JP2016130806A - Toner for electrostatic charge image development - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a toner for electrostatic charge image development that has low-temperature fixability, and is excellent in long-term stability and color reproducibility.SOLUTION: There is provided a toner for electrostatic charge image development that contains a binder resin including at least a crystalline polyester resin, and a compound obtained by reacting a colorant and a metal-containing compound, where the crystalline polyester resin is contained in an amount of 5 to 35 mass% with respect to a resin component forming the binder resin.SELECTED DRAWING: None

Description

  The present invention relates to a toner for developing an electrostatic image.

  In the field of electrostatic image developing toner, development of a low-temperature fixing toner is actively promoted from the viewpoint of energy saving. In addition, due to the recent progress in digital technology, the use of electrophotography has expanded to the light printing field, ensuring a wider color reproduction area, such as Japan Color certification, and stable color reproduction even when printing multiple sheets continuously. As such, there is an increasing market demand for color reproducibility.

  In recent years, a toner containing a crystalline compound such as crystalline polyester has been developed as a fixing aid in order to realize low-temperature fixing (Patent Documents 1 to 3).

JP 2002-351137 A JP 2006-78707 A JP 2013-83979 A

  However, crystalline polyester has low charge retention. For this reason, the toner using crystalline polyester has a problem that the charge amount is low and color reproducibility due to a change in fixing temperature during continuous printing is lowered. Further, there is a problem that the charge amount decreases with use, and there is a problem in durability stability.

  The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a toner for developing an electrostatic image having low-temperature fixability and excellent durability stability and color reproducibility.

  As a result of intensive studies to solve the above problems, the present inventors have found that a compound obtained by reacting a specific colorant and a specific metal-containing compound is present in the toner together with the crystalline polyester resin, thereby reducing the temperature. It was confirmed that an electrostatic image developing toner having fixing properties and excellent durability stability and color reproducibility was obtained, and the present invention was completed. That is, the object of the present invention is to provide a binder resin containing at least a crystalline polyester resin, and the following general formula (1):

In formula (1),
Rx ₁ and Rx ₂ are each independently a substituted or unsubstituted linear, branched or cyclic alkyl group having 1 to 20 carbon atoms,
Lx is a hydrogen atom or a substituted or unsubstituted linear, branched or cyclic alkyl group having 1 to 20 carbon atoms,
Gx ₁ is a substituted or unsubstituted linear, branched or cyclic alkyl group having 2 to 20 carbon atoms,
Gx ₂ is a substituted or unsubstituted, straight or branched alkyl group having 1 to 5 carbon atoms,
Gx ₃ is a hydrogen atom, a halogen atom, a group represented by Gx ₄ —CO—NH—, or a group represented by Gx ₅ —N (Gx ₆ ) —CO—, wherein Gx ₄ is a substituent. Gx ₅ and Gx ₆ are each independently a hydrogen atom or a substituent,
Qx ₁ , Qx ₂ , Qx ₃ , Qx ₄ , and Qx ₅ are each independently a hydrogen atom or a substituent,
A colorant represented by the following general formula (2):

In formula (2),
R ₁ is a substituted or unsubstituted linear, branched or cyclic alkyl group having 1 to 20 carbon atoms,
R ₂ is a hydrogen atom, alkoxycarbonyl group, arylcarbonyl group, aryloxycarbonyl group, sulfamoyl group, sulfinyl group, alkylsulfonyl group, arylsulfonyl group, acyl group, nitrophenyl group, halogen atom, or cyano group,
R ₃ is a substituted or unsubstituted aromatic hydrocarbon-containing group having 9 to 120 carbon atoms,
M is a divalent metal element,
Containing a compound reacted with a metal-containing compound represented by
This is achieved by a toner for developing an electrostatic charge image, in which the crystalline polyester resin is contained in an amount of 5 to 35% by mass based on the resin component forming the binder resin.

  According to the present invention, there is provided an electrostatic charge image developing toner having low temperature fixability and excellent durability stability and color reproducibility.

  Embodiments of the present invention will be described below. In addition, this invention is not limited only to the following embodiment. In this specification, “X to Y” indicating a range means “X or more and Y or less”. Unless otherwise specified, measurement of operation and physical properties is performed under conditions of room temperature (20 to 25 ° C.) / Relative humidity 40 to 50%.

  The toner for developing an electrostatic charge image according to the first embodiment of the present invention includes a binder resin containing at least a crystalline polyester resin, and the following general formula (1):

In formula (1),
Rx ₁ and Rx ₂ are each independently a substituted or unsubstituted linear, branched or cyclic alkyl group having 1 to 20 carbon atoms,
Lx is a hydrogen atom or a substituted or unsubstituted linear, branched or cyclic alkyl group having 1 to 20 carbon atoms,
Gx ₁ is a substituted or unsubstituted linear, branched or cyclic alkyl group having 2 to 20 carbon atoms,
Gx ₂ is a substituted or unsubstituted, straight or branched alkyl group having 1 to 5 carbon atoms,
Gx ₃ is a hydrogen atom, a halogen atom, a group represented by Gx ₄ —CO—NH—, or a group represented by Gx ₅ —N (Gx ₆ ) —CO—, wherein Gx ₄ is a substituent. Gx ₅ and Gx ₆ are each independently a hydrogen atom or a substituent,
Qx ₁ , Qx ₂ , Qx ₃ , Qx ₄ , and Qx ₅ are each independently a hydrogen atom or a substituent,
A colorant represented by the following general formula (2):

In formula (2),
R ₁ is a substituted or unsubstituted linear, branched or cyclic alkyl group having 1 to 20 carbon atoms,
R ₂ is a hydrogen atom, alkoxycarbonyl group, arylcarbonyl group, aryloxycarbonyl group, sulfamoyl group, sulfinyl group, alkylsulfonyl group, arylsulfonyl group, acyl group, nitrophenyl group, halogen atom, or cyano group,
R ₃ is a substituted or unsubstituted aromatic hydrocarbon-containing group having 9 to 120 carbon atoms,
M is a divalent metal element,
Containing a compound reacted with a metal-containing compound represented by
The toner for developing an electrostatic charge image, wherein the crystalline polyester resin is contained in an amount of 5 to 35% by mass with respect to a resin component forming the binder resin.

  That is, in one embodiment of the present invention, a binder resin containing at least a crystalline polyester resin, a compound obtained by reacting a colorant represented by formula (1) and a metal-containing compound represented by formula (2) , And a toner for developing an electrostatic charge image (hereinafter sometimes simply referred to as “toner”). In the present invention, the crystalline polyester and the compound obtained by reacting the colorant represented by the formula (1) and the metal-containing compound represented by the formula (2) are present together in the toner. And an electrostatic charge image developing toner having excellent durability stability and color reproducibility. The mechanism by which the above-described advantages can be achieved in the present invention is unknown, but is presumed as follows. The present invention is not limited by the following inference.

  It is estimated that the colorant represented by the formula (1) and the metal-containing compound represented by the formula (2) react to form an ionic compound. The presence of the ionic compound in the toner can act as a charge control agent and can improve the charge amount of the toner. The formed ionic compound is considered to have good compatibility with the crystalline polyester, and it is presumed that the aggregation of the crystalline polyester is suppressed and uniformly dispersed in the toner. As a result, the sharp melt property of the toner can be improved. As a result, the toner has low temperature fixability, and even when the fixing temperature fluctuates, the color reproducibility (hereinafter referred to as “color due to fusing temperature fluctuation”) is stabilized. In some cases, the toner can exhibit “stabilization of reproducibility”.

  In the present invention, the durability stability means the durability charging property and is evaluated by the stability of the charge amount.

Hereinafter, the electrostatic image developing toner according to the first embodiment will be described.
1. Toner for electrostatic image development [Binder resin]
The electrostatic image developing toner of the first embodiment contains a binder resin. The binder resin contains at least a crystalline polyester resin. The crystalline polyester resin can impart heat resistance, durability, and the like by being used in combination with other resin components. As other resin components, an amorphous polyester resin, a styrene-acrylic resin, an epoxy resin, or the like can be used in combination with the crystalline polyester resin. The other resin component is preferably an amorphous polyester resin or a styrene-acrylic resin from the viewpoint of durability, and more preferably an amorphous polyester resin from the viewpoint of low-temperature fixability. Therefore, as the electrostatic image developing toner of the first embodiment, the binder resin preferably contains a crystalline polyester resin, an amorphous polyester resin and / or a styrene-acrylic resin. More preferably, the binder resin preferably includes a crystalline polyester resin and an amorphous polyester resin. Another resin component may be used independently and may be used in mixture of 2 or more types. The other resin component (the total amount when two or more other resin components are included) is preferably 65 to 95% by mass, more preferably 70 to 90%, based on the resin component forming the binder resin. Including mass%.

  Hereinafter, the resin component constituting the binder resin will be described.

<Crystalline polyester resin>
The toner for developing an electrostatic charge image of the first embodiment contains 5 to 35% by mass of the crystalline polyester resin with respect to the resin component forming the binder resin. The crystalline polyester resin is contained in an amount of 5 to 35% by mass, preferably 10 to 30% by mass, and more preferably 10 to 20% by mass with respect to 100% by mass of the resin component forming the binder resin.

  The crystalline polyester resin is a differential scanning calorimetry among known polyester resins obtained by a polycondensation reaction of a divalent or higher carboxylic acid (polyvalent carboxylic acid) and a divalent or higher alcohol (polyhydric alcohol). In (DSC), a resin having a clear endothermic peak (a shape in which the endothermic spectrum curve goes down to the highest point through the inflection point and reaches the inflection point) instead of a stepwise endothermic change. Specifically, the clear endothermic peak means that the half-value width of the endothermic peak is within 15 ° C. when measured at a heating rate of 10 ° C./min in the differential scanning calorimetry (DSC) described in the examples. It means a peak.

  The crystalline polyester resin is not particularly limited as long as it is defined above. For example, for a resin having a structure in which other components are copolymerized on the main chain of the crystalline polyester resin, the resin is clear as described above. If it shows an endothermic peak, it corresponds to the crystalline polyester resin referred to in the present invention.

  The molecular weight (weight average molecular weight Mw) of the crystalline polyester resin is preferably from 8000 to 40000, preferably from 10,000 to 30000, from the viewpoint of the mechanical strength of the toner and the image strength and manufacturability of the obtained fixed image, and fixability. Further preferred. In such a range, when an amorphous resin is used in the agglomeration / fusion process described later, compatibility is prevented / suppressed, and the resulting toner particles do not have a low melting point as a whole, and are resistant to blocking. Excellent in low temperature fixability.

  The number average molecular weight (Mn) of the crystalline polyester resin is preferably 2,000 to 15,000, more preferably 2,500 to 10,000, from the same viewpoint as described above.

  In the present invention, the resin molecular weight was measured using a molecular weight measurement method by GPC. That is, a THF-soluble substance was measured with a THF solvent using GPC · HLC-8220 (manufactured by Tosoh) and a column “TSKguardcolumnsuperHZ-L + TSKgelSuperHZM-M3” manufactured by Tosoh, and a molecular weight calibration curve prepared from a monodisperse polystyrene standard sample Is used to calculate the molecular weight.

  The melting temperature (Tc) of the crystalline polyester resin is preferably 50 ° C. or higher and lower than 120 ° C., and more preferably 60 ° C. or higher and lower than 90 ° C. It is preferable that the melting temperature of the crystalline polyester resin is in the above range since low temperature fixability and fixability can be appropriately obtained. For the measurement of the melting temperature (Tc) of the crystalline polyester resin, a differential scanning calorimeter (DSC) was used to measure JIS K-7121 when measuring from 0 ° C. to 150 ° C. at a rate of temperature increase of 10 ° C. per minute. : It can obtain | require as a melting peak temperature of the input compensation differential scanning calorimetry shown to 87. A crystalline resin may show a plurality of melting peaks, but in the present invention, the maximum peak temperature is regarded as the melting point.

  The acid value (acid value AV) of the crystalline polyester resin is preferably 5 to 70 mgKOH / g, more preferably 10 to 50 mgKOH / g, still more preferably 12 to 40 mgKOH / g, and particularly preferably 20 ˜30 mg KOH / g. When the acid value of the crystalline polyester resin is within the above range, a balance between the hygroscopicity of the crystalline polyester and the dispersibility of the colorant is good, and a toner having excellent chargeability and image quality can be obtained. The acid value represents the mass of potassium hydroxide (KOH) necessary for neutralizing the acid contained in 1 g of the polyester resin in mg, and is measured according to JIS K0070-1966.

Specifically, it is measured according to the following procedure.
(1) Preparation of Reagent 1.0 g of phenolphthalein is dissolved in 90 ml of ethyl alcohol (95% by volume), and ion exchanged water is added to make 100 ml to prepare a “phenolphthalein solution”.

7 g of JIS special grade potassium hydroxide is dissolved in 5 ml of ion exchange water, and ethyl alcohol (95% by volume) is added to make 1 liter. In order to avoid contact with carbon dioxide gas, it is placed in an alkali-resistant container and allowed to stand for 3 days, followed by filtration to produce a “potassium hydroxide solution”. The orientation is in accordance with the description of JIS K0070-1966.
(2) Operation (a) Main test 2.0 g of the pulverized resin sample is precisely weighed into a 200 ml Erlenmeyer flask, and 100 ml of a mixed solution of toluene / ethanol (2: 1) is added and dissolved over 5 hours. Subsequently, several drops of the phenolphthalein solution is added as an indicator, and titration is performed using the potassium hydroxide solution. Note that the end point of the titration is when the light red color of the indicator lasts for about 30 seconds.
(B) Blank test The same operation as described above is performed except that no sample is used (that is, only a mixed solution of toluene / ethanol (2: 1) is used).
(3) Calculation of acid value The obtained result is substituted into the following formula (1) to calculate the acid value.
Formula (1)
A = [(BC) × f × 5.6] / S
here,
A: Acid value (mgKOH / g),
B: Amount of added potassium hydroxide solution for blank test (ml),
C: Amount of added potassium hydroxide solution in this test (ml),
f: Factor of 0.1 mol / liter potassium hydroxide ethanol solution,
S: Sample (g),
It is.

  The crystalline polyester resin is produced from a polyvalent carboxylic acid component (acid component) and a polyhydric alcohol component (alcohol component). The valences of the polyvalent carboxylic acid component and the polyhydric alcohol component are each preferably 2 to 3, and particularly preferably 2 respectively, so that the valence is particularly preferably 2 respectively. Therefore, preferably, the crystalline polyester resin is synthesized from a dicarboxylic acid component and a diol component, and more preferably an aliphatic dicarboxylic acid (including acid anhydride and acid chloride) and an aliphatic diol. An aliphatic polyester resin obtained by reacting is preferred.

  In the present invention, the term “acid-derived constituent component” refers to a constituent portion that was an acid component prior to the synthesis of the polyester resin in the polyester resin, and the “alcohol-derived constituent component” refers to the component before the synthesis of the polyester resin. Indicates a constituent site that was an alcohol component.

(Acid-derived components)
As the dicarboxylic acid component, aliphatic dicarboxylic acids and aromatic dicarboxylic acids are used, and aliphatic dicarboxylic acids are preferably used, and aromatic dicarboxylic acids may be used in combination. As the aliphatic dicarboxylic acid, it is preferable to use a linear one. By using a linear type, there is an advantage that crystallinity is improved. The dicarboxylic acid component is not limited to one type, and two or more types may be mixed and used.

