performed. It is preferable to treat the functional monomer composition. In such a treatment method, when forming particles of the polymerizable monomer composition, a shearing force is further applied to the composition, and at the same time, coalescence of the particles is promoted. Therefore, it is considered that the particle size distribution of the toner particles is made uniform by causing more particle splitting and coalescence, and each material represented by the colorant in the toner particles is easily dispersed uniformly.
In addition, the fact that more toner particles break up and coalesce means that the number of contact at the liquid-liquid interface between the toner particles and the aqueous medium increases, but when the toner particles are placed in such a state. Further, the uneven distribution of the crystalline resin and the colorant aggregation due to the pigment shock accompanying the colorant are likely to occur. However, since the crystalline resin used in the present invention is familiar with the polymerizable monomer composition, even if the contact number of the liquid-liquid interface is increased, it is stably dispersed and not unevenly distributed in the toner particles. The colorant tends to be uniformly dispersed.

Below, the material used by this invention is demonstrated.
As the polymerizable monomer used in producing the toner particles of the present invention, a vinyl monomer capable of radical polymerization is used. As the vinyl monomer, a monofunctional monomer or a polyfunctional monomer can be used. Monofunctional monomers include styrene; α-methylstyrene, β-methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, 2,4-dimethylstyrene, pn-butylstyrene, p- tert-butyl styrene, pn-hexyl styrene, pn-octyl styrene, pn-nonyl styrene, pn-decyl styrene, pn-dodecyl styrene, p-methoxy styrene, p-phenyl styrene Styrene derivatives such as: methyl acrylate, ethyl acrylate, n-propyl acrylate, iso-propyl acrylate, n-butyl acrylate, iso-butyl acrylate, tert-butyl acrylate, n-amyl acrylate, n-hexyl acrylate, 2-ethylhexyl acrylate , -Acrylic polymerizable monomers such as octyl acrylate, n-nonyl acrylate, cyclohexyl acrylate, benzyl acrylate, dimethyl phosphate ethyl acrylate, diethyl phosphate ethyl acrylate, dibutyl phosphate ethyl acrylate, 2-benzoyloxyethyl acrylate; Methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, iso-propyl methacrylate, n-butyl methacrylate, iso-butyl methacrylate, tert-butyl methacrylate, n-amyl methacrylate, n-hexyl methacrylate, 2-ethylhexyl methacrylate, n-octyl methacrylate , N-nonyl methacrylate, diethyl phosphate ethyl methacrylate Methacrylic polymerizable monomers such as dibutyl phosphate ethyl methacrylate; methylene aliphatic monocarboxylic acid esters; vinyl esters such as vinyl acetate, vinyl propionate, vinyl butyrate, vinyl benzoate, vinyl formate; vinyl And vinyl ethers such as methyl ether, vinyl ethyl ether and vinyl isobutyl ether; vinyl ketones such as vinyl methyl ketone, vinyl hexyl ketone and vinyl isopropyl ketone. Among the above, the polymerizable monomer used in the present invention preferably contains styrene or a styrene derivative.

  As polyfunctional monomers, diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, polyethylene glycol diacrylate, 1,6-hexanediol diacrylate, neopentyl glycol diacrylate, tripropylene glycol diacrylate, polypropylene Glycol diacrylate, 2,2'-bis (4- (acryloxy-diethoxy) phenyl) propane, trimethylolpropane triacrylate, tetramethylolmethane tetraacrylate, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, tetra Ethylene glycol dimethacrylate, polyethylene glycol di Tacrylate, 1,3-butylene glycol dimethacrylate, 1,6-hexanediol dimethacrylate, neopentyl glycol dimethacrylate, polypropylene glycol dimethacrylate, 2,2′-bis (4- (methacryloxy-diethoxy) phenyl) propane, 2 2,2'-bis (4- (methacryloxy-polyethoxy) phenyl) propane, trimethylolpropane trimethacrylate, tetramethylolmethane tetramethacrylate, divinylbenzene, divinylnaphthalene, divinyl ether and the like.

In the present invention, the above monofunctional monomers are used alone or in combination of two or more, or the above monofunctional monomers and polyfunctional monomers are used in combination. Polyfunctional monomers can also be used as crosslinking agents.
As the polymerization initiator used in the present invention, an oil-soluble initiator and / or a water-soluble initiator is used. Preferably, the half-life at the reaction temperature during the polymerization reaction is 0.5 to 30 hours. Moreover, when a polymerization reaction is carried out at an addition amount of 0.5 to 20 parts by mass with respect to 100 parts by mass of the polymerizable monomer, a polymer having a maximum between 10,000 and 100,000 is usually obtained. It is preferable because toner particles having strength and melting characteristics can be obtained.

As polymerization initiators, the following 2,2′-azobis- (2,4-dimethylvaleronitrile), 2,2′-azobisisobutyronitrile, 1,1′-azobis (cyclohexane-1-carbohydrate) were used. Nitrile), 2,2′-azobis-4-methoxy-2,4-dimethylvaleronitrile, azo or diazo polymerization initiators such as azobisisobutyronitrile; benzoyl peroxide, t-butylperoxy 2- Ethyl hexanoate, t-butyl peroxypivalate, t-butyl peroxyisobutyrate, t-butyl peroxyneodecanoate, methyl ethyl ketone peroxide, diisopropyl peroxycarbonate, cumene hydroperoxide, 2,4- Peroxides such as dichlorobenzoyl peroxide and lauroyl peroxide Examples thereof include initiators.
In the present invention, in order to control the degree of polymerization of the polymerizable monomer, a known chain transfer agent, polymerization inhibitor or the like can be further added and used.

  In the method for producing toner particles of the present invention, the polymerizable monomer composition may contain an ester wax or other wax. Specific examples include the following. Petroleum waxes and derivatives thereof such as paraffin wax, microcrystalline wax, petrolactam; montan wax and derivatives thereof; hydrocarbon waxes and derivatives thereof according to Fischer-Tropsch method; polyolefin waxes and derivatives thereof such as polyethylene wax and polypropylene wax; carnauba wax Natural waxes such as candelilla wax and derivatives thereof. Examples of the derivatives include oxides, block copolymers with vinyl monomers, and graft modified products. Furthermore, the following are mentioned. Higher fatty alcohols; fatty acids such as stearic acid and palmitic acid; acid amide waxes; hydrogenated castor oil and derivatives thereof; plant waxes; animal waxes and the like. Among these, ester wax and hydrocarbon wax are preferable from the viewpoint of excellent releasability. Furthermore, it is preferable from the viewpoint of developability that the compound having the same total carbon number is contained in 50 to 95% by mass of wax because of high wax purity.

