JP2009053501A - toner - Google Patents

Abstract

Disclosed is a capsule toner having excellent heat-resistant storage stability and low-temperature fixability, which has a small amount of colorant, has a high concentration, and has good color developability of the colorant.
A toner containing capsule-type toner particles having a surface layer (B) on the surface of toner base particles (A) containing at least a resin (a) containing a polyester as a main component, a colorant and a wax. Then, an enlarged photograph of the cross section of the toner particle is taken, and a straight line connecting the center of the toner particle and the surface of the toner particle in the obtained image of the toner particle is drawn, and 3: 1 from the center of gravity is drawn on the drawn straight line. Set the divided points, and the occupancy ratio of the colorant in the area on the toner particle surface side of the curve formed by connecting the set points is 1.5 times or more than the occupancy ratio of the colorant in the area inside the toner particle of the curve Toner characterized by being.
[Selection figure] None

Description

  The present invention relates to a toner used in a recording method using an electrophotographic method, an electrostatic recording method, a toner jet recording method, or the like. More specifically, the present invention relates to a copying machine and printer in which a toner image is formed on an electrostatic latent image carrier and then transferred onto a transfer material to form a toner image and fixed under thermal pressure to obtain a fixed image. , Relating to toner used in fax machines.

In recent years, energy saving has been considered as a major technical problem in electrophotographic apparatuses, and the amount of heat applied to a fixing apparatus has been greatly reduced. Accordingly, there is a growing need for so-called “low-temperature fixability” that can fix toner with lower energy.
Conventionally, in order to enable fixing at a low temperature, a technique of using a binder resin as a sharp melt is known as an effective method. In this respect, the polyester resin exhibits excellent characteristics.

On the other hand, as another aspect of improving image quality, for the purpose of high resolution and high definition, the toner particle size is reduced and the particle size distribution is sharpened, and spherical shape is used for the purpose of improving transfer efficiency and fluidity. The toner of this type is now being used favorably. As a method for efficiently preparing spherical toner particles having a small particle diameter, a wet method has been used.
As a wet method in which a sharp melt polyester resin can be used, a resin component is dissolved in an organic solvent immiscible with water, and this solution is dispersed in an aqueous phase to form oil droplets. A “dissolution suspension” method for producing toner particles has been proposed (Patent Document 1). According to this method, a spherical toner having a small particle diameter using polyester having excellent low-temperature fixability as a binder resin can be easily obtained.
Furthermore, capsule-type toner particles have been proposed for the purpose of further low-temperature fixability in the toner particles produced by the above-described dissolution suspension method using polyester as a binder resin.

Patent Document 2 proposes the following method.
A polyester resin, a low molecular compound having an isocyanate group, and other components are dissolved and dispersed in ethyl acetate to prepare an oil layer, and droplets are prepared in water. As a result, a compound having an isocyanate group is subjected to interfacial polymerization at the droplet interface to prepare capsule toner particles having polyurethane or polyurea as the outermost shell.

  In Patent Documents 3 and 4, toner base particles are prepared by a dissolution suspension method in the presence of resin fine particles that are any of vinyl resins, polyurethane resins, epoxy resins, polyester resins, or a combination thereof. A technique for preparing toner particles in which the surface of toner base particles is coated with resin fine particles has been proposed.

Patent Document 5 proposes toner particles by a dissolution suspension method using urethane-modified polyester resin fine particles as a dispersant.
Patent Document 6 discloses a core / shell composed of one or more film-like shell layers (P) made of polyurethane resin (a) and one core layer (Q) made of resin (b). Types of toner particles have been proposed.

While a toner having excellent fixability is required, a demand for a color toner image is also increasing. Vivid images can be reproduced by increasing the color space in the secondary color reproduction areas such as red, blue, and green, especially in areas with high brightness.
In order to increase the color space in the high lightness region, it is effective to change the type of the colorant and use a high colorant colorant. However, high-color coloring agents are expensive, and there are only a limited number of coloring agents that can solve the problems of chargeable and weather-resistant toners.
Further, the color space can be widened by reducing the amount of the colorant added and using a toner having a low concentration. However, when an image in a high density region is output, there is a problem that the amount of toner consumption increases, leading to high costs. Further, the difference in the amount of toner applied on the image is large, and unevenness is likely to occur on the image. For this reason, attempts have been made to increase the color developability of colorants that can be normally used.

With respect to dissolution suspension and capsule type toner, as disclosed in Patent Document 7, a technique of using a master batch of a colorant and finely dispersing the dispersion diameter to a number average of 0.5 μm or less has been proposed. Patent Document 8 introduces a technique for increasing the dispersibility of a pigment by using a pigment dispersant.
However, in any case, the uniform dispersion of the colorant is not sufficient, and it is not a satisfactory level in terms of toner coloring power, toner transparency, and color reproducibility, and a vivid full color image is obtained. For this purpose, there was a further need for improvement.
Japanese Patent Laid-Open No. 08-248680 JP 05-297622 A JP 2004-226572 A JP 2004-271919 A Japanese Patent No. 3455523 WO2005 / 073287 JP-A-2005-202420 JP 2004-126160 A

  The present invention has been made in view of the problems as described above, and is a capsule toner excellent in heat-resistant storage stability and low-temperature fixability, having a high concentration with a small amount of colorant, and color development of the colorant. Toner having good properties is provided.

As a result of intensive studies to solve the above problems, the present inventors have found that these problems can be solved by the following toner, and have reached the present invention.
That is, the present invention contains capsule-type toner particles having a surface layer (B) on the surface of toner base particles (A) containing at least a resin (a) mainly composed of polyester, a colorant and a wax. An enlarged photograph of a cross section of the toner particle is taken, and a straight line connecting the center of the toner particle and the surface of the toner particle in the obtained toner particle image is drawn, and the straight line is drawn from the center of gravity on the drawn straight line. The point divided into 3: 1 is set, and the occupation ratio of the colorant in the region on the surface of the toner particle surface of the curve formed by connecting the set points is the occupation of the colorant in the region inside the toner particle of the curve The present invention relates to a toner characterized in that the ratio is 1.5 times or more.

According to a preferred embodiment of the present invention, the toner has a capsule-type structure, and the toner base particles (A) have functions such as low viscosity, releasability, and coloring, and are charged with respect to heat-resistant storage stability and developability. The surface layer (B) is responsible for this function. With this structure, a toner excellent in heat-resistant storage stability and low-temperature fixability can be provided.
Further, according to a preferred embodiment of the present invention, by distributing a large amount of the colorant on the surface of the toner, even when the addition amount of the colorant is reduced, the coloring power of the image is improved, and the saturation and brightness are improved. It became possible to expand the color gamut in areas with high lightness (L *) and expand the area for secondary color reproduction. As a result, the color reproduction range can be expanded.
Furthermore, according to a preferred embodiment of the present invention, it is possible to use an inexpensive colorant with low color development and to reduce the amount of colorant added, and it is possible to supply a process with reduced running cost.

The toner of the present invention contains capsule-type toner particles having a surface layer (B) on the surface of toner base particles (A) containing at least a resin (a) mainly composed of polyester, a colorant and a wax. Toner,
An enlarged photograph of the cross section of the toner particle is taken, and a straight line connecting the center of toner particle and the surface of the toner particle in the obtained toner particle image is drawn, and is divided into 3: 1 from the center of gravity on the drawn straight line. The occupancy rate of the colorant in the region on the surface of the toner particle surface of the curve formed by connecting the set points is 1.5 of the occupancy rate of the colorant in the region inside the toner particle of the curve. It is characterized by being more than double.

The toner of the present invention has a capsule-type structure (capsule structure) having a surface layer (B) on the surface of toner base particles (A) containing at least a resin (a) mainly composed of polyester, a colorant and a wax. have.
When the capsule structure is not adopted, for example, in a toner containing wax, the wax is likely to aggregate due to precipitation of the wax on the surface of the toner, which may cause poor stirring in the developing region and clogging with a cleaner. Further, since the amount of charge varies depending on each colorant due to the colorant appearing on the toner surface, when used as a full color color toner, the behavior of development and transfer in each color changes, and image unevenness is likely to occur. In addition, when carbon black was used as the colorant for black toner, the resistance value of the toner was changed, and the behavior during transfer was easily changed in addition to the change in charge amount. Further, when the low-viscosity toner base particles (A) are used, it is difficult to satisfy the heat resistant storage stability.
In order to eliminate these effects, the surface layer (B) is preferably 1.0% by mass or more and 15.0% by mass or less based on the toner base particles. When it is less than 1.0% by mass, the encapsulation is insufficient and the above-mentioned problems are likely to occur. On the other hand, when it is larger than 15.0% by mass, the properties of the surface layer (B) are strongly reflected even at the time of fixing, and it becomes difficult to exhibit the characteristics of the core that is a sharp melt. More preferably, it is 2.0 mass% or more and 12.0 mass% or less, More preferably, it is 2.5 mass% or more and 10.0 mass% or less.

Furthermore, the present invention is characterized in that the toner base particles (A) are provided with more colorant on the surface layer (B) side. Furthermore, it is preferable to arrange a colorant in a capsule shape near the surface layer (B). Thereby, when the dispersibility of the colorant is low or finely dispersed, the saturation is improved when the lightness (L *) is high, and the coloring power when the amount of the colorant added is reduced. Improvement was achieved.
This is presumed to be due to the following reasons. When the dispersion of the colorant is insufficient, a portion where the colorant is present and a portion where the colorant is not present are mixed, and the reflection density and transmission density of the image cannot be obtained due to the influence of the portion where the colorant is not present. For this reason, when the number of added parts of the colorant is increased, a sufficient density can be obtained, but the transmission density is high, and a drop in brightness occurs in order to obtain the same saturation. On the other hand, when the dispersibility is increased and the colorant is finely dispersed, the concealment ratio on the image by the colorant increases, the density increases, and the color reproducibility increases. However, since the colorant is randomly dispersed, at a minute level, a portion where a large amount of colorant is present and a portion where a small amount is present are generated on the image.
The inventor has intensively studied a method for making the amount of the colorant uniform even at such a minute level. As a result, the following idea was reached. The density, brightness, and color gamut of the toner on the image are determined by the presence of the colorant that can be projected onto the paper. Therefore, it is preferable that the colorant projected with a small amount of coloring material is present evenly even when one toner is viewed. That is, it is not necessary to disperse in three dimensions, and it is necessary to disperse the colorant in two dimensions. Since the angle at which the toner is arranged is unknown, a colorant is arranged in the vicinity of the surface in order to improve the concealing property when viewed from all directions. That is, the idea was reached that a shell structure should be made with a colorant.

  That is, the toner particles used in the present invention are obtained by taking an enlarged photograph of a cross section of the toner particles, drawing a straight line connecting the center of gravity of the toner particle and the surface of the toner particle in the obtained toner particle image, and drawing the straight line. A point divided by 3: 1 from the center of gravity is set on the upper side, and the occupancy ratio of the colorant in the region on the toner particle surface side of the curve formed by connecting the set points is the colorant in the region inside the toner particle of the curve The occupancy ratio is 1.5 times or more. Preferably it is 2.0 times or more, More preferably, it is 3.0 times or more. On the other hand, it is preferable that the occupancy ratio of the colorant in the area on the toner particle surface side is 10 times or less than the occupancy ratio of the colorant in the area inside the toner particle in the curve. That is, it is preferable to arrange most of the colorant in the vicinity of the surface (to constitute a shell structure using the colorant).

