JP6786281B2 - Toner and toner manufacturing method - Google Patents

Description

The present invention relates to toners used in electrophotographic methods, electrostatic recording methods, electrostatic printing methods, toner jet methods, and methods for manufacturing toners.

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

For the purpose of achieving low temperature fixability, it has been proposed to use not only amorphous resin but also crystalline resin as the binder resin. Patent Document 1 proposes that both non-crosslinkable crystalline resin and crosslinkable crystalline resin are used in combination to achieve both fixability and storage stability.
There are also proposals for improving the chargeability of toner. Patent Document 2 proposes that a crystalline resin is contained as a binder resin and a metal compound of a salicylic acid derivative is contained as a charge control agent.

Japanese Unexamined Patent Publication No. 2012-53196 JP-A-2002-351137A

The crosslinkable crystalline resin described in Patent Document 1 tends to have non-uniform dispersion in the amorphous resin, and thus tends to cause poor charging of the toner in long-term use.
Further, as disclosed in Patent Document 2, the charge imparting effect is enhanced only by increasing the compatibility between the crystalline resin and the charge control agent, but the dispersed state of the crystalline resin in the amorphous resin is unstable. This may adversely affect low temperature fixability and hot offset resistance.

Further, for the purpose of improving the fluidity of the toner and maintaining the transportability in the machine and the uniform triboelectric property, various fine particles such as silicon compounds are attached to the surface of the toner as spacers. A method of suppressing the cohesive force between particles is used.
However, in a high-speed developing system, the stress on the toner due to the developing rollers, regulating members, stirring members, etc. in the developing device is greater, and spacer particles are generated on the surface of the toner, especially when a large number of sheets are continuously printed. Easy to bury. As a result, the cohesive force suppressing effect cannot be sufficiently exerted, and it tends to be difficult to maintain stable triboelectric characteristics. In particular, when the above-mentioned crystalline resin is used for the purpose of promoting the plasticization of the amorphous resin, the toughness of the toner is impaired and these burial phenomena are likely to occur.

As described above, even in a system using a crystalline resin, it has not been possible to obtain a toner capable of simultaneously satisfying development stability, low temperature fixability, and hot offset resistance.
An object of the present invention is to provide a toner that solves the above problems and that uses a plasticizer such as a crystalline material, which has excellent charging characteristics, excellent development stability, low temperature fixability, and hot offset resistance. It is to be.

The above problem can be solved by a 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 a non-crystalline polyester resin which is a condensation polymer of an alcohol component and a polycarboxylic acid component containing not less than 80 mol% of an aromatic polyhydric alcohol,
The polyester resin B, polycondensation of an alcohol component containing an aliphatic diol having 6 to 12 carbon atoms or 80 mol%, and a carboxylic acid component containing an aliphatic dicarboxylic acid having 6 to 12 carbon atoms or 80 mol% It is a crystalline polyester resin that is the body ,
The organic metal compound is an organic zirconium compound produced by the reaction of zirconium with an aromatic hydroxycarboxylic acid, and the organic zirconium 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 having excellent development stability, low temperature fixability, and hot offset resistance even in a high-speed development system.

It is a schematic diagram of the thermosphere processing apparatus used for manufacturing the toner of this invention.

Hereinafter, embodiments for carrying out the present invention will be described in detail.
According to the present invention, the toner has toner particles containing polyester resin A, polyester resin B, and an organometallic compound.
The polyester resin A is a non-crystalline polyester resin which is a condensation polymer of an alcohol component and a polycarboxylic acid component containing an aromatic polyhydric alcohol or 80 mol%,
The polyester resin B, polycondensation of an alcohol component containing an aliphatic diol having 6 to 12 carbon atoms or 80 mol%, and a carboxylic acid component containing an aliphatic dicarboxylic acid having 6 to 12 carbon atoms or 80 mol% It is a crystalline polyester resin that is the body ,
The organic metal compound is an organic zirconium compound produced by the reaction of zirconium with an aromatic hydroxycarboxylic acid, and the organic zirconium compound has an aromatic hydroxycarboxylic acid unit of 1.2 to 1 mol per 1 mol of zirconium atom. belt toner to contain 1.8mol is provided.

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

The present inventors consider the action and effect of using the toner of the present invention having such a structure as follows.
The polyester resin A has an amorphous property, and the polyester resin B has a crystallinity.
The crystalline resin in the present invention is a resin in which an endothermic peak is observed in differential scanning calorimetry (DSC).

The carbon number of the alcohol component (aliphatic diol) of the crystalline polyester resin B and the carbon number of the carboxylic acid component (aliphatic carboxylic acid) are set to specific values, and in the amorphous polyester resin A, the aliphatic An aromatic alcohol having a different structure from that of is used. As a result, the degree of compatibility with each of them can be adjusted, whereby the polyester resin B can be arranged in the polyester resin A in a dispersed state in which the plastic effect is easily exhibited.

Further, in the organic zirconium compound contained in the toner of the present invention, the zirconium atom easily coordinates eight, and the oxygen of the carboxyl group or the hydroxyl group in the polyester resin easily coordinates or bonds. As a result, the organic zirconium compound can be prevented from falling out from the toner particles, and the dispersed state of the polyester resin B in the polyester resin A can be fixed. As a result, it is possible to suppress the bias of dispersion due to the reaggregation of the crystalline polyester due to external factors such as long-term standing in a high temperature and high humidity environment.

In addition, the toughness of the toner is increased, and deterioration of the toner such as embedding of an external additive in the developing process of the electrophotographic process is suppressed.
Further, when the melt-kneading step is performed at the time of toner production, the cross-linking reaction by coordinating or bonding the oxygen of the carboxyl group or the hydroxyl group in the polyester resin of the organic zirconium compound is promoted. As a result, the toughness of the toner is increased, and deterioration of the toner such as embedding of an external additive in the developing process of the electrophotographic process is suppressed.

Further, when the heat treatment step at the time of toner production is added, the crystalline polyester resin B can be arranged near the surface of the toner while maintaining the crystallization of the crystalline polyester resin B, and the cross-linking reaction on the toner surface layer can be carried out. It can be promoted, and the above effects are more likely to be exhibited.
It is important that the content of the polyester resin B is 2 parts by mass or more and 20 parts by mass or less with respect to 100 parts by mass of the polyester resin A.
The composition of the toner preferable for achieving the object in the present invention will be described in detail below.

[Polyester resin A]
The polyester resin A used in the toner of the present invention is
It is characterized in that 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 integers 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 and 1,6-hexanediol, bisphenol A, other diols such as hydrogenated bisphenol A, bisphenol derivatives represented by the above formula (a) or diols represented by the above formula (b). It can also be used in combination with.

In addition, examples of the alcohol component that can be used in the polyester resin A include the following. Ethylene glycol, diethylene glycol, triolethylene 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-methylpropantriol, 2-methyl-1,2,4-butanetriol, trimethylol Etan, trimethylol propane, 1,3,5-trihydroxymethylbenzene.
As described above, the main component of the alcohol component constituting the polyester resin A is an aromatic polyhydric alcohol. Here, among the alcohol components constituting the polyester resin A, the aromatic polyhydric alcohol is characterized by being 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 the polyvalent carboxylic acid monomer used in the polyester unit of the polyester resin, the following polyvalent carboxylic acid monomer 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, sebatic 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 valent carboxylic acid, its acid anhydride or its lower alkyl ester include the following. 1,2,4-benzenetricarboxylic acid, 2,5,7-naphthalentricarboxylic acid, 1,2,4-naphthalenetricarboxylic acid, 1,2,4-butanetricarboxylic acid, 1,2,5-hexanetricarboxylic acid, 1,3-Dicarboxy-2-methyl-2-methylenecarboxypropane, 1,2,4-cyclohexanetricarboxylic acid, tetra (methylenecarboxyl) methane, 1,2,7,8-octanetetracarboxylic acid, pyromellitic acid , Empol trimeric acids, their acid anhydrides or their lower alkyl esters. Of these, 1,2,4-benzenetricarboxylic acid, that is, trimellitic acid or a derivative thereof is preferably used because it is inexpensive and reaction control is easy. These divalent carboxylic acids and the like and trivalent or higher carboxylic acids can be used alone or in combination of two or more.

In the present invention, the polyester resin A may be a hybrid resin containing a polyester resin as a main component and other resin components. For example, a hybrid resin of a polyester resin and a vinyl resin can be mentioned. The following method is preferable as a method for obtaining a reaction product of a vinyl-based resin or a vinyl-based copolymer unit and a polyester resin, such as a hybrid resin.
-A method of polymerizing one or both resins 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-based copolymer include unsaturated dicarboxylic acids such as phthalic acid, maleic acid, citraconic acid, and itaconic acid, or anhydrides thereof. Be done. Among the monomers constituting the vinyl-based copolymer component, those capable of reacting with the polyester resin component include those having a carboxyl group or a hydroxy group, acrylic acid or methacrylic acid esters.

Further, in the present invention, as the polyester resin A, if the polyester resin is the main component, various resin compounds conventionally known as binder resins can be used in combination in addition to the above vinyl resin. Examples of such a resin compound include the following. Phenolic resin, natural resin modified phenol resin, natural resin modified malein resin, acrylic resin, methacrylic resin, polyvinyl acetate resin, silicone resin, polyester resin, polyurethane, polyamide resin, furan resin, epoxy resin, xylene resin, polyvinyl butyral, terpen Resin, bearloinden resin, petroleum resin.

The polyester resin A in the present invention can be produced according to a usual polyester synthesis method. For example, it is desired to carry out an esterification reaction or a transesterification reaction between the carboxylic acid monomer and the alcohol monomer described above, and then carry out 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 carried out using a usual esterification catalyst or transesterification catalyst such as sulfuric acid, titanium butoxide, dibutyltin oxide, manganese acetate and magnesium acetate, if necessary.

Further, the polycondensation reaction can be carried out using a usual polymerization catalyst, for example, a known catalyst such as titanium butoxide, dibutyltin oxide, tin acetate, zinc acetate, tin disulfide, antimony trioxide, germanium dioxide and the like. ..
Among these, in the present invention, it is preferable that the tin compound represented by the following formula (i) is used as a catalyst. By using this compound, it is easy to adjust the physical properties such as the softening point and the glass transition point of the resin. For example, the condensation time is longer, but the low molecular weight components can be reduced. As a result, when heat melt kneading is used during toner production, the viscosity of the polyester resin can be stabilized, and pigments and the like can be easily dispersed uniformly.
Further, when the tin compound is present in the binder resin after polycondensation, 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。

(R in the formula indicates an alkyl group having 5 to 15 carbon atoms)
Here, in the present invention, it is optimal that R in the formula of the tin compound represented by the formula (i) is an alkyl group of 5 or more and 15 or less as having a catalytic effect of the esterification reaction.
The amount of the tin compound alkylcarboxylic acid added is preferably 0.01 parts by mass or more and 2 parts by mass or less, and more preferably 0.05 parts by mass or more and 1 part by mass or less with respect to 100 parts by mass of the polyester resin. When it is 0.01 part by mass or more, the reaction time at the time of polyester polymerization does not become too long, and the effect of improving the dispersibility of the pigment can be obtained. Further, if it is 2 parts by mass or less, it does not affect the charging characteristics of the toner and the fluctuation of the charging amount depending on the environment does not become large.