The method for producing toner particles of the present invention will be described below.
The toner particles of the present invention are preferably produced by a suspension polymerization method. In this suspension polymerization method,
(1) Polymerizable monomer (2) Colorant (3) Crystalline resin (4) Amorphous polyester, crosslinking agent, charge control agent, and other additives are uniformly dissolved or dispersed as required. To obtain a polymerizable monomer composition. Thereafter, the polymerizable monomer composition is dispersed in an aqueous medium containing a dispersion stabilizer using an appropriate stirrer, and if necessary, an aromatic solvent and a polymerization initiator are added to perform a polymerization reaction. To obtain toner particles having a desired particle diameter. After the polymerization of the toner particles is completed, the toner particles of the present invention can be obtained by performing filtration, washing and drying by a known method, mixing a fluidity improver if necessary and adhering to the surface.

When toner particles are produced by this suspension polymerization method, the shape of each toner particle is almost spherical, so that the charge amount distribution is uniform. Further, it is easy to obtain a toner that maintains a high transferability with little dependence on external additives.
In the method for producing toner particles by suspension polymerization, a ring having a plurality of slits is formed in the step of granulating the polymerizable monomer composition in an aqueous medium to form particles of the polymerizable monomer composition. Using a stirrer installed coaxially so that a rotor with multi-stage protrusions concentrically formed on a concentric circle and a stator with similar-shaped protrusions are kept at regular intervals and mesh with each other. It is preferred to treat the monomer composition. FIG. 1 shows a system incorporating a mixing device comprising the rotor and stator described above, and FIG. 2 shows a side view of the main body of the mixing device. 4 is a diagram showing a cross section taken along the line AA ′ in FIG. 1, and FIG. 3 is a diagram showing a cross section taken along the line BB ′ in FIG. 5 and 6 show a perspective view of the stator 22 and a perspective view of the rotor 25 of the mixing device, respectively.

Hereinafter, the mixing apparatus will be specifically described. In FIG. 1, a mixture of an aqueous medium and a polymerizable monomer composition is put into a holding tank 208 to obtain a preparation solution. The introduced preparation liquid is supplied from the inlet of the mixing device via the circulation pump 210. In the mixing device, the prepared solution passes through the slits of the rotor 25 and the stator 22 provided in the casing 202, and is centrifuged. To be discharged. When the preparation liquid passes through the mixing device, the preparation liquid is granulated by compression in the centrifugal direction caused by displacement of the slits of the rotor and stator, impact by discharge, and impact by shear between the rotor and stator. . The shape of the rotor and the stator is a shape in which ring-shaped protrusions having a plurality of slits are formed in multiple stages on concentric circles, and are arranged on the same axis so as to mesh with each other at a constant interval. It is preferable. Since the rotor and the stator are arranged so as to mesh with each other, the short path is reduced and the preparation liquid can be sufficiently dispersed. In addition, since the rotor and the stator are alternately arranged in multiple stages in the concentric direction, since the preparation solution is subjected to a lot of shearing and impact when traveling in the centrifugal direction, the particle size uniformity and the inside of the particle are further increased. In addition, the material uniformity between particles can be improved. Since the holding tank 208 has a jacket structure, the processed product can be cooled and heated.

  The circumferential speed of the rotor and the stator is the circumferential speed of the maximum diameter of the rotor and the stator. When the peripheral speed of the rotor 25 is G (m / s), it is preferable to rotate the rotor at 20 ≦ G ≦ 60 and mix the prepared solution. More preferably, the circumferential speed G of the rotor is 30 ≦ G ≦ 40. If the circumferential speed G of the rotor is 20 ≦ G ≦ 60, the shock caused by the compression and discharge of the prepared liquid in the centrifugal direction caused by the displacement of the slits of the rotor and the stator and the impact caused by the shear between the rotor and the stator And more particle coalescence and fragmentation is achieved. Thereby, the particle uniformity of a preparation liquid can be made very high more than before. When the circumferential speed G of the rotor is smaller than 20 m / s, the impact due to the compression and discharge in the centrifugal direction and the impact due to the shear between the rotor and the stator are reduced, and it is difficult to achieve a desired level of particle uniformity. . In addition, with the passage of time, a preparation solution having poor dispersion stability in which the colorant particles aggregate is often generated. Further, when the circumferential speed G of the rotor is larger than 60 m / s, a large pressure loss occurs when discharging from the slits of the rotor and the stator, so that not only a sufficient flow rate cannot be secured but also solid matter such as a colorant. And the polymerizable monomer may be separated. As the above-mentioned mixing device, for example, Cavitron (manufactured by Eurotech) can be suitably used.

Examples of the colorant used in the present invention include a black colorant, a yellow colorant, a magenta colorant, and a cyan colorant.
As the black colorant, carbon black, a magnetic material, and a toned color of each color using a yellow / magenta / cyan colorant shown below are used.
Examples of the yellow colorant include compounds typified by condensed azo compounds, isoindolinone compounds, anthraquinone compounds, azo metal complexes, methine compounds, and allylamide compounds. Specifically, the following C.I. I. Pigment Yellow 12, 13, 14, 15, 17, 62, 73, 74, 83, 93, 94, 95, 97, 109, 110, 111, 120, 128, 129, 138, 147, 150, 151, 154, Examples include 155, 168, 180, 185, 214 and the like.
Examples of the magenta colorant include condensed azo compounds, diketopyrrolopyrrole compounds, anthraquinones, quinacridone compounds, basic dye lake compounds, naphthol compounds, benzimidazolone compounds, thioindigo compounds, and perylene compounds. Specifically, the following C.I. I. Pigment Red 2, 3, 5, 6, 7, 23, 48: 2, 48: 3, 48: 4, 57: 1, 81: 1, 122, 146, 150, 166, 169, 177, 184, 185, 202, 206, 220, 221, 238, 254, 269, C.I. I. Pigment Bio Red 19 and the like can be exemplified.
Examples of cyan colorants include copper phthalocyanine compounds and derivatives thereof, anthraquinone compounds, basic dye lake compounds, and the like. Specifically, C.I. I. Pigment blue 1, 7, 15, 15: 1, 15: 2, 15: 3, 15: 4, 60, 62, 66, and the like.
These colorants can be used alone or in combination and further in the form of a solid solution. The colorant is selected from the viewpoints of hue angle, saturation, lightness, light resistance, OHP transparency, and dispersibility in toner particles. The addition amount of the colorant is preferably 1 to 20 parts by mass with respect to 100 parts by mass of the polymerizable monomer or binder resin.

