JP4665707B2 - Toner for electrophotography - Google Patents

Description

  The present invention relates to an electrophotographic toner (hereinafter sometimes simply referred to as “toner”) used in an apparatus utilizing an electrophotographic process such as a copying machine, a printer, and a facsimile machine, particularly a color copying machine.

  As an electrophotographic process, many methods have been conventionally known (for example, see Patent Document 1). In the electrophotographic process, a latent image is electrically formed on a photoconductor using a photoconductive substance by various means, and this latent image is developed using toner, and the toner latent image on the photoconductor is formed. A plurality of processes in which a toner image is transferred to a film to be transferred such as paper with or without an intermediate transfer member, and then the transferred image is fixed by heating, pressing, heating and pressing, or solvent vapor. Through this, a fixed image is formed. The toner remaining on the photoreceptor is cleaned by various methods as necessary, and the plurality of steps are repeated. In recent years, due to technological advances in the electrophotographic field, such electrophotographic processes have been used not only for copying machines and printers, but also for printing applications. It has been increasingly demanded to have high image quality and hue equivalent to printed matter, and as a toner, high gloss, high color development, high stress resistance corresponding to high speed, and long life are important characteristics. Particularly in recent years, energy saving has become important, and in the electrophotographic process, reduction of power consumption in the fixing process, which consumes the most power, has become a major issue.

  In order to achieve both low temperature fixing property and toner storage property, the number average molecular weight Mn measured by gel permeation chromatography (hereinafter referred to as “GPC”) is 1000 to 4000, and the weight average molecular weight Mw and the number average molecular weight Mn are A color toner using a resin having a ratio Mw / Mn of 45 or more is disclosed (for example, see Patent Document 2). Many other techniques that focus on the rheological properties of the binder resin have been disclosed, but the recent demand for higher speed and lower temperature fixing has reached its limit.

  As an alternative to this, so-called capsule-type toners have been studied in which the surface of toner base particles having low-temperature fixability is covered with a polymer, aiming to achieve both toner storage properties and low-temperature fixability, and various methods are used as manufacturing methods. Has been proposed.

For example, a technique for attaching polymer fine particles to the surface of toner base particles is disclosed (see, for example, Patent Document 3 or 4). These are all wet processing methods. Further, a method is disclosed in which fine particles are electrostatically attached to the surface of the toner base particles and fixed by a mechanical impact force (see, for example, Patent Document 5 or 6). In either case, the shell layer is formed by post-processing, but the adhesion between the core and the shell is weak, and there is a problem that the shell is detached due to stress in the developing machine.
A method is disclosed in which fine particles are adhered and then fixed by solvent vapor (see, for example, Patent Document 7). However, there is a problem that the core and the shell are compatible with each other due to solvent vapor or heat applied during drying, and the core component is exposed on the toner surface. In addition, there is a problem that the toners are fused with each other and the generation of coarse powder and the particle size distribution change.
A method is disclosed in which core particles made of a vinyl polymer are granulated, and the surface of the core particles is polymerized with a hydrophilic monomer having a glass transition temperature higher than that of the polymer forming the core particles. (For example, refer to Patent Document 8). However, since the hydrophilic monomer penetrates into the core particles before the shell layer is polymerized, the compatibility between the core and the shell proceeds. In addition, since a hydrophilic polymer is used, it is likely to be unevenly distributed on the shell surface because it tends to come out in the aqueous phase. However, due to the hydrophilic group, the charging environment stability is deteriorated and the developer life is shortened.

A shell made of a polymer in which the core particles made of colored polymer particles containing a polyfunctional ester compound, Fischer-Tropsch wax and a colorant have a glass transition temperature higher than the glass transition temperature of the polymer component constituting the core particles. A technique for achieving both low-temperature fixability and toner storage stability by using a polymer toner having a core and shell structure coated with (see, for example, Patent Document 9).
However, the compatibility between the core and the shell is not disclosed. If the compatibility between the core layer and the shell layer is high, the core material is exposed on the toner surface, and conversely, if the compatibility between the core layer and the shell layer is low, the shell is exposed. The trade-off relationship that problems such as desorption occur will not be broken. Further, when the compatibility between the core and the shell is poor, there is a problem that the image strength after fixing is lowered. Further, when a resin having a Tg of 80 ° C. or higher is used for the shell under a condition where the compatibility between the core layer and the shell layer is low, the fixing property is greatly affected by the fixing property of the resin for the shell, and the low-temperature fixing property as a toner is deteriorated. .

A method is disclosed in which a crystalline substance is contained in the core, and a material having a solubility parameter of 18 × 10 ⁻³ J ^1/2 m ^3/2 or more is contained in the shell layer (see, for example, Patent Document 10). .) However, if the solubility parameter of the shell resin is simply increased, problems such as shell detachment will occur.
In particular, when a toner is prepared by a wet manufacturing method using a polyester resin as a binder resin, the polyester resin is more charged than the styrene acrylic resin due to the hydrophilicity of the ester group, terminal carboxylic acid, and hydroxyl group It tends to be difficult to obtain the environmental stability of charging. Therefore, it is necessary to strictly control the compatibility between the core and the shell.
Japanese Patent Publication No.42-23910 JP-A-4-240660 Japanese Unexamined Patent Publication No. 57-45558 Japanese Unexamined Patent Publication No. 1-225753 JP-A-2-186363 JP-A-4-188155 JP-A-4-182660 Japanese Patent Laid-Open No. 61-118758 JP 11-218960 A Japanese Patent Laid-Open No. 9-218535

As described above, when a shell layer is formed on the toner, the core layer and the shell layer are detached due to high stress due to recent downsizing and speeding up. When the strength of the shell layer is increased, image glossiness and low-temperature fixability are improved. When the compatibility between the core layer and the shell layer is increased, the effect of preventing the toner internal additives from being exposed to the surface is lowered, and the life of the developer is shortened. Further, when the toner internal additives, particularly the release agent, are exposed on the surface of the toner, there is a problem that powder characteristics and chargeability are deteriorated.
The present invention has been made to solve the above-mentioned problems, and while preventing problems such as exposure of the toner additive to the surface and detachment of the shell layer, low temperature fixability, image glossiness, and developer length. An object of the present invention is to provide a toner for electrophotography which has a long life.

That is, the present invention
<1> An electrophotographic toner having a structure including a core particle containing at least a binder resin, a colorant, and a release agent, and a shell layer covering the core particle, the toner being contained in the core particle. 75% by mass or more of the binder resin is polyester resin A, 75% by mass or more of the shell layer is polyester resin B, and the proportion of isophthalic acid in the total amount of carboxylic acids constituting the polyester resin A (mol%) ) Is 22.5 mol% or more and 35.3 mol% or less, the ratio (mol%) of isophthalic acid in the total amount of carboxylic acid constituting the polyester resin B is 0 mol%, and the polyester resin A and The toner for electrophotography in which the solubility parameter (SP value) of the polyester resin B satisfies the following formula (2).

0.15 (J / cm ³ ) ^1/2 <(SP value of polyester resin B−SP value of polyester resin A) <1.7 (J / cm ³ ) ^1/2 formula (2)

<2> An electrophotographic toner having a structure including a core particle containing at least a binder resin, a colorant, and a release agent, and a shell layer covering the core particle, the toner being contained in the core particle. 75% by mass or more of the binder resin is the polyester resin C, 75% by mass or more of the shell layer is the polyester resin D, and the proportion of dodecenyl succinic acid in the total amount of carboxylic acid constituting the polyester resin C (mol%) ) Is 12.5 mol% or more and 20.0 mol% or less, the ratio (mol%) of dodecenyl succinic acid in the total amount of carboxylic acid constituting the polyester resin D is 0 mol%, and the polyester resin C and The toner for electrophotography in which the solubility parameter (SP value) of the polyester resin D satisfies the following formula (4).

0.15 (J / cm ³ ) ^1/2 <(SP value of polyester resin D−SP value of polyester resin C) <1.7 (J / cm ³ ) ^1/2 formula (4)

<3> The electrophotographic toner according to <1> or <2>, wherein the titanium content in the chloroform soluble component is 5 to 300 ppm by ICP emission spectroscopy.

The inventors of the present invention examined the structure and compatibility of the polyester resin. As a factor related to compatibility, there is a conventionally known SP value. As the SP value is actually closer, the compatibility tends to be better. As a result of further detailed investigation, it was found that the compatibility of the resin is improved even with the same SP value when isophthalic acid or dodecenyl succinic acid is used.
The present inventors presume this mechanism as follows. Since dodecenyl succinic acid has a long C-C chain length as a side chain, the linearity of the molecule is lowered and the intermolecular distance is increased, so that the compatibility is considered to be improved. Moreover, since isophthalic acid has a carboxylic acid at the meta position, the linearity of the molecule is reduced and the intermolecular distance is increased compared to terephthalic acid, so that the compatibility is considered to be improved. Similarly, although orthophthalic acid increases the intermolecular distance more than isophthalic acid, isophthalic acid is preferred because the flexibility of the molecule is excessively increased and the hot offset property is deteriorated and the glass transition temperature may be lowered.

By using a polyester resin mainly composed of isophthalic acid or dodecenyl succinic acid as the material of the core particles, the compatibility with an internal additive such as a mold release agent is improved. The mold is not completely mixed, but is basically incompatible, but at the interface between the materials, it is in a state of being compatible at the molecular level.
On the other hand, the compatibility with the polyester resin forming the shell layer can be considered in the same way, and it is incompatible when viewed in bulk by separating the SP value, but it is compatible when viewed microscopically at the interface. A state can be formed and the adhesion between the core particles and the shell layer can be improved. Further, since the compatibility between the release agent and the shell layer resin is low, there is also an effect of preventing the release agent from being exposed to the outside of the toner. Conventionally, the shell is prevented from being detached by increasing the strength of the shell itself by a cross-linked structure or the like. However, by using the method of the present invention, there is no need to increase the strength of the shell itself, and low temperature fixability and image quality are improved. Can improve the glossiness.

  Further, this effect can be further improved by containing a titanium compound in the toner. Although this mechanism is not clarified, the present inventors presume as follows. This titanium-based compound is derived from a polyester resin polycondensation catalyst, but the titanium-based polycondensation catalyst is generally used as a catalyst for a transesterification reaction of a polyester resin, and promotes a polymerization reaction, Transesterification is caused by inducing a decomposition reaction. This transesterification reaction is caused by the heat applied in the coalescence process at the time of toner preparation, but transesterification is performed at the interface between the binder resin in the core particle and the resin constituting the shell layer. It is estimated that the compatibility is improved and the effect of preventing the peeling between the core particle and the shell layer is improved.

  According to the present invention, an electrophotographic toner that achieves both low-temperature fixability, image glossiness, and long life of a developer while preventing problems such as exposure of the toner additive to the surface and detachment of the shell layer. Can be provided.

The electrophotographic toner of the present invention (hereinafter sometimes referred to as the toner of the present invention) will be described in detail below.
The first electrophotographic toner of the present invention (hereinafter sometimes referred to as the first toner of the present invention) includes core particles containing at least a binder resin, a colorant, and a release agent, and the core An electrophotographic toner having a structure including a shell layer covering particles, wherein 75% by mass or more of the binder resin contained in the core particle is the polyester resin A, and 75% by mass or more of the shell layer. Is the polyester resin B, the amount of isophthalic acid in the polyester resin A and the polyester resin B satisfies the following formula (1), and the solubility parameter (SP value) of the polyester resin A and the polyester resin B is The following formula (2) is satisfied.

Amount of isophthalic acid in polyester resin A> Amount of isophthalic acid in polyester resin B Formula (1)
0.15 (J / cm ³ ) ^1/2 <(SP value of polyester resin B−SP value of polyester resin A) <1.7 (J / cm ³ ) ^1/2 formula (2)

The amount of the polyester resin A in the binder resin contained in the core particles is preferably 85% by mass or more, and more preferably 95% by mass or more.
Further, the amount of the polyester resin B in the shell layer is preferably 85% by mass or more, and more preferably 95% by mass or more.

In the first toner of the present invention, the amount of isophthalic acid in the polyester resin refers to the proportion (mol%) of isophthalic acid in the total amount of carboxylic acid constituting the polyester resin. If the first toner of the present invention does not satisfy the formula (1), the micro-compatibility between the core resin and the release agent is reduced, so that the image strength is reduced and the release agent is exposed to the toner surface. May occur. In addition, the thermal storability of the toner may deteriorate due to the flexibility of isophthalic acid in the shell resin.
Here, the polyester resin A or the polyester resin B indicates the total amount of the polyester resin contained in the core particle or the shell layer, respectively. For example, when the polyester resin A consists of the polyester resin A-1 and the polyester resin A-2, the total amount is the polyester resin A. The same applies to the SP value. For example, the polyester resin A has an SP value of 20 (J / cm ³ ) ^1/2 and 80% by mass of the polyester resin A-1 has an SP value of 22 (J / cm ³ ). ^When the polyester resin A-2 of ^{1/2 comprises} 20% by mass, the SP value of the polyester resin A is 20 × 0.8 + 22 × 0.2, 20.4 (J / cm ³ ) ^1/2 It becomes. Similarly, when the amount of isophthalic acid is, for example, 80% by mass of polyester resin A-1 containing 50 mol% of isophthalic acid as an acid component and 20% by mass of polyester resin A-2 not containing isophthalic acid, the polyester resin The amount of isophthalic acid in A is 50 × 0.8 + 0 × 0.2 and is calculated as 40 mol%.
In the first toner of the present invention, the difference between the amount of isophthalic acid in the polyester resin A and the amount of isophthalic acid in the polyester resin B is preferably 15 to 85 mol%, more preferably 25 to 75 mol%.

  In the first or second toner of the present invention, the SP value of the polyester resin refers to the method of Fedors et al. [Polym. Eng. Sci. , Vol14, p147 (1974)], which is a value defined by the following formula (5).

SP value = (ΔE / V) ^1/2 = (ΣΔei / ΣΔvi) ^1/2 formula (5)

In Formula (5), SP represents a solubility parameter, ΔE represents a cohesive energy (cal / mol), V represents a molar volume (cm ³ / mol), and Δei represents the i-th atom or atomic group. Evaporation energy (cal / atom or atomic group), Δvi represents the molar volume (cm ³ / atom or atomic group) of the i-th atom or atomic group, and i represents an integer of 1 or more.

Note that the SP value represented by the formula (5) is conventionally obtained such that the unit is (cal / cm ³ ) ^1/2 and is expressed in a dimensionless manner. In addition, in the present invention, since the relative difference in SP value between two compounds is significant, in the present invention, the values obtained according to the above-described practice are used and expressed in a dimensionless manner. It was.
For reference, when the SP value represented by the formula (5) is converted to (J / cm ³ ) ^1/2 , 2.046 is converted to SI unit (J / m ³ ) ^1/2 . In that case, 2046 may be multiplied.

In the first toner of the present invention, when the value of (SP value of polyester resin B−SP value of polyester resin A) is less than 0.15 (J / cm ³ ) ^1/2 , the SP value is close. The compatibility of the bulk of the resin is increased, so that the heat storage property of the toner is deteriorated. When the release agent is exposed to the toner surface, the chargeability and toner powder fluidity may be lowered.
Further, when the value of (SP value of polyester resin B−SP value of polyester resin A) is larger than 1.7 (J / cm ³ ) ^1/2 , the SP value is separated, so that the bulk phase of the resin Since the solubility is reduced, the shell layer may be detached due to development stress or the like, or the strength of the fixed image may be reduced.

In the first toner of the present invention, the relationship between the SP value of the polyester resin A and the SP value of the polyester resin B is 0.2 (J / cm ³ ) ^1/2 <(SP value of the polyester resin B−polyester resin). SP value of A) <1.5 (J / cm ³ ) ^1/2 is preferable, 0.3 (J / cm ³ ) ^1/2 <(SP value of polyester resin B−SP value of polyester resin A) < 1.2 (J / cm ³ ) ^1/2 is more preferable.

  The second electrophotographic toner of the present invention (hereinafter sometimes referred to as the second toner of the present invention) is used instead of the polyester resin A and the polyester resin B according to the first toner of the present invention. Using polyester resin C and polyester resin D, the amount of dodecenyl succinic acid in polyester resin C and polyester resin D satisfies the following formula (3), and the solubility parameter (SP value) of polyester resin C and polyester resin D is as follows: The expression (4) is satisfied.

Dodecenyl succinic acid amount in polyester resin C> dodecenyl succinic acid amount in polyester resin D Formula (3)
0.15 (J / cm ³ ) ^1/2 <(SP value of polyester resin D−SP value of polyester resin C) <1.7 (J / cm ³ ) ^1/2 formula (4)

The amount of the polyester resin C in the binder resin contained in the core particles is preferably 85% by mass or more, and more preferably 95% by mass or more.
Further, the amount of the polyester resin D in the shell layer is preferably 85% by mass or more, and more preferably 95% by mass or more.

In the second toner of the present invention, the amount of dodecenyl succinic acid in the polyester resin refers to the proportion (mol%) of dodecenyl succinic acid in the total amount of carboxylic acid constituting the polyester resin. If the second toner of the present invention does not satisfy the formula (3), the micro compatibility between the core resin and the release agent is reduced, so that the image strength is reduced and the release agent is exposed to the toner surface. May occur. In addition, the heat storage property of the toner may deteriorate due to the flexibility of dodecenyl succinic acid in the shell resin.
In the second toner of the present invention, the difference between the amount of dodecenyl succinic acid in the polyester resin C and the amount of dodecenyl succinic acid in the polyester resin D is preferably 5 to 50 mol%, more preferably 10 to 35 mol%.

In the second toner of the present invention, when the value of (SP value of polyester resin D−SP value of polyester resin C) is less than 0.15 (J / cm ³ ) ^1/2 , the SP value is close. The compatibility of the bulk of the resin is increased, so that the heat storage property of the toner is deteriorated. When the release agent is exposed to the toner surface, the chargeability and the toner powder fluidity may be lowered.
Further, if the value of (SP value of polyester resin D−SP value of polyester resin C) is larger than 1.7 (J / cm ³ ) ^1/2 , the SP value is separated, so the resin bulk compatibility Therefore, the shell layer may be detached due to development stress or the like, or the strength of the fixed image may be reduced.

In the second toner of the present invention, the relationship between the SP value of the polyester resin C and the SP value of the polyester resin D is 0.2 (J / cm ³ ) ^1/2 <(SP value of the polyester resin D−polyester resin). SP value of C) <1.5 (J / cm ³ ) ^1/2 is preferable, 0.3 (J / cm ³ ) ^1/2 <(SP value of polyester resin D−SP value of polyester resin C) < 1.2 (J / cm ³ ) ^1/2 is more preferable.

Hereinafter, various materials used for the electrophotographic toner of the present invention will be described.
-Binder resin-
As the polyester resin which is a kind of binder resin used in the present invention, an amorphous polyester resin is preferable. Here, “amorphous polyester resin” means a polyester resin that does not show an endothermic peak corresponding to the crystalline melting point in addition to the endothermic point corresponding to Tg in the DSC chart.
The monomer other than isophthalic acid or dodecenyl succinic acid used in the polyester resin is not particularly limited. For example, monomer components described in Polymer Data Handbook: Basics (Polymer Science Society: Bafukan) can be used. There are some conventionally known divalent or trivalent or higher carboxylic acids and divalent or trivalent or higher alcohols.

Specific examples of these monomer components include divalent carboxylic acids such as succinic acid, glutaric acid, adipic acid, peric acid, azelaic acid, sebacic acid, phthalic acid, isophthalic acid, terephthalic acid, and naphthalene-2. , 6-dicarboxylic acid, naphthalene-2,7-dicarboxylic acid, cyclohexanedicarboxylic acid, malonic acid, mesaconic acid, and other dibasic acids, and their anhydrides and their lower alkyl esters, maleic acid, fumaric acid, itaconic acid And aliphatic unsaturated dicarboxylic acids such as citraconic acid.
Examples of the trivalent or higher carboxylic acid include 1,2,4-benzenetricarboxylic acid, 1,2,5-benzenetricarboxylic acid, 1,2,4-naphthalenetricarboxylic acid, and the like, and anhydrides thereof. And lower alkyl esters. These may be used individually by 1 type and may use 2 or more types together.

  Among these, from the viewpoint of compatibility described above, the polyester resin A used as the core polyester resin in the first toner of the present invention preferably contains 20 to 80 mol% of isophthalic acid in the acid component. % Is more preferable. If the amount is less than 20 mol%, the effect of compatibility is small. If the amount is more than 80 mol%, the resin strength may be excessively reduced or hot offset may be deteriorated. The polyester resin B preferably contains 50% by mole or less, more preferably 20% by mole or less of isophthalic acid in the acid component. The polyester resin B is most preferably free of isophthalic acid, but when the carboxylic acid component is composed of terephthalic acid or a highly linear monomer, the polyester resin B has crystallinity depending on the combination with the alcohol monomer, Tg may increase too much. In this case, crystallinity and Tg can be adjusted by using isophthalic acid in combination.

