JP2014098841A - Toner - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a toner that has a charge amount and start-up performance of the charge amount hardly affected by a change in a temperature/humidity environment.SOLUTION: A toner comprises toner particles containing a metal-containing polymer, colorant, and a binder resin. The metal-containing polymer includes an aromatic compound bonded to metal and a polymer part. The aromatic compound bonded to metal has a structure bonded to metal at a site derived from -COOMand/or -OH of a salicylic acid structure part or a salicylic acid derivative structure part in a partial structure defined separately by an expression.

Description

  The present invention relates to a toner for developing an electrostatic charge image in an image forming method such as electrophotography or electrostatic printing, or a toner for forming a toner image in a toner jet type image forming method.

In recent years, due to demands for speeding up, stabilization, and miniaturization of printers and copiers, it has been desired to reduce the number of parts as the functions of each part increase. In order to obtain stable image density and color stability in the electrophotographic system, it is necessary to always establish certain development conditions in the development process. However, when the charge amount of the toner is unstable, a large load is applied to the system for controlling the developability, such as optimizing the developing bias condition each time, and the size of the apparatus and the manufacturing cost increase. It is often connected to. In order to reduce such a load, it is required to improve the environmental stability of the charge amount of the toner, in particular, the stability of the charge against changes in temperature and humidity.
Many proposals have been made to improve the environmental stability of the toner charge amount. In particular, control using a charge control agent has become mainstream, and toners containing calixarene compounds, those using iron-containing azo dyes, and those using organic boron compounds have been proposed (for example, Patent Documents 1 and 2). ).
However, the toner as described above is still inadequate in the toner charge amount and the rising performance due to changes in the temperature and humidity environment. As a result, there may be a change in the image density at the time of printing, and there may be a problem such as an image fog due to non-uniformity of the charge amount distribution under high temperature and high humidity. Furthermore, in order to obtain the color stability of the image, in addition, the color mixing property of the toner is important, and the transparency of the toner is necessary particularly in the highlight portion.
The colorant used in the toner is mainly a pigment having high fastness from the viewpoint of fading. Various proposals have been made as a technique for dispersing a pigment in a toner. In many cases, a resin having a polarity is often added. Specifically, a polyester (PES) type charge control agent obtained by polycondensation of a monomer containing a sulfonic acid (salt) has been proposed (for example, patents). References 3 and 4).
Here, when the charge control agent is a polyester resin, the compatibility of the polyester resin with the binder resin (binder) and the dispersibility of the pigment are improved. However, in practice, merely changing the composition of the charge control agent is insufficient to improve the dispersibility of the pigment in the toner, and further improvements are desired.

JP 2002-287429 A JP 2004-219507 A JP 2003-096170 A JP 2003-215853 A

Accordingly, an object of the present invention is to provide a toner in which the charge amount and the rising performance of the charge amount are less affected by changes in the temperature and humidity environment.
Another object of the present invention is to improve pigment dispersibility in toner.

The present invention relates to a toner having toner particles containing a metal-containing polymer, a colorant, and a binder resin, the metal-containing polymer having an aromatic compound part bonded with a metal and a polymer part. The aromatic compound part to which the metal is bonded is a metal at a site derived from -COOM ¹ and / or -OH of the salicylic acid structure part or salicylic acid derivative structure part of the partial structure represented by the following formula (1). The present invention relates to a toner characterized by having a structure combined with the toner.

（前記式（１）中、Ｒ^１は、ヒドロキシル基、カルボキシル基、炭素数１以上１８以下のアルキル基、又は、炭素数１以上１８以下のアルコキシ基を示し、Ｒ^２は、ヒドロキシル基、炭素数１以上１８以下のアルキル基、又は、炭素数１以上１８以下のアルコキシ基を示し、Ｍ^１は水素原子、アルカリ金属、−ＮＨ_４、またはこれらの混合物を示す。ａは０以上３以下の整数を示し、ｂは１以上３以下の整数を示し、ｃは０以上４以下の整数を示す。ａが２又は３である場合には、Ｒ^１はそれぞれ独立に選択される。ｃが２、３又は４である場合には、Ｒ^２はそれぞれ独立して選択される。また、＊部で重合体部と連結している。）

(In the formula (1), R ¹ represents a hydroxyl group, a carboxyl group, an alkyl group having 1 to 18 carbon atoms, or an alkoxy group having 1 to 18 carbon atoms, and R ² represents a hydroxyl group, carbon An alkyl group having 1 to 18 carbon atoms, or an alkoxy group having 1 to 18 carbon atoms, M ¹ represents a hydrogen atom, an alkali metal, —NH ₄ , or a mixture thereof, and a is 0 to 3 B represents an integer of 1 to 3, and c represents an integer of 0 to 4. When a is 2 or 3, R ¹ is independently selected, and c is 2. In the case of 3 or 4, each R ² is independently selected, and is connected to the polymer part at * part.)

  According to the present invention, it is possible to obtain a toner in which the charge amount and the rising performance of the charge amount are less affected by changes in the temperature and humidity environment. Further, according to the present invention, it is possible to improve the pigment dispersibility in the toner.

The figure which shows the structure of the apparatus used for the measurement of the triboelectric charge amount of the developer containing a toner.

Hereinafter, the present invention will be described in detail.
In addition to exhibiting the conventional effect of controlling the saturation charge amount by incorporating a specific metal-containing polymer in the toner particles, the present inventors have the charge amount and charge amount rising performance in a temperature and humidity environment. The inventor found that it was difficult to rely on and reached the present invention.
Generally, the triboelectric charge generated on the toner surface is easily affected by the absolute water content on the toner surface. This is because water molecules are greatly involved in charge transfer, and when the frequency of desorption of water molecules on the toner surface increases under high humidity, the charge leakage rate increases, the saturation charge decreases, and the charge rise rate This is thought to be due to a decrease in
However, the presence of the specific metal-containing polymer in the toner particles retains the charge generated by frictional charging on the toner surface even under high temperature and high humidity, and is less susceptible to external temperature and humidity.
The aromatic compound part to which the metal contained in the metal-containing polymer of the present invention is bonded is similar to the structure of the conventional charge control agent, and is considered to have the ability as a charge generation site by frictional charging. . The spread of conjugated systems such as oxygen atoms and aryl groups present in the component is considered to improve the charge transfer rate by increasing the charge transfer rate with the binder resin and the charging member. On the other hand, when excessive charging (overcharging) occurs, the effect of preventing the local overcharging by releasing the charge promptly is expected.
The greatest effect expected in the present invention is that the generated charge is retained inside the molecule due to the presence of a conjugated system extending in the molecule, and is very stable against changes in temperature and humidity, which are external factors. Although the mechanism is not clear, it is presumed that the metal-containing polymer of the present invention has a hydrophobic structure that is hardly affected by water molecules.

  Moreover, the metal-containing polymer of the present invention not only exhibits charging performance but also improves the dispersibility of the pigment. As a result, it is possible to obtain an image output excellent in transparency, color mixing, and color stability. The dispersibility of the pigment present in the toner depends on the wettability between the pigment and the binder resin. It can be considered that when the metal-containing polymer of the present invention is adsorbed on the pigment surface, the pigment is modified to a surface that is easily wetted by the binder resin, and the pigment dispersibility is improved. The mechanism of this adsorption is not clear, but it is thought that the salicylate containing metal in the metal-containing polymer or the metal complex component interacts with the polar group or conjugated system present on the pigment surface to promote the adsorption. It is done. In the metal-containing polymer, the benzyloxy moiety is linked to the tip of the salicylic acid metal complex moiety adsorbed on the pigment molecule. This is considered to suppress the aggregation of the pigment by exhibiting the spacer effect. Further, the metal-containing polymer of the present invention has a main chain structure at the tip of the benzyloxy moiety and exhibits a high spacer effect, so that it is considered that the dispersion state is further stabilized.

  In the present invention, the metal contained in the metal-containing polymer is preferably contained in an amount of 5.0 to 1500 μmol per 1 g of the metal-containing polymer, and is contained in an amount of 10.0 to 1500 μmol per 1 g of the metal-containing polymer. More preferably. When the metal content is less than 5.0 μmol, the adsorbing ability to the pigment tends to be lowered, and the pigment dispersion effect tends to be lowered. Moreover, charging performance becomes favorable by setting it as 1500 micromol or less.

The toner of the present invention is a toner having toner particles containing a metal-containing polymer, a colorant, and a binder resin, the metal-containing polymer comprising an aromatic compound part bonded with a metal, a polymer part, The aromatic compound part to which the metal is bonded is a part derived from -COOM ¹ and / or -OH of the salicylic acid structure part or salicylic acid derivative structure part of the partial structure represented by the following formula (1) It has the structure couple | bonded with the metal in.

In the above formula (1), R ¹ represents a hydroxyl group, a carboxyl group, an alkyl group having 1 to 18 carbon atoms, or an alkoxy group having 1 to 18 carbon atoms, and R ² represents a hydroxyl group or carbon number. An alkyl group having 1 to 18 carbon atoms or an alkoxy group having 1 to 18 carbon atoms is represented, and M ¹ represents a hydrogen atom, an alkali metal, —NH ₄ , or a mixture thereof. a represents an integer of 0 to 3, b represents an integer of 1 to 3, and c represents an integer of 0 to 4. When a is 2 or 3, each R ¹ is independently selected. When c is 2, 3 or 4, each R ² is independently selected. Moreover, it is connected with the polymer part at * part.

Here, suitable examples of the alkyl group include methyl group, ethyl group, propyl group, iso-propyl group, n-butyl group, tert-butyl group, n-pentyl group, iso-pentyl group, hexyl group, A heptyl group, an octyl group etc. are mentioned. Further, as the alkoxyl group, methoxy group, ethoxy group, n-propoxy group, iso-propoxy group, n-butoxy group, iso-butoxy group, tert-butoxy group, n-pentoxy group, iso-pentoxy group, hexyloxy group And a heptoxy group, an oxyoctyl group, an oxy-2-ethylhexyl group, and the like.
The polymer part is not particularly limited as long as the aromatic compound part to which the metal is bonded can be connected by * part. Examples thereof include a vinyl polymer, a polyester polymer, a polyamide polymer, a polyurethane polymer, and a polyether polymer. Moreover, the hybrid type polymer which combined these 2 or more types is also mentioned. Among these, a polyester polymer or a vinyl polymer is preferable in consideration of manufacturability, cost merit, and affinity with a binder resin. More preferably, it is a vinyl polymer, and the metal-containing polymer is a part derived from -COOM ¹ and / or -OH of the salicylic acid structure part or salicylic acid derivative structure part having the structure represented by the following formula (3). It is a structure combined with metal.

（上記式（３）中、Ｒ^１、Ｒ^２、Ｍ^１、ａ、ｂ及びｃは上記式（１）と同義である。Ｒ^３は水素原子またはメチル基を示す。）
また、上記金属含有重合体中の上記金属が結合した芳香族化合物部の含有量は、１０μｍｏｌ／ｇ以上１５００μｍｏｌ／ｇ以下であることが好ましい。上記金属含有重合体中の上記金属が結合した芳香族化合物部の含有量を１０μｍｏｌ／ｇ以上とすることで、良好な摩擦帯電性と顔料分散性が発揮される。また、１５００μｍｏｌ／ｇ以下であることで、結着樹脂との親和性が良好となる。上記金属含有重合体中の上記金属が結合した芳香族化合物部の含有量は、金属含有重合体を合成する際の仕込み比や、反応温度等の反応条件で調節することが可能である。

(In the formula ^{(3), R 1, R} 2, M 1, a, .R 3 b and c are the same as defined for the formula (1) represents a hydrogen atom or a methyl group.)
Moreover, it is preferable that content of the aromatic compound part with which the said metal couple | bonded in the said metal containing polymer was 10 micromol / g or more and 1500 micromol / g or less. By setting the content of the aromatic compound portion to which the metal is bonded in the metal-containing polymer to 10 μmol / g or more, good triboelectric chargeability and pigment dispersibility are exhibited. Moreover, affinity with binder resin becomes favorable because it is 1500 micromol / g or less. The content of the aromatic compound part to which the metal is bonded in the metal-containing polymer can be adjusted by reaction conditions such as a charging ratio when synthesizing the metal-containing polymer and reaction temperature.

The metal bonded at the site derived from —COOM ¹ and / or —OH of the salicylic acid structure portion or the salicylic acid derivative structure portion is Mg, Ca, Sr, Pb, Fe, Co, Ni, Zn, Cu, Al, B , Cr, Fe, Ni, Si, Zr, or Ti, Zn, Al, Si, B, Fe, Cr, or Zr is preferable, and Zn, Al, or Cr is more preferable.
In addition, although the bonding structure with the metal is not clear, it is presumed that the metal salt compound or the metal complex is coordinated at a site derived from —COOM ¹ and / or —OH of the salicylic acid structure portion or the salicylic acid derivative structure portion. ing. In general, such compounds have various coordination valences and coordination numbers depending on the types of metals and ligands, and the central atom of a metal complex may have various coordination numbers of about 2 to 12. Are known. For example, when the central atom is aluminum, a tetracoordinate structure is formed when aluminum chloride or trialkylaluminum is used, and a hexacoordinate structure is formed when tris (8-quinolinolato) aluminum is used.
The structure bonded to the metal at the site derived from —COOM ¹ and / or —OH of the salicylic acid structure portion or salicylic acid derivative structure portion of the structure represented by the formula (3) is represented by the following formula (4) or formula (5): It is estimated that.

In the above formula (4), R ¹ represents a hydroxyl group, a carboxyl group, an alkyl group having 1 to 18 carbon atoms, or an alkoxy group having 1 to 18 carbon atoms, and R ² represents a hydroxyl group or carbon number. An alkyl group having 1 to 18 carbon atoms or an alkoxy group having 1 to 18 carbon atoms is shown. R ³ represents a hydrogen atom or a methyl group. a represents an integer of 0 to 3, b represents an integer of 1 to 3, and c represents an integer of 0 to 4. When a is 2 or 3, each R ¹ is independently selected. When c is 2, 3 or 4, each R ² is independently selected. M ² represents Mg, Ca, Sr, Pb, Fe, Co, Ni, Zn, Cu, Al, B, Cr, Fe, Ni, Si, Zr, or Ti. p is an integer of 1 to 6; r is an integer of 1 to 6; q is an integer of 1 to 4; k is an integer of 0 to 3; x is an integer of 0 to 3; y represents 1 or 2, and (T) ^{y +} represents a cation. However, a dotted line in the structural formula indicates a case where coordination bonding is performed or not. B (boron) is expressed as a metal.

In the above formula (5), R ¹ represents a hydroxyl group, a carboxyl group, an alkyl group having 1 to 18 carbon atoms, or an alkoxy group having 1 to 18 carbon atoms, and R ² represents a hydroxyl group or carbon number. An alkyl group having 1 to 18 carbon atoms or an alkoxy group having 1 to 18 carbon atoms is shown, and R ³ represents a hydrogen atom or a methyl group. a represents an integer of 0 to 3, b represents an integer of 1 to 3, and c represents an integer of 0 to 4. When a is 2 or 3, each R ¹ is independently selected. When c is 2, 3 or 4, each R ² is independently selected. M ² represents Mg, Ca, Sr, Pb, Fe, Co, Ni, Zn, Cu, Al, B, Cr, Fe, Ni, Si, Zr, or Ti. s is an integer of 1 to 6; u is an integer of 1 to 6; t is an integer of 1 to 4; m is a number of 0 to 3; and a in a ⁺ is 0 to 3 In (Z) ^b- represents 1 or 2, and (Z) ^b- represents an anion. (Z) ^Examples of the anion of ^b- include anions such as hydroxide ions, sulfate ions, carbonate ions, hydrogen carbonate ions, acetate ions, lactate ions, and halogen ions. However, a dotted line in the structural formula indicates a case where coordination bonding is performed or not.

The case where M ² in the above formula (4) or formula (5) is metal M and the metal M is divalent, trivalent, or tetravalent will be described.
When the metal M is a trivalent metal (Al ³⁺ , B ³⁺ , Cr ³⁺ , Fe ³⁺ , Ni ³⁺ ), the following structural formulas (6) to (14) are shown.