  Examples of the aliphatic dicarboxylic acid include oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, 1,9-nonanedicarboxylic acid, and 1,10-decanedicarboxylic acid. Acid, 1,10-dodecanedicarboxylic acid (1,10-dodecanedioic acid), 1,11-undecanedicarboxylic acid, 1,12-dodecanedicarboxylic acid, 1,13-tridecanedicarboxylic acid, 1,14-tetradecanedicarboxylic acid Examples thereof include acids, 1,16-hexadecanedicarboxylic acid, 1,18-octadecanedicarboxylic acid, and the like, and lower alkyl esters and acid anhydrides thereof can also be used.

  Examples of the aromatic dicarboxylic acid include terephthalic acid, isophthalic acid, 2,6-naphthalenedicarboxylic acid, 4,4′-biphenyldicarboxylic acid, and the like. Among these, terephthalic acid, isophthalic acid, and t-butylisophthalic acid are preferably used from the viewpoints of availability and emulsification ease.

  As the acid-derived constituent component, other constituent components such as a dicarboxylic acid-derived constituent component having a double bond and a dicarboxylic acid-derived constituent component having a sulfonic acid group may be contained.

  In the present specification, “constituent mol%” means that the acid-derived constituent component in the entire acid-derived constituent component in the polyester resin or the alcohol constituent component in the entire alcohol-derived constituent component is 1 unit (mol). ) Indicates the percentage.

(Constituents derived from alcohol)
As the alcohol component, an aliphatic diol is preferably used, and a diol other than the aliphatic diol may be included as necessary.

  Examples of the aliphatic diol include ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8- Octanediol, 1,9-nonanediol, 1,10-dodecanediol, 1,11-undecanediol, 1,12-dodecanediol, 1,13-tridecanediol, 1,14-tetradecanediol, 1,18- Examples include octadecanediol and 1,20-eicosanediol. Among these, 1,9-nonanediol and 1,10-decanediol are preferable in view of availability, cost, and melting point.

  As the diol component, a branched aliphatic diol can also be used. In this case, from the viewpoint of ensuring crystallinity, it is used together with a linear aliphatic diol and the linear aliphatic diol. It is preferable to use at a higher ratio. By using the linear aliphatic diol in such a high proportion, it is possible to reliably obtain excellent low-temperature fixability in a toner manufactured with ensured crystallinity, and finally form an image. In this case, a decrease in image storability due to a decrease in melting point is suppressed, and further, blocking resistance can be reliably obtained.

  A diol component may be used individually by 1 type, and may be used 2 or more types.

  As the diol component for forming the crystalline polyester resin, the content of the aliphatic diol is preferably 80 component mol% or more, more preferably 90 component mol% or more, and still more preferably 100 component mol%. %. When the content of the aliphatic diol in the diol component is 80 constituent mol% or more, the crystallinity of the crystalline polyester resin can be ensured, and excellent low-temperature fixability can be obtained in the manufactured toner. Glossiness can be obtained in an image formed automatically.

  Examples of the diol other than the aliphatic diol include a diol having a double bond and a diol having a sulfonic acid group. Specifically, examples of the diol having a double bond include 2-butene-1,4. -Diol, 3-butene-1,6-diol, 4-butene-1,8-diol and the like. The content of the diol having a double bond in the diol component is preferably 20 constituent mol% or less. When the content of the diol having a double bond is 20 constituent mol% or less, the resulting polyester resin does not have a greatly reduced melting point, and therefore there is little risk of filming.

  The method for producing the crystalline polyester resin is not particularly limited, and can be produced by a general polyester polymerization method in which an acid component (dicarboxylic acid component) and an alcohol component (diol component) are reacted. Condensation, transesterification, etc. are used separately depending on the type of monomer. The molar ratio (acid component / alcohol component) at the time of reacting the acid component and the alcohol component varies depending on the reaction conditions and the like, and is not limited to this, but the hydroxyl group [OH] of the alcohol component (diol component) and The equivalent ratio [OH] / [COOH] of the acid component (dicarboxylic acid component) to the carboxyl group [COOH] is preferably 1.5 / 1 to 1 / 1.5, more preferably 1.2. /1-1/1.2. When the use ratio of the acid component and the alcohol component is in the above range, a crystalline polyester resin having a desired molecular weight can be obtained with certainty.

  The production of the crystalline polyester resin can be carried out at a polymerization temperature of 180 to 230 ° C., and the reaction is carried out while reducing the pressure in the reaction system as necessary to remove water and alcohol generated during condensation.

  When the monomer is not dissolved or compatible at the reaction temperature, a solvent having a high boiling point may be added as a solubilizer and dissolved. In the polycondensation reaction, the dissolution auxiliary solvent is distilled off. In the case where a monomer having poor compatibility is present in the copolymerization reaction, the monomer having poor compatibility and the monomer and the acid or alcohol to be polycondensed are condensed in advance and then polycondensed together with the main component.

  Catalysts that can be used in the production of the polyester resin include alkali metal compounds such as sodium and lithium; alkaline earth metal compounds such as magnesium and calcium; metal compounds such as zinc, manganese, antimony, titanium, tin, zirconium, and germanium; Examples thereof include phosphorous acid compounds; phosphoric acid compounds; and amine compounds.

  Specifically, sodium acetate, sodium carbonate, lithium acetate, lithium carbonate, calcium acetate, calcium stearate, magnesium acetate, zinc acetate, zinc stearate, zinc naphthenate, zinc chloride, manganese acetate, manganese naphthenate, titanium tetraethoxy , Titanium tetrapropoxide, titanium tetraisopropoxide, titanium tetrabutoxide, antimony trioxide, triphenylantimony, tributylantimony, tin formate, tin oxalate, tetraphenyltin, dibutyltin dichloride, dibutyltin oxide, diphenyltin oxide, zirconium tetra Butoxide, Zirconium naphthenate, Zirconyl carbonate, Zirconyl acetate, Zirconyl stearate, Zirconyl octylate, Germanium oxide, Trif Alkenyl phosphite, tris (2,4-di -t- butyl-phenyl) phosphite, ethyltriphenylphosphonium bromide, triethylamine, compounds such as triphenyl amine.

  The acid value of the polyester resin can be controlled by stopping the reaction when the desired value is reached during synthesis.

  The content of the crystalline polyester resin is preferably 1 to 40% by mass, preferably 3 to 35% by mass, and more preferably 5 to 20% by mass with respect to the whole toner. When the addition amount of the crystalline polyester resin is 40% by mass or less, the occurrence of burying or filming of the external additive is small. When the content is 1% by mass or more, the effect of improving the low-temperature fixability can be effectively obtained.

  In the present invention, two or more crystalline polyester resins may be used.

<Amorphous polyester resin>
In the electrostatic charge image developing toner according to the first embodiment, the non-crystalline polyester resin is preferably 5 to 95% by mass, more preferably 65 to 95% by mass, and more preferably 65% to 95% by mass with respect to the resin component forming the binder resin. Preferably it is 70-90 mass%, Most preferably, it contains 80-90 mass%. By using the amorphous polyester resin in a content within the above range, good low-temperature fixability can be obtained.

  The non-crystalline polyester resin is a polyester resin other than the crystalline polyester resin obtained mainly by condensation polymerization of a polyvalent carboxylic acid component and a polyhydric alcohol component. That is, it usually has no melting point and has a relatively high glass transition temperature (Tg). More specifically, the glass transition temperature (Tg) is preferably 40 to 90 ° C, and particularly preferably 45 to 80 ° C. The glass transition temperature (Tg) is measured by the method described in the examples.

  Moreover, in the case of the polymer which copolymerized other components with respect to the amorphous polyester principal chain, when the other component is 50 mass% or less, this copolymer is also an amorphous polyester resin in this invention.

  Examples of the polyvalent carboxylic acid component in the non-crystalline polyester resin include aromatic carboxylic acids such as terephthalic acid, isophthalic acid, phthalic anhydride, trimellitic anhydride, pyromellitic acid, naphthalenedicarboxylic acid; maleic anhydride, Fumaric acid, succinic acid, alkenyl succinic anhydride, adipic acid, peric acid, azelaic acid, sebacic acid, 1,9-nonanedicarboxylic acid, 1,10-decanedicarboxylic acid, 1,12-dodecanedicarboxylic acid, 1,14 -Aliphatic carboxylic acids such as tetradecanedicarboxylic acid and 1,18-octadecanedicarboxylic acid; alicyclic carboxylic acids such as cyclohexanedicarboxylic acid; and lower alkyl esters and acid anhydrides of these acids. Two or more species can be used. Among these polycarboxylic acids, aromatic carboxylic acids are preferably used, and trivalent or higher carboxylic acids (trimellitic acid) together with dicarboxylic acids to form a crosslinked structure or a branched structure in order to ensure good fixing properties. And acid anhydrides thereof) are preferably used in combination.

  Examples of the polyhydric alcohol component in the amorphous polyester resin include ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, and neopentyl. Glycol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-dodecanediol, 1,11-undecanediol, 1,12-dodecanediol Aliphatic diols such as 1,13-tridecanediol, 1,14-tetradecanediol, 1,18-octadecanediol, 1,20-eicosanediol; alicyclic diols such as cyclohexanediol and cyclohexanedimethanol; Bisfe Lumpur A, bisphenols such as bisphenol F, and their ethylene oxide adducts, aromatic diols such as alkylene oxide adducts of bisphenols, such as propylene oxide adduct. Examples of the trihydric or higher polyhydric alcohol component include glycerin, trimethylolpropane, pentaerythritol, and sorbitol. These polyhydric alcohol components may be used alone or in combination of two or more. Among these polyhydric alcohols, alicyclic diols and aromatic diols are preferable, and among these, aromatic diols are more preferable. In order to secure better fixability, it is also preferable to use a trihydric or higher polyhydric alcohol (glycerin, trimethylolpropane, pentaerythritol) together with the diol in order to take a crosslinked structure or a branched structure. Examples of the polyhydric alcohol component capable of forming an amorphous polyester resin include unsaturated polyvalent compounds such as 2-butyne-1,4 diol, 3-butyne-1,4 diol, and 9-octadezene-7,12 diol. Alcohol and the like can also be used.

  Among these, from the viewpoints of chargeability and toner strength, it is preferable to use an ethylene oxide adduct and a propylene oxide adduct of bisphenol A as the polyhydric alcohol component.

  The softening temperature of the amorphous polyester resin is preferably 70 to 140 ° C, and more preferably 70 to 125 ° C. The acid value of the non-crystalline polyester resin is preferably 5 to 70 mgKOH / g.

  The weight average molecular weight (Mw) of the amorphous polyester resin is preferably 8000 to 40000, and more preferably 10000 to 30000. The number average molecular weight (Mn) of the amorphous polyester resin is preferably 3,000 to 100,000, more preferably 4,000 to 70,000. When the weight average molecular weight (Mw) and the number average molecular weight (Mn) of the non-crystalline polyester resin are within such ranges, the resulting toner has excellent blocking resistance and low temperature fixability.

  The content of the amorphous polyester resin is usually 50 to 95% by mass, preferably 55 to 90% by mass with respect to the whole toner. When the toner is in such a range, the obtained toner has excellent blocking resistance and low temperature fixability.

  In the present invention, two or more amorphous polyester resins may be used.

<Styrene-acrylic resin>
In the electrostatic image developing toner of the first embodiment, the styrene-acrylic resin is preferably 5 to 90% by mass, more preferably 10 to 80% by mass, and still more preferably, based on the resin component forming the binder resin. 20-70 mass% is included. By using the styrene-acrylic resin in the above range, effects such as durability are exhibited.

  The styrene-acrylic resin is an aromatic vinyl monomer and a (meth) acrylic acid ester monomer having an ethylenically unsaturated bond capable of radical polymerization.

  Examples of the aromatic vinyl monomer include styrene, o-methyl styrene, m-methyl styrene, p-methyl styrene, p-methoxy styrene, p-phenyl styrene, p-chloro styrene, p-ethyl styrene, p. -N-butyl styrene, p-tert-butyl styrene, pn-hexyl styrene, pn-octyl styrene, pn-nonyl styrene, pn-decyl styrene, pn-dodecyl styrene, 2, Examples include 4-dimethylstyrene, 3,4-dichlorostyrene, and derivatives thereof.

  These aromatic vinyl monomers can be used alone or in combination of two or more.

Examples of (meth) acrylic acid ester monomers include methyl acrylate, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, cyclohexyl acrylate, phenyl acrylate, methyl methacrylate, ethyl methacrylate, and methacrylic acid. Examples include butyl, hexyl methacrylate, 2-ethylhexyl methacrylate, ethyl β-hydroxyacrylate, propyl γ-aminoacrylate, stearyl methacrylate, dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate, and the like.
These (meth) acrylic acid ester monomers can be used alone or in combination of two or more.

  As the aromatic vinyl monomer and (meth) acrylic acid ester monomer of the styrene-acrylic resin, it is preferable to use a large amount of styrene or a derivative thereof from the viewpoint of obtaining excellent chargeability and image quality characteristics. Specifically, the amount of styrene or its derivative used in all monomers (aromatic vinyl monomer and (meth) acrylic acid ester monomer) used to form a styrene-acrylic resin. It is preferable that it is 50 mass% or more.

  The molecular weight (weight average molecular weight Mw) of the styrene-acrylic resin is preferably 10,000 to 60000, and preferably 15000 to 55000, from the viewpoint of the mechanical strength of the toner and the image strength and manufacturability of the obtained fixed image, and fixability. Further preferred.

  The number average molecular weight (Mn) of the styrene-acrylic resin is preferably 2000 to 30000, more preferably 3000 to 20000, from the same viewpoint as described above.

  In the polymerization of the styrene-acrylic resin, it is preferable to perform the polymerization in the presence of a radical polymerization initiator, and the timing of addition of the radical polymerization initiator is not particularly limited, but it is easy to control radical polymerization. It is preferable to add after mixing the aromatic vinyl monomer and (meth) acrylic acid ester monomer for forming the polymerization of the styrene-acrylic polymer segment.

  Various known polymerization initiators are preferably used as the polymerization initiator. Specifically, for example, hydrogen peroxide, acetyl peroxide, cumyl peroxide, tert-butyl peroxide, propionyl peroxide, benzoyl peroxide, chlorobenzoyl peroxide, dichlorobenzoyl peroxide, bromomethylbenzoyl peroxide, Lauroyl oxide, ammonium persulfate, sodium persulfate, potassium persulfate, diisopropyl peroxycarbonate, tetralin hydroperoxide, 1-phenyl-2-methylpropyl-1-hydroperoxide, pertriphenylacetic acid-tert-butyl hydroperoxide, performic acid- tert-butyl, peracetic acid-tert-butyl, perbenzoic acid-tert-butyl, perphenylacetic acid-tert-butyl, permethoxyacetic acid-tert-butyl, per-N- (3-toluyl) palmitic acid-tert-butyl, etc. Peroxide 2,2′-azobis (2-aminodipropane) hydrochloride, 2,2′-azobis- (2-aminodipropane) nitrate, 1,1′-azobis (1-methylbutyronitrile-3-sulfone) Acid sodium), 4,4′-azobis-4-cyanovaleric acid, poly (tetraethylene glycol-2,2′-azobisisobutyrate) and other azo compounds.

  In the polymerization of styrene-acrylic resin, a commonly used chain transfer agent can be used for the purpose of adjusting the molecular weight of styrene-acrylic resin. The chain transfer agent is not particularly limited, and examples thereof include alkyl mercaptans (preferably n-octyl mercaptan) and mercapto fatty acid esters.

  The chain transfer agent is preferably mixed with the resin material in the mixing step of the aromatic vinyl monomer and the (meth) acrylic acid ester monomer for forming the polymerization of the styrene-acrylic resin.

  The addition amount of the chain transfer agent varies depending on the molecular weight and molecular weight distribution of the desired styrene-acrylic resin, but specifically, it is preferably added in the range of 0.01 to 5% by mass with respect to the monomer.