Further, the toner particles according to the method of the present invention can be made into magnetic toner particles by containing a magnetic material as a colorant. In this case, the magnetic material can also serve as a colorant. Magnetic materials include the following iron oxides such as magnetite, hematite and ferrite; metals such as iron, cobalt and nickel, or aluminum, cobalt, copper, lead, magnesium, tin, zinc, antimony, beryllium and bismuth of these metals. And alloys of metals such as cadmium, calcium, manganese, selenium, titanium, tungsten and vanadium, and mixtures thereof.
The magnetic material is more preferably a surface-modified magnetic material. When a magnetic toner is prepared by a polymerization method, it is preferable to apply a hydrophobic treatment with a surface modifier, which is a substance that does not inhibit polymerization. Examples of such surface modifiers include silane coupling agents and titanium coupling agents.
These magnetic materials preferably have a number average particle diameter of 2 μm or less, more preferably 0.1 to 0.5 μm. The amount to be contained in the toner particles is preferably 20 to 200 parts by mass, more preferably 40 to 150 parts by mass with respect to 100 parts by mass of the polymerizable monomer, with respect to 100 parts by mass of the polymerizable monomer.

In the method of the present invention, a charge control agent may be added to the toner particles in order to stabilize the charging characteristics. As the charge control agent, known ones can be used, and in particular, a charge control agent that has a high charging speed and can stably maintain a constant charge amount is preferable. Further, when the toner particles are produced by a direct polymerization method, a charge control agent having a low polymerization inhibitory property and substantially free from a solubilized product in an aqueous dispersion medium is particularly preferable. Specific compounds include metal compounds of aromatic carboxylic acids such as salicylic acid, alkylsalicylic acid, dialkylsalicylic acid, naphthoic acid, dicarboxylic acid, metal salts or metal complexes of azo dyes or azo pigments, boron compounds as negative charge control agents , Silicon compounds, calixarene. Examples of the positive charge control agent include a quaternary ammonium salt, a polymer compound having the quaternary ammonium salt in the side chain, a guanidine compound, a nigrosine compound, and an imidazole compound.
The amount of these charge control agents used is determined by the toner particle production method including the type of binder resin, the presence / absence of other additives, and a dispersion method, and is not uniquely limited. In the case of internal addition, it is preferably used in the range of 0.1 to 10 parts by mass, more preferably 0.1 to 5 parts by mass with respect to 100 parts by mass of the polymerizable monomer.
In the case of external addition, the amount is preferably 0.005 to 1.0 part by mass, more preferably 0.01 to 0.3 part by mass with respect to 100 parts by mass of the toner particles.

A dispersion stabilizer is added to the aqueous medium. The following inorganic compounds used as dispersion stabilizers are calcium phosphate, magnesium phosphate, aluminum phosphate, zinc phosphate, calcium carbonate, magnesium carbonate, calcium hydroxide, magnesium hydroxide, aluminum hydroxide, calcium metasilicate, sulfuric acid. Examples include calcium, barium sulfate, bentonite, silica, alumina and the like.
Examples of the organic compound include polyvinyl alcohol, gelatin, methyl cellulose, methyl hydroxypropyl cellulose, ethyl cellulose, sodium salt of carboxymethyl cellulose, polyacrylic acid and its salt, starch and the like. These dispersion stabilizers are preferably used in an amount of 0.2 to 20 parts by mass with respect to 100 parts by mass of the polymerizable monomer.

Further, for fine dispersion of these dispersion stabilizers, 0.001 to 0.1 parts by mass of a surfactant may be used. This is to promote the initial action of the dispersion stabilizer. Specific examples include sodium dodecylbenzene sulfate, sodium tetradecyl sulfate, sodium pentadecyl sulfate, sodium octyl sulfate, sodium oleate, sodium laurate, potassium stearate, calcium oleate and the like.
When an inorganic compound is used as the dispersion stabilizer, a commercially available one may be used as it is, but in order to obtain finer particles, the inorganic compound may be generated and used in an aqueous medium.
For example, in the case of calcium phosphate, a sodium phosphate aqueous solution and a calcium chloride aqueous solution may be mixed under high stirring.

Furthermore, in the method of the present invention, a fluidity improver may be added to the toner particles for the purpose of improving the fluidity of the toner particles. As the fluidity improver, the following fluororesin powders such as fine vinylidene fluoride powder and polytetrafluoroethylene fine powder; fatty acid metal salts such as zinc stearate, calcium stearate and lead stearate; titanium oxide powder, oxidation Metal powder such as aluminum powder and zinc oxide powder, or powder obtained by hydrophobizing the above metal oxide; and silica fine powder such as wet process silica and dry process silica, or silica with silane coupling agent and titanium coupling Examples thereof include surface-treated silica fine powder that has been surface-treated with a treating agent such as an agent and silicone oil.
The fluidity improver is preferably used in an amount of 0.01 to 5 parts by mass with respect to 100 parts by mass of the toner particles.

The toner particles according to the present invention can be used as a toner, for example, by externally mixing inorganic fine particles. The method of external addition mixing is well-known, for example, the method of performing a mixing process using a Henschel mixer (Mitsui Miike Kako Co., Ltd.) is mentioned.
The amount of the inorganic fine powder added is preferably 0.01 to 5.0 parts by mass, more preferably 0.1 to 4.0 parts by mass with respect to 100 parts by mass of the toner particles. If the addition amount is within the above range, a sufficient fluidity improving effect can be obtained while suppressing a decrease in fixing property. The inorganic fine powder preferably has a number average primary particle size of 4 to 80 nm, and more preferably 4 to 60 nm.
Examples of the inorganic fine powder include metal oxides such as titanium oxide powder, aluminum oxide powder, and zinc oxide powder; silica fine powder such as wet process silica and dry process silica. Among these, silica fine powder is preferable. The metal oxide or silica fine powder may be surface-treated with a treatment agent such as a silane coupling agent, a titanium coupling agent, or silicone oil. Furthermore, aluminum dope silica, strontium titanate, and hydrotalcite are mentioned. In addition, as an external additive, vinylidene fluoride fine powder, fluorine-based resin powder such as polytetrafluoroethylene fine powder; fatty acid metal salt such as zinc stearate, calcium stearate, lead stearate, etc. can be added. .

The physical property value measuring method of the present invention will be described below.
<Measurement of Interfacial Tension with Water by Suspension Drop Method for Styrene, Amorphous Polyester, and Crystalline Resin with Molecular Weight of 3000 or Less>
The interfacial tension in the present invention was measured by the hanging drop method described below. Specifically, using a FACE solid-liquid interface analyzer Drop Master 700 manufactured by Kyowa Interface Science Co., Ltd. in an environment at a temperature of 25 ° C., measurement was performed with WIDE 1 as the field of view of the lens portion. First, the tip portion of a 0.4 mm inner diameter thin tube that is vertically upward using reverse tension is put into degassed ion-exchanged water.
Next, the thin tube is connected to the syringe part. Styrene or a sample styrene solution is placed in the syringe part. In the measurement method of the present invention, the sample concentration dissolved in styrene was 0.99% by mass. Next, the syringe part is connected to an AUTO DISPENSER AD-31 manufactured by Kyowa Interface Science Co., Ltd., and styrene or a styrene solution of the sample is pushed out from the capillary, thereby creating a droplet at the tip of the capillary in ion exchange water. it can. Then, the interfacial tension with water is calculated from the shape of the droplet. The control and calculation method for creating droplets was performed using a measurement analysis system manufactured by Kyowa Interface Science Co., Ltd. The density difference between water and the styrene solution necessary for the calculation was set to 0.1 g / cm ³ , which is the density difference between water and styrene. The final measurement result of the interfacial tension was the average value of 10 measurements.
In addition, about the component of molecular weight 3000 or less of crystalline resin, the sample was obtained with the following method.