Further, 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 charge stability in a high temperature and high humidity environment. Further, 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.

Further, 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 low molecular weight fixability is that 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 charge 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 3000 or more and 7000 or less from the viewpoint of low temperature fixability. Further, the acid value of the low molecular weight polyester resin A (L) is preferably 10 mgKOH / g or less from the viewpoint of charge 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 and
It is characterized by being obtained by polycondensation with a carboxylic acid component containing 80 mol% or more of an aliphatic dicarboxylic acid having 6 or more and 12 or less carbon atoms.
The polyester resin B is obtained by polycondensation of an alcohol component containing 85 mol% or more of an aliphatic diol having 6 or more and 12 or less carbon atoms and a carboxylic acid component containing 85 mol% or more of an aliphatic dicarboxylic acid having 6 or more and 12 or less carbon atoms. It is preferable that it is.
The aliphatic diol is not particularly limited, but is preferably a chain-like (more preferably linear) aliphatic diol. Butanediol, pentanediol, hexanediol, heptanediol, octanediol, nonanediol, and decanediol are preferably exemplified.

In the present invention, if the main component of the alcohol component of the polyester B is an aliphatic diol, a multivalent alcohol monomer other than the above aliphatic diol can also be used. Examples of the dihydric alcohol monomer among the polyhydric alcohol monomers include the following. Aromatic alcohols such as polyoxyethylene bisphenol A and polyoxypropylene bisphenol A, which are alkylene oxide adducts of bisphenol A; 1,4-cyclohexanedimethanol and the like.
In addition, examples of the trihydric or higher polyhydric alcohol monomer among the polyhydric alcohol monomers include the following. Aromatic alcohols such as 1,3,5-trihydroxymethylbenzene; pentaerythritol, dipentaerythritol, tripentaerythritol, 1,2,4-butantriol, 1,2,5-pentanetriol, glycerin, 2-methyl Aliper alcohols such as propanetriol, 2-methyl-1,2,4-butanetriol, trimethylolethane, and trimethylolpropane.

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

On the other hand, the aliphatic dicarboxylic acid is not particularly limited, but is preferably a chain-like (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 and the like, and hydrolyze these acid anhydrides or lower alkyl esters. It also includes those that have been used.

In the present invention, if the main component of the carboxylic acid component of the polyester B is an aliphatic dicarboxylic acid, 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 of n-dodecylsuccinic acid and n-dodecenylsuccinic acid; alicyclic carboxylic acids such as cyclohexanedicarboxylic acid, acid anhydrides or lower alkyl esters thereof and the like.
Among other carboxylic acid monomers, examples of trivalent or higher valent carboxylic acids include the following. Aromatic carboxylic acids such as 1,2,4-benzenetricarboxylic acid (trimellitic acid), 2,5,7-naphthalenetricarboxylic acid, 1,2,4-naphthalenetricarboxylic acid, pyromellitic acid, 1,2,4 -Aromatic carboxylic acids such as butane tricarboxylic acid, 1,2,5-hexanetricarboxylic acid, 1,3-dicarboxy-2-methyl-2-methylenecarboxypropane, their acid anhydrides or lower alkyl esters and the like. Derivatives, etc.

Further, in the present invention, if the main component is an aliphatic dicarboxylic acid as the carboxylic acid component of the polyester B, it may also contain a monovalent carboxylic acid. 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 conventional polyester synthesis method. For example, it is desired to carry out an esterification reaction or a transesterification reaction between the carboxylic acid monomer and the alcohol monomer described above, and then carry out a polycondensation reaction under reduced pressure or by introducing nitrogen gas according to a conventional method. A polyester resin can be obtained.

The above esterification or transesterification reaction is carried out using a usual esterification catalyst or transesterification catalyst such as sulfuric acid, titanium butoxide, dibutyltin oxide, tin 2-ethylhexanoate, manganese acetate and magnesium acetate, if necessary. be able to.
Further, the polycondensation reaction uses a known 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 amount of catalyst are not particularly limited and may be appropriately determined.

In the esterification or transesterification reaction or polycondensation reaction, all the monomers may be mixed all at once in order to increase the strength of the obtained polyester resin B. Further, in order to reduce the low molecular weight component, a method such as first reacting a divalent monomer and then adding a trivalent or higher valent monomer to react may be used.
The molar ratio (carboxylic acid component / alcohol component) of the alcohol component and the carboxylic acid component, which are the raw material monomers of the polyester resin B, is preferably 0.80 or more and 1.20 or less.

[Organometallic compound]
The organometallic compound used in the present invention is characterized by being an organozirconium compound produced by the reaction of zirconium with an aromatic hydroxycarboxylic acid.
The organic zirconium compound is composed of a compound having a plurality of forms such as a compound having a different coordination number and a number of bonds and a compound having a different structure, and has an aromatic hydroxycarboxylic acid unit per 1 mol of a zirconium atom. Contains 2 to 1.8 mol. By containing such an organic zirconium compound, excellent development stability can be obtained, transferability is also improved, and the utilization rate of toner is improved, so that the consumption efficiency of toner is increased. In order to obtain more excellent developability, it is preferable to contain 1.3 to 1.7 mol of aromatic hydroxycarboxylic acid units with respect to 1 mol of zirconium atom. If it is less than 1.2 mol, the rise of triboelectric charging tends to be delayed, and when the toner remaining in the developer and the replenished toner are mixed during toner replenishment, a decrease in density, uneven density, and an increase in fog are likely to occur. .. If it exceeds 1.8 mol, the image density decreases and fog increases when left for a long period of time.
It is preferable that the aromatic hydroxycarboxylic acid is a compound represented by the following formula (I) in order to obtain a good rising charge and to stabilize the 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 is a hydrogen, an alkyl group, an aryl group, an alalkyl group, a cycloalkyl group, an alkenyl group, an alkoxy group, an aryloxy group, a hydroxyl group, an acyloxy group, an alkoxycarbonyl group, an aryloxycarbonyl group, Represents an acyl group, a carboxyl group, a halogen, a nitro group, an amino group, or a carbamoyl group. Substituents R may be linked to each other to form an aliphatic ring, an aromatic ring or a heterocycle. In this case, the ring may have a substituent R, and the number of substituents R is 1 to 8. They may have, they may be the same, or they may be different. ]
Among them, the aromatic hydroxycarboxylic acid is a sartylic acid having an alkyl group as a substituent to obtain a high charge amount, and high image density and faithful latent image reproduction can be achieved with higher image quality.
Examples of the aromatic hydroxycarboxylic acid used in the present invention include the following. 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 will be given below.

In the present invention, there are a method of adding an organic zirconium compound to the toner and a method of adding the organic zirconium compound to the inside of the toner. The amount to be added in the case of internal addition 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. The amount added when externally added is preferably 0.01 to 5 parts by mass, more preferably 0.05 to 3 parts by mass. In the case of external addition, it is particularly preferable to fix the toner on the surface of the toner mechanically.

In the organic zirconium compound in the present invention, the zirconium atom easily coordinates eight, and the oxygen of the carboxyl group or hydroxyl group easily coordinates or bonds. 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 possible to prevent the toner particles from falling off, and to obtain uniform charge and durability stability of charge. Further, the influence on the transparency of the toner is reduced, which is preferable for the color toner to express vivid colors.

Further, the cross-linking of the polymer chain can be uniformly applied to the entire binder resin in the toner through the coordination of the carboxyl group and the hydroxyl group of the polyester resin component to the zirconium atom. Further, even if recycled paper containing a large amount of filler is used as the recording material, it is possible to effectively suppress the stain of the toner on the fixing member caused by the adhesion of the filler to the fixing member.
Since the organic zirconium compound of the present invention has excellent triboelectricity and a high charge amount can be obtained, it is a suitable charge control agent even when used in a high temperature and high humidity environment requiring a high charge amount. Further, in addition to the good dispersibility of the organic zirconium compound itself, if a binder resin having an acid value is used, it works to improve the dispersibility, so that durability and charge uniformity can be obtained.
Further, the organic zirconium compound of the present invention has a small decrease in the developability of the toner due to being left unattended, and the decrease in image density is small even when the toner is reused after being used in each environment and then resting for a long period of time. can do.

The organic zirconium compound of the present invention is an organic zirconium compound in which an aromatic hydroxycarboxylic acid is coordinated and / or 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 chelate forming numbers and coordination numbers. Further, the zirconium salt includes a metal salt having 1 to 4 aromatic hydroxycarboxylic acid anions, and may be a mixture of those having different numbers of aromatic hydroxycarboxylic acid ions.
Further, those selected from compounds having a structure represented by the following general formulas (II), (III), (IV), (V) and the like can be mentioned.

In the general formula (II), R is hydrogen, alkyl group, aryl group, alalkyl group, cycloalkyl group, alkenyl group, alkoxy group, aryloxy group, hydroxyl group, acyloxy group, alkoxycarbonyl group, aryloxycarbonyl group, acyl. Represents a group, carboxyl group, halogen, nitro group, amino group or carbamoyl group. Substituents R may be linked to each other to form an aliphatic ring, an aromatic ring or a heterocycle, in which case the rings may have 1 to 8 substituents R and are the same. Or it may be 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 acids that serve as ligands in each complex or complex salt may be the same or different, or may be a mixture of complex compounds having different numbers of n or / and m. Further, it may be a mixture of complex salts having different counter ion C1s. The substituent R is preferably an alkyl group, an alkenyl group, a carboxyl group or a hydroxyl group from the viewpoint of improving the dispersibility of the complex or complex salt in the binder resin or improving the chargeability. Further, as C1, hydrogen, sodium, potassium, ammonium or alkylammonium are preferable.