  The polymerization temperature in the polymerization of the styrene-acrylic resin is not particularly limited and can be appropriately selected. For example, the polymerization temperature is preferably 65 ° C. or higher and 125 ° C. or lower, more preferably 70 ° C. or higher and 120 ° C. or lower, and further preferably 75 ° C. or higher and 115 ° C. or lower.

  In the present invention, two or more styrene-acrylic resins may be used.

[Compound obtained by reacting the colorant represented by the formula (1) with the metal-containing compound represented by the formula (2)]
The electrostatic image developing toner of the first embodiment includes a compound obtained by reacting the colorant represented by the formula (1) with the metal-containing compound represented by the formula (2). A colorant represented by formula (1) (hereinafter sometimes referred to as “colorant (1)”) and a metal-containing compound represented by formula (2) (hereinafter “metal-containing compound (2)”). The ionic compound reacts at 1: 1 (molar ratio). Since the colorant (1) and the metal-containing compound (2) exhibit the technical effect of the present invention by forming an ionic compound, the colorant (1) and the metal-containing compound (2) It is preferable that the molar ratio of (1): metal-containing compound (2) is 1: 0.7 to 1.2.

  Hereinafter, the metal-containing compounds represented by the formulas (1) and (2) will be described.

<Colorant represented by Formula (1)>
The electrostatic image developing toner of the first embodiment includes a colorant represented by the following formula (1) as a colorant.

In the above formula (1), Rx ₁ and Rx ₂ are each independently a substituted or unsubstituted linear, branched or cyclic alkyl group having 1 to 20 carbon atoms. Specifically, methyl group, ethyl group, n-propyl group, isopropyl group, 2-methylpropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group, iso- Amyl group, tert-pentyl group, neopentyl group, n-hexyl group, 3-methylpentan-2-yl group, 3-methylpentan-3-yl group, 4-methylpentyl group, 4-methylpentane-2- Yl group, 1,3-dimethylbutyl group, 3,3-dimethylbutyl group, 3,3-dimethylbutan-2-yl group, n-heptyl group, 1-methylhexyl group, 3-methylhexyl group, 4- Methylhexyl group, 5-methylhexyl group, 1-ethylpentyl group, 1- (n-propyl) butyl group, 1,1-dimethylpentyl group, 1,4-dimethylpentyl group, 1,1- Ethylpropyl group, 1,3,3-trimethylbutyl group, 1-ethyl-2,2-dimethylpropyl group, n-octyl group, 2-ethylhexyl group, 2-methylhexane-2-yl group, 2,4- Dimethylpentan-3-yl group, 1,1-dimethylpentan-1-yl group, 2,2-dimethylhexane-3-yl group, 2,3-dimethylhexane-2-yl group, 2,5-dimethylhexane 2-yl group, 2,5-dimethylhexane-3-yl group, 3,4-dimethylhexane-3-yl group, 3,5-dimethylhexane-3-yl group, 1-methylheptyl group, 2- Methylheptyl group, 5-methylheptyl group, 2-methylheptan-2-yl group, 3-methylheptan-3-yl group, 4-methylheptan-3-yl group, 4-methylheptan-4-yl group, 1-D Ruhexyl group, 2-ethylhexyl group, 1-propylpentyl group, 2-propylpentyl group, 1,1-dimethylhexyl group, 1,4-dimethylhexyl group, 1,5-dimethylhexyl group, 1-ethyl-1- Methylpentyl group, 1-ethyl-4-methylpentyl group, 1,1,4-trimethylpentyl group, 2,4,4-trimethylpentyl group, 1-isopropyl-1,2-dimethylpropyl group, 1,1, 3,3-tetramethylbutyl group, n-nonyl group, 1-methyloctyl group, 6-methyloctyl group, 1-ethylheptyl group, 1- (n-butyl) pentyl group, 4-methyl-1- (n -Propyl) pentyl group, 1,5,5-trimethylhexyl group, 1,1,5-trimethylhexyl group, 2-methyloctane-3-yl group, n-decyl group, 1-methyl Nonyl group, 1-ethyloctyl group, 1- (n-butyl) hexyl group, 1,1-dimethyloctyl group, 3,7-dimethyloctyl group, n-undecyl group, 1-methyldecyl group, 1-ethylnonyl group, n-dodecyl group, 1-methylundecyl group, n-tridecyl group, n-tetradecyl group, 1-methyltridecyl group, n-pentadecyl group, n-hexadecyl group, n-heptadecyl group, n-octadecyl group, n -Nonadecyl group, n-eicosyl group, cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, 4-tert-butyl-cyclohexyl group, etc. are mentioned.

  One or more hydrogen atoms of the alkyl group may be substituted with a substituent. Examples of the substituent include alkenyl groups (for example, vinyl group, allyl group, etc.), alkynyl groups (for example, ethynyl group, propargyl group, etc.), aromatic hydrocarbon groups (for example, phenyl group, naphthyl group, etc.), Aromatic heterocyclic group (for example, furyl group, thienyl group, pyridyl group, pyridazyl group, pyrimidyl group, pyrazyl group, triazyl group, imidazolyl group, pyrazolyl group, thiazolyl group, benzoimidazolyl group, benzoxazolyl group, quinazolyl group, Phthalazyl group, etc.), heterocyclic group (eg, pyrrolidyl group, imidazolidyl group, morpholyl group, oxazolidyl group, etc.), alkoxy group (eg, methoxy group, ethoxy group, propyloxy group, pentyloxy group, hexyloxy group, octyloxy group) Group, dodecyloxy group, etc.), cycloalkoxy group (for example, cycl Pentyloxy group, cyclohexyloxy group, etc.), aryloxy group (eg, phenoxy group, naphthyloxy group, etc.), alkylthio group (eg, methylthio group, ethylthio group, propylthio group, pentylthio group, hexylthio group, octylthio group, dodecylthio group) Etc.), a cycloalkylthio group (eg, cyclopentylthio group, cyclohexylthio group, etc.), an arylthio group (eg, phenylthio group, naphthylthio group, etc.), an alkoxycarbonyl group (eg, methyloxycarbonyl group, ethyloxycarbonyl group, butyloxy) Carbonyl group, octyloxycarbonyl group, dodecyloxycarbonyl group, etc.), alkoxyalkylene ether group (for example, methoxyethylene ether group), alkylaminocarbonyl group (for example, diethyl) Aminocarbonyl group), aryloxycarbonyl group (eg, phenyloxycarbonyl group, naphthyloxycarbonyl group, etc.), phosphoryl group (eg, dimethoxyphosphonyl, diphenylphosphoryl), sulfamoyl group (eg, aminosulfonyl group, methylaminosulfonyl group, Dimethylaminosulfonyl group, butylaminosulfonyl group, hexylaminosulfonyl group, cyclohexylaminosulfonyl group, octylaminosulfonyl group, dodecylaminosulfonyl group, phenylaminosulfonyl group, naphthylaminosulfonyl group, 2-pyridylaminosulfonyl group, etc.), acyl group (For example, acetyl group, ethylcarbonyl group, propylcarbonyl group, pentylcarbonyl group, cyclohexylcarbonyl group, octylcarbonyl group, 2 -Ethylhexylcarbonyl group, dodecylcarbonyl group, phenylcarbonyl group, naphthylcarbonyl group, pyridylcarbonyl group, etc.), acyloxy group (for example, acetyloxy group, ethylcarbonyloxy group, butylcarbonyloxy group, octylcarbonyloxy group, dodecylcarbonyloxy group) Group, phenylcarbonyloxy group, etc.), amide group (for example, methylcarbonylamino group, ethylcarbonylamino group, dimethylcarbonylamino group, propylcarbonylamino group, pentylcarbonylamino group, cyclohexylcarbonylamino group, 2-ethylhexylcarbonylamino group) Octylcarbonylamino group, dodecylcarbonylamino group, phenylcarbonylamino group, naphthylcarbonylamino group, etc.), carbamoyl group (eg Aminocarbonyl group, methylaminocarbonyl group, dimethylaminocarbonyl group, propylaminocarbonyl group, pentylaminocarbonyl group, cyclohexylaminocarbonyl group, octylaminocarbonyl group, 2-ethylhexylaminocarbonyl group, dodecylaminocarbonyl group, phenylaminocarbonyl Group, naphthylaminocarbonyl group, 2-pyridylaminocarbonyl group, etc.), ureido group (for example, methylureido group, ethylureido group, pentylureido group, cyclohexylureido group, octylureido group, dodecylureido group, phenylureido group, naphthylureido) Group, 2-pyridylaminoureido group, etc.), sulfinyl group (for example, methylsulfinyl group, ethylsulfinyl group, butylsulfinyl group, cyclo Xylsulfinyl group, 2-ethylhexylsulfinyl group, dodecylsulfinyl group, phenylsulfinyl group, naphthylsulfinyl group, 2-pyridylsulfinyl group, etc.), alkylsulfonyl group (for example, methylsulfonyl group, ethylsulfonyl group, butylsulfonyl group, cyclohexylsulfonyl) Group, 2-ethylhexylsulfonyl group, dodecylsulfonyl group, etc.), arylsulfonyl group (phenylsulfonyl group, naphthylsulfonyl group, 2-pyridylsulfonyl group, etc.), amino group (for example, amino group, ethylamino group, dimethylamino group, Butylamino group, dibutylamino group, cyclopentylamino group, 2-ethylhexylamino group, dodecylamino group, anilino group, naphthylamino group, 2-pyridylamino group, etc.), azo group (for example) Phenylazo group), alkylsulfonyloxy group (for example, methanesulfonyloxy group), cyano group, nitro group, halogen atom (for example, fluorine atom, chlorine atom, bromine atom, etc.), hydroxy group, etc. Furthermore, you may have a substituent. Among these substituents, aromatic hydrocarbon groups (preferably having 6 to 20 carbon atoms), alkoxy groups (preferably having 1 to 10 carbon atoms), cycloalkoxy groups (preferably having 4 to 10 carbon atoms), halogen atoms, hydroxy Group, an alkoxyalkylene ether group (preferably an alkoxy group having 1 to 10 carbon atoms and an alkylene group having 1 to 10 carbon atoms), or an alkylaminocarbonyl group (preferably an alkyl group having 1 to 10 carbon atoms) is preferable.

Rx ₁ and Rx ₂ are preferably each independently an unsubstituted alkyl group or an alkyl group substituted with an alkoxy group, more preferably an unsubstituted alkyl group.

Further, the sum of the number of carbon atoms contained in the alkyl group used in the carbon number and Rx ₂ contained in the alkyl group used in Rx ₁ is preferably 2 or more.

In the above formula (1), Lx is a hydrogen atom or a substituted or unsubstituted linear, branched or cyclic alkyl group having 1 to 20 carbon atoms. Specific examples of the alkyl group are the same as the alkyl groups used in the above Rx ₁ and Rx ₂ , and thus detailed description thereof is omitted here. Further, specific examples of the substituent are the same as the substituents that can be used in the above Rx ₁ and Rx ₂ , and thus detailed description thereof is omitted here. Lx is preferably a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, more preferably a hydrogen atom, a methyl group or an ethyl group, and still more preferably a hydrogen atom.

In the above formula (1), Gx ₁ is a substituted or unsubstituted linear, branched or cyclic alkyl group having 2 to 20 carbon atoms. Specific examples of the alkyl group are the same as the alkyl groups used in Rx ₁ and Rx ₂ except for the methyl group, and thus detailed description thereof is omitted here. Further, specific examples of the substituent are the same as the substituents that can be used in the above Rx ₁ and Rx ₂ , and thus detailed description thereof is omitted here. Gx ₁ is preferably a branched alkyl group, more preferably a tertiary alkyl group, still more preferably an isopropyl group or a t-butyl group, and particularly preferably a t-butyl group.

In the above formula (1), Gx ₂ is a substituted or unsubstituted, straight or branched alkyl group having 1 to 5 carbon atoms. Specific examples of the alkyl group used in Gx ₂ include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, and n-pentyl. Group, iso-amyl group, tert-pentyl group, or neopentyl group. Specific examples of the substituent are the same as the substituents that can be used for the above Rx ₁ and Rx ₂ , and thus detailed description thereof is omitted here. From the viewpoint of obtaining the effects of the present invention more effectively, Gx ₂ is preferably a methyl group or an ethyl group.

In the above formula (1), Gx ₃ is a hydrogen atom, a halogen _atom, a group represented by Gx 4 -CO-NH- or _Gx 5 _-N group represented by (Gx 6) -CO-,, this In this case, Gx ₄ is a substituent, and Gx ₅ and Gx ₆ are each independently a hydrogen atom or a substituent. Specific examples of the substituent used in Gx ₄ , Gx _5, and Gx ₆ include linear, branched, or cyclic having 1 to 20 carbon atoms in addition to the substituent that can be used in Rx ₁ and Rx _2. Of the alkyl group. Gx ₃ is preferably a hydrogen atom or diethylamine carbonyl group.

In the above formula (1), Qx ₁ , Qx ₂ , Qx ₃ , Qx ₄ , and Qx ₅ are each independently a hydrogen atom or a substituent. Specific examples of the substituent used in Qx ₁ , Qx ₂ , Qx ₃ , Qx ₄ , and Qx ₅ include linear groups having 1 to 20 carbon atoms in addition to the substituents that can be used in Rx ₁ and Rx _2. , Branched or cyclic alkyl groups. Qx ₁ , Qx ₂ , Qx ₃ , Qx ₄ , and Qx ₅ are each independently a hydrogen atom, an alkyl group, a halogen atom, an alkoxy group (preferably having 1 to 10 carbon atoms), or an aryl group. Preferably, all are hydrogen atoms.

  Examples of the colorant represented by the formula (1) include the following compounds.

  Examples of the colorant represented by the above formula (1) according to the present invention include, for example, JP-A-63-226653, JP-A-10-193807, JP-A-11-78258, JP-A-6-250357, No. 2-155893, No. 1-110565, No. 2-668, No. 2-28264, No. 2-53865, No. 2-53866, British Patent No. 1,252,418 Specification, Japanese Patent Application Laid-Open No. 64-63194, Japanese Patent Application Laid-Open No. Hei 2-208094, Japanese Patent Application No. 3-205189, Japanese Patent Application No. 2-265911, Japanese Patent Application No. 2-3310087, Japanese Patent Application Laid-Open No. 4-91987, JP-A 63-205288, JP-A 3-226750, British Patent 1,183,515, JP-A 4-190348, JP-A-63-113077, JP-A-3-275767, JP-A-4-13774, JP-A-4-89287, JP-A-7-175187, JP-A-10-60296, JP-A-11-78258. It can be synthesized with reference to conventionally known methods described in Japanese Patent Laid-Open Nos. 2004-138834 and 2006-350300.

  These colorants may be used alone or in combination of two or more. The content of the colorant is preferably 0.5 to 10% by mass and more preferably 1 to 8% by mass with respect to the whole toner.

  In addition to the present colorant, other existing colorants may be added as additives.

  As other existing colorants, generally known dyes and pigments can be used, but pigments are preferably used from the viewpoint of light resistance and water resistance. When using other than the colorant of the formula (1), the other colorant is preferably used in an amount of 0.5 to 1.5 times the colorant of the formula (1).

  Other colorants include carbon black, aniline black, aniline blue, calcoil blue, chrome yellow, ultramarine blue, dupont oil red, quinoline yellow, methylene blue chloride, phthalocyanine blue, malachite green oxalate, lamp black, and rose. Bengal, Quinacridone, Benzicine Yellow, C.I. I. Pigment red 57: 1, C.I. I. Pigment red 185, C.I. I. Pigment red 238, C.I. I. Pigment yellow 12, C.I. I. Pigment yellow 17, C.I. I. Pigment yellow 180, C.I. I. Pigment yellow 97, C.I. I. Pigment yellow 74, C.I. I. Pigment blue 15: 1, C.I. I. Known pigments such as CI Pigment Blue 15: 3 can be used.

