JP2016157101A - Toner and manufacturing method of toner - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a toner that has both excellent coloring power and durability and has the long life.SOLUTION: There is provided a toner comprising toner particles containing a binder resin, pigment, pigment dispersant, and amorphous resin, where the adsorption ratio A1(%) of the pigment dispersant to the pigment is 80% or more and 100% or less; the adsorption ratio A2(%) of the amorphous resin to the pigment is 0% or more and 60% or less; the Rf value(RfL) of the binder resin is 0.50 or more and 1.00 or less; the Rf value(RfH) of the amorphous resin is 0.00 or more and 0.35 or less.SELECTED DRAWING: None

Description

  The present invention relates to a toner used for forming a toner image by developing an electrostatic latent image formed by a method such as electrophotography, electrostatic recording, or toner jet recording, and a method for producing the same.

In recent years, printers and copiers are required to reduce cartridge replacement frequency and toner replenishment frequency (to extend the life of toner), and to improve toner performance. Specifically, there is a demand for a toner having excellent durability capable of obtaining a desired image density with a smaller amount of toner and maintaining stable image quality over a long period of time.
In order to obtain a desired image density with a small amount of toner, it is effective to finely disperse the pigment in the toner and improve the coloring power of the toner. In order to obtain a toner having excellent durability, it is effective to form a core-shell structure in which the toner surface is coated with a resin.
Patent Documents 1 to 4 propose suspension polymerization toners to which a pigment dispersant is added.
In Patent Document 5, the core-shell structure is formed by using a highly polar polyester resin in the suspension polymerization toner.

JP 2006-30760 A Japanese Patent Laid-Open No. 03-113462 JP 2013-182057 A JP 2013-210632 A JP2013-257415A

In the toners described in Patent Documents 1 to 4, the coloring power of the toner is improved by adding a pigment dispersant. However, the toners described in Patent Documents 1 and 2 do not form a core-shell structure, and it is difficult to obtain excellent durability. In addition, regarding the toners listed in Patent Documents 3 and 4, since the polarity of the resin forming the shell is low, it is difficult to form a clear core-shell structure and it is difficult to obtain excellent durability.
On the other hand, with the toner described in Patent Document 5, it is possible to obtain an excellent core-shell structure, but on the other hand, a highly polar polyester resin is adsorbed on the pigment, and the dispersion state of the pigment is not sufficient. There wasn't. That is, there is room for improvement in the coloring power of the toner.
From the above, the present invention provides a long-life toner that achieves both coloring power and durability. The present invention also provides a toner production method for producing the toner.

The present invention is a toner having toner particles containing a binder resin, a pigment, a pigment dispersant and an amorphous resin,
The adsorption rate A1 (%) of the pigment dispersant with respect to the pigment is 80% or more and 100% or less,
Adsorption rate A2 (%) of the amorphous resin with respect to the pigment is 0% or more and 60% or less,
Rf value (RfL) of the binder resin is 0.50 or more and 1.00 or less,
A toner wherein the amorphous resin has an Rf value (RfH) of 0.00 or more and 0.35 or less.
(This A1 was obtained by mixing 20 parts by mass of a solvent obtained by mixing styrene and n-butyl acrylate at a mass ratio of 4: 1, 0.1 part by mass of the pigment dispersant, and 1.0 part by mass of the pigment. The adsorption rate when the mixed solution is measured is shown.
The A2 is a mixture obtained by mixing 20 parts by mass of a solvent obtained by mixing styrene and n-butyl acrylate at a mass ratio of 4: 1, 0.1 part by mass of the amorphous resin, and 1.0 part by mass of the pigment. The adsorption rate when the liquid is measured is shown. )
(The RfL represents the Rf value of the binder resin measured by thin-layer chromatography in a 60 ° C. environment using a solution of the binder resin, silica gel as a stationary phase, and a developing solvent,
The binder resin solution is a mixture of 20 parts by mass of a solvent in which styrene and n-butyl acrylate are mixed at a mass ratio of 4: 1, and 0.1 part by mass of the binder resin.
The developing solvent is a mixture of styrene and n-butyl acrylate at a mass ratio of 1: 1.
The RfH represents the Rf value of the amorphous resin measured by thin-layer chromatography in a 60 ° C. environment using the solution of the amorphous resin, silica gel as a stationary phase, and the developing solvent,
The solution of the amorphous resin is a mixture of 20 parts by mass of a solvent obtained by mixing styrene and n-butyl acrylate at a mass ratio of 4: 1 and 0.1 part by mass of the amorphous resin. )
The present invention also relates to a method for producing a toner having toner particles, wherein the production steps of the toner particles are the following steps (1) or (2):
(1) a granulation step of forming particles of a polymerizable monomer composition containing a polymerizable monomer capable of forming a binder resin, a pigment, a pigment dispersant, and an amorphous resin in an aqueous medium; and A polymerization step for polymerizing the polymerizable monomer contained in the particles of the polymerizable monomer composition;
(2) A dissolution step of preparing a resin solution by dissolving or dispersing a binder resin, a pigment, a pigment dispersant and an amorphous resin in an organic solvent, and a granulation step of forming particles of the resin solution in an aqueous medium And a solvent removal step for producing resin particles by removing an organic solvent contained in the particles of the resin solution,
A toner production method characterized by comprising:

  According to the present invention, it is possible to provide a long-life toner having both excellent coloring power and durability.

The schematic diagram which shows the calculation method of Rf value of this invention Schematic diagram of the device used for charge measurement of the present invention The schematic diagram which shows the image pattern used for coloring power evaluation of this invention

The toner of the present invention has toner particles containing a binder resin, a pigment, a pigment dispersant, and an amorphous resin. The adsorption rate A1 (%) of the pigment dispersant with respect to the pigment is 80% or more and 100% or less, and the adsorption rate A2 (%) of the amorphous resin with respect to the pigment is 0% or more and 60% or less. The Rf value RfL of the adhesion resin is 0.50 or more and 1.00 or less, and the Rf value RfH of the amorphous resin is 0.00 or more and 0.35 or less.
(This A1 was obtained by mixing 20 parts by mass of a solvent obtained by mixing styrene and n-butyl acrylate at a mass ratio of 4: 1, 0.1 part by mass of the pigment dispersant, and 1.0 part by mass of the pigment. The adsorption rate when the mixed solution is measured is shown.
The A2 is a mixture obtained by mixing 20 parts by mass of a solvent obtained by mixing styrene and n-butyl acrylate at a mass ratio of 4: 1, 0.1 part by mass of the amorphous resin, and 1.0 part by mass of the pigment. The adsorption rate when the liquid is measured is shown. )
(The RfL represents the Rf value of the binder resin measured by thin-layer chromatography in a 60 ° C. environment using a solution of the binder resin, silica gel as a stationary phase, and a developing solvent,
The binder resin solution is a mixture of 20 parts by mass of a solvent in which styrene and n-butyl acrylate are mixed at a mass ratio of 4: 1, and 0.1 part by mass of the binder resin.
The developing solvent is a mixture of styrene and n-butyl acrylate at a mass ratio of 1: 1.
The RfH represents the Rf value of the amorphous resin measured by thin-layer chromatography in a 60 ° C. environment using the solution of the amorphous resin, silica gel as a stationary phase, and the developing solvent,
The solution of the amorphous resin is a mixture of 20 parts by mass of a solvent obtained by mixing styrene and n-butyl acrylate at a mass ratio of 4: 1 and 0.1 part by mass of the amorphous resin. )

In view of the above background, the present inventors first focused on the adsorption rate of the pigment dispersant and the amorphous resin to the pigment in order to achieve excellent coloring power.
As shown in Patent Document 3, in order to improve the dispersibility of the pigment by adding the pigment dispersant to the toner, the pigment dispersant needs to be adsorbed to the pigment, and the higher the adsorption rate, the more the pigment The effect of improving the dispersibility of is great.
At this time, when the pigment dispersant and the amorphous resin are added together, the amorphous resin is adsorbed to the pigment, and at the same time, the adsorption rate of the pigment dispersant to the pigment is lowered. This is considered to be because the surface area of the pigment is limited, and the surface of the pigment is adsorbed so as to compete with each other (for example, an amorphous resin) and the adsorption rate of the pigment.
That is, when the pigment dispersant and the amorphous resin are used simultaneously, in order to maximize the effect of the pigment dispersant, not only the adsorption rate of the pigment dispersant to the pigment but also the pigment of the amorphous resin It is also necessary to control the adsorption rate for.
As a result of pursuing the above phenomenon, when the adsorption rate of the amorphous resin to the pigment exceeds the value shown in the present invention, the adsorption rate of the pigment dispersant to the pigment rapidly decreases, and the dispersibility of the pigment becomes remarkable. I found it to decline.

In the present invention, the adsorption rate of the pigment dispersant to the pigment is the adsorption rate A1 (hereinafter also simply referred to as A1), and the adsorption rate of the amorphous resin to the pigment is the adsorption rate A2 (hereinafter also simply referred to as A2). When the A1 is 80% or more and 100% or less and the A2 is 0% or more and 60% or less, a toner having good dispersibility of the pigment can be obtained.
That A1 is 80% or more means that the adsorption rate of the pigment dispersant to the pigment is sufficiently high and has an excellent pigment dispersion effect. In addition, even when an amorphous resin is added, the decrease in the adsorption rate of the pigment dispersant hardly occurs, and the effect of the pigment dispersant can be maximized.
When A1 is less than 80%, the adsorption rate of the pigment dispersant to the pigment is low, and when the amorphous resin is added, the adsorption rate of the pigment dispersant to the pigment is remarkably lowered.
That A2 is 60% or less means that the adsorption rate of the amorphous resin to the pigment is sufficiently low and the adsorption rate of the pigment dispersant to the pigment is difficult to decrease.
When A2 is higher than 60%, it is easy to prevent adsorption of the pigment dispersant to the pigment, and even if A1 is 80% or more, a sufficient pigment dispersion effect cannot be obtained.
A1 is preferably 90% or more and 100% or less, and A2 is preferably 0% or more and 50% or less.

