JP2017044742A - Toner and manufacturing method of toner - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a toner that suppresses bleeding after storage in a high-temperature and high-humidity environment, and exhibits excellent charge stability and durability stability during a large number of printouts after storage in a high-temperature and high-humidity environment.SOLUTION: There is provided a toner obtained by forming, in an aqueous medium, particles of a monomer composition containing a polyester resin A, charge control resin B, colorant, and monomer, and polymerizing the monomer included in the particles of the monomer composition, where the content of styrene in the monomer is 60 mass% or more; the charge control resin B is a polymer having a specific structure; the styrene-hexane solubility index of the polyester resin A is 15.0 or more and 27.0 or less; the absolute value of the difference between the styrene-hexane solubility index of the polyester resin A and the styrene-hexane solubility index of the charge control resin B is 7.0 or less.SELECTED DRAWING: None

Description

  The present invention relates to an image forming method such as an electrophotographic method and an electrostatic printing method, or a toner for forming a toner image in a toner jet type image forming method and a method for producing the toner.

In recent markets, printer devices are required to have higher speed and longer life. In addition, development of toner that melts at a lower temperature is also being promoted. On the other hand, due to the influence of global warming, improvement in storage stability in a higher temperature and higher humidity environment is also required.
Conventionally, when a toner is stored in a high-temperature and high-humidity environment, a phenomenon in which the resin component or release agent of the toner oozes out from the inside of the toner (hereinafter also referred to as bleed) occurs, and the surface property of the toner changes. . This becomes a cause of member contamination during printing or fogging due to poor charging, and becomes a more prominent issue when printing a large number of sheets.
Therefore, a toner that has excellent storage stability and excellent charge stability even during long-term use after storage in a high-temperature and high-humidity environment and high durability is demanded. In particular, when used in a non-magnetic one-component developing device that charges toner by friction with a regulating blade, these problems are serious problems.
In view of the above background, toners that are excellent in storage stability and excellent in charge stability even in long-term use after storage in a high-temperature and high-humidity environment are actively studied. As a solution, improvements have been made to resin components, charge control agents, external additives, and the like used in toners.
As a technique for improving the chargeability of the toner by improving the resin component used in the toner, a toner using a polyester resin having an isosorbide unit has been proposed (Patent Document 1).
Further, there has been proposed a toner that improves the fixability and storage stability of the toner by using a polyester resin having an isosorbide unit (Patent Document 2).
On the other hand, a toner using a polymer having a salicylic acid structure has been proposed as a technique for improving the chargeability of the toner by improving the charge control agent used in the toner (Patent Document 3).

JP 2010-285555 A JP2013-231148A JP 2012-256044 A

The toner described in Patent Document 1 uses an isosorbide unit as one of the polyhydric alcohol components, and is said to be able to improve the fog.
However, as a result of intensive studies, the present inventors have found that there is room for improvement in toner charging stability during long-term use after storage in a high-temperature and high-humidity environment.
The toner described in Patent Document 2 is certainly excellent in fixability and storage stability, but due to the hygroscopic property peculiar to the isosorbide unit, the hygroscopic property of the toner tends to increase and the charge amount of the toner tends to decrease.
The toner described in Patent Document 3 suppresses a decrease in fluidity even when stored in a high-temperature and high-humidity environment, and has a good charge rising property. However, as a result of intensive studies by the present inventors, when bleed occurs when stored in a severer high-temperature and high-humidity environment, there is room for improvement in charging stability and durability stability during long-term use. It became clear that there is.
The present invention has been made in view of the above problems.
That is, the present invention suppresses bleed after storage in a high-temperature and high-humidity environment, and provides a toner having excellent charging stability and durability stability when printing a large number of sheets after storage in a high-temperature and high-humidity environment. To do.

The present invention
Toner obtained by forming particles of a monomer composition containing polyester resin A, charge control resin B, colorant and monomer in an aqueous medium, and polymerizing the monomer contained in the particles of the monomer composition Because
The styrene content in the monomer is 60% by mass or more,
The charge control resin B is a polymer having a structure 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 toner is characterized in that the absolute value of the difference between the styrene-hexane solubility index of the polyester resin A and the styrene-hexane solubility index of the charge control resin B is 7.0 or less.

［前記式（１）中、Ｒ^１は、それぞれ独立して、ヒドロキシ基、カルボキシ基、炭素数１以上１８以下のアルキル基、又は、炭素数１以上１８以下のアルコキシ基を表し、ｈは０以上３以下の整数を表す。］

[In the formula (1), each R ¹ independently represents a hydroxy group, a carboxy group, an alkyl group having 1 to 18 carbon atoms, or an alkoxy group having 1 to 18 carbon atoms, and h is 0. Represents an integer of 3 or less. ]

The present invention also provides:
Dispersing a monomer composition containing polyester resin A, charge control resin B, colorant and monomer in an aqueous medium to form particles of the monomer composition in the aqueous medium; and
A method for producing a toner comprising a step of polymerizing the monomer contained in the particles of the monomer composition,
The styrene content in the monomer is 60% by mass or more,
The charge control resin B is a polymer having a structure 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 toner production method is characterized in that the absolute value of the difference between the styrene-hexane solubility index of the polyester resin A and the styrene-hexane solubility index of the charge control resin B is 7.0 or less.

［前記式（１）中、Ｒ^１は、それぞれ独立して、ヒドロキシ基、カルボキシ基、炭素数１以上１８以下のアルキル基、又は、炭素数１以上１８以下のアルコキシ基を表し、ｈは０以上３以下の整数を表す。］

[In the formula (1), each R ¹ independently represents a hydroxy group, a carboxy group, an alkyl group having 1 to 18 carbon atoms, or an alkoxy group having 1 to 18 carbon atoms, and h is 0. Represents an integer of 3 or less. ]

  According to the present invention, there is provided a toner that suppresses bleed after storage in a high-temperature and high-humidity environment and has excellent charging stability and durability stability when printing a large number of sheets after storage in a high-temperature and high-humidity environment. can do.

Example of transmittance curve obtained by measuring styrene-hexane solubility index Example of schematic configuration diagram of image forming apparatus

Hereinafter, the present invention will be described in detail.
The toner of the present invention is
Toner obtained by forming particles of a monomer composition containing polyester resin A, charge control resin B, colorant and monomer in an aqueous medium, and polymerizing the monomer contained in the particles of the monomer composition Because
The styrene content in the monomer is 60% by mass or more,
The charge control resin B is a polymer having a structure 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 absolute value of the difference between the styrene-hexane solubility index of the polyester resin A and the styrene-hexane solubility index of the charge control resin B is 7.0 or less.

［前記式（１）中、Ｒ^１は、それぞれ独立して、ヒドロキシ基、カルボキシ基、炭素数１以上１８以下のアルキル基、又は、炭素数１以上１８以下のアルコキシ基を表し、ｈは０以上３以下の整数を表す。］

[In the formula (1), each R ¹ independently represents a hydroxy group, a carboxy group, an alkyl group having 1 to 18 carbon atoms, or an alkoxy group having 1 to 18 carbon atoms, and h is 0. Represents an integer of 3 or less. ]

Conventionally, when a toner is stored in a high-temperature and high-humidity environment, the resin component and release agent of the toner bleed from the inside of the toner to the surface, and the surface property of the toner changes. This becomes a cause of member contamination during printing or fogging due to poor charging, and becomes a more prominent issue when printing a large number of sheets.
On the other hand, the toner of the present invention has the above-described configuration, so that bleeding from the inside of the toner can be suppressed even when stored in a high-temperature and high-humidity environment. On the other hand, the toner is uniformly present on the surface of the toner, so that contamination of members can be prevented even when a large number of sheets are printed out, and a toner with good fog can be obtained.

By adopting the configuration of the present invention, the toner has excellent charging stability and durability stability at the time of printing out a large number of sheets after storage in a high temperature and high humidity environment by suppressing bleed after storage in a high temperature and high humidity environment Although the mechanism by which is obtained is not clear, 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.
In order to obtain a toner having a core-shell structure, it is necessary to use a material in which the shell component is separated from the core component binder resin to some extent. For example, when the binder resin constituting the core component is a styrene polymer, it is preferable to use a polyester resin or a polyurethane resin as the shell component. At that time, in order to obtain a toner having excellent durability stability and storage stability, it is necessary that the shell component has excellent durability stability and heat resistance and excellent phase separation with the binder resin of the core component.