  From the viewpoint of compatibility described above, the polyester resin C used as the core polyester resin in the second toner of the present invention preferably contains 5 to 50 mol% of dodecenyl succinic acid in the acid component. It is further preferable to include it. If the amount is less than 5 mol%, the effect of compatibility is small. If the amount is more than 50 mol%, the resin strength may be excessively lowered or hot offset may be deteriorated. The polyester resin D preferably contains 10 mol% or less of dodecenyl succinic acid in the acid component, more preferably 5 mol% or less. The polyester resin D is most preferably free of dodecenyl succinic acid, but if the carboxylic acid component is composed of terephthalic acid or a highly linear monomer, it may have crystallinity depending on the combination with the alcohol monomer, Tg may increase too much, and in this case, crystallinity and Tg can be adjusted by using dodecenyl succinic acid together.

  Examples of the divalent alcohol include hydrogenated bisphenol A, bisphenol derivatives such as ethylene oxide or (and) propylene oxide adducts of bisphenol A, and cyclic aliphatics such as 1,4-cyclohexanediol and 1,4-cyclohexanedimethanol. Alcohol, ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, 1,4-butanediol, 1,5-pentanediol, linear diols such as 1,6-hexanediol, 1,2-propanediol, 1,3 -Branched diols such as butanediol, neopentyl glycol, 2,2-diethyl-1,3-propanediol, etc., and from the viewpoint of chargeability and strength, ethylene oxide of bisphenol A or (and) propylene glycol Sid adduct is used mainly.

  Examples of the trihydric or higher alcohol include glycerin, trimethylolethane, trimethylolpropane, and pentaerythritol. From the viewpoint of low-temperature fixability and image gloss, a trivalent or higher crosslinkable monomer is used. Is preferably 10 mol% or less of the total monomer amount. These may be used individually by 1 type and may use 2 or more types together. If necessary, monovalent acids such as acetic acid and benzoic acid, and monovalent alcohols such as cyclohexanol and benzyl alcohol can be used for the purpose of adjusting the acid value and the hydroxyl value.

Polyester resins can be combined in any combination from the monomer components described above, for example, polycondensation (chemical doujin), polymer experiments (polycondensation and polyaddition: Kyoritsu Publishing) and polyester resin handbook (edited by Nikkan Kogyo Shimbun). Can be synthesized using a conventionally known method as described above, and a transesterification method, a direct polycondensation method, or the like can be used alone or in combination.
Specifically, the reaction can be carried out at a polymerization temperature of 140 to 270 ° C., and the reaction is carried out while reducing the pressure in the reaction system as necessary to remove water and alcohol generated during the condensation. When the monomer is not dissolved or compatible with the reaction temperature, a solvent having a high boiling point may be added as a solubilizing solvent and dissolved.
In the polycondensation reaction, the dissolution auxiliary solvent is distilled off. When a monomer having poor compatibility exists in the copolymerization reaction, the monomer having poor compatibility and the monomer and the acid or alcohol to be polycondensed are condensed in advance and then polycondensed together with the main component. The molar ratio (acid component / alcohol component) at the time of reacting the acid component with the alcohol component varies depending on the reaction conditions and the like, and therefore cannot be generally stated. 1 to 1 / 0.9. In the case of a transesterification reaction, an excess of monomers that can be distilled off under vacuum such as ethylene glycol, propylene glycol, neopentyl glycol, cyclohexanedimethanol is often used.

Catalysts that can be used in the production of the polyester resin include alkali metal compounds such as sodium and lithium, alkaline earth metal compounds such as magnesium and calcium, metal compounds such as zinc, manganese, antimony, titanium, tin, zirconium, and germanium, Examples include phosphorous acid compounds, phosphoric acid compounds, and amine compounds. Specific examples include sodium acetate, sodium carbonate, lithium acetate, lithium carbonate, calcium acetate, calcium stearate, magnesium acetate, zinc acetate, and zinc stearate. , Zinc naphthenate, zinc chloride, manganese acetate, manganese naphthenate, titanium tetraethoxide, titanium tetrapropoxide, titanium tetraisopropoxide, titanium tetrabutoxide, antimony trioxide, triphenylantimony, tributyl Ntimmon, tin formate, tin oxalate, tetraphenyltin, dibutyltin dichloride, dibutyltin oxide, diphenyltin oxide, zirconium tetrabutoxide, zirconium naphthenate, zirconyl carbonate, zirconyl acetate, zirconyl stearate, zirconyl octylate, germanium oxide, triphenylphos Examples thereof include compounds such as phyto, tris (2,4-di-t-butylphenyl) phosphite, ethyltriphenylphosphonium bromide, triethylamine, and triphenylamine.
In the present invention, among these, it is preferable to use a titanium-based catalyst. Two or more kinds can be used in combination, and in that case, it is preferable to use a tin-based catalyst such as dibutyltin oxide from the viewpoint of chargeability.

  The polyester resin preferably has an acid value of 2 to 25 KOHmg / g and a hydroxyl value of 5 to 40 KOHmg / g.

  As the molecular weight of the polyester resin used in the present invention, those having a weight average molecular weight (Mw) of 5000 to 150,000 can be used. In order to obtain an image having particularly high image glossiness, Mw is 5000 to 30000, Mn is preferably 2000 to 10000, more preferably Mw is 6000 to 20000, and Mn is 2500 to 7500. Mw / Mn, which is an index of molecular weight distribution, is preferably 2 to 10. If Mw and Mn are too high, the color developability may be deteriorated. If Mw and Mn are too low, it is difficult to obtain image strength after fixing. This is because hot offset deteriorates.

The molecular weight and molecular weight distribution can be measured by a method known per se, but are generally measured by gel permeation chromatography (hereinafter abbreviated as “GPC”).
The molecular weight distribution was measured under the following conditions. As a GPC device, Tosoh Corporation HLC-8120GPC, SC-8020 device is used, TSK gei, Super HM-H (6.0 mm ID × 15 cm × 2) is used as a column, and for chromatograph manufactured by Wako Pure Chemical Industries, Ltd. THF (tetrahydrofuran) was used. As experimental conditions, the sample concentration was 0.5%, and the flow rate was 0.6 ml / min. Sample injection volume 10 μl, measurement temperature 40 ° C., calibration curve is A-500, F-1, F-10, F-80, F-380, A-2500, F-4, F-40, F-128, Made from 10 samples of F-700. The data collection interval in sample analysis was 300 ms.

  Examples of the resin that can be used as the binder resin in addition to the polyester resin include polystyrene, poly (meth) acrylic acid, and esterified products thereof. Examples of monomers that can be used in this case include styrenes such as styrene, parachlorostyrene, and α-methylstyrene: methyl acrylate, ethyl acrylate, n-propyl acrylate, n-butyl acrylate, and lauryl acrylate. , Esters having a vinyl group such as 2-ethylhexyl acrylate, methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, lauryl methacrylate, 2-ethylhexyl methacrylate, and the like: Vinyl nitriles such as acrylonitrile and methacrylonitrile: Vinyl ethers such as vinyl methyl ether and vinyl isobutyl ether: Vinyl ketones such as vinyl methyl ketone, vinyl ethyl ketone and vinyl isopropenyl ketone: Polyolefins such as ethylene, propylene and butadiene: Single amount And a copolymer obtained by combining two or more of these, or a mixture thereof. Furthermore, epoxy resins, polyester resins, polyurethane resins, polyamide resins, cellulose resins, polyether resins, etc., non-vinyl It is also possible to use a condensation resin, a mixture of these with the vinyl resin, or a graft polymer obtained when a vinyl monomer is polymerized in the presence of these resins. Among these, styrene acrylic copolymer resins, particularly styrene butyl acrylate copolymer resins are preferable from the viewpoint of chargeability and fixability.

In the present invention, the binder resin preferably has a tetrahydrofuran (hereinafter referred to as “THF”) insoluble content of 10% by mass or less based on the total binder resin component. This is because offset resistance is improved when the THF-insoluble content is large, but the glossiness of the image is impaired and the OHP light transmittance is impaired.
The THF-insoluble matter can be measured by dissolving the resin in THF at a concentration of about 10% by mass, filtering with a membrane filter or the like, drying the filter residue, and measuring the weight.

The binder resin of the present invention preferably has a glass transition temperature in the range of 30 ° C to 90 ° C. It is preferable from the viewpoint of low-temperature fixability that the relationship is (glass transition temperature of resin for core particles) <(glass transition temperature of resin for shell layer).
The glass transition temperature of the core particle resin is preferably 30 to 60 ° C., and the glass transition temperature of the shell layer resin is preferably in the range of 50 to 90 ° C.
If the glass transition temperature is low, toner storage properties and filming deteriorate, and if the glass transition temperature is too high, low-temperature fixability deteriorates.

  The glass transition temperature of the resin is increased from 0 to 150 ° C. at 10 ° C./min using, for example, a differential scanning calorimeter (manufactured by Mac Science: DSC3110, thermal analysis system 001) (hereinafter abbreviated as “DSC”). Warm, hold at 150 ° C. for 5 minutes, cool down from 150 ° C. to 0 ° C. with liquid nitrogen at −10 ° C./minute, hold at 0 ° C. for 5 minutes, and again from 0 ° C. to 150 at 10 ° C./minute It can be defined as the onset temperature analyzed from the endothermic curve at the second temperature rise obtained by raising the temperature.

The binder resin used in the present invention has a Tm of 80 to 150 ° C., where Tm is a temperature at which the loss elastic modulus G ″ (measurement frequency 1 rad / s, strain amount 20% or less) of the binder resin is 10,000 Pa. It is preferable to be in the range.
Here, the loss elastic modulus of the binder resin is measured as follows. The measuring device is a rheometer manufactured by Rheometrics, trade name “RDA II” (RHIOS system ver. 4.3), the measuring plate is a parallel plate having a diameter of 8 mm, the zero point adjustment temperature is 90 ° C., the plate With a gap of 3.5 mm, a heating rate of 1 ° C. per minute, an initial measurement strain of 0.01, and a measurement start temperature of 30 ° C., the strain is appropriately adjusted so that the detected torque becomes about 10 gcm as the temperature rises. % And the measurement was terminated when the detected torque was below the lower limit of the guaranteed measurement value.
Moreover, it is preferable that the softening point of the polyester resin used for this invention is 80-140 degreeC, More preferably, it is 95-135 degreeC. If the softening point of the polyester resin is less than 80 ° C., the toner and the image stability of the toner after fixing and storage may be deteriorated. On the other hand, when the softening point exceeds 140 ° C., the low-temperature fixability may be deteriorated.
In the present invention, the softening point of the polyester resin is determined by using a flow tester (manufactured by Shimadzu Corporation: CFT-500C), sample amount: 1.05 g, preheating: 300 ° C. at 65 ° C., plunger pressure: 0.980665 MPa, die size 1 mmφ, temperature increase rate: An intermediate temperature between the melting start temperature and the melting end temperature measured under the conditions of 1.0 ° C./min.

  In the present invention, a crystalline resin can be used in combination as a binder resin for improving the low-temperature fixability. From the viewpoint of compatibility with the amorphous resin, the crystalline resin is crystalline polyester resin, amyl (meth) acrylate, hexyl (meth) acrylate, heptyl (meth) acrylate, octyl (meth) acrylate, ( Nonyl (meth) acrylate, decyl (meth) acrylate, undecyl (meth) acrylate, tridecyl (meth) acrylate, myristyl (meth) acrylate, cetyl (meth) acrylate, stearyl (meth) acrylate, (meth) ) Long chain alkyls such as oleyl acrylate and behenyl (meth) acrylate, vinyl resins using one or more of (meth) acrylic esters of alkenyl, or olefins such as ethylene, propylene, butadiene and isoprene Among them, crystalline polyester resins are preferred.

  The crystalline polyester resin is synthesized from an acid (dicarboxylic acid) component and an alcohol (diol) component. In the present invention, the “crystalline polyester resin” means a step in the differential scanning calorimetry (DSC). It is not a change in the endothermic amount, but has a clear endothermic peak. In the case of a polymer obtained by copolymerizing other components with respect to the crystalline polyester main chain, when the other components are 50% by mass or less, this copolymer is also called crystalline polyester. In the following description, the component that was an acid component before the synthesis of the polyester resin is referred to as “acid-derived component”, and the component that was the alcohol component before the synthesis of the polyester resin is referred to as “alcohol-derived component”. Respectively.

-Acid-derived components-
The acid-derived constituent component is preferably an aliphatic dicarboxylic acid, and particularly preferably a linear carboxylic acid. Examples of the linear carboxylic acid include oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelic acid, sebacic acid, 1,9-nonanedicarboxylic acid, 1,10- Decanedicarboxylic acid, 1,11-undecanedicarboxylic acid, 1,12-dodecanedicarboxylic acid, 1,13-tridecanedicarboxylic acid, 1,14-tetradecanedicarboxylic acid, 1,16-hexadecanedicarboxylic acid, 1,18-octadecane Dicarboxylic acid, etc., or lower alkyl esters and acid anhydrides thereof. Among these, those having 6 to 10 carbon atoms are preferable from the viewpoint of crystal melting point and chargeability. In order to increase the crystallinity, these linear dicarboxylic acids are preferably used in an amount of 95 mol% or more, more preferably 98 mol% or more of the acid component.

  Other monomers are not particularly limited. For example, a conventionally known divalent or carboxylic acid which is a monomer component as described in Polymer Data Handbook: Basics (Science of Polymer Science: Bafukan). And divalent alcohol. Specific examples of these monomer components include divalent carboxylic acids such as phthalic acid, isophthalic acid, terephthalic acid, naphthalene-2,6-dicarboxylic acid, naphthalene-2,7-dicarboxylic acid, and cyclohexanedicarboxylic acid. And dibasic acids such as these, anhydrides thereof, and lower alkyl esters thereof. These may be used individually by 1 type and may use 2 or more types together.

As the acid-derived constituent component, in addition to the above-mentioned aliphatic dicarboxylic acid-derived constituent component, a constituent component such as a dicarboxylic acid-derived constituent component having a sulfonic acid group is preferably included.
The dicarboxylic acid having a sulfonic acid group is effective in that it can favorably disperse a coloring material such as a pigment. Further, when emulsifying or suspending the entire resin in water to produce toner mother particles into fine particles, if there are sulfonic acid groups, emulsification or suspension is possible without using a surfactant, as will be described later. . Examples of such a dicarboxylic acid having a sulfone group include, but are not limited to, 2-sulfoterephthalic acid sodium salt, 5-sulfoisophthalic acid sodium salt, and sulfosuccinic acid sodium salt. Moreover, these lower alkyl esters, acid anhydrides, etc. are also mentioned. Among these, 5-sulfoisophthalic acid sodium salt is preferable in terms of cost. The content of the dicarboxylic acid having a sulfonic acid group is preferably 0.1 to 2.0 mol%, and more preferably 0.2 to 1.0 mol%. When the content is more than 2 mol%, the chargeability is deteriorated. In the present invention, “constituent mol%” refers to the percentage when each constituent component (acid-derived constituent component, alcohol-derived constituent component) in the polyester resin is 1 unit (mol).

-Alcohol-derived components-
The alcohol component is preferably an aliphatic dialcohol, such as ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol. 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,11-dodecanediol, 1,12-undecanediol, 1,13-tridecanediol, 1,14-tetradecanediol 1,18-octadecanediol, 1,20-eicosanediol, and the like. Among these, those having 2 to 10 carbon atoms are preferable from the viewpoint of crystal melting point and chargeability. In order to enhance crystallinity, these linear dialcohols are preferably used in an amount of 95 mol% or more, more preferably 98 mol% or more of the alcohol constituent.

  Examples of other divalent dialcohols include bisphenol A, hydrogenated bisphenol A, ethylene oxide or (and) propylene oxide adducts of bisphenol A, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, diethylene glycol, Examples include propylene glycol, dipropylene glycol, 1,3-butanediol, and neopentyl glycol. These may be used individually by 1 type and may use 2 or more types together.

  If necessary, monovalent acids such as acetic acid and benzoic acid, monovalent alcohols such as cyclohexanol and benzyl alcohol, benzenetricarboxylic acid, and naphthalenetricarboxylic acid for the purpose of adjusting the acid value and hydroxyl value. Trivalent alcohols such as acids and the like, anhydrides thereof, lower alkyl esters thereof, glycerin, trimethylolethane, trimethylolpropane, and pentaerythritol can also be used.

  The crystalline polyester resin can be synthesized in the same manner as the amorphous polyester resin.

  As the catalyst that can be used during the production of the polyester resin, the same catalyst as the amorphous polyester resin can be used.

  The melting point of the crystalline polyester resin of the present invention is 50 to 120 ° C, preferably 60 to 110 ° C. When the melting point is lower than 50 ° C., the storage stability of the toner and the storage stability of the toner image after fixing become a problem. On the other hand, when the temperature is higher than 120 ° C., sufficient low-temperature fixing cannot be obtained as compared with the conventional toner. In the present invention, the melting point of the crystalline polyester resin is measured by the same method as the glass transition temperature measurement of the amorphous polyester resin, and the melting peak temperature of the input compensation differential scanning calorimetry shown in JIS K-7121. Can be obtained as The crystalline resin may show a plurality of melting peaks, but in the present invention, the maximum peak is regarded as the melting point.

  When adding the said crystalline polyester resin, it is preferable that it is 1-40 mass% or less in binder resin. When the amount of the crystalline polyester resin added is large, the external additive is easily buried or filmed. If the amount added is small, the effect of improving the low-temperature fixability cannot be obtained.

In the core particle according to the present invention, a polyester resin (polyester resin E) having an endothermic peak temperature (melting point) analyzed from an endothermic curve measured by a differential scanning calorimeter (DSC) as a binder resin is 50 to 80 ° C. ). By incorporating a polyester resin having a melting point of 50 to 80 ° C. into the core particles, the low-temperature fixability can be further improved.
The content of the polyester resin E in the binder resin is preferably 0 to 30% by mass, and more preferably 2 to 15% by mass for both the first and second toners of the present invention. When the amount of the crystalline polyester resin added is large, the domain size of the crystalline polyester resin becomes large and is easily exposed on the toner surface, which may cause a decrease in toner powder fluidity and a deterioration in chargeability.

  Next, a method for producing the electrophotographic toner of the present invention will be described. The method for producing the electrophotographic toner of the present invention is not particularly limited, but is preferably a wet granulation method. Suitable examples of the wet granulation method include known melt suspension methods, emulsion aggregation methods, and dissolution suspension methods. Hereinafter, the emulsion aggregation method will be described as an example. Further, an amorphous polyester resin will be described as an example of the resin.

  The emulsion aggregation method includes a step of forming an aggregated particle in a dispersion in which at least resin fine particles are dispersed (hereinafter sometimes referred to as an emulsion) to prepare an aggregated particle dispersion (aggregation step), and the aggregated particle. This is a production method including a step of fusing the aggregated particles by heating the dispersion (fusion step) (hereinafter, the production method may be referred to as “aggregation fusion method”). Further, between the aggregation step and the fusion step, a step of adding and mixing the fine particle dispersion in which the fine particles are dispersed in the aggregated particle dispersion and attaching the fine particles to the aggregated particles to form the attached particles (attachment step) ) May be provided. In the adhesion step, the fine particle dispersion is added to and mixed with the aggregated particle dispersion prepared in the aggregation step, and the fine particles are adhered to the aggregated particles to form adhered particles. Corresponds to particles newly added to the aggregated particles as viewed from the aggregated particles, and may be referred to as “additional fine particles” in this specification.

As the additional fine particles, in addition to the resin fine particles, release agent fine particles, colorant fine particles and the like may be used singly or in combination. The method of additionally mixing the fine particle dispersion is not particularly limited. For example, the fine particle dispersion may be performed gradually continuously, or may be performed stepwise by dividing into a plurality of times. In this way, by adding and mixing the fine particles (additional fine particles), the generation of fine particles can be suppressed, and the particle size distribution of the obtained electrophotographic toner can be sharpened, which contributes to high image quality. . Also, by providing the adhesion step, a pseudo shell structure can be formed, and the toner surface exposure of internal additives such as a colorant and a release agent can be reduced, resulting in an improvement in chargeability and life. In addition, it is possible to maintain the particle size distribution during fusion in the fusion process, to suppress fluctuations, and to add a stabilizer such as a surfactant or base or acid to enhance stability during fusion. This is advantageous in that it can be made unnecessary or the amount of addition can be suppressed to the minimum, and cost can be reduced and quality can be improved.
In the present invention, the core-shell structure is formed by the operation of adding the additional fine particles. The binder resin that is the main component of the write-once fine particles is a shell layer resin. If this method is used, the toner shape can be easily controlled by adjusting the temperature, the number of stirring, the pH, and the like in the fusing step.

In the coalescence step, under the same stirring as in the aggregation step, the pH of the suspension of the aggregate is set in the range of 5 to 10 to stop the progress of aggregation, and the glass transition temperature (Tg) of the resin or higher. The aggregates are fused and united by heating at a temperature of.
There is no problem if the heating temperature is equal to or higher than the Tg of the resin. Moreover, as a time of a heating, what is necessary is just to be performed to the extent that coalescence is fully carried out, and what is necessary is just to carry out for about 0.2 to 10 hours. Thereafter, when the temperature is lowered to Tg or less of the resin and the particles are solidified, the particle shape and surface properties change depending on the temperature lowering rate. For example, when the temperature is lowered at a high speed, the spheroidization and the surface are easily smoothed. On the other hand, when the temperature is slowly lowered, the particle shape becomes indefinite and irregularities are likely to occur on the particle surface. Therefore, it is preferable to lower the temperature to at most Tg of the resin at a rate of at least 0.5 ° C./min, preferably at a rate of 1.0 ° C./min or more.