In the above formula (6), R ¹ represents a hydroxyl group, a carboxyl group, an alkyl group having 1 to 18 carbon atoms, or an alkoxy group having 1 to 18 carbon atoms, and R ² represents a hydroxyl group or carbon number. An alkyl group having 1 to 18 carbon atoms or an alkoxy group having 1 to 18 carbon atoms is shown. R ³ represents a hydrogen atom or a methyl group. a represents an integer of 0 to 3, b represents an integer of 1 to 3, and c represents an integer of 0 to 4. When a is 2 or 3, each R ¹ is independently selected. When c is 2, 3 or 4, each R ² is independently selected. k represents 1 or 1/2, y represents 1 or 2, and (T) ^{y +} represents a cation from a hydrogen atom, an alkali metal, an alkaline earth metal, or an ammonium ion.

In the above formula (7), R ¹ represents a hydroxyl group, a carboxyl group, an alkyl group having 1 to 18 carbon atoms, or an alkoxy group having 1 to 18 carbon atoms, and R ² represents a hydroxyl group or carbon number. An alkyl group having 1 to 18 carbon atoms or an alkoxy group having 1 to 18 carbon atoms is shown. R ³ represents a hydrogen atom or a methyl group. a represents an integer of 0 to 3, b represents an integer of 1 to 3, and c represents an integer of 0 to 4. When a is 2 or 3, each R ¹ is independently selected. When c is 2, 3 or 4, each R ² is independently selected.

In the above formula (8), R ¹ represents a hydroxyl group, a carboxyl group, an alkyl group having 1 to 18 carbon atoms, or an alkoxy group having 1 to 18 carbon atoms, and R ² represents a hydroxyl group or carbon number. An alkyl group having 1 to 18 carbon atoms or an alkoxy group having 1 to 18 carbon atoms is shown. R ³ represents a hydrogen atom or a methyl group. a represents an integer of 0 to 3, b represents an integer of 1 to 3, and c represents an integer of 0 to 4. When a is 2 or 3, each R ¹ is independently selected. When c is 2, 3 or 4, each R ² is independently selected. However, a dotted line in the structural formula indicates a case where coordination bonding is performed or not.

In the above formula (9), R ¹ represents a hydroxyl group, a carboxyl group, an alkyl group having 1 to 18 carbon atoms, or an alkoxy group having 1 to 18 carbon atoms, and R ² represents a hydroxyl group or carbon number. An alkyl group having 1 to 18 carbon atoms or an alkoxy group having 1 to 18 carbon atoms is shown. R ³ represents a hydrogen atom or a methyl group. a represents an integer of 0 to 3, b represents an integer of 1 to 3, and c represents an integer of 0 to 4. When a is 2 or 3, each R ¹ is independently selected. When c is 2, 3 or 4, each R ² is independently selected. However, a dotted line in the structural formula indicates a case where coordination bonding is performed or not.

In the above formula (10), R ¹ represents a hydroxyl group, a carboxyl group, an alkyl group having 1 to 18 carbon atoms, or an alkoxy group having 1 to 18 carbon atoms, and R ² represents a hydroxyl group or carbon number. An alkyl group having 1 to 18 carbon atoms or an alkoxy group having 1 to 18 carbon atoms is shown. R ³ represents a hydrogen atom or a methyl group. a represents an integer of 0 to 3, b represents an integer of 1 to 3, and c represents an integer of 0 to 4. When a is 2 or 3, each R ¹ is independently selected. When c is 2, 3 or 4, each R ² is independently selected. k represents 3 or 3/2, y represents 1 or 2, and (T) ^{y +} represents a cation from a hydrogen atom, an alkali metal, an alkaline earth metal, or an ammonium ion.

In the above formula (11), R ¹ represents a hydroxyl group, a carboxyl group, an alkyl group having 1 to 18 carbon atoms, or an alkoxy group having 1 to 18 carbon atoms, and R ² represents a hydroxyl group or carbon number. An alkyl group having 1 to 18 carbon atoms or an alkoxy group having 1 to 18 carbon atoms is shown. R ³ represents a hydrogen atom or a methyl group. a represents an integer of 0 to 3, b represents an integer of 1 to 3, and c represents an integer of 0 to 4. When a is 2 or 3, each R ¹ is independently selected. When c is 2, 3 or 4, each R ² is independently selected.

In the above formula (12), R ¹ represents a hydroxyl group, a carboxyl group, an alkyl group having 1 to 18 carbon atoms, or an alkoxy group having 1 to 18 carbon atoms, and R ² represents a hydroxyl group or carbon number. An alkyl group having 1 to 18 carbon atoms or an alkoxy group having 1 to 18 carbon atoms is shown. R ³ represents a hydrogen atom or a methyl group. a represents an integer of 0 to 3, b represents an integer of 1 to 3, and c represents an integer of 0 to 4. When a is 2 or 3, each R ¹ is independently selected. When c is 2, 3 or 4, each R ² is independently selected. m represents 1 or 1/2, ^b in (Z) ^b- represents 1 or 2, and (Z) ^b- represents a hydroxide ion, a sulfate ion, a carbonate ion, a bicarbonate ion, an acetate ion. , Anion of lactate ion or halogen ion.

In the above formula (13), R ¹ represents a hydroxyl group, a carboxyl group, an alkyl group having 1 to 18 carbon atoms, or an alkoxy group having 1 to 18 carbon atoms, and R ² represents a hydroxyl group or carbon number. An alkyl group having 1 to 18 carbon atoms or an alkoxy group having 1 to 18 carbon atoms is shown. R ³ represents a hydrogen atom or a methyl group. a represents an integer of 0 to 3, b represents an integer of 1 to 3, and c represents an integer of 0 to 4. When a is 2 or 3, each R ¹ is independently selected. When c is 2, 3 or 4, each R ² is independently selected. m represents 2 or 1, ^b in (Z) ^b- represents 1 or 2, and (Z) ^b- represents hydroxide ion, sulfate ion, carbonate ion, bicarbonate ion, acetate ion, lactic acid An anion of either an ion or a halogen ion is shown.

In the above formula (14), R ¹ represents a hydroxyl group, a carboxyl group, an alkyl group having 1 to 18 carbon atoms, or an alkoxy group having 1 to 18 carbon atoms, and R ² represents a hydroxyl group or carbon number. An alkyl group having 1 to 18 carbon atoms or an alkoxy group having 1 to 18 carbon atoms is shown. R ³ represents a hydrogen atom or a methyl group. a represents an integer of 0 to 3, b represents an integer of 1 to 3, and c represents an integer of 0 to 4. When a is 2 or 3, each R ¹ is independently selected. When c is 2, 3 or 4, each R ² is independently selected. k is a number of 1 or 1/2, and y is 1 or 2. (T) ^{y +} is a compound of a trivalent metal M and A shown below, and is specifically represented by (M (A) _n ) ^{y +} . Here, A represents any one of hydroxide ion, sulfate ion, carbonate ion, hydrogen carbonate ion, acetate ion, lactate ion, or halogen ion, n is the number of A, and n is 1 or 2 is shown.

When the metal M is a divalent metal (Mg ²⁺ , Ca ²⁺ , Sr ²⁺ , Pb ²⁺ , Fe ²⁺ , Co ²⁺ , Ni ²⁺ , Zn ²⁺ , Cu ²⁺ ), an estimated structural formula is represented by the following formula ( 15) to (18).

In the above formula (15), R ¹ represents a hydroxyl group, a carboxyl group, an alkyl group having 1 to 18 carbon atoms, or an alkoxy group having 1 to 18 carbon atoms, and R ² represents a hydroxyl group or carbon number. An alkyl group having 1 to 18 carbon atoms or an alkoxy group having 1 to 18 carbon atoms is shown. R ³ represents a hydrogen atom or a methyl group. a represents an integer of 0 to 3, b represents an integer of 1 to 3, and c represents an integer of 0 to 4. When a is 2 or 3, each R ¹ is independently selected. When c is 2, 3 or 4, each R ² is independently selected.

In the above formula (16), R ¹ represents a hydroxyl group, a carboxyl group, an alkyl group having 1 to 18 carbon atoms, or an alkoxy group having 1 to 18 carbon atoms, and R ² represents a hydroxyl group or carbon number. An alkyl group having 1 to 18 carbon atoms or an alkoxy group having 1 to 18 carbon atoms is shown. R ³ represents a hydrogen atom or a methyl group. a represents an integer of 0 to 3, b represents an integer of 1 to 3, and c represents an integer of 0 to 4. When a is 2 or 3, each R ¹ is independently selected. When c is 2, 3 or 4, each R ² is independently selected.

In the above formula (17), R ¹ represents a hydroxyl group, a carboxyl group, an alkyl group having 1 to 18 carbon atoms, or an alkoxy group having 1 to 18 carbon atoms, and R ² represents a hydroxyl group or carbon number. An alkyl group having 1 to 18 carbon atoms or an alkoxy group having 1 to 18 carbon atoms is shown. R ³ represents a hydrogen atom or a methyl group. a represents an integer of 0 to 3, b represents an integer of 1 to 3, and c represents an integer of 0 to 4. When a is 2 or 3, each R ¹ is independently selected. When c is 2, 3 or 4, each R ² is independently selected. m represents 1 or 1/2, ^b in (Z) ^b- represents 1 or 2, and (Z) ^b- represents a hydroxide ion, a sulfate ion, a carbonate ion, a bicarbonate ion, an acetate ion. , Anion of lactate ion or halogen ion.

In the above formula (18), R ¹ represents a hydroxyl group, a carboxyl group, an alkyl group having 1 to 18 carbon atoms, or an alkoxy group having 1 to 18 carbon atoms, and R ² represents a hydroxyl group or carbon number. An alkyl group having 1 to 18 carbon atoms or an alkoxy group having 1 to 18 carbon atoms is shown. R ³ represents a hydrogen atom or a methyl group. a represents an integer of 0 to 3, b represents an integer of 1 to 3, and c represents an integer of 0 to 4. When a is 2 or 3, each R ¹ is independently selected. When c is 2, 3 or 4, each R ² is independently selected. k represents 1 or 1/2, and y represents 1 or 2. (T) ^{y +} is a compound of a divalent metal M and A shown below, and is specifically represented by (M (A) _n ) ^{y +} . Here, A represents any one of hydroxide ion, sulfate ion, carbonate ion, hydrogen carbonate ion, acetate ion, lactate ion, or halogen ion, n is the number of A, and n is 1 or 2 is shown.

When the metal M is a tetravalent metal (Si ⁴⁺ , Zr ⁴⁺ , Ti ⁴⁺ ), the following structural formulas (19) to (20) are shown.

In the above formula (19), R ¹ represents a hydroxyl group, a carboxyl group, an alkyl group having 1 to 18 carbon atoms, or an alkoxy group having 1 to 18 carbon atoms, and R ² represents a hydroxyl group or carbon number. An alkyl group having 1 to 18 carbon atoms or an alkoxy group having 1 to 18 carbon atoms is shown. R ³ represents a hydrogen atom or a methyl group. a represents an integer of 0 to 3, b represents an integer of 1 to 3, and c represents an integer of 0 to 4. When a is 2 or 3, each R ¹ is independently selected. When c is 2, 3 or 4, each R ² is independently selected.

In the above formula (20), R ¹ represents a hydroxyl group, a carboxyl group, an alkyl group having 1 to 18 carbon atoms, or an alkoxy group having 1 to 18 carbon atoms, and R ² represents a hydroxyl group or carbon number. An alkyl group having 1 to 18 carbon atoms or an alkoxy group having 1 to 18 carbon atoms is shown. R ³ represents a hydrogen atom or a methyl group. a represents an integer of 0 to 3, b represents an integer of 1 to 3, and c represents an integer of 0 to 4. When a is 2 or 3, each R ¹ is independently selected. When c is 2, 3 or 4, each R ² is independently selected. m represents 1 or 1/2, ^b in (Z) ^b- represents 1 or 2, and (Z) ^b- represents a hydroxide ion, a sulfate ion, a carbonate ion, a bicarbonate ion, an acetate ion. , Anion of lactate ion or halogen ion.

The metal-containing polymer in the present invention may be produced using any method. For example, it can be produced by the production method (A) or the production method (B).
Production method (A);
(Ai) reacting compound a having a structure represented by the following formula (2) (hereinafter also simply referred to as compound a) with a metal to obtain a metal compound;
(A-ii) A method obtained by undergoing a step of obtaining the metal-containing polymer by polymerizing a vinyl group in the metal compound.

（上記式（２）中、Ｒ^１、Ｒ^２、Ｍ^１、ａ、ｂ及びｃは上記式（１）と同義である。Ｒ^３は水素原子またはメチル基を示す。）

(In the above formula (2), R ¹ , R ² , M ¹ , a, b and c are as defined in the above formula (1). R ³ represents a hydrogen atom or a methyl group.)

Production method (B);
(Bi) a step of obtaining a polymer P by polymerizing a vinyl group in the compound a having the structure represented by the formula (2);
(B-ii) A method obtained by reacting the polymer P with a metal to obtain the metal-containing polymer.

The said compound a in the said manufacturing method (A) and manufacturing method (B) is compoundable using Williamson reaction which is a well-known method. As an example, synthesis can be performed by reacting a vinylphenyl halogenated alkylene compound with a hydroxysalicylic acid compound.
When synthesizing using the Williamson reaction, specific examples of the vinyl phenyl halogenated alkylene that can be used include 4- (chloromethyl) styrene, 4- (bromomethyl) styrene, and 3-methoxy-4- (chloromethyl) styrene. 3-methoxy-4- (bromomethyl) styrene, 2-hydroxy-4- (chloromethyl) styrene, 2-hydroxy-4- (bromomethyl) styrene, 2-methoxy-4- (chloromethyl) styrene, 2-methoxy -4- (bromomethyl) styrene, 3-tert-butyl-4- (chloromethyl) styrene, 3-tert-butyl-4- (bromomethyl) styrene, 3-isooctyl-4- (chloromethyl) styrene, 3-isopropyl -4- (chloromethyl) styrene, 3-methyl-4- (chloro Chill) styrene, 3-ethoxy-4- (chloromethyl) styrene, 3-carboxy-4- (chloromethyl) styrene, 3- (chloromethyl) styrene, 5-methyl-3- (chloromethyl) styrene, 5- Isopropyl-3- (chloromethyl) styrene, 5-isooctyl-3- (chloromethyl) styrene, 5-methoxy-3- (chloromethyl) styrene, 4-ethoxy-3- (chloromethyl) styrene, 4-carboxy- 3- (chloromethyl) styrene, 5-hydroxy-3- (chloromethyl) styrene, 4-hydroxy-3- (chloromethyl) styrene, 4-methoxy-3- (chloromethyl) styrene, 5-tert-butyl- 3- (chloromethyl) styrene, 2- (chloromethyl) styrene, 3-tert-butyl-2- (chloromethyl) ) Styrene, 4- (2-chloroethyl) styrene, 3-methoxy-4- (2-bromoethyl) styrene, 2-hydroxy-4- (2-chloroethyl) styrene, 3-ethoxy-4- (2-chloroethyl) styrene 3- (2-chloroethyl) styrene, 5-isopropyl-3- (2-chloroethyl) styrene, 5-hydroxy-3- (2-chloroethyl) styrene, 4-hydroxy-3- (2-chloroethyl) styrene, 2 -(2-chloroethyl) styrene, 4- (3-chloropropyl) styrene, 2-methoxy-4- (3-chloropropyl) styrene, 2-isopropyl-4- (3-chloropropyl) styrene, 2-isooctyl- 4- (3-chloropropyl) styrene, 3-methoxy-4- (3-chloropropyl) styrene, 3- (3- Having or having a substituent such as chloropropyl) styrene, 5-isooctyl-3- (3-chloropropyl) styrene, 5-methoxy-3- (3-chloropropyl) styrene, 2- (3-chloropropyl) styrene, etc. Vinylalkylene halides that do not.