In the general formula (III), R is hydrogen, alkyl group, aryl group, alalkyl group, cycloalkyl group, alkenyl group, alkoxy group, aryloxy group, hydroxyl group, acyloxy group, alkoxycarbonyl group, aryloxycarbonyl group, acyl. Represents a group, carboxyl group, halogen, nitro group, amino group or carbamoyl group. Substituents R may be linked to each other to form an aliphatic ring, an aromatic ring or a heterocycle, and in this case, the ring may have 1 to 8 substituents R, which are the same. Or it may be different. A represents an anion, a halogen, a hydroxide ion, a carboxylic acid ion, a carbonate ion, a nitrate ion, a sulfate ion, a cyan ion or a thiocyan ion, and A may have ions different from each other. 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, and m represents 0,1,2,3 or 4. Represent. The aromatic hydroxycarboxylic acids that serve as ligands in each complex or each complex salt may be the same or different, or may be a mixture of complex compounds having different numbers of n or / and m. .. It may be a mixture of two or more complex compounds having different cations C1 and / and anion A. When A is a divalent anion, the coefficient k of the counter ion is doubled.

The substituent R is preferably an alkyl group, an alkenyl group, a carboxyl group, or a hydroxyl group from the viewpoint of improving the dispersibility of the complex or complex salt in the binder resin or improving the chargeability. Hydrogen, sodium, potassium, ammonium, or alkylammonium is preferable as C1, and hydroxide ion or carboxylic acid ion is preferable as A.
The zirconium complex or complex salt used in the present invention is a six-coordinated or eight-coordinated complex compound, and some of the eight-coordinated compounds are dinuclear complex compounds with bridging ligands. There is a complex compound. In addition, there are also dinuclear complex compounds in which ligands such as hydroxyl groups are bridged and complex compounds are polymerized one after another.
Typical structures of such complex compounds are illustrated by the following general chemical formulas (a) to (x). The following structures also 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. The general formulas (v) to (x) are shown by omitting the counter cation.

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。

Further, it may be a complex compound having a structure in which the hydroxyl group or the carboxyl group of the aromatic ring is coordinated to different zirconium, and is represented by the formula (y) as a partial structure, for example.

具体的な構造は式（ｚ）で表される。

The 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 the anionic ligand, the neutral ligand, and the countercation are omitted in the formula (z).

In the general formulas (IV) and (V), R is a hydrogen, alkyl group, aryl group, alalkyl group, cycloalkyl group, alkenyl group, alkoxy group, aryloxy group, hydroxyl group, alkoxycarbonyl group, aryloxycarbonyl group, Represents an acyloxy group, an acyl group, a carboxyl group, a halogen, a nitro group, an amino group, an amide group or a carbamoyl group. Substituents R may be linked to each other to form an aliphatic ring, an aromatic ring or a heterocycle, and in this case, the ring may have 1 to 8 substituents R, which are the same. Or it may be different. A1 represents a monovalent anion, a halogen ion, a hydroxide ion, a nitrate ion or a carboxylate ion, A2 represents a divalent anion, a sulfate ion, a hydrogen phosphate ion or a carbonate ion, and l is an integer of 1 to 7. Represents, and n represents 1, 2, 3 or 4. The aromatic hydroxycarboxylic acids that become anions A1, anions A2, and acid ions in each metal salt may be the same or different. Further, it may be a mixture of salts having different numbers of n. 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, an alkenyl group, a carboxyl group, a hydroxyl group or an acyloxy group, and has excellent environmental stability and binding. Excellent dispersibility in the resin and excellent durability can be obtained.

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

The reaction product is obtained by filtering and then washing with water, alcohol, or an aqueous alcohol solution. These organic zirconium compounds may be recrystallized from an aqueous alcohol solution or the like and purified by alcohol washing or water washing. Further, in the case of a complex salt, a complex salt having various counter ions can be obtained by treating the product with a mineral acid, an alkaline agent, or an amine agent. In the present invention, the counter ions of the zirconium complex salt include those having a plurality of types such as hydrogen ion, alkali metal ion, and ammonium ion.
In the present invention, as a means for adjusting the content of the aromatic hydroxycarboxylic acid unit contained in the organic zirconium compound, a method of controlling by the mixing ratio of the zirconium compound and the aromatic hydroxycarboxylic acid and the reaction time can be mentioned. Further, a method of controlling the dropping time and the reaction temperature when dropping aromatic hydroxycarboxylic acids into the zirconium compound solution can also be used.

[Other charge control materials]
If necessary, the toner of the present invention may further contain a charge control agent other than the above-mentioned organometallic compound. Examples of the charge control agent include the following as negative charge control agents. Metallic salicylate compound, metal naphthoate compound, metal dicarboxylic acid compound. Polymer compounds with sulfonic acid or carboxylic acid in the side chain, polymer compounds with sulfonate or sulfonic acid esterified in the side chain, polymer compounds with carboxylate or carboxylic acid esterified 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 may contain wax if necessary. Examples of this wax include the following. Hydrocarbon waxes such as low molecular weight polyethylene, low molecular weight polypropylene, alkylene copolymers, microcrystallin wax, paraffin wax, Fishertropch wax; oxides of hydrocarbon waxes such as polyethylene oxide wax or block copolymers thereof; Waxes containing fatty acid esters such as carnauba wax as the main component; deoxidized waxes obtained by deoxidizing some or all of fatty acid esters such as carnauba wax. In addition, the following can be mentioned. Saturated linear fatty acids such as palmitic acid, stearic acid, and montanic acid; unsaturated fatty acids such as brushzic acid, eleostearic acid, and parinalic acid; stearyl alcohol, aralkyl alcohol, behenyl alcohol, carnaubil alcohol, ceryl alcohol, meli Saturated alcohols such as syl alcohol; polyhydric alcohols such as sorbitol; fatty acids such as palmitic acid, stearic acid, behenic acid and montanic acid, and stearyl alcohol, aralkyl alcohol, behenyl alcohol, carnaubil alcohol, ceryl alcohol and meli Esters with alcohols such as silalic acid; fatty acid amides such as linoleic acid amide, oleic acid amide, lauric acid amide; methylene bisstearic acid amide, ethylene biscapric acid amide, ethylene bislauric acid amide, hexamethylene bisstearic acid Saturated fatty acid bisamides such as acid amides; unsaturated fatty acid amides such as ethylene bisoleic acid amides, hexamethylene bisoleic acid amides, N, N'diorail adipic acid amides, N, N'diorail sebasic acid amides; m -Aromatic bisamides such as xylene bisstearate amide, N, N'distearyl isophthalic acid amide; aliphatic metal salts such as calcium stearate, calcium laurate, zinc stearate, magnesium stearate (generally with metal soap) (It is said); Waxes obtained by grafting an aliphatic hydrocarbon wax with a vinyl monomer such as styrene or acrylic acid; a partial esterified product of a fatty acid such as behenic acid monoglyceride and a polyhydric alcohol; A methyl ester compound having a hydroxyl group obtained by hydrogenation of.

Among these waxes, hydrocarbon waxes such as paraffin wax and Fishertroph wax, and 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 content of the wax 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 binder resin. When the content of the wax is in this range, it tends to be possible to efficiently exhibit the hot offset property at a high temperature.
From the viewpoint of achieving both toner storage stability and hot offset resistance, 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 calorimetry device (DSC). The peak temperature of is preferably 50 ° C. or higher and 110 ° C. or lower.

[Polymer having a structure in which a vinyl resin component reacts with a hydrocarbon compound]
Further, in the toner of the present invention, when a hydrocarbon-based wax is contained as the wax, it is preferable to contain a polymer having a structure in which a vinyl-based resin component and a hydrocarbon compound are reacted in order to disperse the wax in the resin. .. Above all, 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, the compatibility between the wax and the resin is promoted, and adverse effects such as poor charging due to poor wax dispersion and contamination of members are less likely to occur.
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 dispersed state of the wax in the amorphous resin tends to be uniform.

Regarding the graft polymer having a structure in which polyolefin is grafted on a vinyl resin, the polyolefin is not particularly limited as long as it is an unsaturated hydrocarbon polymer or copolymer having one double bond, and various polyolefins may be used. Can be done. In particular, polyethylene-based and polypropylene-based 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 Styrene-based units such as styrene and its derivatives.
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, metaacrylonitrile 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 shaving Unsaturated dibasic acid half esters such as acid methyl half ester, fumaric acid methyl half ester, mesaconic acid methyl half ester; unsaturated dibasic acid esters such as dimethyl maleic acid and dimethyl fumaric acid; acrylic acid, methacrylate, croton Α, β-unsaturated acids such as acids and silicic acids; crotonic acid anhydrides, α, β-unsaturated acid anhydrides such as silicic acid anhydrides, and anhydrides of the α, β-unsaturated acids and lower fatty acids. A vinyl-based unit containing carboxyl groups such as alkenyl malonic acid, alkenyl glutaric acid, alkenyl adipic acid, their acid anhydrides, and their monoesters.

Acrylic acids or methacrylic acid esters such as 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate and 2-hydroxypropyl methacrylate, 4- (1-hydroxy-1-methylbutyl) styrene, 4- (1-hydroxy-1-methyl) Hexyl) A vinyl-based unit containing hydroxyl groups such as styrene.
Methyl acrylate, ethyl acrylate, -n-butyl acrylate, isobutyl acrylate, propyl acrylate, -n-octyl acrylate, dodecyl acrylate, -2-ethylhexyl acrylate, stearyl acrylate, -2- acrylate An ester unit composed of acrylic acid esters such as acrylic acid esters such as chlorethyl and phenyl acrylic acid.

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

[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; a color toned black using a yellow colorant, a magenta colorant, and a cyan colorant. A pigment may be used alone as the colorant, but it is more preferable to use a dye and a pigment in combination to improve the sharpness from the viewpoint of the image quality of a full-color image.
Examples of the magenta coloring 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; C.I. I. Disperse thread 9; C.I. I. Solvent Violet 8, 13, 14, 21, 27; C.I. I. Oil-soluble dyes such as Disper Violet 1, C.I. I. 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.

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

Examples of the yellow coloring pigment include the following. 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; C.I. I. Bat Yellow 1, 3, 20.
Examples of the yellow coloring dye include C.I. I. There is Solvent Yellow 162.
The amount of the colorant used is preferably 0.1 part by mass or more and 30 parts by mass or less 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 oxide such as magnetite, maghematite, and ferrite is 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.

[Liquidity improver]
As the toner of the present invention, a fluidity improver such as an inorganic fine powder can be used. Examples of the fluidity improver include the following. Fluorine resin powder such as vinylidene fluoride fine powder and polytetrafluoroethylene fine powder; fine powder silica such as wet manufacturing silica and dry silica; these silicas are silane coupling agents, titanium coupling agents, silicone oil, etc. Surface-treated silica. A preferable fluidity improver is a fine powder produced by vapor phase oxidation of a silicon halogen compound, and is dry silica or fumed silica.