  The colorant for obtaining the toner of each color can be used singly or in combination of two or more for each color.

<Metal-containing compound represented by Formula (2)>
The electrostatic image developing toner of the first embodiment includes a metal-containing compound represented by the following formula (2) as a colorant.

In the above formula (2), R ₁ is a substituted or unsubstituted linear, branched or cyclic alkyl group having 1 to 20 carbon atoms. Specific examples of the alkyl group are the same as the alkyl groups used in Rx ₁ and Rx ₂ in the formula (1) in the section of the colorant, and thus detailed description thereof is omitted here.

  One or more hydrogen atoms of the alkyl group may be substituted with a substituent. Examples of the substituent include alkenyl groups (eg, vinyl group, allyl group, etc.), alkynyl groups (eg, ethynyl group, propargyl group, etc.), aryl groups (eg, phenyl group, naphthyl group, 4-octyloxybenzene). Etc.), heteroaryl groups (for example, furyl, thienyl, pyridyl, pyridazyl, pyrimidyl, pyrazyl, triazyl, imidazolyl, pyrazolyl, thiazolyl, benzoimidazolyl, benzoxazolyl, quinazolyl , Phthalazyl group, etc.), heterocyclic group (eg, pyrrolidyl group, imidazolidyl group, morpholyl group, oxazolidyl group, etc.), alkoxy group (eg, methoxy group, ethoxy group, propyloxy group, pentyloxy group, hexyloxy group, octyl group) Oxy group, dodecyloxy group, cyclopentyl Xy group, cyclohexyloxy group, etc.), aryloxy group (for example, phenoxy group, naphthyloxy group, etc.), alkylthio group (for example, methylthio group, ethylthio group, propylthio group, pentylthio group, hexylthio group, octylthio group, dodecylthio group, Cyclopentylthio group, cyclohexylthio group, etc.), arylthio group (eg, phenylthio group, naphthylthio group, etc.), alkoxycarbonyl group (eg, methyloxycarbonyl group, ethyloxycarbonyl group, butyloxycarbonyl group, octyloxycarbonyl group, dodecyl) Oxycarbonyl group etc.), aryloxycarbonyl group (eg phenyloxycarbonyl group, naphthyloxycarbonyl group etc.), sulfamoyl group (eg aminosulfonyl group, methylaminos) (Honyl group, dimethylaminosulfonyl group, butylaminosulfonyl group, hexylaminosulfonyl group, cyclohexylaminosulfonyl group, octylaminosulfonyl group, dodecylaminosulfonyl group, phenylaminosulfonyl group, naphthylaminosulfonyl group, 2-pyridylaminosulfonyl group, etc.) An acyl group (for example, acetyl group, ethylcarbonyl group, propylcarbonyl group, pentylcarbonyl group, cyclohexylcarbonyl group, octylcarbonyl group, 2-ethylhexylcarbonyl group, dodecylcarbonyl group, phenylcarbonyl group, naphthylcarbonyl group, pyridylcarbonyl group) Etc.), acyloxy group (for example, acetyloxy group, ethylcarbonyloxy group, butylcarbonyloxy group, octylcarbonyloxy group, Decylcarbonyloxy group, phenylcarbonyloxy group, etc.), amide group (for example, methylcarbonylamino group, ethylcarbonylamino group, dimethylcarbonylamino group, propylcarbonylamino group, pentylcarbonylamino group, cyclohexylcarbonylamino group, 2-ethylhexyl) Carbonylamino group, octylcarbonylamino group, dodecylcarbonylamino group, phenylcarbonylamino group, naphthylcarbonylamino group, etc.), carbamoyl group (for example, aminocarbonyl group, methylaminocarbonyl group, dimethylaminocarbonyl group, propylaminocarbonyl group, Pentylaminocarbonyl group, cyclohexylaminocarbonyl group, octylaminocarbonyl group, 2-ethylhexylaminocarbonyl group, dodecylamino Carbonyl group, phenylaminocarbonyl group, naphthylaminocarbonyl group, 2-pyridylaminocarbonyl group, etc.), ureido group (for example, methylureido group, ethylureido group, pentylureido group, cyclohexylureido group, octylureido group, dodecylureido group, Phenylureido group, naphthylureido group, 2-pyridylaminoureido group, etc.), sulfinyl group (for example, methylsulfinyl group, ethylsulfinyl group, butylsulfinyl group, cyclohexylsulfinyl group, 2-ethylhexylsulfinyl group, dodecylsulfinyl group, phenylsulfinyl group) Naphthylsulfinyl group, 2-pyridylsulfinyl group, etc.), alkylsulfonyl group (for example, methylsulfonyl group, ethylsulfonyl group, butylsulfonate) Group, cyclohexylsulfonyl group, 2-ethylhexylsulfonyl group, dodecylsulfonyl group, etc.), arylsulfonyl group (phenylsulfonyl group, naphthylsulfonyl group, 2-pyridylsulfonyl group etc.), amino group (for example, amino group, ethylamino group, Dimethylamino group, butylamino group, cyclopentylamino group, 2-ethylhexylamino group, dodecylamino group, anilino group, naphthylamino group, 2-pyridylamino group, etc., cyano group, nitro group, halogen atom (for example, chlorine atom, Bromine atom, fluorine atom, iodine atom and the like), and these groups may be further substituted with the same group.

R ₁ is preferably an alkyl group having 1 to 4 carbon atoms, more preferably a linear alkyl group having 1 to 4 carbon atoms, still more preferably a methyl group or an ethyl group, and particularly preferably methyl. It is a group.

In the above formula (2), R ₂ is a hydrogen atom, alkoxycarbonyl group, arylcarbonyl group, aryloxycarbonyl group, sulfamoyl group, sulfinyl group, alkylsulfonyl group, arylsulfonyl group, acyl group, nitrophenyl group, halogen atom, Or it is a cyano group.

  More specifically, a methyloxycarbonyl group, an ethyloxycarbonyl group, a butyloxycarbonyl group, an octyloxycarbonyl group, an alkoxycarbonyl group such as a dodecyloxycarbonyl group; an arylcarbonyl group such as a phenylcarbonyl group; a phenyloxycarbonyl group; Aryloxycarbonyl group such as naphthyloxycarbonyl group; aminosulfonyl group, methylaminosulfonyl group, dimethylaminosulfonyl group, butylaminosulfonyl group, hexylaminosulfonyl group, cyclohexylaminosulfonyl group, octylaminosulfonyl group, dodecylaminosulfonyl group, etc. Alkylsulfonylamino group, and phenylaminosulfonyl group, 3-methyl-4-dodecyloxy-5-t-butylphenylaminosulfonyl group Sulfamoyl group of arylsulfonylamino group such as naphthylaminosulfonyl group, 2-pyridylaminosulfonyl group; methylsulfinyl group, ethylsulfinyl group, butylsulfinyl group, cyclohexylsulfinyl group, 2-ethylhexylsulfinyl group, dodecylsulfinyl group, phenylsulfinyl group, Sulfinyl groups such as naphthylsulfinyl group and 2-pyridylsulfinyl group; alkylsulfonyl groups such as methylsulfonyl group, ethylsulfonyl group, butylsulfonyl group, cyclohexylsulfonyl group, 2-ethylhexylsulfonyl group and dodecylsulfonyl group; phenylsulfonyl group, 4 -Arylsulfonyl groups such as methylphenylsulfonyl group, naphthylsulfonyl group, 2-pyridylsulfonyl group; acetyl group, ethyl Acyl groups such as carbonyl group, propylcarbonyl group, pentylcarbonyl group, hexylcarbonyl group, cyclohexylcarbonyl group, octylcarbonyl group, 2-ethylhexylcarbonyl group, dodecylcarbonyl group, phenylcarbonyl group, naphthylcarbonyl group, pyridylcarbonyl group; halogen An atom (for example, a chlorine atom, a bromine atom, a fluorine atom, an iodine atom, etc.), a cyano group, etc. are mentioned.

R ₂ is preferably an alkoxycarbonyl group (preferably 2 to 10 carbon atoms), an arylcarbonyl group (preferably 2 to 10 carbon atoms), an alkylsulfonyl group (preferably 7 to 10 carbon atoms), an arylsulfonyl group (preferably 6 to 10 carbon atoms), an acyl group (preferably 2 to 10 carbon atoms), and a cyano group, more preferably an alkoxycarbonyl group (preferably 2 to 10 carbon atoms, an acyl group (preferably 2 to 10 carbon atoms, A cyano group, more preferably a cyano group.

In the above formula (2), R ₃ is a substituted or unsubstituted aromatic hydrocarbon-containing group having 9 to 120 carbon atoms.

Here, the aromatic hydrocarbon-containing group having 9 to 120 carbon atoms means that the total number of carbon atoms in R ₃ is 9 to 120, and an aromatic hydrocarbon structure is formed at an arbitrary position in R _3. Refers to the containing group. Examples of the aromatic hydrocarbon structure include an aryl group (for example, a phenyl group, a naphthyl group, etc.). For example, when the aromatic hydrocarbon structure is a phenyl group, an arbitrary substituent having 3 or more carbon atoms is further included. Together with this, R ₃ is formed. In this case, it may have 3 or more substituents having 1 carbon atom, and may have 1 or more substituents each having 1 carbon atom and 2 substituents having 2 carbon atoms. The total number of carbon atoms in R ₃ is preferably 9 to 40, more preferably 12 to 40, and still more preferably 14 to 30.

R ₃ is preferably a group represented by the following formula (3).

In the above formula (3), L represents a linear or branched alkylene group having 1 to 15 carbon atoms, —SO ₂ O—, —OSO ₂ —, —SO ₂ —, —CO—, —O—. _{, -S -, - SO 2 NH} -, - NHSO 2 -, - CONH -, - NHCO -, - COO-, and -OOC- divalent alone or in combination with it based on the linking group selected from In formula *, it is bonded to an oxygen atom adjacent to R ₃ in the general formula (2).

  Specific examples of the linear or branched alkylene group having 1 to 15 carbon atoms include, for example, a methylene group, an ethylene group, a trimethylene group, a tetramethylene group, a propylene group, an ethylethylene group, a pentamethylene group, and a hexamethylene group. Group, 2,2,4-trimethylhexamethylene group, heptamethylene group, octamethylene group, nonamethylene group, decamethylene group, undecamethylene group, dodecamethylene group, tridecamethylene group, tetradecamethylene group, pentadecamethylene group Etc.

L may have a substituent, and examples of the substituent include the same groups as the substituent used in R ₁ of the general formula (2).

The divalent linking group represented by L is preferably an alkylene group or a group containing an alkylene group. The group containing an alkylene group only needs to contain an alkylene group at an arbitrary position in the divalent linking group represented by L. Specifically, the alkylene group, —SO ₂ O—, —OSO _{2 -, - SO 2 -, -} CO -, - O -, - S -, - SO 2 NH -, - NHSO 2 -, - CONH -, - NHCO -, - COO-, and it is selected from -OOC- A group formed by combining one or more divalent linking groups.

L is preferably an alkylene group having 1 to 10 carbon atoms, —R ₆ —O— group, —R ₆ —CO— group, —R ₆ —NHCO— group, —R ₆ —SO ₂ — group, —R _6. A —COS— group, a —NH—SO ₂ — group, a —NH—SO ₂ —R ₆ — group, or a —R ₆ —O—R ₆ —O—R ₆ — group, wherein —R ₆ — Is an alkylene group having 1 to 10 carbon atoms.

R ₄ represents an aryl group (for example, a phenyl group, a naphthyl group, etc.). Specific examples of the divalent linking group represented by L are shown below, but the present invention is not limited thereto. L is bonded to an oxygen atom adjacent to R ₃ in the general formula (2) or R ₄ in *.

R ₃ and R ₄ may have a substituent, and examples of the substituent include the same groups as the substituent used in R ₁ of the general formula (2).

Preferred substituents for substituting L, R ₃ and R ₄ are alkyl groups (preferably having 1 to 20 carbon atoms), alkoxy groups (preferably having 1 to 20 carbon atoms), aryloxy groups, alkylthio groups, arylthio groups, Alkoxycarbonyl group (preferably having 2 to 20 carbon atoms), aryloxycarbonyl group, sulfamoyl group, acyl group, acyloxy group, amide group, alkylaminocarbonyl group (preferably having 2 to 20 carbon atoms), carbamoyl group, alkylsulfonyl group , Arylsulfonyl group, amino group, cyano group, nitro group, halogen atom, more preferably alkyl group, alkoxy group, aryloxy group, alkoxycarbonyl group, aryloxycarbonyl group, sulfamoyl group, acyl group, acyloxy group , Amide group, carbamoyl group There, more preferably, an alkyl group, an alkoxy group, an aryloxy group, an alkoxycarbonyl group, an acyloxy group, an amide group.

R ₄ is preferably a phenyl group, more preferably a phenyl group having a substituent, and further preferably a phenyl group having an alkyl group, an alkoxy group, an aryloxy group, an alkoxycarbonyl group, an acyloxy group, or an amide group. Particularly preferred is a phenyl group having an alkyl group or an alkoxy group.

R ₃ is more preferably a group represented by the following general formula (3-1) or (3-2).

In the general formulas (3-1) and (3-2), L and * represent a group having the same meaning as L and * in the general formula (3), and each X independently represents —O—. , —NHCO—, or —COO—, wherein R ₅ represents a linear or branched alkyl group having 1 to 30 carbon atoms, and n represents an integer of 0 to 3.

R ₅ is preferably an alkyl group having 1 to 20 carbon atoms, and more preferably an alkyl group having 1 to 10 carbon atoms. R ₅ may have a substituent, and examples of the substituent include a group having the same meaning as the substituent used in R ₁ of the general formula (2). R ₅ is preferably a linear alkyl group, and more preferably composed of only carbon atoms and hydrogen atoms.

  n is preferably 0 or 1.

L is preferably an alkylene group having 1 to 10 carbon atoms, —R ₆ —O— group, —R ₆ —CO— group, —R ₆ —NHCO— group, —R ₆ —SO ₂ — group, —R _6. —COS— group, —NH—SO ₂ — group, —NH—SO ₂ —R ₆ — group, or —R ₆ —O—R ₆ —O—R ₆ — group, wherein —R ₆ is It is a C1-C10 alkylene group. More preferably, L is an alkylene group having 1 to 6 carbon atoms or an —R ₆ —O— group (wherein R ₆ preferably has 1 to 5 carbon atoms).

  In the above formula (2), M is a divalent metal element. Examples of the divalent metal include iron, magnesium, nickel, cobalt, copper, palladium, zinc, vanadium, titanium, indium, and tin. From the viewpoint of reactivity with the colorant represented by formula (1), M is preferably magnesium, copper, zinc, cobalt, nickel, iron, vanadyl, titanyl, tin (II) chloride, and more preferably. Are magnesium and copper, more preferably copper (Cu).

The metal-containing compound used in the present invention may have a neutral ligand depending on the central metal, and typical ligands include H ₂ O or NH ₃ .

  Examples of the metal-containing compound (2) include the following structures.

  These metal-containing compounds may be used alone or in combination of two or more. The content of the metal-containing compound is preferably 0.5 to 10% by mass and more preferably 1 to 8% by mass with respect to the entire toner.