In this invention, 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. .
As the polymerization reaction of the monomer contained in the monomer composition particles proceeds, the monomer decreases. That is, as the polymerization proceeds, the solvent for the polyester resin A decreases.
Therefore, 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. This is because the polyester resin A has high solubility in the styrene monomer and thus has high compatibility with the binder resin obtained by polymerizing the monomer having a styrene content of 60% by mass or more. When following such a transition, the thickness of the shell layer is reduced because a part of the polyester resin A used for toner formation is compatible with the binder resin, so that it can be stored in a high temperature and high humidity environment. And in terms of charging stability and contamination of members when printing out a large number of sheets after storage.
On the other hand, when the styrene-hexane solubility index of the polyester resin A is less than 15.0, the polyester resin A is deposited even in a state where a large amount of monomers at the initial stage of the polymerization reaction are present. In the case of following such a transition, since the polarity of the polyester resin A is high, the hygroscopicity of the toner becomes high and the charging stability is inferior.
In addition, it is preferable that the styrene-hexane solubility index of the polyester resin A is 17.0 or more and 25.0 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.
As a specific example of adjusting the styrene-hexane solubility index by the monomer composition of the polyester resin A, for example, a highly polar monomer such as isosorbide is used, and the content ratio is adjusted to change the polarity of the polyester resin A. Alternatively, it is possible to change 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 is 60% by mass or more.
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.
The content of styrene in the monomer is preferably 70% by mass or more and 100% by mass.

In the present invention, the charge control resin B is a polymer having a structure represented by the formula (1), and can stably impart a charge generated by frictional charging. Although the mechanism is not clear, it was generated at the salicylic acid site present in the structure represented by the formula (1) due to the spread of the conjugated system such as an oxygen atom or an aryl group present in the structure represented by the formula (1). It is considered that the charge is transferred to the polyester resin A and other materials constituting the toner to produce an effect of increasing the rise of charge. In addition, when excessive charging (overcharge) occurs, it is expected to have an effect of quickly releasing charges and preventing local overcharging.
The molar content of the structure represented by the formula (1) in the charge control resin B is preferably 250 μmol / g or more and 650 μmol / g or less based on the mass of the charge control resin B.
If the molar content of the structure represented by the formula (1) in the charge control resin B is 250 μmol / g or more based on the mass of the charge control resin B, a stable charge can be imparted to the toner. it can.
On the other hand, when the molar content is 650 μmol / g or less, the effect of the present invention can be further obtained because the influence of the hygroscopic property of the structure represented by the formula (1) can be further reduced.

In the present invention, the absolute value of the difference between the styrene-hexane solubility index of the polyester resin A and the styrene-hexane solubility index of the charge control resin B is 7.0 or less.
When the absolute value of the styrene-hexane solubility index difference is 7.0 or less, the charge control resin B is uniformly present on the toner surface layer with respect to the polyester resin A, and the toner has good charge stability. Indicates.
When the absolute value of the difference between the styrene-hexane solubility index of the polyester resin A and the styrene-hexane solubility index of the charge control resin B exceeds 7.0, the presence state of the charge control resin B on the toner surface layer is biased. In particular, after storage in a high-temperature and high-humidity environment, the toner surface layer tends to be unevenly charged due to bleeding components and the like, and fog occurs.
The absolute value of the difference between the styrene-hexane solubility index of the polyester resin A and the styrene-hexane solubility index of the charge control resin B is preferably less than 4.0.
In order to adjust the absolute value of the difference between the styrene-hexane solubility index of the polyester resin A and the styrene-hexane solubility index of the charge control resin B to the above range, the styrene-hexane solubility of the polyester resin A and the charge control resin B can be used. Adjusting the index respectively. The method for adjusting the styrene-hexane solubility index of the polyester resin A is as described above. Moreover, as a measure for adjusting the styrene-hexane solubility index of the charge control resin B, the difference in the structure represented by the formula (1) in the charge control resin B, the molar content of the structure, or the charge control resin The weight average molecular weight of B can be adjusted.

In the present invention, the polyester resin A preferably contains an isosorbide unit represented by the following formula (2). Polyester resin A containing an isosorbide unit is excellent in durability stability because the orientation of the isosorbide unit is strong.
Moreover, the content rate of the isosorbide unit represented by following formula (2) in the polyester resin A shall be 0.10 mol% or more and 20.00 mol% or less on the basis of all the monomer units which comprise the polyester resin A. Is preferable, and more preferably 0.50 mol% or more and 10.00 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 following formula (2) 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 polyester resin A Tend to decrease. On the other hand, when it exceeds 20.00 mol%, the water absorption of the toner tends to increase, and the charging stability tends to decrease.
In addition, in this invention, a monomer unit means the form with which the monomer substance in a polymer reacted.

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%.
Terephthalic acid has higher symmetry and linearity as a molecular structure than phthalic acid, isophthalic acid, or aliphatic dicarboxylic acid. This is because by using the terephthalic acid at a high ratio, the orientation of the obtained polyester resin A is increased, and a rigid molecule is obtained.
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. The durability stability is further improved, and the charging stability is further improved.

In this invention, it is preferable that the polyester resin A contains the monomer unit derived from ethylene glycol, and the content rate of the monomer unit derived from this ethylene glycol is based on all the alcohol monomer units which comprise the polyester resin A, 15. It is preferable that it is 00 to 43.00 mol%.
When the content ratio of the monomer unit derived from ethylene glycol is in the above range, the obtained polyester resin A has flexibility due to the monomer unit derived from ethylene glycol, and is excellent in durability stability.
Furthermore, when a toner is produced in an aqueous medium due to the polar strength of the monomer unit derived from ethylene glycol, the polyester resin A can easily form a shell layer. As a result, the durability stability is excellent, and since the polarity of the polyester resin A forming the shell layer becomes moderate, the toner is more excellent in charging stability.
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. In addition, in a linear structure diol compound having 3 or more carbon atoms, the flexibility of the polyester resin A tends to be excessive. Therefore, the aliphatic diol compound used for the polyester resin A is preferably ethylene glycol from the viewpoint of the flexibility of the polyester resin A.

In the present invention, the polyester resin A preferably contains an isosorbide unit represented by the formula (2) and a monomer unit derived from ethylene glycol.
The total content of the isosorbide unit represented by the formula (2) and the monomer unit derived from ethylene glycol is 20.00 mol% or more and 65.00 mol% or less based on all alcohol monomer units constituting the polyester resin A. Preferably there is. By adopting this configuration, it is possible to further suppress fogging and member contamination at the time of printing out a large number of sheets after storage in a high temperature and high humidity environment.
The reason is that 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, greatly affecting the shell layer formation, and the polyester resin A forms a strong shell layer. Because.

In the present invention, the content of the polyester resin A in the toner is 1.0 part by mass or more and 25.0 parts by mass with respect to 100 parts by mass of a resin (that is, a binder resin) formed from a monomer containing styrene. Or less, more preferably 1.0 part by mass or more and 10.0 parts by mass or less.
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 durability stability and storage stability. This is preferable. On the other hand, when the amount is 25.0 parts by mass or less, the hygroscopicity of the toner can be suppressed, good charging stability is exhibited, and fixing property is also preferable.

In the present invention, when the 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 10.0 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, the hygroscopic property of the polyester resin A forming the shell layer does not become excessive, which is preferable in terms of charging stability.

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 stability.
On the other hand, when the weight average molecular weight (Mw) of the polyester resin A is 25000 or less, neither the solubility point nor the molecular size point of the polyester resin A is preferable.
Moreover, it is more preferable that 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 storage stability and charging stability of the toner are excellent.

In the present invention, the glass transition temperature (Tg) of the polyester resin A is 65 ° C. or higher and 85 ° C.
It is preferable that it is below, and it is more preferable that it is 68 degreeC or more and 80 degrees C or less.
When the glass transition temperature (Tg) of the polyester resin A is 65 ° C. or higher, it is preferable in terms of high heat resistance and storage stability. 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, dicarboxylic acid or its anhydride (monomer), isosorbide represented by the following formula (A) and dihydric alcohol (monomer) are dehydrated and condensed 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 43-57 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 anhydrides thereof; succinic acid 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) and 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.