On the other hand, even if the coloring power is excellent, if the durability is not excellent at the same time, it is difficult to cope with the long life of the toner. Therefore, the present invention aims to form a clear core-shell structure by adding an amorphous resin in order to obtain a toner having excellent durability.
In order to add an amorphous resin to form a clear core-shell structure, the inventors focused on the difference in polarity between the binder resin and the amorphous resin.
By performing thin layer chromatography of each material (binder resin, amorphous resin) under the measurement conditions shown in the present invention, the polarity of each material can be expressed. The inventors have found that a clear core-shell structure can be formed by controlling the polarity.
In the present invention, the polarities of the binder resin and the amorphous resin can be represented by Rf values obtained by thin layer chromatography.
In the thin layer chromatography used in the present invention, a glass plate using a mixed solvent of styrene and n-butyl acrylate which is a low polarity solvent as a developing solvent and silica gel as a stationary phase is used.
Since silica gel is highly polar, it can be said that a material that is easily moved by a developing solvent has a lower polarity and a material that is difficult to move has a higher polarity. Here, the Rf value is A / B where the origin is the place where the spot of each material solution is hit, the distance that each material has moved is A, and the distance to the tip where the solvent (developing solvent) has risen is B. Indicated by The Rf value is a value unique to the material (FIG. 1). Therefore, the higher the Rf value, the lower the polarity, and the lower the Rf value, the higher the polarity.
As a result of repeated studies on the polarities of the binder resin and the amorphous resin, the present inventors have found that the Rf value RfL (hereinafter also simply referred to as RfL) of the binder resin is 0 as a condition for forming a clear core-shell structure. It was found that the Rf value RfH (hereinafter also simply referred to as RfH) of the amorphous resin is 0.00 or more and 0.35 or less.
RfL of 0.50 or more means that the polarity of the binder resin is sufficiently low, and RfH of 0.35 or less means that the polarity of the amorphous resin is sufficiently high. .
By satisfying the above conditions, a sufficient polarity difference occurs between the binder resin and the amorphous resin, and when the toner particles are produced particularly in an aqueous medium, the amorphous resin selectively adheres to the surface of the toner particles. It is unevenly distributed and a clear core-shell structure can be formed.
When RfL is lower than 0.50 or when RfH is higher than 0.35, the polarity difference between the binder resin and the amorphous resin becomes insufficient, and a clear core-shell structure cannot be formed. As a result, excellent durability cannot be obtained.
RfL is preferably 0.80 or more and 1.00 or less, and RfH is preferably 0.00 or more and 0.25 or less.
The method for controlling RfL is preferably controlled by the composition of the binder resin.
For example, it is easy to control by adjusting the amount of ester bond introduced into the binder resin and adjusting the acid value of the binder resin.
Similarly, the control method of RfH can be controlled by adjusting the amount of ester bond introduced into the amorphous resin and adjusting the acid value of the amorphous resin. Moreover, the method controlled by introducing the alicyclic structure mentioned later is suitable from the viewpoint of coexistence with the adsorption rate A2.
A method for measuring RfL and RfH will be described later.

Furthermore, the present inventors have found that the aforementioned adsorption rate A2 also greatly affects the core-shell structure of the toner particles.
When the adsorption rate A2 is high, the amorphous resin is adsorbed on the pigment, and the amount of the amorphous resin unevenly distributed on the toner particle surface layer is significantly reduced. In addition, the amorphous resin may be unevenly distributed on the surface of the toner particles in a state where the amorphous resin is adsorbed to the pigment, thereby reducing the chargeability of the toner. As a result, the durability of the toner is impaired.
That is, excellent durability can be obtained for the first time by simultaneously satisfying the adsorption rates A2 and RfH. If only one of the physical properties is satisfied, the durability effect exhibited by the present invention cannot be obtained, and the toner life cannot be extended.
As described above, in order to obtain a toner having both excellent durability and coloring power in order to cope with the long life of the toner, the design of the amorphous resin is particularly important. It is necessary to design the adsorption rate A2 to 60% or less and RfH to 0.35 or less.
However, it is generally considered that the adsorptivity between resin and pigment is dominated by van der Waals force, hydrogen bonding force, and acid-base interaction force (references “Ultrafine particle dispersion technology and its evaluation Science & Technology”). Company Publishing Chapter 5 Section 1)). Therefore, when the polarity of the amorphous resin is simply increased, the hydrogen bonding force and the acid-base interaction force increase, and the adsorption rate A2 tends to increase. As described above, the present invention clarifies the material characteristics that can achieve durability and coloring power, and newly designs an amorphous resin according to the conditions, thereby making it possible to achieve both durability and coloring power. Is.

The adsorption rate A1 can be achieved by designing the structure of the pigment adsorption site of the pigment dispersant in accordance with the characteristics of the pigment. For example, a method of increasing the van der Waals force by introducing a chemical structure having π electrons in the pigment adsorption site of the pigment dispersant, or introducing a polar group or a highly polar bond site to form a hydrogen bond strength or acid-base with the pigment. A method for increasing the interaction force is mentioned.
It is also a suitable example to introduce a pigment analog structure into the pigment adsorption site of the pigment dispersant.
That is, the adsorption rate A1 can be controlled by introducing a benzene ring structure, a carboxy group, an amide bond, or the like into the structure of the pigment adsorption site of the pigment dispersant, or by the amount of the pigment adsorption site.
On the other hand, the adsorption rate A2 can be achieved by controlling the composition of the amorphous resin. For example, there is a method of reducing the structure having π electrons by reducing the amount of benzene rings introduced into the amorphous resin. In addition, a technique for reducing the hydrogen bond strength with the pigment and the acid-base interaction force by reducing the polar groups of the amorphous resin is also a suitable example. More specifically, it can be controlled by the content ratio of the monomer unit having an alicyclic structure described later, the amount of ester bond, and the amount of carboxy group.
In addition, the measuring method of adsorption rate A1 and adsorption rate A2 is mentioned later.

In the present invention, the amorphous resin is not limited as long as it satisfies the above conditions, and a conventionally known amorphous resin can be used. For example, polyester resin; styrene acrylic resin; polyamide resin; furan resin; epoxy resin; xylene resin; Especially, in order to satisfy | fill adsorption | suction rate A2 and RfH simultaneously, it is preferable that it is a polyester resin. When the amorphous resin is a polyester resin, it is easy to reduce RfH while keeping the adsorption rate A2 low.
This does not increase the structure having acidic groups, basic groups, and π electrons, and the polarity is adjusted to be high by the amount of ester bonds, the amount of carboxy groups, and the content ratio of monomer units having an alicyclic structure described later. Because it does. As a result, excellent durability can be obtained while maintaining the coloring power.
As the polyester resin, the following dibasic acid or derivative thereof (carboxylic acid halide, ester, acid anhydride) and dihydric alcohol are essential, and if necessary, a tribasic or higher polybasic acid and its A polyester resin prepared by a method of dehydrating and condensing derivatives (carboxylic acid halides, esters, acid anhydrides), monobasic acids, trihydric or higher alcohols, monohydric alcohols, and the like can be used.
Examples of the dibasic acid include maleic acid, fumaric acid, itaconic acid, succinic acid, malonic acid, succinic acid, dodecyl succinic acid, dodecenyl succinic acid, adipic acid, azelaic acid, sebacic acid, decane-1,10-dicarboxylic acid. Aliphatic dibasic acids such as: phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, tetrabromophthalic acid, tetrachlorophthalic acid, het acid, hymic acid, isophthalic acid, terephthalic acid, 2,6-naphthalenedicarboxylic acid, etc. Aromatic dibasic acids; and alicyclic dibasic acids described later.
Examples of the dibasic acid derivative include carboxylic acid halides, esterified products, and acid anhydrides of the above aliphatic dibasic acids, aromatic dibasic acids, and alicyclic dibasic acids.
On the other hand, examples of the divalent alcohol include ethylene glycol, 1,2-propylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, and diethylene glycol. , Acyclic aliphatic diols such as dipropylene glycol, triethylene glycol and neopentyl glycol; bisphenols such as bisphenol A and bisphenol F; ethylene oxide adducts of bisphenol A, propylene oxide adducts of bisphenol A, etc. Examples thereof include alkylene oxide adducts of bisphenol A; aralkylene glycols such as xylylene glycol; alicyclic diols described later.
Examples of the trivalent or higher polybasic acid and its anhydride include, for example, trimellitic acid, trimellitic anhydride, 1,3,5-cyclohexanetricarboxylic acid, 1,2,4-cyclohexanetricarboxylic acid, 1,2, 4,5-cyclohexanetetracarboxylic acid, 1,2,3,4,5,6-cyclohexanehexacarboxylic acid, methylcyclohexentricarboxylic acid, methylcyclohexentricarboxylic acid anhydride, pyromellitic acid, pyromellitic anhydride, etc. .
A part of the polyester resin may be modified with another resin, and the polyester resin may be a block polymer or a graft polymer.

In the present invention, the polyester resin has a unit derived from an alcohol (diol) having an alicyclic structure or a unit derived from a carboxylic acid having an alicyclic structure in at least one of a main chain and a side chain. More preferred.
The content ratio of units derived from alcohol having an alicyclic structure or units derived from carboxylic acid having an alicyclic structure with respect to all monomer units constituting the polyester resin is 0.1 mol% or more and 50 mol% or less. More preferably it is.
The polyester resin contains a unit derived from an alcohol having an alicyclic structure or a unit derived from a carboxylic acid having an alicyclic structure, so that the polarity can be increased without increasing the structure having π electrons. It is. As a result, RfH can be lowered while suppressing an increase in the adsorption rate A2.
Furthermore, when the content ratio of the unit derived from the alcohol having an alicyclic structure or the unit derived from a carboxylic acid having an alicyclic structure is 0.1 mol% or more, the polarity of the polyester resin can be designed sufficiently high. , Better durability can be obtained.
Further, when the content ratio of the unit is 50 mol% or less, the adsorption rate A2 can be kept low, and an excellent coloring power can be obtained. The content ratio of the unit is more preferably 2.0 mol% or more and 30 mol% or less.
Furthermore, it is preferable that the polyester resin has a unit derived from an acyclic aliphatic diol as a unit derived from alcohol. The content ratio of units derived from acyclic aliphatic diol with respect to all monomer units constituting the polyester resin is preferably 10 mol% or more and 30 mol% or less. More preferably, it is 10 mol% or more and 20 mol% or less. As the acyclic aliphatic diol, ethylene glycol is preferable.
In addition, the alicyclic compound in this invention points out the compound containing the cyclic structure which does not have aromaticity. The constituent element may be an alicyclic hydrocarbon whose cyclic structure is composed only of carbon and hydrogen, or an alicyclic heterocyclic compound containing an element other than carbon and hydrogen in the cyclic structure. Among these, it is more preferable that the cyclic structure is an alicyclic hydrocarbon composed of only carbon and hydrogen. By being an alicyclic hydrocarbon, excellent chargeability can be maintained even in a high-humidity environment, so that excellent image quality can be maintained over a longer period of time.
In addition, the following are mentioned as alcohol which has alicyclic structure which can be used concretely, or carboxylic acid which has alicyclic structure.
1,4-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 1,2-cyclohexanedicarboxylic acid, 4-methyl-1,2-cyclohexanedicarboxylic acid, cis-4-cyclohexene-1,2-dicarboxylic acid, cis -1-cyclohexene-1,2-dicarboxylic acid, norbornane dicarboxylic acid, norbornene dicarboxylic acid, 1,3-adamantane dicarboxylic acid, 1,3,5-cyclohexanetricarboxylic acid, 1,2,4-cyclohexanetricarboxylic acid, 1, Cycloaliphatic dibasic or polybasic acids such as 2,4,5-cyclohexanetetracarboxylic acid, 1,2,3,4,5,6-cyclohexanehexacarboxylic acid, methylcyclohexentricarboxylic acid;
1,4-cyclohexanedimethanol, hydrogenated bisphenol A, 1,4-cyclohexanediol, 1,2-cyclohexanediol, 1,3-cyclohexanediol,
Alicyclic diols such as 4- (2-hydroxyethyl) cyclohexanol, 4- (hydroxymethyl) cyclohexanol, 4,4′-bicyclohexanol, 1,3-adamantanediol.
On the other hand, examples of the monomer having an alicyclic heterocyclic structure include isosorbide and spiroglycol as alcohol monomers.
A method for analyzing the composition of the amorphous resin and a method for measuring the ratio of the number of units will be described later.
Further, the side chain in the present invention is defined as “branches, side chains, pendant molecular chains” in the following definitions (Source: Glossary of Polymer Society), and does not include “pendant groups, side groups”.
The description of the glossary of the Polymer Society of Japan is as follows.
1.53 Branch, side chain, pendant molecular chain An oligomer-like or high molecular weight branch extending from a polymer molecular chain.
1.56 Pendant group, side group A side branch extending from a main chain which is neither an oligomer molecular chain nor a polymer molecular chain.
That is, the side chain of the present invention has a repeating unit similarly to the main chain.

