JP2018010114A - Toner and method for manufacturing toner - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a toner that is adaptable for a high-speed developing system, and excellent in development stability, low-temperature fixability, and hot offset resistance.SOLUTION: A toner includes toner particles each containing a polyester resin A, a polyester resin B, and an organic metal compound. The polyester resin A is an amorphous polyester resin obtained through polycondensation of an alcohol component containing 80 mol% or more of aromatic polyhydric alcohol and a polyvalent carboxylic acid component; the polyester resin B is a crystalline polyester resin obtained through polycondensation of an alcohol component containing 80 mol% or more of aliphatic diol having 6 to 12 carbon atoms, inclusive, and a carboxylic acid component containing 80 mol% or more of aliphatic dicarboxylic acid having 6 to 12 carbon atoms, inclusive; the organic metal compound is an organic zirconium compound produced through a reaction between zirconium and aromatic hydroxycarboxylic acid, and the organic zirconium compound contains 1.2 to 1.8 mol of an aromatic hydroxycarboxylic acid unit with respect to 1 mol of a zirconium atom.SELECTED DRAWING: None

Description

  The present invention relates to a toner used in an electrophotographic system, an electrostatic recording system, an electrostatic printing system, and a toner jet system, and a method for producing the toner.

  In recent years, an image forming apparatus using an electrophotographic method has been required to be faster and more reliable. In addition, there are high demands for power saving and shortened wait time, and in order to meet these demands, low-temperature fixability is demanded as a toner. In recent years, from the viewpoint of effective utilization of paper resources, attempts have been made to use paper having a low basis weight and further reduce the amount of paper used by double-sided printing. Therefore, the toner is also required to have hot offset resistance.

In order to achieve low temperature fixability, it has been proposed to use not only an amorphous resin but also a crystalline resin as a binder resin. In patent document 1, the proposal which makes fixing property and preservability compatible is made by using non-crosslinkable crystalline resin and crosslinkable crystalline resin together.
There have also been proposals for improving the chargeability of the toner. In Patent Document 2, a proposal has been made to contain a crystalline resin as a binder resin and a metal compound of a salicylic acid derivative as a charge control agent.

JP 2012-53196 A JP 2002-351137 A

The crosslinkable crystalline resin described in Patent Document 1 is likely to be non-uniformly dispersed in the amorphous resin, thereby easily causing toner charging failure during long-term use.
In addition, as disclosed in Patent Document 2, only by increasing the compatibility between the crystalline resin and the charge control agent, the charge imparting effect is improved, but the dispersion state of the crystalline resin in the amorphous resin is unstable. This may adversely affect low-temperature fixability and hot offset resistance.

In addition, for the purpose of improving the fluidity and maintaining the in-machine transportability and uniform triboelectric chargeability, the toner has various fine particles such as silicon compounds attached as spacers on the surface of the toner. A method for suppressing the cohesive force between particles is used.
However, in the high-speed development system, the stress on the toner due to the developing roller, the regulating member, the stirring member, etc. in the developing device is greater. Especially when a large number of sheets are continuously printed, the spacer particles are formed on the surface of the toner. It is easy to be buried. As a result, the cohesive force suppressing effect cannot be sufficiently exhibited, and it is difficult to maintain stable triboelectric charging characteristics. In particular, when the above-described crystalline resin is used for the purpose of promoting plasticization of an amorphous resin, the toughness of the toner is impaired, and these embedding phenomena are likely to occur.

As described above, even a system using a crystalline resin has not yet achieved a toner that can simultaneously satisfy development stability, low-temperature fixability, and hot offset resistance.
The object of the present invention is to provide a toner that has solved the above-mentioned problems and that has excellent charging characteristics, excellent development stability, low temperature fixability, and hot offset resistance even in a toner using a plasticizer such as a crystalline material. It is to be.

The above problem can be solved by the toner having the following configuration.
That is, according to the present invention, in a toner having toner particles containing polyester resin A, polyester resin B and an organometallic compound,
The polyester resin A is an amorphous polyester resin obtained by condensation polymerization of an alcohol component containing 80 mol% or more of an aromatic polyhydric alcohol and a polyvalent carboxylic acid component,
The polyester resin B is a polycondensation of an alcohol component containing 80 mol% or more of an aliphatic diol having 6 to 12 carbon atoms and a carboxylic acid component containing 80 mol% or more of an aliphatic dicarboxylic acid having 6 to 12 carbon atoms. A crystalline polyester resin obtained by
The organometallic compound is an organozirconium compound produced by a reaction between zirconium and an aromatic hydroxycarboxylic acid, and the organozirconium compound has an aromatic hydroxycarboxylic acid unit of 1.2 to 1 mol per 1 mol of zirconium atom. A toner containing 1.8 mol is provided.

  According to the present invention, it is possible to provide a toner excellent in development stability, low-temperature fixability, and hot offset resistance even in a high-speed development system.

It is the schematic of the thermal spheronization processing apparatus used for manufacture of the toner of this invention.

Hereinafter, embodiments for carrying out the present invention will be described in detail.
According to the present invention, a toner having toner particles containing polyester resin A, polyester resin B and an organometallic compound,
The polyester resin A is an amorphous polyester resin obtained by condensation polymerization of an alcohol component containing 80 mol% or more of an aromatic polyhydric alcohol and a polyvalent carboxylic acid component,
The polyester resin B is a polycondensation of an alcohol component containing 80 mol% or more of an aliphatic diol having 6 to 12 carbon atoms and a carboxylic acid component containing 80 mol% or more of an aliphatic dicarboxylic acid having 6 to 12 carbon atoms. A crystalline polyester resin obtained by
The organometallic compound is an organozirconium compound produced by a reaction between zirconium and an aromatic hydroxycarboxylic acid, and the organozirconium compound has an aromatic hydroxycarboxylic acid unit of 1.2 to 1 mol per 1 mol of zirconium atom. Contains 1.8 mol,
Toner is provided.

That is, the present inventors have found that the following toner can be obtained by using a reaction product of amorphous polyester resin A, crystalline polyester resin B, zirconium and aromatic hydroxycarboxylic acid. It was.
A toner that maintains a low-temperature fixability and hot offset resistance, obtains a high charge amount even when left in a high humidity environment, and does not become overcharged even in a low humidity environment.
The organic zirconium compound of the present invention is also preferable for color toners because a clear color image can be obtained.

The inventors consider the following effects of the use of the toner of the present invention having such a configuration.
The polyester resin A is amorphous and the polyester resin B is crystalline.
The crystalline resin in the present invention is a resin in which an endothermic peak is observed in differential scanning calorimetry (DSC).

  In the polyester resin A that is amorphous, the carbon number of the alcohol component (aliphatic diol) and the carbon number of the carboxylic acid component (aliphatic carboxylic acid) of the polyester resin B that is crystalline are specified values. And aromatic alcohols having different structures are used. By this, each compatibility degree can be adjusted and, thereby, the polyester resin B can be arrange | positioned in the polyester resin A in the dispersion state which is easy to express a plastic effect.

  Further, in the organozirconium compound contained in the toner of the present invention, the zirconium atom is likely to be octacoordinated, and the oxygen of the carboxyl group or hydroxyl group in the polyester resin is likely to be coordinated or bonded. Thereby, the organic zirconium compound can be prevented from falling out of the toner particles, and the dispersed state of the polyester resin B in the polyester resin A can be fixed. Thereby, for example, it is possible to suppress uneven distribution due to re-aggregation of the crystalline polyester due to an external factor such as long-term standing in a high-temperature and high-humidity environment.

Further, the toughness of the toner is increased, and toner deterioration such as embedding of an external additive in the developing process of the electrophotographic process is suppressed.
In the case where the melt-kneading step is performed at the time of toner production, the crosslinking reaction by coordination or bonding of the oxygen of the carboxyl group or hydroxyl group in the polyester resin of the organic zirconium compound is promoted. Thereby, the toughness of the toner is increased, and toner deterioration such as embedding of an external additive in the developing process of the electrophotographic process is suppressed.

In addition, when a heat treatment process is performed at the time of toner production, it is possible to place the crystalline polyester resin B in the vicinity of the surface of the toner while maintaining the crystallization of the crystalline polyester resin B, and to perform a crosslinking reaction on the toner surface layer. This can be promoted, and the above effect is more easily manifested.
It is important that the content of the polyester resin B is 2 to 20 parts by mass with respect to 100 parts by mass of the polyester resin A.
In the present invention, a preferable toner configuration for achieving the object will be described in detail below.

[Polyester resin A]
The polyester resin A used in the toner of the present invention is:
It is obtained by polycondensing an alcohol component containing 80 mol% or more of an aromatic polyhydric alcohol and a polyvalent carboxylic acid component.
The aromatic polyhydric alcohol used in the polyester resin A is not particularly limited, and examples thereof include bisphenol derivatives represented by the following formula (a) and diols represented by the following formula (b).

（式中、Ｒはエチレン又はプロピレン基、ｘ，ｙはそれぞれ１以上の整数であり、かつｘ＋ｙの平均値は２〜７である。）

(In the formula, R is an ethylene or propylene group, x and y are each an integer of 1 or more, and the average value of x + y is 2 to 7.)

  Examples of the bisphenol derivative represented by the above formula (a) include the following. 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-hydroxyphenyl) propane, polyoxypropylene (6) -2,2-bis (4-hydroxyphenyl) propane. In some cases, for example, ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butanediol, neopentyl glycol, 1,4-butenediol, 1,5 -Diols such as pentanediol, 1,6-hexanediol, and other diols such as bisphenol A and hydrogenated bisphenol A are bisphenol derivatives represented by the above formula (a) or diols represented by the above formula (b) Can also be used in combination.

In addition, as an alcohol component which can be used for the polyester resin A, the following are mentioned. Ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butanediol, neopentyl glycol, 1,4-butenediol, 1,5-pentanediol, 1, 6-hexanediol, 1,4-cyclohexanedimethanol, dipropylene glycol, polyethylene glycol, polypropylene glycol, polytetramethylene glycol, sorbit, 1,2,3,6-hexanetetrol, 1,4-sorbitan, pentaerythritol , Dipentaerythritol, tripentaerythritol, 1,2,4-butanetriol, 1,2,5-pentanetriol, glycerin, 2-methylpropanetriol, 2-methyl-1,2,4-butant Ol, trimethylol ethane, trimethylol propane, 1,3,5-trihydroxy methyl benzene.
As described above, the main component of the alcohol component constituting the polyester resin A is an aromatic polyhydric alcohol. Here, in the alcohol component constituting the polyester resin A, the aromatic polyhydric alcohol is contained in a proportion of 80 mol% or more, and is preferably contained in a proportion of 90 mol% or more.

-Polyvalent carboxylic acid monomer As a polyvalent carboxylic acid monomer used for the polyester unit of the polyester resin, the following polyvalent carboxylic acid monomers can be used.
Examples of the divalent carboxylic acid component include the following. Maleic acid, fumaric acid, citraconic acid, itaconic acid, glutaconic acid, phthalic acid, isophthalic acid, terephthalic acid, succinic acid, adipic acid, sebacic acid, azelaic acid, malonic acid, n-dodecenyl succinic acid, isododecenyl succinic acid N-dodecyl succinic acid, isododecyl succinic acid, n-octenyl succinic acid, n-octyl succinic acid, isooctenyl succinic acid, isooctyl succinic acid, anhydrides of these acids and lower alkyl esters thereof. Of these, maleic acid, fumaric acid, terephthalic acid, and n-dodecenyl succinic acid are preferably used.

  Examples of the trivalent or higher carboxylic acid, its acid anhydride or its lower alkyl ester include the following. 1,2,4-benzenetricarboxylic acid, 2,5,7-naphthalenetricarboxylic acid, 1,2,4-naphthalenetricarboxylic acid, 1,2,4-butanetricarboxylic acid, 1,2,5-hexanetricarboxylic acid, 1,3-dicarboxyl-2-methyl-2-methylenecarboxypropane, 1,2,4-cyclohexanetricarboxylic acid, tetra (methylenecarboxyl) methane, 1,2,7,8-octanetetracarboxylic acid, pyromellitic acid , Empole trimer acids, their anhydrides or their lower alkyl esters. Among these, in particular, 1,2,4-benzenetricarboxylic acid, that is, trimellitic acid or its derivative, is inexpensive and easy to control, so that it is preferably used. These divalent carboxylic acids and the like and trivalent or higher carboxylic acids can be used alone or in combination.

In the present invention, the polyester resin A may be a hybrid resin containing other resin components as long as the polyester resin is a main component. For example, a hybrid resin of a polyester resin and a vinyl resin can be given. As a method for obtaining a reaction product of a vinyl resin or vinyl copolymer unit and a polyester resin, such as a hybrid resin, the following method is preferable.
A method in which a polymerization reaction of one or both resins is performed in the presence of a polymer containing a monomer component capable of reacting with each of a vinyl resin, a vinyl copolymer unit, and a polyester resin.

  For example, among the monomers constituting the polyester resin component, those capable of reacting with the vinyl copolymer include, for example, unsaturated dicarboxylic acids such as phthalic acid, maleic acid, citraconic acid and itaconic acid, or anhydrides thereof. It is done. Among the monomers constituting the vinyl copolymer component, those capable of reacting with the polyester resin component include those having a carboxyl group or a hydroxy group, and acrylic acid or methacrylic acid esters.

  In the present invention, as the polyester resin A, if a polyester resin is a main component, various resin compounds conventionally known as binder resins can be used in combination with the above-described vinyl resin. Examples of such resin compounds include the following. Phenol resin, natural resin-modified phenol resin, natural resin-modified male resin, acrylic resin, methacrylic resin, polyvinyl acetate resin, silicone resin, polyester resin, polyurethane, polyamide resin, furan resin, epoxy resin, xylene resin, polyvinyl butyral, terpene Resin, coumaroindene resin, petroleum resin.

The polyester resin A in the present invention can be produced according to a normal polyester synthesis method. For example, the above-mentioned carboxylic acid monomer and alcohol monomer are esterified or transesterified, and then subjected to a polycondensation reaction under reduced pressure or by introducing nitrogen gas according to a conventional method. A polyester resin can be obtained.
The esterification or transesterification reaction can be performed using a normal esterification catalyst or transesterification catalyst such as sulfuric acid, titanium butoxide, dibutyltin oxide, manganese acetate, and magnesium acetate, if necessary.

The polycondensation reaction can be carried out using a conventional polymerization catalyst, for example, a known catalyst such as titanium butoxide, dibutyltin oxide, tin acetate, zinc acetate, tin disulfide, antimony trioxide, germanium dioxide. .
Among these, in this invention, it is preferable that the tin compound represented by following formula (i) is used as a catalyst. By using this compound, it is easy to adjust physical properties such as the softening point and glass transition point of the resin. For example, although the condensation time is longer, the low molecular weight component can be reduced. Thereby, when using hot melt kneading at the time of toner production, the viscosity of the polyester resin can be stabilized, and the pigment and the like are easily dispersed uniformly.
Further, when the tin compound is present in the binder resin after the condensation polymerization, the cohesiveness of the pigment particles is reduced, and the fine dispersibility of the pigment particles in the resin is improved.