  In the present invention, the charge control resin B is preferably a polymer having a structure represented by the following formula (3).

［前記式（３）中、Ｒ^２は、それぞれ独立して、ヒドロキシ基、カルボキシ基、炭素数１以上１８以下のアルキル基、又は、炭素数１以上１８以下のアルコキシ基を表し、Ｒ^３は、水素原子、ヒドロキシ基、炭素数１以上１８以下のアルキル基、又は、炭素数１以上１８以下のアルコキシ基を表し、ｊは１以上３以下の整数を表し、ｉは０以上３以下の整数を表す。］

[In the formula (3), R ² is, independently, a hydroxyl group, a carboxyl group, having 1 to 18 alkyl group carbon atoms or represents a 1 to 18 alkoxy group having a carbon number, R ³ is , A hydrogen atom, a hydroxy group, an alkyl group having 1 to 18 carbon atoms, or an alkoxy group having 1 to 18 carbon atoms, j represents an integer of 1 to 3 and i is an integer of 0 to 3 Represents. ]

  The structure represented by the above formula (3) has a structure in which an aromatic ring and a salicylic acid structure are bonded via an alkyl ether advantageous for electron conduction. It is believed that this large conjugated structure extending from the salicylic acid structure plays a role in holding the charge generated by triboelectric charging inside the molecule while minimizing the influence of external temperature and humidity, and gives a stable charge. .

  Further, the charge control resin B may be a polymer having a monomer unit represented by the following formula (4).

［前記式（４）中、Ｒ^４は、それぞれ独立して、ヒドロキシ基、カルボキシ基、炭素数１以上１８以下のアルキル基、又は、炭素数１以上１８以下のアルコキシ基を表し、Ｒ^５は、水素原子、ヒドロキシ基、炭素数１以上１８以下のアルキル基、又は、炭素数１以上１８以下のアルコキシ基を表し、Ｒ^６は水素原子又はメチル基を表し、ｌは１以上３以下の整数を表し、ｋは０以上３以下の整数を表す。］

[The formula (4), R ⁴ are each independently a hydroxyl group, a carboxyl group, 1 to 18 alkyl group carbon atoms, or represents a 1 to 18 alkoxy group carbon atoms, R ⁵ is , A hydrogen atom, a hydroxy group, an alkyl group having 1 to 18 carbon atoms, or an alkoxy group having 1 to 18 carbon atoms, R ⁶ represents a hydrogen atom or a methyl group, and l is an integer of 1 to 3 And k represents an integer of 0 or more and 3 or less. ]

When the charge control resin B is a polymer having a monomer unit represented by the above formula (4), the effect of the present invention is more suitably exhibited in a toner containing a vinyl resin as a main component. Here, “consisting mainly of vinyl resin” means that 50% by mass or more of the resin contained in the toner is vinyl resin.
The charge control resin B may be a vinyl copolymer having a monomer unit represented by the formula (4) and a vinyl monomer unit.
This is because the charge control resin B is a vinyl copolymer, so that it is easily compatible in a toner containing a vinyl resin as a main component. Compatibilization makes it possible to take an optimal molecular arrangement, and the effect of the present invention is considered to be more remarkable.
Further, since the glass transition temperature (Tg) of the charge control resin B can be easily controlled by using the vinyl copolymer as the charge control resin B, the effect of the present invention is exhibited while maintaining the toner fixing property. This is a preferred embodiment.

On the other hand, the charge control resin B can be a polymer having a polyester structure.
In this case, a polyester structure formed by polycondensation of a polyhydric alcohol component and a polyvalent carboxylic acid component is used as a main chain, and a structure represented by the above formula (1) may be included. Moreover, it is also possible to use the hybrid resin which modified the polyester structure with the vinyl-type monomer as a polymer which has a polyester structure.
When a hybrid resin is used, a known method can be used to adjust the vinyl modification ratio in the hybrid resin. Specifically, an arbitrary modification ratio can be adjusted by changing the charged amount ratio of the polyester structural component and the vinyl monomer component to be used.
The following can be illustrated as a polyhydric alcohol component which comprises the polymer which has this polyester structure.
As the dihydric alcohol component, polyoxypropylene (2.2) -2,2-bis (4-hydroxyphenyl) propane, polyoxypropylene (3.3) -2,2-bis (4-hydroxyphenyl) propane , Polyoxyethylene (2.0) -2,2-bis (4-hydroxyphenyl) propane, polyoxypropylene (2.0) -polyoxyethylene (2.0) -2,2-bis (4-hydroxy) Alkylene oxide adducts of bisphenol A such as phenyl) propane and polyoxypropylene (6) -2,2-bis (4-hydroxyphenyl) propane, ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propylene glycol, 1 , 3-propylene glycol, 1,4-butanediol, neopentyl Coal, 1,4-butenediol, 1,5-pentanediol, 1,6-hexanediol, 1,4-cyclohexanedimethanol, dipropylene glycol, polyethylene glycol, polypropylene glycol, polytetramethylene glycol, bisphenol A, hydrogen Added bisphenol A.
Examples of trihydric or higher alcohol components include sorbitol, 1,2,3,6-hexanetetrol, 1,4-sorbitan, pentaerythritol, dipentaerythritol, tripentaerythritol, 1,2,4-butanetriol, 1 , 2,5-pentanetriol, glycerol, 2-methylpropanetriol, 2-methyl-1,2,4-butanetriol, trimethylolethane, trimethylolpropane, 1,3,5-trihydroxymethylbenzene, etc. It is done.
The polyvalent carboxylic acid component includes aromatic dicarboxylic acids such as phthalic acid, isophthalic acid and terephthalic acid or anhydrides thereof; alkyl dicarboxylic acids such as succinic acid, adipic acid, sebacic acid and azelaic acid or anhydrides thereof. And succinic acid substituted with an alkyl group having 6 to 12 carbon atoms or an anhydride thereof; unsaturated dicarboxylic acids such as fumaric acid, maleic acid and citraconic acid or anhydrides thereof; and the like.
Among them, in particular, a bisphenol derivative as a polyhydric alcohol component, a carboxylic acid component composed of a divalent or higher carboxylic acid, an acid anhydride thereof, or a lower alkyl ester thereof (for example, fumaric acid, maleic acid, maleic anhydride, Preferred examples include polyesters obtained by condensation polymerization of phthalic acid, terephthalic acid, trimellitic acid, pyromellitic acid, etc.) as a polyvalent carboxylic acid component.

In the present invention, the method for producing the charge control resin B is not particularly limited, and can be produced by a known method.
When the charge control resin B is a vinyl (co) polymer, as an example, a monomer containing the structure represented by the formula (1) (the following formula (5)) is polymerized using a polymerization initiator. You can do it.

［前記式（５）中、Ｒ^７は、それぞれ独立して、ヒドロキシ基、カルボキシ基、炭素数１以上１８以下のアルキル基、又は、炭素数１以上１８以下のアルコキシ基を表し、Ｒ^８は、水素原子、ヒドロキシ基、炭素数１以上１８以下のアルキル基、又は、炭素数１以上１８以下のアルコキシ基を表し、Ｒ^９は、水素原子又はメチル基を表し、ｎは１以上３以下の整数を表し、ｍは０以上３以下の整数を表す。］

[In the formula (5), R ⁷ are each independently hydroxy group, a carboxy group, having 1 to 18 alkyl group carbon atoms or represents a 1 to 18 alkoxy group carbon atoms, R ⁸ is , A hydrogen atom, a hydroxy group, an alkyl group having 1 to 18 carbon atoms, or an alkoxy group having 1 to 18 carbon atoms, R ⁹ represents a hydrogen atom or a methyl group, and n is 1 to 3 Represents an integer, and m represents an integer of 0 or more and 3 or less. ]

  Moreover, the following can be mentioned as a specific example of the said monomer (Formula (5)). The examples shown here are merely examples, and the present invention is not limited to these examples.