Specific examples of hydroxysalicylic acid include 2,3-dihydroxybenzoic acid, 5-methyl-2,3-dihydroxybenzoic acid, 5-ethyl-2,3-dihydroxybenzoic acid, and 5-isopropyl-2,3. -Dihydroxybenzoic acid, 5-n-butyl-2,3-dihydroxybenzoic acid, 5-tert-butyl-2,3-dihydroxybenzoic acid, 5-isooctyl-2,3-dihydroxybenzoic acid, 4-carboxy-2 , 3-Dihydroxybenzoic acid, 4-methoxy-2,3-dihydroxybenzoic acid, 4-ethoxy-2,3-dihydroxybenzoic acid, 6-butoxy-2,3-dihydroxybenzoic acid, 4-hydroxy-2,3 -Dihydroxybenzoic acid, 6-hydroxy-2,3-dihydroxybenzoic acid, 2,4-dihydroxybenzoic acid, 6-methyl-2 4-dihydroxybenzoic acid, 6-isopropyl-2,4
-Dihydroxybenzoic acid, 6-tert-butyl-2,4-dihydroxybenzoic acid, 6-isooctyl-2,4-dihydroxybenzoic acid, 5-methoxy-2,4-dihydroxybenzoic acid, 5-ethoxy-2,4 -Dihydroxybenzoic acid, 6-butoxy-2,4-dihydroxybenzoic acid, 6-carboxy-2,4-dihydroxybenzoic acid, 5-hydroxy-6-methyl-2,4-dihydroxybenzoic acid, 2,5-dihydroxy Benzoic acid, 3-methyl-2,5-dihydroxybenzoic acid, 3-isopropyl-2,5-dihydroxybenzoic acid, 3-tert-butyl-2,5-dihydroxybenzoic acid, 3-isooctyl-2,5-dihydroxy Benzoic acid, 3-carboxy-2,5-dihydroxybenzoic acid, 6-methoxy-2,5-dihydroxybenzoic acid 3-tert-butoxy-2,5-dihydroxybenzoic acid, 6-hydroxy-3-methyl-2,5-dihydroxybenzoic acid, 3,4,6-isopropyl-2,5-dihydroxybenzoic acid, 2,6 -Hydroxysalicylic acid such as -dihydroxybenzoic acid, 3-isopropyl-2,6-dihydroxybenzoic acid, 4-tert-butyl-2,6-dihydroxybenzoic acid, 5-methyl-2,6-dihydroxybenzoic acid.
At this time, the base that can be used in the reaction is not particularly limited as long as it does not complicate the reaction system by reacting with a solvent or a substrate. For example, lithium hydroxide, sodium hydroxide, potassium hydroxide, etc. Examples thereof include alkali metal hydroxides, alkali metal carbonates such as lithium carbonate, sodium carbonate, and potassium carbonate.
Specific examples of the reaction solvent that can be used include methanol, ethanol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monomethyl ether, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, ethylene glycol diethyl ether, and triethylene glycol dimethyl ether. , Tetraethylene glycol dimethyl ether, ethylene glycol, propylene glycol and other alcohol-based, ether-based, and glycol-based organic solvents; N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, dimethyl sulfoxide Aprotic polar solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, etc. Esters such as ethyl acetate, butyl acetate, ethyl propionate, and cellosolve acetate; Hydrocarbons such as hexane, octane, petroleum ether, cyclohexane, benzene, toluene, and xylene; Halogenated carbonization such as trichloroethylene, dichloromethane, and chloroform And organic solvents such as hydrogens. In this reaction, it is preferable to add a base in order to accelerate the reaction and capture the hydrogen halide compounded during the ether bond formation.
Further preferred examples of compound a are shown in Table 1.

In the production method (A), examples of the method of reacting compound a with a metal include a method of reacting an aromatic compound with a metal reagent in water and / or an organic solvent (preferably in an organic solvent). In general, a reaction product in an organic solvent can be taken out by dispersing it in an appropriate amount of water, collecting the precipitate by filtration, washing with water and drying. Moreover, after reaction, after concentrating an organic solvent, it can also take out by filtering, washing with water, and drying.
Examples of organic solvents used when reacting compound a with metal include methanol, ethanol, isopropanol, n-butanol, tert-butanol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol dimethyl ether (monoglyme), Alcohols such as ethylene glycol diethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, diethylene glycol dimethyl ether (diglyme), triethylene glycol dimethyl ether (triglyme), tetraethylene glycol dimethyl ether (tetraglyme), ethylene glycol, propylene glycol, Ether-based and glycol-based organic solvents; tetrahydrofura , N, N- dimethylformamide, N, N- dimethylacetamide, N- methyl-2-pyrrolidone, such as aprotic polar solvents such as dimethyl sulfoxide, can be mentioned water soluble organic solvent. In addition, a common water-insoluble organic solvent can be used in combination with these water-soluble organic solvents.
The amount of the organic solvent used is not particularly limited, but is 2 or more and 50 or less by mass with respect to compound a.
Examples of suitable metal reagents include zinc agents such as zinc chloride, zinc sulfate, n-propoxy zinc and n-butoxy zinc; calcium agents such as calcium chloride and calcium bicarbonate; magnesium chloride and hydrogen carbonate. Magnesium agents such as magnesium and magnesium carbonate; strontium agents such as strontium hydroxide and strontium nitrate; aluminum chloride, aluminum sulfate, basic aluminum sulfate, aluminum acetate, basic aluminum acetate, aluminum nitrate, aluminum lactate, aluminum n- Aluminizing agents such as propoxide, aluminum isopropoxide, t-butoxyaluminum; titanating agents such as titanium chloride, titanium sulfate, n-propoxytitanium, isopropoxytitanium, n-butoxytitanium; zirco chloride Zirconium, zirconium sulfate, n-propoxyzirconium, ethoxyzirconium, isopropoxyzirconium, butoxyzirconium, etc .; chrominating agents such as chromium lactate, chromium formate, chromium sulfate, chromium chloride, and chromium nitrate; ferric chloride , ferric sulfate, ferrous sulfate, ferric nitrate, ferrous ferric _{(Fe 3 C l7 · xH 2} O, Fe 3 C l8 · xH 2 O) chloride iron-complexing agent, such as, boric acid Boronating agents such as boron trichloride, trimethoxyborane and triethoxyborane; and siliconating agents such as silicon tetrachloride, ethoxysilane, methoxysilane, butoxysilane and isopropoxysilane;
The metal reagent is preferably used in an amount of 0.02 to 5.0 equivalents relative to Compound a. More preferably, it is 0.05 equivalent or more and 3.0 equivalent or less.
The method of reacting with the metal is the same as in the production method (B) in the step of reacting the polymer P with the metal to obtain the metal-containing polymer, except that the compound a is replaced with the polymer P. Can do.
The metal compound obtained by reacting compound a with a metal in this way is presumed to be the following formula (21) or formula (22). Similar to the metal-containing polymer described above, the coordination valence and coordination number vary depending on the type of metal and ligand, and various coordination numbers of 2 to 12 are taken. Therefore, although the metal compound is represented by the formula (21) or the formula (22), it is not always composed of a single structure, and may be a mixture of a plurality of coordination forms. .
The amount of metal contained in the metal compound can be adjusted by the mixing ratio of the metal reagent and compound a, the reaction temperature, the reaction time, and the like. As a metal amount, it is preferable that it is 5.00 mol% or more and less than 100.00 mol% with respect to the compound a. Within this range, the hydrophobic effect upon metal complexation is more effectively exhibited.

In the above formula (21), R ¹ represents a hydroxyl group, a carboxyl group, an alkyl group having 1 to 18 carbon atoms, or an alkoxy group having 1 to 18 carbon atoms, and R ² represents a hydroxyl group or carbon number. An alkyl group having 1 to 18 carbon atoms or an alkoxy group having 1 to 18 carbon atoms is shown. R ³ represents a hydrogen atom or a methyl group. a represents an integer of 0 to 3, b represents an integer of 1 to 3, and c represents an integer of 0 to 4. When a is 2 or 3, each R ¹ is independently selected. When c is 2, 3 or 4, each R ² is independently selected. M ² is Mg, Ca, Sr, Pb, Fe, Co, Ni, Zn, Cu
, Al, B, Cr, Fe, Ni, Si, Zr, or Ti. p is an integer of 1 to 6; r is an integer of 1 to 6; q is an integer of 1 to 4; k is an integer of 0 to 3; x is an integer of 0 to 3; y represents 1 or 2, and (T) ^{y +} represents a cation. However, a dotted line in the structural formula indicates a case where coordination bonding is performed or not. B (boron) is expressed as a metal.

In the formula (22), R ¹ represents a hydroxyl group, a carboxyl group, an alkyl group having 1 to 18 carbon atoms, or an alkoxy group having 1 to 18 carbon atoms, and R ² represents a hydroxyl group or carbon number. An alkyl group having 1 to 18 carbon atoms or an alkoxy group having 1 to 18 carbon atoms is shown. R ³ represents a hydrogen atom or a methyl group. a represents an integer of 0 to 3, b represents an integer of 1 to 3, and c represents an integer of 0 to 4. When a is 2 or 3, each R ¹ is independently selected. When c is 2, 3 or 4, each R ² is independently selected. M ² represents Mg, Ca, Sr, Pb, Fe, Co, Ni, Zn, Cu, Al, B, Cr, Fe, Ni, Si, Zr, or Ti. s is an integer of 1 to 6; u is an integer of 1 to 6; t is an integer of 1 to 4; m is an integer of 0 to 3; and a in a ⁺ is 0 to 3 In (Z) ^b- represents 1 or 2, and (Z) ^b- represents an anion. (Z) ^Examples of the anion of ^b- include anions such as hydroxide ions, sulfate ions, carbonate ions, hydrogen carbonate ions, acetate ions, lactate ions, and halogen ions. However, a dotted line in the structural formula indicates a case where coordination bonding is performed or not.

In the production method (A), a metal-containing polymer is obtained by polymerizing a vinyl group in a metal compound. Moreover, in the manufacturing method (B), the polymer P is obtained by polymerizing the vinyl group in the compound a. Here, the main chain structures of the metal-containing polymer and the polymer P are not particularly limited as long as they are obtained by polymerization with respective vinyl groups. Examples thereof include vinyl polymers, polyester polymers, polyamide polymers, polyurethane polymers, polyether polymers, and the like. Moreover, the hybrid type polymer which combined these 2 or more types is also mentioned. Among them, a polyester polymer or a vinyl polymer is preferable because the dispersion state is further stabilized when the affinity with the binder resin is increased. More preferably, it is copolymerized with a vinyl monomer. When the metal-containing polymer and the polymer P are vinyl polymers, the affinity increases in toner particles containing a vinyl resin as a main component, and they are easily compatible. For this reason, it is possible to further stabilize the dispersion state of the adsorbed pigment and the vinyl resin component. When the metal-containing polymer and the polymer P are vinyl polymers, the metal-containing polymer is estimated to be the formula (4) or the formula (5), and the polymer P is represented by the formula (3). It becomes a structure.
The vinyl monomer copolymerized with each of the metal compound and compound a is not particularly limited. Specifically, styrene and its derivatives such as styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, α-methylstyrene; ethylene unsaturated monoolefins such as ethylene, propylene, butylene and isobutylene; Vinyl halides such as vinyl, vinylidene chloride, vinyl bromide, vinyl fluoride; vinyl ester acids such as vinyl acetate, vinyl propionate, vinyl benzoate; acrylic acid-n-butyl, acrylic acid-2-ethylhexyl, etc. Acrylic acid esters; Methacrylic acid esters obtained by changing the acrylic acid of the acrylic acid esters to methacrylic acid; Methacrylic acid amino esters such as dimethylaminoethyl methacrylate and diethylaminoethyl methacrylate; Vinyl methyl ether, vinyl ethyl ether Vinyl ethers; vinyl ketones such as vinyl methyl ketone; N-vinyl compounds such as N-vinyl pyrrole; vinyl naphthalenes; acrylic acid or methacrylic acid derivatives such as acrylonitrile, methacrylonitrile, acrylamide, acrylic acid, methacrylic acid, etc. Can be mentioned. In addition, you may use a vinyl monomer in combination of 2 or more type as needed.
Various polymerization initiators such as peroxide polymerization initiators and azo polymerization initiators can be used as the polymerization initiator that can be used when each of the above-described metal compound and compound a is polymerized. Examples of the peroxide polymerization initiator that can be used include peroxyesters, peroxydicarbonates, dialkyl peroxides, peroxyketals, ketone peroxides, hydroperoxides, and diacyl peroxides. Examples of the inorganic system include persulfate and hydrogen peroxide. Specifically, t-butyl peroxyacetate, t-butyl peroxypivalate, t-butyl peroxyisobutyrate, t-hexyl peroxyacetate, t-hexyl peroxypivalate, t-hexyl peroxyiso Peroxyesters such as butyrate, t-butylperoxyisopropyl monocarbonate, t-butylperoxy 2-ethylhexyl monocarbonate; diacyl peroxides such as benzoyl peroxide; peroxydicarbonates such as diisopropyl peroxydicarbonate; 1 , 1-di-t-hexylperoxycyclohexane and other peroxyketals; di-t-butyl peroxide and other dialkyl peroxides; and other examples include t-butyl peroxyallyl monocarbonate and the like. It is. Examples of the azo polymerization initiator that can be used include 2,2′-azobis- (2,4-dimethylvaleronitrile), 2,2′-azobisisobutyronitrile, 1,1′-azobis (cyclohexane- 1-carbonitrile), 2,2′-azobis-4-methoxy-2,4-dimethylvaleronitrile, azobisisobutyronitrile, dimethyl-2,2′-azobis (2-methylpropionate), etc. Illustrated.
If necessary, two or more of these polymerization initiators can be used simultaneously. It is preferable that the usage-amount of the polymerization initiator used in this case is 0.100 mass part or more and 20.0 mass parts or less with respect to 100 mass parts of polymerizable monomers. As the polymerization method, any method such as solution polymerization, suspension polymerization, emulsion polymerization, dispersion polymerization, precipitation polymerization, bulk polymerization and the like can be used, and it is not particularly limited.

On the other hand, the metal-containing polymer of the present invention can be a polymer having a polyester structure. It is a copolymer having a polyester structure formed by polycondensation of at least a polyhydric alcohol component and a polyvalent carboxylic acid component, and having a structure represented by formula (4) or formula (5). In this case, a hybrid resin modified with a vinyl monomer can be used as the resin having a polyester structure. A known method can be used to adjust the vinyl modification ratio in the hybrid resin. Specifically, an arbitrary modification ratio can be adjusted by changing the charged amount ratio of the polyester resin component to be used and the vinyl monomer component.
The following are mentioned as a polyhydric alcohol component which comprises the resin which has the said polyester structure. Specifically, for example, as the dihydric alcohol component, polyoxypropylene (2.2) -2,2-bis (4-hydroxyphenyl) propane, polyoxypropylene (3.3) -2,2-bis ( 4-hydroxyphenyl) propane, polyoxyethylene (2.0) -2,2-bis (4-hydroxyphenyl) propane, polyoxypropylene (2.0) -polyoxyethylene (2.0) -2,2 -Alkylene oxide adducts of bisphenol A such as bis (4-hydroxyphenyl) propane, polyoxypropylene (6) -2,2-bis (4-hydroxyphenyl) propane, ethylene glycol, diethylene glycol, triethylene glycol, 1, 2-propylene glycol, 1,3-propylene glycol, 1,4-butanediol, Opentyl glycol, 1,4-butenediol, 1,5-pentanediol, 1,6-hexanediol, 1,4-cyclohexanedimethanol, dipropylene glycol, polyethylene glycol, polypropylene glycol, polytetramethylene glycol, bisphenol A And hydrogenated bisphenol A.
Examples of the trivalent or higher alcohol component include sorbitol, 1,2,3,6-hexanetetrol, 1,4-sorbitan, pentaerythritol, dipentaerythritol, tripentaerythritol, 1,2,4-butanetriol, 1,2,5-pentanetriol, glycerol, 2-methylpropanetriol, 2-methyl-1,2,4-butanetriol, trimethylolethane, trimethylolpropane, 1,3,5-trihydroxymethylbenzene, etc. Can be mentioned.
Examples of the polyvalent carboxylic acid component include aromatic dicarboxylic acids such as phthalic acid, isophthalic acid and terephthalic acid or anhydrides thereof; alkyl dicarboxylic acids such as succinic acid, adipic acid, sebacic acid and azelaic acid or anhydrides thereof; And succinic acid substituted with an alkyl group having 6 to 12 carbon atoms or an anhydride thereof; unsaturated dicarboxylic acids such as fumaric acid, maleic acid and citraconic acid or the anhydride thereof; and the like.
Among them, in particular, a carboxylic acid component (for example, fumaric acid, maleic acid, maleic anhydride, phthalate, which includes a bisphenol derivative as a diol component and a divalent or higher carboxylic acid or an acid anhydride thereof, or a lower alkyl ester thereof) A polyester resin obtained by polycondensation of these compounds using acid, terephthalic acid, trimellitic acid, pyromellitic acid, or the like as an acid component can be preferably used.
As a method for hybridizing the polyester resin with a vinyl monomer, a known method can be used. Specific examples include a method of vinyl-modifying polyester with a peroxide-based initiator and a method of preparing a hybrid resin by graft-modifying a polyester resin having an unsaturated group.
Moreover, as a vinyl monomer which can be used for hybridization of a polyester resin in the present invention, the above-described vinyl monomers can be used.