（式中Ｒは、炭素数５〜１５のアルキル基を示す）
ここで本発明において、式（ｉ）で表されるスズ化合物の式中Ｒは、５以上１５以下のアルキル基であることが、エステル化反応の触媒効果を有する物として最適なものである。
また上記アルキルカルボン酸スズ化合物の添加量としては、ポリエステル樹脂１００質量部に対して０．０１質量部以上２質量部以下が好ましく、０．０５質量部以上１質量部以下がより好ましい。０．０１質量部以上であれば、ポリエステル重合時の反応時間が長くなりすぎたりせず、顔料の分散性を向上させる効果が得られる。また２質量部以下であれば、トナーの帯電特性に影響を及ぼしたり、環境による帯電量の変動が大きくなったりしない。

(Wherein R represents an alkyl group having 5 to 15 carbon atoms)
Here, in the present invention, R in the formula of the tin compound represented by formula (i) is an alkyl group of 5 or more and 15 or less, which is optimal as a product having a catalytic effect of the esterification reaction.
Moreover, as addition amount of the said alkyl carboxylate tin compound, 0.01 mass part or more and 2 mass parts or less are preferable with respect to 100 mass parts of polyester resins, and 0.05 mass part or more and 1 mass part or less are more preferable. If it is 0.01 mass part or more, the reaction time at the time of polyester polymerization will not become long, and the effect which improves the dispersibility of a pigment will be acquired. On the other hand, if it is 2 parts by mass or less, the charging characteristics of the toner will not be affected, and fluctuations in the charge amount due to the environment will not increase.

  In addition, the peak molecular weight of the amorphous polyester resin A used in the present invention is preferably 8,000 or more and 13,000 or less from the viewpoint of low temperature fixability and hot offset resistance. The acid value of the amorphous polyester resin A is preferably 15 mgKOH / g or more and 30 mgKOH / g or less from the viewpoint of charging stability in a high temperature and high humidity environment. Furthermore, the hydroxyl value of the binder resin of the present invention is preferably 2 mgKOH / g or more and 20 mgKOH / g or less from the viewpoint of low-temperature fixability and storage stability.

  The amorphous polyester resin A may be used by mixing a high molecular weight polyester resin A (H) and a low molecular weight polyester resin A (L). The content ratio (H / L) of the high molecular weight polyester resin A (H) and the low molecular weight polyester resin A (L) is 10/90 or more and 60/40 or less on a mass basis. It is preferable from the viewpoint of hot offset resistance.

The peak molecular weight of the high molecular weight polyester resin A (H) is preferably 10,000 or more and 20,000 or less from the viewpoint of hot offset resistance. The acid value of the high molecular weight polyester resin A (H) is preferably 15 mgKOH / g or more and 30 mgKOH / g or less from the viewpoint of charging stability in a high temperature and high humidity environment.
The weight average molecular weight (Mw) of the low molecular weight polyester resin A (L) is preferably from 3000 to 7000 from the viewpoint of low-temperature fixability. The acid value of the low molecular weight polyester resin A (L) is preferably 10 mgKOH / g or less from the viewpoint of charging stability in a high temperature and high humidity environment.

[Polyester resin B]
The polyester resin B used in the present invention is
An alcohol component containing 80 mol% or more of an aliphatic diol having 6 to 12 carbon atoms;
It is obtained by polycondensation with a carboxylic acid component containing 80 mol% or more of an aliphatic dicarboxylic acid having 6 to 12 carbon atoms.
Polyester resin B is obtained by condensation polymerization of an alcohol component containing 85 mol% or more of an aliphatic diol having 6 to 12 carbon atoms and a carboxylic acid component containing 85 mol% or more of an aliphatic dicarboxylic acid having 6 to 12 carbon atoms. It is preferable that
The aliphatic diol is not particularly limited, but is preferably a chain (more preferably linear) aliphatic diol. Preferred examples include butanediol, pentanediol, hexanediol, heptanediol, octanediol, nonanediol, and decanediol.

In the present invention, if an aliphatic diol is the main component of the alcohol component of polyester B, a polyhydric alcohol monomer other than the aliphatic diol can also be used. The following are mentioned as a dihydric alcohol monomer among this polyhydric alcohol monomer. Aromatic alcohols such as polyoxyethylenated bisphenol A and polyoxypropylenated bisphenol A, which are adducts of alkylene oxide of bisphenol A; 1,4-cyclohexanedimethanol and the like.
Moreover, the following are mentioned as a polyhydric alcohol monomer more than trivalence among this polyhydric alcohol monomer. Aromatic alcohols such as 1,3,5-trihydroxymethylbenzene; pentaerythritol, dipentaerythritol, tripentaerythritol, 1,2,4-butanetriol, 1,2,5-pentanetriol, glycerin, 2-methyl Aliphatic alcohols such as propanetriol, 2-methyl-1,2,4-butanetriol, trimethylolethane, and trimethylolpropane.

  Furthermore, in the present invention, if an aliphatic diol is a main component as an alcohol component of polyester B, a monovalent alcohol may be used together. Examples of the monovalent alcohol include monofunctional groups such as n-butanol, isobutanol, sec-butanol, n-hexanol, n-octanol, lauryl alcohol, 2-ethylhexanol, decanol, cyclohexanol, benzyl alcohol, and dodecyl alcohol. And alcohol.

  On the other hand, the aliphatic dicarboxylic acid is not particularly limited, but is preferably a chain (more preferably linear) aliphatic dicarboxylic acid. Specific examples include oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, speric acid, glutaconic acid, azelaic acid, sebacic acid, etc., and hydrolyzing these acid anhydrides or lower alkyl esters Also included.

In the present invention, if an aliphatic dicarboxylic acid is a main component as the carboxylic acid component of the polyester B, a polyvalent carboxylic acid other than the aliphatic dicarboxylic acid can also be used. Among the other polyvalent carboxylic acid monomers, examples of the divalent carboxylic acid include the following. Aromatic carboxylic acids such as isophthalic acid and terephthalic acid; aliphatic carboxylic acids such as n-dodecyl succinic acid and n-dodecenyl succinic acid; alicyclic carboxylic acids such as cyclohexanedicarboxylic acid, acid anhydrides or lower alkyl esters thereof.
Moreover, the following are mentioned as polyvalent carboxylic acid more than trivalence among other carboxylic acid monomers. 1,2,4-benzenetricarboxylic acid (trimellitic acid), 2,5,7-naphthalenetricarboxylic acid, 1,2,4-naphthalenetricarboxylic acid, aromatic carboxylic acid such as pyromellitic acid, 1,2,4 -Aliphatic carboxylic acids such as butanetricarboxylic acid, 1,2,5-hexanetricarboxylic acid, 1,3-dicarboxyl-2-methyl-2-methylenecarboxypropane, acid anhydrides or lower alkyl esters thereof, etc. Derivatives and the like.

Furthermore, in this invention, if aliphatic dicarboxylic acid is made into a main component as a carboxylic acid component of polyester B, you may contain monovalent carboxylic acid together. Examples of the monovalent carboxylic acid include the following. Monocarboxylic acids such as benzoic acid, naphthalenecarboxylic acid, salicylic acid, 4-methylbenzoic acid, 3-methylbenzoic acid, phenoxyacetic acid, biphenylcarboxylic acid, acetic acid, propionic acid, butyric acid, octanoic acid, decanoic acid, dodecanoic acid, stearic acid acid.
The polyester B in the present invention can be produced according to a normal polyester synthesis method. For example, the above-mentioned carboxylic acid monomer and alcohol monomer are esterified or transesterified, and then subjected to a polycondensation reaction under reduced pressure or by introducing nitrogen gas according to a conventional method. A polyester resin can be obtained.

The esterification or transesterification reaction is carried out using a normal esterification catalyst or transesterification catalyst such as sulfuric acid, titanium butoxide, dibutyltin oxide, tin 2-ethylhexanoate, manganese acetate, magnesium acetate, etc., if necessary. be able to.
In addition, the polycondensation reaction may be carried out using a conventional polymerization catalyst such as titanium butoxide, dibutyltin oxide, tin 2-ethylhexanoate, tin acetate, zinc acetate, tin disulfide, antimony trioxide, germanium dioxide and the like. Can be done using. The polymerization temperature and the catalyst amount are not particularly limited, and may be determined appropriately.

In the esterification or transesterification reaction or polycondensation reaction, all the monomers may be mixed together in order to increase the strength of the resulting polyester resin B. In order to reduce the low molecular weight component, a method in which a divalent monomer is first reacted and then a trivalent or higher monomer is added and reacted may be used.
The molar ratio (carboxylic acid component / alcohol component) between the alcohol component and the carboxylic acid component, which are raw material monomers of the polyester resin B, is preferably 0.80 or more and 1.20 or less.

[Organic metal compound]
The organometallic compound used in the present invention is an organozirconium compound produced by a reaction between zirconium and an aromatic hydroxycarboxylic acid.
The organic zirconium compound is composed of a plurality of forms of compounds such as compounds having different coordination number and bond number of aromatic hydroxycarboxylic acid and compounds having different structures, and 1 unit of aromatic hydroxycarboxylic acid unit per 1 mol of zirconium atom. Contains 2 to 1.8 mol. By containing such an organozirconium compound, excellent development stability can be obtained, transferability is improved, and toner utilization is improved, so that toner consumption efficiency is increased. In order to obtain better developability, it is preferable to contain 1.3 to 1.7 mol of an aromatic hydroxycarboxylic acid unit per 1 mol of zirconium atom. If the amount is less than 1.2 mol, the rising of frictional charge tends to be delayed, and when toner is replenished, when the toner remaining in the developing device and the replenished toner are mixed, density reduction, density unevenness, and increase in fog are likely to occur. . When it exceeds 1.8 mol, a decrease in image density, an increase in fog, etc. are observed when left for a long period of time.
The aromatic hydroxycarboxylic acid is preferably a compound represented by the following formula (I) in order to obtain good charge start-up and to stabilize developability such as image density, fog and image quality.

［一般式（Ｉ）において、Ｒは水素、アルキル基、アリール基、アルアルキル基、シクロアルキル基、アルケニル基、アルコキシ基、アリールオキシ基、水酸基、アシルオキシ基、アルコキシカルボニル基、アリールオキシカルボニル基、アシル基、カルボキシル基、ハロゲン、ニトロ基、アミノ基、又はカルバモイル基を表す。置換基Ｒは相互に連結して脂肪族環、芳香族環あるいは複素環を形成しても良く、この場合この環に置換基Ｒを有していても良く、置換基Ｒは１から８個持っていてもよく、それぞれ同じであっても、異なっていてもよい。］
中でも芳香族ヒドロキシカルボン酸が、アルキル基を置換基として有するサルチル酸であることが高い帯電量を得、高画像濃度、忠実な潜像再現をより高い高画像品質を達成できる。
本発明で用いられる芳香族ヒドロキシカルボン酸としては以下のものが挙げられる。サリチル酸、５−メチルサリチル酸、３，５−ジメチルサリチル酸、３，５−ジ−ｔｅｒｔ−ブチルサリチル酸、５−メトキシサリチル酸、３−メチル−５−プロピルサリチル酸、及び５−ｔｅｒｔ−ヘプチルサリチル酸。
以下に、本発明で用いられる芳香族ヒドロキシカルボン酸の構造式の具体例を挙げる。

[In the general formula (I), R represents hydrogen, alkyl group, aryl group, aralkyl group, cycloalkyl group, alkenyl group, alkoxy group, aryloxy group, hydroxyl group, acyloxy group, alkoxycarbonyl group, aryloxycarbonyl group, An acyl group, a carboxyl group, a halogen, a nitro group, an amino group, or a carbamoyl group is represented. The substituents R may be linked to each other to form an aliphatic ring, an aromatic ring or a heterocyclic ring. In this case, the ring may have a substituent R, and the substituent R is 1 to 8 You may have, and each may be the same or different. ]
Above all, when the aromatic hydroxycarboxylic acid is a salicylic acid having an alkyl group as a substituent, a high charge amount can be obtained, and high image density and faithful latent image reproduction can be achieved with higher image quality.
The following are mentioned as aromatic hydroxycarboxylic acid used by this invention. Salicylic acid, 5-methylsalicylic acid, 3,5-dimethylsalicylic acid, 3,5-di-tert-butylsalicylic acid, 5-methoxysalicylic acid, 3-methyl-5-propylsalicylic acid, and 5-tert-heptylsalicylic acid.
Specific examples of the structural formula of the aromatic hydroxycarboxylic acid used in the present invention are given below.

  In the present invention, there are a method of adding an organic zirconium compound to the toner, a method of adding it inside the toner, and a method of adding it externally. When added internally, the addition amount is preferably 0.1 to 10 parts by mass, more preferably 0.5 to 5 parts by mass with respect to 100 parts by mass of the binder resin. Moreover, as an addition amount in the case of external addition, 0.01-5 mass parts is preferable, and 0.05-3 mass parts is more preferable. In the case of external addition, it is particularly preferable to fix the toner surface to the toner surface mechanically.

  In the organozirconium compound of the present invention, the zirconium atom is likely to be octacoordinated, and the oxygen of the carboxyl group or hydroxyl group is likely to be coordinated or bonded. When a binder resin having an acid value such as a polyester resin having a carboxyl group as a functional group is used as the binder resin, it is prevented from falling out of the toner particles, and uniform charge and durable durability of charge can be obtained. Further, the influence on the transparency of the toner is reduced, which is preferable for expressing a vivid color for the color toner.

Further, the polymer chain can be uniformly crosslinked throughout the binder resin in the toner through coordination of the carboxyl group and hydroxyl group of the polyester resin component to the zirconium atom. Even if recycled paper containing a large amount of filler is used as the recording material, it is possible to effectively suppress toner contamination on the fixing member caused by the filler adhering to the fixing member.
The organozirconium compound of the present invention is excellent in frictional chargeability and can provide a high charge amount. Therefore, the organozirconium compound is a suitable charge control agent for use in a high-temperature and high-humidity environment that requires a high charge amount. Furthermore, in addition to the good dispersibility of the organic zirconium compound itself, when a binder resin having an acid value is used, the dispersibility is improved, so that durability and charging uniformity can be obtained.
Further, the organozirconium compound of the present invention has a small decrease in developability of the toner due to standing, for example, a decrease in image density is small even when it is reused after being used in each environment and resting for a long time. can do.

The organic zirconium compound of the present invention is an organic zirconium compound in which an aromatic hydroxycarboxylic acid is coordinated or / and bonded to a zirconium atom, and is a zirconium complex, a zirconium complex salt, a zirconium salt, or a mixture thereof.
Examples of these zirconium complexes or zirconium complex salts include complex compounds in which 1 to 4 aromatic hydroxycarboxylic acids are chelated and complex compounds in which 1 to 6 aromatic hydroxycarboxylic acid anions are coordinated. It may be a mixture of different chelates and coordination numbers. Further, examples of the zirconium salt include metal salts having 1 to 4 aromatic hydroxycarboxylic acid anions, and a mixture of compounds having different numbers of aromatic hydroxycarboxylic acid ions may be used.
Furthermore, what is chosen from the compound which has a structure which can be represented by general formula (II), (III), (IV), (V) etc. which are shown below is mentioned.

  In the general formula (II), R is hydrogen, alkyl group, aryl group, aralkyl group, cycloalkyl group, alkenyl group, alkoxy group, aryloxy group, hydroxyl group, acyloxy group, alkoxycarbonyl group, aryloxycarbonyl group, acyl. Represents a group, a carboxyl group, a halogen, a nitro group, an amino group or a carbamoyl group. The substituents R may be connected to each other to form an aliphatic ring, an aromatic ring or a heterocyclic ring. In this case, the ring may have 1 to 8 substituents R, and each is the same. Or different. C1 represents a monovalent cation, hydrogen, alkali metal, ammonium or alkylammonium. l represents an integer of 1 to 8, n represents 2, 3 or 4, and m represents 0, 2 or 4. The aromatic hydroxycarboxylic acid which becomes a ligand in each complex or complex salt may be the same or different, and may be a mixture of complex compounds having different numbers of n and / or m. Moreover, the mixture of the complex salt from which C1 of a counter ion differs may be sufficient. As the substituent R, an alkyl group, an alkenyl group, a carboxyl group or a hydroxyl group is preferable from the viewpoint of improving the dispersibility of the complex or complex salt in the binder resin or improving the chargeability. C1 is preferably hydrogen, sodium, potassium, ammonium or alkylammonium.