The metal-containing compound (2) is preferably synthesized by reacting a divalent metal compound with a raw material compound represented by the following formula (2-1). Examples of the divalent metal compound used include metal chloride (II), metal acetate (II), and metal perchlorate. _R 1, _{R 2} and _{R 3} in formula (2-1) is the same as _R 1, _{R 2} and _{R 3} in formula (2).

  A method for synthesizing such a specific metal-containing compound can be synthesized in accordance with a method described in “Chelate Chemistry (5) Complex Chemistry Experimental Method [I] (Edited by Nanedo)”.

  Here, the electrostatic image developing toner according to the first embodiment of the present invention contains a compound obtained by reacting the colorant represented by the formula (1) with the metal-containing compound represented by the formula (2). The

  The reaction conditions of the colorant represented by formula (1) and the metal-containing compound represented by formula (2) are not particularly limited, and the colorant represented by formula (1) and formula (2) The metal-containing compound represented is mixed in a solvent, for example, preferably 50 to 95 ° C., more preferably 60 to 90 ° C., still more preferably 75 to 87 ° C., preferably 5 to 250 minutes, more preferably 10 The reaction compound can be obtained by stirring for -60 minutes, more preferably 15-30 minutes. Specifically, for example, a dispersion of a metal-containing compound in a dispersion containing a colorant such as a dispersion of a colorant (colorant fine particle dispersion) or a resin fine particle dispersion containing a colorant or a wax-containing resin fine particle dispersion. By adding the liquid (metal-containing compound fine particle dispersion), the dispersion once becomes cloudy, but the dispersion (supernatant) becomes transparent by stirring. Thereby, it is considered that the reaction between the colorant represented by the formula (1) and the metal-containing compound represented by the formula (2) is completed and a reaction compound is formed. As the solvent used in the reaction, a solvent used when preparing the toner is preferably used, and specific solvents are those described in the section of the toner preparation method.

[Other additives]
In addition to the components as described above, various components such as a release agent and inorganic fine particles (inorganic powder) and organic fine particles as external additives may be added to the toner according to the exemplary embodiment as necessary. it can.

<Release agent (wax)>
The release agent constituting the toner is not particularly limited, and known ones can be used. Specifically, for example, low molecular weight polyolefins such as polyethylene, polypropylene and polybutene; plant waxes such as synthetic ester wax, carnauba wax, rice wax, candelilla wax, wood wax, jojoba oil; montan wax, paraffin wax , Minerals such as microcrystalline wax and Fischer-Tropsch wax, petroleum-based wax; and modified products thereof.

  The addition amount of the release agent is usually 0.5 to 25% by mass, preferably 2 to 15% by mass with respect to the whole toner. Within such a range, there are effects of preventing hot offset and ensuring separability.

  Moreover, as a magnitude | size of a mold release agent, 10-1000 nm and 50-500 nm are preferable at a volume average particle diameter, Furthermore, 80-300 nm is especially preferable.

<Charge control agent>
Various known compounds can be used as the charge control agent.

  The amount of the charge control agent added is usually 0.1 to 10% by mass, preferably 0.5 to 5% by mass with respect to 100% by mass of the binder resin in the finally obtained toner particles. .

  As a magnitude | size of a charge control agent particle | grain, 10-1000 nm and 50-500 nm are preferable at a number average primary particle diameter, Furthermore, 80-300 nm is especially preferable.

<External additive>
From the viewpoint of improving the charging performance, fluidity, and cleaning properties of the toner, particles such as known inorganic fine particles and organic fine particles and a lubricant can be added as external additives to the surface of the toner particles.

  Inorganic fine particles can be added for various purposes, and preferred are inorganic fine particles such as silica fine particles, titanium oxide fine particles, alumina fine particles, cerium oxide fine particles, and strontium titanate fine particles. If necessary, these inorganic fine particles may be hydrophobized. These known inorganic fine particles can be used alone or in combination of two or more. Further, the silica fine particles may be subjected to various surface treatments, and for example, those subjected to surface treatment with a silane coupling agent, a titanium coupling agent, silicone oil or the like are preferably used.

  As the organic fine particles, spherical organic fine particles having a number average primary particle diameter of about 10 to 2000 nm can be used. Specifically, homopolymers such as styrene and methyl methacrylate and organic fine particles made of these copolymers can be used.

  The lubricant is used for the purpose of further improving the cleaning property and transferability. Examples of the lubricant include zinc stearate, salts of aluminum, copper, magnesium, calcium, and zinc oleate. Of higher fatty acids, such as salts of manganese, iron, copper, magnesium, zinc of palmitic acid, salts of copper, magnesium, calcium, zinc of linoleic acid, salts of calcium, zinc of ricinoleic acid, salts of calcium, etc. Metal salts are mentioned. A variety of these external additives may be used in combination.

  The addition amount of the external additive is preferably 0.1 to 10.0% by mass with respect to the toner particles.

  Examples of the method of adding the external additive include a method of adding using various known mixing apparatuses such as a Turbuler mixer, a Henschel mixer, a Nauter mixer, and a V-type mixer.

[Toner for developing electrostatic image]
The softening point of the toner for developing an electrostatic charge image according to the first embodiment of the present invention is preferably 70 to 120 ° C., more preferably 80 to 110 ° C., from the viewpoint of obtaining low temperature fixability for the toner. .

  The softening point of the toner is measured by a flow tester shown below.

Specifically, first, in an environment of 20 ° C. and 50% RH, 1.1 g of a sample (toner) was placed in a petri dish and left flat for 12 hours or more, and then a molding machine “SSP-10A” (Shimadzu) Pressed with a force of 3820 kg / cm ² for 30 seconds to produce a cylindrical molded sample having a diameter of 1 cm. Then, the molded sample was subjected to a flow tester “24 ° C. and 50% RH in a flow tester“ CFT-500D "(manufactured by Shimadzu Corporation), with a load of 196 N (20 kgf), a starting temperature of 60 ° C., a preheating time of 300 seconds, and a heating rate of 6 ° C./min (1 mm diameter × 1 mm) more, extruded from the time of preheating ends with piston diameter 1 cm, offset method temperature T _offset measured by setting the offset value 5mm at a melt temperature measurement method of temperature ramps is the softening point That.

  The average particle diameter of the toner for developing an electrostatic charge image of the present invention is preferably 3 to 9 μm, and more preferably 3 to 8 μm, for example, on a volume basis median diameter. This particle size can be controlled by the concentration of the coagulant used, the addition amount of the organic solvent, the fusing time, the composition of the polymer, and the like, for example, when the emulsion aggregation method described later is employed.

  When the volume-based median diameter is in the above range, the transfer efficiency is increased, the image quality of halftone is improved, and the image quality of fine lines and dots is improved.

  The volume-based median diameter of the toner particles is measured and calculated using a measuring device in which “Multisizer 3” (manufactured by Beckman Coulter) is connected to a computer system equipped with data processing software “Software V3.51”. Is. Specifically, 0.02 g of toner is added to 20 mL of a surfactant solution (for example, a surfactant solution obtained by diluting a neutral detergent containing a surfactant component 10 times with pure water for the purpose of dispersing toner particles). Then, ultrasonic dispersion is performed for 1 minute to prepare a toner dispersion, and this toner dispersion is placed in a beaker containing “ISOTON II” (manufactured by Beckman Coulter) in a sample stand. Pipet until the indicated concentration is 8%. Here, a reproducible measurement value can be obtained by setting the concentration range. In the measurement apparatus, the measurement particle count is 25000, the aperture diameter is 50 μm, the frequency value is calculated by dividing the measurement range of 1 to 30 μm into 256, and the volume integrated fraction is 50 % Particle diameter is defined as the volume-based median diameter.

  The electrostatic charge image developing toner according to the first embodiment of the present invention has an average circularity of 0.930 to 1.000 for each toner particle constituting the toner from the viewpoint of improving the transfer efficiency. Is more preferable, and 0.940 to 0.995 is more preferable.

  In the present invention, the average circularity of toner particles is measured using “FPIA-2100” (manufactured by Sysmex).

  Specifically, the sample (toner particles) is blended with an aqueous solution containing a surfactant, subjected to ultrasonic dispersion treatment for 1 minute to disperse, and then subjected to measurement conditions HPF by “FPIA-2100” (manufactured by Sysmex). In the (high-magnification imaging) mode, photographing is performed at an appropriate density of 3,000 to 10,000 HPF detections, and the circularity of each toner particle is calculated according to the following formula (T). Calculated by adding the degree and dividing by the total number of toner particles.

2. Method for Producing Toner for Developing Electrostatic Image The method for producing the toner of the present invention is not particularly limited, and kneading and pulverization method, suspension polymerization method, emulsion aggregation method, dissolution suspension method, polyester elongation method, dispersion polymerization method And publicly known methods.

  Among these, it is preferable to employ an emulsion aggregation method from the viewpoints of particle size uniformity, shape controllability, and ease of forming a core-shell structure, which are advantageous for high image quality and high charge stability.

  In the emulsion aggregation method, a dispersion of resin fine particles (hereinafter, also referred to as “resin fine particles”) dispersed with a surfactant or a dispersion stabilizer is used as needed to form toner particle constituents such as colorant fine particles. By mixing with the dispersion and adding an aggregating agent, the toner particles are aggregated until a desired toner particle size is obtained, and thereafter or simultaneously with the aggregation, fusion between the resin fine particles is performed to control the shape of the toner particles. It is a method of forming.

  Here, the resin fine particles may be composite particles formed of a plurality of layers having two or more layers made of resins having different compositions.

  The resin fine particles can be produced, for example, by an emulsion polymerization method, a miniemulsion polymerization method, a phase inversion emulsification method, or the like, or can be produced by combining several production methods. When an internal additive is contained in the resin fine particles, it is preferable to use a miniemulsion polymerization method.

  When an internal additive is contained in the toner particles, the resin fine particles may contain an internal additive, or a dispersion of internal additive fine particles consisting of only the internal additive is separately prepared and the internal additive is added. The agent fine particles may be aggregated together when the resin fine particles are aggregated.

  The toner particles according to the present invention may have, for example, a core-shell structure in which the surface of core particles made of a core resin is coated with a shell layer made of a shell resin, or a single layer structure. May be.

  When the toner particles are configured to have a core-shell structure, resin particles having different compositions may be added at the time of aggregation to cause aggregation.

  The electrostatic charge image developing toner according to the first embodiment of the present invention is preferably produced by an emulsion aggregation method when it has a single layer structure, and is preferably produced by an emulsion polymerization aggregation method when it has a core-shell structure.

  Hereinafter, preferred embodiments of the toner production method of the present invention will be specifically described.

  The production method of the electrostatic image developing toner according to the first embodiment of the present invention preferably has a process selected from the following.

(1) Preparation Step of Each Fine Particle Dispersion (1M-1) A wax-containing preparation for preparing a dispersion in which a wax-containing first resin fine particle containing a first resin and a wax is dispersed in an aqueous medium. Step 1 of preparing resin fine particle dispersion (1M-2) Second step of preparing a dispersion in which second resin fine particles are formed by the second resin in the aqueous medium and the second resin fine particles are dispersed. (1U) Wax-containing first obtained by dispersing wax-containing first and second resin fine particles containing a first resin, a second resin, and a wax in an aqueous medium. And wax-containing first and second resin fine particle dispersion preparation steps for preparing a second resin fine particle dispersion (1A) A dispersion in which colorant fine particles by a colorant are dispersed in an aqueous medium Preparation of Colorant Fine Particle Dispersion (Colorant Dispersion) Preparation Step (1B) Metal-containing compound fine particle dispersion (metal) for preparing a dispersion in which metal-containing compound fine particles are dispersed in an aqueous medium Dispersion of Containing Compound) Preparation Step (1C) Shell resin fine particle dispersion preparation step of forming a shell resin fine particle dispersion in which shell resin fine particles are formed in an aqueous medium and the shell resin fine particles are dispersed. (2) Mixing step of coloring agent fine particle dispersion and resin fine particle dispersion (first particle (core particle) forming step)
(2M-1) In a water-based medium, the wax-containing first resin fine particle dispersion, the second resin fine particle dispersion, and the colorant fine particle dispersion are mixed, and the wax-containing first resin fine particles, the second First particle forming step of aggregating resin fine particles and colorant fine particles to form first particles (core particles) (2U) Wax-containing first and second resin fine particle dispersions and a colorant in an aqueous medium First particle forming step of mixing fine particle dispersion and aggregating wax-containing first and second resin fine particles and colorant fine particles to form first particles (core particles). (3) First particles (3M) A shell resin fine particle dispersion is added to an aqueous medium in which first particles (core particles) are dispersed to form first particles (core particles). Shell tree on the surface of Shelling step for agglomerating and fusing fine particles to form second particles having a core-shell structure (4) Mixing the first fine particles or the dispersion containing the second particles with the fine metal compound dispersion A step of aggregating the first particles or the second particles and the metal-containing compound fine particles to form toner base particles. (5) An aging step of adjusting the shape of the toner base particles by aging with thermal energy. (6) Toner A cleaning step of filtering the first particles or the second particles (toner base particles) from the dispersion of the base particles (aqueous medium) and removing the surfactant from the toner base particles. Drying step of drying toner base particles (8) External additive addition step of adding an external additive to the dried toner base particles.

  In the electrostatic charge image developing toner according to the first embodiment of the present invention, it is preferable to use a crystalline polyester resin as the first resin and an amorphous polyester resin as the second resin. In this case, since the electrostatic charge image developing toner may have a single layer structure, the steps (1) to (4) include the steps (1A), (1B), (2U) and (4). preferable.

That is, as a method for producing a toner for developing an electrostatic image,
A dispersion containing a binder resin containing at least a crystalline polyester resin, and the following general formula (1):

In formula (1),
Rx ₁ and Rx ₂ are each independently a substituted or unsubstituted linear, branched or cyclic alkyl group having 1 to 20 carbon atoms,
Lx is a hydrogen atom or a substituted or unsubstituted linear, branched or cyclic alkyl group having 1 to 20 carbon atoms,
Gx ₁ is a substituted or unsubstituted linear, branched or cyclic alkyl group having 2 to 20 carbon atoms,
Gx ₂ is a substituted or unsubstituted, straight or branched alkyl group having 1 to 5 carbon atoms,
Gx ₃ is a hydrogen atom, a halogen atom, a group represented by Gx ₄ —CO—NH—, or a group represented by Gx ₅ —N (Gx ₆ ) —CO—, wherein Gx ₄ is a substituent. Gx ₅ and Gx ₆ are each independently a hydrogen atom or a substituent,
Qx ₁ , Qx ₂ , Qx ₃ , Qx ₄ , and Qx ₅ are each independently a hydrogen atom or a substituent,
A step (a) of mixing a dispersion containing a colorant represented by:
The dispersion obtained in the step (1) is added to the following general formula (2):

In formula (2),
R ₁ is a substituted or unsubstituted linear, branched or cyclic alkyl group having 1 to 20 carbon atoms,
R ₂ is a hydrogen atom, an alkoxycarbonyl group, an aryloxycarbonyl group, a sulfamoyl group, a sulfinyl group, an alkylsulfonyl group, an arylsulfonyl group, an acyl group, a halogen atom, or a cyano group,
R ₃ is a substituted or unsubstituted aromatic hydrocarbon-containing group having 9 to 120 carbon atoms,
M is a divalent metal element,
And a step (b) of mixing a dispersion containing a metal-containing compound represented by:

  If necessary, third resin fine particles (amorphous polyester resin or styrene-acrylic resin) can be further coated as a shell.

  In the case of using a styrene-acrylic resin as the first resin and a crystalline polyester resin as the second resin, the electrostatic image developing toner preferably has a core-shell structure. 1M-1), (1M-2), (1A), (1B), (1C), (2M), (3) and (4).

