JP2017040742A - Method for manufacturing toner and toner - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for manufacturing a toner which is excellent in durability and storage stability even in long-term use, and is excellent in coloring power.SOLUTION: There is provided a method for manufacturing a toner including a step of forming particles of a monomer composition containing a monomer containing styrene, a colorant and a polyester resin A in an aqueous medium, and polymerizing the monomer contained in the particles of the monomer composition, where a content of styrene in the monomer is 60 mass% or more, the polyester resin A contains an isosorbide unit, and a styrene-hexane solubility parameter of the polyester resin A is 15.0 or more and 27.0 or less.SELECTED DRAWING: None

Description

  The present invention relates to a method for producing a toner for developing an electrostatic image used for image formation by electrophotography and the toner.

In recent years, quality requirements for image forming apparatuses such as copiers and printers have become strict, and the performance required for toner has become high. In particular, full-color copying machines or full-color printers are required to realize high-quality printing regardless of the type of paper, and further improvements in durability and coloring power are required. The toner is also required to have better durability and coloring power.
In response to this requirement, there is a method in which a toner having high image quality and excellent storage stability can be obtained by using a polyester resin obtained by using a diol component containing isosorbide and 1,3-propanediol (Patent Document 1). ).
However, in long-term use, there are still some problems regarding durability.
In addition, there is a method of obtaining a toner excellent in chargeability and storage stability by using a polyester resin obtained by using isosorbide and two kinds of divalent acid monomers (Patent Document 2).
However, in long-term use, there are still some problems regarding durability.

JP 2012-73304 A Japanese Patent No. 4740313

  The present invention provides a method for producing a toner that is excellent in durability and storage stability even in long-term use and excellent in coloring power.

The present invention
A toner production method comprising a step of forming particles of a monomer composition containing a monomer containing styrene, a colorant and a polyester resin A in an aqueous medium, and polymerizing the monomer contained in the particles of the monomer composition. There,
The styrene content in the monomer is 60% by mass or more,
The polyester resin A contains an isosorbide unit represented by the following formula (1),
The polyester resin A has a styrene-hexane solubility index of 15.0 or more and 27.0 or less.
The present invention also provides:
A toner obtained by forming particles of a monomer composition containing a monomer containing styrene, a colorant, and polyester resin A in an aqueous medium and polymerizing the monomer contained in the particles of the monomer composition. And
The styrene content in the monomer is 60% by mass or more,
The polyester resin A contains an isosorbide unit represented by the following formula (1),
The toner is characterized in that the polyester resin A has a styrene-hexane solubility index of 15.0 or more and 27.0 or less.

  According to the present invention, it is possible to provide a method for producing a toner that is excellent in durability and storage stability even in long-term use and excellent in coloring power.

Example of transmittance curve obtained by measuring styrene-hexane solubility index

Hereinafter, the present invention will be described in detail.
The present invention relates to a toner comprising a step of forming particles of a monomer composition containing a monomer containing styrene, a colorant and polyester resin A in an aqueous medium, and polymerizing the monomer contained in the particles of the monomer composition. A manufacturing method of
The styrene content in the monomer is 60% by mass or more,
The polyester resin A contains an isosorbide unit represented by the following formula (1),
The polyester resin A has a styrene-hexane solubility index of 15.0 or more and 27.0 or less.

The reason why the effect of the present invention is manifested is not necessarily clear, but the present inventors consider as follows.
A toner having a core-shell structure can be obtained by forming particles of a monomer composition obtained using the appropriate material in an aqueous medium and polymerizing the monomers contained in the particles.
As the shell component, the shell layer cannot be formed unless it is a material that is phase-separated to some extent from the binder resin of the core component and has an affinity for the aqueous medium.
In the present invention, the binder resin constituting the core component is a styrene polymer formed from a monomer containing styrene, and the shell component is the polyester resin A. Since the polyester resin has many ester bonds, it has a certain affinity with an aqueous medium. In addition, the polyester resin A contains an isosorbide unit represented by the above formula (1). Since the isosorbide unit has an affinity with an aqueous medium, when the particles of the monomer composition containing the polyester resin A are formed in the aqueous medium, the polyester resin A is distributed on the aqueous medium side. Easy to form.
Here, in order to make the toner excellent in durability and storage stability, it is necessary that the shell component is excellent in durability and heat resistance, and excellent in phase separation from the binder resin of the core component.
The polyester resin A containing the isosorbide unit represented by the above formula (1) is excellent in durability because the orientation of the isosorbide unit is strong.
However, the polyester resin A containing the isosorbide unit represented by the formula (1) is simply used, the monomer composition particles are formed in an aqueous medium, and the monomer contained in the monomer composition particles is polymerized. Even if the toner is manufactured, the dispersibility of the pigment is lowered.
Along with this, the distribution of the polyester resin A becomes non-uniform, so that the toner is often inferior in terms of durability, storage stability and coloring power.
On the other hand, the effect of this invention is acquired by making content of styrene in this monomer 60 mass% or more, and making the styrene-hexane solubility index of polyester resin A 15.0 or more and 27.0 or less.

In the step of polymerizing the monomer contained in the monomer composition particles, when the polyester resin A has low solubility and does not dissolve in the monomer, the polyester resin A becomes a foreign substance for a colorant that does not dissolve in the monomer. . As a result, since the dispersion state of the colorant is disturbed in the process, the coloring power of the toner is reduced.
Further, at that time, the dispersion state of the colorant is disturbed and the distribution of the dispersion diameter of the colorant becomes broad in the process of aggregation of the colorant, so that unevenness occurs in toner particle formation. As a result, unevenness occurs in the presence state of the polyester resin A containing the isosorbide unit represented by the formula (1). For this reason, the shell formation in the toner is also uneven, resulting in undesirable results in terms of durability and storage stability.

Also, as the polymerization reaction proceeds, the amount of monomer decreases. That is, as the polymerization proceeds, the solvent of the polyester resin A decreases.
Therefore, even if the polyester resin A is dissolved in the monomer at the start of the polymerization reaction, if the styrene-hexane solubility index of the polyester resin A is less than 15.0, there are many monomers in the initial stage of the polymerization reaction. Even in the state, the polyester resin A is deposited. As a result, since the precipitated polyester resin A disturbs the dispersion state of the colorant, the effect of the present invention cannot be obtained.
On the contrary, when the styrene-hexane solubility index of the polyester resin A exceeds 27.0, the polyester resin A precipitates and does not form a shell layer unless the polymerization reaction is late.
When such a transition is followed, the dispersion state of the colorant does not deteriorate, but conversely, the formation of the shell layer is sweet and the durability is inferior.
When the styrene-hexane solubility index of the polyester resin A is large, it indicates that the solubility of the polyester resin A in the styrene monomer is high. In this case, the compatibility with a binder resin obtained by polymerizing a monomer having a styrene content of 60% by mass or more in the monomer is also high.
Therefore, a part of the used polyester resin A is compatible with the binder resin. Therefore, since the thickness of the shell layer is reduced, the durability is inferior.
In addition, it is preferable that the styrene-hexane solubility index of the polyester resin A is 17.0 or more and 22.0 or less.
The styrene-hexane solubility index of the polyester resin A is most affected by the monomer composition of the polyester resin A.
Moreover, although it is influenced also by the acid value and molecular weight of the polyester resin A, if it does not fluctuate significantly, the influence will be small compared with a monomer composition.
When adjusting a styrene-hexane solubility index with the monomer composition of the polyester resin A, it is good to adjust with the content rate of the isosorbide unit shown by Formula (1) in the polyester resin A. Furthermore, it can also be adjusted by changing the ester concentration of the polyester resin A by using a monomer having a low molecular weight such as ethylene glycol and adjusting the content ratio.

In the present invention, the content of styrene in the monomer containing styrene is 60% by mass or more and 100% by mass or less.
When the styrene content is less than 60% by mass, the correlation between the styrene-hexane solubility index of the polyester resin A and the manifestation of the effect of the present invention decreases, and the shell formation in the toner deviates from the optimum state.
Moreover, since the solubility to the monomer of the isosorbide unit site | part shown by Formula (1) will fall that content of styrene is less than 60 mass%, the part which the polyester resin A is not melt | dissolving in a micro unit generate | occur | produces. To do. As a result, the solubility of the polyester resin A is uneven in the molecule, and the effects of the present invention are hardly exhibited.
The content of styrene in the monomer is preferably 70% by mass or more and 100% by mass or less.

In the present invention, the polyester resin A preferably contains a monomer unit derived from terephthalic acid, and the content ratio of the monomer unit derived from terephthalic acid is 85 on the basis of all dicarboxylic acid monomer units constituting the polyester resin A. It is preferably 0.000 mol% or more and 100.00 mol% or less, more preferably 95.00 mol% or more and 100.00 mol% or less, and even more preferably 100.00 mol%. Here, the monomer unit refers to a form in which the monomer substance in the polymer has reacted.
Terephthalic acid has higher symmetry and linearity as a molecular structure than phthalic acid, isophthalic acid, or aliphatic dicarboxylic acid. By using the terephthalic acid in a high ratio, the orientation of the obtained polyester resin A is increased, and the resulting resin becomes a rigid molecule, thereby forming a stronger shell layer.
In particular, when the content ratio of the monomer unit derived from terephthalic acid is 100.00 mol% based on the total dicarboxylic acid monomer units constituting the polyester resin A, the composition unevenness of the polyester resin A is reduced, so that the strength is further increased. A shell can be formed.
In addition, when the content ratio of the monomer unit derived from terephthalic acid is 100.00 mol%, the π-electron interaction derived from the benzene ring is strongly expressed due to the high orientation of terephthalic acid, and the molecular orientation is more enhanced. Increases durability, improves durability, and excellent chargeability.