The amorphous resin preferably has a weight average molecular weight (Mw) of 5,000 or more and 50,000 or less. By satisfying the above range, more excellent durability can be obtained when the amorphous resin is unevenly distributed on the surface of the toner particles.
The weight average molecular weight (Mw) is more preferably 11,000 or more and 40000 or less.
The weight average molecular weight (Mw) of the amorphous resin can be controlled by conditions such as polymerization temperature and polymerization time when the amorphous resin is produced. A method for measuring the weight average molecular weight (Mw) of the amorphous resin will be described later.

The acid value of the amorphous resin is preferably 1.0 mgKOH / g or more and 30.0 mgKOH / g or less. By satisfying the above range, the charging characteristics of the toner are hardly affected by the surrounding environment, and thus excellent durability can be maintained over a long period of time.
The method for controlling the acid value of the amorphous resin varies depending on the resin constituting the amorphous resin.
When the amorphous resin is a polyester resin, the ratio of the acid monomer to the alcohol monomer, the molecular weight, the amount of the monovalent acid monomer and / or the alcohol monomer, the trivalent acid monomer and / or at the time of producing the amorphous resin It can be controlled by adjusting the amount of alcohol monomer.
Moreover, when this amorphous resin is a styrene acrylic resin, it can control by adjusting the quantity of the polymerizable monomer which has a carboxy group like acrylic acid or methacrylic acid. A method for measuring the acid value of the amorphous resin will be described later.
The content of the amorphous resin is preferably 1.0 part by mass or more and 10.0 parts by mass or less, and is 2.0 parts by mass or more and 7.0 parts by mass or less with respect to 100 parts by mass of the binder resin. More preferably.

In the present invention, the pigment dispersant is not limited as long as it satisfies the adsorption rate A1, and a known one can be used.
In the present invention, the pigment dispersant preferably contains a pigment adsorption site that is adsorbed to the pigment and a styrene acrylic resin site. The pigment dispersant preferably has a structure in which a pigment adsorption site and a styrene acrylic resin site are bonded via a linking group.
The pigment dispersant having the structure maintains the pigment dispersion because the pigment adsorption site is adsorbed on the surface of the pigment and the styrene acrylic resin site, which is a dispersion component for the resin, is spread around the pigment. Further, since the styrene acrylic resin portion can be designed to have a low polarity, it is difficult to adsorb on the pigment surface and spreads firmly around the pigment, so that the dispersion of the pigment can be maintained well. A method for analyzing the composition of the pigment dispersant will be described later.
The compound that can be used as the pigment adsorption site of the pigment dispersant can be selected from the viewpoint of the van der Waals force, the hydrogen bonding force, and the acid-base interaction force.
Specifically, sulfonic acid group, carboxy group, phosphoric acid group, hydroxyl group, amino group, quaternary ammonium group, quaternary pyridium group, quaternary imidazole group, amine, imine, nitrile group, nitro group, nitroso group, ester Examples thereof include compounds having a bond, an amide bond, or a urethane bond, and analogs of pigments.

Hereinafter, although it demonstrates using a suitable specific example, it is not necessarily limited to these.
Examples of the pigment dispersant include a compound having a pigment adsorption site represented by the following formula (1) and a styrene acrylic resin site. This pigment dispersant has a structure in which a pigment adsorption site represented by the following formula (1) and a styrene acrylic resin site are bonded via a divalent linking group.

［前記式（１）中、
Ｒ^１、Ｒ^２はそれぞれ独立して置換又は無置換のアルキル基、置換又は無置換のフェニル基、−ＯＲ^５基、又は−ＮＲ^６Ｒ^７基を表す。Ｒ^５、Ｒ^６及びＲ^７はそれぞれ独立して水素原子、置換又は無置換のアルキル基、置換又は無置換のフェニル基、又はアラルキル基を表す。
Ａｒは置換又は無置換のアリール基を表す。
Ｒ^１、Ｒ^２、及びＡｒの少なくとも一つは、スチレンアクリル樹脂部位と結合する連結基を有する置換基である。該置換基は、上記Ｒ^１、Ｒ^２またはＡｒで示した基と同義である。
Ｒ^１及びＡｒの少なくとも一つが、前記スチレンアクリル樹脂部位と結合する連結基を有する置換基である場合、前記連結基は、アミド基［−Ｃ（＝Ｏ）−ＮＨ−］、エステル基［−Ｃ（＝Ｏ）−Ｏ−］、ウレタン基［−ＮＨ−Ｃ（＝Ｏ）−Ｏ−］、ウレア基［−ＮＨ−Ｃ（＝Ｏ）−ＮＨ−］、アルキレン基、フェニレン基、−Ｏ−で示される基、−ＮＲ^８−で示される基、及び−ＮＨＣＨ（ＣＨ_２ＯＨ）−で示される基からなる群より選ばれる二価の連結基であり、Ｒ^８は水素原子、アルキル基、フェニル基又はアラルキル基を表す。
Ｒ^２が前記スチレンアクリル樹脂部位と結合する連結基を有する置換基である場合、前記連結基は、アミド基［−Ｃ（＝Ｏ）−ＮＨ−］、エステル基［−Ｃ（＝Ｏ）−Ｏ−］、ウレタン基［−ＮＨ−Ｃ（＝Ｏ）−Ｏ−］、ウレア基［−ＮＨ−Ｃ（＝Ｏ）−ＮＨ−］、アルキレン基、フェニレン基、−Ｏ−で示される基、−ＮＲ^９−で示される基、及び−ＮＨＣＨ（ＣＨ_２ＯＨ）−で示される基からなる群より選ばれる二価の連結基であり、Ｒ^９は、水素原子、アルキル基、フェニル基、又はアラルキル基を表す。］

[In the formula (1),
R ¹ and R ² each independently represents a substituted or unsubstituted alkyl group, a substituted or unsubstituted phenyl group, —OR ⁵ group, or —NR ⁶ R ⁷ group. R ⁵ , R ⁶ and R ⁷ each independently represents a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted phenyl group, or an aralkyl group.
Ar represents a substituted or unsubstituted aryl group.
At least one of R ¹ , R ² , and Ar is a substituent having a linking group that binds to the styrene acrylic resin moiety. This substituent is synonymous with the group shown by said R < ¹ >, R < ² > or Ar.
When at least one of R ¹ and Ar is a substituent having a linking group bonded to the styrene acrylic resin moiety, the linking group includes an amide group [—C (═O) —NH—], an ester group [— C (═O) —O—], urethane group [—NH—C (═O) —O—], urea group [—NH—C (═O) —NH—], alkylene group, phenylene group, —O A divalent linking group selected from the group consisting of a group represented by —, a group represented by —NR ⁸ —, and a group represented by —NHCH (CH ₂ OH) —, and R ⁸ represents a hydrogen atom or an alkyl group. Represents a phenyl group or an aralkyl group.
When R ² is a substituent having a linking group bonded to the styrene acrylic resin moiety, the linking group includes an amide group [—C (═O) —NH—], an ester group [—C (═O) — O—], urethane group [—NH—C (═O) —O—], urea group [—NH—C (═O) —NH—], alkylene group, phenylene group, group represented by —O—, A divalent linking group selected from the group consisting of a group represented by —NR ⁹ — and a group represented by —NHCH (CH ₂ OH) —, wherein R ⁹ is a hydrogen atom, an alkyl group, a phenyl group, or Represents an aralkyl group. ]

In the present invention, examples of the alkyl group for R ¹ and R ² in the formula (1) include a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an n-pentyl group, an n-hexyl group, and an isopropyl group. And an alkyl group having a linear structure, a branched structure or a cyclic structure such as a group, an isobutyl group, a sec-butyl group, a tert-butyl group and a cyclohexyl group.
In the present invention, examples of the aralkyl group in R ¹ and R ² in the formula (1) include:
Examples include a benzyl group and a phenethyl group.
Moreover, the following groups are mentioned as a substituent of the substituted alkyl group of R < ¹ >, R < ² >, R < ⁵ >, R < ⁶ > and R < ⁷ > in Formula (1), and a substituent of a substituted phenyl group. That is, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a halogen atom, a nitro group, an amino group, a carbamoyl group, a ureido group, a hydroxyl group, a cyano group, and a trifluoromethyl group.
In the present invention, Ar represents a substituted or unsubstituted aryl group, and examples thereof include a phenyl group and a naphthyl group. Examples of the substituent include alkyl groups having 1 to 6 carbon atoms, alkoxy groups having 1 to 6 carbon atoms, halogen atoms, hydroxyl groups, carbamoyl groups, ureido groups, amino groups, carboxyl groups, alkoxycarbonyl groups, and carboxy groups. Amide group etc. are mentioned.
From the viewpoint of affinity for the pigment, R ¹ is preferably an alkyl group having 1 to 6 carbon atoms, a phenyl group, an —OCH ₃ group, or an —OCH ₂ C ₆ H ₅ group. R ² is preferably a —NR ⁶ R ⁷ group, R ⁶ is preferably a hydrogen atom, and R ⁷ is preferably a phenyl group.