In addition, when the charge control resin B is a vinyl copolymer, other vinyl monomers that can be used together with the monomer (formula (5)) are not particularly limited.
Specific examples of the vinyl monomer include the following compounds.
Styrene and its derivatives such as styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, α-methylstyrene; unsaturated monoolefins such as ethylene, propylene, butylene, isobutylene; vinyl chloride, vinylidene chloride Vinyl halides such as vinyl bromide and vinyl fluoride; vinyl ester acids such as vinyl acetate, vinyl propionate and vinyl benzoate; acrylics such as acrylic acid-n-butyl and acrylic acid-2-ethylhexyl Acid esters; methacrylic acid esters obtained by changing acrylic acid of the above acrylic acid esters to methacrylic acid; methacrylic acid amino esters such as dimethylaminoethyl methacrylate and diethylaminoethyl methacrylate; vinyl methyl ether, vinyl ethyl ether like Vinyl ether compounds; vinyl ketones such as vinyl methyl ketone; N- vinyl compounds such as N- vinyl pyrrole, vinyl naphthalenes; acrylonitrile, methacrylonitrile, acrylamide, acrylic acid and methacrylic acid.

Various polymerization initiators such as peroxide polymerization initiators and azo polymerization initiators can be used as the polymerization initiator that can be used when the monomer is polymerized or copolymerized.
Examples of the peroxide polymerization initiator include the following.
Peroxyesters, peroxydicarbonates, dialkyl peroxides, peroxyketals, ketone peroxides, hydroperoxides, diacyl peroxides as organic systems.
Examples of the inorganic system include persulfate and hydrogen peroxide.
Specifically, t-butyl peroxyacetate, t-butyl peroxypivalate, t-butyl peroxyisobutyrate, t-hexyl peroxyacetate, t-hexyl peroxypivalate, t-hexyl peroxyiso Peroxyesters such as butyrate, t-butylperoxyisopropyl monocarbonate, t-butylperoxy 2-ethylhexyl monocarbonate; diacyl peroxides such as benzoyl peroxide; peroxydicarbonates such as diisopropyl peroxydicarbonate; 1 Peroxyketals such as 1, -di-t-hexylperoxycyclohexane; dialkyl peroxides such as di-t-butyl peroxide; and other t-butyl peroxyallyl monocarbonate It is.
Examples of the azo polymerization initiator include 2,2′-azobis- (2,4-dimethylvaleronitrile), 2,2′-azobisisobutyronitrile, 1,1′-azobis (cyclohexane-1-carbohydrate). Nitrile), 2,2′-azobis-4-methoxy-2,4-dimethylvaleronitrile, azobisisobutyronitrile, dimethyl-2,2′-azobis (2-methylpropionate) and the like. .
These polymerization initiators may be used alone or in combination of two or more.
The amount of the polymerization initiator used is preferably 0.1 parts by mass or more and 20.0 parts by mass or less with respect to 100 parts by mass of the monomer. As the polymerization method, any method such as solution polymerization, suspension polymerization, emulsion polymerization, dispersion polymerization, precipitation polymerization and bulk polymerization can be used, and it is not particularly limited.

On the other hand, when the charge control resin B is a polymer having a polyester structure, various known production methods can be used. For example,
(A) A method of converting a structure represented by the formula (1) into a structure having a substituent as a substituent by an organic reaction using a reaction residue of a carboxy group or a hydroxyl group contained in a polyester structure;
(B) A method for producing a polyester using a polyhydric alcohol or polycarboxylic acid having a structure represented by the formula (1);
In the case of a hybrid resin,
(C) a method of hybridizing an unsaturated group-containing polyester containing a structure represented by the formula (1) using a vinyl monomer;
(D) a method of hybridizing an unsaturated group-containing polyester using a vinyl monomer having a structure represented by the formula (1);
Etc.

As a specific method of the above (A), when a structure represented by the formula (1) is introduced by an organic reaction, a compound having a structure such as the following formula (6) is used as the carboxy group present in the polyester structure. And amidation method.

［前記式（６）中、ＣＯＯＨとＯＨは隣り合う位置に結合し、Ｒ^１０は、それぞれ独立して、ヒドロキシ基、カルボキシ基、炭素数１以上１８以下のアルキル基、又は、炭素数１以上１８以下のアルコキシ基を表し、ｐは０以上３以下の整数を表す。］

[In the formula (6), COOH and OH are bonded to adjacent positions, and R ¹⁰ is independently a hydroxy group, a carboxy group, an alkyl group having 1 to 18 carbon atoms, or one or more carbon atoms. Represents an alkoxy group of 18 or less, and p represents an integer of 0 or more and 3 or less. ]

  Specific examples of the method (D) include a method of hybridizing an unsaturated group-containing polyester using a vinyl monomer having a structure represented by the above formula (5).

In the present invention, the weight average molecular weight (Mw) calculated by gel permeation chromatography (GPC) of the charge control resin B is preferably 1,000 or more and 100,000 or less. When the weight average molecular weight (Mw) of the charge control resin B is in the above range, the effects of the present invention are more suitably exhibited.
If the weight average molecular weight (Mw) of the charge control resin B is 1000 or more, uneven distribution among the resins of the structure represented by the formula (1) in the charge control resin B tends to be suppressed. On the other hand, if it is 100,000 or less, the uneven distribution of the charge control resin B between the toners tends to be suppressed. As a result, stable charging stability as a toner can be obtained, and the effects of the present invention can be further exhibited.
In the present invention, a known method can be used as a method for adjusting the weight average molecular weight (Mw) of the charge control resin B. For example, it is as follows.
When the charge control resin B is a vinyl (co) polymer, the charge control resin B can be arbitrarily adjusted depending on the charging ratio of the vinyl monomer and the polymerization initiator, the polymerization temperature, and the like.
On the other hand, when the charge control resin B is a polymer having a polyester structure, it can be arbitrarily adjusted depending on the charging ratio of the acid component and the alcohol component and the polymerization time. In the case of a hybrid resin, in addition to adjusting the molecular weight of the polyester structure, it is possible to adjust the molecular weight of the vinyl-modified unit.
Specifically, it can be arbitrarily adjusted in the vinyl modification reaction step by the amount of polymerization initiator, polymerization temperature and the like. In the present invention, as the vinyl monomer that can be used for hybridization of the polyester structure, the above-described vinyl monomers can be used.

Further, from the viewpoint of charge stability and fixability, the charge control resin B preferably has a narrow molecular weight distribution. The ratio (Mw / Mn) of the weight average molecular weight (Mw) and the number average molecular weight (Mn) calculated by gel permeation chromatography (GPC) of the charge control resin B is 1.0 or more and 6.0 or less. And more preferably 1.0 or more and 4.0 or less.
Further, the content of the charge control resin B may be 0.010 parts by mass or more and 20.000 parts by mass or less with respect to 100 parts by mass of a resin (that is, a binder resin) formed from a monomer containing styrene. Preferably, it is 0.025 parts by mass or more and 10.000 parts by mass or less.
The styrene-hexane solubility index of the charge control resin B is preferably 15.0 or more and 27.0 or less, and more preferably 17.0 or more and 25.0 or less.
The styrene-hexane solubility index of the charge control resin B can be adjusted to the above range by the method described above.

The toner of the present invention may be a magnetic toner containing a magnetic material. In that case, the magnetic material can also serve as a colorant.
Examples of the magnetic material include iron oxides such as magnetite, maghemite, and ferrite, and iron oxides including other metal oxides; metals such as Fe, Co, and Ni, or these metals and Al and Co. , Cu, Pb, Mg, Ni, Sn, Zn, Sb, Ca, Mn, Se, alloys with metals such as Ti, and mixtures thereof.
Specifically, triiron tetraoxide _{(Fe 3 O} 4), iron sesquioxide _{(γ-Fe 2 O 3)} , iron oxide, zinc (ZnFe ₂ O _4), oxidized iron-copper (CuFe ₂ O _4), iron oxide Examples thereof include neodymium (NdFe ₂ O ₃ ), iron barium oxide (BaFe ₁₂ O ₁₉ ), iron magnesium oxide (MgFe ₂ O ₄ ), and iron oxide manganese (MnFe ₂ O ₄ ).
These magnetic materials can be used alone or in combination of two or more.
A particularly suitable magnetic material is triiron tetroxide or iron sesquioxide fine powder.
These magnetic materials preferably have a number average particle size of 0.1 μm to 2 μm, and more preferably 0.1 μm to 0.3 μm.
The magnetic characteristics when 795.8 kA / m (10 k Oersted) is applied are preferably such that the coercive force (Hc) is 1.6 kA / m or more and 12 kA / m or less (20 Oersted or more and 150 Oersted or less). The saturation magnetization ([sigma] s) is preferably at less ^5am 2 / kg or more 200 Am ² / kg, more preferably not more than 50 Am ² / kg or more 100 Am ² / kg. On the other hand, the residual magnetization (.sigma.r) is preferably at most ^2Am 2 / kg or more 20 Am ² / kg.
The content of the magnetic material in the toner is preferably 10.0 parts by mass or more and 200 parts by mass or less with respect to 100 parts by mass of a resin (that is, a binder resin) formed from a monomer containing styrene. More preferably, it is 20.0 parts by mass or more and 150 parts by mass or less.