  In the present invention, the colorant and the metal-containing compound are not added to the dispersion at the same time when the toner particles are formed, but the metal-containing compound is added after the particles containing the colorant are aggregated and grown. preferable. By carrying out like this, an electric charge disperse | distributes and the effect as a charge control agent is exhibited more.

  Hereinafter, each process is explained in full detail.

(1) Preparation of each fine particle dispersion (resin fine particle dispersion)
The fine resin particle dispersion such as the first resin, the second resin, and the shell resin can be prepared by dispersing the resin in an aqueous medium. Since the resin is uniformly dispersed, the resin dispersion treatment is preferably performed in a state where the surfactant concentration is set to a critical micelle concentration (CMC) or higher in the aqueous medium.

  The resin dispersion treatment can be performed using, for example, mechanical energy, and various known dispersers can be used. Such a disperser is not particularly limited, and is a low speed shear disperser, a high speed shear disperser, a friction disperser, a high pressure jet disperser, an ultrasonic disperser, a high pressure impact disperser Ultima. Specifically, for example, HJP30006 (manufactured by Sugino Machine Co., Ltd.), Claremix W Motion CLM-0.8 (manufactured by M Technique Co., Ltd.), ultrasonic homogenizer US-150T (manufactured by Nippon Seiki Seisakusho) ) And the like.

  The average particle diameter of the resin fine particles obtained in the resin fine particle dispersion preparing step is preferably in the range of, for example, 50 to 500 nm in terms of volume-based median diameter.

  In this specification, the volume-based median diameter of the resin fine particles, the colorant fine particles, and the metal-containing compound fine particles is “MICROTRAC UPA-150” (manufactured by HONEYWELL), sample refractive index 1.59, sample specific gravity 1 .05 (in terms of spherical particles), solvent refractive index of 1.33, solvent viscosity of 0.797 (30 ° C.) and 1.002 (20 ° C.), 0 points by adding ion-exchanged water to the measurement cell It is a value measured by adjusting.

  In the present specification, the “aqueous medium” refers to a medium composed of 50 to 100% by mass of water and 0 to 50% by mass of a water-soluble organic solvent. Examples of the water-soluble organic solvent include methanol, ethanol, isopropanol, butanol, acetone, methyl ethyl ketone, ethyl acetate, dimethylformamide, methyl cellosolve, and tetrahydrofuran. Of these, it is preferable to use an organic organic solvent such as methanol, ethanol, isopropanol, and butanol, ethyl acetate, or methyl ethyl ketone, which is an organic solvent that does not dissolve the resin. Preferably, only water is used as the aqueous medium.

  A dispersion stabilizer is preferably added to the aqueous medium in order to prevent aggregation of dispersed droplets.

  As the dispersion stabilizer, various known surfactants such as a cationic surfactant, an anionic surfactant, and a nonionic surfactant can be used.

  Specific examples of the cationic surfactant include dodecyl ammonium bromide, dodecyl trimethyl ammonium bromide, dodecyl pyridinium chloride, dodecyl pyridinium bromide, hexadecyl trimethyl anonium bromide and the like.

  Specific examples of nonionic surfactants include dodecyl polyoxyethylene ether, hexadecyl polyoxyethylene ether, norylphenyl polyoxyethylene ether, lauryl polyoxyethylene ether, sorbitan monooleate polyoxyethylene ether, styrylphenyl poly Examples thereof include oxyethylene ether and monodecanoyl sucrose.

  Specific examples of anionic surfactants include aliphatic soaps such as sodium stearate and sodium laurate, sodium lauryl sulfate, sodium dodecyl sulfate, sodium dodecylbenzene sulfonate, polyoxyethylene (2) sodium lauryl ether sulfate, etc. Can be mentioned.

  Surfactant can be used individually by 1 type or in combination of 2 or more type as needed.

  In the aqueous medium, a flocculant may be used to promote emulsification / aggregation. The flocculant is not particularly limited, but one selected from metal salts is preferably used. Examples of the metal salt include monovalent metal salts such as alkali metal salts such as sodium, potassium and lithium; divalent metal salts such as calcium, magnesium, manganese and copper; and trivalent metal salts such as iron and aluminum. Etc. Specific examples of the metal salt include sodium chloride, potassium chloride, lithium chloride, calcium chloride, magnesium chloride, zinc chloride, copper sulfate, magnesium sulfate, and manganese sulfate. These can be used individually by 1 type or in combination of 2 or more types.

  Further, when the resin is dispersed in the aqueous medium, the resin fine particle dispersion may be prepared by adding the aqueous medium after dissolving the resin in the water-soluble organic solvent.

(Colorant fine particle dispersion)
The colorant fine particle dispersion can be prepared by dispersing a colorant in an aqueous medium. The colorant dispersion treatment is preferably performed in a state where the surfactant concentration in the aqueous medium is not less than the critical micelle concentration (CMC) since the colorant is uniformly dispersed. As the disperser used for the dispersion treatment of the colorant, various known dispersers can be used, and the same ones as described in the section of the resin fine particle dispersion can be used.

  The average particle diameter of the colorant fine particles obtained in the colorant fine particle dispersion preparing step is preferably in the range of, for example, 10 to 300 nm in terms of volume-based median diameter.

  As the aqueous medium, surfactant and the like used in the colorant fine particle dispersion, the same resin fine particle dispersion as that described above can be used.

  In addition, the content of the colorant fine particles in the colorant fine particle dispersion is preferably in the range of 10 to 50% by mass, and more preferably in the range of 15 to 40% by mass. Within such a range, there is an effect of ensuring color reproducibility.

  The colorant may be introduced into the toner particles by, for example, dissolving or dispersing in advance in the monomer solution for forming the core resin in the wax-containing core resin fine particle dispersion preparation step.

(Metal-containing compound fine particle dispersion)
The metal-containing compound fine particle dispersion can be prepared by dispersing the metal-containing compound in an aqueous medium. The dispersion treatment of the metal-containing compound is preferably performed in a state where the surfactant concentration is set to a critical micelle concentration (CMC) or higher in the aqueous medium because the colorant is uniformly dispersed. As the disperser used for the dispersion treatment of the metal-containing compound, various known dispersers can be used, and the same ones described in the section of the resin fine particle dispersion can be used.

  The average particle size of the metal-containing compound fine particles obtained in the metal-containing compound fine particle dispersion preparing step is preferably in the range of, for example, 50 to 500 nm in terms of volume-based median diameter.

  As the aqueous medium, surfactant and the like used in the metal-containing compound fine particle dispersion, the same resin fine particle dispersion as that described above can be used.

(Resin fine particle dispersion containing wax)
The wax-containing resin fine particle dispersion means a resin fine particle dispersion containing wax, and the resin is the first resin and / or the second resin.

  In the wax-containing resin fine particle dispersion preparing step, resin fine particles containing wax and resin are formed, and this is used for the first particle (core particle) forming step.

  Specifically, the wax-containing resin fine particles include a wax and, if necessary, a polymerizable monomer for forming a resin or a resin in an aqueous medium containing a surfactant having a critical micelle concentration (CMC) or less. Accordingly, a solution in which other toner components such as a charge control agent are dissolved or dispersed is added, and mechanical energy is applied at a temperature equal to or higher than the melting point of the wax to form droplets. When a polymerizable monomer is used as the resin, a water-soluble radical polymerization initiator is added to advance the polymerization reaction in the droplets. An oil-soluble polymerization initiator may be contained in the droplet. In such a wax-containing resin fine particle dispersion preparation step, mechanical emulsification (formation of droplets) is compulsory by applying mechanical energy. Examples of the means for applying mechanical energy include means for applying strong stirring or ultrasonic vibration energy such as homomixer, ultrasonic wave, and manton gorin.

  In some cases, after dissolving the resin and wax in an organic solvent such as ethyl acetate, the solution is added to an aqueous surfactant solution and finely dispersed by mechanical means, and then the solvent is removed.

  The wax-containing resin fine particles formed in the step of preparing the wax-containing resin fine particle dispersion may have a structure of two or more layers made of resins having different compositions. In this case, an emulsion polymerization treatment ( A method of adding a polymerization initiator and a polymerizable monomer to a dispersion of resin fine particles prepared by the first stage polymerization) and polymerizing the system (second stage polymerization) can be employed. In this case, the wax may be contained in any layer, but it is preferably contained in the intermediate layer particularly in the case of a three-layer structure.

  When a surfactant is used in the wax-containing resin fine particle dispersion preparation step, the same surfactant as the surfactant that can be used in the above resin fine particle dispersion preparation step, for example, is used. Can be used.

  The average particle diameter of the resin fine particles obtained in the wax-containing resin fine particle dispersion preparing step is preferably in the range of, for example, 50 to 500 nm in terms of volume-based median diameter.

(2) Mixing step of coloring agent fine particle dispersion and resin fine particle dispersion (first particle (core particle) forming step)
Specific examples of the first particle (core particle) forming step include the above (2M-1) and (2U).

  In the first particle (core particle) formation step, fine particles of other toner constituent components such as a charge control agent are aggregated together with resin fine particles and colorant fine particles that become the first particles (core particles) as necessary. It can also be made.

  As a specific method for agglomerating and fusing the resin fine particles and colorant fine particles to be the first particles (core particles), an aggregating agent is added to an aqueous medium so as to have a critical aggregation concentration or more, and then the core resin is added. By heating to a temperature above the glass transition point of the fine particles and above the melting peak temperature (° C.) of these mixtures, fine particles such as resin fine particles and colorant fine particles that become the first particles (core particles) In order to proceed with salting out and simultaneously proceed with fusion and grow to the desired particle size, add a coagulation terminator to stop particle growth, and further control the particle shape as necessary In this method, heating is continued.

[Flocculant]
The flocculant used in the core particle forming step is not particularly limited, but a material selected from metal salts is preferably used. Examples of the metal salt include monovalent metal salts such as alkali metal salts such as sodium, potassium and lithium; divalent metal salts such as calcium, magnesium, manganese and copper; and trivalent metal salts such as iron and aluminum. Etc. Specific metal salts can include sodium chloride, potassium chloride, lithium chloride, calcium chloride, magnesium chloride, zinc chloride, copper sulfate, magnesium sulfate, manganese sulfate, and the like. It is particularly preferable to use a divalent metal salt. These can be used individually by 1 type or in combination of 2 or more types.

  When a surfactant is used in the first particle (core particle) formation step, the same surfactant as the surfactant that can be used, for example, in the above-described resin fine particle dispersion preparation step is used. Can be used.

As for the particle size of the first particle (core particle) obtained in the first particle (core particle) formation step, for example, the volume-based median diameter (D ₅₀ ) is preferably 2 to 9 μm, more preferably. 4-7 μm. The volume-based median diameter of the first particles (core particles) is measured by “Coulter Multisizer 3” (manufactured by Coulter Beckman).

(3) Shelling step for coating the first particles to form a core-shell structure Specific examples of the shelling step include (3M) above.

  In the shelling step, the shell resin fine particles are added to the dispersion of the first particles (core particles), and the shell resin fine particles are aggregated and fused on the surfaces of the first particles (core particles). The surface of the particles (core particles) is covered with a shell layer to form second particles.

  Specifically, the dispersion of the first particles (core particles) is added with the dispersion of the shell resin fine particles while maintaining the temperature in the first particle (core particle) formation step, and the heating and stirring are continued. A shell layer having a thickness of 100 to 300 nm is coated on the surface of the first particle (core particle) by slowly aggregating and fusing the shell resin fine particles on the surface of the first particle (core particle) over several hours. To form second particles. The heating and stirring time is preferably 1 to 7 hours, particularly preferably 3 to 5 hours.

  Note that when the toner is not a core-shell structure but a single layer structure, the shelling step can be omitted.

(4) Step of adding metal-containing compound fine particles and forming toner base particles The metal compound fine particle dispersion is mixed with the dispersion containing the first particles or the second particles obtained in the above step, The toner base particles are formed by aggregating the first or second particles and the metal-containing compound fine particles. The temperature and time for adding the metal-containing compound fine particle dispersion are not particularly limited. For example, from the viewpoint of setting the circularity of the toner base particles to a desired range, it is preferably 70 to 95 ° C, more preferably 75 to 90 ° C. More preferably, the mixture is stirred at 80 to 87 ° C., preferably for 60 to 300 minutes, more preferably for 120 to 250 minutes. Thereby, the coloring agent represented by Formula (1) and the metal containing compound represented by Formula (2) fully react, and a reaction compound can be obtained.

(5) Ripening step The toner particle shape in the toner can be made uniform to some extent by controlling the heating temperature in the first particle (core particle) forming step and the shelling step, but the shape can be made more uniform. In order to plan, it goes through an aging process.

  This aging step is controlled by controlling the heating temperature and time so that the surface of the toner base particles formed with a uniform particle size and a narrow distribution has a smooth but uniform shape. Specifically, in the first particle (core particle) forming step and the shelling step, the heating temperature is lowered to suppress the progress of fusion between the resin fine particles to promote the leveling, and also in this ripening step. The toner base particles are controlled to have a desired average circularity, that is, to have a uniform surface, by lowering the heating temperature and increasing the time.

(6) Washing step to (7) Drying step The washing step and the drying step can be performed by employing various known methods.

(8) External additive addition step This external additive addition step is a step of adding and mixing external additives as necessary to the dried toner base particles.

  The toner base particles prepared through the steps up to the drying step can be used as toner particles as they are, but are known on the surface from the viewpoint of improving charging performance, fluidity, or cleaning properties as a toner. It is preferable to add particles such as inorganic fine particles and organic fine particles and a lubricant as external additives.

  Various external additives may be used in combination. The amount of these external additives added is 0.05 to 5 parts by mass, preferably 0.1 to 3 parts by mass with respect to 100 parts by mass of the toner base particles.

  Examples of the method of adding the external additive include a dry method in which the external additive is added in powder form to the dried toner base particles. Examples of the mixing device include mechanical mixing devices such as a Henschel mixer and a coffee mill. It is done.

  Further, for example, the wax is not limited to the method of introducing into the core particles by the mini-emulsion method that is contained during the polymerization of the styrene-acrylic resin that constitutes the core resin as described above. A method of introducing a dispersion of wax fine particles, which is introduced into the core particles by aggregating them together with core resin fine particles not containing wax and colorant fine particles to form core particles in the core particle forming step, is adopted. You can also.

  In the toner manufacturing method of the present invention, it is preferable to employ a method in which the wax is introduced into the first particles (core particles) by the miniemulsion method.

<Developer>
The developer of the present invention is characterized by containing the toner of the first embodiment, but the toner for developing an electrostatic image is used as it is as a one-component developer containing one component or as a two-component developer. be able to. When used as a two-component developer, it is preferably mixed with a carrier.

  There is no restriction | limiting in particular as a carrier which can be used for a two-component developer, A well-known carrier can be used. For example, magnetic metals such as iron oxide, nickel and cobalt, magnetic oxides such as ferrite and magnetite, etc., and using these as a core material, a resin-coated carrier having a resin coating layer on the core material surface, a magnetic dispersion type carrier, etc. Can be mentioned. Further, a resin-dispersed carrier in which a conductive material or the like is dispersed in a matrix resin may be used.

  The carrier preferably has a volume average particle diameter of 15 to 100 μm, more preferably 25 to 60 μm. The volume average particle diameter (volume reference median diameter) of the carrier can be measured by the method described in the examples.

  Examples of the coating resin used for the carrier include polyethylene, polypropylene, polystyrene, polyvinyl acetate, polyvinyl alcohol, polyvinyl butyral, polyvinyl chloride, polyvinyl ether, polyvinyl ketone, vinyl chloride-vinyl acetate copolymer, styrene-acrylic acid copolymer. Examples include polymers, straight silicone resins composed of organosiloxane bonds or modified products thereof, fluororesins, polyester resins, polycarbonates, phenol resins, epoxy resins, and the like, but are not limited thereto.