  Furthermore, when the aromatic compound part to which the metal represented by the above formula (1) is bonded is coexistent with the sulfonic acid or sulfonic acid ester represented by the following formula (23), the charge amount rising performance can be further improved. Found that is possible. Although the reason is not clear, it is considered that the aromatic compound portion to which the metal represented by the formula (1) is bonded has a function of accumulating charges and a function of appropriately equalizing charges. Since the balance between charge accumulation and homogenization can be adjusted by coexisting the sulfonic acid and sulfonic acid ester represented by the following formula (23) that strongly exhibits the charge accumulation function, We believe that the start-up performance will be better. The coexistence method is not particularly limited, and a method of synthesizing the polymer B having the structure of the formula (23) and blending it with the metal-containing polymer at the time of producing the toner, or the above metal compound or compound a and the following formula (23 ) And a polymerizable monomer having a partial structure as a copolymer. Since the improvement of the rising performance of the charge amount is more effective when the two kinds of structural sites are present closer to each other, a method of using a copolymer existing in the same molecule is more preferable.

  In the above formula (23), B1 represents an alkylene structure having 1 or 2 carbon atoms which may have a substituent, or an aromatic ring which may have a substituent. R10 represents a hydrogen atom or an alkyl group having 1 to 12 carbon atoms. The substituent in the alkylene structure is a hydroxyl group, an alkyl group having 1 to 12 carbon atoms, an aryl group having 6 to 12 carbon atoms, or an alkoxyl group having 1 to 12 carbon atoms. The substituent in the aromatic ring is a hydroxyl group, an alkyl group having 1 to 12 carbon atoms, or an alkoxyl group having 1 to 12 carbon atoms.

  When the polymer B having the formula (23) is produced and blended with the metal-containing polymer at the time of toner production, the production method of the polymer B is not particularly limited, and a known method is used. The main chain structure of the polymer B is not particularly limited as long as it can be linked to the partial structure represented by the formula (23). Examples thereof include vinyl polymers, polyester polymers, polyamide polymers, polyurethane polymers, polyether polymers, and the like. Moreover, the hybrid type polymer which combined these 2 or more types is also mentioned. Among these, a polyester polymer or a vinyl polymer is preferable in consideration of manufacturability, cost merit, and affinity with a binder resin. More preferred is a vinyl polymer having a unit represented by the following formula (24).

In the above formula (24), B ² represents an alkylene structure having 1 or 2 carbon atoms which may have a substituent, or an aromatic ring which may have a substituent. R ¹¹ represents a hydrogen atom or an alkyl group having 1 to 12 carbon atoms. R ¹² represents a hydrogen atom or a methyl group. The substituent in the alkylene structure is a hydroxyl group, an alkyl group having 1 to 12 carbon atoms, an aryl group having 6 to 12 carbon atoms, or an alkoxyl group having 1 to 12 carbon atoms. The substituent in the aromatic ring is a hydroxyl group, an alkyl group having 1 to 12 carbon atoms, or an alkoxyl group having 1 to 12 carbon atoms.
As the monomer used when the polymer B is a vinyl polymer, a vinyl monomer represented by the following formula (25) is preferably used.

In the above formula (25), B ³ represents an alkylene structure having 1 or 2 carbon atoms which may have a substituent, or an aromatic ring which may have a substituent. R ¹³ represents a hydrogen atom or an alkyl group having 1 to 12 carbon atoms. R ¹⁴ represents a hydrogen atom or a methyl group. The substituent in the alkylene structure is a hydroxyl group, an alkyl group having 1 to 12 carbon atoms, an aryl group having 6 to 12 carbon atoms, or an alkoxyl group having 1 to 12 carbon atoms. The substituent in the aromatic ring is a hydroxyl group, an alkyl group having 1 to 12 carbon atoms, or an alkoxyl group having 1 to 12 carbon atoms.
Specific examples of the vinyl monomer represented by the above formula (25) include the following. 2-acrylamido-2-methylpropanesulfonic acid, 2-acrylamidobenzenesulfonic acid, 2-methacrylamideamidobenzenesulfonic acid, 3-acrylamidobenzenesulfonic acid, 3-methacrylamideamidobenzenesulfonic acid, 4-acrylamidobenzenesulfonic acid, 4- Methacrylamidobenzenesulfonic acid, 2-acrylamido-5-methylbenzenesulfonic acid, 2-methacrylamideamido-5-methylbenzenesulfonic acid, 2-acrylamido-5-methoxybenzenesulfonic acid, 2-methacrylamide-5-methoxybenzenesulfone Examples thereof include acids and alkyl esters having 1 to 12 carbon atoms. A sulfonic acid structure, methyl ester or ethyl ester is preferable, and a sulfonic acid structure or sulfonic acid methyl ester structure is more preferable.

On the other hand, when the polymer B is a polyester resin, various known production methods can be used. For example,
i) A method of converting to a structure represented by the above formula (23) by an organic reaction using a reaction residue of a carboxyl group or a hydroxyl group contained in a polyester structure;
ii) A method for producing a polyester using a polyhydric alcohol or polyvalent carboxylic acid having a structure represented by the above formula (23) as a substituent;
iii) A method in which a functional group that can easily introduce a structure represented by the above formula (23) as a substituent is introduced into a polyhydric alcohol or polycarboxylic acid in advance;
Etc.

In the case of a hybrid resin,
iv) A method of hybridizing a polyester resin containing a structure represented by the above formula (23) as a substituent with a vinyl monomer;
v) A method of polymerizing a vinyl monomer having a carboxyl group such as acrylic acid or methacrylic acid and then converting the carboxyl group into a structure represented by the above formula (23) by an organic reaction;
vi) A method of hybridizing a polyester resin using a vinyl monomer having a structure represented by the above formula (23);
Etc.
As a method for hybridizing the polyester resin with a vinyl monomer, a known method can be used, and it is effective as the method iv). Specific examples include a method of vinyl-modifying polyester with a peroxide-based initiator and a method of preparing a hybrid resin by graft-modifying a polyester resin having an unsaturated group.
On the other hand, as a specific method of v), when the structure represented by the above formula (23) is introduced, the carboxyl group present in the resin is substituted with an amino group at the bonding portion with the polymer portion of the above formula (23). Examples thereof include a method of amidation using the introduced compound.
Further, as a specific method of vi), as the vinyl monomer that can be used, the polymerizable monomer represented by the above formula (25) can be used.
On the other hand, when the aromatic compound part to which the metal represented by the formula (1) is bonded and the sulfonic acid or sulfonic acid ester of the formula (23) is copolymerized to be incorporated into the metal-containing polymer, the metal-containing polymer It can be produced by mixing the vinyl monomer of formula (25) during the polymerization reaction. It is possible to adjust the balance between charge accumulation and homogenization by changing the mixing ratio at the time of copolymerization.

In the present invention, regarding the molecular weight of the metal-containing polymer, the weight average molecular weight calculated by gel permeation chromatography (GPC) is preferably 1,000 or more and 1,000,000 or less. As a more preferable range, the weight average molecular weight is 2,000 or more and 200,000 or less. When the molecular weight of the metal-containing polymer is within the above range, contamination of members such as a sleeve and a carrier is satisfactorily suppressed.
Further, from the viewpoint of charging characteristics and fixability, it is preferable that the molecular weight distribution of the metal-containing polymer is narrow. The ratio (Mw / Mn) between the weight average molecular weight (Mw) and the number average molecular weight (Mn) calculated by gel permeation chromatography is preferably 1.0 or more and 6.0 or less.
In addition, as a method of adjusting the molecular weight of the metal-containing polymer within a specified range, it can be adjusted by reaction conditions such as a raw material charge ratio, a reaction temperature, a reaction time, a reaction solvent amount, and the like.

  In the toner of the present invention, the content of the metal-containing polymer is not particularly limited, but it is more preferable that the metal contained in the metal-containing polymer is contained in an amount of preferably 0.1 μmol or more and 200 μmol or less per 1 g of the toner. When it is added so as to contain 1.0 μmol or more and 100 μmol or less, the function is more effectively exhibited. If it is less than 0.1 μmol / g, the charge amount tends to decrease. In addition, the pigment dispersion effect tends to decrease. On the other hand, if it exceeds 200 μmol / g, charge-up may be likely to occur. The control of the content in the toner of the present invention can be adjusted by the amount of the metal-containing polymer charged when the toner is produced.

  In the toner of the present invention, the binder resin used is not particularly limited. For example, styrene resin, acrylic resin, styrene-acrylic resin, polyethylene resin, polyethylene-vinyl acetate resin, vinyl acetate resin, polybutadiene resin, phenol resin, polyurethane resin, polybutyral resin, polyester resin, and the like can be given. Among these, styrenic resins, acrylic resins, styrene-acrylic resins, polyester resins, and the like are desirable in terms of toner characteristics. Further, the metal-containing polymer itself may be used as the binder resin. Even when a metal-containing polymer is used as a binder resin, the amount of metal contained in 1 g of toner is preferably adjusted to fall within the above range. Examples of the adjusting method include a method of adjusting with the amount of metal compound charged at the time of producing the metal-containing polymer, a method of adjusting with the amount of metal-containing polymer charged at the time of toner production, and the like.

Examples of the colorant that can be used in the toner of the present invention include known colorants such as various conventionally known dyes and pigments.
Examples of the color pigment for magenta include C.I. I. Pigment red 3, 5, 17, 22, 23, 38, 41, 112, 122, 123, 146, 149, 178, 179, 190, 202, C.I. I. Pigment Violet 19, 23. Such a pigment may be used alone, or a dye and a pigment may be used in combination.
Examples of the color pigment for cyan include C.I. I. Pigment Blue 15, 15: 1, 15: 3 or a copper phthalocyanine pigment in which 1 to 5 phthalimidomethyl groups are substituted on the phthalocyanine skeleton.
Examples of the color pigment for yellow include C.I. I. Pigment yellow 1, 3, 12, 13, 14, 17, 55, 74, 83, 93, 94, 95, 97, 98, 109, 110, 154, 155, 166, 180, 185.
As the black colorant, carbon black, aniline black, acetylene black, titanium black, and those that are toned in black using the yellow, magenta, and cyan colorants shown above can be used.
The content of these colorants is preferably 3 parts by mass or more and 30 parts by mass or less with respect to 100 parts by mass of the binder resin.

The toner of the present invention can also be used as a magnetic toner, and in this case, the following magnetic materials are used. Iron oxide including magnetite, maghemite, ferrite, or other metal oxides; metals such as Fe, Co, Ni, or these metals and Al, Co, Cu, Pb, Mg, Ni, Sn, Alloys with metals such as Zn, Sb, Ca, Mn, Se, Ti, and mixtures thereof. More specifically, triiron tetroxide (Fe ₃ O ₄ ), iron sesquioxide (γ-Fe ₂ O ₃ ), zinc iron oxide (ZnFe ₂ O ₄ ), copper iron oxide (CuFe ₂ O ₄ ), oxidation Examples thereof include iron neodymium (NdFe ₂ O ₃ ), iron barium oxide (BaFe ₁₂ O ₁₉ ), iron magnesium oxide (MgFe ₂ O ₄ ), and iron oxide manganese (MnFe ₂ O ₄ ). The magnetic materials described above are used alone or in combination of two or more. A particularly suitable magnetic material is a fine powder of triiron tetroxide or γ-iron sesquioxide.
These magnetic materials preferably have an average particle size of 0.1 μm to 2 μm, and more preferably 0.1 μm to 0.3 μm. The magnetic characteristics when 795.8 kA / m (10 K Oersted) is applied are preferably such that the coercive force (Hc) is 1.6 kA / m or more and 12 kA / m or less (20 Oersted or more and 150 Oersted or less), and saturation magnetization (σs ) Is preferably ⁵ Am ² / kg or more and 200 Am ² / kg or less, more preferably 50 Am ² / kg or more and 100 Am ² / kg or less. Residual magnetization (.sigma.r) is, ^2Am 2 / kg or more 20 Am ² / kg or less being preferred.
The magnetic material is preferably used in the range of 10 to 200 parts by mass, and more preferably in the range of 20 to 150 parts by mass with respect to 100 parts by mass of the binder resin.

The toner of the present invention may contain a release agent. The release agent includes aliphatic hydrocarbon waxes such as low molecular weight polyethylene, low molecular weight polypropylene, microcrystalline wax and paraffin wax; oxides of aliphatic hydrocarbon waxes such as oxidized polyethylene wax; aliphatic hydrocarbon waxes Block copolymers of these: waxes based on fatty acid esters such as carnauba wax, sazol wax, and montanic acid ester wax; Examples thereof include partially esterified products of fatty acids such as monoglycerides and polyhydric alcohols; methyl ester compounds having a hydroxyl group obtained by hydrogenating vegetable oils and fats.
As for the molecular weight distribution of the release agent, the main peak is preferably in the region of molecular weight 400 or more and 2400 or less, and more preferably in the region of 430 or more and 2000 or less. Thereby, preferable thermal characteristics can be imparted to the toner. The amount of the release agent added is preferably 2.5 parts by mass or more and 40.0 parts by mass or less, and 3.0 parts by mass or more and 15.0 parts by mass or less with respect to 100 parts by mass of the binder resin. More preferably.

The toner particles may be mixed with a fluidity improver by a mixing machine such as a Henschel mixer so that the toner particles have a fluidity improver on the surface of the toner particles. Examples of the fluidity improver include fluorine resin powders such as vinylidene fluoride fine powder and polytetrafluoroethylene fine powder; silica fine powder obtained by a wet process, silica fine powder such as a silica fine powder obtained by a dry process, and silica fine powders. Treated silica fine powder surface treated with a treatment agent such as silane coupling agent, titanium coupling agent, silicone oil; titanium oxide fine powder; alumina fine powder, treated titanium oxide fine powder, treated alumina oxide fine powder . The fluidity improver preferably has a specific surface area of 30 m ² / g or more, more preferably 50 m ² / g or more, as measured by a BET method using nitrogen adsorption. The addition amount of the fluidity improver is preferably 0.01 parts by mass or more and 8.0 parts by mass or less, more preferably 0.1 parts by mass or more and 4.0 parts by mass with respect to 100 parts by mass of the toner particles. It is as follows.

  The weight average particle diameter (D4) of the toner of the present invention is preferably 3.0 μm or more and 15.0 μm or less, more preferably 4.0 μm or more and 12.0 μm or less.

The toner of the present invention can be mixed with a magnetic carrier and used as a two-component developer. As magnetic carriers, surface oxidized or unoxidized iron, lithium, calcium, magnesium, nickel, copper, zinc, cobalt, manganese, chromium, rare earth metal particles, their alloy particles, oxide particles and ferrite are atomized. Can be used.
In the developing method in which an AC bias is applied to the developing sleeve, it is preferable to use a coated carrier in which the surface of the magnetic carrier core is coated with a resin. As a coating method, a method in which a coating solution prepared by dissolving or suspending a coating material such as a resin in a solvent is attached to the surface of the magnetic carrier core, or a method in which the magnetic carrier core and the coating material are mixed with powder is used. It is done.
Examples of the coating material for the magnetic carrier core include silicone resin, polyester resin, styrene resin, acrylic resin, polyamide, polyvinyl butyral, and aminoacrylate resin. These may be used alone or in plurality. The treatment amount of the coating material is preferably 0.1% by mass or more and 30% by mass or less, more preferably 0.5% by mass or more and 20% by mass or less with respect to the magnetic carrier core particles. The magnetic carrier preferably has a volume-based 50% particle size (D50) of 10 μm to 100 μm, and more preferably 20 μm to 70 μm. When preparing a two-component developer, the mixing ratio is preferably 2 or more and 15% by mass or less, more preferably 4% by mass or more and 13% by mass or less as the toner concentration in the developer.