  In the general formula (III), R represents hydrogen, alkyl group, aryl group, aralkyl group, cycloalkyl group, alkenyl group, alkoxy group, aryloxy group, hydroxyl group, acyloxy group, alkoxycarbonyl group, aryloxycarbonyl group, acyl Represents a group, a carboxyl group, a halogen, a nitro group, an amino group or a carbamoyl group. The substituents R may be connected to each other to form an aliphatic ring, an aromatic ring, or a heterocyclic ring. In this case, the ring may have 1 to 8 substituents R, which are the same. Or different. A represents an anion, a halogen, a hydroxide ion, a carboxylate ion, a carbonate ion, a nitrate ion, a sulfate ion, a cyan ion or a thiocyan ion, and A may have mutually different ions. C1 represents a monovalent cation, hydrogen, a monovalent metal ion, ammonium or alkylammonium. l represents an integer of 1 to 8, n represents 1, 2, 3, or 4, k represents 1, 2, 3, 4, 5, or 6, m represents 0, 1, 2, 3, or 4 Represent. The aromatic hydroxycarboxylic acids serving as ligands in each complex or each complex salt may be the same or different, and may be a mixture of complex compounds having different numbers of n and / or m. . It may be a mixture of two or more complex compounds having different cations C1 and / or anions A. When A is a divalent anion, the coefficient k of the counter ion is doubled.

As the substituent R, an alkyl group, an alkenyl group, a carboxyl group, or a hydroxyl group is preferable from the viewpoint of improving the dispersibility of the complex or complex salt in the binder resin or improving the chargeability. C1 is preferably hydrogen, sodium, potassium, ammonium, or alkylammonium, and A is preferably a hydroxide ion or a carboxylate ion.
The zirconium complex or complex salt used in the present invention is a hexacoordinate or octacoordinate complex compound. In the octacoordinate, a ligand-bridged binuclear complex compound is formed, and the hexacoordination in the formula is There is a complex compound. There are also binuclear complex compounds in which a complex compound is polymerized one after another by bridging a ligand such as a hydroxyl group.
Typical structures of such complex compounds are exemplified by the following general chemical formulas (a) to (x). The following structures include those having no ligand L. In the formula, X and Y represent —O— and —COO—, A represents an anionic ligand, L represents a neutral ligand, and C represents a counter cation. In general formulas (v) to (x), the counter cation is omitted.

また、芳香族環の水酸基又はカルボキシル基が異なるジルコニウムに配位した構造を有する錯化合物であってもよく、例えば部分構造として式（ｙ）に示されるものである。

Moreover, the complex compound which has a structure coordinated to the zirconium from which the hydroxyl group or carboxyl group of an aromatic ring differs may be shown, for example by Formula (y) as a partial structure.

具体的な構造は式（ｚ）で表される。

A specific structure is represented by the formula (z).

ここで、ｐは１以上の整数を表し、ｑは２以上の整数を表し、式（ｚ）ではアニオン配位子、中性配位子及び対カチオンは省略してある。

Here, p represents an integer of 1 or more, q represents an integer of 2 or more, and in the formula (z), an anionic ligand, a neutral ligand and a counter cation are omitted.

  In the general formulas (IV) and (V), R is hydrogen, alkyl group, aryl group, aralkyl group, cycloalkyl group, alkenyl group, alkoxy group, aryloxy group, hydroxyl group, alkoxycarbonyl group, aryloxycarbonyl group, An acyloxy group, an acyl group, a carboxyl group, a halogen, a nitro group, an amino group, an amide group or a carbamoyl group is represented. The substituents R may be connected to each other to form an aliphatic ring, an aromatic ring or a heterocyclic ring. In this case, the ring may have 1 to 8 substituents R, which are the same. Or different. A1 represents a monovalent anion, halogen ion, hydroxide ion, nitrate ion or carboxylate ion, A2 represents a divalent anion, sulfate ion, hydrogen phosphate ion or carbonate ion, and l is an integer of 1 to 7 N represents 1, 2, 3 or 4. In each metal salt, the anion A1, the anion A2, and the aromatic hydroxycarboxylic acids to be acid ions may be the same or different. Moreover, the mixture of the salt from which the number of n differs may be sufficient. From the viewpoint of improving the dispersibility of the metal salt in the binder resin or improving the chargeability, the substituent is preferably an alkyl group, alkenyl group, carboxyl group, hydroxyl group or acyloxy group, and has excellent environmental stability and binding. Excellent dispersibility in the resin and excellent durability can be obtained.

The organozirconium compound of the present invention is synthesized as follows.
It is synthesized by dissolving a zirconium compound in water, alcohol or an aqueous alcohol solution, and adding an aromatic hydroxycarboxylic acid and an alkali metal salt thereof, or adding an aromatic hydroxycarboxylic acid and an alkali agent. Zirconium compounds include zirconium chloride oxide, zirconium sulfate, organic acid zirconium and the like.

The reaction product is obtained by filtration and washing with water, alcohol, or an aqueous alcohol solution. These organic zirconium compounds may be recrystallized with an alcohol aqueous solution and purified by alcohol washing or water washing. In the case of complex salts, complex salts having various counter ions can be obtained by treating the product with a mineral acid, an alkali agent, and an amine agent. In this invention, what has multiple types, such as a hydrogen ion, an alkali metal ion, and an ammonium ion, is included in the counter ion of a zirconium complex salt.
Examples of means for adjusting the content of the aromatic hydroxycarboxylic acid unit contained in the organic zirconium compound in the present invention include a method of controlling by the mixing ratio and reaction time of the zirconium compound and the aromatic hydroxycarboxylic acid. Moreover, the method of controlling the dripping time and reaction temperature at the time of dripping aromatic hydroxycarboxylic acid to a zirconium compound solution can also be utilized.

[Other charge control materials]
The toner of the present invention may further contain a charge control agent other than the organometallic compound as necessary. Examples of the charge control agent include the following as negative charge control agents. Salicylic acid metal compound, naphthoic acid metal compound, dicarboxylic acid metal compound. Polymer type compound having sulfonic acid or carboxylic acid in the side chain, Polymer type compound having sulfonate or sulfonate ester in the side chain, Polymer type compound having carboxylate or carboxylic ester in the side chain . Boron compounds, urea compounds, silicon compounds, calixarene. The charge control agent may be added internally or externally to the toner particles.

[wax]
The toner of the present invention can contain a wax if necessary. Examples of the wax include the following. Low molecular weight polyethylene, low molecular weight polypropylene, alkylene copolymer, hydrocarbon wax such as microcrystalline wax, paraffin wax, Fischer-Tropsch wax; oxide of hydrocarbon wax such as oxidized polyethylene wax or block copolymer thereof; Waxes mainly composed of fatty acid esters such as carnauba wax; those obtained by partially or fully deoxidizing fatty acid esters such as deoxidized carnauba wax. Furthermore, the following are mentioned. Saturated linear fatty acids such as palmitic acid, stearic acid, and montanic acid; unsaturated fatty acids such as brassic acid, eleostearic acid, and parinalic acid; stearyl alcohol, aralkyl alcohol, behenyl alcohol, carnauvyl alcohol, seryl alcohol, Saturated alcohols such as sil alcohols; polyhydric alcohols such as sorbitol; fatty acids such as palmitic acid, stearic acid, behenic acid, montanic acid, and stearyl alcohol, aralkyl alcohol, behenyl alcohol, carnauvyl alcohol, seryl alcohol, Esters with alcohols such as sil alcohols; Fatty acid amides such as linoleic acid amide, oleic acid amide, lauric acid amide; Methylene bis stearic acid amide, ethylene biscapric acid Saturated fatty acid bisamides such as amide, ethylene bis lauric acid amide, hexamethylene bis stearic acid amide; ethylene bis oleic acid amide, hexamethylene bis oleic acid amide, N, N 'dioleyl adipic acid amide, N, N' dioleyl Unsaturated fatty acid amides such as sebacic acid amides; aromatic bisamides such as m-xylene bis-stearic acid amide, N, N ′ distearyl isophthalic acid amide; calcium stearate, calcium laurate, zinc stearate, magnesium stearate Aliphatic metal salts such as those commonly referred to as metal soaps; Waxes grafted to aliphatic hydrocarbon waxes using vinylic monomers such as styrene and acrylic acid; Fatty acids such as behenic acid monoglycerides And polyvalent arco Le portions ester; methyl ester compounds having hydroxyl groups obtained by hydrogenation of vegetable fats and oils.

Among these waxes, hydrocarbon waxes such as paraffin wax and Fischer-Tropsch wax or fatty acid ester waxes such as carnauba wax are preferable from the viewpoint of improving low-temperature fixability and hot offset resistance. In the present invention, a hydrocarbon wax is more preferable in that the hot offset resistance is further improved.
The wax content is preferably 1.0 parts by mass or more and 15 parts by mass or less with respect to 100 parts by mass of the binder resin. When the content of the wax is within this range, it is easy to efficiently exhibit hot offset properties at high temperatures.
The maximum endothermic peak existing in the temperature range of 30 ° C. or higher and 200 ° C. or lower in the endothermic curve at the time of temperature rise measured by a differential scanning calorimeter (DSC) from the viewpoint of compatibility between toner storage stability and hot offset resistance. The peak temperature is preferably 50 ° C. or higher and 110 ° C. or lower.

[Polymer having structure in which vinyl resin component and hydrocarbon compound are reacted]
In the toner of the present invention, when a hydrocarbon wax is contained as the wax, it is preferable to contain a polymer having a structure in which a vinyl resin component and a hydrocarbon compound are reacted in order to disperse the wax in the resin. . Among them, it is preferable to further contain a graft polymer having a structure in which a polyolefin is grafted on a vinyl resin or a graft polymer in which a vinyl monomer is graft-polymerized on a polyolefin.
When the polymer is contained, compatibility between the wax and the resin is promoted, and it is difficult to cause adverse effects such as charging failure and member contamination due to defective wax dispersion.
In addition, the content of the polymer having a structure in which the vinyl resin component and the hydrocarbon compound are reacted is preferably 1.0 part by mass or more and 15 parts by mass or less with respect to 100 parts by mass of the amorphous resin. When the content is in this range, the dispersion state of the wax in the amorphous resin tends to be uniform.

Regarding the graft polymer having a structure in which a polyolefin is grafted to a vinyl resin, the polyolefin is not particularly limited as long as it is a polymer or copolymer of an unsaturated hydrocarbon having one double bond, and various polyolefins should be used. Can do. In particular, polyethylene and polypropylene are preferably used.
Examples of the monomer having a vinyl group include the following. Styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, p-methoxystyrene, p-phenylstyrene, p-chlorostyrene, 3,4-dichlorostyrene, p-ethylstyrene, 2,4-dimethyl Styrene, pn-butyl styrene, p-tert-butyl styrene, pn-hexyl styrene, pn-octyl styrene, pn-nonyl styrene, pn-decyl styrene, pn-dodecyl styrene Styrenic units such as styrene and derivatives thereof.
Amino group-containing α-methylene aliphatic monocarboxylic acid esters such as dimethylaminoethyl methacrylate and diethylaminoethyl methacrylate; vinyl-based units containing N atoms such as acrylic acid or methacrylic acid derivatives such as acrylonitrile, methacrylonitrile and acrylamide.

  Unsaturated dibasic acids such as maleic acid, citraconic acid, itaconic acid, alkenyl succinic acid, fumaric acid, mesaconic acid; unsaturated such as maleic acid anhydride, citraconic acid anhydride, itaconic acid anhydride, alkenyl succinic acid anhydride Dibasic acid anhydride: maleic acid methyl half ester, maleic acid ethyl half ester, maleic acid butyl half ester, citraconic acid methyl half ester, citraconic acid ethyl half ester, citraconic acid butyl half ester, itaconic acid methyl half ester, alkenyl succinic acid Half-esters of unsaturated dibasic acids such as acid methyl half ester, fumaric acid methyl half ester and mesaconic acid methyl half ester; Unsaturated dibasic acid esters such as dimethylmaleic acid and dimethylfumaric acid; Acrylic acid, Methacrylic acid Α, β-unsaturated acids such as crotonic acid and cinnamic acid; α, β-unsaturated acid anhydrides such as crotonic acid anhydride and cinnamic acid anhydride, and anhydrous α and β-unsaturated acids and lower fatty acids. A vinyl-based unit containing a carboxyl group such as alkenyl malonic acid, alkenyl glutaric acid, alkenyl adipic acid, acid anhydrides thereof, and monoesters thereof.

Acrylic acid or methacrylic acid ester such as 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 4- (1-hydroxy-1-methylbutyl) styrene, 4- (1-hydroxy-1-methyl) (Hexyl) Vinyl-based units containing hydroxyl groups such as styrene.
Methyl acrylate, ethyl acrylate, acrylate-n-butyl, acrylate isobutyl, propyl acrylate, acrylate-n-octyl, dodecyl acrylate, 2-ethylhexyl acrylate, stearyl acrylate, acrylate-2- An ester unit comprising an acrylic ester such as chloroethyl and acrylic ester such as phenyl acrylate.

Methyl methacrylate, ethyl methacrylate, propyl methacrylate, methacrylate-n-butyl, methacrylate isobutyl, methacrylate-n-octyl, methacrylate-decyl, methacrylate-2-ethylhexyl, stearyl methacrylate, phenyl methacrylate, methacryl Ester units composed of methacrylic acid esters such as α-methylene aliphatic monocarboxylic acid esters such as dimethylaminoethyl acid and diethylaminoethyl methacrylate.
The graft polymer in which a vinyl monomer is graft-polymerized to the polyolefin used in the present invention is obtained by a known method such as the reaction between these polymers described above or the reaction between the monomer of one polymer and the other polymer. Can be obtained.
As a constituent unit of the vinyl resin, it is preferable to contain a styrene-based unit, and further acrylonitrile or methacrylonitrile.

[Colorant]
Examples of the colorant that can be contained in the toner of the present invention include the following.
Examples of the black colorant include carbon black; those prepared by using a yellow colorant, a magenta colorant, and a cyan colorant and adjusting the color to black. As the colorant, a pigment may be used alone, but it is more preferable from the viewpoint of the image quality of a full-color image to improve the sharpness by using a dye and a pigment together.
Examples of the magenta colored pigment include the following. C. I. Pigment Red 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 21, 22, 23, 30, 31, 32, 37, 38, 39, 40, 41, 48: 2, 48: 3, 48: 4, 49, 50, 51, 52, 53, 54, 55, 57: 1, 58, 60, 63, 64, 68, 81: 1, 83, 87, 88, 89, 90, 112, 114, 122, 123, 146, 147, 150, 163, 184, 202, 206, 207, 209, 238, 269, 282; I. Pigment violet 19; C.I. I. Bat red 1, 2, 10, 13, 15, 23, 29, 35.

  Examples of the magenta coloring dye include the following. C. I. Solvent Red 1, 3, 8, 23, 24, 25, 27, 30, 49, 81, 82, 83, 84, 100, 109, 121; I. Disper thread 9; I. Solvent violet 8, 13, 14, 21, 27; C.I. I. Oil-soluble dyes such as Disper Violet 1, C.I. I. B. Basic Red 1, 2, 9, 12, 13, 14, 15, 17, 18, 22, 23, 24, 27, 29, 32, 34, 35, 36, 37, 38, 39, 40; I. Basic dyes such as Basic Violet 1, 3, 7, 10, 14, 15, 21, 25, 26, 27, 28.