In the present invention, in order to make a shell structure using a colorant, for example, the following method can be used, but it is not limited thereto.
As the technique, it is possible to use the production of toner particles by the above-described dissolution suspension method. That is, at least a resin (a) mainly composed of polyester, a colorant and a wax are dissolved or dispersed in an organic medium in an aqueous medium (aqueous phase) in which fine particles containing the resin (b) are dispersed. Toner particles are obtained by dispersing the resulting solution or dispersion, removing the solvent from the resulting dispersion and drying.
Here, in order to form a shell structure with a colorant, it is possible to make the colorant hydrophilic so that it can easily come out near the surface of the oil phase.
Further, for example, the resin (a) containing the polyester as a main component is a resin containing at least two kinds of resins, and the hydrophilicity (for example, acid value) of one resin is set to the hydrophilicity of the other resin. Set larger than (for example, acid value). Then, the colorant is preliminarily mixed (for example, kneaded) with the resin having a high hydrophilicity (for example, acid value) to prepare a mixture containing the colorant. Next, in the step of dissolving or dispersing the resin (a) containing the polyester as a main component, the colorant and the wax in the organic medium, the prepared mixture may be dissolved or dispersed in the organic medium. By performing the above operation, the colorant can be dispersed in the vicinity of the surface of the toner particles.

The toner base particles (A) used in the present invention are described in detail below.
The toner base particles (A) used in the present invention contain at least a resin (a) mainly composed of polyester, a colorant and a wax. Therefore, you may contain other additives other than the above as needed. Here, the “main component” means that the polyester component occupies 50% by mass or more based on the total amount of the resin (a).

The resin (a) containing the polyester as a main component preferably contains at least a resin (a1) synthesized from an aliphatic diol.
The aliphatic diol is preferably an aliphatic diol having 2 to 8 carbon atoms, more preferably 2 to 6 carbon atoms.
Examples of the aliphatic diol having 2 to 8 carbon atoms include ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, Examples thereof include neopentyl glycol, 1,4-butenediol, 1,7-heptanediol, and 1,8-octanediol. Among these, α, ω-linear alkanediol is preferable, and 1,4-butanediol and 1,6-hexanediol are more preferable. Furthermore, from the viewpoint of durability, the content of the aliphatic diol is preferably 30 to 100 mol%, more preferably 50 to 100 mol%, in the alcohol component constituting the polyester.
In addition to the aliphatic diol, the following alcohol may be contained, but the content of the following alcohol is preferably 50 mol% or less, more preferably 30 mol% or less in the alcohol component. As the alcohol, polyoxypropylene (2.2)
Examples include -2,2-bis (4-hydroxyphenyl) propane and polyoxyethylene (2.2) -2,2-bis (4-hydroxyphenyl) propane.

On the other hand, the following are mentioned as a carboxylic acid component which forms polyester.
C1-C20 alkyl such as phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, pyromellitic aromatic polyvalent carboxylic acid, fumaric acid, maleic acid, adipic acid, succinic acid, dodecenyl succinic acid, octenyl succinic acid Aliphatic carboxylic acids such as succinic acid substituted with a group or an alkenyl group having 2 to 20 carbon atoms, anhydrides of these acids, and alkyl (1 to 8 carbon atoms) esters of those acids.
From the viewpoint of chargeability, the carboxylic acid preferably contains an aromatic polyvalent carboxylic acid compound, and the content thereof is preferably 30 to 100 mol%, and 50 to 100 mol% in the carboxylic acid component. Is more preferable.
In addition, from the viewpoint of fixability, the raw material monomer may contain a trivalent or higher polyvalent monomer, that is, a trivalent or higher polyhydric alcohol and / or a trivalent or higher polyvalent carboxylic acid compound. .

The production of the polyester is not particularly limited, and may be performed according to a known method. For example, it can be produced by subjecting an alcohol component and a carboxylic acid component to polycondensation in an inert gas atmosphere at a temperature of 180 to 250 ° C. using an esterification catalyst as necessary.
The resin (a1) preferably contains as a main component a polyester using the aliphatic diol as an alcohol component. On the other hand, even when the resin (a) contains a polyester using a bisphenol monomer as an alcohol component, there is no significant difference in the melting characteristics of the resin (a). However, toner base particles using the resin (a) have poor granulation properties and it tends to be difficult to obtain spherical toner base particles.

  The resin (a) contains a resin other than the resin (a1), such as polyester, styrene-acrylic resin, a mixed resin of polyester and styrene acrylic, and an epoxy resin in which the amount of the aliphatic diol is outside the above range. May be. In that case, 50 mass% or more is preferable with respect to the whole quantity of resin (a), and, as for content of resin (a1) which used the specific amount aliphatic diol as an alcohol component, 70 mass% or more is more preferable.

Furthermore, in the present invention, the molecular weight of the resin (a1) is one of the more preferable embodiments in which the peak molecular weight is 8000 or less, preferably less than 5500. Furthermore, it is one of the preferable embodiments that the ratio of the molecular weight of 100,000 or more is 5.0% or less, more preferably 1.0% or less.
When the peak molecular weight exceeds 8000, and the ratio of the molecular weight of 100,000 or more is more than 5.0%, the fixability may be impaired depending on the type and amount of the resin in the surface layer.
In the present invention, the proportion of the resin (a) having a molecular weight of 1000 or less is preferably 10.0% or less, more preferably less than 7.0%.
When the ratio of the molecular weight of 1000 or less is more than 10.0%, a low molecular weight component that is relatively unstable to heat may contaminate the member.
In the present invention, the method for preparing the resin (a) can be preferably used in order to make the ratio of the molecular weight of 1000 or less particularly 10.0% or less.

  In the present invention, when the molecular weight of the toner is adjusted, a binder resin having two or more kinds of molecular weights may be mixed and used.

A preferable acid value of the resin (a1) is 20 mgKOH / g or less. Moreover, although described also about resin (a2), it is preferable to make it smaller than the acid value of resin (a2). If the acid value of the resin (a1) is larger than the acid value of the resin (a2), the resin (a1) is likely to be unevenly distributed near the surface of the toner base particles (A), and the colorant is added to the surface of the toner base particles (A). It is difficult to localize in the vicinity, and as a result, it becomes difficult to obtain the effect of the present application.

The resin (a) containing the polyester as a main component more preferably contains at least the resin (a1) and the resin (a2). Furthermore, the acid value of the resin (a2) is particularly preferably larger than the acid value of the resin (a1).
The resin (a2) is preferably a polyester like the resin (a1). When the resin (a2) is a polyester, the alcohol component, acid component, and trivalent or higher polyvalent monomer used can be the monomers described in the resin (a1). Moreover, the manufacturing method can also use the same method as resin (a1).

  In the present invention, the molecular weight of the resin (a2) is preferably such that the peak molecular weight is 5000 or more and 20000 or less. It is preferable to design the resin with a high viscosity with respect to the resin (a1).

The acid value of the resin (a2) is preferably 10 mgKOH / g or more, more preferably 15 mgKOH / g or more. Increasing the acid value can be achieved by increasing the amount of dicarboxylic acid at the time of polyester production, or by adding an acid component at the end of the polyester condensation reaction and capping the ends with carboxylic acid.
As described above, the resin (a2) preferably has a larger acid value than the resin (a1). By increasing the acid value compared to the resin (a1), the resin (a2) moves to the surface layer (B) side (that is, the surface of the toner base particles (A)) when the oil phase is dispersed in the aqueous phase. It becomes easy to do. Here, if the colorant is mixed and dispersed in the resin (a2) in advance, the colorant tends to be present in the vicinity of the surface of the toner base particles (A), and as a result, a shell structure of the colorant can be formed.
Furthermore, in order to increase the affinity with water, a hydrophilic functional group can be introduced into the resin (a2). Examples thereof include a sulfone group and an amino group. These functional groups are also effective for giving affinity to the surface layer (B). When the hydrophilic functional group is excessively introduced, the resin (a2) is more likely to come out on the surface than the surface layer (B), which is not preferable. That is, it is preferable that the following relationship is satisfied in terms of solubility parameter value (SP value). However, the SP value of each material is represented by SP [material].
SP [resin (a1)] <SP [resin (a2)] <SP [surface layer (B)] <SP [water].

  It is preferable that the addition amount of resin (a2) is more than the addition amount of the coloring agent used. Moreover, it is preferable that content of resin (a2) is 5 to 30 mass% with respect to resin (a) which has polyester as a main component. If it is less than 5% by mass, the dispersion of the colorant tends to be insufficient. On the other hand, if it is larger than 30% by mass, it is difficult for the colorant to be present on the surface of the toner base particles (A).

Examples of the wax used in the present invention include the following.
Low molecular weight polyethylene, low molecular weight polypropylene, low molecular weight olefin copolymer, aliphatic hydrocarbon wax such as microcrystalline wax, paraffin wax, Fischer-Tropsch wax; oxide of aliphatic hydrocarbon wax such as oxidized polyethylene wax; fat A wax mainly composed of a fatty acid ester such as an aromatic hydrocarbon ester wax; and a partially or fully deoxidized fatty acid ester such as a deoxidized carnauba wax; a partial ester of a fatty acid and a polyhydric alcohol such as behenic acid monoglyceride A methyl ester compound having a hydroxyl group obtained by hydrogenating vegetable oils and fats.
The wax particularly preferably used in the present invention is, in the dissolution suspension method, easy preparation of the wax dispersion, easy incorporation into the prepared toner, seepage from the toner during fixing, releasability Therefore, ester wax is preferable.

In the present invention, the ester wax only needs to have at least one ester bond in one molecule, and either natural wax or synthetic wax may be used.
Examples of the synthetic ester wax include a monoester wax synthesized from a long-chain linear saturated fatty acid and a long-chain linear saturated alcohol. The long-chain linear saturated fatty acid is represented by the general formula C _n H _{2n + 1} COOH, and those with n = about 5 to 28 are preferably used. The long-chain linear saturated alcohol is preferably represented by C _n H _{2n + 1} OH, where n = about 5 to 28.
Specific examples of long-chain linear saturated fatty acids include capric acid, undecyl acid, lauric acid, tridecyl acid, myristic acid, palmitic acid, pentadecylic acid, heptadecanoic acid, tetradecanoic acid, stearic acid, nonadecanoic acid, aramonic acid, Examples include behenic acid, lignoceric acid, serotic acid, heptacosanoic acid, montanic acid and melicic acid.
On the other hand, specific examples of the long-chain linear saturated alcohol include amyl alcohol, hexyl alcohol, heptyl alcohol, octyl alcohol, capryl alcohol, nonyl alcohol, decyl alcohol, undecyl alcohol, lauryl alcohol, tridecyl alcohol, and myristyl alcohol. , Pentadecyl alcohol, cetyl alcohol, heptadecyl alcohol, stearyl alcohol, nonadecyl alcohol, eicosyl alcohol, seryl alcohol and heptadecanool.
Examples of the ester wax having two or more ester bonds per molecule include, for example, trimethylolpropane tribehenate, pentaerythritol tetrabehenate, pentaerythritol diacetate dibehenate, glycerin tribehenate, Examples include 18-octadecanediol-bis-stearate and polyalkanol esters (tristearyl trimellitic acid, distearyl maleate).

Examples of natural ester waxes include candelilla wax, carnauba wax, rice wax, wax, jojoba oil, beeswax, lanolin, castor wax, montan wax and derivatives thereof.
Other modified waxes include polyalkanoic acid amide (ethylenediamine dibehenyl amide); polyalkylamide (trimellitic acid tristearyl amide); and dialkyl ketone (distearyl ketone).
The wax may be partially saponified.