<Preparation of components having molecular weight of 3000 or less of crystalline resin>
The component having a molecular weight of 3000 or less of the crystalline resin was a component fractionated around the elution time of the crystalline resin having a molecular weight of 3000 in the following gel permeation chromatography (GPC). Therefore, in the molecular weight distribution measured by gel permeation chromatography (GPC) of the crystalline resin, the resin component was eluted after the elution time when the molecular weight was 3000. Specifically, it is collected by the following method.

<Preparation method of component having molecular weight of 3000 or less of crystalline resin>
[Device configuration]
LC-908 (manufactured by Nippon Analysis Industry Co., Ltd.)
JRS-86 (manufactured by the company: repeat injector)
JAR-2 (manufactured by: Autosampler)
FC-201 (Gilson company: fraction collector)
[Column structure]
JAIGEL-1H to 5H (diameter 20 × 600 mm: preparative column)
[Measurement condition]
Temperature: 40 ° C
Solvent: THF
Flow rate: 5 ml / min.
Detector: RI
A sample for fractionation was prepared using the same method as that for measuring the peak molecular weight of the crystalline resin described below. On the other hand, in the fractionation method, the elution time at which the molecular weight of the crystalline resin was 3000 was measured in advance, and the components fractionated after the elution time (including the elution time at which the molecular weight was 3000) were used as relevant components. The solvent was removed from the collected sample to obtain a measurement sample.

<Measurement of Content Ratio and Peak Molecular Weight (Mp) of Crystalline Resin with Molecular Weight of 3000 or Less>
The content ratio and peak molecular weight (Mp) of the crystalline resin having a molecular weight of 3000 or less in the present invention are measured by the following measuring method in terms of the molecular weight measured by gel permeation chromatography (GPC).
The measurement sample was prepared as follows.
The measurement sample and THF were mixed at a concentration of 5 mg / ml, sufficiently shaken, and the THF and the sample were mixed well (until the sample was completely united), and then allowed to stand at room temperature for 24 hours. Then, what passed the sample processing filter (Maishori disk H-25-2 Tosoh company make, Excro disk 25CR Gelman Science Japan company make) was prepared as a sample of GPC.
The molecular weight distribution and peak molecular weight (Mp) of the prepared sample were measured using a GPC measuring device (HLC-8120G PC manufactured by Tosoh Corporation) under the following measurement conditions according to the operation manual of the device.
<Measurement conditions>
Equipment: High-speed GPC “HLC8120 GPC” (manufactured by Tosoh Corporation)
Column: Seven series of Shodex KF-801, 802, 803, 804, 805, 806, 807 (manufactured by Showa Denko KK)
Eluent: THF
Flow rate: 1.0 ml / min
Oven temperature: 40.0 ° C
Sample injection volume: 0.10 ml
In calculating the molecular weight of the sample, a calibration curve was obtained from standard polystyrene resin (TSK Standard Polystyrene F-850, F-450, F-288, F-128, F-80, F-40, F- manufactured by Tosoh Corporation). 20, F-10, F-4, F-2, F-1, A-5000, A-2500, A-1000, A-500) were used.
The content ratio of the crystalline resin having a molecular weight of 3000 or less was calculated from the obtained molecular weight distribution result by the area ratio of components having a molecular weight of 3000 or less.

<Measurement of endothermic peak top in differential scanning calorimetry (DSC) of crystalline resin>
The peak top of the endotherm of the crystalline resin is measured according to ASTM D3418-82 using a differential scanning calorimeter “Q1000” (manufactured by TA Instruments).
The temperature correction of the device detection unit uses the melting points of indium and zinc, and the correction of heat uses the heat of fusion of indium.
Specifically, about 10 mg of crystalline resin is precisely weighed, placed in an aluminum pan, and an empty aluminum pan is used as a reference, and the temperature is raised within a measurement temperature range of 30 to 120 ° C. Measurement is performed at a rate of 10 ° C./min. In the measurement, the temperature is once raised to 120 ° C., subsequently lowered to 30 ° C., and then the temperature is raised again. The maximum endothermic peak of the DSC curve in the temperature range of 30 to 120 ° C. in the second temperature raising process is defined as the maximum endothermic peak of the endothermic curve in the DSC measurement of the crystalline resin of the present invention.

<Measurement of peak molecular weight (Mp) and weight average molecular weight (Mw) of amorphous polyester>
The molecular weight distribution of the THF-soluble matter of the amorphous polyester is measured by gel permeation chromatography (GPC) as follows.
First, an amorphous polyester is dissolved in tetrahydrofuran (THF) over 24 hours at room temperature. The obtained solution is filtered through a solvent-resistant membrane filter “Maescho Disc” (manufactured by Tosoh Corporation) having a pore diameter of 0.2 μm to obtain a sample solution. The sample solution is adjusted so that the concentration of the component soluble in THF is about 0.8% by mass. Using this sample solution, measurement is performed under the following conditions.
Apparatus: HLC8120 GPC (detector: RI) (manufactured by Tosoh Corporation)
Column: Seven series of Shodex KF-801, 802, 803, 804, 805, 806, 807 (manufactured by Showa Denko KK)
Eluent: Tetrahydrofuran (THF)
Flow rate: 1.0 ml / min
Oven temperature: 40.0 ° C
Sample injection volume: 0.10 ml
In calculating the molecular weight of the sample, standard polystyrene resin (for example, trade name “TSK Standard Polystyrene F-850, F-450, F-288, F-128, F-80, F-40, F-20, F— 10, F-4, F-2, F-1, A-5000, A-2500, A-1000, A-500 ", manufactured by Tosoh Corporation) are used.

<Measurement of glass transition temperature (Tg) of amorphous polyester>
The glass transition temperature (Tg) of the amorphous polyester is measured according to ASTM D3418-82 using a differential scanning calorimeter “Q1000” (manufactured by TA Instruments).
The temperature correction of the device detection unit uses the melting points of indium and zinc, and the correction of heat uses the heat of fusion of indium.
Specifically, about 10 mg of amorphous polyester is precisely weighed and placed in an aluminum pan, and an empty aluminum pan is used as a reference. Measurement is performed at ° C / min. In this temperature raising process, a specific heat change is obtained in the temperature range of 40 ° C to 100 ° C. At this time, the intersection of the intermediate point line of the baseline before and after the change in specific heat and the differential heat curve is defined as the glass transition temperature Tg of the amorphous polyester.