The following are mentioned as a cyan coloring pigment. C. I. Pigment blue 2, 3, 15: 2, 15: 3, 15: 4, 16, 17; I. Bat Blue 6; C.I. I. Acid Blue 45, a copper phthalocyanine pigment in which 1 to 5 phthalimidomethyl groups are substituted on the phthalocyanine skeleton.
Examples of cyan coloring dyes include C.I. I. There is Solvent Blue 70.

The following are mentioned as a yellow coloring pigment. C. I. Pigment Yellow 1, 2, 3, 4, 5, 6, 7, 10, 11, 12, 13, 14, 15, 16, 17, 23, 62, 65, 73, 74, 83, 93, 94, 95, 97, 109, 110, 111, 120, 127, 128, 129, 147, 151, 154, 155, 168, 174, 175, 176, 180, 181, 185; I. Bat yellow 1, 3, 20
Examples of yellow coloring dyes include C.I. I. There is Solvent Yellow 162.
The amount of the colorant used is preferably 0.1 to 30 parts by mass with respect to 100 parts by mass of the binder resin.

[Magnetic material]
The toner of the present invention may be a magnetic toner or a non-magnetic toner. When used as a magnetic toner, it is preferable to use magnetic iron oxide as the magnetic material. As the magnetic iron oxide, iron oxides such as magnetite, maghematite, and ferrite are used. The amount of magnetic iron oxide contained in the toner is preferably 25.0 parts by mass or more and 95.0 parts by mass or less when the total of the polyester resin A and the polyester resin B is 100.0 parts by mass. More preferably, it is 30.0 parts by mass or more and 45.0 parts by mass or less.

[Flowability improver]
A fluidity improver such as an inorganic fine powder can be used in the toner of the present invention. Examples of the fluidity improver include the following. Fluorine-based resin powders such as vinylidene fluoride fine powder and polytetrafluoroethylene fine powder; wet-process silica, fine-powder silica such as dry-process silica; these silicas as silane coupling agents, titanium coupling agents, or silicone oils, etc. Silica treated by surface treatment. A preferable fluidity improver is a fine powder produced by vapor phase oxidation of a silicon halogen compound, and is dry process silica or fumed silica.

Among these, a treated silica fine powder obtained by hydrophobizing a silica fine powder produced by vapor phase oxidation of a silicon halogen compound is preferably used. The treated silica fine powder preferably has a degree of hydrophobicity of 30 or more and 98 or less titrated by a methanol titration test.
Examples of the method for hydrophobizing the silica fine powder include a method of chemically treating with an organosilicon compound that reacts with the silica fine powder or an organosilicon compound that physically adsorbs the silica fine powder. A preferred method is a method in which a fine silica powder produced by vapor phase oxidation of a silicon halide compound is treated with an organosilicon compound. Examples of organosilicon compounds include the following. Hexamethyldisilazane, trimethylsilane, trimethylchlorosilane, trimethylethoxysilane, dimethyldichlorosilane, methyltrichlorosilane, allyldimethylchlorosilane, allylphenyldichlorosilane, benzyldimethylchlorosilane, bromomethyldimethylchlorosilane, α- Chlorethyltrichlorosilane, β-chloroethyltrichlorosilane, chloromethyldimethylchlorosilane, triorganosilyl mercaptan, trimethylsilyl mercaptan, triorganosilyl acrylate, vinyldimethylacetoxysilane, dimethylethoxysilane, dimethyldimethoxysilane, diphenyldiethoxysilane, 1 -Hexamethyldisiloxane, 1,3-divinyltetramethyldisiloxane, 1,3-diphenyltetramethyl Rudisiloxane and dimethylpolysiloxane. These are used alone or in a mixture of two or more.

The silica fine powder may be treated with silicone oil, or may be treated with a combination of silicone oil and the organosilicon compound. As the silicone oil, those having a viscosity at 25 ° C. of 30 mm ² / s or more and 1000 mm ² / s or less are preferable. Examples thereof include dimethyl silicone oil, methylphenyl silicone oil, α-methylstyrene modified silicone oil, chlorophenyl silicone oil, and fluorine modified silicone oil.

Examples of the method for hydrophobizing the silica fine powder with silicone oil include the following methods. A method in which silica fine powder treated with a silane coupling agent and silicone oil are directly mixed using a mixer such as a Henschel mixer; a method in which silicone oil is sprayed onto a silica fine powder as a base. Alternatively, after dissolving or dispersing silicone oil in an appropriate solvent, silica fine powder is added and mixed to remove the solvent. The silicone oil-treated silica is more preferably obtained by heating the silica in an inert gas at a temperature of 200 ° C. or higher (more preferably 250 ° C. or higher) to stabilize the surface coating after the silicone oil treatment.
The inorganic fine powder is preferably used in an amount of 0.1 to 8.0 parts by weight, more preferably 0.1 to 4.0 parts by weight with respect to 100.0 parts by weight of the toner particles.

[Other external additives]
In the present invention, other external additives may be added to improve fluidity and adjust the triboelectric charge amount.
As the external additive, inorganic fine particles such as silica, titanium oxide, aluminum oxide, and strontium titanate are preferable. For mixing the toner particles and the external additive, a known mixer such as a Henschel mixer can be used. However, the mixing is not particularly limited as long as the mixing is possible.

[Career]
The toner of the present invention is preferably mixed with a magnetic carrier and used as a two-component developer in that a stable image can be obtained over a long period of time.
Examples of the magnetic carrier include iron powder whose surface is oxidized or non-oxidized iron powder, metal particles such as iron, lithium, calcium, magnesium, nickel, copper, zinc, cobalt, manganese, rare earth, and alloys thereof. Magnetic materials such as particles, oxide particles, ferrite, etc., and magnetic materials dispersed resin carriers (so-called resin carriers) containing a magnetic material and a binder resin that holds the magnetic material in a dispersed state are used. it can.

[Production method]
The toner production method of the present invention is not particularly limited as long as it is a conventionally known toner production method such as an emulsion aggregation method, a melt kneading method, or a dissolution suspension method, but the melt kneading method is preferable from the viewpoint of the dispersibility of raw materials.
The melt-kneading method is characterized in that a toner composition that is a raw material of toner particles is melt-kneaded, and the obtained kneaded product is pulverized. An example of the manufacturing method will be described.

  In the raw material mixing step, polyester resin A, polyester resin B, organometallic compound, and, if necessary, other components such as wax and colorant are weighed and mixed in a predetermined amount as materials constituting the toner particles and mixed. . Examples of the mixing apparatus include a double-con mixer, a V-type mixer, a drum-type mixer, a super mixer, a Henschel mixer, a Nauta mixer, a mechano hybrid (manufactured by Nippon Coke Industries, Ltd.), and the like.

  Next, the mixed material is melt-kneaded to disperse other raw materials and the like in the binder resin. In the melt-kneading process, a batch kneader such as a pressure kneader or a Banbury mixer, or a continuous kneader can be used. From the advantage that continuous production is possible, a single-screw or twin-screw extruder has become the mainstream. Yes. For example, KTK type twin screw extruder (manufactured by Kobe Steel Co., Ltd.), TEM type twin screw extruder (manufactured by Toshiba Machine Co., Ltd.), PCM kneading machine (manufactured by Ikekai Co., Ltd.), twin screw extruder (Keikei) -C-Kei), Co-Kneader (Bus), Kneedex (Nippon Coke Kogyo Co., Ltd.). Furthermore, the resin composition obtained by melt-kneading may be rolled with two rolls or the like and cooled with water or the like in the cooling step.

Next, the cooled product of the resin composition is pulverized to a desired particle size in the pulverization step. In the pulverization process, for example, after coarse pulverization with a pulverizer such as a crusher, hammer mill, feather mill, etc. Finely pulverize with a mill (made by Freund Turbo) or an air jet type pulverizer.
After that, if necessary, inertial class elbow jet (manufactured by Nippon Steel & Mining Co., Ltd.), centrifugal classifier type turboplex (manufactured by Hosokawa Micron Corporation), TSP separator (manufactured by Hosokawa Micron Corporation), Faculty (Hosokawa Micron) Classification is carried out using a classifier or a sieving machine (manufactured by Kogyo Co., Ltd.) to obtain toner particles.

The emulsion aggregation method will be described as another production method.
The emulsion aggregation method is a production method in which core particles are produced by preparing resin particles sufficiently small in advance with respect to a target particle diameter and aggregating the resin particles in an aqueous medium. In the emulsion aggregation method, toner particles are produced through an emulsification step, an aggregation step, a fusion step, a cooling step, and a washing step of resin fine particles. If necessary, a shelling process may be added after the cooling process to obtain a core-shell toner.

<Emulsification process of resin fine particles>
Resin fine particles mainly composed of a polyester resin can be prepared by a known method. For example, by dissolving the resin in an organic solvent and adding it to an aqueous medium, dispersing the particles in an aqueous medium with a dispersing agent such as a homogenizer together with a surfactant and a polymer electrolyte, and then removing the solvent by heating or decompressing, A resin particle dispersion can be prepared. Any organic solvent can be used as long as it dissolves the resin, but tetrahydrofuran, ethyl acetate, chloroform and the like are preferable from the viewpoint of solubility.

  In addition, the resin, a surfactant, a base, and the like are added to an aqueous medium, and the mixture is emulsified and dispersed in an aqueous medium substantially free of an organic solvent by a disperser that applies high-speed shearing force such as CLEARMIX, homomixer, and homogenizer. Is preferable from the viewpoint of environmental load. In particular, the content of the organic solvent having a boiling point of 100 ° C. or lower is preferably 100 μg / g or lower. When the amount is outside the above range, a new process for removing and collecting the organic solvent is required when the toner is produced, which imposes a load on wastewater treatment measures. The content of the organic solvent in the aqueous medium can be measured using gas chromatography (GC).

  Although it does not specifically limit as surfactant used at the time of emulsification, For example, the following are mentioned. Anionic surfactants such as sulfate ester, sulfonate, carboxylate, phosphate, and soap; cationic surfactants such as amine salt type and quaternary ammonium salt type; polyethylene glycol type, alkylphenol Nonionic surfactants such as ethylene oxide adducts and polyhydric alcohols. The said surfactant may be used individually by 1 type, and may use 2 or more types together.

  The volume-based median diameter of the resin fine particles is preferably from 0.05 μm to 1.0 μm, and more preferably from 0.05 μm to 0.4 μm. If it exceeds 1.0 μm, it becomes difficult to obtain toner particles having a volume-based median diameter of 4.0 μm or more and 7.0 μm or less that are suitable as toner particles. The volume-based median diameter can be measured by using a dynamic light scattering particle size distribution meter (Nanotrack UPA-EX150: manufactured by Nikkiso Co., Ltd.).

<Aggregation process>
The agglomeration step refers to mixing the above-mentioned resin fine particles, colorant fine particles, and release agent fine particles as necessary to prepare a mixed solution, and then aggregating the particles contained in the prepared mixed solution, Is a step of forming. As a method for forming the agglomerates, for example, a method in which a flocculant is added and mixed in the above mixed solution, and a temperature, mechanical power, and the like are appropriately added can be preferably exemplified.
Examples of the flocculant include metal salts of monovalent metals such as sodium and potassium; metal salts of divalent metals such as calcium and magnesium; metal salts of trivalent metals such as iron and aluminum.

The addition / mixing of the flocculant is preferably performed at a temperature not higher than the glass transition temperature (Tg) of the resin particles contained in the mixed solution. When the above mixing is performed under this temperature condition, aggregation proceeds in a stable state. The said mixing can be performed using a well-known mixing apparatus, a homogenizer, a mixer, etc.
The weight average particle diameter of the aggregate formed here is not particularly limited, but is usually controlled to 4.0 μm or more and 7.0 μm or less so as to be the same as the weight average particle diameter of the toner particles to be obtained. Good. Control can be easily performed, for example, by appropriately setting and changing the temperature at the time of addition / mixing of the flocculant and the like and the conditions of the stirring and mixing. The particle size distribution of the toner particles can be measured with a particle size distribution analyzer (Coulter Multisizer III: manufactured by Beckman Coulter, Inc.) using a Coulter method.

<Fusion process>
The fusing step is a step of producing particles in which the agglomerate surface is smoothed by heating and fusing the agglomerates above the glass transition point (Tg) of the resin. Before entering the primary fusing step, a chelating agent, a pH adjusting agent, a surfactant and the like can be appropriately added in order to prevent fusion between toner particles.
Examples of chelating agents include alkali metal salts such as ethylenediaminetetraacetic acid (EDTA) and its Na salt, sodium gluconate, sodium tartrate, potassium citrate and sodium citrate, both nitrotriacetate (NTA) salts, COOH and OH There are many water-soluble polymers (polyelectrolytes) that contain the following functionalities.

  The heating temperature may be between the glass transition temperature (Tg) of the resin contained in the aggregate and the temperature at which the resin is thermally decomposed. As the heating / fusion time, a short time is sufficient if the heating temperature is high, and a long time is required if the heating temperature is low. That is, the heating / fusion time depends on the temperature of heating and cannot be defined unconditionally, but is generally 10 minutes to 10 hours.

<Cooling process>
The cooling step is a step of cooling the temperature of the aqueous medium containing the particles to a temperature lower than the glass transition point (Tg) of the core resin. If the cooling is not performed to a temperature lower than Tg, coarse particles are generated. The specific cooling rate is 0.1 ° C./min or more and 50 ° C./min or less.

<Shelling process>
In the present invention, if necessary, a shelling step can be added before the following washing and drying step. The shelling step is a step of newly adding resin fine particles to the particles produced in the previous steps and attaching them to form a shell.
The binder resin fine particles added here may have the same structure as the binder resin fine particles used for the core, or may be binder resin fine particles having a different structure.

The resin constituting such a shell layer is not particularly limited, and known resins used for toners, for example, vinyl polymers such as polyester resins and styrene-acrylic copolymers, epoxy resins, polycarbonate resins, and polyurethane resins. Etc. can be used. Of these, a polyester resin or a styrene-acrylic copolymer is preferable, and a polyester resin is more preferable from the viewpoints of fixability and durability. A polyester resin has a lower molecular weight than a vinyl polymer because it has flexibility compared to a vinyl polymer such as a styrene-acrylic copolymer when it has a rigid aromatic ring in the main chain. Can provide equivalent mechanical strength. Therefore, a polyester resin is preferable as a resin suitable for low-temperature fixability.
In the present invention, the binder resin constituting the shell layer may be used alone or in combination of two or more.

<Washing and drying process>
The particles produced through the above steps are washed and filtered with ion-exchanged water whose pH is adjusted with sodium hydroxide or potassium hydroxide, and then washed with ion-exchanged water and filtered a plurality of times. Thereafter, it is dried to obtain emulsion aggregation toner particles.
If necessary, additives such as inorganic fine powder and resin particles are added to the surface of the toner particles obtained by a melt-kneading method, and mixed and dispersed, and then the additives are subjected to surface treatment with hot air in the dispersed state. It is preferable to perform a heat treatment step for fixing the toner to the toner particle surface.

For example, the toner can be obtained by performing surface treatment with hot air using the surface treatment apparatus shown in FIG. 1 and classifying it as necessary.
The mixture quantitatively supplied by the raw material quantitative supply means 1 is guided to the introduction pipe 3 installed on the vertical line of the raw material supply means by the compressed gas adjusted by the compressed gas adjusting means 2. The mixture that has passed through the introduction pipe is uniformly dispersed by a conical projection-like member 4 provided at the center of the raw material supply means, and is guided to a radially extending eight-direction supply pipe 5 where heat treatment is performed. Led to.
At this time, the flow of the mixture supplied to the processing chamber is regulated by the regulating means 9 for regulating the flow of the mixture provided in the processing chamber. Therefore, the mixture supplied to the processing chamber is heat-treated while swirling in the processing chamber and then cooled.