Of the above, more preferable waxes are synthetic ester waxes composed of long-chain straight-chain saturated fatty acids and long-chain straight-chain saturated alcohols, or natural waxes based on the above esters.
The reason for this is not clear, but it is thought that the mobility in the molten state is increased due to the wax having a linear structure. In other words, it is necessary for the wax to permeate into the toner surface layer through a relatively polar substance such as polyester as a binder resin or a reaction product of diol and diisocyanate on the surface layer at the time of fixing. Therefore, it seems that it is advantageous that the wax has a linear structure as much as possible in order to pass between such highly polar substances.

  Further, in the present invention, it is more preferable that the ester is a monoester in addition to the linear structure described above. For the same reason as described above, in a bulky structure in which esters are bonded to the branched chains, it penetrates through a highly polar substance such as polyester or the surface layer of the present invention and oozes out to the surface. The authors speculate that it may be difficult.

In the present invention, it is one of preferable modes to use a hydrocarbon wax other than the ester wax in combination as necessary.
Examples of hydrocarbon waxes other than the ester wax include petroleum-based natural waxes such as paraffin wax, microcrystalline wax, petrolatum, and derivatives thereof, Fischer-Tropsch wax, polyolefin wax, and derivatives thereof (polyethylene wax, polypropylene wax). And natural waxes such as synthetic hydrocarbons, ozokerite and ceresin.

  In the present invention, the wax content in the toner is preferably 5.0 to 20.0% by mass, more preferably 5.0 to 15.0% by mass. When the amount is less than 5.0% by mass, the releasability of the toner cannot be maintained. When the amount is more than 20.0% by mass, the wax is likely to be exposed on the toner surface, which may cause a decrease in heat resistant storage stability.

  In the present invention, the wax preferably has a maximum endothermic peak at 60 ° C. or higher and 90 ° C. or lower in DSC measurement. If the maximum endothermic peak is lower than 60 ° C., the wax is likely to be exposed on the toner surface, which may cause a decrease in heat resistant storage stability. On the other hand, if the maximum endothermic peak is higher than 90 ° C., the wax does not melt properly at the time of fixing, and the low-temperature fixability and offset resistance may be poor.

The following are mentioned as a coloring agent used for this invention.
Examples of the colorant for yellow include compounds typified by condensed azo compounds, isoindolinone compounds, anthraquinone compounds, azo metal complexes, methine compounds, and allylamide compounds.
Specific examples include the following.
C. I. Pigment Yellow 12, 13, 14, 15, 17, 62, 74, 83, 93, 94, 95, 97, 109, 110, 111, 120, 128, 129, 138, 147, 150, 151, 154, 155, 168, 180, 185, 213, 214. These can be used alone or in combination of two or more.

Examples of the colorant for magenta include condensed azo compounds, diketopyrrolopyrrole compounds, anthraquinones, quinacridone compounds, basic dye lake compounds, naphthol compounds, benzimidazolone compounds, thioindigo compounds, and perylene compounds.
Specific examples include the following.
C. I. Pigment Red 2, 3, 5, 6, 7, 23, 48: 2, 48: 3, 48: 4, 57: 1, 81: 1, 122, 146, 150, 166, 169, 177, 184, 185, 202, 206, 220, 221, 238, 254, 269, C.I. I. Pigment Bio Red 19. These can be used alone or in combination of two or more.

Examples of the colorant for cyan include copper phthalocyanine compounds and derivatives thereof, anthraquinone compounds, and basic dye lake compounds.
Specific examples include the following.
C. I. Pigment blue 1, 7, 15, 15: 1, 15: 2, 15: 3, 15: 4, 60, 62, 66. These can be used alone or in combination of two or more.

  Examples of black colorants include the following. Furnace black, channel black, acetylene black, thermal black, lamp black carbon black. Further, metal oxides such as magnetite and ferrite are also used.

  In the present invention, when a dye or pigment having extremely high solubility in water is used as a colorant, it may be dissolved in water during the production process, and granulation may be disturbed or a desired color may not be obtained. .

  In the present invention, when used as a colorant for a normal color toner, the content of the colorant is preferably 2.0% by mass or more and 15.0% by mass or less based on the toner. When it is less than 2.0% by mass, the coloring power is lowered. On the other hand, when it is more than 15.0% by mass, the color space tends to be small. More preferably, it is 2.5 mass% or more and 12.0 mass% or less. Further, a light color toner having a reduced density can be preferably used in combination with a normal color toner. In this case, the content of the colorant is preferably 0.5% by mass or more and 5.0% by mass or less with respect to the toner. More preferably, it is 0.7 mass% or more and 3.0 mass% or less.

  The colorant preferably has a number average particle diameter of 200 nm or less in an image of the toner particles obtained by taking an enlarged photograph of the cross section of the toner particles. More preferably, it is 150 nm or less. On the other hand, the number average particle diameter is preferably 50 nm or more. When it exceeds 200 nm, the particle size is large and the shell of the colorant is difficult to form. Therefore, it tends to cause a reduction in coloring power and a color gamut.

In the present invention, a charge control agent can be used as necessary. The charge control agent may be contained in the toner base particles (A) or in the surface layer (B).
Examples of the charge control agent include the following. Nigrosine dyes, triphenylmethane dyes, metal-containing azo complex dyes, molybdate chelate pigments, rhodamine dyes, alkoxy amines, quaternary ammonium salts (including fluorine-modified quaternary ammonium salts), alkylamides, simple substances of phosphorus Alternatively, a compound, a simple substance or compound of tungsten, a fluorine-based activator, a salicylic acid metal salt, and a salicylic acid derivative metal salt.
Specific examples include the following. Bontron N-03 of nigrosine dye, Bontron P-51 of quaternary ammonium salt, Bontron S-34 of metal-containing azo dye, E-82 of oxynaphthoic acid metal complex, E-84 of salicylic acid metal complex, Phenolic condensate E-89 (above, manufactured by Orient Chemical Co., Ltd.), quaternary ammonium salt molybdenum complex TP-302, TP-415 (above, manufactured by Hodogaya Chemical Co., Ltd.), quaternary ammonium salt Copy charge PSY VP2038, copy blue PR of triphenylmethane derivative, copy charge of quaternary ammonium salt NEG VP2036, copy charge NX
VP434 (above, manufactured by Hoechst), LRA-901, LR-147 (manufactured by Nippon Carlit Co., Ltd.), copper phthalocyanine, perylene, quinacridone, azo pigment, other sulfonic acid groups, carboxyl groups and quaternary ammonium salts A high molecular compound having a functional group of

Next, the surface layer (B) used in the present invention will be described.
The surface layer (B) used in the present invention contains the resin (b).
Examples of resins that can be used as the resin (b) include the following resins.
Vinyl resin, polyurethane resin, epoxy resin, polyester resin, polyamide resin, polyimide resin, silicon resin, phenol resin, melamine resin, urea resin, aniline resin, ionomer resin, polycarbonate resin. Two or more of these resins may be used in combination.
The resin (b) used in the present invention is preferably a resin that can form an aqueous dispersion. Accordingly, vinyl resins, polyurethane resins, epoxy resins, and polyester resins are preferable because an aqueous dispersion of fine spherical resin particles can be easily obtained.
In order to reduce the viscosity of the surface layer (B), a polyurethane resin or polyester resin having polyester as a constituent element is preferable. Furthermore, resin (b) is a resin containing a compound in which a diol component and a diisocyanate component are formed by a urethane bond because it exhibits a moderate affinity for a solvent, water dispersibility, viscosity adjustment, and ease of particle size alignment. preferable. In particular, a polyurethane resin is preferable.

The solubility parameter value (SP value) of the surface layer (B), that is, SP [surface layer (B)] is the solubility parameter value (SP value) of the resin (a2), that is, SP [resin (a2)]. It is preferable to make it larger. By making the SP value of the surface layer (B) larger than that of the resin (a2), the surface layer (B) can uniformly cover the surface of the toner base particles (A).
As a method for increasing the SP value of the surface layer (B), when a polyester resin is used for the surface layer (B), it can be adjusted by the functional group amount of a carboxylic acid group or a sulfonic acid group. Preferably, the amount of the functional group of the sulfonic acid group is increased. In addition, when a polyurethane resin is used for the surface layer (B), it can be adjusted by the functional group amount of the carboxylic acid group and sulfonic acid group, but it can be adjusted by increasing the bonding ratio of the urethane bond. I can do it.

Hereinafter, the polyurethane resin will be described in detail. A polyurethane resin is a reaction product of a diol component and a diisocyanate component, and resins having various functions can be obtained by adjusting the diol component and the diisocyanate component.
Examples of the diisocyanate component used for the resin (b) include the following.
Carbon number (excluding carbon in NCO group, the same shall apply hereinafter) 6 to 20 aromatic diisocyanate, C2 to C18 aliphatic diisocyanate, C4 to C15 alicyclic diisocyanate, C8 to C15 aroma Hydrocarbon diisocyanates and modified products of these diisocyanates (urethane group, carbodiimide group, allophanate group, urea group, burette group, uretdione group, uretoimine group, isocyanurate group, oxazolidone group-containing modified product), and these two types A mixture of the above.

Examples of the aromatic diisocyanate include the following.
1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate, 1,5-naphthylene diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate (TDI), crude tolylene diisocyanate (crude TDI), 2,4′-diphenylmethane diisocyanate, 4,4′-diphenylmethane diisocyanate (MDI), crude MDI [crude diaminophenylmethane [condensation product of formaldehyde and aromatic amine (aniline) or a mixture thereof]].

Examples of the aliphatic diisocyanate include the following.
Ethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate (HDI), dodecamethylene diisocyanate, 1,6,11-undecane triisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, lysine diisocyanate, 2,6-diisocyanatomethyl carbonate Proate, bis (2-isocyanatoethyl) fumarate, bis (2-isocyanatoethyl) carbonate, 2-isocyanatoethyl-2,6-diisocyanatohexanoate.

The following are mentioned as said alicyclic diisocyanate.
Isophorone diisocyanate (IPDI), dicyclohexylmethane-4,4′-diisocyanate (hydrogenated MDI), cyclohexylene diisocyanate, methylcyclohexylene diisocyanate (hydrogenated TDI), bis (2-isocyanatoethyl) -4-cyclohexene-1, 2-dicarboxylate, 2,5-norbornane diisocyanate, 2,6-norbornane diisocyanate.

  Examples of the aromatic hydrocarbon diisocyanate include the following. m-xylylene diisocyanate, p-xylylene diisocyanate (XDI), α, α, α ′, α′-tetramethylxylylene diisocyanate (TMXDI).

Examples of the modified diisocyanate (modified diisocyanate) include urethane group, carbodiimide group, allophanate group, urea group, burette group, uretdione group, uretoimine group, isocyanurate group, and oxazolidone group-containing modified product.
Examples of the modified diisocyanate include the following.
Modified MDI (urethane-modified MDI, carbodiimide-modified MDI, trihydrocarbyl phosphate-modified MDI), a modified product of an isocyanate of urethane-modified TDI, and a mixture of two or more thereof (for example, modified MDI and urethane-modified TDI (isocyanate-containing prepolymer)) Combined use].

  Of these, preferred are aromatic diisocyanates having 6 to 15 carbon atoms, aliphatic diisocyanates having 4 to 12 carbon atoms, and alicyclic diisocyanates having 4 to 15 carbon atoms, and particularly preferred are TDI, MDI, HDI, water. Attached MDI and IPDI.

In the present invention, in addition to the diisocyanate component described above, a trifunctional or higher functional isocyanate compound may be used. Examples of the trifunctional or higher functional isocyanate compound include polyallyl polyisocyanate (PAPI), 4,4 ′, 4 ″ -triphenylmethane triisocyanate, m-isocyanatophenylsulfonyl isocyanate and p-isocyanatophenylsulfonyl isocyanate. Can be mentioned.