<Measurement of acid value of amorphous polyester>
The acid value is the number of mg of potassium hydroxide necessary for neutralizing the acid contained in 1 g of the sample. The acid value of the amorphous polyester is measured according to JIS K 0070-1992. Specifically, it is measured according to the following procedure.
(1) Preparation of Reagent 1.0 g of phenolphthalein is dissolved in 90 ml of ethyl alcohol (95 vol%), and ion exchanged water is added to make 100 ml to obtain a phenolphthalein solution.
7 g of special grade potassium hydroxide is dissolved in 5 ml of water, and ethyl alcohol (95 vol%) is added to make 1 l. In order not to touch carbon dioxide, etc., put in an alkali-resistant container and let stand for 3 days, then filter to obtain a potassium hydroxide solution. The obtained potassium hydroxide solution is stored in an alkali-resistant container. The factor of the potassium hydroxide solution was as follows: 25 ml of 0.1 mol / l hydrochloric acid was placed in an Erlenmeyer flask, a few drops of the phenolphthalein solution were added, titrated with the potassium hydroxide solution, and the hydroxide required for neutralization. Determined from the amount of potassium solution. As the 0.1 mol / l hydrochloric acid, one prepared according to JIS K 8001-1998 is used.
(2) Operation (A) Main test A 2.0 g sample of the pulverized amorphous polyester is precisely weighed into a 200 ml Erlenmeyer flask, and 100 ml of a mixed solution of toluene / ethanol (2: 1) is added and dissolved over 5 hours. To do. Subsequently, several drops of the phenolphthalein solution is added as an indicator, and titration is performed using the potassium hydroxide solution. The end point of titration is when the light red color of the indicator lasts for about 30 seconds.
(B) Blank test Titration is performed in the same manner as above except that no sample is used (that is, only a mixed solution of toluene / ethanol (2: 1) is used).
(3) The acid value is calculated by substituting the obtained result into the following formula.
A = [(C−B) × f × 5.61] / S
Here, A: acid value (mgKOH / g), B: addition amount (ml) of a potassium hydroxide solution in a blank test, C: addition amount (ml) of a potassium hydroxide solution in this test, f: potassium hydroxide Solution factor, S: sample (g).

<Measurement of Mass Ratio (Crystal Part / Amorphous Part) of Crystalline Polyester Part and Amorphous Vinyl Part of Crystalline Resin>
The mass ratio of the crystalline polyester part and the amorphous vinyl part (crystalline part / amorphous part) of the crystalline resin was measured by nuclear magnetic resonance spectroscopy (1H-NMR) [400 MHz, CDC13, room temperature (
25 ° C.)].
Measuring apparatus: FT NMR apparatus JNM-EX400 (manufactured by JEOL Ltd.)
Measurement frequency: 400MHz
Pulse condition: 5.0μs
Frequency range: 10500Hz
Number of integrations: 64 times The mass ratio (crystalline part / amorphous part) between the crystalline polyester part and the amorphous vinyl part was calculated from the integrated value of the obtained spectrum.

  The present invention will be specifically described with reference to the following examples. In this embodiment, all are based on mass unless otherwise specified.

(Crystalline Resin Production Example 1)
In an autoclave equipped with a decompression device, water separation device, nitrogen gas introduction device, temperature measurement device, and stirring device,
Sebacic acid 120 parts by weight 1,12-dodecanediol 140 parts by weight Potassium oxalate titanate 0.70 parts by weight was charged, and the reaction was performed at 200 ° C. for 6 hours under a nitrogen atmosphere and at normal pressure. Thereafter, the pressure was further reduced by 10 to 20 mmHg. Then, the mixture was reacted at 220 ° C. for 1.0 hour to obtain Resin 1.
Next, 180 parts by mass of xylene and the obtained resin 1 were placed in a pressure resistant reactor equipped with a dropping funnel, a Liebig condenser and a stirrer, and the temperature was raised to 200 ° C. in a nitrogen atmosphere. A mixture prepared by adding a mixture of 30 parts by mass of styrene, 3.2 parts by mass of acrylic acid, and 2 parts by mass of di-t-butyl peroxide to a dropping funnel was added dropwise under pressure (0.31 MPa) over 2 hours. After the dropwise addition, the reaction was further carried out at 200 ° C. for 3 hours to complete the polymerization, and the xylene was removed under reduced pressure while heating at 75 ° C., followed by washing with cyclohexane to obtain a crystalline resin 1. Table 2 shows the physical properties of the obtained crystalline resin.

(Production Examples 2 to 15 of crystalline resin)
In Production Example 1 of the crystalline resin, as shown in Table 2, crystalline resins 2 to 15 were obtained by changing the type and amount of the polyester monomer. Table 2 shows the physical properties of the obtained crystalline resin.

(Example of production of amorphous polyester 1)
In an autoclave equipped with a decompression device, a water separation device, a nitrogen gas introduction device, a temperature measurement device, and a stirring device, 0.025 part of the polyester monomer and tetrabutoxy titanate described in Table 1 were charged, and under nitrogen atmosphere and normal pressure Reaction was performed at 210 degreeC for 5 hours. Thereafter, 0.010 part of tetrabutoxy titanate was added, reacted at 220 ° C. for 3 hours, and further reacted under reduced pressure of 10 to 20 mmHg for 2 hours to obtain amorphous polyester 1. The obtained physical properties are shown in Table 1.

(Example of production of amorphous polyester 2)
In the production example of amorphous polyester 1, amorphous polyester 2 was obtained in the same manner except that the amount of the polyester monomer charged was changed as shown in Table 1. The obtained physical properties are shown in Table 1.
(Example of production of amorphous polyester 3)
In the production example of amorphous polyester 1, the amount of the polyester monomer was changed as shown in Table 1, and the amorphous polyester 3 was prepared in the same manner except that the additional tetrabutoxy titanate was changed to 0.020 part. Obtained. The obtained physical properties are shown in Table 1.
(Production Example of Amorphous Polyester 4)
In the production example of amorphous polyester 3, amorphous polyester 4 was obtained in the same manner except that the amount of the polyester monomer charged was changed as shown in Table 1. The obtained physical properties are shown in Table 1.
(Production Example of Amorphous Polyester 5)
In the production example of amorphous polyester 3, amorphous polyester 5 was obtained by the same method except that the amount of the polyester monomer charged was changed as shown in Table 1. The obtained physical properties are shown in Table 1.
(Production Example of Amorphous Polyester 6)
In the production example of amorphous polyester 4, amorphous polyester 6 was obtained in the same manner except that the amount of the polyester monomer charged was changed as shown in Table 1. The obtained physical properties are shown in Table 1.