  Examples of the core material of the carrier include magnetic metals such as iron, nickel, and cobalt, magnetic oxides such as ferrite and magnetite, and glass beads. However, in order to use the carrier for the magnetic brush method, it is a magnetic material. It is preferable. The volume average particle diameter of the carrier core material is generally in the range of 10 to 200 μm, and preferably in the range of 25 to 100 μm.

  In order to coat the surface of the core material of the carrier with a resin, there may be mentioned a method of coating with a coating layer forming solution prepared by dissolving the coating resin and, if necessary, various additives in an appropriate solvent. The solvent is not particularly limited and may be appropriately selected in consideration of the coating resin to be used, coating suitability, and the like.

  The mixing ratio (mass ratio) between the toner of the present invention and the carrier in the two-component developer is not particularly limited, but from the viewpoints of chargeability and storage stability, toner: carrier = 1: 100 to 30: 100. Is preferable, and the range of 3: 100 to 20: 100 is more preferable.

<Image forming method>
The above toner can be suitably used in an image forming method including a fixing step by a contact heating method. Specifically, as an image forming method, an electrostatic latent image formed electrostatically on, for example, an image carrier using the toner as described above, and a developer in a developing device by a friction charging member. By revealing the toner image by charging to obtain a toner image, transferring the toner image to the recording material, and then fixing the toner image transferred on the recording material to the recording material by a contact heating type fixing process, A visible image is obtained. That is, the toner of the present invention is used for developing an electrostatic image.

<Fixing method>
As a suitable fixing method using the toner of the present invention, a so-called contact heating method can be mentioned. Examples of the contact heating method include a heat pressure fixing method, a heat roll fixing method, and a pressure contact heat fixing method in which fixing is performed by a rotating pressure member including a fixedly arranged heating body.

  In the fixing method of the hot roll fixing method, usually, an upper roller provided with a heat source inside a metal cylinder made of iron or aluminum whose surface is coated with fluororesin, etc., and a lower roller formed of silicone rubber or the like Is used.

  As the heat source, a linear heater is used, and the surface temperature of the upper roller is heated to about 120 to 200 ° C. by this heater. A pressure is applied between the upper roller and the lower roller, and the lower roller is deformed by this pressure, so that a so-called nip is formed in the deformed portion. The width of the nip is 1 to 10 mm, preferably 1.5 to 7 mm. The fixing linear velocity is preferably 40 mm / sec to 600 mm / sec. If the nip width is too small, heat cannot be uniformly applied to the toner, which may cause uneven fixing. On the other hand, if the nip width is too large, it is contained in the toner particles. There is a possibility that the melting of the polyester resin is promoted and fixing offset occurs.

  As mentioned above, although embodiment of this invention was described, this invention is not limited to said aspect, A various change can be added.

  Hereinafter, representative embodiments of the present invention will be shown and the present invention will be further described, but the present invention is of course not limited to these embodiments. In the examples, unless otherwise specified, “part” represents “part by mass” and “%” represents “% by mass”.

  <Synthesis of Colorant (1-1)>

Add 50 ml of toluene and 0.53 g of morpholine with stirring to 1.93 g of intermediate 1 and 1.53 g of intermediate 2, stir, heat to reflux, and react for 8 hours while dehydrating through an ester tube. After completion of the reaction, the reaction solution was concentrated, purified by column chromatography, and recrystallized from a mixed solvent of ethyl acetate / hexane to obtain DX-1: 2.71 g. The product was identified by MASS, ¹ H-NMR, and IR spectrum, and confirmed to be the target product. The purity of the obtained colorant (1-1) was 98% as a result of analysis by ¹ H-NMR. When visible absorption spectrum measurement (solvent: ethyl acetate) of the colorant (1-1) was performed, the maximum absorption wavelength was 535 nm, and the molar absorption coefficient was 71000 (L / mol · cm).

Hereinafter, the colorant represented by the formula (1) used in the examples was synthesized using the corresponding raw materials (by changing the corresponding substituents) in the same manner as described above. . Each purity was analyzed by ¹ H-NMR and confirmed to be 95% or more.

  <Synthesis of metal-containing compound (Compound No. 2-8 (metal: Cu))>

(Synthesis of Compound B)
Add 500g of compound A, 21.5g of cyanoacetic acid, 1.31g of p-toluenesulfonic acid monohydrate and 300ml of toluene to a 500ml three-necked flask and heat and reflux for 2h while dehydrating using an ester tube Then, after distilling off the solvent under reduced pressure, 94.4 g of Compound B was obtained by adding 500 ml of acetone and recrystallizing.

(Synthesis of Compound C)
To a 100 ml three-necked flask, 5 g of Compound B, 25 ml of toluene, 3.3 g of triethylamine and 2.42 g of calcium chloride were added and heated to 80 ° C. and stirred. After the internal temperature reached 80 ° C., 2.1 g of acetyl chloride was added dropwise over 1 h. After completion of the dropwise addition, the mixture was cooled, separated with dilute hydrochloric acid, neutralized with pure water, and the solvent was distilled off. 4.3 g of compound C was obtained by adding 50 ml of toluene and 50 ml of ethyl acetate and recrystallizing.

(Synthesis of metal-containing compound 2-8)
2 g of Compound C and 80 ml of acetone were added to a 200 ml three-necked flask and heated and stirred until the internal temperature reached 55 ° C. Thereafter, 0.55 g of copper acetate monohydrate was dissolved in 5 ml of a solvent of MeOH / water = 5/1 and added dropwise over 30 minutes. After completion of the dropwise addition, 1.4 g of metal-containing compound 2-8 (metal: Cu) was obtained by filtering the precipitated solid. The obtained metal compound 2-8 (metal: Cu) had a transmittance of 98% at 500 nm (solvent: THF) and a purity of 98%.

  Hereinafter, the metal-containing compounds represented by the formula (2) used in the examples are synthesized in the same manner as described above using corresponding raw materials (by changing the corresponding substituents). It was. The purity of each metal-containing compound was confirmed to be 90% or more by measuring the transmittance at 500 nm.

<Preparation of Toner 1>
Synthesis of crystalline polyester resin [C-PEs1] In a flask, 10 parts by mass of 1,9-nonanediol and 10 parts by mass of 1,10-dodecanedioic acid, and catalyst Ti (OBu) ₄ (based on the polyvalent carboxylic acid component) , 0.014% by mass), and the air in the container was depressurized by depressurization, and the mixture was refluxed at 180 ° C. for 6 hours with mechanical stirring under an inert atmosphere with nitrogen gas. Thereafter, unreacted monomer components were removed by distillation under reduced pressure, the temperature was gradually raised to 220 ° C., the mixture was stirred for 12 hours, sampled when it became a viscous state, and a crystalline polyester resin [C-PEs1] Got. The acid value of the crystalline polyester resin [C-PEs1] was 23 mgKOH / g. The resulting crystalline polyester resin [C-PEs1] had a melting temperature (Tc) of 78 ° C., a weight average molecular weight of 12,000, and a number average molecular weight of 4000.

Synthesis of Amorphous Polyester Resin [A-PEs1] In a reaction vessel equipped with a cooling tube, a stirrer, and a nitrogen introduction tube, 316 parts by mass of bisphenol A propylene oxide 2-mole adduct, 80 parts by mass of terephthalic acid, 34 fumaric acid Part by mass and 2 parts by mass of titanium tetraisopropoxide as a polycondensation catalyst were added in 10 portions and reacted at 200 ° C. for 10 hours while distilling off the water produced under a nitrogen stream. Subsequently, it was made to react under reduced pressure of 13.3 kPa (100 mmHg), and it pick_out | removed when the softening point became 104 degreeC, and obtained amorphous polyester resin [A-PEs1]. The obtained amorphous polyester resin [A-PEs1] had a glass transition temperature (Tg) of 60 ° C., a weight average molecular weight of 15,000, and a number average molecular weight of 10,000.

Preparation of wax-containing resin fine particle dispersion (1) [Step (1U)]
90 parts by mass of a crystalline polyester resin [C-PEs1] and 510 parts by mass of an amorphous polyester resin [A-PEs1] were added and dissolved in 2400 parts by mass of ethyl acetate (manufactured by Kanto Chemical Co., Inc.). Thereafter, 30 parts by mass of paraffin wax (melting point: 73 ° C.) was added as a release agent and dissolved by heating. Next, the mixture was mixed with 2400 parts by mass of a sodium lauryl sulfate solution having a concentration of 0.26% by mass prepared in advance, and ultrasonicated with an ultrasonic homogenizer “US-150T” (manufactured by Nippon Seiki Seisakusho) at 300 μA for 30 minutes. After dispersion, using a diaphragm vacuum pump “V-700” (manufactured by BUCHI) while being heated to 50 ° C., the ethyl acetate was completely removed while stirring for 6 hours under reduced pressure. A wax-containing resin fine particle dispersion (1) having a median diameter (D ₅₀ ) of 250 nm and a solid content of 20% by mass was prepared.

Preparation of Colorant Dispersion Liquid (1) [Step (1A)]
A surfactant aqueous solution was prepared by stirring and dissolving 63 parts by mass of sodium n-dodecyl sulfate in 880 parts by mass of ion-exchanged water. To this surfactant aqueous solution, 80 parts by mass of the compound represented by (1-1) and 100 parts by mass of quinacridone are gradually added as a colorant, and then “CLEAMIX (registered trademark) W motion CLM-0.8. "(M Technique Co., Ltd.) was used for dispersion treatment to prepare a colorant dispersion (1) having a solid content of 16% by mass in which particles of the colorant (1-1) were dispersed.

  The volume-based median diameter of the colorant particles in this colorant dispersion (1) was 260 nm.

  The volume-based median diameter is “MICROTRAC UPA-150” (manufactured by HONEYWELL), sample refractive index 1.59, sample specific gravity 1.05 (in terms of spherical particles), solvent refractive index 1.33, solvent viscosity. The measurement was performed by adjusting the zero point by introducing ion-exchanged water into the measurement cell under the measurement conditions of 0.797 (30 ° C.) and 1.002 (20 ° C.).

Preparation of dispersion (1) of metal-containing compound [Step (1B)]
89 parts by mass of the metal-containing compound (Compound No. 2-3 (metal: Cu)) shown in Table 1 was added to a solution obtained by dissolving 16 parts by mass of sodium dodecyl sulfate in 530 parts by mass of ion-exchanged water, and stirring and By applying ultrasonic waves, a dispersion liquid of a metal-containing compound (1) having a solid content of 14% by mass was prepared. The volume-based median diameter was 270 nm.

Preparation of toner base particles (1) [Steps (2U), (4) and (5)]
In a 5 L stainless steel reactor equipped with a stirrer, a cooling tube, and a temperature sensor, 2250 parts by mass of the wax-containing resin fine particle dispersion (1), 1400 parts by mass of ion-exchanged water, and 138 parts by mass of the colorant dispersion (1) are added. The pH was adjusted to 10 using a 5 mol / liter aqueous sodium hydroxide solution while stirring. Next, with stirring, an aqueous magnesium chloride solution in which 60 parts by mass of magnesium chloride hexahydrate was dissolved in 60 parts by mass of ion-exchanged water was added dropwise over 10 minutes, the internal temperature was raised to 75 ° C., and “Multisizer 3 ”(Beckman Coulter, Aperture diameter: 50 μm) was used to measure the particle size. When the average particle size reached 6.5 μm, 125 parts by mass of the metal-containing compound dispersion (1) was added dropwise. Thereafter, when the supernatant of the reaction solution becomes transparent (the reaction between the colorant and the metal-containing compound is completed to form a reaction compound), 50 parts by mass of sodium chloride is dissolved in 200 parts by mass of ion-exchanged water. The aqueous solution was added, and the mixture was further heated and stirred, and the internal temperature was cooled to 25 ° C. when the average circularity reached 0.960 using a flow type particle image measurement device “FPIA-2100” (manufactured by Sysmex). The toner base particles (1) thus obtained had a volume-based median diameter (D ₅₀ ) of 6.1 μm.

Washing step and drying step [steps (6) and (7)]
The dispersion of toner base particles (1) was subjected to solid-liquid separation with a centrifugal separator to form a wet cake of toner base particles (1). The wet cake was washed with ion-exchanged water at 35 ° C. until the electric conductivity of the droplet became 5 μS / cm by a centrifuge. Thereafter, the toner was transferred to a “flash jet dryer” (manufactured by Seishin Enterprise Co., Ltd.) and dried until the water content became 0.5% by mass to obtain toner base particles (1).

External additive processing step [step (8)]
To the toner base particles (1), 1% by mass of hydrophobic silica having a number average primary particle size of 12 nm, 0.3% by mass of hydrophobic silica having a number average primary particle size of 80 nm, hydrophobic titania (number average) Toner 1 was prepared by adding 0.3% by mass (primary particle size = 20 nm) and mixing with a Henschel mixer. The obtained toner 1 had a volume-based median diameter (D ₅₀ ) of 6.1 μm and a softening point of 99 ° C.

<Preparation of Toner 2>
In the preparation of the wax-containing resin fine particle dispersion (1), the crystalline polyester resin and the amorphous polyester resin are 30 parts by mass of the crystalline polyester resin [C-PEs1] and the amorphous polyester resin [A-PEs1]. It was produced in the same manner as Toner 1 except that the amount was changed to 570 parts by mass.

<Preparation of Toner 3>
The crystalline polyester resin [C-PEs1] 210 parts by mass of the crystalline polyester resin and the amorphous polyester resin at the time of preparation of the wax-containing resin fine particle dispersion (1), and the amorphous polyester resin [A-PEs1] It was produced in the same manner as Toner 1 except that the amount was changed to 390 parts by mass.

<Preparation of Toner 4>
Core: Crystalline polyester / styrene-acrylic resin Shell: Non-crystalline polyester resin Preparation of dispersion 1 of resin particles for shell [Step (1C)]
As a shell resin, 100 parts by mass of an amorphous polyester resin [A-PEs1] was dissolved in 400 parts by mass of ethyl acetate.

  Subsequently, 25 mass parts of 5.0 mass% sodium hydroxide aqueous solution was added, and the resin solution was formed. This resin solution was put into a container having a stirrer, and 400 parts by mass of a 0.26 mass% sodium lauryl sulfate aqueous solution was dropped and mixed over 30 minutes while stirring the resin solution. During the dropping of the sodium lauryl sulfate aqueous solution, the liquid in the reaction vessel became cloudy, and after the entire amount of the sodium lauryl sulfate aqueous solution was dropped, an emulsion was formed in which the resin solution particles were uniformly dispersed.

  Next, the emulsion was heated to 40 ° C., and using a diaphragm vacuum pump “V-700” (manufactured by BUCHI), ethyl acetate was distilled off under a reduced pressure of 150 hPa to obtain a solid content of 20% by mass. The “resin particle dispersion 1 for shell” was obtained. The volume-based median diameter of the particle diameter of the shell resin particles in dispersion 1 of the shell resin particles was 245 nm.

Preparation of Wax-Containing Styrene-Acrylic Resin Fine Particle Dispersion 1 [Step (1M-1)]
(First stage polymerization)
An anion obtained by dissolving 2.0 parts by mass of anionic surfactant “sodium lauryl sulfate” in 2900 parts by mass of ion-exchanged water in a reaction vessel equipped with a stirrer, a temperature sensor, a temperature controller, a cooling pipe and a nitrogen introducing unit. The internal temperature was raised to 80 ° C. while charging the surfactant solution and stirring at a stirring speed of 230 rpm under a nitrogen stream.