  Further, in the association step in which the aggregation step and the coalescence step are performed simultaneously, particles are grown by adding pH or a flocculant while heating at a temperature equal to or higher than the Tg of the resin to obtain a desired particle size. As in the case of the coalescence process, the temperature is lowered to a temperature equal to or lower than the Tg of the resin at a rate of at least 0.5 ° C./minute, and particle growth is stopped simultaneously with solidification. Moreover, you may adjust pH before and after temperature fall. Since the aggregation process and the coalescence process can be performed simultaneously by taking the association process in this way, it is preferable in terms of simplification of the process, but it becomes difficult to make the core-shell structure described above.

  After the fusion / particle formation process is completed, the particles are washed and dried to obtain a toner. Considering the charging property of the toner, it is preferable to sufficiently perform substitution washing with ion-exchanged water, and the degree of washing is generally monitored by the conductivity of the filtrate. Finally, the conductivity is 25 μS / cm or less. It is preferable to do so. A step of neutralizing ions with an acid or alkali at the time of washing may be included, and it is preferable that the treatment with an acid has a pH of 4.0 or less, and the treatment with an alkali has a pH of 8.0 or more. The solid-liquid separation after washing is not particularly limited, but from the viewpoint of productivity, suction filtration, pressure filtration such as a filter press, and the like are preferably used. Further, the drying method is not particularly limited, but from the viewpoint of productivity, freeze drying, flash jet drying, fluidized drying, vibration fluidized drying, etc. are preferably used, and the final toner moisture content is 1% by mass or less. It is preferably dried to 0.7% by mass or less.

  When an amorphous polyester resin is used in the emulsion aggregation method, an emulsification step of emulsifying the amorphous polyester resin to form emulsified particles (droplets), and an agglomeration forming aggregates of the emulsified particles (droplets) And a coalescing step in which the aggregates are fused and thermally united at a temperature equal to or higher than the glass transition temperature of the amorphous polyester resin.

  In the emulsification step, the emulsified particles (droplets) of the amorphous polyester resin are sheared into a solution obtained by mixing an aqueous medium and a mixed liquid (polymer liquid) containing a polyester resin and, if necessary, a colorant. Formed by applying force. At that time, the viscosity of the polymer liquid can be lowered to form emulsified particles by heating to a temperature equal to or higher than the glass transition temperature of the amorphous polyester resin. Moreover, a dispersing agent can also be used for stabilization of emulsified particles and thickening of the aqueous medium. Hereinafter, such a dispersion of emulsified particles may be referred to as a “resin particle dispersion”.

  Examples of the emulsifier used when forming the emulsified particles include a homogenizer, a homomixer, a pressure kneader, an extruder, and a media disperser. The size of the emulsified particles (droplets) of the polyester resin is preferably 0.005 to 0.5 μm, more preferably 0.01 to 0.3 μm in terms of the average particle size (volume average particle size). If it is 0.005 μm or less, it is almost dissolved in water, making it difficult to produce particles, and if it is 0.5 μm or more, it is difficult to obtain particles having a desired particle size of 3.0 to 7.5 μm. The average particle size of the resin fine particles can be measured by, for example, a Doppler scattering type particle size distribution measuring device (manufactured by Nikkiso Co., Ltd., Microtrac UPA 9340) or a laser diffraction type particle size distribution measuring device (manufactured by Horiba, LA-700).

  In addition, if the melt viscosity of the resin during emulsification is high, it does not decrease to the desired particle size, so by raising the temperature using an emulsifier that can pressurize above atmospheric pressure, emulsifying in a state where the resin viscosity is lowered, A resin particle dispersion having a desired particle size can be obtained.

  In the emulsification step, a method of previously adding a solvent to the resin may be used for the purpose of improving the emulsifiability by lowering the viscosity of the resin. The solvent used is not particularly limited as long as it dissolves the polyester resin, but is not limited to ketone solvents such as tetrahydrofuran (THF), methyl acetate, ethyl acetate, and methyl ethyl ketone, and benzene solvents such as benzene, toluene, and xylene. However, it is preferable to use a ketone solvent such as ethyl acetate or methyl ethyl ketone from the viewpoint of solubility and solvent removal.

  In addition, for the purpose of improving the affinity with water as a medium and controlling the particle size distribution, an alcohol solvent such as ethanol or isopropyl alcohol may be directly added to water or a resin.

  For the purpose of controlling the particle size distribution, a salt such as sodium chloride or potassium chloride, ammonia or the like may be added. Of these, ammonia is preferably used.

  A dispersant may be added for the purpose of controlling the particle size distribution. Examples of the dispersant include water-soluble polymers such as polyvinyl alcohol, methyl cellulose, carboxymethyl cellulose, and sodium polyacrylate; sodium dodecylbenzenesulfonate, sodium octadecyl sulfate, sodium oleate, sodium laurate, and potassium stearate. Anionic surfactants such as; cationic surfactants such as laurylamine acetate and lauryltrimethylammonium chloride; zwitterionic surfactants such as lauryldimethylamine oxide; polyoxyethylene alkyl ether, polyoxyethylene alkylphenyl ether, Surfactants such as nonionic surfactants such as polyoxyethylene alkylamine; tricalcium phosphate, aluminum hydroxide, calcium sulfate, calcium carbonate Um, and inorganic compounds such as barium carbonate. Of these, anionic surfactants are preferably used. As the usage-amount of the said dispersing agent, 0.01-20 mass parts is preferable with respect to 100 mass parts of said polyester resins (binder resin).

  In the emulsification step, the polyester resin is copolymerized with a dicarboxylic acid having a sulfonic acid group (that is, a suitable amount of a dicarboxylic acid-derived component having a sulfonic acid group is included in the acid-derived component). ) And a dispersion stabilizer such as a surfactant can be reduced, or emulsified particles can be formed without using it, but the hygroscopicity of the resin is increased and the chargeability may be deteriorated. The addition amount is preferably 10 mol% or less in the acid component, but it is better not to add as much as possible when emulsifiability can be secured by the hydrophilicity of the polyester resin main chain, the acid value of the terminal, the amount of hydroxyl value, etc. .

Further, a phase inversion emulsification method may be used. In the phase inversion emulsification method, at least a polyester resin is dissolved in an organic solvent, a neutralizing agent or a dispersion stabilizer is added as necessary, and an aqueous solvent is dropped under stirring to obtain emulsified particles. In this method, the solvent in the resin dispersion is removed to obtain an emulsion. At this time, the order of adding the neutralizing agent and the dispersion stabilizer may be changed.
Examples of the organic solvent (resin dissolving solvent) for dissolving the resin include formic acid esters, acetic acid esters, butyric acid esters, ketones, ethers, benzenes, and halogenated carbons. Specifically, esters such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, t-butyl such as formic acid, acetic acid, butyric acid, acetone, MEK, MPK, MIPK, MBK, MIBK Such as methyl ketones, ethers such as diethyl ether and diisopropyl ether, heterocyclic substituents such as toluene, xylene and benzene, carbon tetrachloride, methylene chloride, 1,2-dichloroethane, 1,1,2-trichloroethane, trichloroethylene , Chloroform, monochlorobenzene, dichloroethylidene and other halogenated carbons can be used singly or in combination of two or more, but they are easily available, easy to recover during solvent removal, and environmentally friendly To low-boiling solvents such as acetates, methyl ketones, and ethers. Used preferred, in particular, acetone, methyl ethyl ketone, acetic acid, ethyl acetate, butyl acetate is preferred. When the organic solvent remains in the resin fine particles, it becomes a VOC causative substance even in a trace amount, and it is preferable to use a solvent having a relatively high volatility.

  As the aqueous solvent, ion-exchanged water is basically used, but a water-soluble organic solvent may be included so as not to destroy the oil droplets. Examples of water-soluble organic solvents include methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, t-butanol, 1-pentanol and other short carbon chain alcohols; ethylene glycol monomethyl ether, ethylene glycol Examples include ethylene glycol monoalkyl ethers such as monoethyl ether and ethylene glycol monobutyl ether; ethers, diols, THF, acetone and the like. The mixing ratio of these water-soluble organic solvents to ion-exchanged water is preferably 1% to 50%, preferably 1% to 30%, and used as an aqueous component. In addition, the water-soluble organic solvent may be added to the resin solution and used in addition to the ion-exchanged water to be added. In the case of adding a water-soluble organic solvent, the wettability between the resin and the resin dissolving solvent can be adjusted, and a function of reducing the liquid viscosity after the resin is dissolved can be expected.

If necessary, a dispersant may be added to the resin solution and the aqueous component so that the emulsion is stably dispersed. As the dispersant, a hydrophilic colloid is formed in an aqueous component, and in particular, cellulose derivatives such as hydroxymethyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose; polyvinyl alcohol, polyvinyl pyrrolidone, polyacrylamide, polyacrylate, Examples thereof include synthetic polymers such as polymethacrylate, and dispersion stabilizers such as gelatin, gum arabic, and agar. Solid fine powders such as silica, titanium oxide, alumina, tricalcium phosphate, calcium carbonate, calcium sulfate, and barium carbonate can also be used. These dispersion stabilizers are usually added so that the concentration in the aqueous component is 0 to 20% by mass, preferably 0 to 10% by mass.
A surfactant is also used as the dispersant. As examples of the surfactant, those similar to those used in the colorant dispersion described later can be used. For example, in addition to natural surfactant components such as saponins, cationic surfactants such as alkylamine hydrochlorides / acetates, quaternary ammonium salts, glycerols, fatty acid soaps, sulfates, alkylnaphthalene sulfonates, sulfones Anionic surfactants such as acid salts, phosphoric acid, phosphate esters, sulfosuccinates and the like can be mentioned, and anionic surfactants and nonionic surfactants are preferably used.
In order to adjust the pH of the emulsion, a neutralizing agent may be added. As the neutralizing agent for the initial period, general acids such as nitric acid, hydrochloric acid, sodium hydroxide, ammonia, and alkali can be used.
As a method for removing the organic solvent from the emulsion, a method in which the organic solvent is volatilized at room temperature or under heating, and a method in which this is combined with reduced pressure are preferably used.

  In order to form an aggregate in the aggregation step, it is preferable to use a flocculant. Examples of the flocculant used include a surfactant having a polarity opposite to that of the surfactant used in the dispersant, a general inorganic metal compound (inorganic metal salt), or a polymer thereof. The metal element constituting the inorganic metal salt has a divalent or higher charge belonging to the 2A, 3A, 4A, 5A, 6A, 7A, 8, 1B, 2B, 3B group in the periodic table (long periodic table). Yes, as long as it dissolves in the form of ions in the aggregated system of resin fine particles.

  Specific examples of preferred inorganic metal salts include metal salts such as calcium chloride, calcium nitrate, barium chloride, magnesium chloride, zinc chloride, aluminum chloride, aluminum sulfate, and polyaluminum chloride, polyaluminum hydroxide, calcium polysulfide. And inorganic metal salt polymers. Among these, an aluminum salt and a polymer thereof are particularly preferable. In general, in order to obtain a sharper particle size distribution, even if the valence of the inorganic metal salt is divalent to monovalent, bivalent to trivalent or higher, and even to the same valence, the polymerization type inorganic metal salt weight Combined is more suitable. By changing the cohesive force between materials with this valence and addition amount, the viscoelasticity of the toner can be controlled, and the stability of the particles can be improved and the particle size distribution can be sharpened. The toner of the present invention preferably contains an aggregating agent. It is preferable that at least one metal element selected from aluminum, zinc, and calcium contained in the toner of the present invention is added as a flocculant. The amount of the flocculant added varies depending on the type and valence of the flocculant, but is generally 0.05 to 0.1% by mass. The aggregating agent does not always remain in the toner due to outflow into the aqueous medium or formation of coarse powder during the toner forming process. In particular, when the amount of solvent in the resin is large during the toner forming process, the solvent and the aggregating agent interact and easily flow out into the aqueous medium, so it is necessary to adjust appropriately according to the residual solvent amount.

  The toner of the present invention preferably contains 0.05 to 0.30% of at least one metal element selected from aluminum, zinc and calcium in terms of elemental composition ratio. These metal atoms form an ionic bridge with the polar component of the polyester resin, thereby improving the strength of the fixed image and improving hot offset. On the other hand, if the content is too large, the melt viscosity also increases, and the fixed image gloss may be lowered and the low-temperature fixability may be impaired. Here, the content of the metal element is determined from the total elemental analysis using a fluorescent X-ray apparatus. The sample was 6 g of toner, pressure-molded with a pressure molder with a load of 10 t and a pressurization time of 1 minute. Using a fluorescent X-ray (XRF-1500) manufactured by Shimadzu Corporation, the measurement conditions were a tube voltage of 40 kV, It is obtained from the elemental composition ratio measured at a tube current of 90 mA and a measurement time of 30 minutes. The metal element is preferably added as a flocculant during toner preparation.

  Examples of the colorant used in the toner of the present invention include yellow pigments such as yellow lead, zinc yellow, yellow iron oxide, cadmium yellow, chrome yellow, Hansa Yellow, Hansa Yellow 10G, Benzidine Yellow G, Benzidine Yellow GR, and Slen Yellow. , Quinoline yellow, permanent yellow NCG and the like. I. Pigment yellow 17, C.I. I. Pigment yellow 74, C.I. I. Pigment yellow 97, C.I. I. Pigment yellow 180, C.I. I. Pigment Yellow 185 or the like is preferably used.

  Examples of magenta pigments include Bengala, Cadmium Red, Lead Red, Mercury Sulfide, Watch Young Red, Permanent Red 4R, Resol Red, Brilliantamine 3B, Brilliantamine 6B, Daypon Oil Red, Pyrazolone Red, Rhodamine B Lake, Lake Red C Pigment Red 31, 146, 147, 150, 176, 238, 269 and the like are mentioned as Rose Bengal, Eoxin Red, Alizarin Lake, and Naphthol pigments, and Pigment Red 122, 202, and 209 as quinacridone pigments. Among these, CI Pigment Red 185, 238, 269, and 122 are particularly preferable from the viewpoints of manufacturability and chargeability.

  Cyan pigments include bitumen, cobalt blue, alkali blue lake, Victoria blue lake, fast sky blue, induslen blue BC, aniline blue, ultramarine blue, chalcoil blue, methylene blue chloride, phthalocyanine blue, phthalocyanine green, malachite green oxare. Rate, and the like. I. Pigment blue 15: 1, C.I. I. Pigment Blue 15: 3 is preferably used.

  Examples of the orange pigment include red chrome yellow, molybdenum orange, permanent orange GTR, pyrazolone orange, vulcan orange, benzidine orange G, indanthrene brilliant orange RK, and indanthrene brilliant orange GK. Examples of purple pigments include manganese purple, fast violet B, and methyl violet lake. Examples of the green pigment include chromium oxide, chromium green, pigment green, malachite green lake, final yellow green G and the like. Examples of white pigments include zinc white, titanium oxide, antimony white, and zinc sulfide.

  Examples of extender pigments include barite powder, barium carbonate, clay, silica, white carbon, talc, and alumina white. Also, acridine, xanthene, azo, benzoquinone, azine, anthraquinone, thioindico, dioxazine, thiazine, azomethine, indico, thioindico, phthalocyanine, aniline black, polymethine, triphenyl Various dyes such as methane, diphenylmethane, thiazine, thiazole, and xanthene are also used. These colorants are used alone or in combination.

  Examples of the black pigment used for the black toner include carbon black, copper oxide, manganese dioxide, aniline black, activated carbon and the like, and carbon black is particularly preferably used. Since carbon black has relatively good dispersibility, it does not require any special dispersion, but it is preferably produced by the same production method as that for the colorant.

  The colorant used in the toner of the present invention is selected from the viewpoints of hue angle, saturation, brightness, weather resistance, OHP permeability, and dispersibility in the toner. The colorant can be added in the range of 4 to 15% by mass with respect to the total weight of the toner constituting solids. When using a magnetic substance etc. as a black coloring agent, unlike other coloring agents, it can add at 12-240 mass%. Specifically, a material that is magnetized in a magnetic field is used, but a ferromagnetic powder such as iron, cobalt, or nickel, or a compound such as ferrite or magnetite is used. When obtaining toner in the aqueous phase, it is necessary to pay attention to the aqueous phase migration of the magnetic material, and it is preferable to modify the surface of the magnetic material in advance, for example, to perform a hydrophobic treatment or the like.

  The dispersant used in the colorant dispersion of the present invention is generally a surfactant. Examples of the surfactant include anionic surfactants such as sulfate ester, sulfonate, phosphate, and soap; cationic surfactants such as amine salt type and quaternary ammonium salt type; polyethylene glycol Suitable examples include nonionic surfactants such as polyphenols, alkylphenol ethylene oxide adducts, and polyhydric alcohols. Among these, an ionic surfactant is preferable, and an anionic surfactant and a cationic surfactant are more preferable. The nonionic surfactant is preferably used in combination with the anionic surfactant or the cationic surfactant. The said surfactant may be used individually by 1 type, and may use 2 or more types together. Moreover, it is preferable that it is the same polarity as the dispersing agent used for other dispersion liquids, such as a mold release agent dispersion liquid.

  Specific examples of the anionic surfactant include fatty acid soaps such as potassium laurate, sodium oleate and sodium castor oil; sulfates such as octyl sulfate, lauryl sulfate, lauryl ether sulfate and nonyl phenyl ether sulfate; lauryl sulfonate , Dodecyl sulfonate, dodecyl benzene sulfonate, triisopropyl naphthalene sulfonate, dibutyl naphthalene sulfonate, etc., sodium alkyl naphthalene sulfonate, naphthalene sulfonate formalin condensate, monooctyl sulfosuccinate, dioctyl sulfosuccinate, lauric acid amide sulfonate, oleic acid amide sulfonate Sulfonates such as lauryl phosphate, isopropyl phosphate, Phosphoric acid esters such as alkenyl phenyl ether phosphates; dialkyl sodium sulfosuccinates of sodium dioctyl sulfosuccinate, sodium lauryl sulfosuccinate 2, polyoxyethylene sulfo sulfosuccinate salts such as succinic acid lauryl disodium and the like. Of these, alkylbenzene sulfonate compounds such as dodecylbenzene sulfonate and its branched products are preferred.

  Specific examples of the cationic surfactant include laurylamine hydrochloride, stearylamine hydrochloride, oleylamine acetate, stearylamine acetate, stearylaminopropylamine acetate, and other amine salts; lauryltrimethylammonium chloride, dilauryldimethylammonium Chloride, distearyl ammonium chloride, distearyl dimethyl ammonium chloride, lauryl dihydroxyethyl methyl ammonium chloride, oleyl bis polyoxyethylene methyl ammonium chloride, lauroyl aminopropyl dimethyl ethyl ammonium etosulphate, lauroyl aminopropyl dimethyl hydroxyethyl ammonium perchlorate, alkylbenzene dimethyl Ammonium chloride, alkylto Such as quaternary ammonium salts such as ammonium chloride.

  Specific examples of the nonionic surfactant include polyoxyethylene octyl ether, polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether and other alkyl ethers; Alkylphenyl ethers such as oxyethylene nonylphenyl ether; alkyl esters such as polyoxyethylene laurate, polyoxyethylene stearate, polyoxyethylene oleate; polyoxyethylene lauryl amino ether, polyoxyethylene stearyl amino ether, polyoxy Alkylamines such as ethylene oleyl amino ether, polyoxyethylene soybean amino ether, polyoxyethylene beef tallow amino ether; Alkyl amides such as xylethylene lauric acid amide, polyoxyethylene stearic acid amide, polyoxyethylene oleic acid amide; vegetable oil ethers such as polyoxyethylene castor oil ether, polyoxyethylene rapeseed oil ether; lauric acid diethanolamide, stearin Alkanolamides such as acid diethanolamide and oleic acid diethanolamide; sorbitan ester ethers such as polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan monooleate And the like.

  The addition amount of the dispersant used is preferably 2% by mass or more and 30% by mass or less, and more preferably 5% by mass or more and 20% by mass or less with respect to the colorant. If the amount of the dispersant is too small, the particle size may not be reduced, or the storage stability of the dispersion may be reduced. On the other hand, when the amount is too large, the amount of the dispersant remaining in the toner increases, and the chargeability and powder fluidity of the toner may be reduced.

  The aqueous dispersion medium to be used is preferably one having few impurities such as metal ions such as distilled water and ion exchange water. In addition, alcohol or the like can be added for the purpose of defoaming or adjusting the surface tension. Moreover, polyvinyl alcohol, a cellulose polymer, etc. can also be added for viscosity adjustment.

The toner of the present invention contains a release agent for the purpose of improving fixability and image storage stability. The release agent used is preferably a substance having a main maximum endothermic peak measured in accordance with ASTM D3418-8 at 60 to 120 ° C. and a melt viscosity of 1 to 50 mPas at 140 ° C.
When the melting point is less than 60 ° C., the change temperature of the wax is too low, the blocking resistance is inferior, and the developability deteriorates when the temperature in the copying machine increases. When the temperature exceeds 120 ° C., the change temperature of the wax is too high, and fixing at a high temperature may be performed, but this is not desirable from the viewpoint of energy saving. Further, when the melt viscosity is higher than 50 mPas, the elution from the toner is weak, and the fixing peelability is insufficient.