The following are mentioned as a diol component used for resin (b).
Alkylene glycol (ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butanediol, 1,6-hexanediol, octanediol, decanediol, dodecanediol, tetradecanediol, neopentyl glycol, 2,2-diethyl-1,3-propanediol, etc.);
Alkylene ether glycols (diethylene glycol, triethylene glycol, dipropylene glycol, polyethylene glycol, polypropylene glycol, polytetramethylene ether glycol, etc.);
Alicyclic diols (such as 1,4-cyclohexanedimethanol, hydrogenated bisphenol A);
Bisphenols (bisphenol A, bisphenol F, bisphenol S, etc.);
Alkylene oxide (ethylene oxide, propylene oxide, butylene oxide, etc.) adduct of the above alicyclic diol;
Alkylene oxide (ethylene oxide, propylene oxide, butylene oxide, etc.) adducts of the above bisphenols;
In addition, polylactone diol (such as poly ε-caprolactone diol), polybutadiene diol.
The alkyl part of the above-described alkylene ether glycol may be linear or branched. In the present invention, a branched alkylene glycol can also be preferably used.
Among these, an alkyl structure is preferable in view of solubility (affinity) in ethyl acetate, and an alkylene glycol having 2 to 12 carbon atoms is preferably used.

In the present invention, in addition to the diol component described above, a polyester oligomer having a terminal hydroxyl group (terminal diol polyester oligomer) can also be used as a suitable diol component.
At this time, the molecular weight (number average molecular weight) of the terminal diol polyester oligomer is preferably 3000 or less, more preferably 800 or more and 2000 or less.
When the molecular weight of the terminal diol polyester oligomer is larger than the above, the reactivity with the isocyanate-terminated compound is lowered, and the properties of the polyester become too strong and become soluble in ethyl acetate.
The content of the terminal diol polyester oligomer described above is preferably 1 mol% or more and 1 in the monomer constituting the reaction product of the diol component and the diisocyanate component.
It is 0 mol% or less, More preferably, it is 3 mol% or more and 6 mol% or less.
When the terminal diol polyester oligomer is contained in an amount exceeding 10 mol%, the reaction product of the diol component and the diisocyanate component may be soluble in ethyl acetate. On the other hand, when the amount of the terminal diol polyester oligomer is less than 1 mol%, the reaction product of the diol component and the diisocyanate component becomes too hard to inhibit the fixing property, or the affinity with the resin (a) decreases. Thus, the surface layer may be difficult to form.

The polyester skeleton of the terminal diol polyester oligomer and the polyester skeleton of the resin (a) are preferably the same in order to form favorable capsule-type toner particles. This is related to the affinity between the toner base particles and the reaction product of the diol component and diisocyanate component of the surface layer.
The terminal diol polyester oligomer may have an ether bond modified with ethylene oxide, propylene oxide or the like.

The resin (b) can be used in combination with a compound in which an amino compound and an isocyanate compound are urea-bonded in addition to a resin containing a compound in which a diol component and a diisocyanate component are formed by a urethane bond.
The following are mentioned as said amino compound.
Diaminoethane, diaminopropane, diaminobutane, diaminohexane, piperazine, 2,5-dimethylpiperazine, amino-3-aminomethyl-3,5,5-trimethylcyclohexane (isophoronediamine, IPDA), 4,4'-diaminodicyclohexyl Methane, 1,4-diaminocyclohexane, aminoethylethanolamine, hydrazine, and hydrazine hydrate diamines;
Triamines such as triethylamine, diethylenetriamine, and 1,8-diamino-4-aminomethyloctane.

  In addition to the above, the resin (b) may be used in combination with a reaction product of an isocyanate compound and a compound having a highly reactive hydrogen group such as a carboxylic acid group, a cyano group, and a thiol group. Is possible.

The resin containing a compound formed by urethane bond between the diol component and the diisocyanate component preferably has a carboxylic acid group, a sulfonic acid group, a carboxylate or a sulfonate in the side chain. These can be easily produced by introducing a carboxylic acid group, a sulfonic acid group, a carboxylate or a sulfonate into the side chain of the diol component or diisocyanate component.
For example, as a diol component in which a carboxylic acid group or a carboxylate is introduced into the side chain, dimethylolacetic acid, dimethylolpropionic acid, dimethylolbutanoic acid, dimethylolbutyric acid, dimethylolpentanoic acid dihydroxylcarboxylic acids and metal salts thereof Can be mentioned.
On the other hand, examples of the diol component in which a sulfonic acid group or a sulfonate is introduced into the side chain include sulfoisophthalic acid, N, N-bis (2-hydroxyethyl) -2-aminoethanesulfonic acid, and metal salts thereof. Can do.
The content of the diol component in which a carboxylic acid group, a sulfonic acid group, a carboxylate salt or a sulfonate salt is introduced into the side chain is based on the total monomers constituting the compound formed by urethane bond between the diol component and the diisocyanate component , Preferably, it is 10 mol% or more and 50 mol% or less, More preferably, it is 20 mol% or more and 30 mol% or less.
When the diol component is less than 10 mol%, the dispersibility of the resin fine particles tends to deteriorate and the granulation property may be impaired. On the other hand, when it is more than 50 mol%, the reaction product of the diol component and the diisocyanate component may be dissolved in the aqueous medium, and the function as a dispersant may not be achieved.

The surface layer (B) is preferably formed of resin fine particles containing the resin (b). The method for preparing the resin fine particles is not particularly limited, and an emulsion polymerization method or a method in which the resin is dissolved or melted in a solvent to be liquefied and granulated by suspending it in an aqueous medium. Can be used.
During the preparation, a known surfactant or dispersant can be used, or the resin constituting the resin fine particles can be made self-emulsifying.

The solvent that can be used in preparing the resin fine particles by dissolving the resin in a solvent is not particularly limited, but includes the following.
Hydrocarbon solvents such as ethyl acetate, xylene and hexane, halogenated hydrocarbon solvents such as methylene chloride, chloroform and dichloroethane, methyl acetate, ethyl acetate, butyl acetate, isopropyl acetate ester solvents, diethyl ether ether solvents, acetone , Ketone solvents of methyl ethyl ketone, diisobutyl ketone, cyclohexanone and methylcyclohexane, alcohol solvents of methanol, ethanol and butanol.

  In the present invention, it is one of preferred modes to use, as a dispersant, resin fine particles containing a compound in which a diol component and a diisocyanate component are formed by a urethane bond. The following method can be suitably exemplified as the method for producing the resin fine particles. That is, it is a method of producing a prepolymer having a diisocyanate component, rapidly dispersing it in water, and subsequently adding the diol component, thereby extending the chain or crosslinking. More specifically, a prepolymer having a diisocyanate component and other necessary components as necessary are dissolved or dispersed in a solvent having high solubility in water such as acetone or alcohol among the above solvents, and this is dissolved in water. In this method, the prepolymer having the diisocyanate component is rapidly dispersed, and the diol component is subsequently added to prepare a reaction product of the diol component and the diisocyanate component having desired physical properties.

The resin fine particles containing the resin (b) preferably have a number average particle size of 10 nm to 120 nm, more preferably 30 nm to 100 nm, in order for the toner particles to form a capsule structure.
When the number average particle size is smaller than 10 nm, the granulation stability tends to be reduced as in the case where the coating amount of the resin fine particles is small. As a result, formation of the capsule structure becomes difficult, and the heat resistant storage stability tends to deteriorate.
On the other hand, when the number average particle size is larger than 120 nm, the dispersibility in the aqueous phase is lowered, as in the case where the coating amount of the resin fine particles is large, and the particles are coalesced or irregularly shaped. It tends to produce particles.

Hereinafter, a simple method for preparing the toner particles used in the present invention will be described, but the present invention is not limited thereto.
The toner particles are obtained by dissolving at least a resin (a) mainly composed of polyester, a colorant and a wax in an organic medium in an aqueous medium (aqueous phase) in which resin fine particles containing the resin (b) are dispersed. It is obtained by dispersing the dissolved product or dispersion (oil phase) obtained by dispersing, removing the solvent from the obtained dispersion and drying.
In the above system, the resin fine particles function as a dispersant when suspending the dissolved or dispersed material (oil phase) in the aqueous phase. By preparing toner particles by the above method, capsule-type toner particles can be easily prepared without requiring an aggregation step on the toner surface.

In the method for preparing the oil phase, examples of the organic medium for dissolving the resin (a) include the following.
Hydrocarbon solvents such as ethyl acetate, xylene, hexane, halogenated hydrocarbon solvents such as methylene chloride, chloroform, dichloroethane, ester solvents such as methyl acetate, ethyl acetate, butyl acetate, isopropyl acetate, ether solvents such as diethyl ether, acetone , Methyl ethyl ketone, diisobutyl ketone, cyclohexanone and methylcyclohexane ketone solvents.

The resin (a) is preferably used in the form of a resin dispersion dissolved in the organic medium. In this case, although it varies depending on the viscosity and solubility of the resin, it is preferable to blend in the organic medium in the range of 40% by mass to 60% by mass as a resin component in consideration of ease of production in the next step. In addition, heating at the melting point or lower of the organic medium during dissolution is preferable because the solubility of the resin is increased.
The colorant and wax are also preferably dispersed in the organic medium. That is, it is preferable to prepare a wax dispersion and a colorant dispersion by respectively dispersing a wax and a colorant that have been mechanically pulverized in a wet or dry manner in an organic medium. The oil phase can be prepared by blending a desired amount of the resin dispersion, wax dispersion, colorant dispersion, and organic medium, and dispersing the above components in the organic medium.
The dispersibility of the wax and the colorant can also be improved by adding a dispersant and a resin that match each of them. Since these differ depending on the wax, colorant, binder resin, and organic solvent used, they can be selected and used as appropriate.

The dispersion of the colorant will be described in more detail.
In the present invention, the colorant is preferably added to the oil phase after previously mixed with the resin. Examples of the mixing method with the resin include a method of melting and kneading and taking out as a resin kneaded product (dry method), and a method of dispersing in the presence of a solvent (wet method).
In a method of melt-kneading and taking out as a resin kneaded product (dry type), a colorant and a resin, and other additives as necessary are mixed, and then sufficiently kneaded and kneaded with a kneader or a roll type disperser. The obtained melt-kneaded product is pulverized and then dissolved and dispersed in a solvent to obtain a colorant dispersion.
On the other hand, in the method of dispersing in the presence of a solvent (wet process), a colorant and a resin, and optionally other additives and a solvent are mixed, and media dispersion in a bead mill or paint shaker is performed. In this method, the used media is collected to obtain a colorant dispersion.
In addition, it is preferable to use the said resin (a2) as resin used here. That is, the colorant is preferably mixed with the resin (a2) in advance.
More specifically, the toner particles are prepared in advance by preparing a mixture containing at least the colorant and the resin (a2), and dissolving or dispersing the prepared mixture and the mixture containing at least the resin (a1) in an organic medium. The obtained dissolved or dispersed material is preferably obtained by dispersing in a water-based medium in which resin fine particles containing the resin (b) are dispersed, removing the solvent from the obtained dispersion, and drying.
Examples of the other additives include commercially available colorant dispersants and waxes.

  The aqueous medium may be water alone or a solvent miscible with water may be used in combination. Examples of miscible solvents include alcohols (methanol, isopropanol, ethylene glycol), dimethylformamide, tetrahydrofuran, cellosolves (methylcellosolve), and lower ketones (acetone, methylethylketone). It is also a preferred method to mix an appropriate amount of the organic medium used as the oil phase in the aqueous medium. This seems to have the effect of enhancing droplet stability during granulation and making the aqueous medium and the oil phase more easily suspended.