In the present invention, the polyester resin A contains an isosorbide unit represented by the formula (1), and the content ratio of the isosorbide unit represented by the formula (1) is based on all monomer units constituting the polyester resin A. It is preferably 0.10 mol% or more and 20.00 mol% or less, more preferably 0.50 mol% or more and 10.00 mol% or less, and further preferably 1.00 mol% or more and 8.00 mol% or less.
This is because the orientation of isosorbide units is very high and the rigidity of the resulting polyester resin A is improved.
When the content ratio of the isosorbide unit represented by the formula (1) in the polyester resin A is less than 0.10 mol% based on the total monomer units constituting the polyester resin A, the rigidity of the resulting polyester resin A is It tends to decrease. On the other hand, when it exceeds 20.00 mol%, the solubility with respect to the monomer containing styrene tends to decrease, the dispersion state of the colorant tends to be disturbed, and the coloring power tends to decrease.

In the present invention, the polyester resin A preferably contains a monomer unit derived from ethylene glycol, and the content ratio of the monomer unit derived from ethylene glycol is based on the total alcohol monomer units constituting the polyester resin A. It is preferably from 00 mol% to 43.00 mol%, more preferably from 15.00 mol% to 43.00 mol%.
When the content ratio of the monomer unit derived from ethylene glycol is in the above range, the resulting polyester resin A not only has rigidity due to the isosorbide unit, but also has flexibility due to the monomer unit derived from ethylene glycol. Excellent.
Furthermore, when a toner is produced in an aqueous medium due to the polar strength of the isosorbide unit and the monomer unit derived from ethylene glycol, the polyester resin A can easily form a shell layer. As a result, the toner resin is excellent in durability and the polarity of the polyester resin A forming the shell layer is moderate.
Further, in the present invention, 1,2-propanediol, 1,2-butanediol, 2,3-butanediol, 2-methyl-1,3-3-is used as the aliphatic diol compound used in the production of the polyester resin A. Propanediol or neopentyl glycol may be used. However, those aliphatic diol compounds having a branched structure in which an alkyl group such as a methyl group is bonded to the carbon atom to which the hydroxyl group is bonded or the adjacent carbon atom are sterically hindered by the branched alkyl group. Cheap. Therefore, it is preferable to use ethylene glycol as the aliphatic diol compound in view of the flexibility of the polyester resin A.
Further, in the case of a diol compound having a linear structure having 3 or more carbon atoms, the flexibility of the polyester resin A tends to be excessive. Therefore, in the present invention, the aliphatic diol used in the polyester resin A preferably contains ethylene glycol.

In this invention, it is preferable that the polyester resin A contains the monomer unit derived from the isosorbide unit shown by Formula (1), and ethylene glycol. The total content of the isosorbide unit represented by the formula (1) and the monomer unit derived from ethylene glycol is 20.00 mol% or more and 60.00 mol% or less based on all alcohol monomer units constituting the polyester resin A. It is preferable. This is because the above-described effects are particularly great, and fog and image density reduction can be suppressed even during long-term use.
This is because among the monomer units constituting the polyester resin A, the isosorbide unit and the monomer unit derived from ethylene glycol are particularly strong in polarity and greatly affect the formation of the shell.
Since the polyester resin A has the above-described configuration, the polyester resin A easily forms a strong shell layer and has an appropriate polarity to have an appropriate hygroscopic property in a high-temperature and high-humidity environment. It is more excellent in terms of durability and chargeability.

Further, when the particles of the monomer composition are formed in an aqueous medium, the molecules of the polyester resin A in the monomer composition are derived from ethylene glycol in addition to the strength of orientation due to the isosorbide unit and the monomer unit derived from terephthalic acid. The monomer unit can give the molecule an appropriate degree of freedom. As a result, the molecules of the polyester resin A are moderately spread in the monomer composition, and the molecular size becomes an appropriate size. Therefore, when the orientation is too strong, the molecular size is reduced, and the solubility with respect to the monomer that functions as a solvent molecule is not too low.
In addition, the degree of molecular freedom is too high and the molecular size becomes too large, and the colorant is not depleted and aggregated. Therefore, while maintaining the toner with a high coloring power, the orientation of the molecules is moderately strong, so that a shell layer having a sufficient strength is formed, and a toner having excellent durability and coloring power can be obtained.
In particular, the polyester resin A has a total content of isosorbide units represented by formula (1) and monomer units derived from ethylene glycol of 20.00 mol% or more based on the total alcohol monomer units constituting the polyester resin A 60 When the content ratio of the monomer units derived from terephthalic acid is 100 mol% based on the total dicarboxylic acid monomer units constituting the polyester resin A, the above-described effect is large and the coloring power of the toner is high. It is preferable because the toner is prevented from being fused and fixed to the developer carrying member or the toner layer regulating member.

In the present invention, the content of the polyester resin A in the toner is 1.0 part by mass or more and 20.0 parts by mass with respect to 100 parts by mass of a resin (that is, a binder resin) formed from a monomer containing styrene. Preferably, it is 1.0 to 15.0 parts by mass, more preferably 1.0 to 10.0 parts by mass.
When the content of the polyester resin A is 1.0 part by mass or more with respect to 100 parts by mass of the binder resin, it is sufficient to form a shell layer on the surface of the toner, and has durability and storage stability. This is preferable. On the other hand, when the amount is 20.0 parts by mass or less, it is easy to maintain the dispersion state of the colorant in the coloring power of the toner, and it is preferable in terms of fixing properties.

In the present invention, when a toner is produced in an aqueous medium, the acid value of the polyester resin A is preferably 1.0 mgKOH / g or more and 30.0 mgKOH / g or less, and 1.0 mgKOH / g or more and 15.0 mgKOH / g. More preferably, it is g or less.
When the acid value of the polyester resin A is 1.0 mgKOH / g or more, since the polyester resin A is distributed on the aqueous phase side, the formation of the shell layer becomes even less uneven in the toner production process. It is preferable in terms of storage stability.
On the other hand, when the acid value of the polyester resin A is 30.0 mgKOH / g or less, since the hygroscopicity of the polyester resin A forming the shell layer does not become excessive, particularly in terms of chargeability in a high temperature and high humidity environment. preferable.

In the present invention, the weight average molecular weight (Mw) of the polyester resin A is preferably 5000 or more and 25000 or less, and more preferably 8000 or more and 20000 or less.
When the weight average molecular weight (Mw) of the polyester resin A is 5000 or more, since the polyester resin A is strong as a molecule, it is preferable in terms of durability.
On the other hand, when the weight average molecular weight (Mw) of the polyester resin A is 25000 or less, neither the solubility point of the polyester resin A nor the molecular size is too large, which is preferable in terms of the coloring power of the toner.

  More preferably, the weight average molecular weight (Mw) of the polyester resin A is 8000 or more and 20000 or less, and the acid value of the polyester resin A is 1.0 mgKOH / g or more and 15.0 mgKOH / g or less. By satisfying the above range, the moderately strong polyester resin A has a moderate polarity and forms a strong shell, so that the toner has excellent storage stability and chargeability.

In the present invention, the glass transition temperature (Tg) of the polyester resin A is preferably 65 ° C. or higher and 85 ° C. or lower, and more preferably 68 ° C. or higher and 80 ° C. or lower.
When the glass transition temperature (Tg) of the polyester resin A is 65 ° C. or higher, the heat resistance is high and the storage stability is preferable. On the other hand, when the glass transition temperature (Tg) of the polyester resin A is 85 ° C. or less, it is preferable in terms of toner fixing properties.

In the present invention, the polyester resin A can be produced by, for example, a method utilizing a dehydration condensation reaction from a carboxylic acid compound and an alcohol compound, or a transesterification reaction. The catalyst may be a general acidic or alkaline catalyst used in the esterification reaction, such as zinc acetate or a titanium compound. Thereafter, it may be highly purified by a recrystallization method, a distillation method or the like.
A preferred production method is a dehydration condensation reaction using a carboxylic acid compound and an alcohol compound because of the diversity of raw materials and the ease of reaction.
Specifically, dehydration condensation of dicarboxylic acid or its anhydride (monomer), isosorbide represented by the following formula (2) and divalent alcohol (monomer) at a reaction temperature of 180 to 260 ° C. in a nitrogen atmosphere. The method of doing is mentioned. Moreover, as long as the effect of this invention is not inhibited, it is also possible to use trifunctional or more polybasic acid or its anhydride, monobasic acid, trivalent or more alcohol, monohydric alcohol, etc. as needed.
Moreover, it is preferable that 43-57 mol% is an alcohol monomer and 57-43 mol% is an acid monomer in all the monomer components.

  The divalent alcohol is not particularly limited, but ethylene glycol, neopentyl glycol, 2-ethyl-1,3-hexanediol, hydrogenated bisphenol A, a bisphenol derivative represented by the following formula (I), or the following formula ( And diols represented by II).