  The viscosity of the release agent used in the present invention is measured by an E-type viscometer. For the measurement, an E-type viscometer (manufactured by Tokyo Keiki Co., Ltd.) equipped with an oil circulation type thermostat is used. For the measurement, a cone plate / cup combination plate having a cone angle of 1.34 degrees is used. A sample is put into the cup, the temperature of the circulation device is set to 140 ° C., an empty measurement cup and cone are set to the measurement device, and the temperature is kept constant while circulating the oil. When the temperature is stabilized, 1 g of the sample is put in the measuring cup, and the cone is left still for 10 minutes. After stabilization, rotate the cone and measure. The rotational speed of the cone is 60 rpm. The measurement is performed three times, and the average value is taken as the viscosity η.

The release agent preferably has an endothermic start temperature of 40 ° C. or higher according to a DSC curve measured by a suggested scanning calorimeter. More preferably, it is 50 ° C. or higher. When the temperature is lower than 40 ° C., toner aggregation occurs in the copying machine and the toner bottle. The endothermic start temperature depends on the molecular weight distribution of the wax, which has a low molecular weight, and the type and amount of polar groups of the structure.
In general, the higher the molecular weight, the higher the endothermic start temperature as well as the melting point. However, in this method, the inherent low melting temperature and low viscosity of the wax are lost. Therefore, it is effective to select and remove only those having a low molecular weight from the molecular weight distribution of the wax. Examples of this method include molecular distillation, solvent fractionation, and gas chromatographic fractionation.

  Also, if the maximum endothermic peak is below 50 ° C., offset tends to occur during fixing. On the other hand, if the peak exceeds 140 ° C., the fixing temperature becomes high, the smoothness of the surface of the fixed image cannot be obtained, and the glossiness is impaired. DSC is measured using, for example, DSC-7 manufactured by PerkinElmer. The temperature correction of the detection part of the apparatus uses the melting points of indium and zinc, and the correction of heat quantity uses the heat of fusion of indium. For the sample, an aluminum pan is used, and an empty pan is set as a control, and measurement is performed at a heating rate of 10 ° C./min.

  Specific examples of the release agent include, for example, low molecular weight polyolefins such as polyethylene, polypropylene, and polybutene, silicones that exhibit a softening point upon heating, oleic acid amide, erucic acid amide, ricinoleic acid amide, stearic acid amide, and the like. Fatty acid amides, plant waxes such as carnauba wax, rice wax, candelilla wax, tree wax and jojoba oil, animal waxes such as beeswax, ester waxes such as fatty acid esters and montanic acid esters And mineral-based / petroleum-based waxes such as montan wax, ozokerite, ceresin, paraffin wax, microcrystalline wax, Fischer-Tropsch wax, and modified products thereof.

  The release agent is dispersed in water together with a polymer electrolyte such as an ionic surfactant, a polymer acid or a polymer base, heated to a temperature higher than the melting point, and has a strong shearing ability and a pressure discharge type disperser (Gorin homogenizer, manufactured by Gorin Co., Ltd.) can be dispersed in the form of fine particles to prepare a dispersion. The particle size of the release agent particle dispersion is measured, for example, with a Doppler scattering particle size distribution measuring device or a laser diffraction particle size distribution measuring device (LA-700, manufactured by Horiba, Ltd.).

  In the release agent used in the toner of the present invention, the ratio of the dispersant to the release agent in the release agent dispersion is preferably 1% by mass or more and 20% by mass or less. More preferably, it is 2 mass% or more and 10 mass% or less. If the proportion of the dispersant is too small, the release agent may not be sufficiently dispersed and storage stability may be poor. If the proportion of the dispersant is too large, the chargeability of the toner, particularly the environmental stability, may be deteriorated. As the dispersant, an optimal one for the type of wax can be selected from the same dispersants that can be used for the colorant.

  Inorganic or organic fine particles can be added to the toner of the present invention. Due to the reinforcing effect of the fine particles, the storage elastic modulus of the toner is increased, and offset resistance and releasability from the fixing device may be improved. The fine particles may improve the dispersibility of internal additives such as a colorant and a release agent. Examples of the inorganic fine particles include silica, hydrophobized silica, alumina, titanium oxide, calcium carbonate, magnesium carbonate, tricalcium phosphate, colloidal silica, alumina-treated colloidal silica, cationic surface-treated colloidal silica, anion surface-treated colloidal silica, and the like. They can be used alone or in combination. Among them, colloidal silica is preferably used from the viewpoint of OHP transparency and dispersibility in the toner. The particle size is preferably 5 to 50 nm. It is also possible to use fine particles having different particle diameters in combination. The fine particles can be added directly at the time of toner production. However, in order to improve dispersibility, it is preferable to use those finely dispersed in a water-soluble medium such as water in advance using an ultrasonic disperser. In the dispersion, the dispersibility can be improved by using an ionic surfactant, a polymer acid, a polymer base, or the like.

  In addition, a known material such as a charge control agent may be added to the toner of the present invention. The average particle size of the material added at that time is required to be 1 μm or less, and preferably 0.01 to 1 μm. When the average particle size exceeds 1 μm, the particle size distribution of the finally obtained electrophotographic toner is broadened or free particles are generated, which tends to deteriorate performance and reliability. On the other hand, when the average particle size is within the above range, there are no disadvantages, and the uneven distribution among the toners is reduced, the dispersion in the toners is improved, and the variation in performance and reliability is advantageous. The average particle diameter can be measured using, for example, a microtrack.

  The means for preparing the various additive dispersions is not particularly limited. For example, a rotary shear type homogenizer, a ball mill having a media, a sand mill, a dyno mill, and the like, as well as a colorant dispersion and a release agent dispersion. A dispersion apparatus known per se, such as an apparatus similar to that for production, can be mentioned, and an optimum apparatus can be selected and used as appropriate.

  The toner of the present invention preferably has a charge amount in the range of 10 to 70 μC / g, more preferably in the range of 15 to 50 μC / g. If the charge amount is less than 10 μC / g, background stains are likely to occur, and if it exceeds 70 μC / g, the image density tends to decrease. The ratio of the charge amount under high humidity of 30 ° C. and 80 RH% and low humidity of 10 ° C. and 20 RH% is preferably in the range of 0.5 to 1.5, and in the range of 0.7 to 1.2. More preferred. When the ratio is within the range, a clear image can be obtained without being affected by the environment. Needless to say, the charge amount when the external additive is not added is important, although the charge amount contributes greatly to the charge amount. In addition, it is necessary to reduce the total amount of surfactants used in colorant dispersions and release agent dispersions, and to thoroughly wash away remaining surfactants and ions. It is preferable to wash so that the degree becomes 0.01 mS / cm or less. Also, drying of the toner is important, and it is preferable to dry the toner so that the water content is 0.5% by mass or less.

  As the toner of the present invention, a toner having a weight average molecular weight (Mw) of 5000 to 150,000 can be used. In order to obtain an image having particularly high image gloss, Mw is 5000 to 30000 and Mn is 2000 to 10,000. It is preferable that Mw is 6000 to 20000, and Mn is more preferably 2500 to 7500. Mw / Mn, which is an index of molecular weight distribution, is preferably 2 to 10. If Mw and Mn are too high, the color developability may be deteriorated. If Mw and Mn are too low, it is difficult to obtain image strength after fixing. This is because hot offset deteriorates. On the other hand, when the molecular weight distribution represented by the ratio (Mw / Mn) is within the numerical range, the light transmittance and the colorability can be improved. When the value of Mw / Mn is large, that is, when Mw is large or Mn is small, it is difficult to obtain photographic level image gloss.

  The toner of the present invention preferably has a titanium content of 5 to 300 ppm, more preferably 10 to 200 ppm, and particularly preferably 20 to 150 ppm, as determined by IPC emission spectroscopy in the chloroform-soluble component. When the titanium content in the toner is 5 to 300 ppm, the charge amount and the charge in the standing state are stabilized.

  In addition, inorganic fine particles and organic fine particles can be externally added and mixed as fluidity aids, cleaning aids, abrasives, and the like to the toner finally heated as described above.

  Examples of the inorganic fine particles include all particles usually used as external additives on the toner surface, such as silica, alumina, titanium oxide, calcium carbonate, magnesium carbonate, tricalcium phosphate, and cerium oxide. These inorganic fine particles preferably have a hydrophobic surface, and are used to control various toner properties such as chargeability, powder properties, and storage stability, and system suitability such as developability and transferability. It is done.

  As organic fine particles, for example, it is used as an external additive for normal toner surfaces such as vinyl resins such as styrene polymers, (meth) acrylic polymers, ethylene polymers, polyester resins, silicone resins, and fluorine resins. All particles that are made are listed. These particles are added for the purpose of improving transferability, and the primary particle size is preferably 0.05 to 1.0 μm.

  Further, a lubricant can be added. Examples of the lubricant include fatty acid amides such as ethylene bisstearyl acid amide and oleic acid amide, fatty acid metal salts such as zinc stearate and calcium stearate, and higher alcohols such as unilin. These are generally added for the purpose of improving the cleaning property, and those having a primary particle size of 0.1 to 5.0 μm are used.

  In the toner of the present invention, at least two of the inorganic fine particles are used, and at least one of the inorganic fine particles has an average primary particle size of 30 nm to 200 nm, more preferably 30 nm to 180 nm. preferable. As the toner particle size is reduced, non-electrostatic adhesion to the photoconductor increases, which causes transfer defects and image loss called hollow characters, and causes uneven transfer such as superimposed images. Therefore, it is preferable to add a large external additive having an average primary particle diameter of 30 nm to 200 nm to improve transferability. If the average primary particle diameter is less than 30 nm, the initial toner fluidity is good, but the non-electrostatic adhesion between the toner and the photoreceptor cannot be sufficiently reduced, resulting in a decrease in transfer efficiency and loss of image. In addition, the uniformity of the image is deteriorated, and the fine particles are embedded in the toner surface due to the stress in the developing device over time, and the charging property is changed to cause problems such as a decrease in copy density and fogging on the background portion. On the other hand, if the average primary particle diameter is larger than 200 nm, the particles are easily detached from the toner surface and the fluidity is deteriorated. Specifically, silica, alumina, and titanium oxide are preferable, and it is particularly preferable to add hydrophobized silica as an essential component. It is particularly preferable to use silica and titanium oxide in combination. It is also preferable to improve the transferability by using organic fine particles having a particle size of 80 to 500 nm in combination.

  Examples of the hydrophobizing agent for hydrophobizing the external additive include known materials, such as silane coupling agents, titanate coupling agents, aluminate coupling agents, and zirconium coupling agents. Examples include silicone oil and polymer coating treatment. These hydrophobizing agents can be used alone or in combination. Among these, a silane coupling agent and silicone oil can be preferably used. As the silane coupling agent, any type such as chlorosilane, alkoxysilane, silazane, and special silylating agent can be used. Specific examples thereof include methyltrichlorosilane, dimethyldichlorosilane, trimethylchlorosilane, and phenyltrichlorosilane. , Diphenyldichlorosilane, tetramethoxysilane, methyltrimethoxysilane, dimethyldimethoxysilane, ethyltrimethoxysilane, propyltrimethoxysilane, phenyltrimethoxysilane, diphenyldimethoxysilane, tetraethoxysilane, methyltriethoxysilane, dimethyldiethoxysilane , Ethyltriethoxysilane, propyltriethoxysilane, phenyltriethoxysilane, diphenyldiethoxysilane, butyltrimethoxysilane, Rutriethoxysilane, isobutyltrimethoxysilane, hexyltrimethoxysilane, octyltrimethoxysilane, decyltrimethoxysilane, hexadecyltrimethoxysilane, trimethyltrimethoxysilane, hexamethyldisilazane, N, O- (bistrimethylsilyl) acetamide, N, N-bis (trimethylsilyl) urea, tert-butyldimethylchlorosilane, vinyltrichlorosilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltriacetoxysilane, γ-methacryloxypropyltrimethoxysilane, β- (3.4 Epoxycyclohexyl) ethyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropyl Tildiethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-chloropropyltrimethoxysilane, etc., and trifluoropropyltrimethoxysilane, tridecafluorooctyltrimethoxy in which some hydrogen atoms are changed to fluorine atoms Silane, heptadecafluorodecyltrimethoxysilane, heptadecafluorodecylmethyldimethoxysilane, tridecafluoro-1,1,2,2-tetrahydrooctyltriethoxysilane, 3,3,3-trifluoropropyltrimethoxysilane, hepta Fluorine-based silane compounds such as decafluoro-1,1,2,2-tetrahydrodecyltriethoxysilane, 3-heptafluoroisopropoxypropyltriethoxysilane, and amino-based silane compounds in which some of the hydrogen atoms are substituted with amino groups It can be exemplified, but the invention is not limited thereto.

  Silicone oils include dimethyl silicone oil, methyl hydrogen silicone oil, methylphenyl silicone oil, cyclic dimethyl silicone oil, epoxy-modified silicone oil, carboxyl-modified silicone oil, carbinol-modified silicone oil, methacryl-modified silicone oil, and mercapto-modified. Silicone oil, polyether-modified silicone oil, methylstyryl-modified silicone oil, alkyl-modified silicone oil, amino-modified silicone oil, fluorine-modified silicone oil, and the like can be used, but are not limited thereto. When the hydrophobized particles are used, the charge amount under high humidity can be improved, and as a result, the environmental stability of charging can be improved. In the toner of the present invention, it is preferable that at least one or more external additives are subjected to silicone oil processing.

  As a method for hydrophobizing particles, for example, a treatment agent mixed and diluted with a solvent such as tetrahydrofuran, toluene, ethyl acetate, methyl ethyl ketone, acetone or the like is dropped or sprayed on fine particles that are forcibly stirred by a blender or the like. And after mixing, washing and filtering as necessary, drying by heating, crushing the aggregate after drying with a blender or mortar, etc. After leaching, dry, or fine particles are dispersed in water to form a slurry, and then the treatment agent solution is dropped, and then the fine particles are settled and dried by heating and pulverized, or directly processed into fine particles A conventionally known method such as a method of spraying an agent can be used. The amount of the treatment agent attached to the fine particles is preferably 0.01 to 50% by mass and more preferably 0.1 to 25% by mass with respect to the fine particles. The amount of adhesion can be changed by a method such as increasing the amount of treatment agent mixed at the stage of treatment or changing the number of cleaning steps after treatment. Further, the amount of treatment agent attached can be quantified by XPS or elemental analysis. If the amount of processing agent attached is small, the chargeability may decrease at high humidity. If the amount is too large, the charge will be excessive under low humidity, or the free processing agent may flow into the developer powder. May worsen sex.

  The external additive is adhered or fixed to the toner surface by applying a mechanical impact force with a sample mill or a Henschel mixer.

  Using the toner of the present invention, a one-component developer composed only of the toner or a two-component developer composed of the toner and a carrier can be obtained. As the developer, a two-component developer having excellent charge maintenance and stability is preferable. The carrier is preferably a carrier coated with a resin, and more preferably a carrier coated with a nitrogen-containing resin.

Examples of the nitrogen-containing resin include acrylic resins containing dimethylaminoethyl methacrylate, dimethylacrylamide, acrylonitrile and the like, amino resins containing urea, urethane, melamine, guanamine, aniline, amide resins, and urethane resins. These copolymer resins may also be used.
Two or more of the nitrogen-containing resins may be used in combination as the carrier coating resin. Moreover, you may use combining the said nitrogen containing resin and resin which does not contain nitrogen. The nitrogen-containing resin may be used in the form of fine particles and dispersed in a resin not containing nitrogen. In particular, a urea resin, a urethane resin, a melamine resin, and an amide resin are preferable because they have high negative chargeability and high resin hardness, and can suppress a decrease in charge amount due to peeling of the coating resin.

In general, the carrier needs to have an appropriate electric resistance value, and specifically, an electric resistance value of about 10 ⁹ to 10 ¹⁴ Ωcm is required. For example, when the electrical resistance value is as low as 10 ⁶ Ωcm as in the case of an iron powder carrier, the carrier adheres to the image portion of the photoreceptor due to charge injection from the sleeve, or the latent image charge escapes through the carrier, and the latent image This causes problems such as disturbance of images and loss of images. On the other hand, if the insulating resin is coated thickly, the electrical resistance value becomes too high and carrier charges are difficult to leak, resulting in an edged image. This causes a problem of an edge effect that the image density of the image becomes very thin. Therefore, it is preferable to disperse the conductive fine powder in the resin coating layer in order to adjust the resistance of the carrier.

  Specific examples of the conductive fine powder include metals such as gold, silver and copper; carbon black; and semiconductive oxides such as titanium oxide and zinc oxide; titanium oxide, zinc oxide, barium sulfate and boric acid. Examples thereof include a surface of aluminum, potassium titanate powder or the like covered with tin oxide, carbon black, or metal. Among these, carbon black is preferable from the viewpoint of production stability, cost, and conductivity.

Examples of the method for forming the resin coating layer on the surface of the carrier core material include an immersion method in which a powder of the carrier core material is immersed in the solution for forming the coating layer, and a solution for forming the coating layer on the surface of the carrier core material. Spraying method for spraying, fluidized bed method for spraying the solution for forming the coating layer in a state where the carrier core material is floated by flowing air, and a kneader for mixing the carrier core material and the coating layer forming solution in a kneader coater to remove the solvent. Examples of the coater method include a powder coat method in which a coating resin is finely divided and mixed in a carrier core material and a kneader coater at a temperature equal to or higher than the melting point of the coating resin and cooled to form a coating. The kneader coater method and the powder coating method are particularly preferably used.
The average film thickness of the resin coating layer formed by the above method is usually 0.1 to 10 μm, preferably 0.2 to 5 μm.

The core material used for the carrier (carrier core material) is not particularly limited, and examples thereof include magnetic metals such as iron, steel, nickel, and cobalt, or magnetic oxides such as ferrite and magnetite, glass beads, and the like. From the viewpoint of using the magnetic brush method, a magnetic carrier is desirable. As an average particle diameter of a carrier core material, generally 10-100 micrometers is preferable and 20-80 micrometers is more preferable.
The mixing ratio (weight ratio) of the electrophotographic toner of the present invention and the carrier in the two-component developer is in the range of toner: carrier = 1: 100-30: 100, and 3: 100-20: A range of about 100 is more preferable.

EXAMPLES Hereinafter, although this invention is demonstrated further in detail using an Example, this invention is not limited by the following Example.
As a method for producing the toner of the present invention, the following resin fine particle dispersion, colorant particle dispersion, and release agent particle dispersion were prepared, and the metal salt flocculant was stirred and mixed at a predetermined ratio. Is added and ionically neutralized to form agglomerated particles. Next, an inorganic hydroxide is added to adjust the pH of the system from weakly acidic to a neutral range, and then the mixture is heated to a temperature equal to or higher than the glass transition point of the resin fine particles to be fused and united. After completion of the reaction, a desired toner is obtained through sufficient washing and solid-liquid separation and drying processes. Hereinafter, each adjustment method will be described.

[Measurement of molecular weight distribution]
The molecular weight distribution was performed under the following conditions. Tosoh Corporation HLC-8120GPC, SC-8020 apparatus was used, TSK gei, SuperHM-H (6.0 mm ID × 15 cm × 2) was used as a column, and THF (tetrahydrofuran) was used as an eluent. As experimental conditions, the sample concentration was 0.5%, the flow rate was 0.6 ml / min, the sample injection volume was 10 μl, the measurement temperature was 40 ° C., and the calibration curves were A-500, F-1, F-10, F-80, F− It produced from 10 samples of 380, A-2500, F-4, F-40, F-128, F-700. The data collection interval in sample analysis was 300 ms.

[Measurement of Tg]
Using a differential scanning calorimeter (manufactured by Mac Science: DSC3110, thermal analysis system 001) (hereinafter abbreviated as “DSC”), the temperature is raised from 0 to 150 ° C. at 10 ° C./min, and held at 150 ° C. for 5 minutes. The temperature was lowered from 150 ° C. to 0 ° C. using liquid nitrogen at −10 ° C./min, held at 0 ° C. for 5 minutes, and again raised from 0 ° C. to 150 at 10 ° C./min. The onset temperature analyzed from the endothermic curve at the time of the second temperature rise was defined as Tg.

[Measurement of acid value]
It measured by the potentiometric titration method using the acetone-toluene mixed solution according to JIS-K0070: 92.

[Measurement of dispersion particle size of dispersion liquid]
Measured with Microtrac UPA.