  Examples of combinations of substituents in the above formula (1) will be described below, but the present invention is not limited to these examples. Specific examples include the following formulas (2) to (5).

［前記式（２）中、Ａｒは上記式（１）と同義であり、Ｍｅはメチル基を表し、Ｌはスチレンアクリル樹脂部位と結合するための二価の連結基を表す。］

[In said Formula (2), Ar is synonymous with the said Formula (1), Me represents a methyl group, L represents the bivalent coupling group for couple | bonding with a styrene acrylic resin site | part. ]

［前記式（３）中、Ｍｅはメチル基を表し、Ｅｔはエチル基を表し、Ｌはスチレンアクリル樹脂部位と結合するための二価の連結基を表す。］

[In said Formula (3), Me represents a methyl group, Et represents an ethyl group, L represents the bivalent coupling group for couple | bonding with a styrene acrylic resin site | part. ]

［前記式（４）中、Ｍｅはメチル基を表し、Ｌはスチレンアクリル樹脂部位と結合するための二価の連結基を表す。］

[In said Formula (4), Me represents a methyl group, L represents the bivalent coupling group for couple | bonding with a styrene acrylic resin site | part. ]

［前記式（５）中、Ｍｅはメチル基を表し、Ｌはスチレンアクリル樹脂部位と結合するための二価の連結基を表す。］

[In said Formula (5), Me represents a methyl group and L represents the bivalent coupling group for couple | bonding with a styrene acrylic resin site | part. ]

Moreover, as a styrene acrylic resin site | part contained in this pigment dispersant, the copolymer of a styrene-type monomer and an acrylic-type monomer and / or a methacryl-type monomer is mentioned.
Examples of the styrene monomer include styrene; α-methylstyrene, β-methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, 2,4-dimethylstyrene, and pn-butylstyrene. P-tert-butyl styrene, pn-hexyl styrene, pn-octyl styrene, pn-nonyl styrene, pn-decyl styrene, pn-dodecyl styrene, p-methoxy styrene, and and styrene derivatives such as p-phenylstyrene.
Examples of acrylic monomers include methyl acrylate, ethyl acrylate, n-propyl acrylate, iso-propyl acrylate, n-butyl acrylate, iso-butyl acrylate, tert-butyl acrylate, n-amyl acrylate, and n-hexyl acrylate. 2-ethylhexyl acrylate, n-octyl acrylate, stearyl acrylate, behenyl acrylate, cyclohexyl acrylate, benzyl acrylate, dimethyl phosphate ethyl acrylate, diethyl phosphate ethyl acrylate, dibutyl phosphate ethyl acrylate, 2-benzoyloxyethyl acrylate, etc. Is mentioned.
Examples of the methacrylic monomer include methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, iso-propyl methacrylate, n-butyl methacrylate, iso-butyl methacrylate, tert-butyl methacrylate, n-amyl methacrylate, and n-hexyl methacrylate. 2-ethylhexyl methacrylate, n
-Octyl methacrylate, stearyl methacrylate, behenyl methacrylate, diethyl phosphate ethyl methacrylate, dibutyl phosphate ethyl methacrylate and the like.
In the present invention, the content of the pigment dispersant is preferably 0.1 parts by mass or more and 3.0 parts by mass or less, and 0.4 parts by mass or more and 1.5 parts by mass with respect to 100 parts by mass of the binder resin. It is more preferable that the amount is not more than parts.
The amount of the pigment dispersant used is preferably 2.0 parts by mass or more and 20.0 parts by mass or less, and 4.0 parts by mass or more and 15.0 parts by mass or less with respect to 100 parts by mass of the pigment. It is more preferable.

In the present invention, a known resin that is usually used for toners can be used as the binder resin. Among these, from the viewpoint of forming a core-shell structure on the toner particles, a styrene acrylic resin capable of designing a large value of RfL is preferable.
Examples of the polymerizable monomer constituting the styrene acrylic resin include those similar to the styrene acrylic resin used in the pigment dispersant. Furthermore, you may add a polyfunctional monomer.
As polyfunctional monomers, diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, polyethylene glycol diacrylate, 1,6-hexanediol diacrylate, neopentyl glycol diacrylate, tripropylene glycol diacrylate, polypropylene Glycol diacrylate, 2,2′-bis (4- (acryloxydiethoxy) phenyl) propane, trimethylolpropane triacrylate, tetramethylolmethane tetraacrylate, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, Tetraethylene glycol dimethacrylate, polyethylene glycol dimeta Chlorate, 1,3-butylene glycol dimethacrylate, 1,6-hexanediol dimethacrylate, neopentyl glycol dimethacrylate, polypropylene glycol dimethacrylate, 2,2′-bis (4- (methacryloxydiethoxy) phenyl) propane, Examples include 2,2'-bis (4- (methacryloxypolyethoxy) phenyl) propane, trimethylolpropane trimethacrylate, tetramethylolmethane tetramethacrylate, divinylbenzene, divinylnaphthalene, and divinyl ether.

In the present invention, examples of the pigment include conventionally known pigments.
Examples of the black pigment include carbon black.
Examples of yellow pigments include monoazo compounds; disazo compounds; condensed azo compounds; isoindolinone compounds; isoindoline compounds; benzimidazolone compounds; anthraquinone compounds; azo metal complexes; methine compounds; Can be mentioned. More specifically, C.I. I. Pigment yellow 74, 93, 95, 109, 111, 128, 155, 174, 180, 185 and the like.
Magenta pigments include monoazo compounds; condensed azo compounds; diketopyrrolopyrrole compounds; anthraquinone compounds; quinacridone compounds; basic dye lake compounds; naphthol compounds: benzimidazolone compounds; thioindigo compounds; Can be mentioned. More specifically, C.I. I. Pigment Red 2,3,5,6,7,23,48: 2,48: 3,48: 4,57: 1,81: 1,122,144,146,150,166,169,177,184, 185, 202, 206, 220, 221, 238, 254, 269, C.I. I. And CI Pigment Bio Red 19.
Examples of cyan pigments include cyan pigments represented by copper phthalocyanine compounds and derivatives thereof, anthraquinone compounds; basic dye lake compounds, and the like. More specifically, C.I. I. Pigment Blue 1,7,15,15: 1,15: 2,15: 3,15: 4,60
62, 66.
Among them, it is preferable to use a pigment having an aromatic ring in the structure because the adsorption rate can be easily controlled from the viewpoint of van der Waals force. In addition to the pigment, various dyes conventionally known as colorants can also be used.
The pigment content is preferably 1.0 part by mass or more and 20.0 parts by mass or less with respect to 100 parts by mass of the binder resin.

In the present invention, it is preferable that an external additive is externally added to the toner particles in order to improve the image quality of the toner. As the external additive, inorganic fine powder such as silica fine powder, titanium oxide fine powder, or aluminum oxide fine powder is preferably used.
These inorganic fine powders are preferably hydrophobized with a hydrophobizing agent such as a silane coupling agent, silicone oil or a mixture thereof.
Furthermore, in the toner of the present invention, external additives other than those described above may be mixed with the toner particles as necessary.
The total addition amount of the inorganic fine powder is preferably 1.0 part by mass or more and 5.0 parts by mass or less with respect to 100 parts by mass of the toner particles (toner particles before adding the external additive).

In the present invention, the toner can be produced by a known production method such as a pulverization method, suspension polymerization method, emulsion aggregation method, or dissolution suspension method, and the production method is not particularly limited.
In the present invention, as a method for producing a toner,
The production process of the toner particles is the following process (1) or (2):
(1) a granulating step of forming particles of a polymerizable monomer composition containing a polymerizable monomer, a pigment, a pigment dispersant, and an amorphous resin to form a binder resin in an aqueous medium; and A polymerization step of polymerizing a polymerizable monomer contained in the particles of the polymerizable monomer composition;
(2) A dissolution step of preparing a resin solution by dissolving or dispersing a binder resin, a pigment, a pigment dispersant and an amorphous resin in an organic solvent, and a granulation step of forming particles of the resin solution in an aqueous medium And a solvent removal step for producing resin particles by removing an organic solvent contained in the particles of the resin solution,
It is preferable to have either.
In the case of efficiently producing toner particles having a core-shell structure, a method of producing toner particles in an aqueous medium is preferable.
That is, the toner particles are
(1) a granulating step of forming particles of a polymerizable monomer composition containing a polymerizable monomer, a pigment, a pigment dispersant, and an amorphous resin to form a binder resin in an aqueous medium; and Toner particles obtained through a polymerization step of polymerizing a polymerizable monomer contained in the particles of the polymerizable monomer composition, or (2) a binder resin, a pigment, a pigment dispersant, and an amorphous property A dissolving step of preparing a resin solution by dissolving or dispersing a resin in an organic solvent, a granulating step of forming particles of the resin solution in an aqueous medium, and an organic contained in the particles of the resin solution Toner particles obtained through a solvent removal process for producing resin particles by removing the solvent are preferred.
Due to the toner particles obtained through the above process, a highly polar amorphous resin is unevenly distributed at the oil-water interface formed during the granulation process. As a result, a clearer core-shell structure can be formed, and excellent durability can be obtained.
Hereinafter, the production method using the suspension polymerization method of the above (1) will be exemplified and further described, but it is not limited to the following.
Polymerizability in which polymerizable monomers, pigments, pigment dispersants, and amorphous resins are mixed and dissolved or dispersed using a disperser such as a homogenizer, ball mill, colloid mill, or ultrasonic disperser. A monomer composition is prepared. At this time, in the polymerizable monomer composition, a known release agent or charge control agent, a solvent for viscosity adjustment, a crystalline resin, a plasticizer, a chain transfer agent, and other, if necessary Additives can be added as appropriate.
Next, the polymerizable monomer composition is put into an aqueous medium containing a dispersion stabilizer prepared in advance and suspended using a high-speed disperser such as a high-speed stirrer or an ultrasonic disperser. , Granulate.
When polymerizing the polymerizable monomer contained in the particles of the polymerizable monomer composition, a polymerization initiator may be used. The polymerization initiator may be mixed with other additives when preparing the polymerizable monomer composition, or may be mixed into the polymerizable monomer composition just before being suspended in the aqueous medium. Also good. Moreover, it can also be added in the state melt | dissolved in the polymerizable monomer and other solvent as needed during granulation or after completion of granulation, ie, just before starting a polymerization reaction.
The suspension after granulation is heated, and the polymerization reaction is carried out with stirring so that the particles of the polymerizable monomer composition in the suspension maintain the particle state and the particles do not float or settle. To complete the process and remove the solvent as necessary to form an aqueous dispersion of toner particles.
Thereafter, the toner particles can be obtained by washing as necessary and drying and classifying by various methods. Further, the toner can be obtained by externally adding the inorganic fine powder or the like to the toner particles.