  In the present invention, it is preferable to disperse and use resin fine particles containing the resin (b) in an aqueous medium. The resin fine particles containing the resin (b) are used in a desired amount according to the stability of the oil phase in the next step and the encapsulation of the toner base particles (A).

  A known surfactant, dispersant, dispersion stabilizer, water-soluble polymer, or viscosity modifier can be added to the aqueous medium.

The main surfactants include anionic surfactants, cationic surfactants, amphoteric surfactants and nonionic surfactants. These can be arbitrarily selected according to the polarity at the time of toner particle formation.
Alkylbenzene sulfonate, α-olefin sulfonate, phosphate anionic surfactants; alkylamine salts, aminoalcohol fatty acid derivatives, polyamine fatty acid derivatives, amine salts of imidazoline, alkyltrimethylammonium salts, dialkyldimethylammonium salts Salt, alkyldimethylbenzylammonium salt, pyridinium salt, alkylisoquinolinium salt, quaternary ammonium salt type cationic surfactant of benzethonium chloride; nonionic surfactant such as fatty acid amide derivative, polyhydric alcohol derivative; alanine, Examples include amphoteric surfactants of dodecyl di (aminoethyl) glycine, di (octylaminoethyl) glycine, and N-alkyl-N, N-dimethylammonium betaine.

The following are mentioned as said dispersing agent.
Acids such as acrylic acid, methacrylic acid, α-cyanoacrylic acid, α-cyanomethacrylic acid, itaconic acid, crotonic acid, fumaric acid, maleic acid or maleic anhydride;
Β-hydroxyethyl acrylate, β-hydroxyethyl methacrylate, β-hydroxypropyl acrylate, β-hydroxypropyl methacrylate, γ-hydroxypropyl acrylate, γ-hydroxypropyl methacrylate, -3-chloro-acrylate 2-hydroxypropyl, methacrylic acid-3-chloro-2-hydroxypropyl, diethylene glycol monoacrylate, diethylene glycol monomethacrylate, glycerol monoacrylate, glycerol monomethacrylate, N-methylolacrylamide, N-methylol A (meth) acrylic monomer containing a hydroxyl group of methacrylamide;
Ethers of vinyl alcohol or vinyl methyl ether, vinyl ethyl ether, vinyl propyl ether with vinyl alcohol;
Esters of vinyl acetate, vinyl propionate, vinyl butyrate with vinyl alcohol and compounds containing carboxyl groups;
Acrylamide, methacrylamide, diacetone acrylamide or their methylol compounds;
Acrylic acid chloride, methacrylic acid chloride acid chlorides;
Homopolymers or copolymers of vinyl pyridine, vinyl pyrrolidone, vinyl imidazole, ethyleneimine nitrogen atoms, or those having heterocycles thereof;
Polyoxyethylene, polyoxypropylene, polyoxyethylene alkylamine, polyoxypropylene alkylamine, polyoxyethylene alkylamide, polyoxypropylene alkylamide, polyoxyethylene nonylphenyl ether, polyoxyethylene lauryl phenyl ether, polyoxyethylene stearyl Phenyl esters, polyoxyethylenes of polyoxyethylene nonylphenyl ester;
Cellulose of methyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose.
When a dispersant is used, the dispersant can remain on the surface of the toner particles, but it is preferable to dissolve and remove it from the charged surface of the toner.

In the present invention, in order to maintain a more preferable dispersion state, a solid dispersion stabilizer may be used.
The above dispersion stabilizer is used for the following reason. That is, the organic medium in which the resin (a) as the main component of the toner is dissolved has a high viscosity. Therefore, the dispersion stabilizer surrounds the oil droplets formed by finely dispersing the organic medium with high shearing force to prevent the oil droplets from reaggregating and stabilize.
As dispersion stabilizers, inorganic dispersion stabilizers and organic dispersion stabilizers can be used. In the case of inorganic dispersion stabilizers, the toner particles are granulated in the state of adhering to the particle surface after dispersion, so that they have an affinity with the solvent. Those which can be removed by acid of hydrochloric acid which is not present are preferred. For example, calcium carbonate, calcium chloride, sodium hydrocarbon, potassium hydrocarbon, sodium hydroxide, potassium hydroxide, hydroxyapatite, and calcium triphosphate can be used.

The dispersion method used when preparing the toner particles is not particularly limited, and low-speed shearing, high-speed shearing, friction, high-pressure jet, and ultrasonic general-purpose devices can be used, but the dispersion particle size is about 2 to 20 μm. In order to achieve this, a high-speed shearing type is preferable.
There is no restriction | limiting in particular as a stirring apparatus which has a rotary blade, If it is a general thing as an emulsifier and a disperser, it can be used.
For example, Ultra Tarrax (manufactured by IKA), Polytron (manufactured by Kinematica), TK Auto Homo Mixer (manufactured by Special Mechanized Industries), Ebara Milder (manufactured by Ebara Corporation), TK Homomic Line Flow (Made by Special Machine Industries Co., Ltd.), colloid mill (made by Shinko Pantech Co., Ltd.), slasher, trigonal wet pulverizer (made by Mitsui Miike Chemical Co., Ltd.), Cavitron (made by Eurotech), fine flow mill Examples thereof include a continuous emulsifier (manufactured by Taiheiyo Kiko Co., Ltd.), a batch type of CLEARMIX (manufactured by M Technique Co., Ltd.), a batch type of FILMIX (manufactured by Tokushu Kika Kogyo Co., Ltd.), or a continuous-use emulsifier.
When a high-speed shearing disperser is used, the rotational speed is not particularly limited, but is usually 1000 to 30000 rpm, preferably 3000 to 20000 rpm.
In the case of a batch system, the dispersion time is usually 0.1 to 5 minutes. The temperature during dispersion is usually 10 to 150 ° C. (under pressure), preferably 10 to 100 ° C.

In order to remove the organic solvent from the obtained emulsified dispersion, a method in which the temperature of the entire system is gradually raised and the organic solvent in the droplets is completely removed by evaporation can be employed.
Alternatively, it is possible to spray the emulsified dispersion in a dry atmosphere, completely remove the water-insoluble organic solvent in the droplets to form toner particles, and evaporate and remove the aqueous dispersant together.
In that case, as the dry atmosphere in which the emulsified dispersion is sprayed, air, nitrogen, carbon dioxide, a gas obtained by heating combustion gas, particularly various air streams heated to a temperature higher than the boiling point of the highest boiling solvent used are generally used. It is done.
Sufficient quality can be obtained even in a short time such as spray dryer, belt dryer or rotary kiln.
When the particle size distribution at the time of emulsification dispersion is wide, and washing and drying processes are performed while maintaining the particle size distribution, the particle size distribution can be adjusted by classification into a desired particle size distribution.
The dispersant used is preferably removed from the obtained dispersion as much as possible, but more preferably it is carried out simultaneously with the classification operation.
In the above production method, it is possible to further provide a heating step after removing the organic solvent. By providing the heating step, the toner surface is smoothed and the sphericity can be adjusted.

The classification operation is carried out in a liquid by a cyclone, decanter, and centrifugal separation, and the fine particle portion can be removed. Of course, the classification operation may be performed after obtaining the powder after drying, but it is preferable to perform the classification in a liquid in terms of efficiency.
The obtained unnecessary fine particles or coarse particles can be returned to the dissolving step and used for forming particles. At that time, fine particles or coarse particles may be wet.

In the present invention, the toner preferably has a weight average particle size of 2.0 μm or more and 10.0 μm or less.
When the weight average particle diameter of the toner is smaller than 2.0 μm, there is a possibility that the toner is charged up after a long period of use or the like and the density is lowered.

On the other hand, when the weight average particle diameter of the toner is larger than 10.0 μm, the line image is liable to be scattered and dropped, and the fine line reproducibility tends to be inferior.

In the present invention, the sphericity SF-1 of the toner is preferably from 100 to 140, more preferably from 100 to 130.
When the SF-1 value is larger than 140, the transfer characteristics tend to be lowered, and the image may be deteriorated. On the other hand, if the SF-1 value is 100, it indicates a shape close to a true sphere, and therefore a toner shape closer to 100 is preferable.

In the toner particles used in the present invention, it is more preferable that the toner base particles (A) are completely covered with the surface layer (B).
The inventors consider that the following is important in order to develop good fixing characteristics after the toner base particles (A) are completely covered with the surface layer (B).
In the present invention, when resin fine particles are used for forming the surface layer (B), the resin fine particles are 1.0% by mass or more and 15.0% by mass or less with respect to the toner base particles (A). It is preferable.
When the amount of the resin fine particles is less than 1.0% by mass, depending on the particle size of the resin fine particles and the particle size of the toner, the surface layer may not be completely covered and the heat resistant storage stability may be poor.
On the other hand, when the amount of the resin fine particles is more than 15.0% by mass, the heat of the fixing member is difficult to be transferred to the inside of the toner and tends to impair the low-temperature fixing property, and the surface layer with high polarity increases, so that the wax is stained. It may be difficult to remove and may have poor offset resistance.

In the toner of the present invention, inorganic fine particles can be preferably used as an external additive for assisting the fluidity, developability and chargeability of the toner.
The primary particle diameter of the inorganic fine particles is preferably 5 nm to 2 μm, and more preferably 5 nm to 500 nm. Moreover, it is preferable that the specific surface area by BET method of an inorganic fine particle is 20-500 m < ² > / g.
The use ratio of the inorganic fine particles is preferably 0.01 to 5 parts by mass, and more preferably 0.01 to 2.0 parts by mass with respect to 100 parts by mass of the toner particles. The inorganic fine particles may be used alone or in combination of a plurality of types.

Specific examples of the inorganic fine particles include the following.
For example, silica, alumina, titanium oxide, barium titanate, magnesium titanate, calcium titanate, strontium titanate, zinc oxide, tin oxide, silica sand, clay, mica, wollastonite, diatomaceous earth, chromium oxide, cerium oxide, Bengala, antimony trioxide, magnesium oxide, zirconium oxide, barium sulfate, barium carbonate, calcium carbonate, silicon carbide, silicon nitride.

The external additive is preferably made hydrophobic by using a surface treatment agent in order to prevent deterioration of the flow characteristics and charging characteristics of the toner under high humidity.
Examples of the surface treatment agent include a silane coupling agent, a silylating agent, a silane coupling agent having a fluorinated alkyl group, an organic titanate coupling agent, an aluminum coupling agent, silicone oil, and modified silicone oil.

The toner of the present invention is a fatty acid such as zinc stearate, calcium stearate, stearic acid or the like as an external additive (cleaning improver) for removing the developer after transfer remaining on the photoreceptor or primary transfer medium. Examples thereof include polymer fine particles produced by soap-free emulsion polymerization of metal salts, polymethyl methacrylate fine particles, or polystyrene fine particles. The polymer fine particles preferably have a relatively narrow particle size distribution and a volume average particle size of 0.01 to 1 μm.

  When the toner of the present invention is used for a two-component developer, it may be used by mixing with a magnetic carrier. The ratio of the magnetic carrier to the toner in the developer is 1 to 10 toners per 100 parts by mass of the magnetic carrier. Part by mass is preferred. As the magnetic carrier, iron powder, ferrite powder, magnetite powder, magnetic resin carrier, and conventionally known ones having an average particle diameter of 20 to 200 μm can be used.

  A method for measuring various physical properties of the toner of the present invention will be described below.