  The heat for heat-treating the supplied mixture is supplied from the heat supply means 7, distributed by the distribution member 12, and introduced into the processing chamber by swirling the hot air spirally by the swirling member 13 for swirling the hot air. Is done. As the structure, the turning member 13 for turning hot air has a plurality of blades, and the turning of hot air can be controlled by the number and angle of the blades. The temperature of the hot air supplied into the processing chamber is preferably 100 ° C. or higher and 300 ° C. or lower, more preferably 130 ° C. or higher and 170 ° C. or lower, at the outlet of the hot air supply means 7. If the temperature at the outlet of the hot air supply means is within the above range, it is possible to uniformly spheroidize the toner particles while suppressing fusing and coalescence of the toner particles due to overheating of the mixture. Become. The circularity at this time is preferably 0.955 or more and 0.980 or less. Hot air is supplied from the hot air supply means outlet 11.

Further, the heat-treated toner particles subjected to the heat treatment are cooled by the cold air supplied from the cold air supply means 8, and the temperature supplied from the cold air supply means 8 is preferably -20 ° C to 30 ° C. If the temperature of the cold air is within the above range, the heat-treated toner particles can be efficiently cooled, and the fusion and coalescence of the heat-treated toner particles are suppressed without hindering uniform spheroidization of the mixture. be able to. The absolute moisture content of the cold air is preferably 0.5 g / m ³ or more and 15.0 g / m ³ or less.
Next, the cooled heat-treated toner particles are recovered by the recovery means 10 at the lower end of the processing chamber. In addition, a blower (not shown) is provided at the tip of the collecting means, and is thereby configured to be sucked and conveyed.

The powder particle supply port 14 is provided so that the swirling direction of the supplied mixture and the swirling direction of the hot air are the same direction. It is provided in the outer peripheral part of a process chamber so that the turning direction may be maintained. Further, the cold air supplied from the cold air supply means 8 is configured to be supplied from the outer peripheral portion of the apparatus to the peripheral surface of the processing chamber in a horizontal and tangential direction. The swirling direction of the pre-heat treatment toner particles supplied from the powder supply port, the swirling direction of the cold air supplied from the cold air supplying means, and the swirling direction of the hot air supplied from the hot air supplying means are all the same direction. Therefore, turbulent flow does not occur in the processing chamber, the swirling flow in the apparatus is strengthened, a strong centrifugal force is applied to the toner particles before heat treatment, and the dispersibility of the toner particles before heat treatment is further improved, so there are few coalesced particles Thus, heat-treated toner particles having a uniform shape can be obtained.
Thereafter, external additives such as inorganic fine powder and resin particles selected as necessary may be added to externally add other inorganic fine particles to improve fluidity and charge stability. Examples of the mixing apparatus include a double-con mixer, a V-type mixer, a drum-type mixer, a super mixer, a Henschel mixer, a Nauta mixer, a mechano hybrid (manufactured by Nippon Coke Industries, Ltd.), and the like.
Next, methods for measuring physical properties related to the present invention will be described.

<Measuring method of softening point (Tm) of polyester resin A>
The softening point of the resin is measured by using a constant load extrusion type capillary rheometer “Flow Characteristic Evaluation Device Flow Tester CFT-500D” (manufactured by Shimadzu Corporation) according to the manual attached to the device. In this device, while applying a constant load from the top of the measurement sample with the piston, the measurement sample filled in the cylinder is heated and melted, and the melted measurement sample is pushed out from the die at the bottom of the cylinder, and the piston drop amount at this time A flow curve showing the relationship between temperature and temperature can be obtained.

  In the present invention, the “melting temperature in the 1/2 method” described in the manual attached to the “flow characteristic evaluation apparatus Flow Tester CFT-500D” is the softening point. The melting temperature in the 1/2 method is calculated as follows. First, ½ of the difference between the piston lowering amount Smax at the time when the outflow ends and the piston lowering amount Smin at the time when the outflow starts is obtained (this is X. X = (Smax−Smin) / 2). Then, the temperature of the flow curve when the piston descending amount is X in the flow curve is the melting temperature in the 1/2 method.

The measurement sample is about 1.0 g of resin compression molded at a pressure of about 10 MPa using a tablet molding compressor (for example, NT-100H, manufactured by NPA System Co., Ltd.) in an environment of 25 ° C. for about 60 seconds. Then, a cylindrical shape having a diameter of about 8 mm is used.
The measurement conditions of CFT-500D are as follows.

Test mode: Temperature rising start temperature: 50 ° C
Achieving temperature: 200 ° C
Measurement interval: 1.0 ° C
Temperature increase rate: 4.0 ° C./min
Piston cross-sectional area: 1.000 cm ²
Test load (piston load): 10.0 kgf (0.9807 MPa)
Preheating time: 300 seconds Die hole diameter: 1.0 mm
Die length: 1.0mm

<Measurement of Glass Transition Temperature (Tg) of Polyester Resin A>
The glass transition temperature of the 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, about 5 mg of resin is precisely weighed and placed in an aluminum pan, and an empty aluminum pan is used as a reference, and the heating rate is 10 ° C./min between a measurement range of 30 to 200 ° C. Measure with. The temperature is raised to 180 ° C. and held for 10 minutes, then the temperature is lowered to 30 ° C., and then the temperature is raised again. In the second temperature raising process, a specific heat change is obtained in the temperature range of 30 to 100 ° C. At this time, the intersection of the intermediate point line of the baseline before and after the change in specific heat and the differential heat curve is defined as the glass transition temperature (Tg) of the resin.

<Measurement of weight average molecular weight and peak molecular weight of polyester resin A and polyester resin B>
The molecular weight distribution of the THF soluble part of the resin is measured by gel permeation chromatography (GPC) as follows.
The column is stabilized in a heat chamber at 40 ° C., tetrahydrofuran (THF) is allowed to flow through the column at this temperature as a solvent at a flow rate of 1 mL / min, and about 100 μL of a THF sample solution is injected and measured. In measuring the molecular weight of a sample, the molecular weight distribution of the sample is calculated from the relationship between the logarithmic value of a calibration curve prepared from several types of monodisperse polystyrene standard samples and the count value. As a standard polystyrene sample for preparing a calibration curve, for example, one having a molecular weight of about 10 ² to 10 ⁷ manufactured by Tosoh Corporation or Showa Denko Co., Ltd., and at least about 10 standard polystyrene samples may be used. Is appropriate. The detector uses an RI (refractive index) detector. The column is preferably a combination of a plurality of commercially available polystyrene gel columns, for example, the following combinations. Showa Denko combination and of shodex GPC KF-801,802,803,804,805,806,807,800P made of (stock), manufactured by Tosoh Corporation of _{TSKgel G1000H (H XL), G2000H} (H XL), G3000H A combination of (H _XL ), G4000H (H _XL ), G5000H (H _XL ), G6000H (H _XL ), G7000H (H _XL ), and TSKgourd column.

Moreover, a sample is produced as follows.
Place 50 mg of the sample in 10 mL of THF and let stand at 25 ° C. for several hours, then shake well, mix well with THF (until the sample is united), and let stand for more than 12 hours. The total standing time in THF is 24 hours. After that, a sample processed filter (pore size 0.2 μm or more, 0.5 μm or less, for example, Mysori Disc H-25-2 (manufactured by Tosoh Corporation)) can be used as a GPC sample.

<Measurement of melting point of polyester resin B and wax>
The melting point of the crystalline polyester resin B and the wax is the DSC curve measured according to ASTM D3418-82 using a differential scanning calorimeter “Q2000” (manufactured by TA Instruments). To do.
The temperature correction of the device detection unit uses the melting points of indium and zinc, and the correction of heat uses the heat of fusion of indium. Specifically, about 2 mg of a sample is precisely weighed, placed in an aluminum pan, and an empty aluminum pan is used as a reference. Measurement is performed at ° C / min. In the measurement, the temperature is once raised to 200 ° C., subsequently lowered to 30 ° C., and then the temperature is raised again. The maximum endothermic peak temperature of the DSC curve in the temperature range of 30 to 200 ° C. in the second temperature raising process is defined as the melting point. There is no holding time after the temperature is raised to 200 ° C., and the temperature is lowered to 30 ° C. as soon as 200 ° C. is reached.

<Measurement of acid value of polyester resin A>
The acid value is the number of mg of potassium hydroxide necessary for neutralizing the acid contained in 1 g of the sample. The acid value in the present invention is measured according to JIS K 0070-1992. Specifically, it is measured according to the following procedure.
Titration is performed using a 0.1 mol / L potassium hydroxide ethyl alcohol solution (manufactured by Kishida Chemical Co., Ltd.). The factor of the potassium hydroxide ethyl alcohol solution can be determined using a potentiometric titrator (potentiometric titrator AT-510 manufactured by Kyoto Electronics Industry Co., Ltd.). 100 mL of 0.100 mol / L hydrochloric acid is placed in a 250 mL tall beaker, titrated with the potassium hydroxide ethyl alcohol solution, and determined from the amount of the potassium hydroxide ethyl alcohol solution required for neutralization. As the 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 (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 parameters Titration mode: Blank titration Titration style: Total titration Maximum titration: 20 mL
Waiting time before titration: 30 seconds Titration direction: Automatic control parameter end point judgment potential: 30 dE
End point determination differential value: 50 dE / dmL
End point detection range setting: Not set Control speed mode: Standard gain: 1
Data collection potential: 4 mV
Data collection titration: 0.1 mL

main exam;
0.100 g of a measurement sample is precisely weighed in a 250 mL tall beaker, and 150 mL of a mixed solution of toluene / ethanol (3: 1) is added and dissolved over 1 hour. Titrate with the potassium hydroxide ethyl alcohol solution using the 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 / 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
(In the formula, A: acid value (mgKOH / g), B: addition amount of potassium hydroxide ethyl alcohol solution in blank test (mL), C: addition amount of potassium hydroxide ethyl alcohol solution in this test (mL), f: Factor of potassium hydroxide solution, S: Sample (g))

<Measuring method of hydroxyl value of polyester resin A>
The hydroxyl value is the number of mg of potassium hydroxide required to neutralize acetic acid bonded to a hydroxyl group when 1 g of a sample is acetylated. The hydroxyl value in the present invention is measured according to JIS K 0070-1992. Specifically, it is measured according to the following procedure.
Add 25.0 g of special grade acetic anhydride to a 100 mL volumetric flask, add pyridine to bring the total volume to 100 mL, and shake well to obtain an acetylating reagent. The obtained acetylating reagent is stored in a brown bottle so as not to come into contact with moisture, carbon dioxide gas and the like.

Titration is performed using a 1.0 mol / L potassium hydroxide ethyl alcohol solution (manufactured by Kishida Chemical Co., Ltd.). The factor of the potassium hydroxide ethyl alcohol solution can be determined using a potentiometric titrator (potentiometric titrator AT-510 manufactured by Kyoto Electronics Co., Ltd.). 100 mL of 1.00 mol / L hydrochloric acid is placed in a 250 mL tall beaker, titrated with the potassium hydroxide solution, and determined from the amount of the potassium hydroxide ethyl alcohol solution required for neutralization. As the 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 (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 parameters Titration mode: Blank titration Titration style: Total titration Maximum titration: 80 mL
Waiting time before titration: 30 seconds Titration direction: Automatic control parameter end point judgment potential: 30 dE
End point determination differential value: 50 dE / dmL
End point detection range setting: Not set Control speed mode: Standard gain: 1
Data collection potential: 4 mV
Data collection titration: 0.5 mL

main exam;
2.00 g of the pulverized measurement sample is precisely weighed into a 200 mL round bottom flask, and 5.00 mL of the acetylating reagent is accurately added to this using a whole pipette. At this time, if the sample is difficult to dissolve in the acetylating reagent, a small amount of special grade toluene is added and dissolved.
Place a small funnel in the mouth of the flask and immerse 1 cm of the bottom of the flask in a 97 ° C. glycerin bath and heat. At this time, in order to prevent the temperature of the neck of the flask from rising due to the heat of the bath, it is preferable to cover the base of the neck of the flask with a cardboard having a round hole.

After 1 hour, the flask is removed from the glycerin bath and allowed to cool. After standing to cool, 1.00 mL of water is added from the funnel and shaken to hydrolyze acetic anhydride. The flask is again heated in the glycerin bath for 10 minutes for further complete hydrolysis. After cooling, wash the funnel and flask walls with 5.00 mL of ethyl alcohol.
The obtained sample is transferred to a 250 mL tall beaker, and 100 mL of a mixed solution of toluene / ethanol (3: 1) is added and dissolved over 1 hour. Titrate with the potassium hydroxide ethyl alcohol solution using the potentiometric titrator.

Blank test;
Titration similar to the above operation is performed except that no sample 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 solution, S: Sample (g), D: Acid value of resin (mgKOH / g).

<Measurement of weight average particle diameter (D4) of toner>
The weight average particle diameter (D4) of the toner is a precision particle size distribution measuring apparatus “Coulter Counter Multisizer 3” (registered trademark, manufactured by Beckman Coulter, Inc.) having a 100 μm aperture tube. Measured with 25,000 effective measurement channels using the dedicated software “Beckman Coulter Multisizer 3 Version 3.51” (manufactured by Beckman Coulter, Inc.) for setting measurement conditions and analyzing measurement data Then, the measurement data is analyzed and calculated. As the electrolytic aqueous solution used for the measurement, a special grade sodium chloride dissolved in deionized water to a concentration of about 1% by mass, for example, “ISOTON II” (manufactured by Beckman Coulter, Inc.) can be used. .

Prior to measurement and analysis, the dedicated software is set as follows.
In the “Standard measurement method (SOM) change screen” of the dedicated software, set the total count in the control mode to 50,000 particles, set the number of measurements once, and set the Kd value to “standard particles 10.0 μm” (Beckman The value obtained using Coulter Co.) is set. The threshold and noise level are automatically set by pressing the threshold / noise level measurement button. Also, the current is set to 1600 μA, the gain is set to 2, the electrolyte is set to ISOTON II, and the aperture tube flash 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.

Specific measurement methods are as follows (1) to (7).
(1) About 200 mL of the electrolytic solution is placed in a 250 mL round bottom beaker made exclusively for Multisizer 3 and set on a sample stand, and the stirrer rod is stirred counterclockwise at 24 rpm. The dirt and bubbles in the aperture tube are removed by the “aperture flush” function of the analysis software.
(2) About 30 mL of the electrolytic aqueous solution is put into a 100 mL flat bottom beaker made of glass, and about 0.3 mL of the following diluent is added thereto as a dispersant.
・ Decontamination of "Contaminone N" (Nonionic surfactant, anionic surfactant, 10% by weight aqueous solution of neutral detergent for cleaning precision measuring instruments with pH 7 consisting of organic builder, manufactured by Wako Pure Chemical Industries, Ltd.) Diluted solution diluted 3 times by mass with ionized water.

(3) Built-in two oscillators with an oscillation frequency of 50 kHz with a phase shifted by 180 degrees, and in an aquarium of an ultrasonic disperser “Ultrasonic Dispersion System Tetora150” (manufactured by Nikki Bios Co., Ltd.) having an electrical output of 120 W Is charged with a predetermined amount of deionized water, and about 2 mL of the contamination N is added to the 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, about 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 the 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) In the round bottom beaker (1) installed in the sample stand, the electrolyte aqueous solution (5) in which the toner is dispersed is dropped using a pipette, and the measurement concentration is adjusted to about 5%. To do. The 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) is 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 diameter (D4).