On the other hand, known colorants such as various conventionally known dyes and pigments can be used as the colorant when used as a non-magnetic toner.
Examples of the black colorant include carbon black, aniline black, acetylene black, titanium black, and those adjusted to black using the following yellow, magenta, and cyan colorants.
Examples of the pigment-based yellow colorant include compounds typified by condensed azo compounds, isoindolinone compounds, anthraquinone compounds, azo metal complexes, methine compounds, and allylamide compounds. Specifically, C.I. I. Pigment Yellow 3, 7, 10, 12, 13, 14, 15, 17, 23, 24, 60, 62, 74, 75, 83, 93, 94, 95, 99, 100, 101, 104, 108, 109, 110 111, 117, 123, 128, 129, 138, 139, 147, 148, 150, 155, 166, 168, 169, 177, 179, 180, 181, 183, 185, 191: 1, 191, 192, 193 199.
Examples of the dye-based yellow colorant include C.I. I. solvent Yellow 33, 56, 79, 82, 93, 112, 162, 163, C.I. I. Disperse Yellow 42, 64, 201, 211 are listed.
Examples of the magenta colorant include condensed azo compounds, diketopyrrolopyrrole compounds, anthraquinone compounds, quinacridone compounds, basic dye lake compounds, naphthol compounds, benzimidazolone compounds, thioindigo compounds, and perylene compounds. Specifically, C.I. I. Pigment Red 2, 3, 5, 6, 7, 23, 48: 2, 48: 3, 48: 4, 5
7: 1, 81: 1, 122, 146, 150, 166, 169, 177, 184, 185, 202, 206, 220, 221, 238, 254, 269, C.I. I. And CI Pigment Bio Red 19.
Examples of cyan colorants include copper phthalocyanine compounds and derivatives thereof, anthraquinone compounds, and basic dye lake compounds. Specifically, C.I. I. Pigment blue 1, 7, 15, 15: 1, 15: 2, 15: 3, 15: 4, 60, 62, 66.
These colorants can be used alone or in combination, and further in a solid solution state. The colorant is selected from the viewpoints of hue angle, saturation, brightness, weather resistance, OHT transparency, and dispersibility in the toner. The content of the colorant is preferably 1.0 part by mass or more and 20.0 parts by mass or less with respect to 100 parts by mass of a resin (that is, a binder resin) formed from a monomer containing styrene.

The toner of the present invention may contain a release agent. Examples of the release agent include the following.
Aliphatic hydrocarbon waxes such as low molecular weight polyethylene, low molecular weight polypropylene, microcrystalline wax, paraffin wax; oxides of aliphatic hydrocarbon waxes such as oxidized polyethylene wax; block copolymerization of aliphatic hydrocarbon waxes Products; waxes based on fatty acid esters such as carnauba wax, sazol wax and montanic acid ester wax; deoxidized part or all of fatty acid esters such as deoxidized carnauba wax; like behenic acid monoglyceride A partially esterified product of a fatty acid and a polyhydric alcohol; a methyl ester compound having a hydroxy group obtained by hydrogenating vegetable oils and fats.
As for the molecular weight distribution of the release agent, the main peak is preferably in the region of molecular weight 400 or more and 2400 or less, and more preferably in the region of 430 or more and 2000 or less. Thereby, preferable thermal characteristics can be imparted to the toner.
The content of the release agent is preferably 2.5 parts by mass or more and 40.0 parts by mass or less with respect to 100 parts by mass of a resin (that is, a binder resin) formed from a monomer containing styrene. More preferably, it is 3.0 to 15.0 parts by mass.

The present invention
Dispersing a monomer composition containing polyester resin A, charge control resin B, colorant and monomer in an aqueous medium to form particles of the monomer composition in the aqueous medium; and
A method for producing a toner comprising a step of polymerizing the monomer contained in the particles of the monomer composition,
The styrene content in the monomer is 60% by mass or more,
The charge control resin B is a polymer having a structure represented by the above formula (1),
The polyester resin A has a styrene-hexane solubility index of 15.0 or more and 27.0 or less,
The toner production method is characterized in that the absolute value of the difference between the styrene-hexane solubility index of the polyester resin A and the styrene-hexane solubility index of the charge control resin B is 7.0 or less.

In the present invention, as described above, the suspension polymerization method is used as a toner production method.
A specific procedure will be described below, but the present invention is not limited to this.
First, a monomer containing styrene, a polyester resin A, a charge control resin B and a colorant, and, if necessary, a release agent and other additives are mixed and dissolved or dispersed uniformly with a stirrer or the like. A monomer composition is prepared.
The obtained monomer composition is added to an aqueous dispersion containing a dispersant, and dispersed using a high-speed disperser such as a high-speed stirrer or an ultrasonic disperser to form particles of the monomer composition. .
Then, the monomer contained in the particles is polymerized by light or heat. The particles obtained by the polymerization may be converted into toner through filtration, washing, drying processes, and the like.
In the case of producing by the suspension polymerization method, a polymerization initiator may be used, or may be added at the same time when other additives are added to the monomer, or particles of the monomer composition may be added in an aqueous medium. You may mix immediately before forming. Further, immediately after the formation of the particles, a polymerization initiator dissolved in a monomer or a solvent may be added before starting the polymerization reaction.

In the present invention, as the monomer, the above-mentioned vinyl monomers can be used.
Examples of the aqueous medium include water; alcohols such as methyl alcohol, ethyl alcohol, modified ethyl alcohol, isopropyl alcohol, n-butyl alcohol, isobutyl alcohol, tert-butyl alcohol, sec-butyl alcohol; methyl cellosolve, cellosolve, isopropyl Examples include ether alcohols such as cellosolve, butyl cellosolve, and diethylene glycol monobutyl ether. Other water-soluble compounds include ketones such as acetone, methyl ethyl ketone, and methyl isobutyl ketone; esters such as ethyl acetate; ethers such as ethyl ether and ethylene glycol; acetals such as methylal and diethyl acetal; formic acid and acetic acid , Selected from acids such as propionic acid, and preferably water or alcohols.
These aqueous media can be used in combination of two or more.
The concentration of the monomer composition with respect to the aqueous medium is preferably 1% by mass or more and 80% by mass or less, and more preferably 10% by mass or more and 65% by mass or less with respect to the aqueous medium.

As a dispersant for dispersing the monomer composition in an aqueous medium, known inorganic compounds and organic compounds can be used.
The following are mentioned as an inorganic compound.
Calcium phosphate, magnesium phosphate, aluminum phosphate, zinc phosphate, calcium carbonate, magnesium carbonate, calcium hydroxide, magnesium hydroxide, aluminum hydroxide, calcium metasilicate, calcium sulfate, barium sulfate, bentonite, silica, alumina.
On the other hand, examples of the organic compound include the following.
Polyvinyl alcohol, gelatin, methyl cellulose, methyl hydroxypropyl cellulose, ethyl cellulose, sodium salt of carboxymethyl cellulose, polyacrylic acid and its salt, starch.
It is preferable that the usage-amount of a dispersing agent is 0.2 to 20.0 mass parts with respect to 100 mass parts of monomer compositions.
As the polymerization initiator, the polymerization initiators exemplified in the charge control resin B can be similarly used.