<Method for Measuring Colorant Occupancy in Toner>
A toner dispersed in a water-soluble resin was put in a cryomicrotome (ULTRACUT N FC4E manufactured by Reichert). The apparatus was cooled to −80 ° C. with liquid nitrogen, and the water-soluble resin in which the toner was dispersed was frozen. The frozen water-soluble resin was trimmed with a glass knife so that the cutting surface shape was about 0.1 mm wide and about 0.2 mm long. Next, an ultra-thin section (thickness setting: 70 nm) of toner containing a water-soluble resin was prepared using a diamond knife, and moved onto a TEM observation grid mesh using an eyelash probe. After returning the ultra-thin section of the toner containing the water-soluble resin to room temperature, the water-soluble resin was dissolved in pure water to obtain an observation sample of a transmission electron microscope (TEM). The sample was observed with a transmission electron microscope H-7500 (manufactured by Hitachi, Ltd.) at an acceleration voltage of 100 kV, and an enlarged photograph of the cross section of the toner particles was taken. The cross section of the toner particles was arbitrarily selected. The magnification of the enlarged photograph was 5000 to 10,000 times.

An image obtained by the above photography was read at 600 dpi via an interface and introduced into an image analysis apparatus Win ROOF Version 5.0 (manufactured by Microsoft-Mitani Corp.). The introduced image information was converted into binary image data, and the contour and center of gravity of the selected toner particle cross section were calculated.
FIG. 1 shows a schematic diagram of an enlarged photograph of a cross section of the read toner particles.
Next, a straight line connecting the obtained toner particle centroid and the surface of the toner particle is drawn, and a point divided 3: 1 from the centroid is set on the drawn line, and a curve is formed by connecting the set points. It was created (broken line in FIG. 1). The curve divides the toner particle cross section into two regions (the toner particle surface side and the toner particle inside). The areas of these two regions (the area on the toner particle surface side (Ss) and the area inside the toner particles (Si)) were determined. Furthermore, the area of the colorant portion in each region was determined from the binarized image. That is, the partial area (Cs) of the colorant on the toner particle surface side and the partial area (Ci) of the colorant on the toner particle inner side were determined. Using these areas, the occupation ratio of the colorant in each region was determined by the following formulas (1) and (2).
Colorant occupancy ratio (Rs) of toner particle surface side area
Rs = Cs / Ss (1)
Colorant occupancy ratio (Ri) of the area inside the toner particles
Ri = Ci / Si (2)

From the above formulas (1) and (2), the ratio (R) of the colorant occupancy ratio in the area on the toner particle surface side to the colorant occupancy ratio in the area inside the toner particles is determined as follows.
R = Rs / Ri (3)
The above operation was performed on 100 images obtained by photography, and the number average value of the ratio (R) was determined and used in the present application.

<Measuring method of number average particle diameter of colorant present in toner particles>
The image used in the measurement of the colorant occupancy rate was read at 600 dpi via an interface, and introduced into an image analysis device Win ROOF Version 5.0 (manufactured by Microsoft Corporation-Mitani Corporation). The introduced image information was converted into binary image data, and the particle size of the colorant present in the selected toner particle cross section was measured. Ten images are arbitrarily selected, the particle size of the colorant dispersed in each of the selected toner particle cross-sectional images is obtained, and the number average of the colorants present in the toner particles is obtained. The diameter.

<Measurement method of softening point (Tm) of resin>
The softening point (Tm) of the resin was measured by a flow tester which is a constant load extrusion type capillary rheometer.
That is, the softening point (Tm) of the resin was measured using the elevated flow tester CFT500C type manufactured by Shimadzu Corporation under the following conditions. Based on the obtained data, a flow tester curve was created (displayed in FIGS. 3A and 3B). From this figure, the softening point (Tm) of the resin was determined.
In the figure, the outflow start temperature (Tfb) is defined as the softening point (Tm).
<Measurement conditions>
Load: 10 kgf / cm ² (9.807 × 10 ⁵ Pa)
Temperature increase rate: 4.0 ° C./min
Die diameter: 1.0mm
Die length: 1.0mm

<Measuring method of temperature showing melting point of wax and maximum endothermic peak of wax>
The melting point of the wax and the temperature showing the maximum endothermic peak of the wax were calculated by measuring the wax under the following conditions using a differential scanning calorimeter (DSC) Q1000 (manufactured by TA Instruments).
<Measurement conditions>
・ Modulation mode ・ Temperature increase rate: 0.5 ℃ / min
Modulation temperature amplitude: ± 1.0 ° C / min
-Measurement start temperature: 25 ° C
-Measurement end temperature: 130 ° C

In the above measurement, the temperature showing the maximum endothermic peak of the wax was taken as the melting point of the wax.
The maximum endothermic peak means a peak having the largest endothermic amount when there are a plurality of peaks.

<Measuring method of glass transition temperature (Tg) of resin>
The glass transition temperature (Tg) of the resin was measured using a differential scanning calorimeter (DSC) Q1000 (manufactured by TA Instruments) under the same conditions as in “Method of measuring temperature showing melting point of wax and maximum endothermic peak of wax”. Measurements were made and calculated.
As shown in FIG. 2, the DSC curve was obtained by taking “Reversing Heat Flow” on the vertical axis, and the onset value shown in FIG. 2 was defined as the glass transition temperature (Tg) of the present invention.

<Method of measuring molecular weight distribution, peak molecular weight, and number average molecular weight by gel permeation chromatograph (GPC)>
The molecular weight distribution, peak molecular weight, and number average molecular weight of the resin by gel permeation chromatography (GPC) were measured by GPC (gel permeation chromatography) using THF (THF) soluble content of the resin as a solvent. The measurement conditions are as follows.
(1) Preparation of measurement sample Resin (sample) and THF were mixed at a concentration of about 0.5 to 5 mg / ml (for example, about 5 mg / ml) and left at room temperature for several hours (for example, 5 to 6 hours). After that, the mixture was sufficiently shaken, and the THF and the sample were mixed well until there was no unity of the sample. Furthermore, it left still at room temperature for 12 hours or more (for example, 24 hours). At this time, the time from the start of mixing the sample and THF to the end of standing was set to 24 hours or longer.
Then, a sample processing filter (pore size 0.45 to 0.5 μm, Mysori Disc H-25-2 [manufactured by Tosoh Corp.], Excro Disc 25CR [manufactured by Gelman Science Japan Ltd.] can be preferably used) is passed. Was used as a GPC sample.
(2) Sample measurement The column was stabilized in a heat chamber at 40 ° C., and THF as a solvent was passed through the column at this temperature at a flow rate of 1 ml / min, so that the sample concentration was 0.5 to 5 mg / ml. Measurement was performed by injecting 50 to 200 μl of a THF sample solution of the prepared resin.
In measuring the molecular weight of the sample, the molecular weight distribution of the sample was calculated from the relationship between the logarithmic value of the calibration curve prepared from several monodisperse polystyrene standard samples and the number of counts.
As a standard polystyrene sample for creating a calibration curve, Pressure Chemical
Co. Manufactured by Toyo Soda Kogyo Co., Ltd. and having molecular weights of 6 × 10 ² , 2.1 × 10 ³ , 4 × 10 ³ , 1.75 × 10 ⁴ , 5.1 × 10 ⁴ , 1.1 × 10 ⁵ , 3 .9 × 10 ⁵ , 8.6 × 10 ⁵ , 2 × 10 ⁶ , 4.48 × 10 ⁶ were used. An RI (refractive index) detector was used as the detector.
In addition, as the column, in order to accurately measure the molecular weight region of 1 × 10 ³ to 2 × 10 ⁶ , a plurality of commercially available polystyrene gel columns were used in combination as described below. The GPC measurement conditions in the present invention are as follows.

[GPC measurement conditions]
Apparatus: LC-GPC 150C (manufactured by Waters)
Column: KF801, 802, 803, 804, 805, 806, 807 (manufactured by Shodex) Column temperature: 40 ° C
Mobile phase: THF (tetrahydrofuran)

<Method for measuring acid value of resin>
The acid value is the number of mg of potassium hydroxide necessary to neutralize the acid contained in 1 g of the sample. The acid value of the binder resin is measured according to JIS K 0070-1966. 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 vol%), and ion exchange water is added to make 100 ml to obtain a “phenolphthalein solution”.
Dissolve 7 g of special grade potassium hydroxide in 5 ml of water and add ethyl alcohol (95 vol%) to make 1 liter. Place in an alkali-resistant container so as not to touch carbon dioxide gas, leave it for 3 days, and filter to obtain a “potassium hydroxide solution”. The obtained potassium hydroxide solution is stored in an alkali-resistant container. The orientation is performed according to JIS K 0070-1996.
(2) Operation (A) Main test 2.0 g of the pulverized binder 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 titrated with the potassium hydroxide solution. The end point of titration is when the light red color of the indicator lasts for about 30 seconds.
(B) Blank test Titration is performed in the same manner as described above except that no sample is used (that is, only a mixed solution of toluene / ethanol (2: 1) is used).
(3) The acid value is calculated by substituting the obtained result into the following formula.
A = [(BC) × f × 5.61] / S
Here, A: acid value (mgKOH / g), B: addition amount (ml) of potassium hydroxide solution in blank test, C: addition amount (ml) of potassium hydroxide solution in this test, f: potassium hydroxide Solution factor, S: sample (g).

<Measurement Method of Toner Weight Average Particle Size (D4) and Number Average Particle Size (Dn)>
For the weight average particle diameter (D4) and number average particle diameter (Dn) of the toner, Coulter Counter Multisizer II (manufactured by Coulter Inc.) was used. As the electrolytic solution, approximately 1% NaCl aqueous solution was prepared using first grade sodium chloride. For example, ISTON R-II (manufactured by Coulter Scientific Japan) can be suitably used as the electrolytic solution.
As a measuring method, 0.1 ml of a surfactant (preferably alkylbenzene sulfonate) is added as a dispersant to 100 ml of the electrolytic solution, and 5 mg of a measurement sample is further added.
The electrolyte in which the sample is suspended is subjected to a dispersion treatment for about 3 minutes with an ultrasonic disperser, and the volume and number of toner particles having a particle diameter of 2.00 to 40.30 μm are measured using the 100 μm aperture as the aperture. Was measured for each of the following channels. From the volume distribution and number distribution of the obtained toner, the weight average particle diameter D4 and the number average particle diameter Dn were calculated, respectively. As channels, 2.00 to 2.52 μm; 2.52 to 3.17 μm; 3.17 to 4.00 μm; 4.00 to 5.04 μm; 5.04 to 6.35 μm; 6.35 to 8. 00μm; 8.00 to 10.08 μm; 10.08 to 12.70 μm; 12.70 to 16.00 μm; 16.00 to 20.20 μm; 20.20 to 25.40 μm; 25.40 to 32.00 μm; 13 channels of 32.00-40.30 μm were used.

<Measuring method of particle diameter of resin fine particles and wax particles in wax dispersion>
The particle size of the resin fine particles and the wax particles in the wax dispersion is measured using a Microtrac particle size distribution measuring device HRA (X-100) (manufactured by Nikkiso Co., Ltd.) with a range of 0.001 μm to 10 μm. The average particle diameter (nm) was measured. As dilution solvents, water was selected for the resin fine particles, and ethyl acetate was selected for the wax particles.

  EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not restrict | limited at all to this. In addition, the number of parts in the following composition is part by mass unless otherwise specified.