[Measurement of toner particle size]
Using a Multisizer II manufactured by Nikka Kisha Co., Ltd., the aperture diameter was 50 μm, and the measurement was performed at a measurement concentration of 10% using isotone as a diluent. The particle size distribution is a particle size range divided based on the particle size distribution measured using Multisizer II (divided number: 1.26 to 50.8 μm in 16 channels, 0.1 intervals on the log scale) Specifically, channel 1 is 1.26 μm or more and less than 1.59 μm, channel 2 is 1.59 μm or more and less than 2.00 μm, channel 3 is 2.00 μm or more and less than 2.52 μm, and so on. , And the log values of the lower limit value on the left side are (log1.26 =) 0.1, (log1.59 =) 0.2, (log2.00 =) 0.3,..., 1.6 In other words, the cumulative distribution is subtracted from the small particle diameter side, and the particle diameter that becomes 16% cumulative is the volume D16v, the number D16p, and the particle diameter that is 50% cumulative is the volume D50v. (Volume average particle size), number 50p, 84% accumulation becomes volume particle diameter D84v, defined as the number D84p.
The particle size distribution GSD (vol) up is calculated as follows.
GSD (vol) up = (D84v / D50v) ^1/2
The particle size distribution GSD (pop) down is calculated as follows.
GSD (pop) down = (D50p / D16p) ^1/2

[Measurement of SP value]
The SP value of the resin in the toner was determined as follows.
Place 3.000 g of toner on a filter paper for Noriyama Kiriyama (No. 5C) with a diameter of 95 mm, spread the toner over the entire filter paper with a spatula, pick up the filter paper with tweezers, turn the filter paper over, and see the toner detachment from the filter paper Remove the excess toner on the filter paper by flicking the tweezers with your finger until you cannot confirm with. At this time, the amount of the adhered toner is calculated from the measured weight of the filter paper before and after the toner adhesion. This toner weight is defined as Tw1 (g).
Prepare a filter device consisting of a 95mm diameter Buchner type Kiriyama funnel, suction funnel and portable aspirator ("MDA-050", ULVAC Kiko), set a new filter paper in the funnel, and apply the filter paper with ethyl acetate while suctioning . Once the suction is stopped, the filter paper with toner attached is set on the funnel so that it overlaps the filter paper that has been applied, and a new filter paper is placed on top of the filter paper. Add.
The filtered ethyl acetate solution is evaporated to dryness and the weight of the resin dissolved in ethyl acetate is measured. Let this resin content be Tw2 (g). Filter with additional ethyl acetate at 45 ° C. until the value of Tw2 / Tw1 is 0.05 (5% by mass). By this method, the amount of ethyl acetate at which Tw2 / Tw1 becomes 0.05 is calculated. Let this amount of ethyl acetate be Ac1 (g). Similarly, the amount of ethyl acetate at which Tw2 / Tw1 becomes 0.10 is calculated. Let this ethyl acetate amount be Ac2 (g). The toner was re-prepared and set in a funnel, and then filtered through ethyl acetate Ac1 (g) heated to 45 ° C. The obtained filtrate was discarded, followed by ethyl acetate (Ac2 (g) heated to 45 ° C. -Ac1 (g)) and the filtrate obtained is evaporated to dryness. This dissolved content is a dissolved material near the extreme surface of the toner, and can be regarded as a material constituting the shell. This is subjected to composition analysis by H1-NMR to estimate a resin constituent monomer. The NMR measurement was performed using a JEOL EX-400FT-NMR spectrometer (399.65 MHz), and the chemical shift was based on chloroform in chloroform-d. From the estimated monomer composition, the SP value is calculated by the Fedors method. Before measuring NMR, it is filtered through a membrane filter to remove dust. This is the SP value of the shell material.
Next, in the same manner as described above, dissolve in ethyl acetate at 45 ° C. until Tw2 / Tw1 becomes 0.5. Here, the resin component in the toner component remaining on the filter paper is subjected to NMR measurement to obtain the monomer structure, and the SP value is calculated. This resin component can be regarded as a core component from which the toner surface component has been removed.
In this way, the SP values of the core constituent resin and the shell constituent resin are calculated.

[Measurement of Toner Shape Factor SF1]
The shape factor SF1 indicates SF1 = (ML ² / A) × (π / 4) × 100 (ML: absolute maximum length of toner particles, A: projected area of toner particles). The SF1 takes in an optical microscope of toner dispersed on a slide glass into a Luzex image analyzer through a video camera, obtains the maximum length and projected area of 100 or more toner particles, calculates by the above formula, did.

[Quantitative determination of titanium content in toner]
10 g of a solution obtained by dissolving 10 g of toner in 190 g of chloroform is placed in each test tube and covered with aluminum foil. At this time, in order to balance in the centrifuge, the sample amount is finely adjusted so that the weights including the test tubes are the same. The test tube containing the sample is centrifuged at 3500 rpm for 15 minutes with a centrifuge (“H-18”, Kokusan Co., Ltd.), and the resulting supernatant is collected. 250.0 mg of the dried product obtained by drying the collected supernatant was weighed with a balance capable of weighing to 0.01 mg (“AT-200”, METTLER TOLEDO Co., Ltd.), placed in a 25 ml volumetric flask, and chloroform. Add 5 ml and dissolve. After dissolution, the sample is prepared by adding xylene to the marked line of the volumetric flask to dilute it, and using a high frequency inductively coupled plasma emission spectrometer (IPC-AES, Seiko Electronics Co., Ltd., SPS1200VR), a diffraction grating : Main spectrometer 3600 lines / mm, slit: incident 20 μm, output 40 μm, photomal: R306, torch: organic solvent torch, nebulizer: glass concentric, argon gas flow rate: plasma gas 18 liter / min, auxiliary gas 1.8 Under the conditions of liter / minute, carrier gas 0.11 MPa, RF power: 1.8 kW, analysis wavelength: 334.9 nm, photometric height: 15 mm, integration time: 1 second, number of integrations 3 times, the titanium standard solution is Using Metallo-Organic Standard (5000 μg / g) manufactured by Conostan Quantified.

[Measurement of toner moisture content]
The toner water content (water content after toner drying) was measured by the following method.
3 g of toner was weighed on a plastic dish and allowed to stand in a constant temperature bath at a temperature of 30 ° C. and a humidity of 20 RH% for 12 hours. Immediately after the humidity-adjusted toner was taken out of the thermostatic bath, the moisture content was measured at a heating temperature of 150 ° C. using the total amount of toner with a moisture meter (“HB43”, METTLER TOLEDO). If it takes time to take out the thermostat and move to the moisture meter, care should be taken not to change the amount of water in the toner by, for example, putting the toner in a bag with a chuck. The amount of water here refers to the amount of water remaining in the toner, and when 0.1 g of water remains in 1 g of toner, the amount of water is defined as 10%.

[Adjustment of cyan colorant dispersion]
Cyan pigment (Daiichi Seika Co., Ltd .: ECB-301) 200 parts by mass Anionic surfactant (Daiichi Kogyo Seiyaku Co., Ltd., Neogen SC) 20 parts by mass (as an active ingredient, 10% by mass with respect to the colorant)
780 parts by mass of ion-exchanged water 280 parts by mass of ion-exchanged water and an anionic interface in a stainless steel container whose liquid level is about 1/3 of the height of the container when all of the above components are added. After adding 20 parts by mass of the activator to sufficiently dissolve the surfactant, all of the pigment was added, and the mixture was stirred using a stirrer until there was no wet pigment, and was sufficiently degassed. After the defoaming, the remaining ion-exchanged water was added and dispersed using a homogenizer (manufactured by LKA, Ultra Tarrax T50) at 5000 rpm for 10 minutes, and then stirred for one day with a stirrer to defoam. After defoaming, the mixture was dispersed again at 6000 rpm for 10 minutes using a homogenizer, and then defoamed by stirring for one day with a stirrer. Subsequently, the dispersion was dispersed at a pressure of 240 MPa using a high-pressure impact disperser Ultimateizer (manufactured by Sugino Machine Co., Ltd., HJP30006). The dispersion was equivalent to 25 passes in terms of the total amount of waste and the processing capacity of the apparatus. The supernatant obtained after leaving the obtained dispersion for 72 hours was collected, and ion exchange water was added to adjust the solid content concentration to 15% by mass. The average particle diameter D50 of the obtained colorant dispersion was 115 nm. As the average particle diameter D50 of the dispersion, an average value of three measured values excluding the maximum value and the minimum value among the five times measured by Microtrack was used.

[Magenta Colorant Dispersion Adjustment]
A magenta colorant dispersion was obtained in the same manner except that the colorant was changed to magenta R122 pigment (manufactured by Dainichi Seika Co., Ltd .: ECR-186Y) by adjusting the cyan colorant dispersion. The volume average particle diameter D50v was 121 nm.

[Preparation of yellow colorant dispersion]
A yellow colorant dispersion was obtained in the same manner except that the colorant was changed to yellow Y74 pigment (manufactured by Clariant Japan, Inc .: Hansa Brill. Yellow 5GX03) by adjusting the cyan colorant dispersion. The volume average particle diameter D50v was 138 nm.

[Adjustment of black colorant dispersion]
A black colorant dispersion was obtained in the same manner except that the colorant was changed to carbon black (manufactured by Cabot: Regal 330) by adjusting the cyan colorant dispersion. The volume average particle diameter D50v was 105 nm.

[Adjustment of release agent (release agent 1) dispersion]
270 parts by mass of polyalkylene wax (manufactured by Nippon Seiki Co., Ltd., HNP-9, melting point 78 ° C., 180 ° C., viscosity 2.5 mPa · s)
Anionic surfactant (Daiichi Kogyo Seiyaku Co., Ltd., Neogen RK) 8.4 parts by mass (as an active ingredient, 3.0% by mass with respect to the release agent)
721.6 parts by mass of ion-exchanged water The above components were sufficiently dispersed while being heated to 95 ° C. with a homogenizer (IKA, Ultra Tarrax T50), and then dispersed with a pressure discharge type homogenizer (Gorin, Gorin homogenizer). Thus, a release agent dispersion was obtained. The volume average particle diameter D50 was 225 nm. Thereafter, ion exchange water was added to adjust the solid content concentration to 25.0% by mass.

[Synthesis of Amorphous Polyester Resin (Amorphous Resin) 1A]
310 parts by mass of bisphenol A propylene oxide adduct (manufactured by Sanyo Chemical Industries, Ltd., New Pole BP-3P)
Cyclohexanedimethanol (reagent) 28.8 parts by mass Terephthalic acid (reagent) 89.7 parts by mass Isophthalic acid (reagent) 59.8 parts by mass Cyclohexanedicarboxylic acid 17.4 parts by mass A stirrer, thermometer, condenser, After placing in a reaction vessel equipped with a nitrogen gas introduction tube and replacing the inside of the reaction vessel with dry nitrogen gas, 0.1 part by mass of titanium tetrabutoxide (reagent) was added and about 180 ° C. under a nitrogen gas stream was added. The reaction was allowed to stir for 8 hours. Further, 0.2 parts by mass of titanium tetrabutoxide (reagent) was added, the temperature was raised to about 220 ° C., and the reaction was stirred for about 6.0 hours, and then the pressure inside the reaction vessel was reduced to 10.0 mmHg, Under stirring for about 6.0 hours, a light yellow transparent amorphous polyester resin 1A was obtained. The Tg by DSC was 52 ° C., the Mw by GPC was 12000, the Mn was 4700, 9 KOH mg / g, and the SP value calculated by the Fedors method was 20.7 (J / cm ³ ) ^1/2 .

[Synthesis of Amorphous Polyester Resin (Amorphous Resin) 2A]
315 parts by mass of bisphenol A ethylene oxide adduct (manufactured by Sanyo Chemical Industries, Ltd., New Pole BPE-20)
Terephthalic acid (reagent) 132.9 parts by mass Cyclohexanedicarboxylic acid 34.8 parts by mass Using the above components, a substantially transparent amorphous polyester resin 2A was obtained by the same synthesis method as the synthesis of amorphous polyester resin 1A. It was. The Tg by DSC was 61 ° C., the Mw by GPC was 11000, the Mn was 4200, 11 KOH mg / g, and the SP value calculated by the Fedors method was 21.4 (J / cm ³ ) ^1/2 .

[Synthesis of Amorphous Polyester Resin (Amorphous Resin) 3A]
275 parts by mass of bisphenol A propylene oxide adduct (manufactured by Sanyo Chemical Industries, Ltd., New Pole BP-2P)
63 parts by mass of bisphenol A ethylene oxide adduct (manufactured by Sanyo Chemical Industries, Ltd., New Pole BPE-20)
Terephthalic acid (reagent) 116 parts by mass Cyclohexanedicarboxylic acid 52 parts by mass Using the above components, a substantially transparent amorphous polyester resin 3A was obtained by the same synthesis method as the synthesis of amorphous polyester resin 1A. The Tg by DSC was 62 ° C., the Mw by GPC was 13000, the Mn was 4900, 9 KOH mg / g, and the SP value calculated by the Fedors method was 20.9 (J / cm ³ ) ^1/2 .

[Synthesis of Crystalline Polyester Resin (Crystalline Resin) 1A]
1,8-octanedicarboxylic acid (reagent) 315 parts by mass 1,9-nonanediol (reagent) 132.9 parts by mass The above components were placed in a reaction vessel equipped with a stirrer, thermometer, condenser, and nitrogen gas inlet tube. After the inside of the reaction vessel was replaced with dry nitrogen gas, 0.2 part by mass of titanium tetrabutoxide (reagent) was added, and the mixture was stirred and reacted at about 170 ° C. for about 10 hours under a nitrogen gas stream. Furthermore, the temperature was raised to about 220 ° C., 0.1 parts by mass of titanium tetrabutoxide (reagent) was added, the inside of the reaction vessel was reduced to 10.0 mmHg, and the mixture was stirred and reacted for about 10 hours under reduced pressure. A polyester resin 1A was obtained. The melting point by DSC was 67 ° C., the Mw by GPC was 18000, the Mn was 6800, the acid value was 7 KOH mg / g, and the SP value calculated by the Fedors method was 18.6 (J / cm ³ ) ^1/2 .

[Synthesis of Crystalline Polyester Resin (Crystalline Resin) 2A]
1,10-decanedicarboxylic acid (reagent) 315 parts by mass 1,9-nonanediol (reagent) 132.9 parts by mass Using the above components, the same method as the synthesis of crystalline polyester resin 1A, crystalline polyester resin 2A was obtained. The melting point by DSC was 67 ° C., the Mw by GPC was 18000, the Mn was 6800, the acid value was 7 KOH mg / g, and the SP value calculated by the Fedors method was 18.4 (J / cm ³ ) ^1/2 .

[Preparation of Amorphous Polyester Resin Dispersion 1A]
The obtained amorphous polyester resin 1A was dispersed using a disperser in which Cavitron CD1010 (manufactured by Eurotech Co., Ltd.) was modified to a high temperature and high pressure type. In a composition ratio of 79% by mass of ion-exchanged water, 1% by mass of an anionic surfactant (Daiichi Kogyo Seiyaku Co., Ltd .: Neogen RK) (as an active ingredient), and a concentration of amorphous resin of 20% by mass, ammonia The pH was adjusted to 8.5, the Cavitron was operated under the conditions of a rotor rotation speed of 60 Hz, a pressure of 5 Kg / cm ² and a heat exchanger heating of 140 ° C., and an amorphous polyester having an average particle size of 260 nm A resin dispersion 1A was obtained.

[Preparation of Amorphous Polyester Resin Dispersion 2A]
The obtained amorphous polyester resin 2A was dispersed by the same method as the preparation of the amorphous polyester resin dispersion 1A to obtain an amorphous polyester resin dispersion 2A having an average particle size of 250 nm.

[Preparation of Amorphous Polyester Resin Dispersion 3A]
The obtained amorphous polyester resin 3A was dispersed by the same method as the preparation of the amorphous polyester resin dispersion 1A to obtain an amorphous polyester resin dispersion 3A having an average particle size of 270 nm.

[Preparation of crystalline polyester resin dispersion 1A]
200 parts by mass of crystalline polyester resin 1A was put in 800 parts by mass of distilled water, heated to 85 ° C., adjusted to pH 9.0 with ammonia, and an anionic surfactant (Daiichi Kogyo Seiyaku Co., Ltd .: Neogen) RK) 0.4 parts by mass (as an active ingredient) was added and dispersed at 8000 rpm for 7 minutes with a homogenizer (IKA Japan: Ultra Tarax T50) while heating to 85 ° C., and a crystalline polyester resin dispersion 1A was obtained. The average particle size was 230 nm.

[Preparation of crystalline polyester resin dispersion 2A]
200 parts by mass of crystalline polyester resin 2A was put in 800 parts by mass of distilled water, heated to 85 ° C., adjusted to pH 9.0 with ammonia, and an anionic surfactant (Daiichi Kogyo Seiyaku Co., Ltd .: Neogen) RK) 0.4 parts by mass (as an active ingredient) was added and dispersed at 8000 rpm for 7 minutes with a homogenizer (IKA Japan: Ultra Tarax T50) while heating to 85 ° C., and a crystalline polyester resin dispersion 2A was obtained. The average particle size was 280 nm.

[Synthesis of Amorphous Polyester Resin (Amorphous Resin) 1B]
345 parts by mass of bisphenol A propylene oxide adduct (manufactured by Sanyo Chemical Industries, Ltd., New Pole BP-2P)
Terephthalic acid (reagent) 132.8 parts by mass Dodecenyl succinic anhydride (reagent) 53.3 parts by mass The above components were placed in a reaction vessel equipped with a stirrer, thermometer, condenser and nitrogen gas inlet tube, and the reaction vessel was dried. After substituting with nitrogen gas, 0.1 part by mass of titanium tetrabutoxide (reagent) was added and allowed to react with stirring at about 180 ° C. for about 8 hours under a nitrogen gas stream. Further, 0.2 parts by mass of titanium tetrabutoxide (reagent) was added, the temperature was raised to about 220 ° C., and the reaction was stirred for about 6.0 hours. Under stirring for about 8.0 hours, a light yellow transparent amorphous polyester resin 1B was obtained. The Tg by DSC was 57 ° C., the Mw by GPC was 14000, the Mn was 6000, the oxidation was 10 KOH mg / g, and the SP value calculated by the Fedors method was 20.7 (J / cm ³ ) ^1/2 .

[Synthesis of Amorphous Polyester Resin (Amorphous Resin) 2B]
315 parts by mass of bisphenol A ethylene oxide adduct (manufactured by Sanyo Chemical Industries, Ltd., New Pole BPE-20)
Terephthalic acid (reagent) 132.9 parts by mass Cyclohexanedicarboxylic acid 34.8 parts by mass Using the above components, a substantially transparent amorphous polyester resin 2B is obtained by the same synthesis method as the synthesis of amorphous polyester resin 1B. It was. The Tg by DSC was 61 ° C., the Mw by GPC was 11000, the Mn was 4200, 11 KOH mg / g, and the SP value calculated by the Fedors method was 21.4 (J / cm ³ ) ^1/2 .

[Synthesis of Amorphous Polyester Resin (Amorphous Resin) 3B]
275 parts by mass of bisphenol A propylene oxide adduct (manufactured by Sanyo Chemical Industries, Ltd., New Pole BP-2P)
63 parts by mass of bisphenol A ethylene oxide adduct (manufactured by Sanyo Chemical Industries, Ltd., New Pole BPE-20)
Terephthalic acid (reagent) 116 parts by mass Cyclohexanedicarboxylic acid 52 parts by mass Using the above components, a substantially transparent amorphous polyester resin 3B was obtained by the same synthesis method as the synthesis of amorphous polyester resin 1B. The Tg by DSC was 62 ° C., the Mw by GPC was 13000, the Mn was 4900, 9 KOH mg / g, and the SP value calculated by the Fedors method was 20.9 (J / cm ³ ) ^1/2 .

[Synthesis of Amorphous Polyester Resin (Amorphous Resin) 4B]
388 parts by mass of bisphenol A propylene oxide adduct (manufactured by Sanyo Chemical Industries, Ltd., New Pole BP-3P)
116 parts by mass of terephthalic acid (reagent) 52 parts by mass of cyclohexanedicarboxylic acid (reagent) Using the above components, a substantially transparent amorphous polyester resin 4B was obtained by the same synthesis method as the synthesis of amorphous polyester resin 1B. . The Tg by DSC was 57 ° C., the Mw by GPC was 12000, the Mn was 4800, 11 KOH mg / g, and the SP value calculated by the Fedors method was 20.6 (J / cm ³ ) ^1/2 .

[Synthesis of Crystalline Polyester Resin (Crystalline Resin) 1B]
1,8-octanedicarboxylic acid (reagent) 315 parts by mass 1,9-nonanediol (reagent) 132.9 parts by mass The above components were put in a reaction vessel equipped with a stirrer, thermometer, condenser, and nitrogen gas inlet tube. After replacing the inside of the reaction vessel with dry nitrogen gas, 0.2 part by mass of titanium tetrabutoxide (reagent) was added, and the reaction was stirred at about 170 ° C. for about 10 hours under a nitrogen gas stream. Further, the temperature is raised to about 220 ° C., 0.1 parts by mass of titanium tetrabutoxide (reagent) is added, the inside of the reaction vessel is reduced to 10.0 mmHg, and the mixture is stirred and reacted for about 10 hours under reduced pressure. A polyester resin 1B was obtained. The melting point by DSC was 67 ° C., the Mw by GPC was 18000, the Mn was 6800, the acid value was 7 KOH mg / g, and the SP value calculated by the Fedors method was 18.6 (J / cm ³ ) ^1/2 .