(Example of production of amorphous polyester 7)
In an autoclave equipped with a decompression device, a water separation device, a nitrogen gas introduction device, a temperature measurement device, and a stirring device, 0.200 parts of the polyester monomer and dibutyltin oxide listed in Table 1 were charged, and 210 under a nitrogen atmosphere and normal pressure. The reaction was carried out at 5 ° C. for 5 hours. Thereafter, the mixture was reacted at 220 ° C. for 3 hours, and further reacted under reduced pressure of 10 to 20 mmHg for 2 hours. Thereafter, an appropriate amount of trimellitic acid was added at the same temperature to adjust the acid value, and amorphous polyester 7 was obtained. The physical properties are shown in Table 1.

(Toner Production Example 1)
To 900 parts by mass of ion-exchanged water heated to 60 ° C., 2.3 parts by mass of tricalcium phosphate is added and stirred at 10,000 rpm using a TK homomixer (made by Tokushu Kika Kogyo Co., Ltd.). Got. Further, the following materials were uniformly dissolved and mixed at 100 r / min with a propeller stirrer to prepare a resin-containing monomer.
-Styrene 50 parts by mass-n-Butyl acrylate 30 parts by mass-Crystalline resin 1 10 parts by mass-Amorphous polyester resin 1 5 parts by mass In addition, the following materials are dispersed with an attritor and contain a fine particulate colorant content Got the body.
-Styrene 30 parts by mass-C.I. I. Pigment Blue 15: 3 7.4 parts by mass, charge control agent Bontron E-88 (manufactured by Orient Chemical Co., Ltd.) 5.0 parts by mass, wax HNP-10 (manufactured by Nippon Seiki Co., Ltd.) 10.0 parts by mass After obtaining a polymerizable monomer composition by uniformly mixing the fine colorant-containing monomer and the resin-containing monomer, the polymerizable monomer composition is heated to 60 ° C., and then The polymerizable monomer composition is charged into the aqueous medium, and the polymerizable monomer composition is granulated with the apparatus shown in FIGS. Composition particles were formed. In addition, the circumferential speed G (m / s) of the rotor 25 in FIG. 4 was set to 35 (m / s).
Then, 10.0 parts by mass of a polymerization initiator tert-butyl peroxypivalate and 3 parts by mass of toluene were added thereto, and granulation was continued for 10 minutes.
Then, it moved to the propeller-type stirring apparatus, and it was made to react at 75 degreeC for 5 hours, stirring at 100 r / min, Then, it heated up to 85 degreeC, and also reacted for 5 hours, and the polymerization reaction was performed. After completion of the polymerization reaction, the slurry containing the particles was cooled to room temperature (25 ° C.), and hydrochloric acid was added to the suspension to dissolve the calcium phosphate salt, followed by filtration and washing to obtain wet colored particles. The colored particles were dried at a temperature of 40 ° C. for 12 hours to obtain toner particles 1.
100 parts by mass of toner particles 1 and 1.6 parts by mass of hydrophobic silica fine powder having a BET value of 300 m ² / g and a primary particle size of 8 nm were mixed with a Henschel mixer (Mitsui Miike Chemical Co., Ltd.). Thus, toner 1 was obtained. Table 2 shows the physical properties of Toner 1.

(Toner Production Examples 2 to 4)
C. of Toner Production Example 1 I. Pigment Blue 15: 3 to C.I. I. Pigment yellow 93, C.I. I. Toners 2 to 4 were obtained in the same manner except that they were changed to CI Pigment Red 269 and Carbon Black. Table 2 shows the physical properties of each toner.

(Toner Production Example 5)
A toner 5 was obtained in the same manner as in Toner Production Example 1 except that the crystalline resin 1 was changed to the crystalline resin 2. The physical properties are shown in Table 2.
(Toner Production Example 6)
Toner 6 was obtained in the same manner as in Toner Production Example 1 except that crystalline resin 1 was changed to crystalline resin 3. The physical properties are shown in Table 2.
(Toner Production Example 7)
Toner 7 was obtained in the same manner as in Toner Production Example 1 except that crystalline resin 1 was changed to crystalline resin 4. The physical properties are shown in Table 2.

(Toner Production Example 8)
A toner 8 was obtained in the same manner as in Toner Production Example 1 except that the crystalline resin 1 was changed to the crystalline resin 5. The physical properties are shown in Table 2.
(Toner Production Example 9)
A toner 9 was obtained in the same manner as in Toner Production Example 1 except that the crystalline resin 1 was changed to the crystalline resin 6. The physical properties are shown in Table 2.
(Toner Production Example 10)
A toner 10 was obtained in the same manner as in Toner Production Example 1 except that the crystalline resin 1 was changed to the crystalline resin 7. The physical properties are shown in Table 2.

(Toner Production Example 11)
Toner 11 was obtained in the same manner as in Toner Production Example 9 except that amorphous polyester resin 1 was changed to amorphous polyester resin 2. The physical properties are shown in Table 2.

(Toner Production Example 12)
Toner 12 was obtained in the same manner as in Toner Production Example 10 except that amorphous polyester resin 1 was changed to amorphous polyester resin 3. The physical properties are shown in Table 2.

(Toner Production Example 13)
Toner 13 was obtained in the same manner as in Toner Production Example 1 except that amorphous polyester resin 1 was changed to amorphous polyester resin 4. The physical properties are shown in Table 2.

(Toner Production Example 14)
Toner 14 was obtained in the same manner as in Toner Production Example 1 except that amorphous polyester resin 1 was changed to amorphous polyester resin 5. The physical properties are shown in Table 2.

(Toner Production Example 15)
Toner 15 was obtained in the same manner as in Toner Production Example 1 except that amorphous polyester resin 1 was changed to amorphous polyester resin 6. The physical properties are shown in Table 2.

(Toner Production Example 16)
Toner 15 was obtained in the same manner as in Toner Production Example 1 except that amorphous polyester resin 1 was changed to amorphous polyester resin 7. The physical properties are shown in Table 2.

(Toner Production Example 17)
A toner 17 was obtained in the same manner as in Toner Production Example 12 except that the crystalline resin 7 was changed to the crystalline resin 8. The physical properties are shown in Table 2.
(Toner Production Example 18)
Toner 18 was obtained in the same manner as in Toner Production Example 17 except that toluene was changed to xylene. The physical properties are shown in Table 2.
(Toner Production Example 19)
Toner 19 was obtained in the same manner as in Toner Production Example 17 except that toluene was changed to heptane. The physical properties are shown in Table 2.