Examples of means for producing toner particles include a kneading and pulverizing method, a suspension polymerization method, a dissolution suspension method, and an emulsion aggregation method. Among them, the suspension polymerization method, dissolution suspension method, and emulsion aggregation method in which toner particles are prepared in an aqueous medium are preferable. More preferably, the toner particles are produced by a suspension polymerization method. The reason for this is that in the step of granulating in an aqueous medium (granulation step), the metal-containing polymer can be effectively localized on the surface of the toner particles, resulting in uniform chargeability and good particle size distribution. This is because is more effectively exhibited.
In the method for producing toner particles by suspension polymerization, first, a colorant is uniformly dissolved and mixed or dispersed in a polymerizable monomer constituting a binder resin by a stirrer or the like. In particular, when the colorant is a pigment, it is preferably treated with a disperser to obtain a pigment dispersion paste. The polymerizable monomer and the metal-containing polymer, and if necessary, the wax, the polymerization initiator, and other additives are uniformly dissolved and mixed or dispersed with a stirrer to produce a polymerizable monomer composition. To do. Even if the metal-containing polymer is added after the preparation of the pigment dispersion paste, the effect of pigment dispersion can be obtained. However, if the polymer is mixed at the time of preparation of the pigment dispersion paste, the effect of pigment dispersion can be obtained better. The polymerizable monomer composition thus obtained is added to a dispersion medium (preferably an aqueous medium) containing a dispersion stabilizer, and a high-speed disperser such as a high-speed stirrer or an ultrasonic disperser is used as a stirrer. Is finely dispersed to the toner particle size (granulation step). Then, the polymerizable monomer in the polymerizable monomer composition finely dispersed in the granulation step is subjected to a polymerization reaction with light or heat (polymerization step) to obtain toner particles.

As a method of dispersing the pigment in an organic medium such as the polymerizable monomer, a known method can be used. For example, if necessary, a resin and a pigment dispersant are dissolved in an organic medium, and the pigment powder is gradually added while being stirred, so that the solvent is sufficiently blended. Further, by applying mechanical shearing force with a dispersing machine such as a ball mill, paint shaker, dissolver, attritor, sand mill, or high speed mill, the pigment can be stably finely dispersed, that is, dispersed into uniform fine particles.
As the polymerizable monomer that can be suitably used in the suspension polymerization method, the aforementioned vinyl monomers can be used in the same manner.
In the method for producing toner particles by the suspension polymerization method, a dispersion medium that can be used is determined based on solubility in a dispersion medium such as a binder resin, an organic medium, a polymerizable monomer, and a polymer P. However, an aqueous type is preferable. Examples of water-based dispersion media that can be used include water; alcohols such as methyl alcohol, ethyl alcohol, modified ethyl alcohol, isopropyl alcohol, n-butyl alcohol, isobutyl alcohol, tert-butyl alcohol, sec-butyl alcohol; Ether alcohols such as cellosolve, cellosolve, isopropyl cellosolve, butyl cellosolve, diethylene glycol monobutyl ether, and other water-soluble ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, etc .; esters such as ethyl acetate; ethyl Selected from ethers such as ether and ethylene glycol; acetals such as methylal and diethyl acetal; acids such as formic acid, acetic acid and propionic acid. Particularly preferably it is an alcohol. Two or more of these solvents can be mixed and used. The concentration of the liquid mixture or the polysynthetic monomer composition with respect to the dispersion medium is preferably 1% by mass or more and 80% by mass or less, and more preferably 10% by mass or more and 65% by mass or less with respect to the dispersion medium.
As a dispersion stabilizer that can be used when an aqueous dispersion medium is used, known ones can be used. Specific examples include inorganic compounds such as calcium phosphate, magnesium phosphate, aluminum phosphate, zinc phosphate, calcium carbonate, magnesium carbonate, calcium hydroxide, magnesium hydroxide, aluminum hydroxide, calcium metasilicate, calcium sulfate, barium sulfate. , Bentonite, silica, alumina and the like. As the organic compound, polyvinyl alcohol, gelatin, methyl cellulose, methyl hydroxypropyl cellulose, ethyl cellulose, sodium salt of carboxymethyl cellulose, polyacrylic acid and its salt, starch and the like can be dispersed in an aqueous phase. The concentration of the dispersion stabilizer is preferably 0.2 parts by mass or more and 20.0 parts by mass or less with respect to 100 parts by mass of the liquid mixture or the polymerizable monomer composition.
As the polymerization initiator used for the production of toner particles by the suspension polymerization method, those described above can be used. In the production of toner particles by suspension polymerization, a known crosslinking agent may be added. A preferable addition amount is 0 to 15.0 parts by mass with respect to 100 parts by mass of the polymerizable monomer.
In the dissolution suspension method, for example, a metal-containing polymer is dissolved or dispersed in an organic solvent together with other necessary components, suspended and granulated in an aqueous medium, and then the organic solvent contained in the droplets is removed. Thus, toner particles can be produced.
In the emulsion aggregation method, for example, a metal-containing polymer is finely dispersed in an aqueous medium by a method such as phase inversion emulsification, mixed with fine particles of other necessary components, and toner particles are controlled by controlling their zeta potential in the aqueous medium. The toner particles can be produced by agglomeration to a diameter.
The toner particles are sufficiently mixed together with a fluidity improver by a mixing machine such as a Henschel mixer, whereby a toner having a fluidity improver on the surface of the toner particles can be obtained.

In the toner of the present invention, in addition to the fluidity improver, inorganic fine powder can be added to the surface of the toner particles. Such an inorganic fine powder is added to and mixed with toner particles in order to improve toner fluidity and uniform charge, and the added inorganic fine powder exists in a state of being uniformly attached to the surface of the toner particles.
The inorganic fine powder preferably has a number average particle diameter (D1) of primary particles of 4 nm or more and 80 nm or less.
As the inorganic fine powder, an inorganic fine powder selected from silica, alumina, titania or a double oxide thereof can be used. Examples of the double oxide include aluminum silicate fine powder and strontium titanate fine powder. Further, as the silicic acid fine powder, both a so-called dry method produced by vapor phase oxidation of silicon halide or dry silica called fumed silica, and so-called wet silica produced from water glass or the like can be used. is there. Dry silica is preferred because it has few silanol groups on the surface and inside of the silicate fine powder and little production residue such as Na ₂ O, SO ₃ ²⁻ . In dry silica, it is also possible to obtain composite fine powders of silica and other metal oxides by using other metal halogen compounds such as aluminum chloride and titanium chloride together with silicon halogen compounds in the production process. They are also included.
The addition amount of the inorganic fine powder having a number average particle diameter (D1) of primary particles of 4 nm or more and 80 nm or less may be 0.1 parts by mass or more and less than 5.0 parts by mass with respect to 100 parts by mass of the toner particles. preferable.
Further, the toner used in the present invention has other additives, for example, a lubricant such as a zinc stearate powder, an abrasive such as a cerium oxide powder and a silicon carbide powder, within a range that does not substantially adversely affect the toner. Further, developability improvers such as an anti-caking agent and organic and / or inorganic fine particles having reverse polarity can be used. These additives can also be used after hydrophobizing the surface.

The measuring method of each physical property value is described below.
<Measurement of molecular weight of polymer>
The molecular weight of the polymer was measured by gel permeation chromatography (GPC) as follows.
First, a measurement sample is dissolved in tetrahydrofuran (THF) at room temperature for 24 hours. Then, the obtained solution is filtered through a solvent-resistant membrane filter “Mysholy disk” (manufactured by Tosoh Corporation) having a pore diameter of 0.2 μm to obtain a sample solution. The sample solution is adjusted so that the concentration of the component soluble in THF is 0.8% by mass. Using this sample solution, measurement is performed under the following conditions.
Apparatus: HLC8120 GPC (detector: RI) (manufactured by Tosoh Corporation)
Column: Seven series of Shodex KF-801, 802, 803, 804, 805, 806, 807 (manufactured by Showa Denko KK)
Eluent: Tetrahydrofuran (THF)
Flow rate: 1.0 ml / min
Oven temperature: 40.0 ° C
Sample injection volume: 0.10 ml
In calculating the molecular weight of the measurement sample, standard polystyrene resin (trade name “TSK Standard Polystyrene F-850, F-450, F-288, F-128, F-80, F-40, F-20, F-10” F-4, F-2, F-1, A-5000, A-2500, A-1000, A-500 "manufactured by Tosoh Corporation) were used.

<Quantification of amount of metal in compound a, polymer P, metal-containing polymer>
The amount of metal in the compound a, the polymer P, and the metal-containing polymer is quantified by fluorescent X-ray. The measurement of fluorescent X-rays conforms to JIS K 0119-1969, and is specifically as follows.
As a measuring device, a wavelength dispersion type fluorescent X-ray analyzer “Axios” (manufactured by PANalytical) and attached dedicated software “SuperQ ver. 4.0F” (manufactured by PANalytical) for setting measurement conditions and analyzing measurement data ) Is used. Rh is used as the anode of the X-ray tube, the measurement atmosphere is vacuum, the measurement diameter (collimator mask diameter) is 27 mm, and the measurement time is 10 seconds. Further, when measuring a light element, it is detected by a proportional counter (PC), and when measuring a heavy element, it is detected by a scintillation counter (SC).
As a measurement sample, 4 g of a sample was put in a dedicated aluminum ring for pressing and leveled, and then tablet compression machine “BRE-32” (manufactured by Maekawa Tester) was used for 60 seconds at 20 MPa. Pressed pellets are used that are molded to a thickness of 2 mm and a diameter of 39 mm.
The measurement is performed under the above conditions, the element is identified based on the obtained X-ray peak position, and the concentration is calculated from the count rate (unit: cps) which is the number of X-ray photons per unit time.
Using this measurement result and a calibration curve prepared in advance for the metal element to be quantified, the metal element is quantified.

<Quantification of amount of metal in toner (ICP-AES)>
The amount of metal in the toner is quantified by a combined induction plasma emission spectroscopic analyzer (ICP-AES (manufactured by SII)). As a pretreatment, acid decomposition is performed on 100.0 mg of each sample using 8.00 ml of nitric acid. Thereafter, ultrapure water was added to a total of 50.00 g to obtain a measurement sample. A calibration curve is created from 6 points of 0, 0.50, 1.00, 5.00, 10.00, and 20.00 ppm, and the amount of metal contained in each sample is quantified. In addition, the ultrapure water was added to 8.0 ml of nitric acid, and what was set to 50.00 g as a whole was measured as a blank, and the metal amount of the blank was deducted.

<Structural analysis of polymers, etc.>
The structures of the polymer and the polymerizable monomer can be determined using a nuclear magnetic resonance apparatus ( ¹ H-NMR, ¹³ C-NMR) and an FT-IR spectrum. The apparatus used in the present invention is described below.
(I) ¹ H-NMR, ¹³ C-NMR
FT-NMR JNM-EX400 manufactured by JEOL (solvent: heavy chloroform)
(Ii) FT-IR spectrum AVATAR360FT-IR manufactured by Nicolet

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

  EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples. In the present example, “part” means “part by mass”.

<Synthesis Example of Compound a-1>
(Process 1)
100 g of 2,5-dihydroxybenzoic acid and 1441 g of 80% sulfuric acid were heated and mixed at 50 ° C. To this dispersion, 144 g of tert-butyl alcohol was added and stirred at 50 ° C. for 30 minutes. Thereafter, 144 g of tert-butyl alcohol was added to this dispersion and stirring was performed for 30 minutes three times. The reaction solution was cooled to room temperature and poured slowly into 1 kg of ice water. The precipitate was filtered, washed with water, and then washed with hexane. This precipitate was dissolved in 200 mL of methanol and reprecipitated in 3.6 L of water. After filtration, it was dried at 80 ° C. to obtain 74.9 g of a salicylic acid intermediate represented by the following formula (26).

(Process 2)
25.0 g of the obtained salicylic acid intermediate was dissolved in 150 mL of methanol, 36.9 g of potassium carbonate was added, and the mixture was heated to 65 ° C. To this reaction solution, a mixed solution of 18.7 g of 4- (chloromethyl) styrene and 100 mL of methanol was added dropwise, and reacted at 65 ° C. for 3 hours. The reaction solution was cooled and then filtered, and the filtrate was concentrated to obtain a crude product. The crude product was dispersed in 1.5 L of water at pH = 2 and extracted by adding ethyl acetate. Thereafter, it was washed with water and dried over magnesium sulfate, and ethyl acetate was distilled off under reduced pressure to obtain a precipitate. The precipitate was washed with hexane and purified by recrystallization from toluene and ethyl acetate to obtain 20.1 g of compound a-1 represented by the following formula (27).

<Synthesis Example of Compound a-2>
A salicylic acid intermediate was obtained in the same manner as in the synthesis of compound a-1 (step 1) except that 144 g of tert-butyl alcohol was changed to 253 g of 2-octanol. A compound a-2 of the following formula (28) was obtained in the same manner as in the synthesis example of the compound a-1 (step 2) except that 32 g of the obtained salicylic acid intermediate was used.

<Synthesis Example of Compound a-3>
Except that the salicylic acid intermediate of the above formula (26) was changed to 18 g of 2,5-dihydroxy-3-methoxybenzoic acid, the same method as in the synthesis example of the compound a-1 (step 2), Compound a-3 was obtained.

<Synthesis Example of Compound a-4>
78.6 g of 2,4-dihydroxybenzoic acid was dissolved in 400 mL of methanol, 152.0 g of potassium carbonate was added, and the mixture was heated to 60 ° C. A solution obtained by mixing and dissolving 87.9 g of 4- (chloromethyl) styrene and 100 ml of methanol was added dropwise to the reaction solution, and reacted at 60 ° C. for 2.5 hours. The resulting reaction solution was cooled, filtered, and washed with methanol.
The obtained precipitate was dispersed in 1 L of water at pH = 1 with hydrochloric acid. Then, it washed with filtered water and dried at 80 degreeC, and obtained 55.7g of compounds a-4 of following formula (30).

<Synthesis Example of Compound a-5>
2,3.9 g of 2,3-dihydroxybenzoic acid was dissolved in 280 mL of methanol, 106 g of K2CO3 was added thereto, and the mixture was stirred at 65 ° C. for 30 minutes. 4-chloromethylstyrene 61.7g was dripped at this in 1 hour. After reacting under reflux for 3 hours, the mixture was allowed to cool to room temperature, and the precipitate was filtered and washed with methanol. Methanol in the filtrate was removed under reduced pressure to obtain a brown semi-solid. This brown semi-solid was dispersed in ethyl acetate and water and adjusted to pH 1 with hydrochloric acid. The ethyl acetate layer was washed with saturated brine, dried over magnesium sulfate, and the solvent was removed under reduced pressure to obtain 124.3 g of a pale yellow solid. This pale yellow solid was recrystallized with toluene to obtain 54.5 g of compound a-5 of the following formula (31).

<Synthesis Example of Compound a-6>
100.0 g of 2,5-dihydroxybenzoic acid was dissolved in 2000 mL of methanol, 88.3 g of potassium carbonate was added, and the mixture was heated to 67 ° C. To this reaction solution, 102.0 g of 4- (chloromethyl) styrene was added dropwise over 22 minutes and reacted at 67 ° C. for 12 hours. After cooling the obtained reaction liquid, methanol was distilled off under reduced pressure, washed with hexane, and filtered. The residue was dissolved in methanol and further dropped into water for reprecipitation, and the precipitate was filtered. This reprecipitation operation was repeated twice, and the residue was dried at 80 ° C. for 48 hours to obtain 48.7 g of compound a-6 of the following formula (32).