[Synthesis of Crystalline Polyester Resin (Crystalline Resin) 2B]
1,10-decanedicarboxylic acid (reagent) 315 parts by mass 1,9-nonanediol (reagent) 132.9 parts by mass Using the above components, the same method as the synthesis of crystalline polyester resin 1B, crystalline polyester resin 2B was obtained. The melting point by DSC was 67 ° C., the Mw by GPC was 18000, the Mn was 6800, the acid value was 7 KOH mg / g, and the SP value calculated by the Fedors method was 18.4 (J / cm ³ ) ^1/2 .

[Preparation of Amorphous Polyester Resin Dispersion 1B]
The obtained amorphous polyester resin 1B was dispersed using a disperser in which Cavitron CD1010 (manufactured by Eurotech Co., Ltd.) was modified to a high temperature and high pressure type. In a composition ratio of 79% by mass of ion-exchanged water, 1% by mass of an anionic surfactant (Daiichi Kogyo Seiyaku Co., Ltd .: Neogen RK) (as an active ingredient), and a concentration of amorphous resin of 20% by mass, ammonia The pH was adjusted to 8.5, the Cavitron was operated under the conditions of a rotor rotation speed of 60 Hz, a pressure of 5 Kg / cm ² and a heat exchanger heating of 140 ° C., and an amorphous polyester having an average particle size of 260 nm Resin dispersion 1B was obtained.

[Preparation of Amorphous Polyester Resin Dispersion 2B]
The obtained amorphous polyester resin 2B was dispersed by the same method as the preparation of the amorphous polyester resin dispersion 1B to obtain an amorphous polyester resin dispersion 2B having an average particle size of 250 nm.

[Preparation of Amorphous Polyester Resin Dispersion 3B]
The obtained amorphous polyester resin 3B was dispersed by the same method as the preparation of the amorphous polyester resin dispersion 1B to obtain an amorphous polyester resin dispersion 3B having an average particle size of 270 nm.

[Preparation of Amorphous Polyester Resin Dispersion 4B]
The obtained amorphous polyester resin 4B was dispersed by the same method as the preparation of the amorphous polyester resin dispersion 1B to obtain an amorphous polyester resin dispersion 4B having an average particle size of 270 nm.

[Preparation of crystalline polyester resin dispersion 1B]
200 parts by mass of crystalline polyester resin 1B was put in 800 parts by mass of distilled water, heated to 85 ° C., adjusted to pH 9.0 with ammonia, and an anionic surfactant (Daiichi Kogyo Seiyaku Co., Ltd .: Neogen) RK) 0.4 parts by mass (as an active ingredient) was added and dispersed at 8000 rpm for 7 minutes with a homogenizer (IKA Japan: Ultra Tarax T50) while heating to 85 ° C., and a crystalline polyester resin dispersion 1B was obtained. The average particle size was 230 nm.

[Preparation of crystalline polyester resin dispersion 2B]
200 parts by mass of crystalline polyester resin 2B was put into 800 parts by mass of distilled water, heated to 85 ° C., adjusted to pH 9.0 with ammonia, and an anionic surfactant (Daiichi Kogyo Seiyaku Co., Ltd .: Neogen) RK) 0.4 parts by mass (as an active ingredient) was added and dispersed at 8000 rpm for 7 minutes with a homogenizer (IKA Japan: Ultra Tarax T50) while heating to 85 ° C., and a crystalline polyester resin dispersion 2B was obtained. The average particle size was 280 nm.

[Adjustment of additional fine particles 1A]
Amorphous polyester resin dispersion 2A 210 parts by mass (amorphous polyester resin concentration 20% by mass)
1.05 parts by weight of anionic surfactant (0.63 parts by weight as an active ingredient)
(Daiichi Kogyo Seiyaku Co., Ltd .: Neogen RK, 60% by mass of active ingredient)
After mixing, 1.0 mass% nitric acid aqueous solution was added to adjust the pH to 3.0 to adjust the additional fine particles 1A.

[Adjustment of additional fine particles 2A]
Amorphous polyester resin dispersion 3A 210 parts by mass (amorphous polyester resin concentration 20% by mass)
1.05 parts by weight of anionic surfactant (0.63 parts by weight as an active ingredient)
(Daiichi Kogyo Seiyaku Co., Ltd .: Neogen RK, 60% by mass of active ingredient)
After mixing, 1.0 mass% nitric acid aqueous solution was added to adjust the pH to 3.0 to adjust the additional fine particles 2A.

[Adjustment of additional fine particles 1B]
Amorphous polyester resin dispersion 2B 210 parts by mass (amorphous polyester resin concentration 20% by mass)
1.05 parts by weight of anionic surfactant (0.63 parts by weight as an active ingredient)
(Daiichi Kogyo Seiyaku Co., Ltd .: Neogen RK, 60% by mass of active ingredient)
After mixing, 1.0 mass% nitric acid aqueous solution was added to adjust the pH to 3.0 to adjust the additional fine particles 1B.

[Adjustment of additional fine particles 2B]
Amorphous polyester resin dispersion 3B 210 parts by mass (amorphous polyester resin concentration 20% by mass)
1.05 parts by weight of anionic surfactant (0.63 parts by weight as an active ingredient)
(Daiichi Kogyo Seiyaku Co., Ltd .: Neogen RK, 60% by mass of active ingredient)
After mixing, 1.0 mass% nitric acid aqueous solution was added to adjust the pH to 3.0 to adjust the additional fine particles 2B.

[Example 1A]
Ion-exchanged water 225 parts by mass Amorphous polyester resin dispersion 1A 423.4 parts by mass (amorphous polyester resin concentration 20% by mass)
8.6 parts by mass of crystalline polyester resin dispersion 1A (crystalline polyester resin concentration 20% by mass)
Anionic surfactant 2.14 parts by mass (1.28 parts by mass as an active ingredient)
(Daiichi Kogyo Seiyaku Co., Ltd .: Neogen RK, 60% by mass of active ingredient)
Was placed in a 3 liter reaction vessel equipped with a thermometer, a pH meter, and a stirrer, and maintained at a temperature of 30 ° C. and a stirring rotation speed of 150 rpm for 30 minutes while controlling the temperature with a mantle heater from the outside. afterwards,
Cyan colorant dispersion 55 parts by weight Release agent dispersion 61.8 parts by weight were added and maintained for 5 minutes, and then a 1.0% by weight aqueous nitric acid solution was added to adjust the pH to 2.7.
While removing the stirrer and the mantle heater and dispersing at 3000 rpm with a homogenizer (IKA Japan, Inc .: Ultra Tarax T50)
After adding 1/2 of a mixed solution of 0.33 parts by mass of polyaluminum chloride, 37.5 parts by mass of nitric acid aqueous solution, the dispersion rotational speed was set to 5000 rpm, and the remaining 1/2 was reduced to 1 The mixture was added over a period of 6 minutes, and the dispersion was rotated at 6500 rpm for 6 minutes while being careful not to entrain bubbles.

  A reaction vessel was equipped with a stirrer and a mantle heater, and the temperature was raised to 42 ° C. at 0.5 ° C./min while adjusting the number of revolutions of the stirrer so that the slurry was sufficiently stirred. After being held, the particle size was measured with a Coulter counter [TA-II] type (aperture diameter: 50 μm, manufactured by Coulter, Inc.) every 10 minutes while raising the temperature at 0.05 ° C./min. When the diameter reached 5.0 μm, additional fine particles 1A were added over 3 minutes. After the addition for 30 minutes, the pH was adjusted to 9.0 using a 5 mass% aqueous sodium hydroxide solution. Thereafter, while adjusting the pH to 9.0 every 5 ° C., the temperature was raised to 96 ° C. at a temperature rising rate of 1 ° C./min and maintained at 96 ° C. When the particle shape and surface properties were observed every 30 minutes with an optical microscope and a scanning electron microscope (FE-SEM), the particles were almost spherical in the second hour. Solidified.

  The slurry after cooling was passed through a mesh with an opening of 20 μm to remove coarse powder, and then the reaction product was filtered under reduced pressure with an aspirator and washed with ion-exchanged water. When the filtrate has a conductivity of 50 mS or less, the cake-like particles are taken out, put into ion-exchanged water of 10 times the weight of the particles, and stirred with a three-one motor. The pH was adjusted to 3.8 with 0.0 mass% nitric acid aqueous solution and held for 10 minutes. Thereafter, filtration and washing with water were performed again, and when the conductivity of the filtrate became 10 mS or less, water flow was stopped and solid-liquid separation was performed. The obtained cake-like particles were vacuum-dried in an oven at 40 ° C. for 24 hours. The obtained powder was crushed with a sample mill and then vacuum dried in an oven at 40 ° C. for 5 hours to obtain a toner.

  A sample mill was prepared by adding 1.0 part by mass of hydrophobic silica (manufactured by Nippon Aerosil Co., Ltd., RY50) and 0.8 part by mass of hydrophobic titanium oxide (manufactured by Nippon Aerosil Co., Ltd., T805) to 100 parts of the obtained toner. And blended for 30 seconds at 13000 rpm. Thereafter, the cyan toner was prepared by sieving with a vibrating sieve having an opening of 45 μm.

[Example 2A]
Ion-exchanged water 225 parts by mass Amorphous polyester resin dispersion 1A 423.4 parts by mass (amorphous polyester resin concentration 20% by mass)
8.6 parts by mass of crystalline polyester resin dispersion 1A (crystalline polyester resin concentration 20% by mass)
Anionic surfactant 2.14 parts by mass (1.28 parts by mass as an active ingredient)
(Daiichi Kogyo Seiyaku Co., Ltd .: Neogen RK, 60% by mass of active ingredient)
Was placed in a 3 liter reaction vessel equipped with a thermometer, a pH meter, and a stirrer, and maintained at a temperature of 30 ° C. and a stirring rotation speed of 150 rpm for 30 minutes while controlling the temperature with a mantle heater from the outside. afterwards,
Cyan colorant dispersion 55 parts by weight Release agent dispersion 61.8 parts by weight were added and maintained for 5 minutes, and then a 1.0% by weight aqueous nitric acid solution was added to adjust the pH to 2.7.
While removing the stirrer and the mantle heater and dispersing at 3000 rpm with a homogenizer (IKA Japan, Inc .: Ultra Tarax T50)
After adding 1/2 of a mixed solution of 0.33 parts by mass of polyaluminum chloride, 37.5 parts by mass of nitric acid aqueous solution, the dispersion rotational speed was set to 5000 rpm, and the remaining 1/2 was reduced to 1 The mixture was added over a period of 6 minutes, and the dispersion was rotated at 6500 rpm for 6 minutes while being careful not to entrain bubbles.

  A reaction vessel was equipped with a stirrer and a mantle heater, and the temperature was raised to 42 ° C. at 0.5 ° C./min while adjusting the number of revolutions of the stirrer so that the slurry was sufficiently stirred. After being held, the particle size was measured with a Coulter counter [TA-II] type (aperture diameter: 50 μm, manufactured by Coulter, Inc.) every 10 minutes while raising the temperature at 0.05 ° C./min. When the diameter reached 5.0 μm, additional fine particles 2A were added over 3 minutes. After the addition for 30 minutes, the pH was adjusted to 9.0 using a 5 mass% aqueous sodium hydroxide solution. Thereafter, while adjusting the pH to 9.0 every 5 ° C., the temperature was raised to 96 ° C. at a temperature rising rate of 1 ° C./min and maintained at 96 ° C. When the particle shape and surface properties were observed every 30 minutes with an optical microscope and a scanning electron microscope (FE-SEM), the particles were almost spherical in the second hour. Solidified.

  The slurry after cooling was passed through a mesh with an opening of 20 μm to remove coarse powder, and then the reaction product was filtered under reduced pressure with an aspirator and washed with ion-exchanged water. When the filtrate has a conductivity of 50 mS or less, the cake-like particles are taken out, put into ion-exchanged water of 10 times the weight of the particles, and stirred with a three-one motor. The pH was adjusted to 3.8 with 0.0 mass% nitric acid aqueous solution and held for 10 minutes. Thereafter, filtration and washing with water were performed again, and when the conductivity of the filtrate became 10 mS or less, water flow was stopped and solid-liquid separation was performed. The obtained cake-like particles were vacuum-dried in an oven at 40 ° C. for 24 hours. The obtained powder was crushed with a sample mill and then vacuum dried in an oven at 40 ° C. for 5 hours to obtain a toner.

  A sample mill was prepared by adding 1.0 part by mass of hydrophobic silica (manufactured by Nippon Aerosil Co., Ltd., RY50) and 0.8 part by mass of hydrophobic titanium oxide (manufactured by Nippon Aerosil Co., Ltd., T805) to 100 parts of the obtained toner. And blended for 30 seconds at 13000 rpm. Thereafter, the cyan toner was prepared by sieving with a vibrating sieve having an opening of 45 μm.

[Example 3A]
Ion-exchanged water 225 parts by mass Amorphous polyester resin dispersion 1A 335 parts by mass (amorphous polyester resin concentration 20% by mass)
97 parts by mass of crystalline polyester resin dispersion 1A (crystalline polyester resin concentration 20% by mass)
Anionic surfactant 2.14 parts by mass (1.28 parts by mass as an active ingredient)
(Daiichi Kogyo Seiyaku Co., Ltd .: Neogen RK, 60% by mass of active ingredient)
Was placed in a 3 liter reaction vessel equipped with a thermometer, a pH meter, and a stirrer, and maintained at a temperature of 30 ° C. and a stirring rotation speed of 150 rpm for 30 minutes while controlling the temperature with a mantle heater from the outside. afterwards,
Cyan colorant dispersion 55 parts by weight Release agent dispersion 61.8 parts by weight were added and maintained for 5 minutes, and then a 1.0% by weight aqueous nitric acid solution was added to adjust the pH to 2.7.
While removing the stirrer and the mantle heater and dispersing at 3000 rpm with a homogenizer (IKA Japan, Inc .: Ultra Tarax T50)
After adding 1/2 of a mixed solution of 0.33 parts by mass of polyaluminum chloride, 37.5 parts by mass of nitric acid aqueous solution, the dispersion rotational speed was set to 5000 rpm, and the remaining 1/2 was reduced to 1 The mixture was added over a period of 6 minutes, and the dispersion was rotated at 6500 rpm for 6 minutes while being careful not to entrain bubbles.

  A reaction vessel was equipped with a stirrer and a mantle heater, and the temperature was raised to 42 ° C. at 0.5 ° C./min while adjusting the number of revolutions of the stirrer so that the slurry was sufficiently stirred. After being held, the particle size was measured with a Coulter counter [TA-II] type (aperture diameter: 50 μm, manufactured by Coulter, Inc.) every 10 minutes while raising the temperature at 0.05 ° C./min. When the diameter reached 5.0 μm, additional fine particles 1B were added over 3 minutes. After the addition for 30 minutes, the pH was adjusted to 9.0 using a 5 mass% aqueous sodium hydroxide solution. Thereafter, while adjusting the pH to 9.0 every 5 ° C., the temperature was raised to 90 ° C. at a temperature rising rate of 1 ° C./min and held at 90 ° C. When the particle shape and surface properties were observed every 30 minutes with an optical microscope and a scanning electron microscope (FE-SEM), the particles became almost spherical in 1.5 hours, so the temperature was lowered to 20 ° C. at 1 ° C./min. The particles were solidified.

  The slurry after cooling was passed through a mesh with an opening of 20 μm to remove coarse powder, and then the reaction product was filtered under reduced pressure with an aspirator and washed with ion-exchanged water. When the filtrate has a conductivity of 50 mS or less, the cake-like particles are taken out, put into ion-exchanged water of 10 times the weight of the particles, and stirred with a three-one motor. The pH was adjusted to 3.8 with 0.0 mass% nitric acid aqueous solution and held for 10 minutes. Thereafter, filtration and washing with water were performed again, and when the conductivity of the filtrate became 10 mS or less, water flow was stopped and solid-liquid separation was performed. The obtained cake-like particles were vacuum-dried in an oven at 40 ° C. for 24 hours. The obtained powder was crushed with a sample mill and then vacuum dried in an oven at 40 ° C. for 5 hours to obtain a toner.

  A sample mill was prepared by adding 1.0 part by mass of hydrophobic silica (manufactured by Nippon Aerosil Co., Ltd., RY50) and 0.8 part by mass of hydrophobic titanium oxide (manufactured by Nippon Aerosil Co., Ltd., T805) to 100 parts of the obtained toner. And blended for 30 seconds at 13000 rpm. Thereafter, the cyan toner was prepared by sieving with a vibrating sieve having an opening of 45 μm.

[Example 4A]
Ion-exchanged water 225 parts by mass Amorphous polyester resin dispersion 1A 270 parts by mass (amorphous polyester resin concentration 20% by mass)
162 parts by mass of crystalline polyester resin dispersion 2A (crystalline polyester resin concentration 20% by mass)
Anionic surfactant 2.14 parts by mass (1.28 parts by mass as an active ingredient)
(Daiichi Kogyo Seiyaku Co., Ltd .: Neogen RK, 60% by mass of active ingredient)
Was placed in a 3 liter reaction vessel equipped with a thermometer, a pH meter, and a stirrer, and maintained at a temperature of 30 ° C. and a stirring rotation speed of 150 rpm for 30 minutes while controlling the temperature with a mantle heater from the outside. afterwards,
Cyan colorant dispersion 55 parts by weight Release agent dispersion 61.8 parts by weight were added and maintained for 5 minutes, and then a 1.0% by weight aqueous nitric acid solution was added to adjust the pH to 2.7.
While removing the stirrer and the mantle heater and dispersing at 3000 rpm with a homogenizer (IKA Japan, Inc .: Ultra Tarax T50)
After adding 1/2 of a mixed solution of 0.33 parts by mass of polyaluminum chloride, 37.5 parts by mass of nitric acid aqueous solution, the dispersion rotational speed was set to 5000 rpm, and the remaining 1/2 was reduced to 1 The mixture was added over a period of 6 minutes, and the dispersion was rotated at 6500 rpm for 6 minutes while being careful not to entrain bubbles.

  A reaction vessel was equipped with a stirrer and a mantle heater, and the temperature was raised to 42 ° C. at 0.5 ° C./min while adjusting the number of revolutions of the stirrer so that the slurry was sufficiently stirred. After being held, the particle size was measured with a Coulter counter [TA-II] type (aperture diameter: 50 μm, manufactured by Coulter, Inc.) every 10 minutes while raising the temperature at 0.05 ° C./min. When the diameter reached 5.0 μm, additional fine particles 1A were added over 3 minutes. After the addition for 30 minutes, the pH was adjusted to 9.0 using a 5 mass% aqueous sodium hydroxide solution. Thereafter, while adjusting the pH to 9.0 every 5 ° C., the temperature was raised to 88 ° C. at a temperature rising rate of 1 ° C./min and held at 88 ° C. When the particle shape and surface properties were observed every 30 minutes with an optical microscope and a scanning electron microscope (FE-SEM), the particles became almost spherical in 1.5 hours, so the temperature was lowered to 20 ° C. at 1 ° C./min. The particles were solidified.

  The slurry after cooling was passed through a mesh with an opening of 20 μm to remove coarse powder, and then the reaction product was filtered under reduced pressure with an aspirator and washed with ion-exchanged water. When the filtrate has a conductivity of 50 mS or less, the cake-like particles are taken out, put into ion-exchanged water of 10 times the weight of the particles, and stirred with a three-one motor. The pH was adjusted to 3.8 with 0.0 mass% nitric acid aqueous solution and held for 10 minutes. Thereafter, filtration and washing with water were performed again, and when the conductivity of the filtrate became 10 mS or less, water flow was stopped and solid-liquid separation was performed. The obtained cake-like particles were vacuum-dried in an oven at 40 ° C. for 24 hours. The obtained powder was crushed with a sample mill and then vacuum dried in an oven at 40 ° C. for 5 hours to obtain a toner.

  A sample mill was prepared by adding 1.0 part by mass of hydrophobic silica (manufactured by Nippon Aerosil Co., Ltd., RY50) and 0.8 part by mass of hydrophobic titanium oxide (manufactured by Nippon Aerosil Co., Ltd., T805) to 100 parts of the obtained toner. And blended for 30 seconds at 13000 rpm. Thereafter, the cyan toner was prepared by sieving with a vibrating sieve having an opening of 45 μm.

[Comparative Example 1A]
Ion-exchanged water 225 parts by mass Amorphous polyester resin dispersion 3A 432 parts by mass (amorphous polyester resin concentration 20% by mass)
Anionic surfactant 2.14 parts by mass (1.28 parts by mass as an active ingredient)
(Daiichi Kogyo Seiyaku Co., Ltd .: Neogen RK, 60% by mass of active ingredient)
Was placed in a 3 liter reaction vessel equipped with a thermometer, a pH meter, and a stirrer, and maintained at a temperature of 30 ° C. and a stirring rotation speed of 150 rpm for 30 minutes while controlling the temperature with a mantle heater from the outside. afterwards,
Cyan colorant dispersion 55 parts by weight Release agent dispersion 61.8 parts by weight were added and maintained for 5 minutes, and then a 1.0% by weight aqueous nitric acid solution was added to adjust the pH to 2.7.
While removing the stirrer and the mantle heater and dispersing at 3000 rpm with a homogenizer (IKA Japan, Inc .: Ultra Tarax T50)
After adding 1/2 of a mixed solution of 0.33 parts by mass of polyaluminum chloride, 37.5 parts by mass of nitric acid aqueous solution, the dispersion rotational speed was set to 5000 rpm, and the remaining 1/2 was reduced to 1 The mixture was added over a period of 6 minutes, and the dispersion was rotated at 6500 rpm for 6 minutes while being careful not to entrain bubbles.