  The toner of the present invention can be used as a one-component developer or as a two-component developer mixed with a magnetic carrier.

Below, the measuring method of each physical property value prescribed | regulated by this invention is described.
<Measurement Method of Adsorption Rate A1 of Pigment Dispersant to Pigment and Adsorption Rate A2 of Amorphous Resin to Pigment>
The adsorption rate A1 and the adsorption rate A2 are measured as follows.
(1) Weigh the following materials and glass beads into a 50 ml pressure bottle.
Pigment: 1.0g
Pigment dispersant or amorphous resin: 0.1 g
Styrene (solvent): 16.0 g
n-butyl acrylate (solvent): 4.0 g
Glass beads (diameter 0.8mm): 30.0g
(2) The above is mixed, shaken with a paint shaker (manufactured by Toyo Seiki Co., Ltd.) for 10 hours, and the pigment is dispersed in a solvent.
(3) The dispersion after shaking is separated with a centrifuge (manufactured by Eppendorf, mini spin plus: 14.5 krpm, 30 minutes), and the supernatant is taken.
(4) The supernatant is filtered with Milex LH 0.45 μm (manufactured by Nippon Millipore), and the filtrate (that is, a mixture of the above materials excluding glass beads) is analyzed by gel permeation chromatography (GPC). The analysis conditions of GPC are in accordance with the method for measuring the weight average molecular weight (Mw) of the pigment dispersant and amorphous resin described later. That is, after the obtained filtrate is dissolved in tetrahydrofuran (THF), it is filtered through a solvent-resistant membrane filter to obtain a sample solution, and the obtained sample solution is measured under the conditions described later. The peak area of the obtained chromatogram (vertical axis: electrical strength depending on concentration, horizontal axis: retention time) is defined as S1. The vertical axis is not particularly limited as long as it is an index depending on the concentration.
(5) Similarly, a solution in which the following materials are mixed is filtered through Millex LH 0.45 μm (manufactured by Nippon Millipore), and the filtrate is analyzed by GPC. The peak area of the obtained chromatogram is defined as S2. In addition, in order to obtain | require with the area ratio of S1 and S2 below, the chromatogram which calculates | requires peak areas S1 and S2 produces the chromatogram using the vertical axis | shaft and horizontal axis of the same contraction scale.
Pigment dispersant or resin: 0.1 g
Styrene: 16.0g
n-butyl acrylate: 4.0 g
(6) Based on the following formula, the adsorption rate of the pigment dispersant or amorphous resin to the pigment is calculated. Adsorption rate (%) = (1−S1 / S2) × 100

<Measurement method of Rf value RfL of binder resin and Rf value RfH of amorphous resin>
The Rf value RfL of the binder resin and the Rf value RfH of the amorphous resin are measured as follows.
(1) The following materials are weighed in a 50 ml pressure bottle to prepare a binder resin or amorphous resin solution.
Binder resin or amorphous resin: 0.1 g
Styrene: 16.0g
n-butyl acrylate: 4.0 g
(2) As a plate for thin layer chromatography, a glass plate “TLC Lux Plate Silica Gel 60 F254 Horizontal 5 cm × Development direction 10 cm (manufactured by Merck Millipore)” using silica gel as a stationary phase is used.
The above-mentioned solution is collected using a capillary with a diameter of 0.5 mm, and a spot with a diameter of 3 mm is hit at a position 1.5 cm from the bottom of the glass plate.
(3) A liquid in which styrene and n-butyl acrylate as a developing solvent are mixed at a mass ratio of 1: 1 is weighed so as to have a height of 1 cm and heated to 60 ° C. To do.
(4) The lower 1 cm of the glass plate is immersed in a developing solvent and developed.
(5) While maintaining the temperature at 60 ° C., the development is continued until the developing solvent rises to a position 1 cm from the upper end of the glass plate. The distance that the developing solvent has risen is measured and is designated as B.
(6) The glass plate is sufficiently dried.
(7) Using an ultraviolet light (As One Handy UV Lamp SLUV-6), the glass plate is irradiated with ultraviolet light having a wavelength of 254 nm, and the distance A where each material is developed is measured. (8) Calculate as Rf value = A / B.

<Analyzing Method of Composition of Pigment Dispersant and Amorphous Resin>
The analysis of the composition of the pigment dispersant and the amorphous resin was performed by measuring the NMR spectrum of each material.
The NMR spectrum measurement of the pigment dispersant and the amorphous resin was performed using nuclear magnetic resonance spectroscopy ( ¹ H-NMR) [400 MHz, CDCl 3, room temperature (25 ° C.)].
Measuring apparatus: FT NMR apparatus JNM-EX400 (manufactured by JEOL Ltd.)
Measurement frequency: 400MHz
Pulse condition: 5.0μs
Frequency range: 10500Hz
Integration count: 64 times Composition analysis was performed from the NMR spectrum measured by the above-described method.

<Method for Measuring Weight Average Molecular Weight (Mw) of Pigment Dispersant, Amorphous Resin, and Toner>
The weight average molecular weight (Mw) of the pigment dispersant, amorphous resin, and toner is measured by gel permeation chromatography (GPC) as follows. The weight average molecular weight of the toner is a weight average molecular weight obtained by measuring the THF soluble content of the toner.
First, a pigment dispersant, an amorphous resin, or a toner is dissolved in tetrahydrofuran (THF) over 24 hours at room temperature. Then, the obtained solution is filtered through a solvent-resistant membrane filter “Mysholy disk” (manufactured by Tosoh Corporation) having a pore diameter of 0.2 μm to obtain a sample solution. The sample solution is adjusted so that the concentration of the component soluble in THF is 0.8% by mass. Using this sample solution, measurement is performed under the following conditions.
Apparatus: HLC8120 GPC (detector: RI) (manufactured by Tosoh Corporation)
Column: Seven series of Shodex KF-801, 802, 803, 804, 805, 806, 807 (manufactured by Showa Denko KK)
Eluent: Tetrahydrofuran (THF)
Flow rate: 1.0 ml / min
Oven temperature: 40.0 ° C
Sample injection volume: 0.10 ml
In calculating the molecular weight of the sample, standard polystyrene resin (trade names “TSK Standard Polystyrene F-850, F-450, F-288, F-128, F-80, F-40, F-20, F-10, F-4, F-2, F-1, A-5000, A-2500, A-1000, A-500 ", manufactured by Tosoh Corporation) are used.

<Method for measuring acid value of amorphous resin>
The acid value of the amorphous resin is measured according to JIS K1557-1970.
A specific measurement method is shown below.
2 g of the pulverized sample is precisely weighed (W (g)). A sample is put into a 200 ml Erlenmeyer flask, 100 ml of a mixed solution of toluene / ethanol (2: 1) is added and dissolved for 5 hours. At this time, you may heat as needed. Add phenolphthalein solution as indicator.
The solution is titrated with a burette using a 0.1 mol / L KOH alcohol solution. The amount of the KOH alcohol solution at this time is S (ml). A blank test is performed, and the amount of the KOH alcohol solution at this time is defined as B (ml).
The acid value is calculated by the following formula. Note that “f” in the formula is a factor of the KOH solution. Acid value (mgKOH / g) = [(SB) × f × 5.61] / W

<Measuring method of glass transition temperature Tg (° C.) of amorphous resin and toner>
The glass transition temperature Tg (° C.) of the amorphous resin and the toner is measured in accordance with ASTM D3418-82 using a differential scanning calorimeter “Q1000” (manufactured by TA Instruments).
The temperature correction of the device detection unit uses the melting points of indium and zinc, and the correction of heat uses the heat of fusion of indium.
Specifically, 2 mg of a measurement sample is precisely weighed and placed in an aluminum pan, and an empty aluminum pan is used as a reference. The measurement range is 0 ° C. to 100 ° C., and the heating rate is 10 ° C. / The temperature is raised at a rate of minutes. Hold at 100 ° C. for 15 minutes, and then cool at a rate of 10 ° C./min between 100 ° C. and 0 ° C. Hold at 0 ° C. for 10 minutes, and then measure between 0 ° C. and 100 ° C. at a rate of temperature increase of 10 ° C./min.
Before and after the specific heat change of the specific heat change curve in the second temperature rise process, the straight line that is equidistant from the extended straight line of each baseline and the curve of the step-like change part of the glass transition Is the glass transition temperature Tg (° C.).

<Measurement method of charge amount>
In the apparatus (suction machine 1) shown in FIG. 2, 0.1 g of a developer whose charge is to be measured is placed in a metal measuring container 2 having a 635 mesh screen 3 at the bottom, and a metal lid 4 is provided. . At this time, the mass of the entire measurement container 2 is weighed and is defined as W1 (g). Next, in the suction device 1 (at least the portion in contact with the measurement container 2) is sucked from the suction port 7 and the air volume control valve 6 is adjusted to set the pressure of the vacuum gauge 5 to 1.0 kPa. In this state, suction is performed for 1 minute to remove the toner by suction. The potential of the electrometer 9 at this time is set to V (volt). Here, 8 is a capacitor, and the capacity is C (mCF). The mass of the entire measurement container after the suction is measured and is defined as W2 (g). The toner charge amount (mC / kg) is calculated by the following equation.
Charge amount (mC / kg) = (C × V) / (W1-W2)