Among them, treated silica fine powder obtained by hydrophobizing 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 hydrophobization of 30 or more and 98 or less as titrated by the methanol titration test.
Examples of the method for hydrophobizing the silica fine powder include a method of chemically treating the silica fine powder 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 of treating silica fine powder produced by vapor phase oxidation of a silicon halogen compound with an organosilicon compound. Examples of the organosilicon compound include the following. Hexamethyldisilazane, trimethylsilane, trimethylchlorsilane, trimethylethoxysilane, dimethyldichlorsilane, methyltrichlorosilane, allyldimethylchlorsilane, allylphenyldichlorosilane, benzyldimethylchlorosilane, brommethyldimethylchlorsilane, α- Chlorethyl trichlorosilane, β-chloroethyl trichlorosilane, chlormethyldimethylchlorsilane, triorganosilyl mercaptan, trimethylsilyl mercaptan, triorganosilyl acrylate, vinyldimethylacetoxysilane, dimethylethoxysilane, dimethyldimethoxysilane, diphenyldiethoxysilane, 1 -Hexamethyldisiloxane, 1,3-divinyltetramethyldisiloxane, 1,3-diphenyltetramethyldisiloxane, and dimethylpolysiloxane. These are used in one or a mixture of two or more.

The silica fine powder may be treated with silicone oil, or may be treated with a silicone oil and the above-mentioned organosilicon compound in combination. The silicone oil preferably has a viscosity at 25 ° C. of 30 mm ² / s or more and 1000 mm ² / s or less. For example, dimethyl silicone oil, methyl phenyl silicone oil, α-methylstyrene modified silicone oil, chlorphenyl silicone oil, and fluorine modified silicone oil can be mentioned.

Examples of the method for hydrophobizing silica fine powder with silicone oil include the following methods. A method of directly mixing silica fine powder treated with a silane coupling agent and silicone oil using a mixer such as a Henshell mixer; a method of spraying silicone oil on the base silica fine powder. Alternatively, a method in which silicone oil is dissolved or dispersed in an appropriate solvent, and then silica fine powder is added and mixed to remove the solvent. The silicone oil-treated silica is more preferably one in which the silica is heated in an inert gas at a temperature of 200 ° C. or higher (more preferably 250 ° C. or higher) after the treatment with the silicone oil to stabilize the surface coating.
The inorganic fine powder is preferably 0.1 parts by mass or more and 8.0 parts by mass or less, and more preferably 0.1 parts by mass or more and 4.0 parts by mass or less with respect to 100.0 parts by mass of the toner particles.

[Other external additives]
In the present invention, other external additives may be added in order to improve the 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. A known mixer such as a Henschel mixer can be used for mixing the toner particles and the external additive, but the mixing is not particularly limited as long as the toner particles can be mixed.

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

[Production method]
The method for producing the toner 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, and a dissolution-suspension method, but a melt-kneading method is preferable from the viewpoint of dispersibility of raw materials.
The melt-kneading method is characterized in that a toner composition which 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, an organometallic compound, and if necessary, wax, a colorant, and other other components are weighed and mixed in a predetermined amount as materials constituting the toner particles. .. Examples of the mixing device include a double-con mixer, a V-type mixer, a drum-type mixer, a super mixer, a Henschel mixer, a Nauta mixer, and a mechano hybrid (manufactured by Nippon Coke Industries Co., Ltd.).

Next, the mixed materials are melt-kneaded to disperse other raw materials and the like in the binder resin. In the melt-kneading process, batch-type kneaders such as pressure kneaders and Bambary mixers and continuous-type kneaders can be used, and single-screw or twin-screw extruders have become mainstream due to the advantage of continuous production. There is. For example, KTK type twin-screw extruder (manufactured by Kobe Steel, Ltd.), TEM type twin-screw extruder (manufactured by Toshiba Machine Co., Ltd.), PCM kneader (manufactured by Ikekai Co., Ltd.), twin-screw extruder (Ktk). -C.K.), Co-kneader (Bus), Kneedex (Nippon Coke Industries Co., Ltd.), etc. Further, 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.

The cooled product of the resin composition is then pulverized to a desired particle size in the pulverization step. In the crushing process, after coarse crushing with a crusher such as a crusher, a hammer mill, or a feather mill, for example, a cryptron system (manufactured by Kawasaki Heavy Industries, Ltd.), a super rotor (manufactured by Nisshin Engineering Co., Ltd.), a turbo Finely pulverize with a mill (manufactured by Freund Turbo Co., Ltd.) or an air jet crusher.
After that, if necessary, inertial classification type elbow jet (manufactured by Nittetsu Mining Co., Ltd.), centrifugal force classification method turboplex (manufactured by Hosokawa Micron Co., Ltd.), TSP separator (manufactured by Hosokawa Micron Co., Ltd.), faculty (manufactured by Hosokawa Micron Co., Ltd.) Classify using a classifier or sieve such as (manufactured by Co., Ltd.) to obtain toner particles.

The emulsification and agglutination method will be described as another production method.
The emulsification agglutination method is a production method for producing core particles by preparing resin fine particles sufficiently small with respect to a target particle size in advance and agglutinating the resin fine particles in an aqueous medium. In the emulsification / aggregation method, toner particles are produced through an emulsification step, an aggregation step, a fusion step, a cooling step, and a cleaning step of resin fine particles. Further, if necessary, a shelling step may be added after the cooling step to obtain a core-shell toner.

<Emulsification process of resin fine particles>
Resin fine particles containing a polyester resin as a main component can be prepared by a known method. For example, the resin is dissolved in an organic solvent, added to an aqueous medium, particles are dispersed in the aqueous medium together with a surfactant and a polymer electrolyte by a disperser such as a homogenizer, and then heated or depressurized to remove the solvent. A resin particle dispersion can be prepared. As the organic solvent used for dissolution, any 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, etc. are added to an aqueous medium, and emulsified and dispersed in an aqueous medium that does not substantially contain an organic solvent by a disperser such as a clear mix, a homomixer, or a homogenizer that applies a high-speed shearing force. 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 less. If it is outside the above range, a new step of removing and recovering the organic solvent is required when manufacturing the toner, which imposes a burden on wastewater treatment measures. The organic solvent content in the aqueous medium can be measured by using gas chromatography (GC).

The surfactant used at the time of emulsification is not particularly limited, and examples thereof include the following. Anionic surfactants such as sulfate ester salt type, sulfonate type, carboxylate type, phosphoric acid ester type, and soap type; 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 surfactant may be used alone or in combination of two or more.

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

<Aggregation process>
In the agglomeration step, the above-mentioned resin fine particles, coloring material fine particles, and mold release agent fine particles are mixed as required to prepare a mixed solution, and then the particles contained in the prepared mixed solution are agglomerated to form an agglomerate. It is a process of forming. As a method for forming the agglomerates, for example, a method in which a flocculant is added / mixed in the mixed solution and temperature, mechanical power, etc. 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; and metal salts of trivalent metals such as iron and aluminum.

The addition / mixing of the flocculant is preferably performed at a temperature equal to or lower than the glass transition temperature (Tg) of the resin particles contained in the mixed solution. When the above mixing is carried out under this temperature condition, aggregation proceeds in a stable state. The above mixing can be performed using a known mixing device, homogenizer, mixer or the like.
The weight average particle size of the aggregates 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 about the same as the weight average particle size of the toner particles to be obtained. It is good to do. The control can be easily performed, for example, by appropriately setting / changing the temperature at the time of adding / mixing the coagulant or the like and the conditions of the stirring / 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 Co., Ltd.) by the Coulter method.

<Fusion process>
The fusion step is a step of producing particles having a smoothed surface of the agglomerates by heating and fusing the agglomerates above the glass transition point (Tg) of the resin. Before entering the primary fusion step, a chelating agent, a pH adjuster, a surfactant and the like can be appropriately added in order to prevent fusion between the 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, nitrotriacetate (NTA) salt, both COOH and OH. There are many water-soluble polymers (polymer electrolytes) containing the functionality of.

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 heating temperature and cannot be unconditionally defined, 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 cooling is not performed to a temperature lower than Tg, coarse particles will be generated. The specific cooling rate is 0.1 ° C./min or more and 50 ° C./min or less.

<Shell process>
Further, 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 and adhering resin fine particles to the particles produced in the previous steps 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 the binder resin fine particles having a different structure.

The resin constituting such a shell layer is not particularly limited, and is known as a resin used for toner, for example, a vinyl polymer such as a polyester resin or a styrene-acrylic copolymer, an epoxy resin, a polycarbonate resin, or a polyurethane resin. Etc. can be used. Of these, polyester resin or styrene-acrylic copolymer is preferable, and polyester resin is more preferable from the viewpoint of fixability and durability. When a polyester resin has a rigid aromatic ring in the main chain, it is more flexible than a vinyl-based polymer such as a styrene-acrylic copolymer, and therefore has a lower molecular weight than a vinyl-based polymer. Can also impart the same 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 may be used 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 and filtered with ion-exchanged water a plurality of times. After that, it is dried to obtain emulsified aggregated toner particles.
If necessary, an additive such as inorganic fine powder or resin particles is added to the surface of the toner particles obtained by a melt-kneading method or the like to mix and disperse the toner particles, and the dispersed state is treated by surface treatment with hot air. It is preferable to carry out a heat treatment step of fixing the toner particles to the surface of the toner particles.

For example, toner can be obtained by performing surface treatment with hot air using the surface treatment apparatus shown in FIG. 1 and classifying 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 the conical protruding member 4 provided in the central portion of the raw material supply means, and is guided to the supply pipe 5 in eight directions that spread radially to perform the heat treatment. Guided to.
At this time, the flow of the mixture supplied to the treatment chamber is regulated by the regulating means 9 provided in the treatment chamber for regulating the flow of the mixture. Therefore, the mixture supplied to the treatment chamber is heat-treated while swirling in the treatment 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 by spirally swirling the hot air into the processing chamber by the swirling member 13 for swirling the hot air. Will be done. As its configuration, the swirling member 13 for swirling the hot air has a plurality of blades, and the swirling of the hot air can be controlled by the number and angles thereof. The temperature of the hot air supplied to the treatment chamber at the outlet of the hot air supply means 7 is preferably 100 ° C. or higher and 300 ° C. or lower, and more preferably 130 ° C. or higher and 170 ° C. or lower. 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 the fusion 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 heat-treated toner particles 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. When 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 the uniform spheroidizing treatment of the mixture. be able to. The absolute water 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. A blower (not shown) is provided at the tip of the collecting means, and the suction is conveyed by the blower.