<Synthesis Example of Compound a-7>
78.6 g of the salicylic acid intermediate of the above formula (26) was dissolved in 400 mL of methanol, 152.0 g of potassium carbonate was added thereto, and the mixture was stirred at 60 ° C. for 30 minutes. To this, 83.5 g of a mixture of 3- (chloromethyl) methylstyrene and 4- (chloromethyl) styrene (trade name “CMS-P”, manufactured by AGC Seikagaku Co.) dissolved in 50 mL of methanol was added dropwise over 1 hour. . After reacting under reflux for 3 hours, the mixture was allowed to cool to room temperature, and the precipitate was filtered and washed with methanol. The precipitate was added to 1 L of water, adjusted to pH 1 with hydrochloric acid, stirred for 30 minutes, filtered and washed with water. It dried at 80 degreeC for 48 hours, and obtained 76.2g of compounds a-7 of the following formula (33).

<Synthesis Example of Metal Compound M-1>
70.4 g of 20% sodium hydroxide solution was added to 400 mL of water, and then 40.0 g of compound a-1 was added and heated to 90 ° C. To this solution, 60.0 g of a 25.7% aqueous aluminum sulfate solution was added to 340 mL of water, and a solution heated to 90 ° C. was added over 30 minutes, followed by heating and stirring for 2 hours. Then, it filtered, washed with water, and dried at 80 degreeC for 48 hours, and obtained 40.1g of metal compound M-1.
About the obtained metal compound M-1, aluminum was quantified with the fluorescent X ray, and it was confirmed that 5.50 wt% was contained. From the obtained result, it was confirmed that 70.0 mol% of aluminum was contained with respect to compound a-1.

<Synthesis Example of Metal Compound M-2>
A metal compound M-2 was obtained in the same manner as in the synthesis example of the metal compound M-1, except that the compound a-1 was changed to the compound a-2. Table 2 shows the aluminum content in the metal compound M-2.

<Synthesis Example of Metal Compound M-3>
A metal compound M-3 was obtained in the same manner as in the synthesis example of the metal compound M-1, except that the compound a-1 was changed to the compound a-3. Table 2 shows the aluminum content in the metal compound M-3.

<Synthesis Example of Metal Compound M-4>
90.6 g of a 25.7% aluminum sulfate aqueous solution was added to 519 mL of water and heated to 95 ° C. To this solution, 73.7 g of 20% sodium hydroxide solution was added to 500 mL of water, then 50.0 g of compound a-4 was added, the solution heated to 95 ° C. was added over 25 minutes, and the mixture was heated and stirred for 3 hours. Then, it filtered, washed with water, and dried at 80 degreeC for 48 hours, and 57.2g of white metal compound M-4 was obtained. Table 2 shows the aluminum content in the metal compound M-4.

<Synthesis Example of Metal Compound M-5>
A metal compound M-5 was obtained in the same manner as in the synthesis example of the metal compound M-1, except that the compound a-1 was changed to the compound a-5. Table 2 shows the aluminum content in the metal compound M-5.

<Synthesis Example of Metal Compound M-6>
77.2 g of 25.7% aluminum sulfate aqueous solution was added to 440 mL of water and heated to 90 ° C. To this, 16.2 g of 20.5% aqueous sodium hydroxide solution and 10.8 g of compound a-6 were added to 130 mL of water, and the solution was heated to 90 ° C., and the dissolved solution was added dropwise over 30 minutes. The mixture was allowed to react for hours, cooled to room temperature, filtered, and washed with water. After drying at 80 ° C. for 12 hours, 10.5 g of metal compound M-6 was obtained. Table 2 shows the aluminum content in the metal compound M-6.

<Synthesis Example of Metal Compound M-7>
16.21 g of 20.5% sodium hydroxide aqueous solution and 10.81 g of compound a-6 were added to 500 ml of water and heated to 90 ° C. To this, 59.44 g of 26.8% zinc chloride aqueous solution was added dropwise over 30 minutes, heated to 95 ° C., reacted for 2 hours, cooled to room temperature, filtered and washed with water. After drying overnight at 80 ° C., 13.16 g of a white solid was obtained.
Table 2 shows the zinc content determined by fluorescent X-ray with respect to the obtained metal compound M-7.

<Synthesis Example of Metal Compound M-8>
16.21 g of 20.5% sodium hydroxide aqueous solution and 10.81 g of compound a-6 were added to 500 ml of water and heated to 90 ° C. To this, 84.85 g of a 26.8% chromium sulfate aqueous solution was dropped over 30 minutes, heated to 95 ° C., reacted for 2 hours, cooled to room temperature, filtered and washed with water. After drying at 80 ° C. overnight, 12.87 g of a white solid was obtained.
Table 2 shows the chromium content determined by fluorescent X-ray for the obtained metal compound M-8.

<Synthesis Example of Metal Compound M-9>
40.0 g of compound a-1, 400 ml of water and 70.4 g of 20% sodium hydroxide solution were added and heated to 40 ° C. A solution prepared by dissolving 4.67 g of 25.7% aluminum sulfate in 340 mL of water was added to this liquid, and the reaction was stirred at 60 ° C. for 5 hours. After cooling the obtained reaction solution to room temperature, 10% HCl was added so that the pH of the reaction solution was 5.0. Thereafter, the reaction solution was extracted with toluene, and the organic layer was washed with water and concentrated. The obtained concentrate was dispersed with methanol, filtered, and dried at 80 ° C., thereby obtaining 38.1 g of metal compound M-9.
Table 2 shows the aluminum content determined by fluorescent X-ray of the obtained metal compound M-9.

<Synthesis Example of Metal Compound M-10>
70.4 g of 20% sodium hydroxide solution was added to 400 mL of water, and then 40.0 g of compound a-1 was added and heated to 90 ° C. To this solution, 43.0 g of a 25.7% aluminum sulfate aqueous solution was added to 340 mL of water, and a solution heated to 90 ° C. was added over 30 minutes, followed by heating and stirring for 2 hours. Then, it filtered, washed with water, and dried at 80 degreeC for 48 hours, and 37.2g of metal compound M-10 was obtained.
Table 2 shows the aluminum content determined by fluorescent X-ray for the obtained metal compound M-10.

<Synthesis Example of Metal Compound M-11>
A metal compound M-11 was obtained in the same manner as in the synthesis example of the metal compound M-1, except that the compound a-1 was changed to the compound a-7. Table 2 shows the aluminum content in the metal compound M-11.

<Synthesis Example of Polymer B-1>
In a reaction vessel equipped with a stirrer, a condenser, a thermometer, and a nitrogen introduction tube, 200 parts of xylene was charged and refluxed under a nitrogen stream.
-6.0 parts of 2-acrylamido-2-methylpropanesulfonic acid-78.0 parts of styrene-16.0 parts of 2-ethylhexyl acrylate-dimethyl-2,2'-azobis (2-methylpropionate) 5.00 The parts were mixed and added dropwise to the reaction vessel with stirring for 10 hours. Thereafter, distillation was performed to distill off the solvent, followed by drying at 40 ° C. under reduced pressure to obtain a polymer B-1.

<Synthesis example of polymer B-2>
A polymer B-2 was synthesized in the same manner as the polymer B-1, except that the following materials were used, to obtain a polymer B-2.
・ Methyl 2-acrylamido-5-methoxybenzenesulfonate 16.0 parts ・ Styrene 74.0 parts ・ N-butyl acrylate 10.0 parts ・ Dimethyl-2,2′-azobis (2-methylpropionate) 00 copies

<Synthesis example of metal-containing polymer-1>
A reaction vessel equipped with a stirrer, a condenser, a thermometer, and a nitrogen introduction tube was charged with 60.0 parts of toluene and refluxed under a nitrogen stream.
Next, the following raw materials and solvent were mixed to prepare a monomer mixture.
Metal compound M-1 4.00 parts Styrene 96.0 parts Xylene 60.0 parts In addition to this monomer mixture, t-butylperoxyisopropyl monocarbonate (75% hydrocarbon-based as a polymerization initiator) 10.0 parts of solvent diluted product) was mixed and added dropwise to the reaction vessel over 30 minutes. The mixture was stirred at 125 ° C. for 4 hours, and cooled to room temperature after completion of the reaction. The obtained polymer-containing composition was added dropwise to a mixed solution of 1400 parts of methanol and 10 parts of acetone over 10 minutes with stirring to precipitate and crystallize the resin composition. The obtained resin composition was filtered and rinsed twice with 200 parts of methanol. The obtained resin powder was dried at 60 ° C. under reduced pressure for 10 hours to obtain a metal-containing polymer-1.

<Synthesis example of metal-containing polymer-2 to metal-containing polymer-17>
Except for changing the raw material composition, the mixing ratio, and the amount of the polymerization initiator as described in Table 3, in the same manner as in the synthesis example of metal-containing polymer-1, metal-containing polymer-2 to metal-containing polymer- 17 was obtained.
Table 3 shows the metal amount, molecular weight, and reaction conditions during synthesis of the obtained metal-containing polymer-2 to metal-containing polymer-17.

<Synthesis Example of Metal-Containing Polymer-18>
Propylene glycol 90.0 parts, terephthalic acid 104.8 parts, trimellitic acid 5.00 parts, adipic acid 10.0 parts, anhydrous, in a reactor equipped with a condenser, stirrer, thermometer and nitrogen inlet tube 24.0 parts of maleic acid and 2.00 parts of tetrastearyl titanate were added as a condensation catalyst and reacted for 6 hours while distilling off the water produced at 230 ° C. under a nitrogen stream. Subsequently, it was made to react under reduced pressure of 5-20 mmHg for 8 hours, and the unsaturated polyester resin 1 was obtained. This unsaturated polyester resin 1 had an acid value of 36.2 mgKOH / g, a hydroxyl value of 10.1 mgKOH / g, Mw of 14600, and Mw / Mn of 2.2.
Next, 200 parts of toluene and 100 parts of the unsaturated polyester resin 1 were charged into a reaction vessel equipped with a cooling pipe, a stirrer, a thermometer, and a nitrogen introduction pipe, and stirred at 50 ° C. in a nitrogen stream. next,
Metal compound M-1 4.00 parts Styrene 20.0 parts Toluene 50.0 parts To this monomer mixture, t-butylperoxyisopropyl monocarbonate (75% hydrocarbon-based as a polymerization initiator) was further added. 3.50 parts of solvent diluted product) was mixed and added dropwise to the reaction vessel over 30 minutes. The mixture was stirred at 110 ° C. for 3 hours and cooled to room temperature. The obtained polymer-containing composition was added dropwise to a mixed solution of 2800 parts of methanol and 20 parts of acetone over 10 minutes with stirring to precipitate and crystallize the resin composition. The obtained resin composition was filtered and rinsed twice with 300 parts of methanol. The obtained resin powder was dried at 60 ° C. under reduced pressure for 10 hours to obtain a metal-containing polymer-18.
The obtained metal-containing polymer-18 had Mw of 43500 and Mw / Mn of 2.5. Moreover, as a result of quantifying aluminum by fluorescent X-rays, it was confirmed that 1774 ppm was contained. From the obtained results, it was confirmed that the metal-containing polymer-18 contained 65.8 μmol / g of aluminum.

<Synthesis example of metal-containing polymer-19>
9.91 g of compound a-1 and 60.09 g of styrene were dissolved in 42 ml of toluene and stirred for 1 hour. Then, it heated to 110 degreeC under nitrogen stream (50 ml / min). To this solution, a mixed solution of 42 ml of toluene and 4.62 g of tert-butyl peroxyisopropyl monocarbonate (manufactured by NOF Corporation, trade name: Perbutyl I) was added dropwise over 22 minutes. After further reacting at 110 ° C. for 4 hours, the mixture was cooled and dropped into 1000 ml of methanol to obtain a white precipitate. After the reaction solution was filtered, the resulting precipitate was dissolved in 300 ml of tetrahydrofuran. Then, it was dripped at 1500 ml of methanol, the white precipitate was deposited, and it filtered. The obtained residue was dried at 90 ° C. under reduced pressure to obtain 57.56 g of polymer P-1. The weight average molecular weight (Mw) of the obtained polymer P-1 was 16160 and Mw / Mn = 4.1.
To a mixed solution of 180 ml of N, N-dimethylformamide (DMF) and 30 ml of methanol was added 5.21 g of a 20.0% pure sodium hydroxide solution. This sodium hydroxide solution was added dropwise over 40 minutes to a solution in which 30 g of polymer P-1 was dissolved in 90 ml of N, N-dimethylformamide and heated to 65 ° C. 3.14 g of aluminum chloride hexahydrate was dissolved in a mixed solution of 90 ml of N, N-dimethylformamide and 10 ml of water and added dropwise to the solution containing sodium hydroxide at 65 ° C. over 19 minutes. The reaction solution was stirred at 65 ° C. for 15 minutes, filtered at 65 ° C., the residue was washed by shaking with 200 ml of N, N-dimethylformamide twice, dispersed in 1000 ml of water, and stirred for 1 hour. The dispersion was filtered, washed with water until the electrical conductivity of the filtrate reached 114.4 μS / cm, and the residue was dried at 80 ° C. for 12 hours under reduced pressure. 24.03 g of Compound-19 was obtained.
As a result of quantitative determination of aluminum by fluorescent X-ray, it was confirmed that 9600 ppm was contained. From the obtained results, it was confirmed that the metal-containing polymer-19 contained 355.8 μmol / g of aluminum.

<Synthesis example of metal-containing polymer-20>
26.86 g of compound a-1 and 93.14 g of styrene were dissolved in 72 ml of DMF. Thereafter, 7.92 g of tert-butyl peroxyisopropyl monocarbonate (trade name: Perbutyl I, manufactured by NOF Corporation) was added to the solution, and the mixture was stirred at room temperature under a nitrogen stream. This mixed solution was added dropwise to 72 ml of DMF heated to 110 ° C. under a nitrogen stream in 27 minutes. After further reacting at 110 ° C. for 4 hours, the mixture was cooled and added dropwise to 800 ml of methanol to precipitate a rubbery light yellow product. After removing the supernatant by decantation, the product was dissolved in 300 ml of tetrahydrofuran, and a solid was precipitated using 4000 ml of methanol, filtered, and dried at 80 ° C. under reduced pressure for 16 hours to obtain 96.50 g of polymer P-2. It was. The weight average molecular weight (Mw) of the obtained polymer P-2 was 12413, and Mw / Mn = 2.5.
35.0 g of polymer P-2 was dissolved in 105 ml of DMF. 11.6 g of 20% aqueous sodium hydroxide solution was added to a mixed solution of 105 ml of DMF and 35 ml of methanol, added to the polymer P-2 solution over 28 minutes, heated to 65 ° C., and 105 ml of DMF was added. A solution obtained by adding 7.0 g of aluminum chloride hexahydrate to a mixed solvent of 12 ml of water and 105 ml of DMF was added to this liquid over 10 minutes, and the mixture was heated and stirred at 65 ° C. for 15 minutes. Thereafter, the mixture was filtered, washed with water until the electric conductivity of the filtrate reached 300 μS / cm or less, and dried at 80 ° C. for 24 hours to obtain 30.3 g of metal-containing polymer-20.
As a result of quantifying aluminum by fluorescent X-ray, it is confirmed that 22,000 ppm is contained. From the obtained results, it was confirmed that 815.4 μmol / g of aluminum was contained in the metal-containing polymer-20.