（式中、Ｒはエチレン又はプロピレン基を示し、ｘ及びｙはそれぞれ１以上の整数を示し、かつ、ｘ＋ｙの平均値は２〜１０を示す。）

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

  The dicarboxylic acid is not particularly limited, but phthalic acid, terephthalic acid, isophthalic acid, phthalic anhydride, diphenyl-P · P′-dicarboxylic acid, naphthalene-2,7-dicarboxylic acid, naphthalene-2,6-dicarboxylic acid Benzenedicarboxylic acids or their anhydrides such as, diphenylmethane-P.P'-dicarboxylic acid, benzophenone-4,4'-dicarboxylic acid, 1,2-diphenoxyethane-P.P'-dicarboxylic acid; Alkyl dicarboxylic acids such as adipic acid, sebacic acid, azelaic acid, glutaric acid, cyclohexanedicarboxylic acid, triethylenedicarboxylic acid, malonic acid or their anhydrides; amber substituted with an alkyl or alkenyl group having 6 to 18 carbon atoms Acid or anhydride; fumaric acid, maleic acid, citraconic acid, itacone Unsaturated dicarboxylic acids or their anhydrides such as and the like.

Preferred alcohol monomers are bisphenol derivatives represented by the above formula (I), ethylene glycol. On the other hand, preferable carboxylic acid monomers include terephthalic acid or its anhydride, succinic acid, n-dodecenyl succinic acid or its anhydride, dicarboxylic acid such as fumaric acid, maleic acid and maleic anhydride. Particularly preferred is terephthalic acid.
In the present invention, the polyester resin A can be obtained by synthesizing from a dicarboxylic acid and a diol. However, in some cases, a small amount of a trivalent or higher polycarboxylic acid or polyol is not added so long as the effects of the present invention are not impaired. May be used.
Trivalent or higher polycarboxylic acids include trimellitic acid, pyromellitic acid, cyclohexanetricarboxylic acids, 2,5,7-naphthalenetricarboxylic acid, 1,2,4-naphthalenetricarboxylic acid, 1,2,4-butanetricarboxylic acid Acid, 1,2,5-hexanetricarboxylic acid, 1,3-dicarboxy-2-methylenecarboxypropane, 1,3-dicarboxy-2-methyl-methylenecarboxypropane, tetra (methylenecarboxy) methane, 1,2 , 7,8-octanetetracarboxylic acid and their anhydrides.
Trivalent or higher polyols include sorbitol, 1,2,3,6-hexanetetrol, 1,4-sorbitan, pentaerythritol, dipentaerythritol, tripentaerythritol, sucrose, 1,2,4-butanetriol. Glycerin, 2-methylpropanetriol, 2-methyl-1,2,4-butanetriol, trimethylolethane, trimethylolpropane, and 1,3,5-trihydroxymethylbenzene.
In the present invention, from the viewpoint of efficiently expressing the effect of the polyester resin A, the content of the trivalent or higher polycarboxylic acid is 10.00 mol% or less based on the total acid monomer units constituting the polyester resin A. It is preferable that Similarly, the content ratio of the trivalent or higher polyol is preferably 10.00 mol% or less based on all alcohol monomer units constituting the polyester resin A.

The present invention relates to a toner comprising a step of forming particles of a monomer composition containing a monomer containing styrene, a colorant and polyester resin A in an aqueous medium, and polymerizing the monomer contained in the particles of the monomer composition. It is a manufacturing method.
Hereinafter, although a specific example is given and demonstrated, it is not necessarily limited to these.
First, in the styrene-containing monomer, add the colorant and polyester resin A, and if necessary, wax, charge control agent, cross-linking agent and other additives, and dissolve uniformly with a homogenizer or ultrasonic disperser. Alternatively, the monomer composition is prepared by dispersing.
The obtained monomer composition is dispersed in an aqueous medium containing a dispersion stabilizer by an ordinary stirring means, a homomixer, a homogenizer, or the like to form particles of the monomer composition in the aqueous medium.
At this time, the stirring speed and time are adjusted so that the monomer composition particles (droplets) have a desired toner particle size, and granulation is performed to form the monomer composition particles.
Thereafter, stirring may be performed to such an extent that the particle state is maintained by the action of the dispersion stabilizer and the sedimentation of the particles is prevented.
Then, toner particles are obtained through a process of polymerizing the monomer contained in the particles of the monomer composition.
In the polymerization step, a polymerization initiator may be added. The polymerization temperature may be 40 ° C. or higher, usually 50 to 95 ° C. (preferably 55 to 85 ° C.).
The temperature may be raised in the latter half of the polymerization reaction, and the pH may be changed as necessary. Further, in order to remove unreacted monomers and by-products that cause odors during fixing, the aqueous medium may be partially distilled off in the latter half of the reaction or after the completion of the reaction. After completion of the polymerization reaction, the produced toner particles are washed, collected by filtration, and dried.

The pH in the aqueous medium during the granulation is not particularly limited, but is preferably pH 4.0 to p.
H13.0, more preferably pH 4.0 to pH 7.5, still more preferably pH 4.5 to pH 7.5. By adjusting the pH to the above range, dissolution of the dispersion stabilizer and decomposition of the toner component can be prevented, and stable granulation can be performed. In addition, when granulation is performed in the acidic region, it is possible to suppress an excessive content of the metal derived from the dispersion stabilizer in the toner, and a toner satisfying the provisions of the present invention can be obtained. It becomes easy to be done.
On the other hand, the toner particles are preferably washed at a pH of 3 or less, more preferably at a pH of 1.5 or less. By carrying out the cleaning of the toner particles at the above pH, the dispersion stabilizer present on the surface of the toner particles can be reduced. The acid used for adjusting the pH is not particularly limited, and an inorganic acid such as hydrochloric acid or sulfuric acid can be used.

Examples of the dispersion stabilizer include magnesium phosphate, tricalcium phosphate, aluminum phosphate, zinc phosphate, magnesium carbonate, calcium carbonate, magnesium hydroxide, calcium hydroxide, aluminum hydroxide, calcium metasilicate, calcium sulfate, sulfuric acid Examples include barium and hydroxyapatide.
Further, as the dispersion stabilizer, one containing at least magnesium, calcium, barium, zinc, aluminum, or phosphorus is used, but any of magnesium, calcium, aluminum, or phosphorus is contained. Preferably it is. This is because the adsorptivity with the polyester resin A distributed on the surface of the toner particles and forming the shell layer is strong.
For example, hydroxyapatite is preferable because it has a strong adsorptivity with the polyester resin A that is distributed on the surface of the toner particles and forms a shell layer.
An organic compound such as polyvinyl alcohol, gelatin, methylcellulose, methylhydroxypropylcellulose, ethylcellulose, sodium salt of carboxymethylcellulose, and starch may be used in combination with the dispersion stabilizer.
The dispersion stabilizer is preferably used in an amount of 0.01 to 2.0 parts by mass with respect to 100 parts by mass of the monomer.
Further, in order to make the dispersion stabilizer finer, a surfactant of 0.001% by mass to 0.1% by mass may be used in combination. Specifically, commercially available nonionic, anionic and cationic surfactants can be used. For example, sodium dodecyl sulfate, sodium tetradecyl sulfate, sodium pentadecyl sulfate, sodium octyl sulfate, sodium tetradecyl sulfate, sodium pentadecyl sulfate, sodium octyl sulfate, sodium oleate, sodium laurate, potassium stearate, and calcium oleate are preferably used. .

Examples of the stirring means used when forming the particles of the monomer composition in an aqueous medium include a paddle blade, an inclined paddle blade, three receding blades, an anchor blade, a full zone (made by Shinko Pantech), Max. What has stirring blades, such as a blend (made by Sumitomo Heavy Industries), a super mix (made by Satake Chemical Machinery Co., Ltd.), and a Hi-F mixer (made by Soken Chemical Co., Ltd.), can be used.
Moreover, the stirring means which can provide a high shearing force and can achieve uniform circulation is more preferable. As the high shear stirrer, one having a stirring chamber formed by a stirring rotor rotating at high speed and a screen provided so as to surround the stirring rotor is preferably used. Specific examples include Ultra Thalax (manufactured by IKA), Polytron (manufactured by Kinematica), TK auto homomixer (manufactured by Special Machine Industries), Claremix (manufactured by Mtechnics), and the like.