  A reaction vessel was equipped with a stirrer and a mantle heater, and the temperature was raised to 42 ° C. at 0.5 ° C./min while adjusting the number of revolutions of the stirrer so that the slurry was sufficiently stirred. After being held, the particle size was measured with a Coulter counter [TA-II] type (aperture diameter: 50 μm, manufactured by Coulter, Inc.) every 10 minutes while raising the temperature at 0.05 ° C./min. When the diameter reached 5.0 μm, additional fine particles 1A were added over 3 minutes. After the addition for 30 minutes, the pH was adjusted to 9.0 using a 5 mass% aqueous sodium hydroxide solution. Thereafter, while adjusting the pH to 9.0 every 5 ° C., the temperature was raised to 96 ° C. at a temperature rising rate of 1 ° C./min and maintained at 96 ° C. When the particle shape and surface property were observed with an optical microscope and a scanning electron microscope (FE-SEM) every 30 minutes, the particles were almost spherical in 4 hours, so the temperature was lowered to 20 ° C. at 1 ° C./min. Solidified.

  The slurry after cooling was passed through a mesh with an opening of 20 μm to remove coarse powder, and then the reaction product was filtered under reduced pressure with an aspirator and washed with ion-exchanged water. When the filtrate has a conductivity of 50 mS or less, the cake-like particles are taken out, put into ion-exchanged water of 10 times the weight of the particles, and stirred with a three-one motor. The pH was adjusted to 3.8 with 0.0 mass% nitric acid aqueous solution and held for 10 minutes. Thereafter, filtration and washing with water were performed again, and when the conductivity of the filtrate became 10 mS or less, water flow was stopped and solid-liquid separation was performed. The obtained cake-like particles were vacuum-dried in an oven at 40 ° C. for 24 hours. The obtained powder was crushed with a sample mill and then vacuum dried in an oven at 40 ° C. for 5 hours to obtain a toner.

  A sample mill was prepared by adding 1.0 part by mass of hydrophobic silica (manufactured by Nippon Aerosil Co., Ltd., RY50) and 0.8 part by mass of hydrophobic titanium oxide (manufactured by Nippon Aerosil Co., Ltd., T805) to 100 parts of the obtained toner. And blended for 30 seconds at 13000 rpm. Thereafter, the cyan toner was prepared by sieving with a vibrating sieve having an opening of 45 μm.

[Comparative Example 2A]
Ion-exchanged water 225 parts by mass Amorphous polyester resin dispersion 3A 335 parts by mass (amorphous polyester resin concentration 20% by mass)
97 parts by mass of crystalline polyester resin dispersion 1A (crystalline polyester resin concentration 20% by mass)
Anionic surfactant 2.14 parts by mass (1.28 parts by mass as an active ingredient)
(Daiichi Kogyo Seiyaku Co., Ltd .: Neogen RK, 60% by mass of active ingredient)
Was placed in a 3 liter reaction vessel equipped with a thermometer, a pH meter, and a stirrer, and maintained at a temperature of 30 ° C. and a stirring rotation speed of 150 rpm for 30 minutes while controlling the temperature with a mantle heater from the outside. afterwards,
Cyan colorant dispersion 55 parts by weight Release agent dispersion 61.8 parts by weight were added and maintained for 5 minutes, and then a 1.0% by weight aqueous nitric acid solution was added to adjust the pH to 2.7.
While removing the stirrer and the mantle heater and dispersing at 3000 rpm with a homogenizer (IKA Japan, Inc .: Ultra Tarax T50)
After adding 1/2 of a mixed solution of 0.33 parts by mass of polyaluminum chloride, 37.5 parts by mass of nitric acid aqueous solution, the dispersion rotational speed was set to 5000 rpm, and the remaining 1/2 was reduced to 1 The mixture was added over a period of 6 minutes, and the dispersion was rotated at 6500 rpm for 6 minutes while being careful not to entrain bubbles.

  A reaction vessel was equipped with a stirrer and a mantle heater, and the temperature was raised to 42 ° C. at 0.5 ° C./min while adjusting the number of revolutions of the stirrer so that the slurry was sufficiently stirred. After being held, the particle size was measured with a Coulter counter [TA-II] type (aperture diameter: 50 μm, manufactured by Coulter, Inc.) every 10 minutes while raising the temperature at 0.05 ° C./min. When the diameter reached 5.0 μm, additional fine particles 1A were added over 3 minutes. After the addition for 30 minutes, the pH was adjusted to 9.0 using a 5 mass% aqueous sodium hydroxide solution. Thereafter, while adjusting the pH to 9.0 every 5 ° C., the temperature was raised to 90 ° C. at a temperature rising rate of 1 ° C./min and held at 90 ° C. When the particle shape and surface properties were observed every 30 minutes with an optical microscope and a scanning electron microscope (FE-SEM), the particles were almost spherical in the second hour. Solidified.

  The slurry after cooling was passed through a mesh with an opening of 20 μm to remove coarse powder, and then the reaction product was filtered under reduced pressure with an aspirator and washed with ion-exchanged water. When the filtrate has a conductivity of 50 mS or less, the cake-like particles are taken out, put into ion-exchanged water of 10 times the weight of the particles, and stirred with a three-one motor. The pH was adjusted to 3.8 with 0.0 mass% nitric acid aqueous solution and held for 10 minutes. Thereafter, filtration and washing with water were performed again, and when the conductivity of the filtrate became 10 mS or less, water flow was stopped and solid-liquid separation was performed. The obtained cake-like particles were vacuum-dried in an oven at 40 ° C. for 24 hours. The obtained powder was crushed with a sample mill and then vacuum dried in an oven at 40 ° C. for 5 hours to obtain a toner.

  A sample mill was prepared by adding 1.0 part by mass of hydrophobic silica (manufactured by Nippon Aerosil Co., Ltd., RY50) and 0.8 part by mass of hydrophobic titanium oxide (manufactured by Nippon Aerosil Co., Ltd., T805) to 100 parts of the obtained toner. And blended for 30 seconds at 13000 rpm. Thereafter, the cyan toner was prepared by sieving with a vibrating sieve having an opening of 45 μm.

[Comparative Example 3A]
Ion-exchanged water 225 parts by mass Amorphous polyester resin dispersion 1A 233.3 parts by mass (amorphous polyester resin concentration 20% by mass)
Crystalline polyester resin dispersion 2A 198.7 parts by mass (crystalline polyester resin concentration 20% by mass)
Anionic surfactant 2.14 parts by mass (1.28 parts by mass as an active ingredient)
(Daiichi Kogyo Seiyaku Co., Ltd .: Neogen RK, 60% by mass of active ingredient)
Was placed in a 3 liter reaction vessel equipped with a thermometer, a pH meter, and a stirrer, and maintained at a temperature of 30 ° C. and a stirring rotation speed of 150 rpm for 30 minutes while controlling the temperature with a mantle heater from the outside. afterwards,
Cyan colorant dispersion 55 parts by weight Release agent dispersion 61.8 parts by weight were added and maintained for 5 minutes, and then a 1.0% by weight aqueous nitric acid solution was added to adjust the pH to 2.7.
While removing the stirrer and the mantle heater and dispersing at 3000 rpm with a homogenizer (IKA Japan, Inc .: Ultra Tarax T50)
After adding 1/2 of a mixed solution of 0.33 parts by mass of polyaluminum chloride, 37.5 parts by mass of nitric acid aqueous solution, the dispersion rotational speed was set to 5000 rpm, and the remaining 1/2 was reduced to 1 The mixture was added over a period of 6 minutes, and the dispersion was rotated at 6500 rpm for 6 minutes while being careful not to entrain bubbles.

  A reaction vessel was equipped with a stirrer and a mantle heater, and the temperature was raised to 42 ° C. at 0.5 ° C./min while adjusting the number of revolutions of the stirrer so that the slurry was sufficiently stirred. After being held, the particle size was measured with a Coulter counter [TA-II] type (aperture diameter: 50 μm, manufactured by Coulter, Inc.) every 10 minutes while raising the temperature at 0.05 ° C./min. When the diameter reached 5.0 μm, additional fine particles 1A were added over 3 minutes. After the addition for 30 minutes, the pH was adjusted to 9.0 using a 5 mass% aqueous sodium hydroxide solution. Thereafter, while adjusting the pH to 9.0 every 5 ° C., the temperature was raised to 90 ° C. at a temperature rising rate of 1 ° C./min and held at 90 ° C. When the particle shape and surface property were observed with an optical microscope and a scanning electron microscope (FE-SEM) every 30 minutes, the particles became almost spherical at 2.5 hours, so the temperature was lowered to 20 ° C. at 1 ° C./min. The particles were solidified.

  The slurry after cooling was passed through a mesh with an opening of 20 μm to remove coarse powder, and then the reaction product was filtered under reduced pressure with an aspirator and washed with ion-exchanged water. When the filtrate has a conductivity of 50 mS or less, the cake-like particles are taken out, put into ion-exchanged water of 10 times the weight of the particles, and stirred with a three-one motor. The pH was adjusted to 3.8 with 0.0 mass% nitric acid aqueous solution and held for 10 minutes. Thereafter, filtration and washing with water were performed again, and when the conductivity of the filtrate became 10 mS or less, water flow was stopped and solid-liquid separation was performed. The obtained cake-like particles were vacuum-dried in an oven at 40 ° C. for 24 hours. The obtained powder was crushed with a sample mill and then vacuum dried in an oven at 40 ° C. for 5 hours to obtain a toner.

  A sample mill was prepared by adding 1.0 part by mass of hydrophobic silica (manufactured by Nippon Aerosil Co., Ltd., RY50) and 0.8 part by mass of hydrophobic titanium oxide (manufactured by Nippon Aerosil Co., Ltd., T805) to 100 parts of the obtained toner. And blended for 30 seconds at 13000 rpm. Thereafter, the cyan toner was prepared by sieving with a vibrating sieve having an opening of 45 μm.

[Example 1B]
Deionized water 225 parts by mass Amorphous polyester resin dispersion 1B 432 parts by mass (amorphous polyester resin concentration 20% by mass)
Anionic surfactant 2.14 parts by mass (1.28 parts by mass as an active ingredient)
(Daiichi Kogyo Seiyaku Co., Ltd .: Neogen RK, 60% by mass of active ingredient)
Was placed in a 3 liter reaction vessel equipped with a thermometer, a pH meter, and a stirrer, and maintained at a temperature of 30 ° C. and a stirring rotation speed of 150 rpm for 30 minutes while controlling the temperature with a mantle heater from the outside. afterwards,
Cyan colorant dispersion 55 parts by weight Release agent dispersion 61.8 parts by weight were added and maintained for 5 minutes, and then a 1.0% by weight aqueous nitric acid solution was added to adjust the pH to 2.7.
While removing the stirrer and the mantle heater and dispersing at 3000 rpm with a homogenizer (IKA Japan, Inc .: Ultra Tarax T50)
After adding 1/2 of a mixed solution of 0.33 parts by mass of polyaluminum chloride, 37.5 parts by mass of nitric acid aqueous solution, the dispersion rotational speed was set to 5000 rpm, and the remaining 1/2 was reduced to 1 The mixture was added over a period of 6 minutes, and the dispersion was rotated at 6500 rpm for 6 minutes while being careful not to entrain bubbles.

  A reaction vessel was equipped with a stirrer and a mantle heater, and the temperature was raised to 42 ° C. at 0.5 ° C./min while adjusting the number of revolutions of the stirrer so that the slurry was sufficiently stirred. After being held, the particle size was measured with a Coulter counter [TA-II] type (aperture diameter: 50 μm, manufactured by Coulter, Inc.) every 10 minutes while raising the temperature at 0.05 ° C./min. When the diameter reached 5.0 μm, additional fine particles 1B were added over 3 minutes. After the addition for 30 minutes, the pH was adjusted to 9.0 using a 5 mass% aqueous sodium hydroxide solution. Thereafter, while adjusting the pH to 9.0 every 5 ° C., the temperature was raised to 96 ° C. at a temperature rising rate of 1 ° C./min and maintained at 96 ° C. When the particle shape and surface properties were observed every 30 minutes with an optical microscope and a scanning electron microscope (FE-SEM), the particles became almost spherical at 3.0 hours, so the temperature was lowered to 20 ° C. at 1 ° C./min. The particles were solidified.

  The slurry after cooling was passed through a mesh with an opening of 20 μm to remove coarse powder, and then the reaction product was filtered under reduced pressure with an aspirator and washed with ion-exchanged water. When the filtrate has a conductivity of 50 mS or less, the cake-like particles are taken out, put into ion-exchanged water of 10 times the weight of the particles, and stirred with a three-one motor. The pH was adjusted to 3.8 with 0.0 mass% nitric acid aqueous solution and held for 10 minutes. Thereafter, filtration and washing with water were performed again, and when the conductivity of the filtrate became 10 mS or less, water flow was stopped and solid-liquid separation was performed. The obtained cake-like particles were vacuum-dried in an oven at 40 ° C. for 24 hours. The obtained powder was crushed with a sample mill and then vacuum dried in an oven at 40 ° C. for 5 hours to obtain a toner.

  A sample mill was prepared by adding 1.0 part by mass of hydrophobic silica (manufactured by Nippon Aerosil Co., Ltd., RY50) and 0.8 part by mass of hydrophobic titanium oxide (manufactured by Nippon Aerosil Co., Ltd., T805) to 100 parts of the obtained toner. And blended for 30 seconds at 13000 rpm. Thereafter, the cyan toner was prepared by sieving with a vibrating sieve having an opening of 45 μm.

[Example 2B]
Deionized water 225 parts by mass Amorphous polyester resin dispersion 1B 432 parts by mass (amorphous polyester resin concentration 20% by mass)
Anionic surfactant 2.14 parts by mass (1.28 parts by mass as an active ingredient)
(Daiichi Kogyo Seiyaku Co., Ltd .: Neogen RK, 60% by mass of active ingredient)
Was placed in a 3 liter reaction vessel equipped with a thermometer, a pH meter, and a stirrer, and maintained at a temperature of 30 ° C. and a stirring rotation speed of 150 rpm for 30 minutes while controlling the temperature with a mantle heater from the outside. afterwards,
Cyan colorant dispersion 55 parts by weight Release agent dispersion 61.8 parts by weight were added and maintained for 5 minutes, and then a 1.0% by weight aqueous nitric acid solution was added to adjust the pH to 2.7.
While removing the stirrer and the mantle heater and dispersing at 3000 rpm with a homogenizer (IKA Japan, Inc .: Ultra Tarax T50)
After adding 1/2 of a mixed solution of 0.33 parts by mass of polyaluminum chloride, 37.5 parts by mass of nitric acid aqueous solution, the dispersion rotational speed was set to 5000 rpm, and the remaining 1/2 was reduced to 1 The mixture was added over a period of 6 minutes, and the dispersion was rotated at 6500 rpm for 6 minutes while being careful not to entrain bubbles.

  A reaction vessel was equipped with a stirrer and a mantle heater, and the temperature was raised to 42 ° C. at 0.5 ° C./min while adjusting the number of revolutions of the stirrer so that the slurry was sufficiently stirred. After being held, the particle size was measured with a Coulter counter [TA-II] type (aperture diameter: 50 μm, manufactured by Coulter, Inc.) every 10 minutes while raising the temperature at 0.05 ° C./min. When the diameter reached 5.0 μm, additional fine particles 2B were added over 3 minutes. After the addition for 30 minutes, the pH was adjusted to 9.0 using a 5 mass% aqueous sodium hydroxide solution. Thereafter, while adjusting the pH to 9.0 every 5 ° C., the temperature was raised to 96 ° C. at a temperature rising rate of 1 ° C./min and maintained at 96 ° C. When the particle shape and surface property were observed with an optical microscope and a scanning electron microscope (FE-SEM) every 30 minutes, the particles became almost spherical at 2.5 hours, so the temperature was lowered to 20 ° C. at 1 ° C./min. The particles were solidified.

  The slurry after cooling was passed through a mesh with an opening of 20 μm to remove coarse powder, and then the reaction product was filtered under reduced pressure with an aspirator and washed with ion-exchanged water. When the filtrate has a conductivity of 50 mS or less, the cake-like particles are taken out, put into ion-exchanged water of 10 times the weight of the particles, and stirred with a three-one motor. The pH was adjusted to 3.8 with 0.0 mass% nitric acid aqueous solution and held for 10 minutes. Thereafter, filtration and washing with water were performed again, and when the conductivity of the filtrate became 10 mS or less, water flow was stopped and solid-liquid separation was performed. The obtained cake-like particles were vacuum-dried in an oven at 40 ° C. for 24 hours. The obtained powder was crushed with a sample mill and then vacuum dried in an oven at 40 ° C. for 5 hours to obtain a toner.

  A sample mill was prepared by adding 1.0 part by mass of hydrophobic silica (manufactured by Nippon Aerosil Co., Ltd., RY50) and 0.8 part by mass of hydrophobic titanium oxide (manufactured by Nippon Aerosil Co., Ltd., T805) to 100 parts of the obtained toner. And blended for 30 seconds at 13000 rpm. Thereafter, the cyan toner was prepared by sieving with a vibrating sieve having an opening of 45 μm.

[Example 3B]
Ion-exchanged water 225 parts by mass Amorphous polyester resin dispersion 1B 335 parts by mass (amorphous polyester resin concentration 20% by mass)
97 parts by mass of crystalline polyester resin dispersion 1B (crystalline polyester resin concentration 20% by mass)
Anionic surfactant 2.14 parts by mass (1.28 parts by mass as an active ingredient)
(Daiichi Kogyo Seiyaku Co., Ltd .: Neogen RK, 60% by mass of active ingredient)
Was placed in a 3 liter reaction vessel equipped with a thermometer, a pH meter, and a stirrer, and maintained at a temperature of 30 ° C. and a stirring rotation speed of 150 rpm for 30 minutes while controlling the temperature with a mantle heater from the outside. afterwards,
Cyan colorant dispersion 55 parts by weight Release agent dispersion 61.8 parts by weight were added and maintained for 5 minutes, and then a 1.0% by weight aqueous nitric acid solution was added to adjust the pH to 2.7.
While removing the stirrer and the mantle heater and dispersing at 3000 rpm with a homogenizer (IKA Japan, Inc .: Ultra Tarax T50)
After adding 1/2 of a mixed solution of 0.33 parts by mass of polyaluminum chloride, 37.5 parts by mass of nitric acid aqueous solution, the dispersion rotational speed was set to 5000 rpm, and the remaining 1/2 was reduced to 1 The mixture was added over a period of 6 minutes, and the dispersion was rotated at 6500 rpm for 6 minutes while being careful not to entrain bubbles.

  A reaction vessel was equipped with a stirrer and a mantle heater, and the temperature was raised to 42 ° C. at 0.5 ° C./min while adjusting the number of revolutions of the stirrer so that the slurry was sufficiently stirred. After being held, the particle size was measured with a Coulter counter [TA-II] type (aperture diameter: 50 μm, manufactured by Coulter, Inc.) every 10 minutes while raising the temperature at 0.05 ° C./min. When the diameter reached 5.0 μm, additional fine particles 1B were added over 3 minutes. After the addition for 30 minutes, the pH was adjusted to 9.0 using a 5 mass% aqueous sodium hydroxide solution. Thereafter, while adjusting the pH to 9.0 every 5 ° C., the temperature was raised to 90 ° C. at a temperature rising rate of 1 ° C./min and held at 90 ° C. When the particle shape and surface properties were observed every 30 minutes with an optical microscope and a scanning electron microscope (FE-SEM), the particles became almost spherical in 1.5 hours, so the temperature was lowered to 20 ° C. at 1 ° C./min. The particles were solidified.

  The slurry after cooling was passed through a mesh with an opening of 20 μm to remove coarse powder, and then the reaction product was filtered under reduced pressure with an aspirator and washed with ion-exchanged water. When the filtrate has a conductivity of 50 mS or less, the cake-like particles are taken out, put into ion-exchanged water of 10 times the weight of the particles, and stirred with a three-one motor. The pH was adjusted to 3.8 with 0.0 mass% nitric acid aqueous solution and held for 10 minutes. Thereafter, filtration and washing with water were performed again, and when the conductivity of the filtrate became 10 mS or less, water flow was stopped and solid-liquid separation was performed. The obtained cake-like particles were vacuum-dried in an oven at 40 ° C. for 24 hours. The obtained powder was crushed with a sample mill and then vacuum dried in an oven at 40 ° C. for 5 hours to obtain a toner.

  A sample mill was prepared by adding 1.0 part by mass of hydrophobic silica (manufactured by Nippon Aerosil Co., Ltd., RY50) and 0.8 part by mass of hydrophobic titanium oxide (manufactured by Nippon Aerosil Co., Ltd., T805) to 100 parts of the obtained toner. And blended for 30 seconds at 13000 rpm. Thereafter, the cyan toner was prepared by sieving with a vibrating sieve having an opening of 45 μm.