In the present invention, in order to increase the mechanical strength of the toner and to control the molecular weight of the binder resin of the toner, a crosslinking agent may be used when polymerizing the monomer. As the crosslinking agent, a known crosslinking agent can be used.
Specifically, as a bifunctional cross-linking agent, divinylbenzene, bis (4-acryloxypolyethoxyphenyl) propane, ethylene glycol diacrylate, 1,3-butylene glycol diacrylate, 1,4-butanediol diacrylate, 1,5-pentanediol diacrylate, 1,6-hexanediol diacrylate, neopentyl glycol diacrylate, diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, polyethylene glycol # 200, # 400, # 600 Each diacrylate, dipropylene glycol diacrylate, polypropylene glycol diacrylate, polyester type diacrylate (MANDA Nippon Kayaku), and Relate include those instead dimethacrylate.
Polyfunctional crosslinkers include pentaerythritol triacrylate, trimethylol ethane triacrylate, trimethylol propane triacrylate, tetramethylol methane tetraacrylate, oligoester acrylate and its methacrylate, 2,2-bis (4-methacryloxypolyethoxy Phenyl) propane, diallyl phthalate, triallyl cyanurate, triallyl isocyanurate and triallyl trimellitate. The addition amount of these crosslinking agents is preferably 0.10 parts by mass or more and 5.00 parts by mass or less with respect to 100.00 parts by mass of the monomer.

In the toner of the present invention, inorganic fine particles may be externally added to the toner for the purpose of improving the fluidity of the toner and making the charge uniform.
Examples of the inorganic fine particles include silica fine particles such as silica fine particles by a wet production method and silica fine particles by a dry production method, and the silica fine particles on the surface by a treatment agent such as a silane coupling agent, a titanium coupling agent, and silicone oil. Examples thereof include treated silica fine particles.
The inorganic fine particles preferably have a specific surface area of 30.0 m ² / g or more, more preferably 50.0 m ² / g or more, as measured by a BET method using nitrogen adsorption.
The addition amount of the inorganic fine particles is preferably 0.01 parts by weight or more and 8.0 parts by weight or less, and more preferably 0.10 parts by weight or more and 4.0 parts by weight or less with respect to 100 parts by weight of the toner particles.

Below, it describes about the measuring method of each physical-property value based on this invention.
<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.

<Structural analysis of polyester resin A, charge control resin B and monomer>
The structures of the polyester resin A, the charge control resin B, and the monomer can be determined using a nuclear magnetic resonance apparatus ( ¹ H-NMR), and the composition ratio can be calculated.
The apparatus used below will be described.
Measuring apparatus: FT NMR apparatus JNM-EX400 (manufactured by JEOL Ltd.)
Measurement frequency: 400MHz
Pulse condition: 5.0μs
Frequency range: 10500Hz
Integration count: 64 times Measurement temperature: 30 ° C
50 mg of a sample is put into a sample tube having an inner diameter of 5 mm, and deuterated chloroform (CDCl3) is added as a solvent. The sample tube is placed in a constant temperature bath at 40 ° C., and the sample is dissolved to prepare a measurement sample. Measurement is performed under the above conditions using the measurement sample.
Note that the molar content of the structure represented by the formula (1) in the charge control resin B can be calculated by the acid value measurement described above in addition to the nuclear magnetic resonance apparatus described above.
Specifically, the structure of the monomer contained in the charge control resin B is analyzed using a nuclear magnetic resonance apparatus, and the constituent monomer is identified. Next, from the above acid value measurement, it is quantified from the relationship between the structure represented by the formula (1) contained in the charge control resin B and the acid value, and calculated as the molar content.

<Molecular weight measurement of resin>
The weight average molecular weight (Mw) and number average molecular weight (Mn) of the polyester resin A, the charge control resin B, and other resins 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.
The resin is added to THF (tetrahydrofuran), and the solution which is allowed to stand at room temperature for 24 hours 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.
Note that the amount of THF in the sample solution is adjusted so that the concentration of the resin is 0.8% by mass. In addition, when the resin is difficult to dissolve in THF, a basic solvent such as N, N-dimethylformamide (DMF) can be used.
Measurement is performed using the sample solution under the following conditions.
Apparatus: HLC8120 GPC (detector: RI) (manufactured by Tosoh Corporation)
Column: Seven series of Shodex KF-801, 802, 803, 804, 805, 806, 807 (manufactured by Showa Denko KK)
Eluent: Tetrahydrofuran (THF)
Flow rate: 1.0 mL / min
Oven temperature: 40.0 ° C
Sample injection volume: 0.10 mL
In calculating the molecular weight of the sample, the molecular weight distribution of the sample is calculated from the relationship between the logarithmic value of the calibration curve created by 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, manufactured by Tosoh Corporation. F-10, F-4, F-2, F-1, A-5000, A-2500, A-1000, A-500 ".

<Measurement of acid value of resin>
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 × 5.611] / 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 resin>
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 was transferred to a 250 mL tall beaker, and toluene and ethanol (3:
Add 100 mL of the mixed solution of 1) and dissolve for 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 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.

<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 is set to 256 particle size bin, and the particle size range is set to 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).

  EXAMPLES The present invention will be specifically described below with reference to examples and comparative examples, but the present invention is not limited to these examples. In the examples and comparative examples, “part” and “%” are 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. . Table 3 shows the physical properties of the obtained polyester resin A.
The composition of the obtained polyester resin A was a composition according to the preparation amount shown in Table 2.

<Production example of polyester resin A2-18>
The same operations as for the polyester resin A1 were carried out at the raw material monomer charge amounts shown in Table 2 to produce polyester resins A2-18. Table 3 shows the physical properties of the obtained polyester resin A.
The composition of the obtained polyester resin A was a composition according to the preparation amount shown in Table 2.

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の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
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＋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): propylene oxide 2-mol adduct of bisphenol A EG: ethylene 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 + isosorbide) in all alcohol monomers constituting polyester resin A

[Synthesis Example of Monomer (Formula (5))]
<Synthesis Example of Monomer C-1>
18 g of 2,4-dihydroxybenzoic acid was dissolved in 150 mL of methanol. To this solution, 36.9 g of potassium carbonate was added and heated to 65 ° C. A solution obtained by mixing and dissolving 18.7 g of 4- (chloromethyl) styrene and 100 mL of methanol was prepared, and this was dropped into a solution containing a salicylic acid intermediate, and reacted at 65 ° C. for 3 hours. The obtained reaction solution was cooled and then filtered, and methanol in the filtrate was distilled off under reduced pressure to obtain a precipitate. The precipitate was dispersed in 1.50 L of water at pH = 2, and extracted by adding ethyl acetate. Then, after washing with water, it was dried with magnesium sulfate, and ethyl acetate was distilled off under reduced pressure to obtain a precipitate. The precipitate was washed with hexane and recrystallized with toluene / ethyl acetate to obtain 20.1 g of monomer C-1 having a structure represented by the following formula (7).

<Synthesis Example of Monomer C-2>
(Process 1)
100 g of 2,5-dihydroxybenzoic acid and 1441 g of 80% sulfuric acid were mixed while heating to 50 ° C., 144 g of tert-butyl alcohol was added to the mixture, and the mixture was stirred at 50 ° C. for 30 minutes. Next, 144 g of tert-butyl alcohol was added to the mixed solution, and the mixture was stirred at 50 ° C. for 30 minutes three times. The reaction solution was cooled to room temperature and then slowly poured into 1.00 kg of ice water, and the precipitate was filtered. The precipitate was washed with water and further washed with hexane. The precipitate obtained here was dissolved in 200 mL of methanol and reprecipitated in 3.60 L of water. After filtration, 74.9 g of a salicylic acid intermediate represented by the following formula (8) was obtained by drying at 80 ° C.

(Process 2)
25.0 g of the salicylic acid intermediate was dissolved in 150 mL of methanol. To this solution, 36.9 g of potassium carbonate was added and heated to 65 ° C. A solution obtained by mixing and dissolving 18.7 g of 4- (chloromethyl) styrene and 100 mL of methanol was prepared, and this was dropped into a solution containing a salicylic acid intermediate, and reacted at 65 ° C. for 3 hours. The obtained reaction solution was cooled and then filtered, and methanol in the filtrate was distilled off under reduced pressure to obtain a precipitate. The precipitate was dispersed in 1.50 L of water at pH = 2, and extracted by adding ethyl acetate. Then, after washing with water, it was dried with magnesium sulfate, and ethyl acetate was distilled off under reduced pressure to obtain a precipitate. The precipitate was washed with hexane and recrystallized with toluene / ethyl acetate to obtain 20.1 g of monomer C-2 having a structure represented by the following formula (9).