[Preparation of resin fine particle dispersion 1]
100 parts by mass of a polyester diol having a number average molecular weight of about 2000 obtained from a 40:50:10 molar mixture of propylene glycol, ethylene glycol and butanediol and a molar mixture of terephthalic acid and isophthalic acid. 16 parts by mass of propylene glycol 94 parts by mass of methylolpropanoic acid / sodium N, N-bis (2-hydroxyethyl) -2-aminoethanesulfonate
8 parts by mass, 30 parts by mass of tolylene diisocyanate

The raw material was dissolved in 60 parts by mass of acetone and reacted at 67 ° C. for 1 hour.
Next, 271 parts by mass (1.2 mol) of isophorone diisocyanate was added, and the mixture was further reacted at 67 ° C. for 30 minutes and cooled.
After adding 100 parts by mass of acetone to the reaction product, 80 parts by mass (0.8 mol) of triethylamine was added and stirred.
The acetone solution was added dropwise to 1000 parts by mass of ion-exchanged water with stirring at 500 rpm to prepare a fine particle dispersion.
Then, an elongation solution was carried out by adding an aqueous solution in which 50 parts by mass of triethylamine was dissolved in 100 parts by mass of 10% aqueous ammonia and reacting at 50 ° C. for 8 hours. Furthermore, ion-exchanged water was added until the solid content became 20% by mass to obtain a resin fine particle dispersion-1. Table 1 shows the Tg and Tm of the resin obtained by drying the resin fine particle dispersion-1 and the particle size in the dispersion.

[Preparation of resin fine particle dispersion 2]
In an autoclave equipped with a thermometer and a stirrer,
・ 116 parts by weight of dimethyl terephthalate
・ Dimethyl isophthalate 66 parts by weight
・ 3-sodium sulfoisophthalate methyl ester 3 parts by weight
・ Trimellitic anhydride 5 parts by weight
-150 parts by weight of propylene glycol-0.1 parts by weight of tetrabutoxytitanate were charged and heated at 200 ° C for 120 minutes to conduct a transesterification reaction. Next, the temperature of the reaction system was raised to 220 ° C., and the reaction was continued for 60 minutes at a pressure of 1-10 mmHg to obtain a polyester resin.
After dissolving 40 parts by mass of the polyester resin, 15 parts by weight of methyl ethyl ketone, and 10 parts by mass of tetrahydrofuran at 80 ° C., 60 parts by mass of 80 ° C. water was added with stirring, the solvent was removed under reduced pressure, and ion-exchanged water was added. Was added to obtain a fine resin particle dispersion-2 having a solid content of 20% by mass. Table 1 shows the characteristics of the resin obtained by drying the resin fine particle dispersion-2.

[Preparation of resin fine particle dispersion 3]
The following was charged into a reaction vessel equipped with a cooling tube, a nitrogen introducing tube and a stirrer to obtain a composition.
Styrene 330 parts by weight n-butyl acrylate 110 parts by weight Acrylic acid 10 parts by weight 2-butanone (solvent) 50 parts by weight 2,2′-azobis (2,4-dimethylvaleronitrile) 8 weight as a polymerization initiator A part was dissolved in the above composition to prepare a polymerizable monomer composition. After polymerizing the polymerizable monomer composition at 60 ° C. for 8 hours, the temperature was raised to 150 ° C., the solvent was removed under reduced pressure, and the product was taken out from the reaction vessel. After the reaction product was cooled to room temperature, it was pulverized and granulated to obtain a linear vinyl resin. 100 parts by mass of the resin and 400 parts by mass of toluene were mixed and heated to 80 ° C. to dissolve the resin to obtain a resin solution.
Next, 360 parts of ion-exchanged water and 40 parts by weight of a 48.5% aqueous solution of sodium dodecyl diphenyl ether disulfonate (“Eleminol MON-7”, manufactured by Sanyo Chemical Industries) are mixed, and the resin solution is added and mixed and stirred. A milky white liquid was obtained. Toluene was removed under reduced pressure, and ion-exchanged water was added to obtain Resin Fine Particle Dispersion-3 having a solid content of 20% by mass. Table 1 shows the characteristics of the resin obtained by drying the resin fine particle dispersion-3.

[Preparation of resin fine particle dispersion 4]
120 parts by mass of a polyester diol having a number average molecular weight of about 2000, obtained from a 40:50:10 molar mixture of propylene glycol, ethylene glycol and butanediol and a molar mixture of terephthalic acid and isophthalic acid. 94 parts by mass of dimethylolpropanoic acid 3- (2,3-dihydroxypropoxy) -1-propanesulfonic acid
8 parts by mass, 30 parts by mass of tolylene diisocyanate

The raw material was dissolved in 60 parts by mass of acetone and reacted at 67 ° C. for 1 hour.
Next, 271 parts by mass of isophorone diisocyanate was added, and the mixture was further reacted at 67 ° C. for 30 minutes and cooled.
After adding 100 parts by mass of acetone to the reaction product, 80 parts by mass of triethylamine was added and stirred.
The acetone solution was added dropwise to 1000 parts by mass of ion-exchanged water with stirring at 500 rpm to prepare a fine particle dispersion.
Then, an elongation solution was carried out by adding an aqueous solution in which 50 parts by mass of triethylamine was dissolved in 100 parts by mass of 10% aqueous ammonia and reacting at 50 ° C. for 8 hours. Furthermore, ion-exchanged water was added until the solid content became 20% by mass to obtain resin fine particle dispersion-4. Table 1 shows the characteristics of the resin obtained by drying the resin fine particle dispersion-4.

<Preparation of polyester resin solution-1>
The following was put into a reaction vessel equipped with a cooling tube, a nitrogen introducing tube and a stirrer.
-1,3-butanediol 1036 parts by mass-terephthalic acid dimethyl ester 892 parts by mass-1,6-hexanedioic acid 205 parts by mass-tetrabutoxy titanate (condensation catalyst) 3 parts by mass Methanol produced in a nitrogen stream at 180 ° C Was allowed to react for 8 hours while distilling off. Next, while gradually raising the temperature to 230 ° C., the reaction was performed for 4 hours while distilling off the produced propylene glycol and water in a nitrogen stream, and further the reaction was performed under a reduced pressure of 20 mmHg, and the softening point was 150 ° C. Removed at the time. The resin taken out was cooled to room temperature and then pulverized and granulated to obtain polyester-1 which is a linear polyester resin. Polyester-1 had a Tg of 38 ° C. and an acid value of 15 mgKOH / g.
Next, 50 parts by mass of ethyl acetate is put into a sealed container with stirring wings, and 50 parts by mass of the polyester-1 is added to the mixture while stirring at 100 rpm, and the polyester resin solution is stirred at room temperature for 3 days. -1 was prepared.

<Preparation of polyester resin solution-2>
The following was put into a reaction vessel equipped with a cooling tube, a nitrogen introducing tube and a stirrer.
-1,2-propanediol 799 parts by mass-terephthalic acid dimethyl ester 815 parts by mass-1,5-pentanedioic acid 238 parts by mass-tetrabutoxy titanate (condensation catalyst) 3 parts by mass Methanol produced under nitrogen flow at 180 ° C Was allowed to react for 8 hours while distilling off. Then, while gradually raising the temperature to 230 ° C., the reaction was carried out for 4 hours while distilling off the produced propylene glycol and water under a nitrogen stream, and the reaction was further carried out for 1 hour under a reduced pressure of 20 mmHg. Subsequently, the mixture was cooled to 180 ° C., 173 parts by mass of trimellitic anhydride was added, reacted for 2 hours under sealed at normal pressure, reacted at 220 ° C. and normal pressure, and taken out when the softening point reached 180 ° C. The resin taken out was cooled to room temperature and then pulverized and granulated to obtain polyester-2 which is a nonlinear polyester resin. Polyester-2 had a Tg of 62 ° C. and an acid value of 2 mgKOH / g.
Next, 50 parts by mass of ethyl acetate is put into a sealed container with stirring blades, and 50 parts by mass of the above polyester-2 is added to the agitation at 100 rpm, and the polyester resin solution is stirred at room temperature for 3 days. -2 was adjusted.

<Preparation of polyester resin solution-3>
The following was put into a reaction vessel equipped with a cooling tube, a nitrogen introducing tube and a stirrer.
-1,2 propanediol 858 parts by mass-terephthalic acid dimethyl ester 873 parts by mass-1,6-hexanedioic acid 219 parts by mass-tetrabutoxy titanate (condensation catalyst) 3 parts by mass Methanol produced at 180 ° C under a nitrogen stream The reaction was allowed to proceed for 8 hours while evaporating. Next, while gradually raising the temperature to 230 ° C., the reaction was performed for 4 hours while distilling off the produced propylene glycol and water in a nitrogen stream, and further the reaction was performed under a reduced pressure of 20 mmHg, and the softening point was 150 ° C. Removed at the time. The resin taken out was cooled to room temperature and then pulverized and granulated to obtain polyester-3, which is a linear polyester resin. Polyester-3 had a Tg of 44 ° C. and an acid value of 13 mgKOH / g.
Next, 50 parts by mass of ethyl acetate is put into a sealed container with stirring blades, and 50 parts by mass of the above polyester-3 is added to the agitation at 100 rpm, and the polyester resin solution is stirred at room temperature for 3 days. -3 was adjusted.

<Preparation of polyester resin solution-4>
The following was put into a reaction vessel equipped with a cooling tube, a nitrogen introducing tube and a stirrer.
・ 928 parts by mass of 1,4-butanediol, 776 parts by mass of dimethyl terephthalate, 292 parts by mass of 1,6-hexanedioic acid, 3 parts by mass of tetrabutoxy titanate (condensation catalyst), and methanol produced at 160 ° C. under a nitrogen stream. Was allowed to react for 8 hours while distilling off. Next, while gradually raising the temperature to 210 ° C., the reaction was carried out for 4 hours while distilling off the produced propylene glycol and water under a nitrogen stream, and the reaction was further carried out for 1 hour under a reduced pressure of 20 mmHg. Next, the mixture was cooled to 160 ° C., 173 parts by weight of trimellitic anhydride and 125 parts by weight of 1,3-propanedioic acid were added, reacted for 2 hours under normal pressure sealing, and then reacted at 200 ° C. and normal pressure, and the softening point was 170 ° C. When it became, it took out. The resin taken out was cooled to room temperature and then pulverized and granulated to obtain polyester-4, which is a nonlinear polyester resin. Polyester-4 had a Tg of 53 ° C. and an acid value of 25 mgKOH / g.
Next, 50 parts by mass of ethyl acetate is put into a hermetic container with stirring wings, and 50 parts by mass of the above polyester-4 is added to the agitation at 100 rpm, and the polyester resin solution is stirred at room temperature for 3 days. -4 was prepared.

<Preparation of polyester resin solution-5>
The following was put into a reaction vessel equipped with a cooling tube, a nitrogen introducing tube and a stirrer.
-1,2-propanediol 799 parts by mass-terephthalic acid dimethyl ester 815 parts by mass-1,5-pentanedioic acid 238 parts by mass-tetrabutoxy titanate (condensation catalyst) 3 parts by mass Methanol produced under nitrogen flow at 180 ° C Was allowed to react for 8 hours while distilling off. Then, while gradually raising the temperature to 230 ° C., the reaction was carried out for 4 hours while distilling off the produced propylene glycol and water under a nitrogen stream, and the reaction was further carried out for 1 hour under a reduced pressure of 20 mmHg. Subsequently, it cooled to 180 degreeC, 173 mass parts of trimellitic anhydride was added, and it took out when it reacted at 180 degreeC under normal pressure sealing for 1 hour. The resin taken out was cooled to room temperature and then pulverized and granulated to obtain polyester-5, which is a non-linear polyester resin. Polyester-5 had a Tg of 55 ° C. and an acid value of 14 mgKOH / g.
Next, 50 parts by mass of ethyl acetate is put into a sealed container with stirring blades, and 50 parts by mass of the above polyester-5 is added to the agitation at 100 rpm, and the polyester resin solution is stirred at room temperature for 3 days. -5 was prepared.