<Measuring method of average circularity of toner>
The average circularity of the toner is measured with a flow type particle image analyzer “FPIA-3000” (manufactured by Sysmex Corporation) under the measurement and analysis conditions during calibration.
The measurement principle of the flow-type particle image analyzer “FPIA-3000” (manufactured by Sysmex Corporation) is to capture flowing particles as a still image and perform image analysis. The sample added to the sample chamber is fed into the flat sheath flow cell by a sample suction syringe. The sample fed into the flat sheath flow is sandwiched between sheath liquids to form a flat flow. The sample passing through the flat sheath flow cell is irradiated with strobe light at 1/60 second intervals, and the flowing particles can be photographed as a still image. Further, since the flow is flat, the image is taken in a focused state. The particle image is picked up by a CCD camera, and the picked-up image is image-processed at an image processing resolution of 512 × 512 pixels (0.37 × 0.37 μm per pixel), the contour of each particle image is extracted, and the particle image The projected area S, the peripheral length L, etc. are measured.

Next, the equivalent circle diameter and the circularity are obtained using the area S and the peripheral length L. The equivalent circle diameter is the diameter of a circle having the same area as the projected area of the particle image, and the circularity C is a value obtained by dividing the circumference of the circle obtained from the equivalent circle diameter by the circumference of the projected particle image. And is calculated by the following formula.
Circularity C = 2 × (π × S) 1/2 / L
When the particle image is circular, the circularity is 1.000, and the greater the degree of unevenness around the particle image, the smaller the circularity. After calculating the circularity of each particle, the range of the circularity of 0.200 to 1.000 is divided into 800, the arithmetic average value of the obtained circularity is calculated, and the value is defined as the average circularity.

  A specific measurement method is as follows. First, about 20 mL of ion-exchanged water from which impure solids and the like are previously removed is placed in a glass container. As a dispersant, “Contaminone N” (a nonionic surfactant, an anionic surfactant, a 10% by weight aqueous solution of a neutral detergent for washing a pH 7 precision measuring instrument comprising an organic builder, Wako Pure Chemical Industries, Ltd. About 0.2 mL of a diluted solution obtained by diluting (made in ()) with ion-exchanged water about 3 times by mass is added. Further, about 0.02 g of a measurement sample is added, and dispersion treatment is performed for 2 minutes using an ultrasonic disperser to obtain a dispersion for measurement. In that case, it cools suitably so that the temperature of a dispersion liquid may become 10 to 40 degreeC. As the ultrasonic disperser, a desktop type ultrasonic cleaner disperser (for example, “VS-150” (manufactured by Vervo Crea)) having an oscillation frequency of 50 kHz and an electric output of 150 W is used. Then, a predetermined amount of ion exchange water is put in the water tank, and about 2 mL of the contamination N is added to the water tank.

  For the measurement, the flow type particle image analyzer equipped with a standard objective lens (10 times) was used, and a particle sheath “PSE-900A” (manufactured by Sysmex Corporation) was used as the sheath liquid. The dispersion liquid prepared according to the procedure is introduced into the flow type particle image analyzer, and 3000 toner particles are measured in the total count mode in the HPF measurement mode. Then, by setting the binarization threshold at the time of particle analysis to 85% and specifying the analysis particle diameter, the number ratio (%) of particles in the range and the average circularity can be calculated. The average circularity of the toner was set to an equivalent circle diameter of 1.98 μm to 39.96 μm, and the average circularity of the toner was determined.

In measurement, automatic focus adjustment is performed using standard latex particles (for example, “RESEARCH AND TEST PARTICLES Latex Microsphere Suspensions 5200A” manufactured by Duke Scientific) diluted with ion-exchanged water before starting the measurement. Thereafter, it is preferable to perform focus adjustment every two hours from the start of measurement.
In the examples of the present application, a flow-type particle image analyzer that has been issued a calibration certificate issued by Sysmex Corporation, which has been calibrated by Sysmex Corporation, was used. The measurement was performed under the measurement and analysis conditions when the calibration certificate was received, except that the analysis particle diameter was limited to a circle equivalent diameter of 1.98 μm or more and less than 39.69 μm.

<Method for quantifying zirconium atoms>
About 100 mg of the organometallic compound is precisely weighed in a beaker, thermally decomposed with an acid such as hydrochloric acid or nitric acid, the decomposition solution is made up to volume with dilute nitric acid, and further diluted as necessary.
The concentration of zirconium element in the solution obtained by the above pretreatment was calculated by ICP emission spectroscopy.
In the present invention, a sequential type ICP emission spectroscopic analyzer SPS1200VR manufactured by Seiko Instruments Inc. was used, and the conventional method was followed. The measurement was carried out in a parallel test with 3 repetitions (n = 3) from the pretreatment.

<Method for quantifying aromatic hydroxycarboxylic acid>
About 100 mg of an organometallic compound is precisely weighed in a sample tube and thermally decomposed with an acid such as hydrochloric acid or nitric acid to dissociate zirconium and aromatic hydroxycarboxylic acid. To this, 10 mg of n-tridecane (internal standard) and acetonitrile (10 mL) are added and shaken vigorously to dissolve the dissociated aromatic hydroxycarboxylic acid. 1 mL of the lysate was filtered through a 0.5 μm filter, and a silylating agent (0.5 mL) such as N, O-bistrimethylsilylacetamide was added to the filtrate and vigorously shaken to prepare an analytical sample. After standing for about 20 minutes, the sample was subjected to gas chromatography analysis, and the aromatic hydroxycarboxylic acid was quantified according to a conventional method.
The number of moles of zirconium atoms is calculated from the determined content of zirconium atoms and the atomic weight of zirconium, and from the determined content of aromatic hydroxycarboxylic acid and the molecular weight of aromatic hydroxycarboxylic acid, Calculate the number of moles. Then, the ratio between the number of moles of zirconium atoms and the number of moles of aromatic hydroxycarboxylic acid is determined.

Hereinafter, the present invention will be described with reference to production examples and examples. However, the following examples do not limit the technical scope of the present invention. Production Examples 1 to 26 are production examples of crystalline polyester resins. In the following description, the number of parts is based on parts by mass.
<Example of production of polyester resin A>
(Production Example 1 of Low Molecular Weight Polyester Resin A (L))
Polyoxypropylene (2.2) -2,2-bis (4-hydroxyphenyl) propane: 72.0 parts by mass (0.20 mol; 100.0 mol% based on the total number of moles of polyhydric alcohol)
・ Terephthalic acid: 28.0 parts by mass (0.17 mol; 100.0 mol% based on the total number of moles of polyvalent carboxylic acid)
-Tin 2-ethylhexanoate (esterification catalyst): 0.5 parts by mass

The above materials were weighed into a reaction vessel equipped with a cooling tube, a stirrer, a nitrogen introduction tube, and a thermocouple. Next, after the inside of the flask was replaced with nitrogen gas, the temperature was gradually raised while stirring, and the reaction was carried out for 4 hours while stirring at a temperature of 200 ° C.
Further, the pressure in the reaction vessel was lowered to 8.3 kPa, maintained for 1 hour, then cooled to 180 ° C. and returned to atmospheric pressure (first reaction step).

Trimellitic anhydride: 3 parts by mass (0.01 mol; 4.0 mol% based on the total number of polycarboxylic acids)
Tert-Butylcatechol (polymerization inhibitor): 0.1 part by mass Thereafter, the above materials are added, the pressure in the reaction vessel is lowered to 8.3 kPa, and the temperature is maintained at 180 ° C. for 1 hour, and ASTM is performed. After confirming that the softening point measured according to D36-86 reached 94 ° C., the temperature was lowered to stop the reaction (second reaction step). Thus, low molecular weight polyester resin A (L) -1 was obtained. The low molecular weight polyester resin A (L) -1 obtained had a softening point (Tm) of 94 ° C. and a glass transition temperature (Tg) of 57 ° C.

(Production Example 2 of Low Molecular Weight Polyester Resin A (L))
A low molecular weight polyester resin A (L) -2 was obtained in the same manner as in Production Example 1 of the low molecular weight polyester resin A (L) except for the following changes.
Change point: The esterification catalyst was changed from tin 2-ethylhexanoate: 0.5 part by mass to dioctyltin oxide: 0.3 part by mass.
The low molecular weight polyester resin A (L) -2 obtained had a softening point (Tm) of 95 ° C. and a glass transition temperature (Tg) of 58 ° C.

(Production Example 3 of Low Molecular Weight Polyester Resin A (L))
Except for the following changes, a low molecular weight polyester resin A (L) -3 was obtained in the same manner as in Production Example 2 of the low molecular weight polyester resin A (L).
Changed point: 1,4-bis (2-hydroxyethoxy) represented by the following formula (c) from polyoxypropylene (2.2) -2,2-bis (4-hydroxyphenyl) propane Changed to benzene.
The low molecular weight polyester resin A (L) -3 obtained had a softening point (Tm) of 93 ° C. and a glass transition temperature (Tg) of 56 ° C.

(Production Example 4 of Low Molecular Weight Polyester Resin A (L))
・ 1,2-propylene glycol 40.0 parts by mass (0.526 mol)
・ Terephthalic acid 55.0 parts by mass (0.331 mol)
・ 1.0 parts by mass of adipic acid (0.007 mol)
・ Titanium tetrabutoxide 0.6 parts by mass

The above materials were weighed into a reaction vessel equipped with a cooling tube, a stirrer, a nitrogen introduction tube, and a thermocouple. Next, after the inside of the flask was replaced with nitrogen gas, the temperature was gradually raised while stirring, and the reaction was carried out for 8 hours while stirring at a temperature of 220 ° C.
Further, the pressure in the reaction vessel was lowered to 8.3 kPa, maintained for 1 hour, then cooled to 180 ° C. and returned to atmospheric pressure (first reaction step).
-Trimellitic anhydride 4.0 parts by mass (0.021 mol)
-Tert-butylcatechol (polymerization inhibitor) 0.1 part by mass Thereafter, the above materials are added, the pressure in the reaction vessel is lowered to 8.3 kPa, and the temperature is maintained at 180 ° C for 4 hours, ASTM D36 After confirming that the softening point measured according to −86 reached 93 ° C., the temperature was lowered to stop the reaction (second reaction step). In this way, a low molecular weight polyester resin A (L) -4 was obtained. The resulting low molecular weight polyester resin A (L) -4 had a softening point (Tm) of 94 ° C. and a glass transition temperature (Tg) of 57 ° C.

(Production Example 1 of High Molecular Weight Polyester Resin A (H))
Polyoxypropylene (2.2) -2,2-bis (4-hydroxyphenyl) propane: 72.3 parts by mass (0.20 mol; 100.0 mol% based on the total number of moles of polyhydric alcohol)
・ Terephthalic acid: 18.3 parts by mass (0.11 mol; 65.0 mol% based on the total number of moles of polycarboxylic acid)
・ Fumaric acid: 2.9 parts by mass (0.03 mol; 15.0 mol% based on the total number of moles of polycarboxylic acid)
-Tin 2-ethylhexanoate (esterification catalyst): 0.5 parts by mass

The above materials were weighed into a reaction vessel equipped with a cooling tube, a stirrer, a nitrogen introduction tube, and a thermocouple. Next, after the inside of the flask was replaced with nitrogen gas, the temperature was gradually raised while stirring, and the reaction was carried out for 2 hours while stirring at a temperature of 200 ° C.
Further, the pressure in the reaction vessel was lowered to 8.3 kPa, maintained for 1 hour, cooled to 180, and returned to atmospheric pressure (first reaction step).

Trimellitic anhydride: 6.5 parts by mass (0.03 mol; 20.0 mol% based on the total number of moles of polycarboxylic acid)
-Tert-butylcatechol (polymerization inhibitor): 0.1 part by mass Thereafter, the above materials are added, the pressure in the reaction vessel is lowered to 8.3 kPa, and the reaction is performed for 15 hours while maintaining the temperature at 160 ° C. After confirming that the softening point measured according to D36-86 reached 132 ° C., the temperature was lowered to stop the reaction (second reaction step). Thus, high molecular weight polyester resin A (H) -1 was obtained. The obtained high molecular weight polyester resin A (H) -1 had a softening point (Tm) of 132 ° C. and a glass transition temperature (Tg) of 61 ° C.

(Production Example 2 of High Molecular Weight Polyester Resin A (H))
Except for the following changes, a high molecular weight polyester resin A (H) -2 was obtained in the same manner as in Production Example 1 of the high molecular weight polyester resin A (H).
Change point: The esterification catalyst was changed from tin 2-ethylhexanoate: 0.5 part by mass to dioctyltin oxide: 0.3 part by mass.
The obtained high molecular weight polyester resin A (H) -2 had a softening point (Tm) of 133 ° C. and a glass transition temperature (Tg) of 62 ° C.

(Production Example 3 of High Molecular Weight Polyester Resin A (H))
Except for the following changes, a high molecular weight polyester resin A (H) -3 was obtained in the same manner as in Production Example 2 of the high molecular weight polyester resin A (H).
Changed point: 1,4-bis (2-hydroxyethoxy) represented by the above formula (c) from polyoxypropylene (2.2) -2,2-bis (4-hydroxyphenyl) propane Changed to benzene.
The obtained high molecular weight polyester resin A (H) -3 had a softening point (Tm) of 131 ° C. and a glass transition temperature (Tg) of 60 ° C.

(Production Example 4 of High Molecular Weight Polyester Resin A (H))
・ 1,2-propylene glycol 40.0 parts by mass (0.526 mol)
・ Terephthalic acid 55.0 parts by mass (0.331 mol)
・ 1.0 parts by mass of adipic acid (0.007 mol)
・ Titanium tetrabutoxide 0.6 parts by mass

The above materials were weighed into a reaction vessel equipped with a cooling tube, a stirrer, a nitrogen introduction tube, and a thermocouple. Next, after the inside of the flask was replaced with nitrogen gas, the temperature was gradually raised while stirring, and the reaction was carried out for 8 hours while stirring at a temperature of 220 ° C.
Further, the pressure in the reaction vessel was lowered to 8.3 kPa, maintained for 1 hour, then cooled to 180 ° C. and returned to atmospheric pressure (first reaction step).

-Trimellitic anhydride 4.0 parts by mass (0.021 mol)
-Tert-butylcatechol (polymerization inhibitor) 0.1 part by mass Thereafter, the above materials are added, the pressure in the reaction vessel is lowered to 8.3 kPa, and the temperature is maintained at 180 ° C for 4 hours, ASTM D36 After confirming that the softening point measured according to −86 reached 130 ° C., the temperature was lowered to stop the reaction (second reaction step). Thus, high molecular weight polyester resin A (H) -4 was obtained. The obtained high molecular weight polyester resin A (H) -4 had a softening point (Tm) of 132 ° C. and a glass transition temperature (Tg) of 61 ° C.

<Production Example 1 of Polyester Resin B>
-1,6-hexanediol 50.0 parts by mass-Dodecanedioic acid 50.0 parts by mass-Tin dioctylate 1.0 part by mass

  The above materials were weighed into a reaction vessel equipped with a cooling tube, a stirrer, a nitrogen introduction tube, and a thermocouple. Next, after the inside of the flask was replaced with nitrogen gas, the temperature was gradually increased while stirring, the reaction was performed for 6 hours while stirring at a temperature of 140 ° C., and then the reaction was performed while increasing the temperature to 200 ° C. at 10 ° C./hour. To obtain a polyester resin B-1. The obtained polyester resin B-1 had a maximum endothermic peak at 70 ° C. in a DSC curve by weight average molecular weight 10,000 and differential scanning calorimetry.