In the present invention, the monomer contains 60% by mass or more of styrene in the monomer.
In addition to styrene, a vinyl monomer capable of radical polymerization can be used as the monomer.
Examples of the vinyl monomer include monofunctional monomers and polyfunctional monomers.
Monofunctional monomers include α-methylstyrene, β-methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, 2,4-dimethylstyrene, pn-butylstyrene, p-tert- Like butyl styrene, pn-hexyl styrene, pn-octyl styrene, pn-nonyl styrene, pn-decyl styrene, pn-dodecyl styrene, p-methoxy styrene, and p-phenyl styrene Styrene derivatives; methyl acrylate, ethyl acrylate, n-propyl acrylate, iso-propyl acrylate, n-butyl acrylate, iso-butyl acrylate, tert-butyl acrylate, n-amyl acrylate, n-hexyl acrylate, 2-ethylhexyl acrylate, n-o Acrylic monomers such as til acrylate, n-nonyl acrylate, cyclohexyl acrylate, benzyl acrylate, dimethyl phosphate ethyl acrylate, diethyl phosphate ethyl acrylate, dibutyl phosphate ethyl acrylate, and 2-benzoyloxyethyl acrylate; methyl methacrylate, ethyl Methacrylate, n-propyl methacrylate, iso-propyl methacrylate, n-butyl methacrylate, iso-butyl methacrylate, tert-butyl methacrylate, n-amyl methacrylate, n-hexyl methacrylate, 2-ethylhexyl methacrylate, n-octyl methacrylate, n-nonyl Methacrylate, diethyl phosphate ethyl methacrylate And methacrylic monomers such as dibutyl phosphate ethyl methacrylate; methylene aliphatic monocarboxylic acid esters; vinyl esters such as vinyl acetate, vinyl propionate, vinyl butyrate, vinyl benzoate, and vinyl formate; vinyl methyl ether, vinyl ethyl And ethers and vinyl ethers such as vinyl isobutyl ether; vinyl ketones such as vinyl methyl ketone, vinyl hexyl ketone, and vinyl isopropyl ketone.
As polyfunctional monomers, diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, polyethylene glycol diacrylate, 1,6-hexanediol diacrylate, neopentyl glycol diacrylate, tripropylene glycol diacrylate, polypropylene Glycol diacrylate, 2,2'-bis (4- (acryloxy-diethoxy) phenyl) propane, trimethylolpropane triacrylate, tetramethylolmethane tetraacrylate, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, tetra Ethylene glycol dimethacrylate, polyethylene glycol dimethyl Tacrylate, 1,3-butylene glycol dimethacrylate, 1,6-hexanediol dimethacrylate, neopentyl glycol dimethacrylate, polypropylene glycol dimethacrylate, 2,2′-bis (4- (methacryloxy-diethoxy) phenyl) propane, 2 2,2'-bis (4- (methacryloxy-polyethoxy) phenyl) propane, trimethylolpropane trimethacrylate, tetramethylolmethane tetramethacrylate, divinylbenzene, divinylnaphthalene, and divinyl ether.
In the present invention, in addition to styrene, the above monofunctional monomers can be used alone or in combination of two or more, or the above monofunctional monomers and polyfunctional monomers can be used in combination.
The monomer used in addition to styrene is preferably a styrene derivative, an acrylic acid ester monomer such as n-butyl acrylate or 2-ethylhexyl acrylate, or a methacrylic acid ester monomer such as n-butyl methacrylate or 2-ethylhexyl methacrylate. . By using the monomer, the obtained binder resin is excellent in strength and flexibility.

The following are mentioned as said polymerization initiator.
2,2′-azobis- (2,4-dimethylvaleronitrile), 2,2′-azobisisobutyronitrile, 1,1′-azobis (cyclohexane-1-carbonitrile), 2,2
Azo or diazo polymerization initiators such as' -azobis-4-methoxy-2,4-dimethylvaleronitrile and azobisisobutyronitrile; benzoyl peroxide, methyl ethyl ketone peroxide, diisopropyl peroxycarbonate, cumene hydroperoxide , Peroxide-based polymerization initiators such as 2,4-dichlorobenzoyl peroxide and lauroyl peroxide. You may use the said polymerization initiator individually or in combination of 2 or more types. Moreover, it is preferable that the addition amount of a polymerization initiator is 0.5 to 20 mass parts with respect to 100 mass parts of monomers.

The melting point of at least one wax added as necessary is preferably 30 ° C. or higher and 120 ° C. or lower, more preferably 50 ° C. or higher and 100 ° C. or lower. Further, it is preferably a wax that is solid at room temperature. Further, a solid wax having a melting point of 50 ° C. or higher and 100 ° C. or lower is preferable from the viewpoint of toner blocking resistance, multi-sheet durability, low-temperature fixability, and offset resistance.
Examples of the wax include hydrocarbon waxes such as paraffin wax, polyolefin wax, microcrystalline wax and Fischer-Tropsch wax; petroleum waxes such as amide wax and petrolatum and derivatives thereof; montan wax and derivatives thereof; carnauba wax and candelilla Natural waxes such as waxes and derivatives thereof; hydrogenated castor oil and derivatives thereof; plant waxes, animal waxes, higher fatty acids, long chain alcohols, ester waxes, ketone waxes and derivatives thereof such as graft compounds or block compounds are known Wax can be used. These can be used alone or in combination.
The addition amount of the wax is preferably 3 parts by mass or more and 30 parts by mass or less, more preferably 3 parts by mass or more and 20 parts by mass or less, and more preferably 4 parts by mass or more and 15 parts by mass with respect to 100 parts by mass of the monomer. More preferably, it is at most parts.
When the addition amount of the wax is within the above range, the effect of preventing offset and the anti-blocking effect is excellent, and toner drum fusion and toner development sleeve fusion are less likely to occur.

In the present invention, when a hydrocarbon wax is used as the wax, the effect of preventing offset and the anti-blocking effect is excellent, and toner drum fusion and toner development sleeve fusion are less likely to occur.
This suggests that the poor solvent used for the measurement of the styrene-hexane solubility index of the polyester resin A is n-hexane, which is a hydrocarbon, and therefore compatibility with the hydrocarbon wax which is the same hydrocarbon. It is to become.
When the polyester resin A has a styrene-hexane solubility index of 15.0 or more and 27.0 or less, it has a phase separation property that can prevent the hydrocarbon wax from being exposed from the toner surface, and the wax stains at the time of fixing. This is because the polyester resin A has an affinity for the hydrocarbon wax to such an extent that it does not hinder the removal.
Further, DSC-2920 manufactured by TA Instruments Japan is used for measuring the melting point of the wax.
The glass transition temperature is a temperature at a point where a straight line equidistant in the vertical axis direction from a straight line extended from each baseline at the time of measurement and a curve of a step-like change portion of the glass transition intersect.
The melting point is the peak temperature of the maximum endothermic peak measured at the time of temperature rise in the temperature range of 20 ° C. or more and 200 ° C. or less.

As the charge control agent, known charge control agents used for toners can be used.
The addition amount of the charge control agent is preferably 0.01 parts by mass or more and 20 parts by mass or less, and more preferably 0.5 parts by mass or more and 10 parts by mass or less with respect to 100 parts by mass of the monomer.

In the present invention, the colorant is not particularly limited, and a known colorant used for toner can be used. Specific examples are given below.
As a pigment used for a cyan colorant, a copper phthalocyanine compound and a derivative thereof, an anthraquinone compound, and a basic dye lake compound can be used. Specific examples include the following. C. I. Pigment blue 15, C.I. I. Pigment blue 15: 1, C.I. I. Pigment blue 15: 2, C.I. I. Pigment blue 15: 3 and C.I. I. Pigment Blue 15: 4.
As the pigment used for the magenta colorant, condensed azo compounds, diketopyrrolopyrrole compounds, anthraquinone compounds, quinacridone compounds, basic dye lake compounds, naphthol compounds, benzimidazolone compounds, thioindigo compounds and perylene compounds can be used. Specific examples include the following. C. I. Pigment violet 19, C.I. I. Pigment red 31, C.I. I. Pigment red 32, C.I. I. Pigment red 122, C.I. I. Pigment red 150, C.I. I. Pigment red 254, C.I. I. Pigment red 264 and C.I. I. Pigment Red 269.
As the pigment used for the yellow colorant, condensed azo compounds, isoindolinone compounds, anthraquinone compounds, azo metal complexes, methine compounds, and allylamide compounds can be used. Specific examples include the following. C. I. Pigment yellow 74, C.I. I. Pigment yellow 93, C.I. I. Pigment yellow 120, C.I. I. Pigment yellow 139, C.I. I. Pigment yellow 151, C.I. I. Pigment yellow 155, C.I. I. Pigment yellow 180 and C.I. I. Pigment Yellow 185.
As the black colorant, carbon black, a magnetic material, and a color tone adjusted to black using the yellow, magenta, and cyan colorants can be used.
Among these, carbon black, C.I. I. Pigment blue 15: 3, C.I. I. Pigment red 122, C.I. I. Pigment red 150, C.I. I. Pigment red 32, C.I. I. Pigment red 269, C.I. I. Pigment yellow 155, C.I. I. Pigment yellow 93, C.I. I. Pigment yellow 74, C.I. I. Pigment yellow 180 and C.I. I. Pigment Yellow 185 is preferable because the effect of the present invention is high.
The reason is not clear, but it seems to be due to its high affinity with isosorbide units.
In particular, in the case of carbon black, the pH is preferably 6 or more and the oil absorption (DBP) is preferably 30 (cc / 100 g) or more and 120 (cc / 100 g) or less.
The amount of the colorant added is preferably 1 part by mass or more and 20 parts by mass or less with respect to 100 parts by mass of the monomer.