<Synthesis example of metal-containing polymer-21>
8.41 g of compound a-6 and 61.60 g of styrene were dispersed in 42 ml of DMF and heated to 110 ° C. under a nitrogen stream. A mixed solution of 42 ml of DMF and 4.62 g of tert-butyl peroxyisopropyl monocarbonate (manufactured by NOF Corporation, trade name: Perbutyl I) was dropped into the obtained solution over 24 minutes. The reaction was further carried out at 110 ° C. for 4 hours, and then cooled. The obtained reaction solution was added to 300 ml of tetrahydrofuran to prepare a solution. To the resulting solution, 3500 ml of methanol was added to precipitate a solid and filtered. The residue was washed twice with 200 ml of methanol and dried under reduced pressure at 90 ° C. for 30 hours to obtain 59.19 g of polymer P-3. The weight average molecular weight (Mw) of the obtained polymer P-3 was 48190, Mw / Mn = 4.8.
To a mixed solution of 180 ml of N, N-dimethylformamide and 30 ml of methanol, 5.34 g of 20.0% pure sodium hydroxide solution was added. This sodium hydroxide solution was added dropwise to a solution obtained by dissolving 30 g of polymer P-3 in 90 ml of N, N-dimethylformamide over 26 minutes and heated to 65 ° C. 3.22 g of aluminum chloride hexahydrate was dissolved in a mixed solution of 90 ml of N, N-dimethylformamide and 10 ml of water and added dropwise to the solution containing sodium hydroxide at 65 ° C. over 18 minutes. The reaction solution was stirred at 65 ° C. for 15 minutes, filtered at 65 ° C., the residue was washed by shaking with 200 ml of N, N-dimethylformamide twice, dispersed in 1000 ml of water, and stirred for 1 hour. The dispersion was filtered, washed with water until the electrical conductivity of the filtrate reached 118.4 μS / cm, washed, and then the residue was dried at 80 ° C. under reduced pressure for 12 hours to obtain 15.1 of the metal-containing polymer-21. 55 g was obtained. As a result of quantifying aluminum by fluorescent X-ray, it was confirmed that 12600 ppm was contained. From the obtained results, it was confirmed that the metal-containing polymer-21 contained 467.0 μmol / g of aluminum.

<Synthesis Example of Metal-Containing Polymer-22>
9.9 g of compound a-1, 64.3 g of styrene, and 8.3 g of n-butyl acrylate were dissolved in 42 ml of toluene and stirred for 1 hour. Then, it heated to 110 degreeC under nitrogen stream (50 ml / min). To this solution, a mixed solution of 42 ml of toluene and 4.62 g of tert-butyl peroxyisopropyl monocarbonate (manufactured by NOF Corporation, trade name: Perbutyl I) was added dropwise over 22 minutes. After further reacting at 110 ° C. for 4 hours, the mixture was cooled and dropped into 1000 ml of methanol to obtain a white precipitate. After the reaction solution was filtered, the resulting precipitate was dissolved in 300 ml of tetrahydrofuran. Then, it was dripped at 1500 ml of methanol, the white precipitate was deposited, and it filtered. The obtained residue was dried at 90 ° C. under reduced pressure to obtain 58.73 g of polymer P-4. The obtained polymer P-4 had a weight average molecular weight (Mw) of 18710 and Mw / Mn = 3.5.
To a mixed solution of 180 ml of N, N-dimethylformamide and 30 ml of methanol was added 5.21 g of 20.0% pure sodium hydroxide solution. This sodium hydroxide solution was added dropwise to a solution obtained by dissolving 30 g of polymer P-4 in 90 ml of N, N-dimethylformamide over 40 minutes, and heated to 65 ° C. 3.14 g of aluminum chloride hexahydrate was dissolved in a mixed solution of 90 ml of N, N-dimethylformamide and 10 ml of water and added dropwise to the solution containing sodium hydroxide at 65 ° C. over 19 minutes. The reaction solution was stirred at 65 ° C. for 15 minutes, filtered at 65 ° C., the residue was washed by shaking with 200 ml of N, N-dimethylformamide twice, dispersed in 1000 ml of water, and stirred for 1 hour. The dispersion was filtered, washed by sprinkling with water until the electrical conductivity of the filtrate reached 120.3 μS / cm, and the residue was dried at 80 ° C. under reduced pressure for 12 hours to obtain the metal-containing polymer-22. 34 g was obtained. As a result of quantifying aluminum by fluorescent X-ray, it was confirmed that 8900 ppm was contained. From the obtained results, it was confirmed that the metal-containing polymer-22 contained 355.8 μmol / g of aluminum.

<Synthesis Example of Comparative Polymer>
The salicylic acid monomer represented by the following formula (34) was produced using the method described in JP-A 63-270060, Journal of Polymer Science: Polymer Chemistry Edition 18, 2755 (1980).

To a reaction vessel equipped with a stirrer, a condenser, a thermometer, and a nitrogen introduction tube, 60.00 parts of toluene was charged and refluxed under a nitrogen stream.
Next, the following monomers and solvent were mixed to prepare a monomer mixture.
<Monomer composition, mixing ratio>
-Salicylic acid monomer of formula (34) 5.00 parts-Styrene 95.0 parts-Toluene 60.0 parts To this monomer mixture, t-butylperoxyisopropyl monocarbonate (75 % Hydrocarbon solvent diluted product) was mixed and added dropwise to the reaction vessel over 30 minutes. The mixture was stirred at 110 ° C. for 4 hours, and cooled to room temperature after completion of the reaction. The obtained polymer-containing composition was added dropwise to a mixed solution of 1400 parts of methanol and 10 parts of acetone over 10 minutes with stirring to precipitate and crystallize the resin composition. The obtained resin composition was filtered and rinsed twice with 200 parts of methanol. The obtained resin powder was dried at 60 ° C. under reduced pressure for 10 hours to obtain a comparative polymer. Mw of the obtained comparative polymer was 12500 and Mw / Mn was 2.2. As a result of measuring fluorescent X-rays, it was confirmed that no metal was contained.

<Example 1>
Preparation of pigment dispersion paste:
-Styrene 58.5 parts-C.I. I. Pigment Blue 15: 3 9.75 parts / Metal-containing polymer-1 3.00 parts After the above material was well premixed in a container, the mixture was dispersed in a bead mill for 10 hours while maintaining the temperature at 20 ° C. or lower to disperse the pigment. A paste was prepared.

Preparation of toner particles:
350 parts of a 0.1 mol / l-Na ₃ PO ₄ aqueous solution was added to 1200 parts of ion-exchanged water, heated to 60 ° C., and then stirred at 11,000 rpm using CLEARMIX (manufactured by M Technique). did. To this, 52.0 parts of a 1.00 mol / l-CaCl ₂ aqueous solution was added to obtain a dispersion medium containing Ca ₃ (PO ₄ ) ₂ .
- the pigment dispersed paste 47.5 parts Styrene 31.0 parts n-Butyl acrylate 30.0 parts Ester wax 5.00 parts (main component _{C 19 H 39 COOC 20 H 41} , the peak of the maximum endothermic peak temperature 68 .6 ° C)
Saturated polyester resin 10.0 parts (terephthalic acid-propylene oxide modified bisphenol A copolymer, acid value 10.0 mgKOH / g, Mw 16000)
These are heated to 60 ° C. and stirred for 30 minutes to form a monomer mixture. Further, while maintaining at 60 ° C., 10.0 parts of 2,2′-azobis (2,4-dimethylvaleronitrile) as a polymerization initiator was added and dissolved to prepare a polymerizable monomer composition.
The polymerizable monomer composition was charged into the dispersion medium. At 60 ° C., a nitrogen atmosphere was used, and the mixture was stirred for 30 minutes at 10,000 rpm using CLEARMIX to granulate droplets of the polymerizable monomer composition. Thereafter, the mixture was reacted at 75 ° C. for 5 hours while stirring with a paddle stirring blade to complete the polymerization of the polymerizable monomer in the polymerizable monomer composition. After cooling to room temperature, hydrochloric acid was added to dissolve Ca ₃ (PO ₄ ) ₂ on the particle surface, filtered, washed with water, dried, and further classified to obtain toner particles 1.

Toner preparation:
To 100 parts of the obtained toner particles 1, 1.0 part of hydrophobic silica fine powder was mixed and externally added with a Henschel mixer (Mitsui Miike Chemical Co., Ltd.) to obtain toner 1. The hydrophobic silica fine powder has a number average particle diameter of 9 nm and a BET specific surface area of 180 m ² / g of primary particles obtained by treating the surface of the silica fine powder with hexamethyldisilazane and then further treating with silicone oil. belongs to.
Table 4 shows the physical properties of the toner thus obtained. The toner was evaluated as follows, and the results are shown in Table 5. The amount of metal in the toner described in Table 4 is a value calculated from the amount of metal in the polymer used at the time of toner production.

<Evaluation of toner charge amount>
A two-component developer was prepared as follows.
In order to evaluate the charge amount, sample adjustment was performed as follows. 288 g of magnetic carrier F813-300 (manufactured by Powdertech) and 12 g of evaluation toner are put into a 500 cc plastic bottle with a lid, and a reciprocating speed of 4 reciprocations per second with a shaker (YS-LD: Yayoi Co., Ltd.). The mixture was shaken for 1 minute to obtain a two-component developer.

<Evaluation of toner charge amount under high temperature and high humidity>
To measure the amount of charge, 30 g of the above two-component developer is taken, left in a high-temperature and high-humidity environment (30 ° C./80%) for 3 days, and then placed in a 50 cc plastic container and 500 times at a rate of 200 times / minute. Shake and measure using the apparatus of FIG. In the evaluation, the absolute value of the measured charge amount was judged according to the following criteria.
A rank: 60.0 mC / kg or more B rank: 45.0 or more and less than 60.0 mC / kg C rank: 30.0 or more and less than 45.0 mC / kg D rank: 15.0 or more and less than 30.0 mC / kg E rank : Less than 15.0mC / kg

(Measurement method of charge amount)
In a metal measuring container 2 having a screen 3 having a 500 mesh (aperture 25 μm) screen at the bottom shown in FIG. 1, 0.5 g of a two-component developer to be measured for triboelectric charge is placed and a metal lid 4 is placed. The total mass of the measurement container 2 at this time is weighed and is defined as Wl (g). Next, in the suction device 1 (at least the portion in contact with the measurement container 2) is suctioned from the suction port 7 and the air volume control valve 6 is adjusted to set the pressure of the vacuum gauge 5 to 250 mmAq. In this state, suction is performed for 2 minutes to remove the toner by suction.
The potential of the electrometer 9 at this time is set to V (volt). Here, 8 is a capacitor, and the capacity is C (μF). The mass of the entire measurement container after the suction is weighed and is defined as W2 (g). The triboelectric charge amount (mC / kg) of the toner is calculated as follows.
Frictional charge (mC / kg) = (C × V) / (W1-W2)

<Environmental evaluation of toner charge amount>
The toner charge amount is measured in the same manner as described in the above-mentioned evaluation of toner charge amount under high temperature and high humidity except that the two-component developer is left in a low temperature and low humidity environment (15 ° C / 10%). It was. In the evaluation, the absolute value of the ratio of the charge amount at low temperature and low humidity and high temperature and high humidity (charge amount under low temperature and low humidity / charge amount under high temperature and high humidity) is calculated and determined according to the following criteria.
A rank: less than 1.30 B rank: 1.30 or more and less than 1.50 C rank: 1.50 or more and less than 2.00 D rank: 2.00 or more

<Evaluation of rising property of toner charge amount>
A two-component developer was prepared as follows.
270 g of magnetic carrier F813-300 (manufactured by Powder Tech) and 30 g of evaluation toner are put into a 500 cc plastic bottle with a lid, and are shaken at a speed of 200 times / min with a shaker (YS-LD: Yayoi Co., Ltd.). Shake for 1 minute. 300 g of the obtained two-component developer is left to stand for 3 days in a high temperature and high humidity environment (30 ° C./80% RH). This was charged into a developing device of a color laser copying machine CLC5500 (manufactured by Canon Inc.), and idly rotated at 240 rpm using a rotating machine equipped with an external motor. The two-component developer on the developing sleeve was sampled when rotated for 2 minutes (Q2 min) and further rotated for 3 minutes (Q5 min), and the charge amount was measured with the apparatus of FIG. In the evaluation, (Q5min / Q2min) was calculated and judged according to the following standard.
A rank: less than 1.20 B rank: 1.20 or more and less than 1.40 C rank: 1.40 or more and less than 1.60 D rank: 1.60 or more

<Evaluation of pigment dispersibility>
In order to evaluate the pigment dispersibility of the obtained toner, a toner dispersed in a water-soluble resin was placed in a cryomicrotome (ULRACUT N FC4E manufactured by Reichert). The apparatus was cooled to −80 ° C. with liquid nitrogen, and the water-soluble resin in which the toner was dispersed was frozen. The frozen water-soluble resin was trimmed with a glass knife so that the cutting surface shape was about 0.1 mm wide and about 0.2 mm long. Next, an ultra-thin section (thickness setting: 70 nm) of toner containing a water-soluble resin was prepared using a diamond knife, and moved onto a TEM observation grid mesh using an eyelash probe. After returning the ultra-thin section of the toner containing the water-soluble resin to room temperature, the water-soluble resin was dissolved in pure water to prepare an observation sample for a transmission electron microscope (TEM). The sample was observed using a transmission electron microscope H-7500 (manufactured by Hitachi, Ltd.) at an acceleration voltage of 100 kV, and an enlarged photograph of the cross section of the toner particles (magnification is 5000 to 10,000 times) was taken. Toner particles having a cross-sectional particle size in the range of weight average particle size (D ₄ ) ± 1 μm were selected. As the evaluation criteria, although the criteria differ depending on the pigment, the pigment is ranked as the following criteria by observing whether the pigment is dispersed as the primary particle size, whether the pigment is segregated or protrudes to the toner surface layer.
Rank A: The pigment is dispersed in the primary particle size and uniformly present throughout the toner. Rank B: A portion where the pigment is agglomerated is present and unevenly present. Rank C: The pigment is agglomerated and the toner surface Many protruding pigments are observed

<Evaluation of halftone reproducibility>
For the evaluation, the above-described two-component developer and color laser copying machine CLC5500 (manufactured by Canon Inc.) were used. A fixed image was formed on paper (color laser copier paper TKCLA4, manufactured by Canon) by changing the loading amount in seven stages. Toner amount ^{is, 0.10mg / cm 2, 0.20mg /} cm 2, 0.30mg / cm 2, 0.40mg / cm 2, 0.50mg / cm 2, 0.60mg / cm 2, 0.70mg / Cm ² .
(Evaluation of color toner)
For each color toner fixed image, CIE a ^* and b ^* were measured using a Spectroscan manufactured by Gretag Macbeth (measurement condition: D65, viewing angle 2 °). The chromaticity against the loading amount in seven stages was plotted, and a curve connecting each point smoothly was drawn to obtain the relationship between c * and L *. From this relationship, the value of c ^* at L * = 70 and the value of L * at c * = 50 were determined. The value of c * was determined by c * = ((a *) ² + (b *) ² ) ^1/2 .
Rank A: The value of c ^* when L * = 70 is 35.0 or more, and the value of L * when c * = 50 is 65.0 or more. (Image saturation is excellent)
Rank B: The value of c ^* when L * = 70 is 30.0 or more, and the value of L * when c * = 50 is 60.0 or more. (Color reproducibility is narrow but good image)
Rank C: The value of c ^* when L * = 70 is less than 30.0, or L * = less than 60.0 when c * = 50. (Inferior color reproducibility)

(Evaluation of black toner)
As described above, a fixed image similar to the color toner was produced. The image density of each black toner fixed image was measured with a Macbeth reflection densitometer (manufactured by Macbeth).
(Evaluation criteria for black toner)
The difference in image density in toner amount 0.30 mg / cm ² and 0.40 mg / cm ² and (D0.4-D0.3), by the ratio of the image density (D0.7) in toner amount 0.7 mg / cm ² Evaluation was performed as follows.
Rank A: [(D0.4−D0.3) / (D0.7)] <1.10
B rank: 1.10 ≦ [(D0.4−D0.3) / (D0.7)] <1.25
C rank: 1.25 ≦ [(D0.4−D0.3) / (D0.7)]

<Examples 2 to 8>
Toners 2 to 8 were obtained in the same manner as in Example 1 except that the metal-containing polymer-1 was changed to metal-containing polymer-2 to metal-containing polymer-8. Table 4 shows the physical properties of the toner thus obtained. The obtained toner was evaluated in the same manner as in Example 1. The results are shown in Table 5.