<Measurement Method of Toner Weight Average Particle Diameter (D4)>
The weight average particle diameter (D4) of the toner is calculated as follows.
As a measuring device, a precise particle size distribution measuring device “Coulter Counter Multisizer 3” (registered trademark, manufactured by Beckman Coulter, Inc.) using a pore electrical resistance method equipped with an aperture tube of 100 μm is used. For setting the measurement conditions and analyzing the measurement data, the included dedicated software “Beckman Coulter Multisizer 3 Ver.
sion3.51 "(Beckman Coulter, Inc.) is used. The measurement is performed with 25,000 effective measurement channels.
As the electrolytic aqueous solution used for the measurement, special grade sodium chloride is dissolved in ion exchange water so that the concentration becomes 1% by mass, for example, “ISOTON II” (manufactured by Beckman Coulter, Inc.) can be used.
Prior to measurement and analysis, the dedicated software is set as follows.
On the “Change Standard Measurement Method (SOM)” screen of the dedicated software, set the total count in the control mode to 50000 particles, set the number of measurements once, and set the Kd value to “standard particles 10.0 μm” (Beckman Coulter Set the value obtained using By pressing the “Threshold / Noise Level Measurement Button”, the threshold and noise level are automatically set. In addition, the current is set to 1600 μA, the gain is set to 2, the electrolytic aqueous solution is set to ISOTON II, and the “aperture tube flush after measurement” is checked.
In the “Pulse to particle size conversion setting” screen of the dedicated software, the bin interval is set to logarithmic particle size, the particle size bin is set to 256 particle size bin, and the particle size range is set to 2 μm to 60 μm.
The specific measurement method is as follows.
(1) Put 200 mL of the aqueous electrolytic solution into a 250 mL round bottom beaker made exclusively for Multisizer 3, set it on a sample stand, and stir the stirrer rod counterclockwise at 24 rpm. Then, the dirt and bubbles in the aperture tube are removed by the “aperture flush” function of the dedicated software.
(2) Put 30 mL of the electrolytic aqueous solution into a glass 100 mL flat bottom beaker. In this, "Contaminone N" (nonionic surfactant, anionic surfactant, 10% by weight aqueous solution of neutral detergent for pH7 precision measuring instrument cleaning, made by organic builder, manufactured by Wako Pure Chemical Industries, Ltd. 0.3 mL of a diluted solution obtained by diluting 3) with ion-exchanged water.
(3) Two oscillators with an oscillation frequency of 50 kHz are incorporated with the phase shifted by 180 degrees, and an ultrasonic disperser “Ultrasonic Dispersion System Tetora 150” (manufactured by Nikka Ki Bios) having an electrical output of 120 W is prepared. Put 3.3 L of ion exchange water in the water tank of the ultrasonic disperser, and add 2 mL of Contaminone N into this water tank. (4) The beaker of (2) is set in the beaker fixing hole of the ultrasonic disperser, and the ultrasonic disperser is operated. And the height position of a beaker is adjusted so that the resonance state of the liquid level of the electrolyte solution in a beaker may become the maximum.
(5) In a state where the electrolytic aqueous solution in the beaker of (4) is irradiated with ultrasonic waves, 10 mg of toner is added to the electrolytic aqueous solution little by little and dispersed. Then, the ultrasonic dispersion process is continued for another 60 seconds. In ultrasonic dispersion, the temperature of the water tank is appropriately adjusted so as to be 10 ° C. or higher and 40 ° C. or lower.
(6) To the round bottom beaker of (1) installed in a sample stand, the electrolytic aqueous solution of (5) in which toner is dispersed is dropped using a pipette, and the measurement concentration is adjusted to 5%. . Measurement is performed until the number of measured particles reaches 50,000.
(7) The measurement data is analyzed with the dedicated software attached to the apparatus, and the weight average particle diameter (D4) is calculated. The “average diameter” on the “analysis / volume statistics (arithmetic average)” screen when the graph / volume% is set by the dedicated software is the weight average particle diameter (D4).

  EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples. “Part” and “%” used in the examples are all based on mass unless otherwise specified. In addition, toners 1 to 25 were produced as examples, and toners 26 to 38 were produced as comparative examples.

<Manufacture of amorphous resin 1>
To a reaction vessel equipped with a stirrer, thermometer, nitrogen introduction tube, dehydration tube, and decompression device, 100.0 parts of a mixture prepared by mixing raw material monomers in the ratio (mol%) shown in Table 1 was added and stirred. While heating to 130 ° C. Thereafter, 0.52 part of di (2-ethylhexanoic acid) tin was added as an esterification catalyst, the temperature was raised to 200 ° C., and condensation polymerization was performed until a desired molecular weight was obtained, whereby an amorphous resin 1 was obtained. The weight average molecular weight (Mw) of the amorphous resin 1 was 12000, the glass transition temperature (Tg) was 70 ° C., and the acid value was 6.7 mgKOH / g.

<Production of amorphous resin 2-18>
Amorphous resins 2 to 18 were produced in the same manner as in the production of amorphous resin 1 using the raw material monomers and the charge ratio in Table 1. Table 1 shows the physical properties of the obtained amorphous resins 2 to 18.

表中のＴＰＡはテレフタル酸、ＴＭＡはトリメリット酸、ＢＰＡ‐ＰＯはビスフェノールＡのプロピレンオキサイド２ｍｏｌ付加物、ＥＧはエチレングリコールを表す。

In the table, TPA represents terephthalic acid, TMA represents trimellitic acid, BPA-PO represents a 2 mol propylene oxide adduct of bisphenol A, and EG represents ethylene glycol.

<Manufacture of amorphous resin 19>
In a reaction vessel equipped with a stirrer, a condenser, a thermometer, and a nitrogen introduction tube, 200 parts of xylene was charged and refluxed under a nitrogen stream.
As a monomer
2-acrylamido-2-methylpropanesulfonic acid 6.0 parts styrene 72.0 parts 2-ethylhexyl acrylate 18.0 parts dimethyl-2,2'-azobis (2-methylpropionate) 5.0 parts The solution was added dropwise to the reaction vessel with stirring and held at 65 ° C. for 10 hours. Thereafter, distillation was performed to distill off the solvent, followed by drying at 40 ° C. under reduced pressure to obtain an amorphous resin 19.
The physical properties of the obtained amorphous resin 19 are shown in Table 1.

<Production of Pigment Adsorption Site 1 of Pigment Dispersant>
To 30.00 parts of chloroform, 3.11 parts of 4-nitroaniline (manufactured by Tokyo Chemical Industry Co., Ltd.) was added and cooled to 10 ° C. or less, and 1.89 parts of diketene (manufactured by Tokyo Chemical Industry Co., Ltd.) were added. Then, it stirred at 65 degreeC for 2 hours. After completion of the reaction, extraction with chloroform and concentration yielded Compound A.
Next, 40.00 parts of methanol and 5.29 parts of concentrated hydrochloric acid were added to 3.05 parts of 5-amino-2-benzimidazolinone (manufactured by Tokyo Chemical Industry Co., Ltd.), and the mixture was ice-cooled to 10 ° C. or lower. To this solution, 2.10 parts of sodium nitrite dissolved in 6.00 parts of water was added and reacted at the same temperature for 1 hour.
Next, 0.99 parts of sulfamic acid was added, and the mixture was further stirred for 20 minutes (diazonium salt solution). 4.51 parts of the above compound A was added to 70.00 parts of methanol, and the mixture was ice-cooled to 10 ° C. or less, and the diazonium salt solution was added. Thereafter, a solution obtained by dissolving 5.83 parts of sodium acetate in 7.00 parts of water was added and reacted at 10 ° C. or lower for 2 hours.
After completion of the reaction, 300.00 parts of water was added and stirred for 30 minutes, and then the solid was filtered off and purified by recrystallization from N, N-dimethylformamide to obtain Compound B.
Next, 8.58 parts of the compound B and 0.40 part of palladium-activated carbon (palladium 5%) are added to 150.00 parts of N, N-dimethylformamide, and the reaction is performed under a hydrogen gas atmosphere (reaction pressure of 0.1 to 0.1%). 0.4 MPa) and stirred at 40 ° C. for 3 hours. After completion of the reaction, the solution was filtered and concentrated to obtain a pigment adsorption site 1 represented by the formula (6).

［上記式中のＭｅは、メチル基を表す。］

[Me in the above formula represents a methyl group. ]

<Production of Pigment Adsorption Site 2 of Pigment Dispersant>
In production example of pigment adsorption site 1, 3.05 parts of 5-amino-2-benzimidazolinone (manufactured by Tokyo Chemical Industry Co., Ltd.) is changed to 2.75 parts of 3-aminobenzamide (manufactured by Tokyo Chemical Industry Co., Ltd.) did. Other than that was carried out similarly to the manufacture example of the pigment adsorption part 1, and obtained the pigment adsorption part 2 represented by Formula (7).

［上記式中のＭｅは、メチル基を表す。］

[Me in the above formula represents a methyl group. ]

<Production of Styrene Acrylic Resin 1 Used for Pigment Dispersant>
100 parts of xylene, 95 parts of styrene and 5 parts of acrylic acid were charged into a reaction vessel and mixed, and the resulting mixture was heated to 70 ° C.
Under a nitrogen atmosphere, a solution obtained by dissolving 3 parts of tert-butyl hydroperoxide, which is a radical polymerization initiator, in 10 parts of xylene was dropped into the mixed solution over about 30 minutes. Further, the mixture was kept at that temperature for 10 hours to complete the radical polymerization reaction. Further, the mixed solution was depressurized while being heated to remove 60 parts of xylene to obtain a reaction solution.
On the other hand, 500 parts of methanol was charged into a vessel equipped with a stirring blade, and while stirring, the reaction solution was dropped over 1 hour, and the resulting precipitate was filtered and washed, followed by drying, and a styrene acrylic resin. 1 was obtained.

<Manufacture of polyester resin 1 used for pigment dispersant>
Terephthalic acid 50.0 parts Isophthalic acid 45.0 parts Bisphenol A propylene oxide 2-mole adduct 200.0 parts The above materials are put into a 6 liter four-necked flask equipped with a nitrogen introduction tube, a dehydration tube, a stirrer and a thermocouple. The reaction vessel was charged and reacted at 200 ° C. for 6 hours under a nitrogen atmosphere.
Further, 3.0 parts of trimellitic anhydride was added at 210 ° C., the pressure was reduced to 5 kPa, the reaction was continued, and the reaction was continued until the weight average molecular weight (Mw) became 12,000. The resulting resin was designated as polyester resin 1.

<Production of Pigment Dispersant 1>
1.5 parts of pigment adsorption site 1 was added to 500.0 parts of tetrahydrofuran and heated to 65 ° C. to dissolve. After dissolution, the temperature was lowered to 50 ° C., 15.0 parts of styrene acrylic resin 1 (styrene acrylic resin site) was dissolved, and 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide / hydrochloride (EDC / HCl) 2 After adding 0.0 part and stirring at 50 degreeC for 5 hours, 20.0 parts of methanol was added and it was made to react at 65 degreeC for 1 hour. The liquid temperature was gradually returned to room temperature, and the reaction was completed by stirring overnight. After completion of the reaction, the solution was filtered, concentrated and purified by reprecipitation with methanol to obtain Pigment Dispersant 1. This pigment dispersant has a structure represented by the above formula (5) as a pigment adsorption site, and the divalent linking group (L) is an amide group.