Further, 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 in the same direction, and the recovery means 10 of the surface treatment device is a swirling powder particle. It is provided on the outer peripheral portion of the processing chamber so as to maintain the turning direction. Further, the cold air supplied from the cold air supply means 8 is configured to be supplied horizontally and tangentially from the outer peripheral portion of the apparatus to the peripheral surface of the processing chamber. The swirling direction of the toner particles before heat treatment supplied from the powder supply port, the swirling direction of the cold air supplied from the cold air supply means, and the swirling direction of the hot air supplied from the hot air supply means are all in 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 that the number of coalesced particles is small. , Heat-treated toner particles having a uniform shape can be obtained.
After that, if necessary, an external additive such as selected inorganic fine powder or resin particles may be added to externally add other inorganic fine particles to be mixed to improve fluidity and charge stability. Examples of the mixing device include a double-con mixer, a V-type mixer, a drum-type mixer, a super mixer, a Henschel mixer, a Nauta mixer, and a mechano hybrid (manufactured by Nippon Coke Industries Co., Ltd.).
Next, a method for measuring each physical property according 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 thin tube rheometer "Flow Tester CFT-500D" (manufactured by Shimadzu Corporation) and following the manual attached to the device. In this device, while applying a constant load from the top of the measurement sample with a piston, the temperature of the measurement sample filled in the cylinder is raised and melted, and the melted measurement sample is pushed out from the die at the bottom of the cylinder, and the amount of piston drop at this time. A flow curve showing the relationship between and temperature can be obtained.

In the present invention, the softening point is the "melting temperature in the 1/2 method" described in the manual attached to the "flow characteristic evaluation device flow tester CFT-500D". The melting temperature in the 1/2 method is calculated as follows. First, 1/2 of the difference between the piston descent amount Smax at the time when the outflow ends and the piston descent amount Smin at the time when the outflow starts is obtained (this is defined as X. X = (Smax-Smin) / 2). Then, the temperature of the flow curve when the amount of descent of the piston becomes X in the flow curve is the melting temperature in the 1/2 method.

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

Test mode: Hot compress start temperature: 50 ° C
Achieved temperature: 200 ° C
Measurement interval: 1.0 ° C
Temperature rise 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: 1.0 mm

<Measurement of glass transition temperature (Tg) of polyester resin A>
The glass transition temperature of the resin is measured according to ASTM D3418-82 using a differential scanning calorimeter "Q1000" (manufactured by TA Instruments).
The melting points of indium and zinc are used for temperature correction of the device detector, and the heat of fusion of indium is used for the correction of calorific value.
Specifically, about 5 mg of resin is precisely weighed, placed in an aluminum pan, and an empty aluminum pan is used as a reference, and the temperature rise rate is 10 ° C./min in the measurement range of 30 to 200 ° C. Measure with. The temperature is once raised to 180 ° C. and held for 10 minutes, then lowered to 30 ° C., and then the temperature is raised again. In this second heating process, a change in specific heat is obtained in the temperature range of 30 to 100 ° C. The intersection of the line at the midpoint of the baseline before and after the specific heat change at this time and the differential thermal 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 component 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) as a solvent is flowed through the column at this temperature at a flow rate of 1 mL per minute, and about 100 μL of a THF sample solution is injected for measurement. In measuring the molecular weight of a sample, the molecular weight distribution of the sample is calculated from the relationship between the logarithmic value and the count value of the calibration curve prepared from several types of monodisperse polystyrene standard samples. As the standard polystyrene samples for preparing a calibration curve for example, used as manufactured by Tosoh Corporation or Showa Denko molecular weight of Co. Ltd. of about 10 ² to 10 ^7, the use of at least about 10 standard polystyrene samples Appropriate. In addition, an RI (refractive index) detector is used as the detector. As the column, a combination of a plurality of commercially available polystyrene gel columns is preferable, and examples thereof include the following combinations. A combination of shodex GPC KF-801, 802, 803, 804, 805, 806, 807, 800P manufactured by Showa Denko Corporation, and TSKgel G1000H (H _XL ), G2000H (H _XL ), G3000H manufactured by Tosoh Corporation. A combination of (H _XL ), G4000H (H _XL ), G5000H (H _XL ), G6000H (H _XL ), G7000H (H _XL ), TSKgrd volume.

The sample is prepared as follows.
Put 50 mg of the sample in 10 mL of THF, let stand at 25 ° C. for several hours, shake well, mix well with THF (until the sample is no longer integrated), and let stand for another 12 hours or more. The total standing time in THF is set to 24 hours. After that, a sample that has passed through a sample processing filter (a pore size of 0.2 μm or more and 0.5 μm or less, for example, Myshori Disc H-25-2 (manufactured by Tosoh Corporation) can be used) is used as a GPC sample.

<Measurement of melting points of polyester resin B and wax>
The melting point of the crystalline polyester resin B and wax is defined by the peak temperature of the maximum endothermic peak as the melting point in the DSC curve measured according to ASTM D3418-82 using a differential scanning calorimetry device "Q2000" (manufactured by TA Instruments). To do.
The melting points of indium and zinc are used for temperature correction of the device detector, and the heat of fusion of indium is used for the correction of calorific value. 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, and the temperature rise rate is 10 in the measurement temperature range of 30 to 200 ° C. Measure at ° C / min. In the measurement, the temperature is raised to 200 ° C., then lowered to 30 ° C., and then 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 raising the temperature to 200 ° C, and the temperature is lowered to 30 ° C as soon as it reaches 200 ° C.

<Measurement of acid value of polyester resin A>
The acid value is the number of mg of potassium hydroxide required to neutralize the acid contained in 1 g of the sample. The acid value in the present invention is measured according to JIS K 0070-1992, but 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 by using a potentiometric titration device (potentiometric titration measuring device 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, those prepared according to JIS K 8001-1998 are used.
The measurement conditions for acid value measurement are shown below.

Titration device: Potentiometric titration device AT-510 (manufactured by Kyoto Electronics Industry Co., Ltd.)
Electrode: Composite glass electrode double junction type (manufactured by Kyoto Electronics Industry Co., Ltd.)
Control software for titrator: 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 quantification: 20 mL
Waiting time before titration: 30 seconds Titration direction: Automatic control Paramailer End point judgment potential: 30dE
End point judgment derivative 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 test;
Weigh 0.100 g of the measurement sample into a 250 mL tall beaker, add 150 mL of a mixed solution of toluene / ethanol (3: 1), and dissolve over 1 hour. Titration is performed using 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 = [(CB) x f x 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, but specifically, it is measured according to the following procedure.
Put 25.0 g of special grade acetic anhydride in a volumetric flask 100 mL, add pyridine to make the total volume 100 mL, and shake well to obtain an acetylation reagent. The obtained acetylation reagent is stored in a brown bottle so as not to come into contact with moisture, carbon dioxide, etc.

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 by using a potentiometric titration device (potentiometric titration measuring device 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 measuring the hydroxyl value are shown below.

Titration device: Potentiometric titration device AT-510 (manufactured by Kyoto Electronics Industry Co., Ltd.)
Electrode: Composite glass electrode double junction type (manufactured by Kyoto Electronics Industry Co., Ltd.)
Control software for titrator: 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 quantification: 80 mL
Waiting time before titration: 30 seconds Titration direction: Automatic control Paramailer End point judgment potential: 30dE
End point judgment derivative 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 test;
2.00 g of the ground measurement sample is precisely weighed into a 200 mL round bottom flask, and 5.00 mL of the above acetylation reagent is accurately added to this using a whole pipette. At this time, if the sample is difficult to dissolve in the acetylation reagent, a small amount of special grade toluene is added to dissolve the sample.
A small funnel is placed on the mouth of the flask, and the bottom 1 cm of the flask is immersed in a glycerin bath at 97 ° C. and heated. 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 thick paper having a round hole.

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

Blank test;
Titration is performed in the same manner as described above except that the sample is not used.
Substituting the obtained result into the following formula, the hydroxyl value is calculated.
A = [{(BC) x 28.05 x f} / S] + D
Here, A: hydroxyl 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), D: Acid value of resin (mgKOH / g).

<Measurement of weight average particle size (D4) of toner>
The weight average particle size (D4) of the toner is determined by the precision particle size distribution measuring device "Coulter Counter Multisizer 3" (registered trademark, manufactured by Beckman Coulter Co., Ltd.) equipped with an aperture tube of 100 μm by the pore electric resistance method. Using the attached dedicated software "Beckman Coulter Multisizer 3 Version 3.51" (manufactured by Beckman Coulter Co., Ltd.) for setting measurement conditions and analyzing measurement data, measurement is performed with 25,000 effective measurement channels. , The measurement data is analyzed and calculated. As the electrolytic aqueous solution used for the measurement, special grade sodium chloride is dissolved in deionized water so that the concentration becomes about 1% by mass, for example, "ISOTON II" (manufactured by Beckman Coulter, Inc.) can be used. ..

Before performing measurement and analysis, set the dedicated software as follows.
In the dedicated software "Change standard measurement method (SOM) screen", set the total count number 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 Coulter. Set the value obtained using Coulter Co., Ltd. By pressing the threshold / noise level measurement button, the threshold and noise level are automatically set. Also, set the current to 1600 μA, the gain to 2, and the electrolyte to ISOTON II, and check the flash of the aperture tube after measurement. On the "pulse to particle size conversion setting screen" of the dedicated software, the bin spacing is set to logarithmic particle size, the particle size bin is set to 256 particle size bins, and the particle size range is set from 2 μm to 60 μm.

The specific measurement method is as follows (1) to (7).
(1) Approximately 200 mL of the electrolytic aqueous solution is placed in a 250 mL round bottom beaker made of glass dedicated to the Multisizer 3 and set on a sample stand, and the stirrer rod is stirred counterclockwise at 24 rpm. Then, the "aperture flash" function of the analysis software removes dirt and air bubbles in the aperture tube.
(2) About 30 mL of the electrolytic aqueous solution is placed in a 100 mL flat-bottomed beaker made of glass, and about 0.3 mL of the following diluent is added as a dispersant.
・ Removed "Contaminone N" (10% by mass aqueous solution of neutral detergent for cleaning pH 7 precision measuring instruments consisting of nonionic surfactant, anionic surfactant, and organic builder, manufactured by Wako Pure Chemical Industries, Ltd.) A diluted solution diluted 3 times by mass with ionized water.