<Example 9>
The material used for the preparation of the pigment dispersion paste of Example 1 was changed to the following, and the toner was changed in the same manner as in Example 1 except that the pigment dispersion paste used for the preparation of the monomer mixture was changed to 53.5 parts. The toner 9 was produced. Table 4 shows the physical properties of Toner 9 thus obtained. The evaluation of toner 9 was performed in the same manner as in Example 1, and the results are shown in Table 5.
-Styrene 58.5 parts-C.I. I. Pigment Blue 15: 3 9.75 parts, metal-containing polymer-8 12.0 parts

<Example 10>
The material used for the preparation of the pigment dispersion paste of Example 1 was changed to the following, and the toner was changed in the same manner as in Example 1 except that the pigment dispersion paste used for the preparation of the monomer mixture was changed to 46.0 parts. The toner 10 was produced. Table 4 shows the physical properties of Toner 10 thus obtained. The evaluation of the toner 10 was performed in the same manner as in Example 1, and the results are shown in Table 5.
-Styrene 58.5 parts-C.I. I. Pigment Blue 15: 3 9.75 parts, metal-containing polymer-1 0.75 part

<Example 11>
Toner 11 was obtained in the same manner as in Example 1 except that metal-containing polymer-1 was changed to metal-containing polymer-12. Table 4 shows the physical properties of Toner 11 thus obtained. Further, evaluation of the toner 11 was performed in the same manner as in Example 1, and the result is shown in Table 5.

<Example 12>
The material used for the preparation of the pigment dispersion paste of Example 1 was changed to the following, and the toner was changed in the same manner as in Example 1 except that the pigment dispersion paste used for the preparation of the monomer mixture was changed to 48.5 parts. The toner 12 was produced. Table 4 shows the physical properties of Toner 12 thus obtained. In addition, evaluation of the toner 12 was performed in the same manner as in Example 1, and the results are shown in Table 5.
-Styrene 58.5 parts-C.I. I. Pigment Blue 15: 3 9.75 parts, metal-containing polymer-1 3.00 parts, polymer B-1 1.50 parts

<Example 13>
A toner was prepared in the same manner as in Example 12 except that the polymer B-1 was changed to the polymer B-2, and a toner 13 was obtained. Table 4 shows the physical properties of Toner 13 thus obtained. The evaluation of the toner 13 was performed in the same manner as in Example 1, and the results are shown in Table 5.

<Example 14>
Toner 14 was obtained in the same manner as in Example 1 except that metal-containing polymer-1 was changed to metal-containing polymer-9. Table 4 shows the physical properties of Toner 14 thus obtained. The evaluation of the toner 14 was performed in the same manner as in Example 1, and the results are shown in Table 5.

<Example 15>
Toner 15 was obtained in the same manner as in Example 1 except that metal-containing polymer-1 was changed to metal-containing polymer-10. Table 4 shows the physical properties of Toner 15 thus obtained. Further, evaluation of the toner 15 was performed in the same manner as in Example 1, and the results are shown in Table 5.

<Example 16>
Toner 16 was obtained in the same manner as in Example 1 except that metal-containing polymer-1 was changed to metal-containing polymer-11. Table 4 shows the physical properties of Toner 16 thus obtained. The evaluation of the toner 16 was performed in the same manner as in Example 1, and the results are shown in Table 5.

<Example 17>
Toner 17 was obtained in the same manner as in Example 1 except that metal-containing polymer-1 was changed to metal-containing polymer-13. Table 4 shows the physical properties of Toner 17 thus obtained. In addition, evaluation of the toner 17 was performed in the same manner as in Example 1, and the results are shown in Table 5.

<Example 18>
Toner 18 was obtained in the same manner as in Example 1 except that metal-containing polymer-1 was changed to metal-containing polymer-14. Table 4 shows the physical properties of Toner 18 thus obtained. The evaluation of the toner 18 was performed in the same manner as in Example 1, and the results are shown in Table 5.

<Example 19>
Toner 19 was obtained in the same manner as in Example 1 except that the material used for preparing the pigment dispersion paste of Example 1 was changed as follows. Table 4 shows the physical properties of Toner 19 obtained. In addition, evaluation of the toner 19 was performed in the same manner as in Example 1, and the results are shown in Table 5.
・ Styrene 58.5 parts ・ Quinacridone (Pigment violet 19) 9.75 parts ・ Metal-containing polymer-1 3.00 parts

<Example 20>
The material used for the preparation of the pigment dispersion paste of Example 1 was changed to the following, and the toner was changed in the same manner as in Example 1 except that the pigment dispersion paste used for the preparation of the monomer mixture was changed to 48.5 parts. The toner 20 was obtained. Table 4 shows the physical properties of Toner 20 thus obtained. Further, evaluation of the toner 20 was performed in the same manner as in Example 1, and the results are shown in Table 5.
・ Styrene 58.5 parts ・ Carbon black 11.3 parts ・ Metal-containing polymer-1 3.00 parts

<Example 21>
Preparation of polyester resin:
-Bisphenol A-Propylene oxide 2.2 mol adduct 1200 parts-Bisphenol A-Ethylene oxide 2.2 mol adduct 475 parts-Terephthalic acid 249 parts-Trimellitic anhydride 192 parts-Fumaric acid 290 parts-Dibutyltin oxide 0 100 parts were placed in a 4-liter 4-neck flask made of glass, and a thermometer, a stir bar, a condenser, and a nitrogen inlet tube were attached and placed in a mantle heater. Under a nitrogen atmosphere, reaction was carried out at 220 ° C. for 5 hours to obtain a polyester resin. next,
Polyester resin 100 parts Metal-containing polymer-9 5.00 parts C.I. I. Pigment Blue 15: 3 5.00 parts, paraffin wax (HNP-7: manufactured by Nippon Seiki Co., Ltd.) 3.00 parts After sufficiently premixing the toner material with a Henschel mixer (Mitsui Miike Chemical Co., Ltd.), After melt-kneading with a twin-screw extruder, cooling, and coarsely pulverized to a particle size of about 1 to 2 mm using a hammer mill, then finely pulverized with an air jet type pulverizer. Were classified with a multi-division classifier to obtain toner particles.
Toner was produced from the obtained toner particles in the same manner as in Example 1, and toner 21 was obtained.
Table 4 shows the physical properties of the toner thus obtained. The obtained toner was evaluated in the same manner as in Example 1. The results are shown in Table 5.

<Example 22>
Toner 22 was obtained in the same manner as in Example 21 except that the toner material was changed as follows. Table 4 shows the physical properties of Toner 22 thus obtained. Further, evaluation of the toner 22 was performed in the same manner as in Example 1, and the results are shown in Table 5.
-Polyester resin 25.0 parts-Metal-containing polymer-9 75.0 parts-C.I. I. Pigment Blue 15: 3 5.00 parts, paraffin wax (HNP-7: manufactured by Nippon Seiki Co., Ltd.) 3.00 parts

<Example 23>
Toner 23 was obtained in the same manner as in Example 21 except that the toner material was changed as follows. Table 4 shows the physical properties of Toner 23 thus obtained. Further, evaluation of the toner 23 was performed in the same manner as in Example 1, and the results are shown in Table 5.
-Polyester resin 10.0 parts-Metal-containing polymer-9 100 parts-C.I. I. Pigment Blue 15: 3 5.00 parts, paraffin wax (HNP-7: manufactured by Nippon Seiki Co., Ltd.) 3.00 parts

<Example 24>
Toner 24 was obtained in the same manner as in Example 1 except that metal-containing polymer-1 was changed to metal-containing polymer-18. Table 4 shows the physical properties of Toner 24 thus obtained. The evaluation of the toner 24 was performed in the same manner as in Example 1, and the results are shown in Table 5.

<Examples 25 to 27>
Toners 25 to 27 were obtained in the same manner as in Example 1 except that the metal-containing polymer-1 was changed to metal-containing polymer-15 to metal-containing polymer-17. Table 4 shows the physical properties of Toner 25 to 27 obtained. Further, evaluation of toners 25 to 27 was performed in the same manner as in Example 1, and the results are shown in Table 5.

<Examples 28 to 30>
A toner was prepared in the same manner as in Example 1 except that the metal-containing polymer-1 was changed to a metal-containing polymer-19 to a metal-containing polymer-21 to obtain toner 28-30. Table 4 shows the physical properties of Toner 28 to 30 obtained. Further, evaluation of the toners 28 to 30 was performed in the same manner as in Example 1, and the results are shown in Table 5.

<Example 31>
Toner 31 was obtained in the same manner as in Example 21 except that the toner material was changed as follows. Table 4 shows the physical properties of Toner 31 thus obtained. The evaluation of the toner 31 was performed in the same manner as in Example 1, and the results are shown in Table 5.
-Polyester resin 50.0 parts-Metal-containing polymer-22 50.0 parts-C.I. I. Pigment Blue 15: 3 5.00 parts, paraffin wax (HNP-7: manufactured by Nippon Seiki Co., Ltd.) 3.00 parts

<Example 32>
Preparation of toner composition mixture:
Copolymerized polyester resin of bisphenol A propylene oxide 2 mol adduct / bisphenol A ethylene oxide 2 mol adduct / terephthalic acid derivative (1/1/2 [molar ratio]) (Tg 62 ° C., softening point 102 ° C., Mw 21000) 100 Part ・ C. I. Pigment Blue 15: 3 5.00 parts, paraffin wax (melting point 72.3 ° C) 10.0 parts, metal-containing polymer-18 4.00 parts, ethyl acetate 100 parts After the above materials are well premixed in a container This was dispersed for 6 hours with a bead mill while maintaining the temperature at 20 ° C. or lower to prepare a toner composition mixed solution.
Preparation of toner particles:
70.0 parts of 0.100 mol / liter-Na ₃ PO ₄ aqueous solution was put into 240 parts of ion-exchanged water, heated to 60 ° C., and then used at 14,000 rpm using Creamix (manufactured by M Technique). Stir. To this, 12 parts of a 1.00 mol / liter-CaCl ₂ aqueous solution was added to obtain a dispersion medium containing Ca ₃ (PO ₄ ) ₂ . Furthermore, 1.00 part of carboxymethyl cellulose (trade name: Serogen BS-H, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) was added and stirred for 10 minutes.
While the dispersion medium to which carboxymethylcellulose was added was adjusted to 30 ° C. and stirred, 180 parts of the toner composition mixed solution adjusted to 30 ° C. was added, stirred for 1 minute, then stopped to disperse the toner composition A suspension was obtained. The obtained toner composition dispersion suspension is stirred at a constant temperature of 40 ° C., and the gas phase on the surface of the suspension is forcibly renewed by an exhaust device, and is kept for 17 hours to remove the solvent. After cooling to room temperature, hydrochloric acid was added to dissolve Ca ₃ (PO ₄ ) ₂ and filtered, washed with water, dried and classified to obtain toner particles. A toner was prepared from the obtained toner particles in the same manner as in Example 1, and a toner 32 was obtained.
Table 4 shows the physical properties of Toner 32 thus obtained. The obtained toner was evaluated in the same manner as in Example 1. The results are shown in Table 5.

<Comparative Example 1>
A toner was prepared in the same manner as in Example 1 except that the metal-containing polymer-1 was changed to a comparative polymer, and a toner 33 was obtained. Table 4 shows the physical properties of Toner 33 thus obtained. The evaluation of the toner 33 was performed in the same manner as in Example 1, and the results are shown in Table 5.

<Comparative example 2>
Toner 34 was obtained in the same manner as in Example 1 except that the material used for preparing the pigment dispersion paste of Example 1 was changed to the following. Table 4 shows the physical properties of Toner 34 thus obtained. The evaluation of the toner 34 was performed in the same manner as in Example 1, and the results are shown in Table 5.
・ Styrene 58.5 parts ・ Quinacridone (Pigment violet 19) 9.75 parts ・ Comparative polymer 3.00 parts

<Comparative Example 3>
The material used for the preparation of the pigment dispersion paste of Example 1 was changed to the following, and the toner was changed in the same manner as in Example 1 except that the pigment dispersion paste used for the preparation of the monomer mixture was changed to 48.5 parts. The toner 35 was produced. Table 4 shows the physical properties of Toner 35 thus obtained. The evaluation of the toner 35 was performed in the same manner as in Example 1, and the results are shown in Table 5.
・ Styrene 58.5 parts ・ Carbon black 11.3 parts ・ Comparative polymer 3.00 parts

<Comparative Example 4>
Toner 36 was obtained in the same manner as in Example 1 except that the material used for preparing the pigment dispersion paste of Example 1 was changed to the following. Table 4 shows the physical properties of Toner 36 thus obtained. The evaluation of the toner 36 was performed in the same manner as in Example 1, and the results are shown in Table 5.
-Styrene 58.5 parts-C.I. I. Pigment Blue 15: 3 9.75 parts, Polymer B-1 3.00 parts

<Comparative Example 5>
The toner was prepared in the same manner as in Example 1 except that the material used for preparing the pigment dispersion paste of Example 1 was changed to the following, and that the pigment dispersion paste used for preparing the monomer mixture was changed to 45.5 parts. Thus, toner 37 was obtained. Table 4 shows the physical properties of Toner 37 thus obtained. The evaluation of the toner 37 was performed in the same manner as in Example 1, and the results are shown in Table 5.
-Styrene 58.5 parts-C.I. I. Pigment Blue 15: 3 9.75 parts

1 suction machine, 2 measuring container, 3 screen, 4 lid, 5 vacuum gauge, 6 air volume control valve, 7 suction port, 8 condenser, 9 electrometer

Claims (9)

A toner having toner particles containing a metal-containing polymer, a colorant and a binder resin,
The metal-containing polymer has an aromatic compound part to which a metal is bonded, and a polymer part,
The aromatic compound portion to which the metal is bonded is bonded to the metal at a site derived from -COOM ¹ and / or -OH of the salicylic acid structure portion or salicylic acid derivative structure portion of the partial structure represented by the following formula (1). A toner having the structure described above.

(In the formula (1), R ¹ represents a hydroxyl group, a carboxyl group, an alkyl group having 1 to 18 carbon atoms, or an alkoxy group having 1 to 18 carbon atoms, and R ² represents a hydroxyl group, carbon An alkyl group having 1 to 18 carbon atoms, or an alkoxy group having 1 to 18 carbon atoms, M ¹ represents a hydrogen atom, an alkali metal, —NH ₄ , or a mixture thereof, and a is 0 to 3 B represents an integer of 1 to 3, and c represents an integer of 0 to 4. When a is 2 or 3, R ¹ is independently selected, and c is 2. In the case of 3 or 4, each R ² is independently selected, and is connected to the polymer part at * part.)   The toner according to claim 1, wherein the polymer part is a vinyl polymer.   The toner according to claim 1, wherein the metal contained in the metal-containing polymer is Zn, Al, Si, B, Fe, Cr, or Zr.   The toner according to any one of claims 1 to 3, wherein the metal contained in the metal-containing polymer is Zn, Al, or Cr.   5. The toner according to claim 1, wherein the metal contained in the metal-containing polymer is contained in an amount of 1.0 μmol to 100 μmol per 1 g of the toner.   The toner according to any one of claims 1 to 5, wherein the metal contained in the metal-containing polymer is contained in an amount of 10.0 µmol or more and 1500 µmol or less per 1 g of the metal-containing polymer. The metal-containing polymer is
(I) reacting a compound having a structure represented by the following formula (2) with a metal to obtain a metal compound;
(Ii) a step of obtaining the metal-containing polymer by polymerizing a vinyl group in the metal compound;
The toner according to claim 2, wherein the toner is obtained by passing through the toner.

(In the formula (2), R ¹ , R ² , M ¹ , a, b and c have the same meanings as the formula (1). R ³ represents a hydrogen atom or a methyl group.) The metal-containing polymer is
(I) a step of obtaining a polymer P by polymerizing a vinyl group in a compound having a structure represented by the following formula (2);
(Ii) reacting the polymer P with a metal to obtain the metal-containing polymer;
The toner according to claim 2, wherein the toner is obtained by passing through the toner.

(In the formula (2), R ¹ , R ² , M ¹ , a, b and c have the same meanings as the formula (1). R ³ represents a hydrogen atom or a methyl group.)   The toner particles are granulated in an aqueous medium containing a polymerizable monomer, the colorant and the metal-containing polymer, and are contained in the polymerizable monomer composition. The toner according to claim 1, wherein the toner is obtained by polymerizing the polymerizable monomer.

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