<Production of pigment dispersants 2 to 4>
Pigment dispersants 2 to 4 were obtained in the same manner as in the pigment dispersant 1 production method except that the raw materials and the charge amounts shown in Table 2 were changed. The pigment dispersant 2 has a structure represented by the above formula (4) as a pigment adsorption site, and the divalent linking group (L) is an amide group. The pigment dispersants 3 and 4 have a structure represented by the above formula (5) as a pigment adsorption site, and the divalent linking group (L) is an amide group.

<Manufacture of toner 1>
(Aqueous medium manufacturing process)
14 parts of sodium phosphate (manufactured by Lhasa Kogyo Co., Ltd.) was added to 1000 parts of ion-exchanged water in the reaction vessel, and kept at 65 ° C. for 60 minutes while purging with nitrogen.
Next, using a high-speed agitator TK homomixer (made by Tokushu Kika Kogyo Co., Ltd.), while stirring at 12000 rpm, an aqueous solution of calcium chloride in which 7.8 parts of calcium chloride is dissolved in 10 parts of ion-exchanged water is added all at once. Then, an aqueous medium containing a dispersion stabilizer was prepared. Furthermore, 4.5 parts of 10% by mass hydrochloric acid was added to the aqueous medium to adjust the pH to 5.8.
(Manufacturing process of polymerizable monomer composition)
・ Styrene 60.0 parts ・ Carbon black (CB) (trade name “NIPEX35” manufactured by Degussa) 8.0 parts ・ Pigment dispersant 1 0.8 parts Atlite disperser (Mitsui Miike Chemical Co., Ltd.) Then, using zirconia particles having a diameter of 1.7 mm and dispersing at 220 rpm for 5 hours, the zirconia particles were removed to obtain a pigment dispersion.
In the above pigment dispersion, 20.0 parts of styrene, 20.0 parts of n-butyl acrylate (n-BA), 5.0 parts of amorphous resin, 7.0 parts of a release agent, paraffin wax (HNP-9: Nippon Seiki made melting point 75 ℃)
Was added. The above material was kept at 65 ° C., and uniformly dissolved and dispersed at 500 rpm using a high-speed stirring device TK homomixer to obtain a polymerizable monomer composition.
(Granulation process)
While maintaining the temperature of the aqueous medium at 70 ° C. and the rotational speed of the stirrer at 15000 rpm, the polymerizable monomer composition was charged into the aqueous medium, and t-butyl peroxypivalate 9 as a polymerization initiator was added. 0.0 part was added. The mixture was granulated for 10 minutes while maintaining 15000 rpm with the stirring device.
(Polymerization process)
The stirrer is changed from a high-speed stirrer to a propeller stirring blade, and polymerization is performed by maintaining at 70 ° C. while stirring at 150 rpm for 5.0 hours, raising the temperature to 85 ° C., and further heating for 2 hours. A slurry of toner particles was obtained.
(Washing, drying, classification, external addition process)
After completion of the polymerization step, the slurry was cooled, hydrochloric acid was added to the cooled slurry to adjust the pH to 1.4, and the mixture was stirred for 1 hour to dissolve the calcium phosphate salt. Thereafter, the slurry was washed with 10 times the amount of water of the slurry, filtered and dried, and then the particle diameter was adjusted by classification to obtain toner particles (toner particles before adding the external additive).
Hydrophobic silica fine powder (primary particle diameter: 7 nm, BET specific surface area: silica fine powder treated with 20% by mass of dimethyl silicone oil as an external additive with respect to 100.0 parts of the obtained toner particles. Toner 1 was obtained by mixing 1.5 parts of 130 m ^{2 /} g) at a stirring speed of 3000 rpm for 15 minutes using a Henschel mixer (manufactured by Mitsui Miike).

<Production of Toners 2 to 23, 26 to 35, and 38>
As shown in Table 3-1 or Table 3-2, the type and amount of polymerizable monomer, the type and amount of pigment, the type and amount of pigment dispersant, and the type and amount of amorphous resin. Toners 2 to 23, 26 to 35, and 38 were obtained in the same manner as in the manufacturing method of the toner 1 except for changing. In any of the toners, 60.0 parts of styrene was added during the production of the pigment dispersion, and other polymerizable monomers were added after the pigment dispersion was produced.

<Manufacture of Toner 24>
The following materials were put in a reaction vessel equipped with a reflux condenser, a stirrer, and a nitrogen inlet tube under a nitrogen atmosphere.
-Toluene 100.0 parts-Styrene 80.0 parts-N-butyl acrylate 20.0 parts-Methacrylic acid 4.0 parts-T-butyl peroxypivalate 3.0 parts The mixture in the said container is stirred at 200 rpm. The mixture was heated to 70 ° C. and stirred for 10 hours. Furthermore, it heated at 100 degreeC and the solvent was distilled off for 6 hours, and the styrene acrylic resin 2 was obtained.
Then
-Styrene acrylic resin 2 100.0 parts-Carbon black (trade name "NIPEX35" manufactured by Degussa) 8.0 parts-Pigment dispersant 1 0.8 parts-Amorphous resin 1 5.0 parts-Release agent 7.0 parts of paraffin wax (HNP-9: Nippon Seiki, melting point 75 ° C.)
-Ethyl acetate 200.0 parts The above components were mixed and dispersed in a ball mill for 10 hours, and the resulting dispersion was added to 2000 parts of ion-exchanged water containing 3.5% by mass of tricalcium phosphate, and a high-speed stirring device TK. -Granulation was performed with a homomixer at 15000 rpm for 10 minutes. Then, while stirring at 150 rpm with a three-one motor, it was kept at 75 ° C. for 4 hours in a water bath to remove the solvent.
Thereafter, washing, drying, classification, and external addition steps were performed in the same manner as in the production example of toner 1 to obtain toner 24.

<Manufacture of polyester resin 2 for toners 36 and 37>
Terephthalic acid 90.0 parts Sebacic acid 10.0 parts Bisphenol A propylene oxide 2 mol adduct 200.0 parts Four liters of the above materials equipped with a nitrogen introduction tube, a dehydration tube, a stirrer and a thermocouple in the above ratio The flask was charged and the material was reacted at 200 ° C. for 6 hours under a nitrogen atmosphere.
Further, 3.0 parts of trimellitic anhydride was added at 210 ° C., the pressure was reduced to 5 kPa, the reaction was continued, and the reaction was continued until the weight average molecular weight (Mw) became 12,000. The resulting resin was designated as polyester resin 2.

<Manufacture of Toner 36>
A toner 36 was obtained in the same manner as in the production example of the toner 24 except that the styrene acrylic resin 2 was changed to the polyester resin 2 in the production example of the toner 24.

<Manufacture of toner 37>
A toner 37 was obtained in the same manner as in the production example of the toner 24 except that the styrene acrylic resin 2 was changed to the polyester resin 2 and the pigment dispersant 1 was changed to the pigment dispersant 3 in the production example of the toner 24.

<Manufacture of toner 25>
The following materials were put in a reaction vessel equipped with a reflux condenser, a stirrer, and a nitrogen inlet tube under a nitrogen atmosphere.
・ Toluene 100.0 parts ・ Styrene 80.0 parts ・ n-butyl acrylate 20.0 parts ・ t-butyl peroxypivalate 3.0 parts The mixture in the container was stirred at 200 rpm and heated to 70 ° C. Stir for 10 hours. Furthermore, after heating to 100 degreeC and distilling a solvent off for 6 hours, it grind | pulverized coarsely and the styrene acrylic resin 3 was obtained.
Then
-Styrene acrylic resin 3 100.0 parts-Carbon black (trade name "NIPEX35" manufactured by Degussa) 8.0 parts-Pigment dispersant 1 0.8 parts-Amorphous resin 1 5.0 parts-Release agent 7.0 parts of paraffin wax (HNP-9: Nippon Seiki, melting point 75 ° C.)
After pre-mixing the above materials with a Henschel mixer (FM-75 type, manufactured by Mitsui Miike Chemical Co., Ltd.), the melt temperature at the discharge port using a high-speed rotating twin-screw extruder (PCM-30, manufactured by Ikekai Ironworks Co., Ltd.) Was set to 180 ° C. and melt kneaded. The obtained kneaded product was cooled, coarsely pulverized to 1 mm or less with a hammer mill, and then finely pulverized using a turbo mill T250 (manufactured by Turbo Kogyo Co., Ltd.) as a pulverizer. The obtained finely pulverized powder was classified using a multi-division classifier using the Coanda effect. Thereafter, an external addition process was performed in the same manner as in the toner 1 production example, whereby a toner 25 was obtained. The physical properties of the obtained toner are summarized in Table 3-1 and Table 3-2.

<Manufacture of binder resin 1-23, 26-35, and 38>
For toners 1 to 23, 26 to 35, and 38 produced by the suspension polymerization method, only the polymerizable monomer is polymerized under the same production conditions as in the production examples of each toner, and binder resins 1 to 23 in each toner are produced. 26-35 and 38.
The adsorption rate A1, the adsorption rate A2, the Rf value RfL, and the Rf value RfH in the pigment, pigment dispersant, amorphous resin, and binder resin used for each toner were measured according to the methods described above. The results are summarized in Table 4.