In the present invention, various known inorganic and organic additives can be used for the purpose of imparting various properties within a range that does not impair the effects of the present invention.
The additive used preferably has a particle size of 3/10 or less of the weight average particle size (D4) of the toner from the viewpoint of durability when added to the toner. The particle diameter of the additive means the number average particle diameter obtained by observing the surface of the toner with a scanning electron microscope.
The additive may be internally added to the toner or may be contained in the toner as an external additive.
When it is contained as an external additive, inorganic fine particles such as silica fine particles, titanium oxide fine particles, and aluminum oxide fine particles are preferable.
The inorganic fine particles may be subjected to a hydrophobic treatment. As a method for the hydrophobization treatment, various coupling agents such as a silane coupling agent or a titanium coupling agent can be used, but it is preferable to increase the degree of hydrophobicity with silicone oil. This is because moisture adsorption of inorganic fine particles under high humidity can be suppressed, and furthermore, contamination of the regulating member and charging member can be suppressed, so that a high-quality image can be obtained.
The content of the additive is preferably 0.01 parts by mass or more and 5 parts by mass or less, and more preferably 0.02 parts by mass or more and 3 parts by mass or less with respect to 100 parts by mass of the toner.
The additives may be used alone or in combination.

In the present invention, the weight average particle diameter (D4) of the toner is preferably 4.0 μm or more and 12.0 μm or less, and more preferably 4.0 μm or more and 9.0 μm or less.
When the weight average particle diameter (D4) of the toner is in the above range, the specific surface area of the toner is appropriate, and problems with durability and heat resistance are less likely to occur during long-term use. Also excellent.

Hereinafter, methods for measuring various physical properties of toner and raw materials will be described.
<PH measurement of aqueous medium>
One minute before introducing the monomer composition into the aqueous medium, 1.0 liter of the aqueous medium is collected, and the pH meter is immersed in the aqueous medium within 30 seconds. Then, a value 60 seconds after the pH meter is immersed in the aqueous medium is recorded. It is also confirmed that the temperature at the time of measurement is not lower by 2 ° C. or more than the temperature of the aqueous medium at the time of collection. The pH meter used was Yokogawa Electric Corporation HA406. The pH meter calibrates the temperature and pH value in advance according to the manual.

<Structural analysis of polyester resin A and binder resin>
The structure of the polyester resin A and the binder resin is determined using a nuclear magnetic resonance apparatus ( ¹ H-NMR, ¹³ C-NMR) and an FT-IR spectrum. The apparatus used below will be described.
Each resin sample may be collected from the toner and analyzed.
(I) ¹ H-NMR, ¹³ C-NMR
FT-NMR JNM-EX400 manufactured by JEOL (solvent: heavy chloroform)
(Ii) FT-IR spectrum Thermo Fisher Scientific Inc. Made AVATAR360FT-IR

<Measurement of styrene-hexane solubility index>
The styrene-hexane solubility index defined in the present invention is the hexane in which the polyester resin A component starts to precipitate when the poor resin hexane is added to the polyester resin A dissolved in the good solvent styrene. It is specified by the added amount of
In the toner manufacturing method of the present invention, the proportion of styrene contained in the monomer is 60% by mass or more and a large amount of styrene is contained. Therefore, the polymerization reaction proceeds from a state in which the polyester resin A is dissolved in a monomer containing a large amount of styrene, and the monomer containing styrene decreases with the progress of the polymerization reaction.
Adding hexane to the styrene solution of polyester resin A means that the proportion of styrene in the styrene solution of polyester resin A decreases. That is, the method for measuring the styrene-hexane solubility index reproduces the decrease in the monomer containing styrene that occurs when the polymerization reaction actually proceeds.
Therefore, the smaller the styrene-hexane solubility index, the more the polyester resin A is precipitated at the initial stage of the polymerization reaction.
Further, by using hexane, which is a nonpolar solvent, in this measurement, the polyester resin A having higher polarity is precipitated at a stage where the amount of hexane added is smaller. Therefore, the smaller the styrene-hexane solubility index is, the more the polyester resin A precipitated with the progress of the polymerization reaction is present on the toner surface layer side on the water phase side.

(Sample preparation)
A styrene solution (liquid temperature 25 ° C.) in which 4.0 parts by mass of polyester resin A is dissolved in 100.0 parts by mass of styrene is prepared. The resin is dissolved and left for 12 hours or more but less than 24 hours, and is filtered with a sample processing filter (pore size 0.45 μm) to separate styrene insolubles, and the filtrate is used as a measurement sample.
(Measuring method)
As a measuring apparatus, a powder wettability tester (WET-101P) manufactured by Reska Co., Ltd. is used.
The styrene-hexane solubility index is determined from the obtained n-hexane dropping transmittance curve by placing the prepared measurement sample in a tall beaker container and using n-hexane as a dropping reagent.
The tall beaker is made of glass with a diameter of 5 cm and a thickness of 1.75 mm. As a stirrer, a magnetic stirrer having a spindle shape of 25 mm in length and a maximum diameter of 8 mm and coated with a fluororesin is used. Using.
The specific measurement operation is as follows.
While stirring the sample for measurement at a speed of 280 to 300 rpm, n-hexane was continuously added at a dropping rate of 0.8 ml / min, the transmittance was measured with light having a wavelength of 780 nm, and the n-hexane dropping transmittance was measured. Create a curve.
From the obtained n-hexane dropping transmittance curve, the n-hexane concentration (volume%) at the time when the light transmittance is 50% is defined as the styrene-hexane solubility index of the polyester resin A.
An example of the n-hexane dropping transmittance curve is shown in FIG.

<Measurement of acid value of polyester resin A>
The acid value is the number of mg of potassium hydroxide necessary for neutralizing the acid contained in 1 g of the sample. The acid value in the present invention is measured according to JIS K 0070-1992. Specifically, it is measured according to the following procedure.
Titration is performed using a 0.1 mol / L potassium hydroxide ethyl alcohol solution (manufactured by Kishida Chemical Co., Ltd.). The factor of the potassium hydroxide ethyl alcohol solution is determined using a potentiometric titrator (potentiometric titrator AT-510 manufactured by Kyoto Electronics Industry Co., Ltd.).
Specifically, 100 mL of 0.100 mol / L hydrochloric acid is placed in a 250 mL tall beaker, titrated with a potassium hydroxide ethyl alcohol solution, and obtained from the amount of potassium hydroxide ethyl alcohol solution required for neutralization. As 0.100 mol / L hydrochloric acid, one prepared according to JIS K 8001-1998 is used.
The measurement conditions for the acid value measurement are shown below.
Titration device: potentiometric titration device AT-510 (manufactured by Kyoto Electronics Industry Co., Ltd.)
Electrode: Composite glass electrode double junction type (manufactured by Kyoto Electronics Industry Co., Ltd.)
Titrator control software: AT-WIN
Titration analysis software: Tview
The titration parameters and control parameters at the time of titration are as follows.
<Titration parameter>
Titration mode: Blank titration Titration style: Total titration Maximum titration: 20 mL
Waiting time before titration: 30 seconds Titration direction: Automatic <Control parameters>
End point determination potential: 30 dE
End point determination potential value: 50 dE / dmL
End point detection judgment: Not set Control speed mode: Standard gain: 1
Data collection potential: 4 mV
Data collection titration: 0.1 mL
<Main test>
0.100 g of the measurement sample is precisely weighed in a 250 mL tall beaker, and 150 mL of a mixed solution of toluene and ethanol (3: 1) is added and dissolved over 1 hour. Titrate with a potassium hydroxide ethyl alcohol solution using a potentiometric titrator.
<Blank test>
Titration is performed in the same manner as described above, except that no sample is used (that is, only a mixed solution of toluene and ethanol (3: 1) is used).
The acid value is calculated by substituting the obtained result into the following formula.
A = [(C−B) × f × 5.61] / S
Here, A: acid value (mgKOH / g), B: addition amount (mL) of potassium hydroxide ethyl alcohol solution in blank test, C: addition amount (mL) of potassium hydroxide ethyl alcohol solution in final test, f : Factor of potassium hydroxide ethyl alcohol solution, S: Sample (g).