(3) In the water tank of the ultrasonic disperser "Ultrasonic Dispersion System Tetora150" (manufactured by Nikkaki Bios Co., Ltd.), which has two oscillators with an oscillation frequency of 50 kHz and are built in with the phase shifted by 180 degrees. A predetermined amount of deionized water is put into the water tank, and about 2 mL of the contaminanton N is added to the water tank.
(4) The beaker of (2) is set in the beaker fixing hole of the ultrasonic disperser, and the ultrasonic disperser is operated. Then, the height position of the beaker is adjusted so that the resonance state of the liquid level of the electrolytic aqueous solution in the beaker is maximized.

(5) With the electrolytic aqueous solution in the beaker of (4) being irradiated with ultrasonic waves, about 10 mg of toner is added little by little to the electrolytic aqueous solution and dispersed. Then, the ultrasonic dispersion processing is continued for another 60 seconds. In ultrasonic dispersion, the water temperature in the water tank is appropriately adjusted to be 10 ° C. or higher and 40 ° C. or lower.
(6) Using a pipette, the aqueous electrolyte solution of (5) in which toner is dispersed is dropped into the round-bottom beaker of (1) installed in the sample stand, and the measured concentration is adjusted to about 5%. To do. Then, the measurement is performed until the number of particles to be measured reaches 50,000.
(7) The measurement data is analyzed by the dedicated software attached to the device, and the weight average particle size (D4) is calculated. The "average diameter" of the analysis / volume statistical value (arithmetic mean) screen when the graph / volume% is set by 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 by the flow type particle image analyzer "FPIA-3000" (manufactured by Sysmex Corporation) under the measurement and analysis conditions at the time of calibration work.
The measurement principle of the flow-type particle image analyzer "FPIA-3000" (manufactured by Sysmex Corporation) is to image the flowing particles as a still image and perform image analysis. The sample added to the sample chamber is sent to the flat sheath flow cell by the sample suction syringe. The sample sent into the flat sheath flow is sandwiched between the 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. Moreover, since the flow is flat, the image is taken in a focused state. The particle image is captured by a CCD camera, the captured image is image-processed at an image processing resolution of 512 × 512 pixels (0.37 × 0.37 μm per pixel), the outline of each particle image is extracted, and the particle image is obtained. The projected area S, the peripheral length L, and the like are measured.

Next, the equivalent circle diameter and circularity are obtained using the area S and the peripheral length L. The circle equivalent diameter is the diameter of a circle having the same area as the projected area of the particle image, and the circularity C is the value obtained by dividing the circumference length of the circle obtained from the circle equivalent diameter by the circumference length of the particle projection image. It is defined as and 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 on the outer periphery of the particle image, the smaller the circularity. After calculating the circularity of each particle, the range of circularity 0.200 to 1.000 is divided into 800, the arithmetic mean value of the obtained circularity is calculated, and the value is taken as the average circularity.

The specific measurement method is as follows. First, about 20 mL of ion-exchanged water from which impure solids and the like have been removed in advance is placed in a glass container. Among them, as a dispersant, "Contaminone N" (a 10% by mass aqueous solution of a neutral detergent for cleaning a precision measuring instrument with a pH of 7 consisting of a nonionic surfactant, an anionic surfactant, and an organic builder, Wako Pure Chemical Industries, Ltd. ) Is diluted with ion-exchanged water about 3 times by mass, and about 0.2 mL of the diluted solution is added. Further, about 0.02 g of the measurement sample is added, and the dispersion treatment is performed for 2 minutes using an ultrasonic disperser to prepare a dispersion liquid for measurement. At that time, the dispersion is appropriately cooled so that the temperature of the dispersion is 10 ° C. or higher and 40 ° C. or lower. As the ultrasonic disperser, a desktop ultrasonic cleaner disperser having an oscillation frequency of 50 kHz and an electrical output of 150 W (for example, "VS-150" (manufactured by Vervocreer Co., Ltd.)) is used. Then, a predetermined amount of ion-exchanged water is placed in the water tank, and about 2 mL of the contaminanton N is added into 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 adjusted 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 value at the time of particle analysis to 85% and specifying the analysis particle diameter, the number ratio (%) of particles in that range and the average circularity can be calculated. The average circularity of the toner was set to a circle equivalent diameter of 1.98 μm or more and 39.96 μm or less, and the average circularity of the toner was determined.

In the measurement, automatic focus adjustment is performed using standard latex particles (for example, "RESAARCH AND TEST PARTICLES Latex Microsphere Suspensions 5200A" manufactured by Duke Scientific) diluted with ion-exchanged water before the start of the measurement. After that, it is preferable to perform focus adjustment every 2 hours from the start of measurement.
In the embodiment of the present application, a flow-type particle image analyzer that has been calibrated by Sysmex Corporation and has received a calibration certificate issued by Sysmex Corporation was used. The measurement was performed under the measurement and analysis conditions at the time of receiving the calibration certificate, except that the diameter of the analysis particle was limited to the equivalent circle diameter of 1.98 μm or more and less than 39.69 μm.

<Method of quantifying zirconium atom>
Approximately 100 mg of the organometallic compound is precisely weighed in a beaker and decomposed by heating with an acid such as hydrochloric acid or nitric acid.
The concentration of the zirconium element in the solution obtained by the above pretreatment was calculated by ICP emission spectroscopy.
In the present invention, a sequential ICP emission spectroscopic analyzer SPS1200VR manufactured by Seiko Instruments was used, and then a 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>
Approximately 100 mg of an organic metal compound is precisely weighed in a sample tube and decomposed by heating 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 the mixture is vigorously shaken to dissolve the dissociated aromatic hydroxycarboxylic acid. 1 mL of this solution was filtered through a 0.5 μm filter, a silylating agent (0.5 mL) such as N, O-bistrimethylsilylacetamide was added to the filtrate, and the mixture was vigorously shaken to prepare an analysis sample. After allowing to stand for about 20 minutes, the above sample was subjected to gas chromatographic analysis, and then the aromatic hydroxycarboxylic acid was quantified according to a conventional method.
The number of moles of the zirconium atom is calculated from the quantified content of the zirconium atom and the atomic weight of the zirconium, and the quantified content of the aromatic hydroxycarboxylic acid and the molecular weight of the aromatic hydroxycarboxylic acid are used to determine the aromatic hydroxycarboxylic acid. Calculate the number of moles. Then, the ratio of the number of moles of the zirconium atom to the number of moles of the aromatic hydroxycarboxylic acid is obtained.

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 resin. In the following description, the number of copies is based on parts by mass.
<Production example 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 in a cooling tube, a stirrer, a nitrogen introduction tube, and a reaction vessel equipped with a thermocouple. Next, 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, 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 moles of polyvalent carboxylic acid)
-Tert-Butylcatechol (polymerization inhibitor): 0.1 part by mass After that, the above material was added, the pressure in the reaction vessel was lowered to 8.3 kPa, and the reaction was carried out for 1 hour while maintaining the temperature at 180 ° C. 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). In this way, a low molecular weight polyester resin A (L) -1 was obtained. The softened point (Tm) of the obtained low molecular weight polyester resin A (L) -1 was 94 ° C., and the glass transition temperature (Tg) was 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.
-Changes: The esterification catalyst was changed from tin 2-ethylhexanoate: 0.5 parts by mass to dioctyltin oxide: 0.3 parts by mass.
The softened point (Tm) of the obtained low molecular weight polyester resin A (L) -2 was 95 ° C., and the glass transition temperature (Tg) was 58 ° C.

(Production Example 3 of Low Molecular Weight Polyester Resin A (L))
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) except for the following changes.
-Changes: The alcohol component is changed from polyoxypropylene (2.2) -2,2-bis (4-hydroxyphenyl) propane to 1,4-bis (2-hydroxyethoxy) represented by the following formula (c). Changed to benzene.
The softened point (Tm) of the obtained low molecular weight polyester resin A (L) -3 was 93 ° C., and the glass transition temperature (Tg) was 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 part by mass (0.007 mol) of adipic acid
・ Titanium tetrabutoxide 0.6 parts by mass

The above materials were weighed in a cooling tube, a stirrer, a nitrogen introduction tube, and a reaction vessel equipped with a thermocouple. Next, 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, 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 After that, the above material was added, the pressure in the reaction vessel was lowered to 8.3 kPa, and the reaction was carried out for 4 hours while maintaining the temperature at 180 ° C., 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 softened point (Tm) of the obtained low molecular weight polyester resin A (L) -4 was 94 ° C., and the glass transition temperature (Tg) was 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% with respect to the total number of moles of polyvalent carboxylic acid)
Fumaric acid: 2.9 parts by mass (0.03 mol; 15.0 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 in a cooling tube, a stirrer, a nitrogen introduction tube, and a reaction vessel equipped with a thermocouple. Next, 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 polyvalent carboxylic acid)
-Tert-Butylcatechol (polymerization inhibitor): 0.1 part by mass After that, the above material was added, the pressure in the reaction vessel was lowered to 8.3 kPa, and the reaction was carried out 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). In this way, the high molecular weight polyester resin A (H) -1 was obtained. The softened point (Tm) of the obtained high molecular weight polyester resin A (H) -1 was 132 ° C., and the glass transition temperature (Tg) was 61 ° C.

(Production Example 2 of High Molecular Weight Polyester Resin A (H))
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) except for the following changes.
-Changes: The esterification catalyst was changed from tin 2-ethylhexanoate: 0.5 parts by mass to dioctyltin oxide: 0.3 parts by mass.
The softened point (Tm) of the obtained high molecular weight polyester resin A (H) -2 was 133 ° C., and the glass transition temperature (Tg) was 62 ° C.

(Production Example 3 of High Molecular Weight Polyester Resin A (H))
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) except for the following changes.
-Change: The alcohol component is changed from polyoxypropylene (2.2) -2,2-bis (4-hydroxyphenyl) propane to 1,4-bis (2-hydroxyethoxy) represented by the above formula (c). Changed to benzene.
The softened point (Tm) of the obtained high molecular weight polyester resin A (H) -3 was 131 ° C., and the glass transition temperature (Tg) was 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 part by mass (0.007 mol) of adipic acid
・ Titanium tetrabutoxide 0.6 parts by mass

The above materials were weighed in a cooling tube, a stirrer, a nitrogen introduction tube, and a reaction vessel equipped with a thermocouple. Next, 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, 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 After that, the above material was added, the pressure in the reaction vessel was lowered to 8.3 kPa, and the reaction was carried out for 4 hours while maintaining the temperature at 180 ° C., 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). In this way, a high molecular weight polyester resin A (H) -4 was obtained. The softened point (Tm) of the obtained high molecular weight polyester resin A (H) -4 was 132 ° C., and the glass transition temperature (Tg) was 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 parts by mass

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

<Production Examples 2 to 11 of Polyester Resin B>
The types of the alcohol component and the 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 for the above. 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) and (2).
(1) The corresponding aromatic hydroxycarboxylic acid or sodium salt of aromatic hydroxycarboxylic acid is dissolved in water, an aqueous alcohol solution, or an alcohol and reacted with an aqueous solution of zirconium chloride.
(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 values of the aromatic hydroxycarboxylic acid to Zr molar ratio.