(Toner Production Example 20)
To 900 parts by mass of ion-exchanged water heated to 60 ° C., 2.3 parts by mass of tricalcium phosphate is added and stirred at 10,000 rpm using a TK homomixer (made by Tokushu Kika Kogyo Co., Ltd.). Got. Further, the following materials were uniformly dissolved and mixed at 100 r / min with a propeller stirrer to prepare a resin-containing monomer.
-Styrene 50 parts by mass-N-butyl acrylate 20 parts by mass-Crystalline resin 1 10 parts by mass-Amorphous polyester resin 1 5 parts by mass In addition, the following materials are dispersed with an attritor and contain a fine particulate colorant content Got the body.
-Styrene 30 parts by mass-C.I. I. Pigment Blue 15: 3 7.4 parts by mass, charge control resin FCA-1001-NS (manufactured by Fujikura Chemical Co., Ltd.) 1.0 part by mass, wax HNP-51 (manufactured by Nippon Seiki Co., Ltd.) 10.0 parts by mass After uniformly mixing the fine colorant-containing monomer and the resin-containing monomer to obtain a polymerizable monomer composition, the polymerizable monomer composition is heated to 60 ° C., Next, the polymerizable monomer composition is put into the aqueous medium, and granulated at 12000 rpm for 10 minutes with Claremix (manufactured by MTechnic Co., Ltd.) to obtain particles of the polymerizable monomer composition. Formed.
Then, 10.0 parts by mass of a polymerization initiator tert-butyl peroxypivalate and 3 parts by mass of toluene were added thereto, and granulation was continued for 10 minutes.
Then, it moved to the propeller-type stirring apparatus, and it was made to react at 75 degreeC for 5 hours, stirring at 100 r / min, Then, it heated up to 85 degreeC, and also reacted for 5 hours, and the polymerization reaction was performed. After completion of the polymerization reaction, the slurry containing the particles was cooled to room temperature (25 ° C.), and hydrochloric acid was added to the suspension to dissolve the calcium phosphate salt, followed by filtration and washing to obtain wet colored particles. The colored particles were dried at a temperature of 40 ° C. for 12 hours to obtain toner particles 20.
100 parts by mass of toner particles 1 and 1.6 parts by mass of hydrophobic silica fine powder having a BET value of 300 m ² / g and a primary particle size of 8 nm were mixed with a Henschel mixer (Mitsui Miike Chemical Co., Ltd.). Thus, toner 20 was obtained. Table 2 shows the physical properties of Toner 20.

(Toner Production Example 21)
A toner 21 was obtained in the same manner as in Toner Production Example 1 except that the crystalline resin 1 was changed to the crystalline resin 14. The physical properties are shown in Table 2.
(Toner Production Example 22)
A toner 22 was obtained in the same manner as in Toner Production Example 1 except that the crystalline resin 1 was changed to the crystalline resin 15. The physical properties are shown in Table 2.
(Toner Production Example 23)
A toner 23 was obtained in the same manner as in Toner Production Example 1 except that the crystalline resin 1 was changed to the crystalline resin 12. The physical properties are shown in Table 2.
(Toner Production Example 24)
A toner 24 was obtained in the same manner as in Toner Production Example 1 except that the crystalline resin 1 was changed to the crystalline resin 13. The physical properties are shown in Table 2.

(Comparative toner production example 1)
Comparative toner 1 was obtained in the same manner as in Toner Production Example 1 except that crystalline resin 1 was changed to crystalline resin 9. The physical properties are shown in Table 2.
(Comparative toner production example 2)
Comparative toner 2 was obtained in the same manner as in toner production example 1 except that crystalline resin 1 was changed to crystalline resin 10. The physical properties are shown in Table 2.
(Comparative toner production example 3)
Comparative toner 3 was obtained in the same manner as in toner production example 1 except that crystalline resin 1 was changed to crystalline resin 11. The physical properties are shown in Table 2.

<Example 1>
Toner 1 was evaluated for the following evaluation items. The evaluation results are shown in Table 3.

<Preservation test>
(1) Storage stability test The blocking resistance was evaluated in order to evaluate the stability during storage. About 5 g of toner is put in a 100 ml plastic cup, heated from 25 ° C. to 50 ° C. over 12 hours, and then cooled down from 50 ° C. to 25 ° C. over 12 hours as 1 day, and left in that environment for 30 days. After that, the degree of aggregation of the toner was measured as follows and evaluated according to the following criteria.
As the measuring apparatus, a “powder tester” (manufactured by Hosokawa Micron Co., Ltd.) having a vibration table side surface portion connected with a digital display vibrometer “Digivibro MODEL 1332A” (manufactured by Showa Keiki Co., Ltd.) was used. Then, a sieve having a mesh size of 38 μm (400 mesh), a sieve having a mesh size of 75 μm (200 mesh), and a sieve having a mesh size of 150 μm (100 mesh) were stacked in this order on the vibrating table of the powder tester. The measurement was performed as follows in an environment of 23 ° C. and 60% RH.
(1) The vibration width of the vibration table was adjusted in advance so that the displacement value of the digital display vibrometer was 0.60 mm (peak-to-peak).
(2) The toner that has been left for 30 days as described above is left in advance in an environment of 23 ° C. and 60% RH for 24 hours, and 5 g of the toner is precisely weighed and gently placed on a sieve having an opening of 150 μm. It was.
(3) After vibrating the sieve for 15 seconds, the mass of toner remaining on each sieve was measured, and the degree of aggregation was calculated based on the following equation.
Aggregation degree (%) = {(sample mass (g) on a sieve having an opening of 150 μm) / 5 (g)} × 100
+ {(Sample mass on a sieve having an opening of 75 μm (g)) / 5 (g)} × 100 × 0.6
+ {(Sample mass (g) on a sieve having an opening of 38 μm) / 5 (g)} × 100 × 0.2
The evaluation criteria are as follows.
A: The degree of aggregation is less than 20%. B: The degree of aggregation is 20% or more and less than 25%.
C: The degree of aggregation is 25% or more and less than 30%.
D: The degree of aggregation is 30% or more and less than 35%.
E: Aggregation degree is 35% or more.
Among the above evaluations, there are no practical problems if A to C.

<Durability test>
Using toner 1 as a non-magnetic one-component developer, and a modified LBP-7700C (manufactured by Canon) as an image forming apparatus, in a normal temperature and normal humidity environment (temperature 23 ° C., relative humidity 50%) and in a high temperature and high humidity environment Image evaluation was performed at a temperature of 32 ° C. and a relative humidity of 83%. A4 color laser copier paper (manufactured by Canon, 80 g / m ² ) was used as the recording medium. The LBP-7700C was modified as follows.
-The process speed was set to 250 mm / sec by changing the gear and software of the main body of the evaluation machine.
-The cartridge used for evaluation was a cyan cartridge. That is, the product toner was extracted from a commercially available cyan cartridge, the interior was cleaned by air blow, and 200 g of toner 1 was filled. The product toner was extracted from each of the magenta, yellow, and black stations, and magenta, yellow, and black cartridges with the remaining toner amount detection mechanism disabled were inserted.
-The fixing unit can be set manually.
Under the above conditions, up to 30,000 images with a printing ratio of 0.1% are in the intermittent mode (the developer is paused for 10 seconds each time one image is printed, and the toner is deteriorated by the preliminary operation of the developing device at the time of restart. The durability test was conducted in the mode to promote.
In addition, about the following evaluation item, it carried out in each environment at the initial stage (10th sheet) and after durable use.