<Measurement of hydroxyl value of polyester resin A>
The hydroxyl value is the number of mg of potassium hydroxide required to neutralize acetic acid bonded to a hydroxyl group when 1 g of a sample is acetylated. The hydroxyl value in the present invention is measured according to JIS K 0070-1992. Specifically, it is measured according to the following procedure.
Add 25.0 g of special grade acetic anhydride to a 100 mL volumetric flask, add pyridine to bring the total volume to 100 mL, and shake well to obtain an acetylating reagent. The obtained acetylating reagent is stored in a brown bottle so as not to come into contact with moisture, carbon dioxide gas and the like.
Titration is performed using a 1.0 mol / L potassium hydroxide ethyl alcohol solution (manufactured by Kishida Chemical Co., Ltd.). The factor of the potassium hydroxide ethyl alcohol solution is determined using a potentiometric titrator (potentiometric titrator AT-510 manufactured by Kyoto Electronics Co., Ltd.). Specifically, 100 mL of 1.00 mol / L hydrochloric acid is placed in a 250 mL tall beaker, titrated with a potassium hydroxide ethyl alcohol solution, and obtained from the amount of potassium hydroxide ethyl alcohol solution required for neutralization. As 1.00 mol / L hydrochloric acid, one prepared according to JIS K 8001-1998 is used.
The measurement conditions for the hydroxyl value measurement are shown below.
Titration device: potentiometric titration device AT-510 (manufactured by Kyoto Electronics Industry Co., Ltd.)
Electrode: Composite glass electrode double junction type (manufactured by Kyoto Electronics Industry Co., Ltd.)
Titrator control software: AT-WIN
Titration analysis software: Tview
The titration parameters and control parameters at the time of titration are as follows.
<Titration parameter>
Titration mode: Blank titration Titration style: Total titration Maximum titration: 80 mL
Waiting time before titration: 30 seconds Titration direction: Automatic <Control parameters>
End point determination potential: 30 dE
End point determination potential value: 50 dE / dmL
End point detection judgment: Not set Control speed mode: Standard gain: 1
Data collection potential: 4 mV
Data collection titration: 0.5 mL
<Main test>
2.00 g of a measurement sample is precisely weighed in a 200 mL round bottom flask, and 5.00 mL of the acetylating reagent is accurately added to the sample using a whole pipette. At this time, if the sample is difficult to dissolve in the acetylating reagent, a small amount of special grade toluene is added and dissolved.
Place a small funnel in the mouth of the flask and immerse 1 cm of the bottom of the flask in a 97 ° C. glycerin bath and heat. At this time, in order to prevent the temperature of the neck of the flask from rising due to the heat of the bath, it is preferable to cover the base of the neck of the flask with a cardboard having a round hole.
After 1 hour, the flask is removed from the glycerin bath and allowed to cool. After standing to cool, 1.00 mL of water is added from the funnel and shaken to hydrolyze acetic anhydride. The flask is again heated in the glycerin bath for 10 minutes for further complete hydrolysis. After cooling, wash the funnel and flask walls with 5.00 mL of ethyl alcohol.
The obtained sample is transferred to a 250 mL tall beaker, and 100 mL of a mixed solution of toluene and ethanol (3: 1) is added and dissolved over 1 hour. Titrate with a potassium hydroxide ethyl alcohol solution using a potentiometric titrator.
<Blank test>
Titration is performed in the same manner as described above, except that no sample is used (that is, only a mixed solution of toluene and ethanol (3: 1) is used).
The obtained results are substituted into the following formula to calculate the hydroxyl value.
A = [{(BC) × 28.05 × f} / S] + D
Here, A: hydroxyl value (mgKOH / g), B: addition amount (mL) of potassium hydroxide ethyl alcohol solution in blank test, C: addition amount (mL) of potassium hydroxide ethyl alcohol solution in final test, f : Factor of potassium hydroxide ethyl alcohol solution, S: Sample (g), D: Acid value of resin (mgKOH / g).

<Measurement of Weight Average Molecular Weight (Mw) and Number Average Molecular Weight (Mn) of Resin such as Polyester Resin A>
The weight average molecular weight (Mw) and number average molecular weight (Mn) of a resin such as polyester resin A are calculated in terms of polystyrene using gel permeation chromatography (GPC).
When measuring the molecular weight of a resin having an acid group, the column elution rate also depends on the amount of the acid group, so a sample with an acid group capped in advance is prepared.
Methyl esterification is preferable for capping, and a commercially available methyl esterifying agent can be used. Specifically, a method of treating with trimethylsilyldiazomethane is used.
The molecular weight is measured by GPC as follows.
First, a measurement sample is dissolved in tetrahydrofuran (THF) at room temperature for 24 hours. Then, the obtained solution is filtered through a solvent-resistant membrane filter “Mysholy disk” (manufactured by Tosoh Corporation) having a pore diameter of 0.2 μm to obtain a sample solution.
The sample solution is adjusted so that the concentration of the component soluble in THF is 0.8% by mass. Using this sample solution, measurement is performed under the following conditions.
Apparatus: HLC8120 GPC (detector: RI) (manufactured by Tosoh Corporation)
Column: Seven series of Shodex KF-801, 802, 803, 804, 805, 806, 807 (manufactured by Showa Denko KK)
Eluent: Tetrahydrofuran (THF)
Flow rate: 1.0 mL / min
Oven temperature: 40.0 ° C
Sample injection volume: 0.10 mL
In calculating the molecular weight of the measurement sample, the molecular weight distribution of the sample is calculated from the relationship between the logarithmic value of the calibration curve prepared from several monodisperse polystyrene standard samples and the number of counts.
Standard polystyrene samples for preparing calibration curves are trade names “TSK Standard Polystyrene F-850, F-450, F-288, F-128, F-80, F-40, F-20, F-” manufactured by Tosoh Corporation. 10, F-4, F-2, F-1, A-5000, A-2500, A-1000, A-500 ".

<Measurement of Weight Average Particle Size (D4) and Number Average Particle Size (D1) of Toner>
The weight average particle diameter (D4) and number average particle diameter (D1) of the toner are calculated as follows.
As a measuring device, a precise particle size distribution measuring device “Coulter Counter Multisizer 3” (registered trademark, manufactured by Beckman Coulter, Inc.) using a pore electrical resistance method equipped with a 100 μm aperture tube is used.
For setting the measurement conditions and analyzing the measurement data, the attached dedicated software “Beckman Coulter Multisizer 3 Version 3.51” (manufactured by Beckman Coulter, Inc.) is used. The measurement is performed with 25,000 effective measurement channels.
As the electrolytic aqueous solution used for the measurement, special grade sodium chloride is dissolved in ion-exchanged water so as to have a concentration of 1% by mass, for example, “ISOTON II” (manufactured by Beckman Coulter, Inc.).
Prior to measurement and analysis, the dedicated software is set as follows.
On the “Change Standard Measurement Method (SOM)” screen of the dedicated software, set the total count in the control mode to 50000 particles, set the number of measurements once, and set the Kd value to “standard particles 10.0 μm” (Beckman Coulter, Inc.) Set the value obtained using By pressing the “Threshold / Noise Level Measurement Button”, the threshold and noise level are automatically set. In addition, the current is set to 1600 μA, the gain is set to 2, the electrolytic aqueous solution is set to ISOTON II, and the “aperture tube flush after measurement” is checked. In the “Pulse to particle size conversion setting” screen of the dedicated software, the bin interval is set to logarithmic particle size, the particle size bin to 256 particle size bin, and the particle size range from 2 μm to 60 μm.
The specific measurement method is as follows.
(1) Put 200 mL of the aqueous electrolytic solution into a 250 mL round bottom beaker made exclusively for Multisizer 3, set it on a sample stand, and stir the stirrer rod counterclockwise at 24 rpm. Then, the dirt and bubbles in the aperture tube are removed by the “aperture flush” function of the dedicated software.
(2) Put 30 mL of the electrolytic aqueous solution into a glass 100 mL flat bottom beaker. In this, "Contaminone N" (nonionic surfactant, anionic surfactant, 10% by weight aqueous solution of neutral detergent for pH7 precision measuring instrument cleaning, made by organic builder, manufactured by Wako Pure Chemical Industries, Ltd. 0.3 mL of a diluted solution obtained by diluting 3) with ion-exchanged water.
(3) Two oscillators with an oscillation frequency of 50 kHz are incorporated with the phase shifted by 180 degrees, and an ultrasonic disperser “Ultrasonic Dispersion System Tetora 150” (manufactured by Nikka Ki Bios) having an electrical output of 120 W is prepared. Put 3.3 L of ion exchange water in the water tank of the ultrasonic disperser, and add 2 mL of Contaminone N into this water tank. (4) The beaker of (2) is set in the beaker fixing hole of the ultrasonic disperser, and the ultrasonic disperser is operated. And the height position of a beaker is adjusted so that the resonance state of the liquid level of the electrolyte solution in a beaker may become the maximum.
(5) In a state where the electrolytic aqueous solution in the beaker of (4) is irradiated with ultrasonic waves, 10 mg of toner is added to the electrolytic aqueous solution little by little and dispersed. Then, the ultrasonic dispersion process is continued for another 60 seconds. In ultrasonic dispersion, the temperature of the water tank is appropriately adjusted so as to be 10 ° C. or higher and 40 ° C. or lower.
(6) To the round bottom beaker (1) installed in the sample stand, the electrolytic aqueous solution (5) in which the toner is dispersed is dropped using a pipette, and the measurement concentration is adjusted to 5%. Measurement is performed until the number of measured particles reaches 50,000.
(7) The measurement data is analyzed with the dedicated software attached to the apparatus, and the weight average particle diameter (D4) and the number average particle diameter (D1) are calculated. The “average diameter” on the “analysis / volume statistics (arithmetic average)” screen when the graph / volume% is set with the dedicated software is the weight average particle size (D4), and the graph / When the number% is set, the “average diameter” on the “analysis / number statistics (arithmetic average)” screen is the number average particle diameter (D1).

<Measurement of Glass Transition Temperature (Tg) of Toner and Resin>
The glass transition temperature of the toner and each resin is measured in accordance with ASTM D3418-82 using a differential scanning calorimeter “Q1000” (manufactured by TA Instruments).
The temperature correction of the device detection unit uses the melting points of indium and zinc, and the correction of heat uses the heat of fusion of indium.
Specifically, 3 mg of a measurement sample is precisely weighed, placed in an aluminum pan, an empty aluminum pan is used as a control, equilibrated at 20 ° C. for 5 minutes, and then a measurement range of 20 ° C. to 140 ° C. The measurement is performed at a heating rate of 1 ° C./min with a modulation of 1.0 ° C./min. The glass transition temperature is a temperature at a point where a straight line equidistant in the vertical axis direction from a straight line extended from each baseline at the time of measurement and a curve of a step-like change portion of the glass transition intersect.