<Synthesis Example of Monomer C-3>
100.0 g of 2,5-dihydroxybenzoic acid was dissolved in 2 L of methanol, 88.3 g of potassium carbonate was added, and the mixture was heated to 67 ° C. To this solution, 102.0 g of 4- (chloromethyl) styrene was added dropwise over 22 minutes and reacted at 67 ° C. for 12 hours. The obtained reaction liquid was cooled, methanol was distilled off under reduced pressure, and washed with hexane. The residue was dissolved in methanol, dropped into water, reprecipitated, and the precipitate was filtered. This reprecipitation operation was repeated twice, and the residue was 80%.
The monomer C-3 having a structure represented by the following formula (10) was obtained by drying at ° C.

<Synthesis Example of Monomer C-4>
A salicylic acid intermediate was obtained by the same method as the synthesis of monomer C-2 (step 1) except that 144 g of tert-butyl alcohol was changed to 253 g of 2-octanol. Monomer C-4 having a structure represented by the following formula (11) was obtained in the same manner as the synthesis of monomer C-2 (step 2) except that 32 g of the obtained salicylic acid intermediate was used.

<Synthesis Example of Monomer C-5>
Except that the salicylic acid intermediate of formula (8) is changed to 22 g of 2,5-dihydroxy-3-methoxybenzoic acid, it is represented by the following formula (12) in the same manner as the synthesis of monomer C-2 (step 2). Monomer C-5 having a structure as described above was obtained.

<Synthesis Example of Monomer C-6>
Except for changing the salicylic acid intermediate of formula (8) to 18 g of 2,3-dihydroxybenzoic acid, it has the structure represented by the following formula (13) in the same manner as the synthesis of monomer C-2 (step 2). Compound C-6 was obtained.

<Synthesis Example of Monomer C-7>
A monomer other than changing 4- (chloromethyl) styrene to a mixture of 3- (chloromethyl) methylstyrene and 4- (chloromethyl) styrene (trade name “CMS-P” manufactured by AGC Seikagaku Co., Ltd.) Monomer C-7 having a structure represented by the following formula (14) was obtained by the same method as the synthesis of C-2 (step 2).

[Synthesis Example of Charge Control Resin B]
<Synthesis of Charge Control Resin B-1>
12.00 g of monomer C-1 represented by formula (7) and 88.00 g of styrene were dissolved in 40.00 ml of N, N-dimethylformamide (DMF), stirred for 1 hour, and then heated to 110 ° C. Dissolved solution obtained by stirring for 1 hour a solution prepared by adding 3.50 g of tert-butyl peroxyisopropyl monocarbonate (trade name Perbutyl I, manufactured by Nippon Oil & Fats Co., Ltd.) to 40.00 ml of toluene in this reaction solution. Was dripped. The reaction was further carried out at 110 ° C. for 4 hours under introduction of nitrogen. Then, it cooled and it was dripped at methanol 1.00L, and the deposit was obtained. The obtained precipitate was dissolved in 120 ml of THF and then added dropwise to 1.80 L of methanol to precipitate a white precipitate, filtered, and dried at 90 ° C. under reduced pressure to obtain monomer C-1 and styrene. A charge control resin B-1 was obtained.
The composition analysis of the obtained charge control resin B-1 was performed using the aforementioned ¹ H-NMR, and it was confirmed that the monomer C-1 was polymerized. In addition, the acid value of the charge control resin B-1 is 24.8 mgKOH / g, and it is confirmed from the acid value that the structure represented by the formula (1) derived from the monomer C-1 contains 442 μmol / g. It was done. Table 4 shows the amount of charge control resin B charged and the results of composition analysis. Table 4 also shows the acid value of the obtained resin and the molar content of the structure represented by the formula (1).

<Synthesis of charge control resins B-2 to B-12>
Except for changing the type and amount of the monomer containing the structure represented by the formula (1), the type and amount of the vinyl monomer, the addition amount of the polymerization initiator, and the reaction conditions as shown in Table 4. Then, the same operation as the synthesis of the charge control resin B-1 was performed to produce the charge control resins B-2 to B-12. Table 4 shows the physical properties of the obtained resin.

<Synthesis of charge control resin D>
In a 2 L flask equipped with a stirrer, a condenser, a thermometer, and a nitrogen introducing tube, 100 parts of toluene, 350 parts of methanol, 470 parts of styrene, 40 parts of 2-acrylamido-2-methylpropanesulfonic acid, 70 ethyl acrylate-2-ethylhexyl 70 Part, 20 parts of benzyl methacrylate and 10 parts of lauryl peroxide were added, and solution polymerization was carried out at 65 ° C. for 10 hours under stirring and introducing nitrogen. The obtained contents were taken out from the flask, washed with isopropyl alcohol, dried under reduced pressure at 40 ° C. for 96 hours, and then coarsely crushed with a hammer mill, and the coarsely crushed product was further dried under reduced pressure at 40 ° C. for 48 hours. Manufactured. The obtained charge control resin D had physical properties of Mw = 24000, Tg = 67 ° C., and residual monomer = 350 ppm. The obtained charge control resin D had an acid value of 20 mgKOH / g and a styrene-hexane solubility index of 40.0.

<Toner Production Example 1>
Toner 1 was produced by the following procedure.
850 parts by mass of 0.1 mol / L-Na ₃ PO ₄ aqueous solution was added to a container equipped with a high-speed stirrer CLEARMIX (M Technique Co., Ltd.), the rotation speed was adjusted to 15000 rpm, and the mixture was heated to 60 ° C. . Here was added 1.0mol / L-CaCl ₂ aqueous solution 68 parts by mass, to prepare an aqueous medium containing a fine sparingly water-soluble dispersing agent _Ca 3 _{(PO 4) 2.} Moreover, the following material was melt | dissolved at 100 r / min with the propeller-type stirring apparatus, and the solution was prepared.
-Styrene 75.00 parts by mass-n-butyl acrylate 25.00 parts by mass-Polyester resin A-1 4.00 parts by mass-Charge control resin B-1 1.000 parts by mass Next, the following materials are added to the solution. Added.
・ C. I. Pigment Blue 15: 3 6.50 parts by mass / hydrocarbon wax 9.00 parts by mass (the peak temperature of the maximum endothermic peak is 77 ° C., HNP-51, manufactured by Nippon Seiwa Co., Ltd.)
Thereafter, the mixture was heated to a temperature of 60 ° C., and then stirred and dissolved and dispersed with a TK homomixer (manufactured by Tokushu Kika Kogyo Co., Ltd.) at 9000 r / min.
In this, 10.00 parts by mass of a polymerization initiator 2,2′-azobis (2,4-dimethylvaleronitrile) was dissolved to prepare a monomer composition. The monomer composition was put into the aqueous medium and granulated at a temperature of 60 ° C. for 15 minutes while rotating the CLEARMIX at 15000 rpm.
Thereafter, the mixture was transferred to a propeller type stirring device and reacted at a temperature of 70 ° C. for 5 hours while stirring at 100 r / min. Then, the temperature was raised to 80 ° C. and the reaction was further performed for 5 hours to produce toner particles. After completion of the polymerization reaction, the slurry containing the particles was cooled, washed with 10 times the amount of water as the slurry, filtered and dried, and then the particle size was adjusted by classification to obtain toner particles.
Hydrophobic silica fine particles (primary primary) treated with dimethyl silicone oil (20% by mass) as a fluidity improver and frictionally charged to the same polarity (negative polarity) as the toner particles with respect to 100.0 parts by mass of the toner particles. Toner 1 was obtained by mixing 1.5 parts by mass of particle number average particle diameter: 10 nm, BET specific surface area: 170 m ² / g) with a Henschel mixer (manufactured by Mitsui Miike Chemical Co., Ltd.) at 3000 r / min for 15 minutes. .

<Toner Production Examples 2 to 27>
As shown in Table 5, toners 2 to 27 were produced in the same manner as in toner production example 1 except that the types of polyester resin A and charge control resin B were changed.