<Production example 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 The ferrite raw materials were weighed so as to have the above composition ratio. Then, it was pulverized and mixed for 5 hours with a dry vibration mill using stainless beads having a diameter of 1/8 inch.

-Step 2 (temporary firing step):
The obtained pulverized product was made into pellets of about 1 mm square by a roller compactor. Coarse powder was removed from the pellets with a vibrating sieve having an opening of 3 mm, and then fine powder was removed with a vibrating sieve having an opening of 0.5 mm, and then using a burner-type firing furnace, the pellets were used in a nitrogen atmosphere (oxygen concentration 0. It was calcined at a temperature of 1000 ° C. for 4 hours at 01% by volume) 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 (crushing step):
After crushing 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 the mixture was crushed with a wet ball mill for 1 hour. The slurry was pulverized with a wet ball mill using alumina beads having a diameter of 1/16 inch for 4 hours to obtain a ferrite slurry (a finely pulverized product of calcined ferrite).

・ Process 4 (granulation process):
To 100 parts by mass of calcined ferrite, 1.0 part by mass of ammonium polycarboxylic acid as a dispersant and 2.0 parts by mass of polyvinyl alcohol as a binder were added to the ferrite slurry, and a spray dryer (manufacturer: Okawara Kakoki) was used. It was granulated into spherical particles. After adjusting the particle size of the obtained particles, the particles were heated at 650 ° C. for 2 hours using a rotary kiln to remove organic components of the dispersant and the binder.

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

・ Process 6 (sorting process):
After crushing the agglomerated particles, the low magnetic force product is cut by magnetic force beneficiation, sieved with a sieve having a mesh size of 250 μm to remove coarse particles, and 50% particle size (D50) 37.0 μm based on the 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 methacryloyl group at one end and having a weight average molecular weight of 5000)
(4) Toluene 30.0% by mass
(5) Methyl ethyl ketone 30.0% by mass
(6) Azobisisobutyronitrile 2.0% by mass

Of the above materials, (1) to (5) are placed in a four-port separable flask equipped with a reflux condenser, a thermometer, a nitrogen introduction pipe and a stirrer, nitrogen gas is introduced, and a system is made with nitrogen gas. Replaced inside. Then, 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 separated by filtration and vacuum dried to obtain a coating resin 1. The obtained coating resin 1 30 parts by mass 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 (Regal330; 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 in 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.

<Manufacturing example of magnetic carrier 1>
(Resin coating process):
The coating resin solution 1 was added to a vacuum degassing type kneader maintained at room temperature so as to be 2.5 parts by mass as a resin component with respect to 100 parts by mass of the packed core particles 1. After the addition, the mixture was stirred at a rotation speed of 30 rpm for 15 minutes, 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, toluene was distilled off over 2 hours, and then the mixture was cooled. The obtained magnetic carrier is separated into low magnetic force products by magnetic force beneficiation, passed through a sieve having an opening of 70 μm, and then classified by a wind power classifier, and the magnetic carrier having a volume distribution standard of 50% particle size (D50) of 38.2 μm. I got 1.

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

[Example 1]
<Manufacturing 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, Fisher Tropsch wax (peak temperature of maximum heat absorption 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

A twin-screw kneader set at a temperature of 125 ° C. after mixing the raw materials shown in the formulation with a Henschel mixer (FM-75 type, manufactured by Mitsui Mine Co., Ltd.) at a rotation speed of 20 s- ¹ and a rotation time of 5 min. Kneaded with (PCM-30 type, manufactured by Ikekai Co., Ltd.). The obtained kneaded product was cooled and coarsely pulverized to 1 mm or less with a hammer mill to obtain a coarsely crushed product. The obtained pyroclastic material was finely pulverized with a mechanical crusher (T-250, manufactured by Freund Turbo Co., Ltd.). Further, classification was performed using a rotary classifier (200 TSP, manufactured by Hosokawa Micron Co., Ltd.) to obtain toner particles. As for the operating conditions of the rotary classifier (200 TSP, manufactured by Hosokawa Micron Co., Ltd.), the classifying rotor was classified at a rotation 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 an average particle size of 115 nm was added, and the rotation speed was 30 s with a Henschel mixer (FM-75 type, manufactured by Mitsui Mine Co., Ltd.). ^-1 , and the mixture was mixed with a rotation time of 5 min. Using the obtained mixture, heat treatment was performed under the following operating conditions by the surface treatment apparatus shown in FIG. 1 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 water content = 3 g / m ³ , Blower air volume = 20m ³ / min, Injection air flow rate = 1m 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 are 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 Machinery Co., Ltd.) at a rotation speed of 30 s- ¹ and a rotation time of 10 min. Toner 1 was obtained by passing through an ultrasonic vibrating sieve having an opening of 54 μm.
-Number of primary particles surface-treated with 15.0% by mass of isobutyltrimethoxysilane 0.5 parts by mass of titanium oxide fine particles having an average particle size of 50 nm-Average number 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 had an endothermic peak derived from polyester resin B at 70 ° C. and an endothermic peak derived from a wax component at 90 ° C. in the DSC curve obtained by differential scanning calorific value analysis. Had.

<Production example of two-component developer 1>
A V-type mixer (V-10 type: Tokuju Seisakusho Co., Ltd.) so that the toner 1 and the magnetic ferrite carrier particles (number average particle size 35 μm) surface-coated with silicone resin have a toner concentration of 8% by mass. The mixture was mixed 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 the full-color copier imagePRESS C800 manufactured by Canon Inc., and was idle-rotated (no toner replenishment) in advance to stress the developer. Later image evaluation was performed. This evaluation was performed for the purpose of promoting a low printing rate, that is, durability in a state where there is almost no toner replacement.
As a specific method, the above-mentioned two-component developer for evaluation is placed in a developing device taken out from imagePRESS C800, and a developing idle rotation jig capable of rotating a developing roller and a stirring member by the developing device alone is used. I went. With this idle rotation jig, the process speed was set to 450 mm / sec, and the idle rotation was performed 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, and the occurrence of white spots was evaluated.

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

Image quality is evaluated using plain paper CS-680 (68.0 g / m ² ) (sold by Canon Marketing Japan Co., Ltd.) in a normal temperature and humidity environment (temperature 23 ° C / relative humidity 50%) using imagePRESS C800. I went using it. With an X-Rite color reflection densitometer (500 series: manufactured by X-Rite), under development conditions where the solid (FFh) density on paper is 1.40, 17 gradations (00h to FFh, each horizontal band 10 mm) in A4 size × 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 generated after 5 hours of idle rotation)
A: Less than 2 pieces B: 2 pieces or more and less than 5 pieces C: 5 pieces or more and less than 10 pieces D: 10 pieces or more and less than 20 pieces E: 20 pieces or more

(2) Fixability evaluation A developer containing the above two-component developer was mounted on the cyan station of the full-color copier imagePRESS C1 + manufactured by Canon Inc., and modified so that images could 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 by Canon Marketing Japan Inc.) was used.
The development conditions were appropriately adjusted so that the amount of toner on the FFh image (hereinafter, solid part) was 1.2 mg / cm ^2, and 3 cm from the tip of the A4 evaluation paper and 2 cm x 10 cm at the center of the evaluation paper. A solid unfixed image was formed. The unfixed image was humidity-controlled for 24 hours in a room temperature and low humidity environment (temperature 25 ° C./relative humidity 5%).

The fixing device was taken out from the full-color copying machine imagePRESS C800 manufactured by Canon Inc., and the fixing test jig modified so that the process speed and the temperature of the upper and lower fixing members could be controlled independently was installed in a low temperature and low humidity environment (temperature 15 ° C / relative humidity). 10%) was prepared. The process speed was adjusted to 450 mm / sec, the lower belt temperature was fixed at 90 ° C., and the upper belt temperature of the fixing test jig was adjusted every 5 ° C. in the range of 100 to 200 ° C. The above-mentioned humidity-controlled unfixed image was passed through. The fixed image passed through the fuser is rubbed 5 times with a lens cleaning wiper (manufactured by Dasper Ozu Corporation) 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 point at which becomes the fixing temperature was defined. Based on the criterion of not being able to fix when the density drops more than 10%, the lowest upper belt set temperature that does not exceed the image density drop rate of 10% was set as the fixing start temperature and evaluated according to the following evaluation criteria. .. 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) For the evaluation of hot offset resistance, plain paper: CS-680 (A4 68.0 g / m ² ) (sold by Canon Marketing Japan Inc.) was used.
The developing conditions were adjusted so that the amount of toner 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, in the same manner as the low temperature fixability evaluation, in a room temperature and low humidity environment (temperature 23 ° C./relative humidity 10%) using a fixing evaluation jig obtained by modifying the fixing device removed from the full-color copying machine imagePRESS C800 manufactured by Canon Inc. Evaluation was performed.

Reflectometer reflectivity for image output before the evaluation sheet was ( "REFLECTOMETER MODEL TC-6DS", (with) manufactured by Tokyo Denshoku) was determined by the average values measured five points _D A (%). The fixing temperature in the external fixing device was adjusted to 5 ° C. intervals in the range of 100 to 200 ° C., and measuring the reflectance at reflectometer for white portion of a fixed image at each fixing temperature, the maximum value D _B and _(%) did.
Then, D A _(%) and no more than 0.5% the difference is D _{B (%),} the highest fixing temperature of the fixing upper limit temperature was evaluated hot offset resistance at 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 the developing agents 9 to 20 and the comparative developing agents 1 to 8, the polyester resins A (L) -1 to 4 represent the low molecular weight polyester resins A (L) fine particle dispersions (1) to (4). The polyester resins A (H) -1 to 4 represent high molecular weight polyester resins A (H) fine particle dispersions (1) to (4). The polyester resins B-7 to 11 represent the polyester resin B fine particle dispersions (7) to (11). The organometallic compounds 1 to 11 represent the organometallic compound fine particle dispersions (1) to (11).

[Examples 2 to 7]
Toners 2 to 7 were prepared in the same manner as in Example 1 except that the polyester resin B-1 was changed to the polyester resins B-2 to B-7 as shown in Table 4, and two-component development was carried out in the same manner. Agents 2 to 7 were prepared.
Further, the evaluation was carried out in the same manner as in Example 1. The evaluation results are shown in Table 5.