To this surfactant solution, 9.0 parts by mass of a polymerization initiator “potassium persulfate: KPS” was added and the internal temperature was adjusted to 78 ° C.
Solution (1)
Styrene 540 parts by weight n-butyl acrylate 270 parts by weight Methacrylic acid 65 parts by weight n-octyl mercaptan 17 parts by weight of solution (1) was added dropwise over 3 hours, and after completion of the addition, heating and stirring at 78 ° C. for 1 hour Thus, polymerization (first stage polymerization) was performed to prepare “Styrene-acrylic resin dispersion 1a”.

(Second stage polymerization: formation of intermediate layer)
In a flask equipped with a stirrer,
Solution (2)
Styrene 94 parts by weight n-butyl acrylate 60 parts by weight Methacrylic acid 11 parts by weight n-octyl mercaptan 5 parts by weight Paraffin wax (melting point: 73 ° C.) 51 parts by weight as a release agent was added, A monomer solution [2] was prepared by heating to 85 ° C. and dissolving.

  On the other hand, a surfactant solution in which 2 parts by mass of the anionic surfactant “sodium lauryl sulfate” was dissolved in 1100 parts by mass of ion-exchanged water was heated to 90 ° C. After adding 28 parts by mass of “Styrene-acrylic resin dispersion 1a” in terms of solid content of styrene-acrylic resin to this surfactant solution, mechanical disperser “CLEARMIX” having a circulation path (M Technique) The monomer solution [2] was mixed and dispersed for 4 hours to prepare a dispersion containing emulsified particles having a dispersed particle diameter of 350 nm. To this dispersion was added an initiator aqueous solution in which 2.5 parts by mass of a polymerization initiator “KPS” was dissolved in 110 parts by mass of ion-exchanged water, and this system was polymerized by heating and stirring at 90 ° C. for 2 hours. (Second-stage polymerization) was performed to prepare “Styrene-acrylic resin dispersion 1b”.

(Third-stage polymerization: formation of outer layer)
An initiator aqueous solution in which 2.5 parts by mass of a polymerization initiator “KPS” is dissolved in 110 parts by mass of ion-exchanged water is added to the above “styrene-acrylic resin dispersion 1b”. ,
Solution (3)
Styrene 230 mass parts n-butyl acrylate 100 mass parts n-octyl mercaptan Solution (3) which consists of 5.2 mass parts was dripped over 1 hour. After completion of the dropwise addition, polymerization (third stage polymerization) was performed by heating and stirring for 3 hours. Then, it cooled to 28 degreeC and prepared "the wax containing styrene-acrylic resin fine particle dispersion 1" of 30 mass% of solid content. The volume-based median diameter of the wax-containing styrene-acrylic resin fine particle dispersion 1 in the wax-containing styrene-acrylic resin fine particle dispersion 1 was 220 nm.

Preparation of Crystalline Polyester Resin [C-PEs1] Dispersion 1 [Step (1M-2)]
The crystalline polyester resin is prepared in the same manner except that the crystalline polyester resin [C-PEs1] is used in place of the amorphous polyester resin [A-PEs1] in the preparation process of the dispersion 1 of resin fine particles for shell. An aqueous dispersion of fine particles [C-PEs1] was prepared. The volume-based median diameter of the crystalline polyester resin fine particles in the crystalline polyester resin fine particle dispersion 1 was measured to be 250 nm.

Preparation of toner base particles (4) [Steps (2M-1), (3M), (4) and (5)]
In a reaction vessel equipped with a stirrer, a temperature sensor, and a cooling pipe, 1125 parts by mass of “wax-containing styrene-acrylic resin fine particle dispersion 1” and “crystalline polyester resin [C-PEs1] dispersion 1” were 337.5. After adding 1 part by mass and 1380 parts by mass of ion-exchanged water, a 5 mol / liter sodium hydroxide aqueous solution was added to adjust the pH to 10 at 25 ° C. Thereafter, 140 parts by mass of “Colorant particle dispersion 1” was added.

  Next, an aqueous solution in which 60 parts by mass of magnesium chloride was dissolved in 60 parts by mass of ion-exchanged water was added over 10 minutes at 30 ° C. with stirring.

Thereafter, the temperature was raised after being allowed to stand for 3 minutes, and the temperature of the system was raised to 80 ° C. over 60 minutes, and the particle growth reaction was continued while maintaining 80 ° C. In this state, the particle size of the associated particles was measured with “Coulter Multisizer 3” (manufactured by Coulter Beckman), and when the median diameter (D ₅₀ ) on a volume basis reached 6.0 μm, “amorphous polyester resin” 225 parts by mass of [A-PEs1] dispersion 1] was added over 30 minutes, and 120 parts by mass of the dispersion of metal-containing compound 1 was added dropwise when the supernatant of the reaction solution became transparent. When the supernatant of the reaction solution becomes transparent (the reaction between the colorant and the metal-containing compound is completed to form a reaction compound), an aqueous solution in which 53 parts by mass of sodium chloride is dissolved in 210 parts by mass of ion-exchanged water is added. Grain growth was stopped.

Further, the temperature is raised and the mixture is heated and stirred in a state of 90 ° C. to advance the fusing of the particles, and the average circularity measurement apparatus “FPIA-2100” (manufactured by Sysmex) is used (HPF detection). When the average circularity reached 0.945, the mixture was cooled to 30 ° C. to prepare “Dispersion of toner base particle 4”. The toner base particles (4) thus obtained had a volume-based median diameter (D ₅₀ ) of 6.2 μm.

Cleaning step, drying step and external additive treatment step [steps (6), (7) and (8)]
“Toner 4” was prepared in the same manner as Toner 1. The toner 4 thus obtained had a volume-based median diameter (D ₅₀ ) of 6.2 μm and a softening point of 104 ° C.

<Preparation of Toner 5>
The same procedure as in the preparation of the toner 1 was performed except that the colorant was changed to 1-2.

<Preparation of Toner 6>
A toner 6 was obtained in the same manner as in the preparation of the toner 1 except that the substituents of the colorant and the metal-containing compound were changed as shown in Table 1.

<Preparation of Toners 7 to 11>
Toners 7 to 11 were obtained in the same manner as in Toner 1 except that the colorant and the substituents of the metal-containing compound were changed as shown in Table 1.

<Preparation of Toners 12 to 15>
Toners 12 to 15 were obtained in the same manner as in Toner 4 except that the colorant and the substituents of the metal-containing compound were changed as shown in Table 1.

<Preparation of Toner 16>
A toner 16 was obtained in the same manner as in the preparation of the toner 1 except that the metal M of the metal-containing compound was changed to Mg.

<Preparation of Toner 17>
A crystalline polyester resin [C-PEs2] was obtained in the same manner except that the mechanical stirring time during the synthesis of the crystalline polyester resin [C-PEs1] was changed to 12 hours. Subsequent steps were performed in the same manner as in the production method of the toner 1 to obtain the toner 17.

<Preparation of Toner 18>
A crystalline polyester resin [C-PEs3] was obtained in the same manner except that the mechanical stirring time during the synthesis of the crystalline polyester resin [C-PEs1] was changed to 3.5 hours. Subsequent steps were performed in the same manner as in the production method of the toner 1 to obtain the toner 18.

<Preparation of Toners 19 to 20>
Toners 19 to 20 were obtained in the same manner as in the preparation of the toner 16 except that the substituents of the colorant and the metal-containing compound were changed as shown in Table 3.

<Preparation of Toners 21-22>
Toners 21 to 22 were obtained in the same manner as in the preparation of toner 17 except that the substituents of the colorant and the metal-containing compound were changed as shown in Table 3.

<Preparation of Toner 23>
A toner 23 was obtained in the same manner as in the preparation of the toner 18 except that the substituents of the colorant and the metal-containing compound were changed as shown in Table 3.

<Preparation of Toners 24-26>
Toners 24 to 26 were obtained in the same manner as in Toner 1 except that the parts by mass of the dispersion 1 of crystalline polyester [C-PEs1] at the time of preparation of Toner 1 were prepared as shown in Table 5.

<Preparation of Toner 27>
A toner 27 was obtained in the same manner as in the toner 1 except that no metal-containing compound was contained.

[Evaluation of toner performance]
With respect to the toners 1 to 27 obtained above, the charge amount, the fog, the fixability, and the color reproducibility were evaluated as follows, and comprehensive judgment was performed.

(Charge amount)
A commercial copier “bizhub PRO C6501” (manufactured by Konica Minolta) was prepared, and 500,000 character images with a printing rate of 5% were printed on A4-size transfer paper. Variation in quantity (after 500,000 prints-initial) was evaluated.
-Evaluation criteria-
A: Less than 10 μC / g (good)
○: 10 μC / g or more and less than 15 μC / g (practical)
X: 15 μC / g or more (not practical).

(Cover)
As with the charge amount, the fog was evaluated by the white paper density of the transfer material after printing 500,000 character images with a printing rate of 5% and printing a white paper. The white paper density of the transfer material is measured at 20 points of A4 size, and the average value is defined as the white paper density. Density measurement was performed using a reflection densitometer “RD-918” (manufactured by Macbeth).
-Evaluation criteria-
A: The fogging density is less than 0.003 and good level. O: The fogging density is 0.003 or more and less than 0.010, and there is no practical problem. ×: The fogging density is 0.010 or more and practically problematic. Level to be.

(Fixability)
In a commercially available copier “bizhub Pro C6501” (manufactured by Konica Minolta Co., Ltd.), the surface temperature of the heating roller in the fixing device is modified so that it can be changed in increments of 5 ° C. within a range of 140 to 200 ° C. Fixing for fixing a 1.5 cm × 1.5 cm solid image (toner adhesion amount of 3.0 mg / cm ² ) on A4 size high-quality paper (64 g / m ² ) in an environment (temperature 20 ° C., humidity 55% RH) The experiment was repeated while changing the set fixing temperature (surface temperature of the heating roller) to 120 ° C., 135 ° C., and so on in steps of 5 ° C. The solid image obtained in each fixing experiment is folded in half from the middle, and the peelability of the image is visually observed. Among the fixing experiments in which no image peeling occurs, the lowest fixing temperature is set as the minimum fixing temperature. did.
-Evaluation criteria-
A: Good level when the lower limit fixing temperature is 140 ° C. or lower. ○: Good level when the lower limit fixing temperature exceeds 140 ° C. and 160 ° C. or lower. X: When the lower limit fixing temperature exceeds 160 ° C. and higher than 170 ° C. This is a practically problematic level.

(Color reproducibility)
Using “bizhub PRO C6500 (manufactured by Konica Minolta)”, a test chart for color gamut measurement is output in the default mode, and the output test chart for color gamut measurement is “Spectrolina / Scan Bundle (manufactured by Gretag Macbeth)” ”Was measured.

For the evaluation of color gamut measurement, solid images (2 cm × 2 cm) of magenta single color (M) are produced. This solid image is measured under the above-described measurement conditions, expressed in La−a ^* −b ^* coordinates, and the saturation is obtained from the value. A value obtained by subtracting the saturation at the lower limit temperature and the saturation at the lower limit temperature + 20 ° C. in the fixing property evaluation was defined as the change range of the saturation. The change width of the saturation was 1.5 or less, and 1.0 or less was good among them.
-Evaluation criteria-
A: Saturation change width is 1.0 or less and good level ○: Saturation change width is more than 1.0 and 1.5 or less, good level ×: Fog density is greater than 1.5 This is a practically problematic level.

(Comprehensive judgment)
The overall judgment was made as follows for all evaluation items.
-Evaluation criteria-
◎: When there are two or more ◎ in the evaluation item and there is no x ○: When there are three or more ◯ and there is no x in the evaluation item ×: When there is even one x in the evaluation item.

  Tables 1 to 6 show the constitution and evaluation results of each toner.

Claims (4)

Binder resin containing at least a crystalline polyester resin, and the following general formula (1):
In formula (1),
Rx ₁ and Rx ₂ are each independently a substituted or unsubstituted linear, branched or cyclic alkyl group having 1 to 20 carbon atoms,
Lx is a hydrogen atom or a substituted or unsubstituted linear, branched or cyclic alkyl group having 1 to 20 carbon atoms,
Gx ₁ is a substituted or unsubstituted linear, branched or cyclic alkyl group having 2 to 20 carbon atoms,
Gx ₂ is a substituted or unsubstituted, straight or branched alkyl group having 1 to 5 carbon atoms,
Gx ₃ is a hydrogen atom, a halogen atom, a group represented by Gx ₄ —CO—NH—, or a group represented by Gx ₅ —N (Gx ₆ ) —CO—, wherein Gx ₄ is a substituent. Gx ₅ and Gx ₆ are each independently a hydrogen atom or a substituent,
Qx ₁ , Qx ₂ , Qx ₃ , Qx ₄ , and Qx ₅ are each independently a hydrogen atom or a substituent,
A colorant represented by the following general formula (2):
In formula (2),
R ₁ is a substituted or unsubstituted linear, branched or cyclic alkyl group having 1 to 20 carbon atoms,
R ₂ is a hydrogen atom, alkoxycarbonyl group, arylcarbonyl group, aryloxycarbonyl group, sulfamoyl group, sulfinyl group, alkylsulfonyl group, arylsulfonyl group, acyl group, nitrophenyl group, halogen atom, or cyano group,
R ₃ is a substituted or unsubstituted aromatic hydrocarbon-containing group having 9 to 120 carbon atoms,
M is a divalent metal element,
Containing a compound reacted with a metal-containing compound represented by
A toner for developing an electrostatic image, wherein the crystalline polyester resin is contained in an amount of 5 to 35% by mass with respect to a resin component forming the binder resin.   The electrostatic image developing toner according to claim 1, wherein the metal of the metal-containing compound is Cu.   The toner for developing an electrostatic charge image according to claim 1, wherein the acid value of the crystalline polyester is 20 to 30 mg KOH / g. A dispersion containing a binder resin containing at least a crystalline polyester resin, and the following general formula (1):
In formula (1),
Rx ₁ and Rx ₂ are each independently a substituted or unsubstituted linear, branched or cyclic alkyl group having 1 to 20 carbon atoms,
Lx is a hydrogen atom or a substituted or unsubstituted linear, branched or cyclic alkyl group having 1 to 20 carbon atoms,
Gx ₁ is a substituted or unsubstituted linear, branched or cyclic alkyl group having 2 to 20 carbon atoms,
Gx ₂ is a substituted or unsubstituted, straight or branched alkyl group having 1 to 5 carbon atoms,
Gx ₃ is a hydrogen atom, a halogen atom, a group represented by Gx ₄ —CO—NH—, or a group represented by Gx ₅ —N (Gx ₆ ) —CO—, wherein Gx ₄ is a substituent. Gx ₅ and Gx ₆ are each independently a hydrogen atom or a substituent,
Qx ₁ , Qx ₂ , Qx ₃ , Qx ₄ , and Qx ₅ are each independently a hydrogen atom or a substituent,
A step (1) of mixing a dispersion containing a colorant represented by:
The dispersion obtained in the step (1) is added to the following general formula (2):
In formula (2),
R ₁ is a substituted or unsubstituted linear, branched or cyclic alkyl group having 1 to 20 carbon atoms,
R ₂ is a hydrogen atom, alkoxycarbonyl group, arylcarbonyl group, aryloxycarbonyl group, sulfamoyl group, sulfinyl group, alkylsulfonyl group, arylsulfonyl group, acyl group, nitrophenyl group, halogen atom, or cyano group,
R ₃ is a substituted or unsubstituted aromatic hydrocarbon-containing group having 9 to 120 carbon atoms,
M is a divalent metal element,
A step (2) of mixing a dispersion containing a metal-containing compound represented by formula (1):