<Production Examples 2 to 11 of Polyester Resin B>
The types of alcohol component and acid component were changed as shown in Tables 1 and 2, and polyester resins B-2 to B-11 were obtained in the same manner as in Production Example 1 except that. Table 2 shows the physical properties of these polyester resins B.

<Production Example 1 of Organometallic Compound>
The organometallic compound is obtained through the following (1) to (2).
(1) A corresponding aromatic hydroxycarboxylic acid or a sodium salt of an aromatic hydroxycarboxylic acid is dissolved in water, an alcohol aqueous solution or an alcohol and reacted with an aqueous zirconium chloride solution.
(2) The reaction product of aromatic hydroxycarboxylic acid and zirconium is filtered and washed with water.
At this time, various organic zirconium compounds were prepared by adjusting the mixing ratio of aromatic hydroxycarboxylic acid and zirconium chloride, solvent, addition order, addition rate, reaction temperature, and reaction time. Table 3 shows the analytical value of the aromatic hydroxycarboxylic acid to Zr molar ratio.

<Example of production of magnetic core particle 1>
-Process 1 (weighing / mixing process):
Fe ₂ O ₃ 62.0 parts by mass MnCO ₃ 30.0 parts by mass Mg (OH) ₂ 7.0 parts by mass SrCO ₃ 1.0 parts by mass Ferrite raw materials were weighed so that the above composition ratio was the above. Thereafter, the mixture was pulverized and mixed for 5 hours in a dry vibration mill using 1/8 inch diameter stainless steel beads.

-Process 2 (temporary baking process):
The obtained pulverized product was formed into pellets of about 1 mm square using a roller compactor. After removing the coarse powder from the pellets with a vibrating sieve having a mesh opening of 3 mm, and then removing the fine powders with a vibrating sieve having a mesh opening of 0.5 mm, using a burner-type firing furnace, under a nitrogen atmosphere (oxygen concentration of 0.1. And calcined at a temperature of 1000 ° C. for 4 hours to prepare calcined ferrite. The composition of the obtained calcined ferrite is as follows.
(MnO) _a (MgO) _b (SrO) _c (Fe ₂ O ₃ ) _d
In the above formula, a = 0.257, b = 0.117, c = 0.007, d = 0.393

-Step 3 (grinding step):
After pulverizing to about 0.3 mm with a crusher, 30 parts by mass of water was added to 100 parts by mass of calcined ferrite using zirconia beads having a diameter of 1/8 inch, and pulverized with a wet ball mill for 1 hour. The slurry was pulverized for 4 hours by a wet ball mill using alumina beads having a diameter of 1/16 inch to obtain a ferrite slurry (a finely pulverized product of calcined ferrite).

-Process 4 (granulation process):
To the ferrite slurry, 1.0 part by mass of ammonium polycarboxylate as a dispersant and 100 parts by mass of polyvinyl alcohol as a binder are added to 100 parts by mass of the calcined ferrite, and a spray dryer (manufacturer: Okawara Kako) is used. Granulated into spherical particles. After adjusting the particle size of the obtained particles, using a rotary kiln, it was heated at 650 ° C. for 2 hours to remove the organic components of the dispersant and the binder.

-Process 5 (firing process):
In order to control the firing atmosphere, the temperature was raised from room temperature to 1300 ° C. in a nitrogen atmosphere (oxygen concentration: 1.00 vol%) in an electric furnace in 2 hours, and then fired at a temperature of 1150 ° C. for 4 hours. Thereafter, the temperature was lowered to 60 ° C. over 4 hours, returned from the nitrogen atmosphere to the atmosphere, and taken out at a temperature of 40 ° C. or lower.

-Process 6 (screening process):
After crushing the agglomerated particles, the low-magnetic force product is cut by magnetic separation, and the coarse particles are removed by sieving with a sieve having an opening of 250 μm, and a 50% particle size (D50) of 37.0 μm based on volume distribution. Magnetic core particles 1 were obtained.

<Preparation of coating resin 1>
(1) Cyclohexyl methacrylate monomer 26.5% by mass
(2) Methyl methacrylate monomer 0.5% by mass
(3) Methyl methacrylate macromonomer 8.0% by mass
(Macromonomer having a weight average molecular weight of 5000 having a methacryloyl group at one end)
(4) Toluene 30.0% by mass
(5) Methyl ethyl ketone 30.0% by mass
(6) Azobisisobutyronitrile 2.0% by mass

  Among the above materials, (1) to (5) are put into a four-necked separable flask equipped with a reflux condenser, a thermometer, a nitrogen introduction tube and a stirring device, and nitrogen gas is introduced to form a system with nitrogen gas. The inside was replaced. Thereafter, the mixture was heated to 80 ° C., azobisisobutyronitrile was added, and the mixture was refluxed for 5 hours for polymerization. Hexane was injected into the obtained reaction product to precipitate a copolymer, and the precipitate was filtered off and dried under vacuum to obtain coating resin 1. 30 parts by mass of the obtained coating resin 1 was dissolved in a mixed solution consisting of 40 parts by mass of toluene and 30 parts by mass of methyl ethyl ketone to obtain a polymer solution 1 (solid content 30% by mass).

<Preparation of coating resin solution 1>
-Polymer solution 1 (resin solid content concentration 30%) 33.5% by mass
・ Toluene 66.0% by mass
・ Carbon black (Regal 330; manufactured by Cabot) 0.5% by mass
(Primary particle size 25 nm, nitrogen adsorption specific surface area 94 m ² / g, DBP oil absorption 75 mL / 100 g)
The above material was dispersed with a paint shaker for 2 hours using zirconia beads having a diameter of 0.5 mm. The obtained dispersion was filtered through a 5.0 μm membrane filter to obtain a coating resin solution 1.

<Example of production of magnetic carrier 1>
(Resin coating process):
The coating resin solution 1 was added to a vacuum degassing kneader maintained at room temperature so that the resin component was 2.5 parts by mass with respect to 100 parts by mass of the filled core particles 1. After the addition, the mixture was stirred for 15 minutes at a rotational speed of 30 rpm, and after the solvent was volatilized above a certain level (80% by mass or more), the temperature was raised to 80 ° C. while mixing under reduced pressure. The obtained magnetic carrier is separated by low-magnetization by magnetic separation, passed through a sieve having an opening of 70 μm, and then classified by an air classifier, and a magnetic carrier having a 50% particle size (D50) of 38.2 μm based on volume distribution. 1 was obtained.

<Example of production of two-component developer 1>
To 91.0 parts by mass of magnetic carrier 1, 9.0 parts by mass of toner 1 was added and mixed with a V-type mixer (V-20, manufactured by Seishin Enterprise) to obtain two-component developer 1.

[Example 1]
<Production Example of Toner 1>
Low molecular weight polyester resin A (L) -1 75.00 parts by mass High molecular weight polyester resin A (H) -1 25.00 parts by mass Crystalline polyester resin B-1 5.00 parts by mass Organic metal compound 1 1.00 parts by mass and Fischer-Tropsch wax (maximum endothermic peak temperature 90 ° C)
5.00 parts by mass / vinyl resin polymer D 5.00 parts by mass / C.I. I. Pigment Blue 15: 3 5.00 parts by mass

The raw materials shown in the prescription were mixed using a Henschel mixer (FM-75 type, manufactured by Mitsui Mining Co., Ltd.) at a rotation speed of 20 s ⁻¹ and a rotation time of 5 min, and then a twin-screw kneader set at a temperature of 125 ° C. (PCM-30 type, manufactured by Ikekai Co., Ltd.) The obtained kneaded material was cooled and coarsely pulverized to 1 mm or less with a hammer mill to obtain a coarsely pulverized material. The resulting coarsely pulverized product was finely pulverized with a mechanical pulverizer (T-250, manufactured by Freund Turbo). Further, classification was performed using a rotary classifier (200TSP, manufactured by Hosokawa Micron Corporation) to obtain toner particles. The operating conditions of the rotary classifier (200TSP, manufactured by Hosokawa Micron Corporation) were classified at a classification rotor rotational speed of 50.0 s- ¹ . The obtained toner particles had a weight average particle diameter (D4) of 5.8 μm.

To 100 parts by mass of the obtained toner particles, 5.0 parts by mass of silica fine particles having a primary particle number average particle size of 115 nm are added, and the rotation speed is 30 s with a Henschel mixer (FM-75 type, manufactured by Mitsui Mining Co., Ltd.). ⁻¹ and mixing at a rotation time of 5 min. Using the obtained mixture, heat treatment was performed with the surface treatment apparatus shown in FIG. 1 under the following operating conditions to obtain heat-treated toner particles.
Operating conditions: Feed amount = 5 kg / hr, hot air temperature C = 220 ° C., hot air flow rate = 6 m ³ / min, cold air temperature E = 5 ° C., cold air flow rate = 4 m ³ / min, cold air absolute moisture content = 3 g / m ³ , Blower air volume = 20 m ³ / min, Injection air flow rate = 1 m ³ / min
The obtained treated toner particles had an average circularity of 0.963 and a weight average particle diameter (D4) of 6.2 μm.

The following materials were added to 100.0 parts by mass of the obtained toner particles, and mixed with a Henschel mixer (FM-75 type, manufactured by Mitsui Miike Chemical Co., Ltd.) at a rotation speed of 30 s ⁻¹ and a rotation time of 10 min. The toner 1 was obtained by passing through an ultrasonic vibration sieve having an aperture of 54 μm.
・ Number of primary particles surface-treated with 15.0% by mass of isobutyltrimethoxysilane 0.5 mass parts of titanium oxide fine particles having a number average particle size of 50 nm ・ Number average of primary particles surface-treated with 20.0% by mass of hexamethyldisilazane 1.0 part by mass of hydrophobic silica fine particles having a particle size of 15 nm The obtained toner 1 has an endothermic peak derived from polyester resin B at 70 ° C. and an endothermic peak derived from wax component at 90 ° C. in a DSC curve by differential scanning calorimetry. Had.

<Example of production of two-component developer 1>
V-type mixer (V-10 type: Tokuju Seisakusho Co., Ltd.) with toner 1 and magnetic ferrite carrier particles (number average particle size 35 μm) coated with a silicone resin so that the toner concentration is 8% by mass. At 0.5 s ⁻¹ and a rotation time of 5 min. To obtain a two-component developer 1.
The performance of the toner was evaluated according to the following methods (1) to (3).

(1) Development stability evaluation Low printing rate mode The above two-component developer was placed in the cyan station of a full color copier imagePRESS C800 manufactured by Canon Inc. and pre-rotated in advance (no toner replenished) to give stress to the developer. Later image evaluation was performed. This evaluation was performed for the purpose of promoting evaluation of the low printing rate, that is, the durability in a state in which the toner is hardly replaced.
As a specific method, a two-component developer for evaluation is arranged in the developing device taken out from imagePRESS C800, and a developing idle rotating jig capable of rotating the developing roller and the agitating member with the developing device alone is used. I went. With this idling jig, the process speed was set to 450 mm / sec, and idly rotated for 5 hours in a high temperature and high humidity environment (temperature 37.5 ° C./relative humidity 60%). An image was output using the obtained developer to evaluate the occurrence of white spots.

  This white spot is a phenomenon that occurs when the developing carrier flies onto the photosensitive drum together with the toner during development, and the toner around the carrier is not transferred at the primary transfer portion. This is a phenomenon that occurs when the developability of the toner is significantly reduced. The toner in the developer is stressed and the fluidity imparting agent, etc. present on the surface of the toner is buried, causing non-electrostatic attachment between the toner and the carrier. As the landing force increases, it becomes impossible to respond to the flying force due to the electric field.

For image quality evaluation, plain paper CS-680 (68.0 g / m ² ) (sold from Canon Marketing Japan Co., Ltd.) is used under normal temperature and humidity conditions (temperature 23 ° C./relative humidity 50%) using imagePRESS C800. Done using. With an X-Rite color reflection densitometer (500 series: manufactured by X-Rite), 17 gradations (00h to FFh, each horizontal band 10 mm) in A4 size under the development condition of a solid on paper (FFh) density of 1.40 × 290 mm) was output and the number of occurrences was counted.

The evaluation criteria are as follows, and the evaluation results are shown in Table 5. (Number of white spots after 5 hours idling)
A: Less than 2 B: 2 or more and less than 5 C: 5 or more and less than 10 D: 10 or more and less than 20 E: 20 or more

(2) Fixability evaluation A developer unit containing the above two-component developer is mounted on the cyan station of a full color copier imagePRESS C1 + manufactured by Canon Inc. and modified so that an image can be formed with the fixing temperature removed. An unfixed image was formed. For the evaluation, plain paper: OSE TOP COLOR PAPER (A4 100.0 g / m ² ) (sold from Canon Marketing Japan Inc.) was used.
The development conditions are adjusted as appropriate so that the amount of toner on the FFh image (hereinafter, solid portion) is 1.2 mg / cm ² , 3 cm from the leading edge of the A4 evaluation paper, and 2 cm × 10 cm at the center of the evaluation paper A solid unfixed image was formed. The unfixed image was conditioned for 24 hours in a normal temperature and low humidity environment (temperature 25 ° C./relative humidity 5%).

  Take out the fuser from Canon's full-color copier imagePRESS C800 and modify the fixing test jig so that the process speed and upper and lower fixing member temperatures can be controlled independently in a low-temperature, low-humidity environment (temperature 15 ° C / relative humidity) 10%). With the process speed adjusted to 450 mm / sec and the lower belt temperature fixed at 90 ° C., the upper belt temperature of the fixing test jig was adjusted every 5 ° C. within the range of 100 to 200 ° C. The moisture-adjusted unfixed image was passed through. The fixed image that has passed through the fixing device is rubbed 5 times with a lens cleaning wiper (Dasper Ozu Sangyo Co., Ltd.) with a load of 4.9 kPa, and the density reduction rate of the image density before and after rubbing is 10% or less. The fixing temperature was defined as the point at which Based on the criterion that fixing was not possible when the density decreased over 10%, the lowest upper belt set temperature not exceeding 10% of the image density decreasing rate was set as the fixing start temperature, and evaluation was performed according to the following evaluation standards. . The evaluation results are shown in Table 5.

(Evaluation criteria: low temperature fixability)
A: Less than 110 ° C B: 110 ° C or more and less than 140 ° C C: 140 ° C or more and less than 155 ° C D: 155 ° C or more and less than 180 ° C E: 180 ° C or more

(3) Hot offset resistance Plain paper: CS-680 (A4 68.0 g / m ² ) (sold from Canon Marketing Japan Inc.) was used for evaluation.
The development conditions were adjusted so that the amount of toner applied on the paper of the FFh image (hereinafter, solid portion) was 0.07 mg / cm ^2, and an unfixed FFh image was obtained.
After that, as in the low-temperature fixability evaluation, in a normal temperature and low humidity environment (temperature 23 ° C./relative humidity 10%) using a fixing evaluation jig modified from the full color copier imagePRESS C800 manufactured by Canon Inc. Evaluation was performed.

The reflectance of the evaluation paper before image printing was measured by a reflectometer (“REFLECTOMETER MODEL TC-6DS” (manufactured by Tokyo Denshoku)), and an average value measured at five locations was defined as D _A (%). The fixing temperature in the external fixing device is adjusted every 5 ° C. within the range of 100 to 200 ° C., the reflectance of the white background portion of the fixed image at each fixing temperature is measured with a reflectometer, and the maximum value is expressed as D _B (%). did.
The difference between D _A (%) and D _B (%) did not exceed 0.5%, and the highest fixing temperature was set as the upper limit fixing temperature, and hot offset resistance was evaluated according to the following criteria. The evaluation results are shown in Table 5.