[Example 8]
<Manufacturing 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 Part ・ Organic metal compound 1 1.00 part by mass ・ Fisher tropschwax (peak temperature of maximum heat absorption 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

A twin-screw kneader set at a temperature of 125 ° C. after mixing the raw materials shown in the formulation with a Henschel mixer (FM-75 type, manufactured by Mitsui Mine Co., Ltd.) at a rotation speed of 20 s- ¹ and a rotation time of 5 min. Kneaded with (PCM-30 type, manufactured by Ikekai Co., Ltd.). The obtained kneaded product was cooled and coarsely pulverized to 1 mm or less with a hammer mill to obtain a coarsely crushed product. The obtained pyroclastic material was finely pulverized with a mechanical crusher (T-250, manufactured by Freund Turbo Co., Ltd.). Further, classification was performed using a rotary classifier (200 TSP, manufactured by Hosokawa Micron Co., Ltd.) to obtain toner particles. As for the operating conditions of the rotary classifier (200 TSP, manufactured by Hosokawa Micron Co., Ltd.), the classification was performed 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 are 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 Machinery Co., Ltd.) at a rotation speed of 30 s- ¹ and a rotation time of 10 min. Toner 8 was obtained by passing through an ultrasonic vibrating sieve having an opening of 54 μm.
-Number of primary particles 5.0 parts by mass of silica fine particles with an average particle size of 110 nm-Number of primary particles surface-treated with 15.0% by mass of isobutyltrimethoxysilane 1.0 parts by mass of titanium oxide fine particles with an average particle size of 50 nm-Hexa Number of primary particles surface-treated with 20.0% by mass of methyldisilazane 0.8 parts by mass of hydrophobic silica fine particles having an average particle size of 16 nm

<Production example of two-component developer 8>
A V-type mixer (V-10 type: Tokuju Seisakusho Co., Ltd.) so that the toner concentration is 9% by mass with the toner 8 and magnetic ferrite carrier particles (number average particle size 35 μm) surface-coated with silicone resin. The mixture was mixed 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 room temperature with a homogenizer (manufactured by IKA Japan: Ultratarax) at 10,000 rpm for 2 minutes. While stirring, 1000 parts by mass of ion-exchanged water to which 5 parts by mass of potassium hydroxide and 10 parts by mass of sodium dodecylbenzene-sodium sulfonate were added as a surfactant was added dropwise. Tetrahydrofuran was removed by heating this mixed solution to about 75 ° C. Then, it was diluted with ion-exchanged water so that the solid content became 8% to obtain a high molecular weight polyester resin A (H) fine particle dispersion (1) having a volume average particle size of 0.09 μm.

<Production Examples of High Molecular Weight Polyester Resins A (H) Fine Particle Dispersions (2) to (4)>
Similar to the preparation of the high molecular weight polyester resin A (H) fine particle dispersion liquid (1) except that the high molecular weight polyester resin A (H) -1 is changed to the high molecular weight polyester resin A (H) -2 to 4. High molecular weight polyester resin A (H) fine particle dispersions (2) to (4) were obtained.

<Production Examples of Low Molecular Weight Polyester Resins A (L) Fine Particle Dispersions (1) to (4)>
Similar to the preparation of the high molecular weight polyester resin A (H) fine particle dispersion liquid (1) except that the high molecular weight polyester resin A (H) -1 is changed to the low molecular weight polyester resin A (L) -1 to 4. Low molecular weight polyester resin A (L) fine particle dispersions (1) to (4) were obtained.

<Production example of polyester resin B fine particle dispersion liquids (7) to (11)>
Polyester resin B fine particle dispersion in the same manner as the preparation of the high molecular weight polyester resin A (H) fine particle dispersion liquid (1) except that the high molecular weight polyester resin A (H) -1 is changed to polyester resins B-7 to 11. Liquids (7) to (11) were obtained.

<Production example of organometallic compound fine particle dispersion (1)>
-Organic metal compound 1 10.0 parts by mass-Anionic surfactant (manufactured by Daiichi Kogyo Seiyaku Co., Ltd .: Neogen RK) 1.5 parts by mass-Ion-exchanged water 88.5 parts by mass or more are mixed and dissolved. A high-pressure impact disperser nanomizer (manufactured by Yoshida Kikai Kogyo Co., Ltd.) was used to disperse the color material for about 1 hour to prepare an aqueous dispersion of the color material fine particles. 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 Examples of Organometallic Compound Fine Particle Dispersions (2) to (11)>
In the preparation of the organometallic compound fine particle dispersion liquid (1), the organometallic compound fine particle dispersion liquids (2) to (11) are obtained in the same manner except that the organometallic compound 1 is changed to the organometallic compounds 2-11. It was.

<Production example of color material fine particle dispersion>
・ Color material (Cyan pigment Dainichi 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 ・ Ion exchange 88.5 parts by mass or more of water is mixed, dissolved, and dispersed for about 1 hour using a high-pressure impact disperser Nanomizer (manufactured by Yoshida Kikai Kogyo Co., Ltd.) to disperse the coloring material. 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>
-Fishertropsh wax (peak temperature of maximum heat absorption peak 90 ° C) 5.0 parts by mass-Anionic surfactant (manufactured by Dai-ichi 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 container equipped with a stirrer, heat to 90 ° C., and while circulating to Claremix W Motion (manufactured by M Technique Co., Ltd.), shear stirring with a rotor outer diameter of 3 cm and a clearance of 0.3 mm. At the site, the mixture was stirred under the following conditions and dispersed for 60 minutes.
-Rotor rotation speed 19,000r / min, screen rotation speed 19,000r / min
Then, by cooling to 40 ° C. under the cooling treatment conditions of a rotor rotation speed of 1000 r / min, a screen rotation speed of 0 r / min, and a cooling rate of 10 ° C./min, an aqueous dispersion of mold release agent fine particles was obtained. 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]
(Production example 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 (corresponding to resin)
-Organometallic compound fine particle dispersion (1) 1.00 parts by mass (equivalent to organic metal)
-Release agent fine particle dispersion 5.00 parts by mass (equivalent to the release agent)
・ Colorant fine particle dispersion 5.00 parts by mass (equivalent to colorant)
・ 1.5% by mass magnesium sulfate aqueous solution 10 parts by mass

The above was dispersed using a homogenizer (manufactured by IKA: Ultratarax T50). Subsequently, the pH was adjusted to 8.1 with a 0.1 N aqueous sodium hydroxide solution. Then, it was heated to 45 ° C. in a heating water bath while stirring with a stirring blade. After holding at 45 ° C. for 1 hour and observing with an optical microscope, it was confirmed that aggregated particles having an average particle size of about 5.5 μm were formed. After adding 40 parts by mass of a 5 mass% trisodium citrate aqueous solution, the temperature was raised to 85 ° C. and held for 90 minutes while continuing stirring to fuse the core particles. Then, while continuing stirring, water was put into 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 Co., Ltd.) by the Coulter method, the median diameter based on the volume was 5.6 μm.

Then, 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, and the mixture was stirred and washed for 30 minutes. After that, filtration and solid-liquid separation were performed again. Subsequently, 800 parts by mass of ion-exchanged water was added to the solid content, and the mixture was stirred and washed for 30 minutes. After that, filtration and solid-liquid separation were performed again, and this was repeated 5 times. Next, the obtained solid content was dried to obtain toner particles 9.
To 100 parts by mass of the obtained toner particles 9, 1.0 part by mass of silica fine particles having an average number of primary particles of 15.0 nm was added, and the rotation speed was 31.6s ^-1 with a Henschel mixer (FM-75 type). , The mixture was mixed for a rotation time of 5 min, and passed through an ultrasonic vibrating sieve having a mesh size of 54 μm to obtain toner 9.

<Production example of two-component developer 9>
A V-type mixer (V-10 type: Tokuju Seisakusho Co., Ltd.) so that the toner concentration is 9% by mass with the toner 9 and magnetic ferrite carrier particles (number average particle size 35 μm) surface-coated with silicone resin. The mixture was mixed 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.
In addition, Example 9 is described as a reference example.

[Examples 10 to 20 and Comparative Examples 1 to 7]
Toners 10 to 10 are the same 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 are changed as shown in Table 4. 20 and comparative toners 1 to 7 were prepared. Similarly, two-component developing agents 10 to 20 and comparative two-component developing agents 1 to 7 were prepared.
Further, the evaluation was carried out in the same manner as in Example 1. The evaluation results are shown in Table 5.
In addition, Examples 10 to 20 are described as a reference example.

[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 the compound represented by the following formula (VI) (“DTBS-”. A comparative toner 8 was prepared in the same manner as in Example 9 except that the change was made to “Zn”, and a comparative two-component developer 8 was prepared in the same manner.
Further, the evaluation was carried out in the same manner as in Example 1. The evaluation results are shown in Table 5.

1. 1. Raw material quantitative supply means 2. Compressed gas flow rate adjusting means 3. Introduction pipe 4. Protruding member 5. Supply pipe 6. Processing room 7. Hot air supply means 8. Cold air supply means 9. Regulatory means 10. Recovery means 11. Hot air supply means outlet 12. Distributor 13. Swivel member 14. Powder particle supply port

Claims (2)

A step of obtaining a polyester resin A by polycondensing 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.

(R in the formula indicates an alkyl group having 5 to 15 carbon atoms)
A step of melt-kneading a mixture containing the polyester resin A, the polyester resin B and an organometallic compound, and pulverizing the obtained kneaded product to obtain toner particles.
It is a manufacturing method of toner containing
The obtained toner has toner particles containing the polyester resin A, the polyester resin B, and the organometallic compound.
The polyester resin A is an amorphous polyester resin which is a condensed polymer 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 degenerate from an alcohol component containing 80 mol% or more of an aliphatic diol having 6 or more and 12 or less carbon atoms and a carboxylic acid component containing 80 mol% or more of an aliphatic dicarboxylic acid having 6 or more and 12 or less carbon atoms. It is a coalesced crystalline polyester resin,
The organic metal compound is an organic zirconium compound produced by the reaction of zirconium with an aromatic hydroxycarboxylic acid, and the organic zirconium compound has an aromatic hydroxycarboxylic acid unit of 1.2 to 1 mol per zirconium atom. Contains 1.8 mol,
A method for producing toner, which is characterized by the fact that . The method for producing a toner according to claim 1, wherein the content of the polyester resin B is 2 parts by mass or more and 20 parts by mass or less with respect to 100 parts by mass of the polyester resin A.

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