[Evaluation items]
(1) Fog In the measurement of fog, a reflection densitometer manufactured by Tokyo Denshoku Co., Ltd., REFECTMETER MODEL TC-6DS was used. The reflectivity of the non-image part of the standard paper and the printout image was measured, the fog was calculated from the following formula from the measurement result, and evaluated according to the following criteria. Note that a green filter was used as a filter used in the measurement.
Fog (reflectance:%) = reflectance on standard paper (%) − reflectance of sample non-image area (%)
A: Fog is less than 0.3% B: Fog is 0.3% or more and less than 0.5% C: Fog is 0.5% or more and less than 1.0% D: Fog is 1.0% or more

(2) Streaks The solid lines (toner applied amount 0.45 mg / cm ² ) and the developing roller were visually observed and evaluated according to the following criteria.
A: A vertical streak in the paper discharge direction that appears as a development streak is not seen on the developing roller or the solid image. There is no problem in practical use.
B: Although there are 1 to 5 thin circumferential streaks at both ends of the developing roller, no vertical streak in the paper discharge direction, which is seen as a developing streak, is seen on a solid image. There is no problem in practical use.
C: There are several thin circumferential streaks at both ends of the developing roller, and several 1-5 fine developing streaks are also seen on the solid image. However, it is a level that can be erased by image processing and has no practical problem. D: Several thick streaks are seen on the developing roller and the solid image, and cannot be erased even by image processing. A practically problematic level.
E: Many development streaks are observed on the developing roller and the solid image, and cannot be erased even by image processing. A level that is extremely problematic in practical use.

<Fixing test>
(1) Low-temperature fixability A fixing rub test was conducted as fixability. A 10 mm x 10 mm 3-dot 3 space (600 dpi) image for density measurement, adjusted to a toner mass per unit area of 0.5 mg / cm ² on plain paper for A4 copier (105 g / m ² ). The fixed image thus obtained was rubbed five times with sylbon paper applied with a weight of 50 g / cm ² , and the reduction rate of the image density after the rub was evaluated based on the following. When outputting an image, the gear and software of the evaluator body were changed so that the process speed was 330 mm / sec, and the fixing temperature was set to 160 ° C. In addition, as the toner to be evaluated, the toner before being left is used.
In addition, the image density is measured by using a Macbeth reflection densitometer (manufactured by Macbeth Co., Ltd.), measuring the relative density with respect to the printout image of the white background portion where the document density is 0.00, and reducing the image density after rubbing. When the fixing property by the fixing rubbing test is A to C, there is no practical problem.
A: Less than 2.0% B: More than 2.0% and less than 5.0% C: More than 5.0% and less than 10.0% D: More than 10.0% and less than 15.0% E; 15. 0% or more (2) Coloring power
A solid image having a toner loading of 0.50 mg / cm ² on the evaluation paper is prepared, and the image density is measured using a color reflection densitometer (X-RITE 404A: manufactured by X-Rite Co.) for evaluation. did.
A: Image density is 1.40 or more (good)
B: Image density is 1.35 or more and less than 1.40 (no problem in practical use)
C: Image density is 1.20 or more and less than 1.35 (practical limit)
D: Image density is less than 1.20 (practical problem)

<Examples 2 to 24>
In the same manner as in Example 1, toners 2 to 24 were evaluated. The evaluation results are shown in Table 3.
<Comparative Examples 1-3>
Comparative toners 1 to 3 were evaluated in the same manner as in Example 1. The evaluation results are shown in Table 3.

202 Casing 208 Holding tank 210 Circulation pump 211 Heat exchanger 212 Thermometer 21 Liquid inlet 22 Stator 23 Stator protrusion 24 Stator protrusion slit 25 Rotor 26 Stator circumferential groove 27 Rotor protrusion slit 28 Rotation Rotor protrusion 29 Rotor drive shaft 30 Rotor circumferential groove

Claims (7)

A polymerizable monomer composition containing a polymerizable monomer, a colorant, and a crystalline resin is added to an aqueous medium, and the polymerizable monomer composition is granulated in the aqueous medium to form the polymerizable monomer. A method for producing toner particles, comprising: forming particles of a monomer composition; and polymerizing the polymerizable monomer contained in the particles of the polymerizable monomer composition to obtain toner particles. And
The polymerizable monomer is a vinyl monomer,
The crystalline resin is a hybrid resin having a crystalline polyester portion and an amorphous vinyl portion,
Mass ratio of the crystalline polyester part and the amorphous vinyl part of the crystalline resin (crystal part /
A method for producing toner particles, wherein the amorphous part is 70/30 to 98/2.   2. The method for producing toner particles according to claim 1, wherein a content ratio of a molecular weight of 3000 or less in a GPC molecular weight distribution of a tetrahydrofuran soluble part of the crystalline resin is 3 area% or more and 10 area% or less. The polymerizable monomer composition contains an amorphous polyester, and the interfacial tension of the amorphous polyester dissolved in styrene and styrene by water by the hanging drop method is expressed as XSt (mN / m), XaP ( 3. The method for producing toner particles according to claim 1, wherein the following formula (1) is satisfied: mN / m).
10 ≦ XSt−XaP ≦ 15 (1) Interfacial tensions of the amorphous polyester dissolved in styrene and the crystalline resin dissolved in styrene with a molecular weight of 3000 or less with water by the hanging drop method are XaP (mN / m) and XcP ₃₀₀₀ (mN, respectively). / M), the following formula (2) is satisfied: 4. The method for producing toner particles according to claim 3, wherein
−5 ≦ XaP-XcP ₃₀₀₀ ≦ 5 (2) 5. The GPC molecular weight distribution of the tetrahydrofuran-soluble component of the crystalline resin has a peak molecular weight of 1.0 × 10 ⁴ or more and 2.0 × 10 ⁴ or less. 2. A method for producing toner particles according to 1.   The method for producing toner particles according to any one of claims 1 to 5, wherein the particles of the polymerizable monomer composition contain an aromatic solvent.   In the step of forming particles of the polymerizable monomer composition, ring-shaped protrusions having a plurality of slits have a plurality of concentric circles formed in multiple stages on the stator having protrusions having the same shape as the rotor. The toner particles according to any one of claims 1 to 6, wherein the polymerizable monomer composition is treated using a stirrer installed coaxially so as to keep in mesh and mesh with each other. Manufacturing method.

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