  Hereinafter, the present invention will be described in more detail with reference to specific production methods, examples, and comparative examples, but this does not limit the present invention in any way. In addition, parts and% in the following formulations are all based on mass unless otherwise specified.

<Example of production of polyester resin A1>
Terephthalic acid: 29.9 parts by mass Bisphenol A-propylene oxide 2 mol adduct: 48.5 parts by mass Isosorbide: 1.2 parts by mass Ethylene glycol: 4.5 parts by mass Tetrabutoxy titanate: 0.125 parts by mass The above materials were charged into an autoclave equipped with a water separator, a nitrogen gas introducing device, a temperature measuring device, and a stirring device, and reacted at 200 ° C. for 5 hours under a nitrogen atmosphere.
Thereafter, 2.1 parts by mass of trimellitic acid and 0.120 parts by mass of tetrabutoxy titanate were added, reacted at 220 ° C. for 3 hours, and further reacted under reduced pressure of 10-20 mmHg for 2 hours to obtain polyester resin A1. . The physical properties of the obtained polyester resin A are shown in Table 2.
The composition of the obtained polyester resin A was a composition according to the preparation amount shown in Table 1.

<Production Example of Polyester Resin A2-41>
The same operations as for the polyester resin A1 were performed at the raw material monomer charge amounts shown in Table 1 to produce polyester resins A2 to 41. Table 2 shows the physical properties of the obtained polyester resin A.

表中の略号の意味は以下の通り。
ＴＰＡ：テレフタル酸
ＩＰＡ：イソフタル酸
ＴＭＡ：トリメリット酸
ＢＰＡ（ＰＯ）：ビスフェノールＡプロピレンオキサイド２モル付加物
ＥＧ：エチレングリコール
１，２−ＰＧ：１，２−プロピレングリコール
１，３−ＰＧ：１，３−プロピレングリコール
Ａ：ポリエステル樹脂Ａを構成する全ジカルボン酸モノマー中のＴＰＡのｍｏｌ％
Ｂ：ポリエステル樹脂Ａを構成する全モノマー中のイソソルビドのｍｏｌ％
Ｃ：ポリエステル樹脂Ａを構成する全アルコールモノマー中のＥＧのｍｏｌ％
Ｄ：ポリエステル樹脂Ａを構成する全アルコールモノマー中の（ＥＧ＋イソソルビド）のｍｏｌ％

The meanings of the abbreviations in the table are as follows.
TPA: terephthalic acid IPA: isophthalic acid TMA: trimellitic acid BPA (PO): bisphenol A propylene oxide 2 molar adduct EG: ethylene glycol 1,2-PG: 1,2-propylene glycol 1,3-PG: 1, 3-propylene glycol A: mol% of TPA in all dicarboxylic acid monomers constituting polyester resin A
B: mol% of isosorbide in all monomers constituting polyester resin A
C: mol% of EG in all alcohol monomers constituting polyester resin A
D: mol% of (EG + isosorbide) in all alcohol monomers constituting polyester resin A

<Production example of charge control resin 1 having a sulfonic acid group, a sulfonic acid group, or a sulfonic acid ester group>
Toluene 1 was added to a 2 L flask equipped with a stirrer, condenser, thermometer, and nitrogen inlet tube.
00 parts, 350 parts of methanol, 470 parts of styrene, 40 parts of 2-acrylamido-2-methylpropanesulfonic acid, 70 parts of 2-ethylhexyl acrylate, 20 parts of benzyl methacrylate, 10 parts of lauryl peroxide, stirring, nitrogen Solution polymerization was carried out at 65 ° C. for 10 hours under the introduction. After completion of the reaction, the contents were taken out from the flask, washed with isopropyl alcohol, and dried under reduced pressure at 40 ° C. for 96 hours. Thereafter, the mixture was roughly crushed with a hammer mill, and the crushed material was further dried under reduced pressure at 40 ° C. for 48 hours to produce the charge control resin 1.
The physical properties of the obtained charge control resin 1 were Mw = 24000, Tg = 67 ° C., and residual monomer = 350 ppm.
In addition, the acid value of the obtained charge control resin 1 was 20 mgKOH / g.

<Production Example of Hydrophobic Silica Fine Particle 1>
Hydrophobic silica fine particles 1 were obtained by treating 100 parts of silica (AEROSIL 200CF, manufactured by Nippon Aerosil Co., Ltd.) with 10 parts of hexamethyldisilazane and further with 20 parts of dimethyl silicone oil. The number average particle diameter of primary particles of the hydrophobic silica fine particles 1 was 12 nm.

<Example of production of hydrophobic titanium oxide fine particles 1>
100 parts of titanium oxide (P25, manufactured by Nippon Aerosil Co., Ltd.) was treated with 20 parts of γ-mercaptopropyltrimethoxysilane in toluene, filtered and dried to obtain hydrophobic titanium oxide fine particles 1. The number average particle diameter of the primary particles of the hydrophobic titanium oxide fine particles 1 was 25 nm.

<Toner Production Example 1>
To 1000 parts by mass of ion-exchanged water in the reaction vessel, 14 parts by mass of sodium phosphate and 4.5 parts by mass of 10% hydrochloric acid were added and kept at 65 ° C. for 60 minutes while purging with nitrogen. Using a TK homomixer (manufactured by Tokushu Kika Kogyo Co., Ltd.), while stirring at 12,000 rpm, an aqueous solution of calcium chloride in which 8 parts by mass of calcium chloride is dissolved in 10 parts by mass of ion-exchanged water is added all at once. An aqueous medium containing was prepared. The prepared aqueous medium had a pH of 5.5.

(Monomer composition)
-60.0 parts by mass of styrene-7.0 parts by mass of carbon black (manufactured by Orion Engineered Carbons, trade name "Printex35")
Charge control agent (Orient Corporation: Bontron E-89) 0.25 part by mass The above material was charged into an attritor dispersing machine (Mitsui Miike Chemical Co., Ltd.), and further using zirconia particles having a diameter of 1.7 mm, After dispersing at 220 rpm for 5 hours, the zirconia particles were removed to obtain a colorant dispersion.
The following materials were added to the colorant dispersion to prepare a mixed solution.
Styrene 20.0 parts by mass n-butyl acrylate 20.0 parts by mass Polyester resin A1 5.0 parts by mass Charge control resin 1 0.3 parts by mass Fischer-Tropsch wax 9.0 parts by mass (Schumannsazol Product name “C80”: melting point 83.0 ° C.)
The above mixed solution was kept at 65 ° C. in a separate container and stirred at 500 rpm using a TK homomixer (manufactured by Tokushu Kika Kogyo) to uniformly dissolve or disperse each material.
In this, 2.5 parts by mass of a polymerization initiator t-hexyl peroxypivalate (manufactured by NOF Corporation, trade name “Perhexyl PV”, molecular weight: 202, 10 hour half-life temperature: 53.2 ° C.) are dissolved, A monomer composition was prepared.
The monomer composition is charged into the aqueous medium, and TK is purged at 65 ° C. under a nitrogen purge.
The mixture was stirred at 10000 rpm for 5 minutes using a type homomixer (manufactured by Tokushu Kika Kogyo Co., Ltd.) to form particles of the monomer composition at pH 5.5.
Thereafter, while stirring with a paddle stirring blade, the temperature was raised to 65 ° C. for 6 hours, further to 90 ° C., and reacted for 6 hours.
After the completion of the polymerization reaction, the reaction product was cooled, and the dispersion stabilizer was dissolved while stirring for 2 hours in a pH of 2 with 10% hydrochloric acid. The obtained emulsion was filtered under pressure and further washed with 2000 parts by mass or more of ion-exchanged water. The obtained cake was returned to 1000 parts by mass of ion-exchanged water and washed again with stirring for 2 hours in a state where 10% hydrochloric acid was added to adjust the pH to 1 or less.
The emulsion obtained in the same manner as described above was filtered under pressure, washed with 2000 parts by mass or more of ion-exchanged water, sufficiently ventilated, dried and air-classified to obtain toner particles.
100 parts by mass of the obtained toner particles, 1.5 parts by mass of hydrophobic silica fine particles 1 and 0.3 parts by mass of hydrophobic titanium oxide fine particles 1 are added and mixed with a Henschel mixer (manufactured by Mitsui Miike). Toner 1 was obtained. The physical properties of the obtained toner 1 are shown in Table 4.

<Toner Production Examples 2 to 62>
Toners 2 to 62 were produced in the same manner as in Toner Production Example 1 except that the type and content of each raw material were changed as shown in Table 3. Table 4 shows the physical properties of the obtained toners 2-62.
At this time, with respect to the toners 2 to 4 and the toner 57 in which the content (mass%) of styrene in the monomers shown in Table 3 is changed, n-butyl acrylate is increased or decreased in accordance with the increase or decrease of styrene. The total of n-butyl acrylate was made the same.