Each toner obtained was evaluated for performance according to the following method.
[Coloring power]
The toner contained inside was removed from a cartridge for a commercially available color laser printer, Satera LBP7700C (manufactured by Canon Inc.), the inside was cleaned by air blow, and then the toner (150 g) was filled.
In addition, a part of the color laser printer Satera LBP7700C (manufactured by Canon Inc.) was remodeled so that the fixing machine was removed and an unfixed image could be output, and the image density could be adjusted by the controller. Furthermore, it has been modified to work even when only one color process cartridge is installed. The removed fuser was remodeled so that it could be operated by a single fuser, and was further remodeled to an external fuser that can control the process speed and temperature.
The cartridge was mounted on a printer, and as shown in FIG. 3, a band image of width 150 mm × length 30 mm was created after a space of 30 mm above the transfer material.
Further, the controller was set so that the toner application amount of the belt image was 0.35 mg / cm ² . A4 size GF-C081 (manufactured by Canon Inc., 81.4 g / m ² ) was used as the transfer material.
Ten belt images were output and fixed at 160 ° C. using a LBP7700C external fixing machine at a process speed of 300 mm / sec. The image density of the band image was measured to evaluate the coloring power. The image density was measured using “Macbeth reflection densitometer RD918” (manufactured by Macbeth). For the image density, a relative density with respect to the output image of the white background portion having a density of 0.00 is measured, and the output image 10 is measured for each of the left, center, and right portions of the band image for each output image. The average value of the sheets was evaluated. The evaluation criteria are as follows. The results are shown in Table 5.
(Evaluation criteria)
A: Image density is 1.40 or more (particularly excellent in coloring power)
B: Image density is 1.30 or more and less than 1.40 (excellent coloring power)
C: Image density is 1.20 or more and less than 1.30
D: Image density is 1.10 or more and less than 1.20 (slightly inferior in coloring power)
E: Image density is less than 1.10 (inferior coloring power)

[durability]
A commercially available color laser printer (HP Color LaserJet 3525dn, manufactured by HP) was modified and evaluated so as to operate even when only one color process cartridge was installed. The toner contained in the color laser printer was extracted from the cartridge, the interior was cleaned by air blow, and the toner to be evaluated (200 g) was filled instead. Under normal temperature and humidity (23 ° C., 60% RH), a Canon office planner (64 g / m ² ) was used as the image receiving paper, and 50000 charts with a printing rate of 1% were continuously drawn out. After the image was printed, a halftone image was further output, and the presence or absence of vertical streaks in the paper discharge direction on the developing roller and in the halftone image was observed, and durability was evaluated as follows. Note that toner having excellent durability is not easily crushed or cracked, and is difficult to adhere to the developing roller, so that streaks are not easily generated. The results are shown in Table 5.
(Evaluation criteria)
A: Vertical streaks in the paper discharge direction are not seen on the image on the developing roller and the halftone area (particularly excellent in durability)
B: Although there are 1 to 3 fine streaks on the developing roller, no vertical streak in the paper discharge direction is seen on the halftone image (excellent durability).
C: Although there are 4 to 6 fine stripes on the developing roller, no vertical stripe in the paper discharge direction is seen on the halftone image D: 7 to 9 fine stripes are on the developing roller, Vertical streaks in the paper discharge direction can be seen on the halftone image (slightly less durable)
E: Ten or more remarkable vertical streaks in the paper discharge direction are observed on the developing roller and the halftone image (inferior in durability).

[Chargeability]
In order to evaluate the chargeability, the fog density was evaluated. Image output in durability, that is, after outputting 50,000 sheets, after leaving for one week, a Canon office planner (64 g / m ² ) was used as the image receiving paper, and one image having a white background portion was output. . Thereafter, with respect to an image having a white background portion, a fog density (from the difference between the whiteness (reflectance Ds (%)) of the white background portion of the image having the white background portion and the whiteness (average reflectance Dr (%)) of the image receiving paper. %) (= Dr (%) − Ds (%)). In addition, the whiteness was measured by “REFLECTMETER MODEL TC-6DS” (manufactured by Tokyo Denshoku Co., Ltd.). An amberlite filter was used as the filter. The chargeability was evaluated according to the following criteria. The results are shown in Table 5.
(Evaluation criteria)
A: The fog density is less than 0.3% (particularly excellent in chargeability)
B: The fog density is 0.3% or more and less than 0.8% (excellent chargeability)
C: The fog density is 0.8% or more and less than 1.3%
D: The fog density is 1.3% or more and less than 2.0% (slightly inferior in chargeability)
E: The fog density is 2.0% or more (inferior in chargeability)

[Chargeable environmental stability]
In order to evaluate the environmental stability of the charging property, a two-component developer was prepared as follows.
279 g of magnetic carrier F813-300 (Powder Tech) and 21 g of toner to be evaluated are put into a 500 mL plastic bottle with a lid, and 4 reciprocations per second with a shaker (YS-LD: Yayoi Co., Ltd.) The toner was shaken for 1 minute to obtain a two-component developer for each toner.
10 g of the two-component developer was placed in a 50 mL plastic container and left for a whole day and night in an environment of normal temperature and humidity (23 ° C./60% RH). Then shake it 450 times over 3 minutes. Next, the triboelectric charge amount was measured by the means described above, and the obtained charge amount was defined as the charge amount N (mC / kg).
Further, 10 g of the two-component developer was put in a 50 mL plastic container and left standing for one day in a high temperature and high humidity environment (30 ° C./80% RH). Thereafter, the mixture was shaken 450 times over 3 minutes, and the charge amount measured by the same method was defined as charge amount H (mC / kg).
From the obtained charge amount N and charge amount H Charge retention rate (%) = 100 × charge amount H (mC / kg) / charge amount N (mC / kg)
The charge retention rate (%) in a high temperature environment was calculated as follows, and the environmental stability of the chargeability was evaluated according to the following criteria. The results are shown in Table 5.
(Evaluation criteria)
A: Charge retention rate (%) is 70% or more (particularly excellent in environmental stability of charging property)
B: The charge retention rate (%) is 60% or more and less than 70% (excellent environmental stability of chargeability)
C: The charge retention rate (%) is 50% or more and less than 60% D: The charge retention rate (%) is 40% or more and less than 50% (slightly inferior to the environmental stability of the charging property)
E: Charge retention rate (%) is less than 40% (inferior to environmental stability of chargeability)

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

Claims (10)

A toner having toner particles containing a binder resin, a pigment, a pigment dispersant, and an amorphous resin,
The adsorption rate A1 (%) of the pigment dispersant with respect to the pigment is 80% or more and 100% or less,
Adsorption rate A2 (%) of the amorphous resin with respect to the pigment is 0% or more and 60% or less,
Rf value (RfL) of the binder resin is 0.50 or more and 1.00 or less,
A toner wherein the amorphous resin has an Rf value (RfH) of 0.00 or more and 0.35 or less.
(This A1 was obtained by mixing 20 parts by mass of a solvent obtained by mixing styrene and n-butyl acrylate at a mass ratio of 4: 1, 0.1 part by mass of the pigment dispersant, and 1.0 part by mass of the pigment. The adsorption rate when the mixed solution is measured is shown.
The A2 is a mixture obtained by mixing 20 parts by mass of a solvent obtained by mixing styrene and n-butyl acrylate at a mass ratio of 4: 1, 0.1 part by mass of the amorphous resin, and 1.0 part by mass of the pigment. The adsorption rate when the liquid is measured is shown. )
(The RfL represents the Rf value of the binder resin measured by thin-layer chromatography in a 60 ° C. environment using a solution of the binder resin, silica gel as a stationary phase, and a developing solvent,
The binder resin solution is a mixture of 20 parts by mass of a solvent in which styrene and n-butyl acrylate are mixed at a mass ratio of 4: 1, and 0.1 part by mass of the binder resin.
The developing solvent is a mixture of styrene and n-butyl acrylate at a mass ratio of 1: 1.
The RfH represents the Rf value of the amorphous resin measured by thin-layer chromatography in a 60 ° C. environment using the solution of the amorphous resin, silica gel as a stationary phase, and the developing solvent,
The solution of the amorphous resin is a mixture of 20 parts by mass of a solvent obtained by mixing styrene and n-butyl acrylate at a mass ratio of 4: 1 and 0.1 part by mass of the amorphous resin. )   The toner according to claim 1, wherein the amorphous resin is a polyester resin.   The toner according to claim 2, wherein the polyester resin has a unit derived from an alcohol having an alicyclic structure or a unit derived from a carboxylic acid having an alicyclic structure in at least one of a main chain and a side chain.   The content ratio of the unit derived from the alcohol having the alicyclic structure or the unit derived from the carboxylic acid having the alicyclic structure with respect to all the monomer units constituting the polyester resin is 0.1 mol% or more and 50 mol% or less. The toner according to claim 3. The polyester resin has a unit derived from an acyclic aliphatic diol as a unit derived from alcohol,
The toner according to any one of claims 2 to 4, wherein a content ratio of units derived from the acyclic aliphatic diol to all monomer units constituting the polyester resin is 10 mol% or more and 30 mol% or less.   The toner according to claim 1, wherein the pigment dispersant has a pigment adsorption site and a styrene acrylic resin site. The toner according to claim 6, wherein the pigment adsorption site has a structure represented by the following formula (1).

(In the formula (1),
R ¹ and R ² each independently represents a substituted or unsubstituted alkyl group, a substituted or unsubstituted phenyl group, —OR ⁵ group, or —NR ⁶ R ⁷ group.
R ⁵ , R ⁶ and R ⁷ each independently represents a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted phenyl group, or an aralkyl group.
Ar represents a substituted or unsubstituted aryl group.
At least one of R ¹ , R ² , and Ar is a substituent having a linking group that binds to the styrene acrylic resin moiety. This substituent is synonymous with the group shown by said R < ¹ >, R < ² > or Ar.
When at least one of R ¹ and Ar is a substituent having a linking group bonded to the styrene acrylic resin moiety, the linking group is a group represented by —C (═O) —NH—, —C (= A group represented by O) -O-, a group represented by -NH-C (= O) -O-, a group represented by -NH-C (= O) -NH-, an alkylene group, a phenylene group, -O -, a group represented by -NR ⁸ - is a divalent linking group selected from the group consisting of groups represented by, -, a group represented by and -NHCH _(CH 2 OH)
R ⁸ represents a hydrogen atom, an alkyl group, a phenyl group or an aralkyl group.
When R ² is a substituent having a linking group bonded to the styrene acrylic resin moiety, the linking group is a group represented by —C (═O) —NH—, —C (═O) —O—. A group represented by —NH—C (═O) —O—, a group represented by —NH—C (═O) —NH—, an alkylene group, a phenylene group, a group represented by —O—, A divalent linking group selected from the group consisting of a group represented by -NR ⁹ -and a group represented by -NHCH (CH ₂ OH)-;
R ⁹ represents a hydrogen atom, an alkyl group, a phenyl group, or an aralkyl group. )   The toner according to claim 1, wherein the A2 (%) is 0% or more and 50% or less.   The toner according to claim 1, wherein the amorphous resin has a weight average molecular weight (Mw) of 11,000 or more and 40000 or less. A method for producing a toner having toner particles according to any one of claims 1 to 9,
The production process of the toner particles is the following process (1) or (2):
(1) a granulation step of forming particles of a polymerizable monomer composition containing a polymerizable monomer capable of forming a binder resin, a pigment, a pigment dispersant, and an amorphous resin in an aqueous medium; and A polymerization step for polymerizing the polymerizable monomer contained in the particles of the polymerizable monomer composition;
(2) A dissolution step of preparing a resin solution by dissolving or dispersing a binder resin, a pigment, a pigment dispersant and an amorphous resin in an organic solvent, and a granulation step of forming particles of the resin solution in an aqueous medium And a solvent removal step for producing resin particles by removing an organic solvent contained in the particles of the resin solution,
A toner production method comprising:

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