<Toner Production Example 28>
In Toner Production Example 1, C.I. I. Pigment Blue 15: 3 to C.I. I. A toner 28 was obtained in the same manner except that Pigment Violet 19 was used.

<Toner Production Example 29>
In Toner Production Example 1, C.I. I. Pigment Blue 15: 3 to C.I. I. A toner 29 was obtained in the same manner except that Pigment Yellow 155 was used.

<Toner Production Example 30>
In Toner Production Example 1, C.I. I. A toner 30 was obtained in the same manner except that the pigment blue 15: 3 was changed to carbon black.

<Toner Production Example 31>
Toner 31 was obtained in the same manner as in Toner Production Example 1 except that styrene was changed to 65.00 parts by mass and n-butyl acrylate was changed to 35.00 parts by mass.

<Toner Production Example 32>
Toner 32 was obtained in the same manner as in Toner Production Example 1 except that styrene was changed to 80.00 parts by mass and n-butyl acrylate was changed to 20.00 parts by mass.

<Toner Production Examples 33 and 34>
As shown in Table 5, toners 33 and 34 were obtained in the same manner as in Toner Production Example 1 except that the types of polyester resin A and charge control resin B were changed.

<Toner Production Example 35>
Toner 35 was obtained in the same manner as in Toner Production Example 1 except that charge control resin B-1 was changed to charge control resin D.

<Toner Production Example 36>
In Toner Production Example 1, toner was produced in the same manner except that styrene was changed to 57.00 parts by mass, n-butyl acrylate was changed to 43.00 parts by mass, and charge control resin B was changed as shown in Table 5. 36 was obtained.

<Toner Production Example 37>
As shown in Table 5, toner 37 was obtained in the same manner as in toner production example 1 except that the types of polyester resin A and charge control resin B were changed.

<Examples 1-32 and Comparative Examples 1-5>
The following evaluations were performed on toners 1 to 37.

<Evaluation of storage stability under high temperature and high humidity>
About 10 g of toner was put in a 100 ml glass bottle and left to stand for 20 days at a temperature of 45 ° C. and a humidity of 95% RH, and then judged visually.
A: No change B: There is an aggregate, but it loosens immediately C: An aggregate that is difficult to loosen is generated D: No fluidity E: Obvious caking

<Evaluation of durability stability and charging stability after storage in high temperature and high humidity environment>
As the image forming apparatus, the toner was extracted from a toner cartridge of LBP-7700C (manufactured by Canon), which is a commercially available laser printer having the configuration as shown in FIG. The toner cartridge was left in an environment of a temperature of 45 ° C. and a humidity of 95% RH for 20 days. Thereafter, the sample was left for 24 hours in an environment of a temperature of 32.5 ° C. and a humidity of 90% RH, mounted on the cyan station of the laser printer, and a dummy cartridge was mounted on the others, and an image output test was performed.
The image evaluation was performed by repeating the operation of pausing for 1 minute every time two images with a printing rate of 1% were printed, outputting 20000 images, and evaluating by the following method.

<Evaluation of fog>
The fog was measured with a reflectometer (manufactured by Tokyo Denshoku). In the above image output test, an image with a printing rate of 0% was output initially, after 18000 sheets, and after 20000 sheets. Calculated. The fog was evaluated based on the following criteria based on the fog density result.
A: Less than 1.0% B: 1.0% or more and less than 1.5% C: 1.5% or more and less than 2.0% D: 2.0% or more and less than 3.0% E: 3.0% or more

<Evaluation of component contamination>
In the initial stage, after 18000 sheets and 20000 sheets, the member contamination is a halftone image (toner applied amount 0.25 mg / cm ² ) and a second half portion of printed image is a solid image (toner applied amount 0.40 mg / cm ^2). ) Were printed and evaluated according to the following criteria.
A: Vertical stripes in the paper discharge direction are not seen on the developing roller or on the halftone and solid images.
B: Although there are one or two thin circumferential streaks at both ends of the developing roller, no vertical streaks in the paper discharge direction are seen on the halftone and solid images.
C: Although there are 3-5 thin streaks in the circumferential direction at both ends of the developing roller, there are only a few vertical streaks in the paper discharge direction on the halftone and solid images. However, it can be erased by image processing.
D: There are 6 to 20 fine circumferential streaks at both ends of the developing roller, and several fine streaks can be seen on the halftone and solid images. It cannot be erased even with image processing.
E: 21 or more streaks are observed on the developing roller and the halftone image, and cannot be erased even by image processing.

DESCRIPTION OF SYMBOLS 11 Photoconductor, 12 Developing roller, 13 Toner supply roller, 14 Toner, 15 Control blade, 16 Developing device, 17 Laser beam, 18 Charging device, 19 Cleaning device, 20 Cleaning charging device, 21 Stirring blade, 22 Driving roller, 23 transfer roller, 24 bias power supply, 25 tension roller, 26 transfer conveyance belt, 27 driven roller, 28 paper, 29 paper feed roller, 30 suction roller, 31 fixing device

Claims (6)

Toner obtained by forming particles of a monomer composition containing polyester resin A, charge control resin B, colorant and monomer in an aqueous medium, and polymerizing the monomer contained in the particles of the monomer composition Because
The styrene content in the monomer is 60% by mass or more,
The charge control resin B is a polymer having a structure 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,
A toner characterized in that the absolute value of the difference between the styrene-hexane solubility index of the polyester resin A and the styrene-hexane solubility index of the charge control resin B is 7.0 or less.

[In the formula (1), each R ¹ independently represents a hydroxy group, a carboxy group, an alkyl group having 1 to 18 carbon atoms, or an alkoxy group having 1 to 18 carbon atoms, and h is 0. Represents an integer of 3 or less. ] The polyester resin A contains an isosorbide unit represented by the following formula (2), and the content ratio of the isosorbide unit represented by the following formula (2) is based on all monomer units constituting the polyester resin A. The toner according to claim 1, wherein the toner content is 0.10 mol% or more and 20.00 mol% or less.

The polyester resin A contains a monomer unit derived from terephthalic acid,
The toner according to claim 1, wherein a content ratio of the monomer unit derived from terephthalic acid is 85.00 mol% or more based on all dicarboxylic acid monomer units constituting the polyester resin A. 4. The toner according to claim 1, wherein the charge control resin B is a polymer having a structure represented by the following formula (3).

[In the formula (3), R ² is, independently, a hydroxyl group, a carboxyl group, having 1 to 18 alkyl group carbon atoms or represents a 1 to 18 alkoxy group having a carbon number, R ³ is , A hydrogen atom, a hydroxy group, an alkyl group having 1 to 18 carbon atoms, or an alkoxy group having 1 to 18 carbon atoms, j represents an integer of 1 to 3 and i is an integer of 0 to 3 Represents. ] The toner according to claim 1, wherein the charge control resin B is a polymer having a monomer unit represented by the following formula (4).

[In the formula (4), R ⁶ represents a hydrogen atom or a methyl group, and each R ⁴ independently represents a hydroxy group, a carboxy group, an alkyl group having 1 to 18 carbon atoms, or one or more carbon atoms. Represents an alkoxy group having 18 or less, R ⁵ represents a hydrogen atom, a hydroxy group, an alkyl group having 1 to 18 carbon atoms, or an alkoxy group having 1 to 18 carbon atoms, and l is an integer of 1 to 3 And k represents an integer of 0 or more and 3 or less. ] Dispersing a monomer composition containing polyester resin A, charge control resin B, colorant and monomer in an aqueous medium to form particles of the monomer composition in the aqueous medium; and
A method for producing a toner comprising a step of polymerizing the monomer contained in the particles of the monomer composition,
The styrene content in the monomer is 60% by mass or more,
The charge control resin B is a polymer having a structure 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,
A toner manufacturing method, wherein an absolute value of a difference between a styrene-hexane solubility index of the polyester resin A and a styrene-hexane solubility index of the charge control resin B is 7.0 or less.

[In the formula (1), each R ¹ independently represents a hydroxy group, a carboxy group, an alkyl group having 1 to 18 carbon atoms, or an alkoxy group having 1 to 18 carbon atoms, and h is 0. Represents an integer of 3 or less. ]

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