表中の略号の意味は以下の通り。
ＰＲ１２２ ；Ｃ．Ｉ．ピグメントレッド１２２
ＰＲ１５０ ；Ｃ．Ｉ．ピグメントレッド１５０
ＰＹ１５５ ；Ｃ．Ｉ．ピグメントイエロー１５５
ＰＹ１８０ ；Ｃ．Ｉ．ピグメントイエロー１８０
ＰＹ１８５ ；Ｃ．Ｉ．ピグメントイエロー１８５
ＰＹ９３ ；Ｃ．Ｉ．ピグメントイエロー９３
ＰＹ７４ ；Ｃ．Ｉ．ピグメントイエロー７４
ＰＲ２６９ ；Ｃ．Ｉ．ピグメントレッド２６９
ＰＢ１５：３；Ｃ．Ｉ．ピグメントブルー１５：３

The meanings of the abbreviations in the table are as follows.
PR122; C.I. I. Pigment Red 122
PR150; C.I. I. Pigment Red 150
PY155; C.I. I. Pigment Yellow 155
PY180; C.I. I. Pigment Yellow 180
PY185; C.I. I. Pigment Yellow 185
PY93; C.I. I. Pigment Yellow 93
PY74; C.I. I. Pigment Yellow 74
PR269; C.I. I. Pigment Red 269
PB15: 3; C.I. I. Pigment Blue 15: 3

<Example 1>
The process speed of commercially available LBP-2710 (manufactured by Canon Inc.) was modified to 220 mm / s, the toner was extracted from the commercially available magenta cartridge, and the inside was cleaned by air blow. Thereafter, 260 g of toner 1 was filled in the magenta cartridge, and the toner was removed from the other cyan, yellow, and black cartridges and inserted into each station, and various image evaluations were performed. The evaluation results are shown in Table 5.

<Examples 2-56>
Various image evaluations were performed in the same manner as in Example 1 except that the toner 1 was changed to the toners 2 to 56. The evaluation results are shown in Table 5.

<Comparative Examples 1-6>
Various image evaluations were performed in the same manner as in Example 1 except that the toner 1 was changed to the toners 57 to 62. The evaluation results are shown in Table 5.

Various image evaluations were performed as follows.
<Fog>
The fog is measured in a normal temperature and humidity environment (N / N: temperature 25 ° C., humidity 60% RH), in a high temperature and high humidity environment (H / H: temperature 32.5 ° C., humidity 85% RH), and low temperature and low humidity. Durability test is performed in a system that pauses for 1 minute every time two sheets are printed at a printing rate of 1% in each environment under the environment (L / L: temperature 10 ° C., humidity 10% RH). After printing, it was left for 6 days in each environment.
The fog amount of the first image sample after that was measured using REFECT METER MODELTC-6DS manufactured by Tokyo Denshoku Co., Ltd. and calculated from the following formula.
As the recording material used for the durability test, A4-sized plain paper (manufactured by Canon Marketing Japan Inc., GF-C081A4) was used.
Fog amount (%) = (whiteness of recording material before printing out) − (whiteness of non-image forming portion (white background portion) of recording material after printing)

<Image density>
The initial image density is a full-surface solid chart with a toner loading amount of 0.38 (mg / cm ² ) in a normal temperature and normal humidity environment (N / N: temperature 23.5 ° C., humidity 60% RH). One sheet was printed and the image density of the image was measured. The density of the image was measured using REFECT METER MODELTC-6DS manufactured by Tokyo Denshoku. A4 size plain paper (manufactured by Canon Marketing Japan Inc., GF-C081A4) was used as the recording material.

<Fusion and adhesion of toner to developer carrier and toner layer regulating member>
The toner is fused and fixed to the developer carrying member and the toner layer regulating member in a normal temperature and humidity environment (N / N: temperature 23.5 ° C., humidity 60% RH) and a high temperature and high humidity environment (H / H). : Temperature 32.5 ° C., humidity 80% RH). An endurance test was performed by a method of pausing for 1 minute each time two sheets were printed at a printing rate of 1%, and an image sample of the endurance 8000th sheet was visually evaluated from the beginning. As the recording material, A4-sized plain paper (Canon Marketing Japan, GF-C081A4) was used. The evaluation criteria are shown below.
A: Not generated at all on the image B: Slightly generated on the image (minor streaks of 1 to 3 at the end)
C: Generated on the image (4 or more lines at the end)

<Filming to latent image carrier>
Filming on the latent image carrier is performed under a normal temperature and humidity environment (N / N: temperature 23.5 ° C., humidity 60).
% RH) and a low temperature and low humidity environment (L / L: temperature 15 ° C., humidity 10% RH), a durability test was performed by continuous printing at a printing rate of 1%. The image sample of the 2000th durability from the beginning was evaluated visually. As the recording material, A4-sized plain paper (Canon Marketing Japan, GF-C081A4) was used. The evaluation criteria are shown below.
A: Not generated at all B: Slightly generated (longitudinal lines about 2 mm in length are slightly present on the recording material)
C: Occurrence (a lot of vertical lines with a length of about 5 mm are present on the recording material)

<Storage stability of toner>
The storage stability of the toner was evaluated by weighing 200 g of the toner in a 100 ml plastic cup, leaving it in a constant temperature layer at 50 ° C. for 3 days, and then sieving with 200 mesh (opening). As a measuring apparatus, a powder tester (manufactured by Hosokawa Micron Co., Ltd.) having a digital vibrometer (manufactured by DEGIBILATIONMETERMODEL 1332 SHOWA SOKKI CORPORATION) was used.
As a measuring method, an evaluation toner is put on a set 200 mesh sieve (aperture 75 μm), and the displacement value of the digital vibrometer is adjusted to 0.50 mm (peak-to-peak). Vibration was applied for 2 seconds. Thereafter, the storage stability was evaluated from the state of the aggregate of toner remaining on each sieve. The evaluation criteria are shown below.
A: The remaining amount of toner on the mesh is less than 1.0 g and very fluid. B: The remaining amount of toner on the mesh is 1.0 to less than 2.5 g and excellent in fluidity. C: On the mesh. The remaining amount of toner is 2.5 g or more, and there is an agglomerate that cannot be easily loosened.

<Fixability>
In a low-temperature and low-humidity environment (L / L: temperature 15 ° C, humidity 10% RH), turn on the power from the state in which the evaluator and the cartridge filled with the toner are familiar with the environment (that is, after being left in a low-temperature and low-humidity environment for 24 hours). I put it in. Immediately after the weight-up, a 200 μm wide horizontal line pattern (width 200 μm, interval 200 μm) was printed, and the 50th image was used for evaluation of the fixing property.
The fixing property was evaluated by rubbing the image with silver paper for 5 reciprocations with a load of 100 g, and peeling of the image was evaluated by the average of the reduction rate (%) of the reflection density.
The recording material used for the evaluation was a bond paper having a surface smoothness of 10 [sec] or less. The evaluation criteria are shown below.
A: Rate of decrease in reflection density is less than 5% B: Rate of decrease in reflection density is 5% or more and less than 15% C: Rate of decrease in reflection density is 15% or more

<Image density reduction>
A cartridge filled with toner in a normal temperature and humidity environment (N / N: temperature 25 ° C., humidity 60% RH) and in a high temperature and high humidity environment (H / H: temperature 32.5 ° C., humidity 85% RH) After being allowed to stand for 2 weeks, a durability test was conducted in such a manner that every time two sheets were printed at a printing rate of 2%, it was paused for 1 minute. The durability of the 10,000th image sample from the beginning was evaluated using the reduction rate of the image density. For the measurement of the image density, REFLECT METER MODELTC-6DS manufactured by Tokyo Denshoku Co., Ltd. was used. In addition, A4-sized plain paper (Canon Marketing Japan Co., Ltd., GF-C081A4) was used as the recording material. The evaluation criteria are shown below.
A: Concentration reduction rate is less than 5% B: Concentration reduction rate is 5% or more and less than 15% C: Concentration reduction rate is 15% or more

Claims (5)

A toner production method comprising a step of forming particles of a monomer composition containing a monomer containing styrene, a colorant and a polyester resin A in an aqueous medium, and polymerizing the monomer contained in the particles of the monomer composition. There,
The styrene content in the monomer is 60% by mass or more,
The polyester resin A contains an isosorbide unit represented by the following formula (1),
A method for producing a toner, wherein the polyester resin A has a styrene-hexane solubility index of 15.0 or more and 27.0 or less.

The polyester resin A contains a monomer unit derived from terephthalic acid,
2. The toner production method according to claim 1, wherein a content ratio of the monomer unit derived from the terephthalic acid is 85.00 mol% or more based on all dicarboxylic acid monomer units constituting the polyester resin A. 3.   The content ratio of the isosorbide unit represented by the formula (1) in the polyester resin A is 0.10 mol% or more and 20.00 mol% or less based on all monomer units constituting the polyester resin A, Item 3. A method for producing a toner according to Item 1 or 2. The polyester resin A contains a monomer unit derived from ethylene glycol,
The content ratio of the monomer unit derived from the ethylene glycol is 5.00 mol% or more and 43.00 mol% or less based on all alcohol monomer units constituting the polyester resin A. 4. 2. A method for producing the toner according to 1. A toner obtained by forming particles of a monomer composition containing a monomer containing styrene, a colorant, and polyester resin A in an aqueous medium and polymerizing the monomer contained in the particles of the monomer composition. And
The styrene content in the monomer is 60% by mass or more,
The polyester resin A contains an isosorbide unit represented by the following formula (1),
A toner wherein the polyester resin A has a styrene-hexane solubility index of 15.0 or more and 27.0 or less.

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