[Example 4B]
Ion-exchanged water 225 parts by mass Amorphous polyester resin dispersion 1B 270 parts by mass (amorphous polyester resin concentration 20% by mass)
162 parts by mass of crystalline polyester resin dispersion 2B (crystalline polyester resin concentration 20% by mass)
Anionic surfactant 2.14 parts by mass (1.28 parts by mass as an active ingredient)
(Daiichi Kogyo Seiyaku Co., Ltd .: Neogen RK, 60% by mass of active ingredient)
Was placed in a 3 liter reaction vessel equipped with a thermometer, a pH meter, and a stirrer, and maintained at a temperature of 30 ° C. and a stirring rotation speed of 150 rpm for 30 minutes while controlling the temperature with a mantle heater from the outside. afterwards,
Cyan colorant dispersion 55 parts by weight Release agent dispersion 61.8 parts by weight were added and maintained for 5 minutes, and then a 1.0% by weight aqueous nitric acid solution was added to adjust the pH to 2.7.
While removing the stirrer and the mantle heater and dispersing at 3000 rpm with a homogenizer (IKA Japan, Inc .: Ultra Tarax T50)
After adding 1/2 of a mixed solution of 0.33 parts by mass of polyaluminum chloride, 37.5 parts by mass of nitric acid aqueous solution, the dispersion rotational speed was set to 5000 rpm, and the remaining 1/2 was reduced to 1 The mixture was added over a period of 6 minutes, and the dispersion was rotated at 6500 rpm for 6 minutes while being careful not to entrain bubbles.

  A reaction vessel was equipped with a stirrer and a mantle heater, and the temperature was raised to 42 ° C. at 0.5 ° C./min while adjusting the number of revolutions of the stirrer so that the slurry was sufficiently stirred. After being held, the particle size was measured with a Coulter counter [TA-II] type (aperture diameter: 50 μm, manufactured by Coulter, Inc.) every 10 minutes while raising the temperature at 0.05 ° C./min. When the diameter reached 5.0 μm, additional fine particles 1B were added over 3 minutes. After the addition for 30 minutes, the pH was adjusted to 9.0 using a 5 mass% aqueous sodium hydroxide solution. Thereafter, while adjusting the pH to 9.0 every 5 ° C., the temperature was raised to 88 ° C. at a temperature rising rate of 1 ° C./min and held at 88 ° C. When the particle shape and surface properties were observed every 30 minutes with an optical microscope and a scanning electron microscope (FE-SEM), the particles became almost spherical in 1.5 hours, so the temperature was lowered to 20 ° C. at 1 ° C./min. The particles were solidified.

  The slurry after cooling was passed through a mesh with an opening of 20 μm to remove coarse powder, and then the reaction product was filtered under reduced pressure with an aspirator and washed with ion-exchanged water. When the filtrate has a conductivity of 50 mS or less, the cake-like particles are taken out, put into ion-exchanged water of 10 times the weight of the particles, stirred with a three-one motor, and when the particles are sufficiently loosened, 1 The pH was adjusted to 3.8 with 0.0 mass% nitric acid aqueous solution and held for 10 minutes. Thereafter, filtration and washing with water were performed again, and when the conductivity of the filtrate became 10 mS or less, water flow was stopped and solid-liquid separation was performed. The obtained cake-like particles were vacuum-dried in an oven at 40 ° C. for 24 hours. The obtained powder was crushed with a sample mill and then vacuum dried in an oven at 40 ° C. for 5 hours to obtain a toner.

  A sample mill was prepared by adding 1.0 part by mass of hydrophobic silica (manufactured by Nippon Aerosil Co., Ltd., RY50) and 0.8 part by mass of hydrophobic titanium oxide (manufactured by Nippon Aerosil Co., Ltd., T805) to 100 parts of the obtained toner. And blended for 30 seconds at 13000 rpm. Thereafter, the cyan toner was prepared by sieving with a vibrating sieve having an opening of 45 μm.

[Comparative Example 1B]
Ion-exchanged water 225 parts by mass Amorphous polyester resin dispersion 4B 432 parts by mass (amorphous polyester resin concentration 20% by mass)
Anionic surfactant 2.14 parts by mass (1.28 parts by mass as an active ingredient)
(Daiichi Kogyo Seiyaku Co., Ltd .: Neogen RK, 60% by mass of active ingredient)
Was placed in a 3 liter reaction vessel equipped with a thermometer, a pH meter, and a stirrer, and maintained at a temperature of 30 ° C. and a stirring rotation speed of 150 rpm for 30 minutes while controlling the temperature with a mantle heater from the outside. afterwards,
Cyan colorant dispersion 55 parts by weight Release agent dispersion 61.8 parts by weight were added and maintained for 5 minutes, and then a 1.0% by weight aqueous nitric acid solution was added to adjust the pH to 2.7.
While removing the stirrer and the mantle heater and dispersing at 3000 rpm with a homogenizer (IKA Japan, Inc .: Ultra Tarax T50)
After adding 1/2 of a mixed solution of 0.33 parts by mass of polyaluminum chloride, 37.5 parts by mass of nitric acid aqueous solution, the dispersion rotational speed was set to 5000 rpm, and the remaining 1/2 was reduced to 1 The mixture was added over a period of 6 minutes, and the dispersion was rotated at 6500 rpm for 6 minutes while being careful not to entrain bubbles.

  A reaction vessel was equipped with a stirrer and a mantle heater, and the temperature was raised to 42 ° C. at 0.5 ° C./min while adjusting the number of revolutions of the stirrer so that the slurry was sufficiently stirred. After being held, the particle size was measured with a Coulter counter [TA-II] type (aperture diameter: 50 μm, manufactured by Coulter, Inc.) every 10 minutes while raising the temperature at 0.05 ° C./min. When the diameter reached 5.0 μm, additional fine particles 1B were added over 3 minutes. After the addition for 30 minutes, the pH was adjusted to 9.0 using a 5 mass% aqueous sodium hydroxide solution. Thereafter, while adjusting the pH to 9.0 every 5 ° C., the temperature was raised to 96 ° C. at a temperature rising rate of 1 ° C./min and maintained at 96 ° C. When the particle shape and surface property were observed with an optical microscope and a scanning electron microscope (FE-SEM) every 30 minutes, the particles were almost spherical in 4 hours, so the temperature was lowered to 20 ° C. at 1 ° C./min. Solidified.

  The slurry after cooling was passed through a mesh with an opening of 20 μm to remove coarse powder, and then the reaction product was filtered under reduced pressure with an aspirator and washed with ion-exchanged water. When the filtrate has a conductivity of 50 mS or less, the cake-like particles are taken out, put into ion-exchanged water of 10 times the weight of the particles, and stirred with a three-one motor. The pH was adjusted to 3.8 with 0.0 mass% nitric acid aqueous solution and held for 10 minutes. Thereafter, filtration and washing with water were performed again, and when the conductivity of the filtrate became 10 mS or less, water flow was stopped and solid-liquid separation was performed. The obtained cake-like particles were vacuum-dried in an oven at 40 ° C. for 24 hours. The obtained powder was crushed with a sample mill and then vacuum dried in an oven at 40 ° C. for 5 hours to obtain a toner.

  A sample mill was prepared by adding 1.0 part by mass of hydrophobic silica (manufactured by Nippon Aerosil Co., Ltd., RY50) and 0.8 part by mass of hydrophobic titanium oxide (manufactured by Nippon Aerosil Co., Ltd., T805) to 100 parts of the obtained toner. And blended for 30 seconds at 13000 rpm. Thereafter, the cyan toner was prepared by sieving with a vibrating sieve having an opening of 45 μm.

[Comparative Example 2B]
Ion-exchanged water 225 parts by mass Amorphous polyester resin dispersion 3B 335 parts by mass (amorphous polyester resin concentration 20% by mass)
97 parts by mass of crystalline polyester resin dispersion 1B (crystalline polyester resin concentration 20% by mass)
Anionic surfactant 2.14 parts by mass (1.28 parts by mass as an active ingredient)
(Daiichi Kogyo Seiyaku Co., Ltd .: Neogen RK, 60% by mass of active ingredient)
Was placed in a 3 liter reaction vessel equipped with a thermometer, a pH meter, and a stirrer, and maintained at a temperature of 30 ° C. and a stirring rotation speed of 150 rpm for 30 minutes while controlling the temperature with a mantle heater from the outside. afterwards,
Cyan colorant dispersion 55 parts by weight Release agent dispersion 61.8 parts by weight were added and maintained for 5 minutes, and then a 1.0% by weight aqueous nitric acid solution was added to adjust the pH to 2.7.
While removing the stirrer and the mantle heater and dispersing at 3000 rpm with a homogenizer (IKA Japan, Inc .: Ultra Tarax T50)
After adding 1/2 of a mixed solution of 0.33 parts by mass of polyaluminum chloride, 37.5 parts by mass of nitric acid aqueous solution, the dispersion rotational speed was set to 5000 rpm, and the remaining 1/2 was reduced to 1 The mixture was added over a period of 6 minutes, and the dispersion was rotated at 6500 rpm for 6 minutes while being careful not to entrain bubbles.

  A reaction vessel was equipped with a stirrer and a mantle heater, and the temperature was raised to 42 ° C. at 0.5 ° C./min while adjusting the number of revolutions of the stirrer so that the slurry was sufficiently stirred. After being held, the particle size was measured with a Coulter counter [TA-II] type (aperture diameter: 50 μm, manufactured by Coulter, Inc.) every 10 minutes while raising the temperature at 0.05 ° C./min. When the diameter reached 5.0 μm, additional fine particles 1B were added over 3 minutes. After the addition for 30 minutes, the pH was adjusted to 9.0 using a 5 mass% aqueous sodium hydroxide solution. Thereafter, while adjusting the pH to 9.0 every 5 ° C., the temperature was raised to 90 ° C. at a temperature rising rate of 1 ° C./min and held at 90 ° C. When the particle shape and surface properties were observed every 30 minutes with an optical microscope and a scanning electron microscope (FE-SEM), the particles were almost spherical in the second hour. Solidified.

  The slurry after cooling was passed through a mesh with an opening of 20 μm to remove coarse powder, and then the reaction product was filtered under reduced pressure with an aspirator and washed with ion-exchanged water. When the filtrate has a conductivity of 50 mS or less, the cake-like particles are taken out, put into ion-exchanged water of 10 times the weight of the particles, and stirred with a three-one motor. The pH was adjusted to 3.8 with 0.0 mass% nitric acid aqueous solution and held for 10 minutes. Thereafter, filtration and washing with water were performed again, and when the conductivity of the filtrate became 10 mS or less, water flow was stopped and solid-liquid separation was performed. The obtained cake-like particles were vacuum-dried in an oven at 40 ° C. for 24 hours. The obtained powder was crushed with a sample mill and then vacuum dried in an oven at 40 ° C. for 5 hours to obtain a toner.

  A sample mill was prepared by adding 1.0 part by mass of hydrophobic silica (manufactured by Nippon Aerosil Co., Ltd., RY50) and 0.8 part by mass of hydrophobic titanium oxide (manufactured by Nippon Aerosil Co., Ltd., T805) to 100 parts of the obtained toner. And blended for 30 seconds at 13000 rpm. Thereafter, the cyan toner was prepared by sieving with a vibrating sieve having an opening of 45 μm.

  A sample mill was prepared by adding 1.0 part by mass of hydrophobic silica (manufactured by Nippon Aerosil Co., Ltd., RY50) and 0.8 part by mass of hydrophobic titanium oxide (manufactured by Nippon Aerosil Co., Ltd., T805) to 100 parts of the obtained toner. And blended for 30 seconds at 13000 rpm. Thereafter, the cyan toner was prepared by sieving with a vibrating sieve having an opening of 45 μm.

[Comparative Example 3B]
Ion-exchanged water 225 parts by mass Amorphous polyester resin dispersion 1B 233.3 parts by mass (amorphous polyester resin concentration 20% by mass)
Crystalline polyester resin dispersion 2B 198.7 parts by mass (crystalline polyester resin concentration 20% by mass)
Anionic surfactant 2.14 parts by mass (1.28 parts by mass as an active ingredient)
(Daiichi Kogyo Seiyaku Co., Ltd .: Neogen RK, 60% by mass of active ingredient)
Was placed in a 3 liter reaction vessel equipped with a thermometer, a pH meter, and a stirrer, and maintained at a temperature of 30 ° C. and a stirring rotation speed of 150 rpm for 30 minutes while controlling the temperature with a mantle heater from the outside. afterwards,
Cyan colorant dispersion 55 parts by weight Release agent dispersion 61.8 parts by weight were added and maintained for 5 minutes, and then a 1.0% by weight aqueous nitric acid solution was added to adjust the pH to 2.7.
While removing the stirrer and the mantle heater and dispersing at 3000 rpm with a homogenizer (IKA Japan, Inc .: Ultra Tarax T50)
After adding 1/2 of a mixed solution of 0.33 parts by mass of polyaluminum chloride, 37.5 parts by mass of nitric acid aqueous solution, the dispersion rotational speed was set to 5000 rpm, and the remaining 1/2 was reduced to 1 The mixture was added over a period of 6 minutes, and the dispersion was rotated at 6500 rpm for 6 minutes while being careful not to entrain bubbles.

  A reaction vessel was equipped with a stirrer and a mantle heater, and the temperature was raised to 42 ° C. at 0.5 ° C./min while adjusting the number of revolutions of the stirrer so that the slurry was sufficiently stirred. After being held, the particle size was measured with a Coulter counter [TA-II] type (aperture diameter: 50 μm, manufactured by Coulter, Inc.) every 10 minutes while raising the temperature at 0.05 ° C./min. When the diameter reached 5.0 μm, additional fine particles 1B were added over 3 minutes. After the addition for 30 minutes, the pH was adjusted to 9.0 using a 5 mass% aqueous sodium hydroxide solution. Thereafter, while adjusting the pH to 9.0 every 5 ° C., the temperature was raised to 90 ° C. at a temperature rising rate of 1 ° C./min and held at 90 ° C. When the particle shape and surface property were observed with an optical microscope and a scanning electron microscope (FE-SEM) every 30 minutes, the particles became almost spherical at 2.5 hours, so the temperature was lowered to 20 ° C. at 1 ° C./min. The particles were solidified.

  The slurry after cooling was passed through a mesh with an opening of 20 μm to remove coarse powder, and then the reaction product was filtered under reduced pressure with an aspirator and washed with ion-exchanged water. When the filtrate has a conductivity of 50 mS or less, the cake-like particles are taken out, put into ion-exchanged water of 10 times the weight of the particles, and stirred with a three-one motor. The pH was adjusted to 3.8 with 0.0 mass% nitric acid aqueous solution and held for 10 minutes. Thereafter, filtration and washing with water were performed again, and when the conductivity of the filtrate became 10 mS or less, water flow was stopped and solid-liquid separation was performed. The obtained cake-like particles were vacuum-dried in an oven at 40 ° C. for 24 hours. The obtained powder was crushed with a sample mill and then vacuum dried in an oven at 40 ° C. for 5 hours to obtain a toner.

  A sample mill was prepared by adding 1.0 part by mass of hydrophobic silica (manufactured by Nippon Aerosil Co., Ltd., RY50) and 0.8 part by mass of hydrophobic titanium oxide (manufactured by Nippon Aerosil Co., Ltd., T805) to 100 parts of the obtained toner. And blended for 30 seconds at 13000 rpm. Thereafter, the cyan toner was prepared by sieving with a vibrating sieve having an opening of 45 μm.

[Example of carrier production]
Ferrite particles (average particle size 35 μm) 500 parts by mass Toluene 70 parts Perfluorooctylethyl methacrylate / methyl methacrylate copolymer (copolymerization ratio: 15/85, Mw 75000) 10 parts by mass carbon black (VXC72: manufactured by Cabot Corporation) 0 parts by mass First, the above components excluding ferrite particles were stirred for 10 minutes in a sand mill, the dispersed coating solution was weighed, and then this coating solution and ferrite particles were put into a vacuum degassing kneader and stirred at 60 ° C. The mixture was decompressed to -20 mHg and mixed for 30 minutes, and then heated / depressurized and stirred and dried at 90 ° C./−720 mHg for 30 minutes to obtain a carrier. This carrier had a volume resistivity of 10 ¹¹ Ωcm at an applied electric field of 1000 V / cm.

[Adjustment of developer]
After blending 20 parts of the toners of Examples and Comparative Examples with a V-type blender for 20 parts with respect to 500 parts of the carrier, aggregates were removed by a vibrating screen having an aperture of 212 μm to obtain developers.

[Adjustment of toner for supply]
To 20 parts of the carrier, 100 parts of each of the toners of Examples and Comparative Examples were blended for 20 minutes with a V-type blender, and then aggregates were removed by a vibration sieve having an aperture of 212 μm to obtain toners for replenishment.

[Toner surface observation]
The surface of the toner was observed with a scanning electron microscope (FE-SEM) at an observation magnification of 3,500, 10,000, and 20000, and the smoothness of the surface was visually evaluated. The obtained results are shown in Tables 1 and 2.
The toner of the example had a smooth surface property without exposure of the release agent and detachment of the shell, whereas the toner of the comparative example had a lump that appeared to be a release agent exposed on the surface. It was.

[Image evaluation]
In an environmental chamber at room temperature of 30 ° C. and humidity of 80%, each developer is set in the DocuCentre Color 500 CP developer, and replenishment toner is set in the toner cartridge. Adjusted to 0.5 g / m ² . The paper used was C2r paper manufactured by Fuji Xerox Office Supply. First, 100 sheets of A3 size white paper were passed through, and the developer was charged and forcedly deteriorated. Then, the developer on the developing roll was collected, and the charge amount (initial charge amount) was measured by a blow-off tribo. Next, after being allowed to stand for 12 hours, the charge amount was measured again, and fogging when white paper was passed again was evaluated. Visually, the level which cannot be observed was set to (circle), the level observed very slightly was set to (triangle | delta), and the level observed clearly was set to x. The fog level at which there is no problem in actual use is ◯ or higher. The obtained results are shown in Tables 1 and 2.
Each of the toners of the examples exhibited good chargeability, and fog did not occur even after being left for 12 hours. On the other hand, in each toner of the comparative example, the internal additive such as the release agent was exposed on the toner surface, so that the chargeability was lowered and fogging occurred.

[Image strength evaluation]
In the environment room at room temperature of 22 ° C. and humidity of 50%, set each developer in Examples and Comparative Examples to the DocuCentre Color 500 CP cyan, magenta, yellow developer, and supply toner to the toner cartridge. The developing toner amount of each solid color only image on the paper was adjusted to 4.5 g / m ² . The paper used was J paper manufactured by Fuji Xerox Office Supply Co., and a tertiary color image in which cyan, magenta and yellow were superimposed at 100% each was output. The output image here is not actually a color image but a laminated image corresponding to the third color of the same cyan toner. Lightly fold the paper with the output image on the inside, crease the output image with a load of 200 g / cm over 1 minute, then open the image and once with a waste cloth while applying a load of 5 g / cm After rubbing and removing the missing image, the image defect at the crease portion was evaluated. The level that could not be observed visually was marked with ◯, the level that was observed very slightly was marked with Δ, and the level that was clearly observed was marked with ×. The obtained results are shown in Tables 1 and 2.
Each of the toners of the examples had sufficient image strength, whereas the toner of the comparative example contained the polyester resin (core resin) contained in the internal additive and core particles and the shell layer. Since the compatibility with the produced polyester resin (shell resin) is poor, destruction at the interface occurs, and the image strength is lowered.

Claims (3)

An electrophotographic toner having a structure including a core particle containing at least a binder resin, a colorant, and a release agent, and a shell layer covering the core particle,
75% by mass or more of the binder resin contained in the core particles is the polyester resin A, 75% by mass or more of the shell layer is the polyester resin B, and isophthalic acid in the total amount of carboxylic acid constituting the polyester resin A The acid ratio (mol%) is 22.5 mol% or more and 35.3 mol% or less, and the ratio (mol%) of isophthalic acid in the total amount of carboxylic acid constituting the polyester resin B is 0 mol% . An electrophotographic toner in which the solubility parameter (SP value) of the polyester resin A and the polyester resin B satisfies the following formula (2).
0.15 (J / cm ³ ) ^1/2 <(SP value of polyester resin B−SP value of polyester resin A) <1.7 (J / cm ³ ) ^1/2 formula (2) An electrophotographic toner having a structure including a core particle containing at least a binder resin, a colorant, and a release agent, and a shell layer covering the core particle,
75% by mass or more of the binder resin contained in the core particles is the polyester resin C, 75% by mass or more of the shell layer is the polyester resin D, and dodecenyl succinic acid in the total amount of carboxylic acid constituting the polyester resin C. The ratio (mol%) of the acid is 12.5 mol% or more and 20.0 mol% or less, and the ratio (mol%) of dodecenyl succinic acid in the total amount of carboxylic acid constituting the polyester resin D is 0 mol% . An electrophotographic toner in which the solubility parameter (SP value) of the polyester resin C and the polyester resin D satisfies the following formula (4).
0.15 (J / cm ³ ) ^1/2 <(SP value of polyester resin D−SP value of polyester resin C) <1.7 (J / cm ³ ) ^1/2 formula (4) The toner for electrophotography according to claim 1 or 2, wherein the titanium content in the chloroform-soluble component is 5 to 300 ppm by ICP emission spectroscopy.