(Evaluation criteria: Hot offset property)
A: 220 ° C or higher B: 205 ° C or higher and lower than 220 ° C C: 190 ° C or higher and lower than 205 ° C D: 175 ° C or higher and lower than 190 ° C E: Less than 175 ° C

現像剤９〜２０及び比較現像剤１〜８において、ポリエステル樹脂Ａ（Ｌ）−１〜４は、低分子量ポリエステル樹脂Ａ（Ｌ）微粒子分散液（１）〜（４）を表す。ポリエステル樹脂Ａ（Ｈ）−１〜４は、高分子量ポリエステル樹脂Ａ（Ｈ）微粒子分散液（１）〜（４）を表す。ポリエステル樹脂Ｂ−７〜１１は、ポリエステル樹脂Ｂ微粒子分散液（７）〜（１１）を表す。有機金属化合物１〜１１は、有機金属化合物微粒子分散液（１）〜（１１）を表す。

In developers 9 to 20 and comparative developers 1 to 8, polyester resins A (L) -1 to 4 represent low molecular weight polyester resin A (L) fine particle dispersions (1) to (4). Polyester resins A (H) -1 to 4 represent high molecular weight polyester resin A (H) fine particle dispersions (1) to (4). Polyester resins B-7 to 11 represent polyester resin B fine particle dispersions (7) to (11). Organometallic compounds 1 to 11 represent organometallic compound fine particle dispersions (1) to (11).

[Examples 2 to 7]
As shown in Table 4, except that the polyester resins B-2 to B-7 were changed as shown in Table 4, toners 2 to 7 were produced in the same manner as in Example 1, and two-component development was similarly performed. Agents 2 to 7 were prepared.
Furthermore, evaluation was performed in the same manner as in Example 1. The evaluation results are shown in Table 5.

[Example 8]
<Production Example of Toner 8>
Amorphous low molecular weight polyester resin A (L) -1 75.00 parts by mass Amorphous high molecular weight polyester resin A (H) -1 25.00 parts by mass Crystalline polyester resin B-7 5.00 parts by mass Parts / organometallic compound 1 1.00 parts by mass / Fischer-Tropsch wax (peak temperature of maximum endothermic peak 90 ° C.)
5.00 parts by mass / vinyl resin polymer D 5.00 parts by mass / C.I. I. Pigment Blue 15: 3 5.00 parts by mass

The raw materials shown in the prescription were mixed using a Henschel mixer (FM-75 type, manufactured by Mitsui Mining Co., Ltd.) at a rotation speed of 20 s ⁻¹ and a rotation time of 5 min, and then a twin-screw kneader set at a temperature of 125 ° C. (PCM-30 type, manufactured by Ikekai Co., Ltd.) The obtained kneaded material was cooled and coarsely pulverized to 1 mm or less with a hammer mill to obtain a coarsely pulverized material. The resulting coarsely pulverized product was finely pulverized with a mechanical pulverizer (T-250, manufactured by Freund Turbo). Further, classification was performed using a rotary classifier (200TSP, manufactured by Hosokawa Micron Corporation) to obtain toner particles. The operating conditions of the rotary classifier (200TSP, manufactured by Hosokawa Micron Corporation) were classified with the classification rotor rotation speed set to 50.0 s ⁻¹ . The obtained toner particles had a weight average particle diameter (D4) of 5.7 μm.

The following materials were added to 100.0 parts by mass of the obtained toner particles, and mixed with a Henschel mixer (FM-75 type, manufactured by Mitsui Miike Chemical Co., Ltd.) at a rotation speed of 30 s ⁻¹ and a rotation time of 10 min. The toner 8 was obtained by passing through an ultrasonic vibration sieve having an aperture of 54 μm.
Silica fine particles having a number average particle size of 110 nm of primary particles 5.0 parts by mass Titanium oxide fine particles having a number average particle diameter of 50 nm of primary particles surface-treated with 15.0% by mass of isobutyltrimethoxysilane 1.0 part by mass 0.8 mass parts of hydrophobic silica fine particles having a number average particle diameter of 16 nm of primary particles surface-treated with 20.0 mass% of methyldisilazane

<Example of production of two-component developer 8>
V-type mixer (V-10 type: Tokuju Seisakusho Co., Ltd.) with toner 8 and magnetic ferrite carrier particles (number average particle size 35 μm) surface-coated with silicone resin so that the toner concentration is 9% by mass. At 0.5 s ⁻¹ and a rotation time of 5 min. To obtain a two-component developer 8.
Evaluation was performed in the same manner as in Example 1. The evaluation results are shown in Table 5.

<Production Example of High Molecular Weight Polyester Resin A (H) Fine Particle Dispersion (1)>
100 parts by mass of high molecular weight polyester resin A (H) -1 was dissolved in 150 parts by mass of tetrahydrofuran. This tetrahydrofuran solution was stirred at 10,000 rpm for 2 minutes with a homogenizer (manufactured by IKA Japan: Ultratarax) at room temperature. While stirring, 1000 parts by mass of ion-exchanged water added with 5 parts by mass of potassium hydroxide and 10 parts by mass of sodium dodecylbenzene-sulfonate as a surfactant was added dropwise. The mixed solution was heated to about 75 ° C. to remove tetrahydrofuran. Then, it diluted with ion-exchange water so that solid content might be 8%, and obtained high molecular weight polyester resin A (H) fine particle dispersion (1) with a volume average particle diameter of 0.09 micrometer.

<Production Example of High Molecular Weight Polyester Resin A (H) Fine Particle Dispersions (2) to (4)>
Except for changing the high molecular weight polyester resin A (H) -1 to the high molecular weight polyester resin A (H) -2-4, the same as the preparation of the high molecular weight polyester resin A (H) fine particle dispersion (1). High molecular weight polyester resin A (H) fine particle dispersions (2) to (4) were obtained.

<Production Example of Low Molecular Weight Polyester Resin A (L) Fine Particle Dispersions (1) to (4)>
Except for changing the high molecular weight polyester resin A (H) -1 to low molecular weight polyester resins A (L) -1 to 4, the same procedure as in the preparation of the high molecular weight polyester resin A (H) fine particle dispersion (1) is performed. Low molecular weight polyester resin A (L) fine particle dispersions (1) to (4) were obtained.

<Production Example of Polyester Resin B Fine Particle Dispersions (7) to (11)>
Dispersion of polyester resin B fine particles in the same manner as the preparation of the high molecular weight polyester resin A (H) fine particle dispersion (1) except that the high molecular weight polyester resin A (H) -1 is changed to polyester resin B-7 to 11. Liquids (7) to (11) were obtained.

<Production Example of Organometallic Compound Fine Particle Dispersion (1)>
・ Organic compound 1 10.0 parts by mass. Anionic surfactant (Daiichi Kogyo Seiyaku Co., Ltd .: Neogen RK) 1.5 parts by mass. Ion-exchanged water 88.5 parts by mass. An aqueous dispersion of colorant fine particles was prepared by dispersing the colorant for about 1 hour using a high-pressure impact disperser Nanomizer (manufactured by Yoshida Kikai Kogyo Co., Ltd.). The volume-based median diameter measured using a dynamic light scattering particle size distribution diameter (Nanotrack: manufactured by Nikkiso Co., Ltd.) was 0.30 μm.

<Production Example of Organometallic Compound Fine Particle Dispersions (2) to (11)>
In the preparation of the organometallic compound fine particle dispersion (1), the organometallic compound fine particle dispersions (2) to (11) are obtained in the same manner except that the organometallic compound 1 is changed to the organometallic compounds 2 to 11. It was.

<Example of production of colorant fine particle dispersion>
・ Color material (Cyan pigment, manufactured by Daiichi Seika Kogyo Co., Ltd .: Pigment Blue 15: 3) 10 parts by mass ・ Anionic surfactant (Daiichi Kogyo Seiyaku Co., Ltd .: Neogen RK) 1.5 parts by mass 88.5 parts by weight of water Mix and dissolve the above, disperse for about 1 hour using a high-pressure impact disperser Nanomizer (manufactured by Yoshida Kikai Kogyo Co., Ltd.) An aqueous dispersion was prepared. The volume-based median diameter measured using a dynamic light scattering particle size distribution diameter (Nanotrack: manufactured by Nikkiso Co., Ltd.) was 0.20 μm.

<Production Example of Release Agent Fine Particle Dispersion>
-Fischer-Tropsch wax (peak temperature of maximum endothermic peak 90 ° C) 5.0 parts by mass-Anionic surfactant (Daiichi Kogyo Seiyaku Co., Ltd .: Neogen RK) 1.0 parts by mass-Ion-exchanged water 89 parts by mass After putting the above into a mixing vessel equipped with a stirrer, heat it to 90 ° C and circulate it to Claremix W Motion (M Technique Co., Ltd.), shearing stirring with a rotor outer diameter of 3 cm and clearance of 0.3 mm The part was stirred under the following conditions and dispersed for 60 minutes.
・ Rotor speed 19,000r / min, screen speed 19,000r / min
Thereafter, an aqueous dispersion of release agent fine particles was obtained by cooling to 40 ° C. under cooling treatment conditions of a rotor rotational speed of 1000 r / min, a screen rotational speed of 0 r / min, and a cooling rate of 10 ° C./min. The volume-based median diameter measured using a dynamic light scattering particle size distribution diameter (Nanotrack: manufactured by Nikkiso Co., Ltd.) was 0.15 μm.

[Example 9]
(Example of production of toner particles 9)
-Low molecular weight polyester resin A (L) fine particle dispersion (1) 75.00 parts by mass (resin equivalent)
-High molecular weight polyester resin A (H) fine particle dispersion (1) 25.00 parts by mass (resin equivalent)
・ Polyester resin B fine particle dispersion (1) 5.00 parts by mass (resin equivalent)
Organic metal compound fine particle dispersion (1) 1.00 parts by mass (corresponding to organometallic)
-Release agent fine particle dispersion 5.00 parts by mass (equivalent to release agent)
・ Colorant fine particle dispersion 5.00 parts by mass (equivalent to colorant)
・ 10 mass parts of 1.5 mass% magnesium sulfate aqueous solution

  The above was dispersed using a homogenizer (manufactured by IKA: Ultra Tarrax T50). Subsequently, the pH was adjusted to 8.1 with a 0.1N sodium hydroxide aqueous solution. Then, it heated, stirring with a stirring blade to 45 degreeC in the water bath for heating. After maintaining at 45 ° C. for 1 hour, observation with an optical microscope confirmed that aggregated particles having an average particle size of about 5.5 μm were formed. After adding 40 mass parts of 5 mass% trisodium citrate aqueous solution, it heated up to 85 degreeC, continuing stirring, and hold | maintaining for 90 minutes, and the core particle was united. Next, while stirring was continued, water was placed in the water bath and cooled to 25 ° C. Further, when the particle size of the core particles was measured by a particle size distribution analyzer (Coulter Multisizer III: manufactured by Beckman Coulter, Inc.) by the Coulter method, the volume-based median diameter was 5.6 μm.

Thereafter, after filtration and solid-liquid separation, 800 parts by mass of ion-exchanged water whose pH was adjusted to 8 with sodium hydroxide was added to the solid content, followed by stirring and washing for 30 minutes. Thereafter, filtration and solid-liquid separation were performed again. Subsequently, 800 parts by mass of ion-exchanged water was added to the solid content and washed with stirring for 30 minutes. Thereafter, filtration and solid-liquid separation were performed again, and this was repeated 5 times. Next, toner particles 9 were obtained by drying the obtained solid content.
To 100 parts by mass of the obtained toner particles 9, 1.0 part by mass of silica fine particles having a number average particle diameter of 15.0 nm of primary particles is added, and the rotation speed is 31.6 s ⁻¹ with a Henschel mixer (FM-75 type). The toner 9 was obtained by mixing for 5 minutes with a rotation time and passing through an ultrasonic vibration sieve having an aperture of 54 μm.

<Example of production of two-component developer 9>
V-type mixer (V-10 type: Tokuju Seisakusho Co., Ltd.) with toner 9 and magnetic ferrite carrier particles (number average particle size 35 μm) coated with a silicone resin so that the toner concentration is 9% by mass. At 0.5 s ⁻¹ and a rotation time of 5 min. To obtain a two-component developer 9.
Evaluation was performed in the same manner as in Example 1. The evaluation results are shown in Table 5.

[Examples 10 to 20 and Comparative Examples 1 to 7]
In the same manner as in Example 9, except that the high molecular weight polyester resin A (H), the low molecular weight polyester resin A (L), the polyester resin B, and the organometallic compound were changed as shown in Table 4, the toner 10 20 and comparative toners 1-7 were prepared. Similarly, two-component developers 10 to 20 and comparative two-component developers 1 to 7 were produced.
Furthermore, evaluation was performed in the same manner as in Example 1. The evaluation results are shown in Table 5.

[Comparative Example 8]
The high molecular weight polyester resin A (H), the low molecular weight polyester resin A (L), and the polyester resin B were changed as shown in Table 4, and the organometallic compound was changed to a compound (“DTBS- A comparative toner 8 was prepared in the same manner as in Example 9 except that it was also described as “Zn”.
Furthermore, evaluation was performed in the same manner as in Example 1. The evaluation results are shown in Table 5.

1. 1. Raw material fixed supply means 2. compressed gas flow rate adjusting means; Introducing pipe 4. 4. Protruding member Supply pipe 6. Processing chamber 7. Hot air supply means8. Cold air supply means 9. Restricting means 10. Collection means 11. Hot air supply means outlet 12. Distributing member 13. Swivel member 14. Powder particle supply port

Claims (6)

A toner having toner particles containing polyester resin A, polyester resin B and an organometallic compound,
The polyester resin A is an amorphous polyester resin obtained by condensation polymerization of an alcohol component containing 80 mol% or more of an aromatic polyhydric alcohol and a polyvalent carboxylic acid component,
The polyester resin B is a polycondensation of an alcohol component containing 80 mol% or more of an aliphatic diol having 6 to 12 carbon atoms and a carboxylic acid component containing 80 mol% or more of an aliphatic dicarboxylic acid having 6 to 12 carbon atoms. A crystalline polyester resin obtained by
The organometallic compound is an organozirconium compound produced by a reaction between zirconium and an aromatic hydroxycarboxylic acid, and the organozirconium compound has an aromatic hydroxycarboxylic acid unit of 1.2 to 1 mol per 1 mol of zirconium atom. A toner comprising 1.8 mol.   The aromatic hydroxycarboxylic acid is salicylic acid, 5-methylsalicylic acid, 3,5-dimethylsalicylic acid, 3,5-di-tert-butylsalicylic acid, 5-methoxysalicylic acid, 3-methyl-5-propylsalicylic acid, and 5- The toner according to claim 1, wherein the toner is one or more aromatic hydroxycarboxylic acids selected from the group consisting of tert-heptylsalicylic acid.   The toner according to claim 1, wherein the aromatic polyhydric alcohol in the polyester resin A is an alkylene oxide adduct of bisphenol A. A method for producing the toner according to any one of claims 1 to 3,
A step of obtaining the polyester resin A by polycondensation of an alcohol component containing 80 mol% or more of an aromatic polyhydric alcohol and a polyvalent carboxylic acid component using a tin compound represented by the following formula (i) as a catalyst;
A method for producing a toner comprising:

(Wherein R represents an alkyl group having 5 to 15 carbon atoms) Melting and kneading a mixture containing the polyester resin A, the polyester resin B and an organometallic compound, and pulverizing the obtained kneaded material to obtain toner particles;
The method for producing a toner according to claim 4, comprising:   The method for producing a toner according to claim 4, further comprising a step of heat-treating the toner particles.

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