<Preparation of polyester resin solution-6>
The following was put into a reaction vessel equipped with a cooling tube, a nitrogen introducing tube and a stirrer.
-1,2-propanediol 799 parts by mass-terephthalic acid dimethyl ester 815 parts by mass-1,5-pentanedioic acid 238 parts by mass-tetrabutoxy titanate (condensation catalyst) 3 parts by mass Methanol produced under nitrogen flow at 180 ° C Was allowed to react for 8 hours while distilling off. Then, while gradually raising the temperature to 230 ° C., the reaction was carried out for 4 hours while distilling off the produced propylene glycol and water under a nitrogen stream, and the reaction was further carried out for 1 hour under a reduced pressure of 20 mmHg. Subsequently, it cooled to 180 degreeC, 173 mass parts of trimellitic anhydrides were added, and it took out when it reacted at 180 degreeC under normal pressure sealing for 2 hours. The resin taken out was cooled to room temperature and then pulverized and granulated to obtain polyester-6, which is a non-linear polyester resin. Polyester-6 had a Tg of 57 ° C. and an acid value of 17 mgKOH / g.
Next, 50 parts by mass of ethyl acetate is put into a sealed container with stirring blades, and 50 parts by mass of the above polyester-6 is added to the agitation at 100 rpm, and the polyester resin solution is stirred at room temperature for 3 days. -6 was prepared.

<Preparation of Wax Dispersion-1>
Carnauba wax (melting point: 81 ° C.) 20 parts by mass. Ethyl acetate: 80 parts by mass The above was put into a vessel equipped with stirring blades, and the system was heated to 70 ° C. to dissolve the carnauba wax in ethyl acetate.
Next, the system was gradually cooled while gently stirring at 50 rpm, and cooled to 25 ° C. over 3 hours to obtain a milky white liquid.
This solution was put into a heat-resistant container together with 20 parts by mass of 1 mm glass beads and dispersed for 3 hours with a paint shaker to obtain wax dispersion-1. When the wax particle size in the wax dispersion-1 was measured with a Microtrac particle size distribution analyzer HRA (X-100) (manufactured by Nikkiso Co., Ltd.), the number average particle size was 0.15 μm. Information on wax dispersion-1 is shown in Table 2.

<Preparation of Wax Dispersion-2>
-Stearyl stearate (melting point 67 ° C) 16 parts by mass-Nitrile group-containing styrene acrylic resin (65 parts by mass of styrene, 35 parts by mass of n-butyl acrylate, 10 parts by mass of acrylonitrile, peak molecular weight 8500)
8 parts by mass / ethyl acetate 76 parts by mass The above was put into a vessel equipped with stirring blades, and the system was heated to 65 ° C. to dissolve stearyl stearate in ethyl acetate.
Subsequently, the same operation as wax dispersion-1 was performed to obtain wax dispersion-2. When the wax particle size in the wax dispersion-2 was measured with a Microtrac particle size distribution analyzer HRA (X-100) (manufactured by Nikkiso Co., Ltd.), the number average particle size was 0.12 μm.
Information regarding wax dispersion-2 is shown in Table 2.

<Preparation of wax dispersion-3>
Trimethylolpropane tribehenate (melting point: 58 ° C.) 16 parts by mass Nitrile group-containing styrene acrylic resin (styrene 65 parts by mass, n-butyl acrylate 35 parts by mass, acrylonitrile 10 parts by mass, peak molecular weight 8500)
8 parts by mass / ethyl acetate 76 parts by mass The above was put into a vessel equipped with stirring blades, and the system was heated to 60 ° C. to dissolve trimethylolpropane tribehenate in ethyl acetate.
Subsequently, the same operation as wax dispersion-1 was performed to obtain wax dispersion-3. When the wax particle size in the wax dispersion-3 was measured with a Microtrac particle size distribution analyzer HRA (X-100) (manufactured by Nikkiso Co., Ltd.), the number average particle size was 0.18 μm. Information on wax dispersion-3 is shown in Table 2.

<Preparation of Wax Dispersion-4>
Paraffin wax (melting point 74 ° C.) 16 parts by mass Nitrile group-containing styrene acrylic resin (styrene 65 parts by mass, n-butyl acrylate 35 parts by mass, acrylonitrile 10 parts by mass, peak molecular weight 8500)
8 parts by mass / ethyl acetate 76 parts by mass The above was put into a vessel equipped with stirring blades, and the system was heated to 70 ° C. to dissolve paraffin wax in ethyl acetate.
Subsequently, the same operation as wax dispersion-1 was performed to obtain wax dispersion-4. When the wax particle size in the wax dispersion-4 was measured with a Microtrac particle size distribution analyzer HRA (X-100) (manufactured by Nikkiso Co., Ltd.), the number average particle size was 0.15 μm. Information on the wax dispersion-4 is shown in Table 2.

<Preparation of Colorant Dispersion-C1>
A first paste having a solid content of 40% by mass obtained by removing water from the pigment slurry to some extent from the filtration step of Cu phthalocyanine (CI Pigment Blue 15: 3) and without passing through the drying step. Pigment (the remaining 60% by weight is water)
100 parts by mass / 60 parts by mass of the above polyester-4 The above raw materials were charged into a kneader-type mixer, and the temperature was raised under no pressure while mixing. When reaching the maximum temperature (necessarily determined by the boiling point of the solvent in the paste. In this case, about 90 to 100 ° C.), the pigment in the aqueous phase was distributed or transferred to the molten resin phase.
After confirming the transfer, the mixture was further melted and kneaded for 30 minutes to sufficiently transfer the pigment in the paste to the molten resin phase. Thereafter, the mixer was stopped once, hot water was discharged, and the temperature was further raised to 130 ° C., followed by heating and melt-kneading for about 30 minutes to disperse the pigment and distill off the water. After finishing this process, it cooled and obtained the kneaded material. The kneaded product was crushed with a hammer and then roughly crushed with a speed mill (Okada Seiko Co., Ltd.) to obtain a 1 mm mesh pass crushed product. Next, 100 parts by mass of crushed material, 150 parts by mass of ethyl acetate and 200 parts by mass of glass beads are put into a heat-resistant glass container, dispersed for 1 hour with a paint shaker, glass beads are removed with a nylon mesh, and colorant is dispersed. Liquid-C1 was obtained.

<Preparation of Colorant Dispersion-C2>
Copper phthalocyanine pigment C.I. I. Pigment Blue 15: 3 80 parts by mass, polyester-4 120 parts by mass, ethyl acetate 300 parts by mass, glass beads (1 mm) 400 parts by mass And the glass beads were removed with a nylon mesh to obtain a colorant dispersion-C2.

<Preparation of Colorant Dispersion-C3>
Copper phthalocyanine pigment C.I. I. Pigment Blue 15: 3 80 parts by mass, 120 parts by weight of the above polyester-1 300 parts by weight of ethyl acetate, 400 parts by weight of glass beads (1 mm) 400 parts by weight The above materials are put into a heat-resistant glass container and dispersed for 5 hours in a paint shaker. The glass beads were removed with a nylon mesh to obtain a colorant dispersion-C3.

<Preparation of Colorant Dispersion-C4>
A first paste having a solid content of 40% by mass obtained by removing water from the pigment slurry to some extent from the filtration step of Cu phthalocyanine (CI Pigment Blue 15: 3) and without passing through the drying step. Pigment (the remaining 60% by weight is water)
125 parts by mass / polyester-4 50 parts by mass The above raw materials were charged into a kneader-type mixer, and the temperature was raised under no pressure while mixing. When reaching the maximum temperature (necessarily determined by the boiling point of the solvent in the paste. In this case, about 90 to 100 ° C.), the pigment in the aqueous phase was distributed or transferred to the molten resin phase.
After confirming the transfer, the mixture was further melted and kneaded for 30 minutes to sufficiently transfer the pigment in the paste to the molten resin phase. Thereafter, the mixer was stopped once, hot water was discharged, and the temperature was further raised to 130 ° C., followed by heating and melt-kneading for about 30 minutes to disperse the pigment and distill off the water. After finishing this process, it cooled and obtained the kneaded material. The kneaded product was crushed with a hammer and then roughly crushed with a speed mill (Okada Seiko Co., Ltd.) to obtain a 1 mm mesh pass crushed product. Next, 100 parts by mass of crushed material, 150 parts by mass of ethyl acetate and 200 parts by mass of glass beads are put into a heat-resistant glass container, dispersed for 1 hour with a paint shaker, glass beads are removed with a nylon mesh, and colorant is dispersed. Liquid-C4 was obtained.

<Preparation of Colorant Dispersion-C5>
A first paste having a solid content of 40% by mass obtained by removing water from the pigment slurry to some extent from the filtration step of Cu phthalocyanine (CI Pigment Blue 15: 3) and without passing through the drying step. Pigment (the remaining 60% by weight is water)

50 parts by mass / 80 parts by mass of the above polyester-4 The above raw materials were charged into a kneader-type mixer, and the temperature was raised under no pressure while mixing. When reaching the maximum temperature (necessarily determined by the boiling point of the solvent in the paste. In this case, about 90 to 100 ° C.), the pigment in the aqueous phase was distributed or transferred to the molten resin phase.
After confirming the transfer, the mixture was further melted and kneaded for 30 minutes to sufficiently transfer the pigment in the paste to the molten resin phase. Thereafter, the mixer was stopped once, hot water was discharged, and the temperature was further raised to 130 ° C., followed by heating and melt-kneading for about 30 minutes to disperse the pigment and distill off the water. After finishing this process, it cooled and obtained the kneaded material. The kneaded product was crushed with a hammer and then roughly crushed with a speed mill (Okada Seiko Co., Ltd.) to obtain a 1 mm mesh pass crushed product. Next, 100 parts by mass of crushed material, 150 parts by mass of ethyl acetate and 200 parts by mass of glass beads are put into a heat-resistant glass container, dispersed for 1 hour with a paint shaker, glass beads are removed with a nylon mesh, and colorant is dispersed. Liquid-C5 was obtained.

<Preparation of Colorant Dispersion-C6>
A first paste having a solid content of 40% by mass obtained by removing water from the pigment slurry to some extent from the filtration step of Cu phthalocyanine (CI Pigment Blue 15: 3) and without passing through the drying step. Pigment (the remaining 60% by weight is water)

100 parts by mass / 60 parts by mass of the above polyester-5 The above raw materials were charged into a kneader-type mixer, and the temperature was raised under no pressure while mixing. When reaching the maximum temperature (necessarily determined by the boiling point of the solvent in the paste. In this case, about 90 to 100 ° C.), the pigment in the aqueous phase was distributed or transferred to the molten resin phase.
After confirming the transfer, the mixture was further melted and kneaded for 30 minutes to sufficiently transfer the pigment in the paste to the molten resin phase. Thereafter, the mixer was stopped once, hot water was discharged, and the temperature was further raised to 130 ° C., followed by heating and melt-kneading for about 30 minutes to disperse the pigment and distill off the water. After finishing this process, it cooled and obtained the kneaded material. The kneaded product was crushed with a hammer and then roughly crushed with a speed mill (Okada Seiko Co., Ltd.) to obtain a 1 mm mesh pass crushed product. Next, 100 parts by mass of crushed material, 150 parts by mass of ethyl acetate and 200 parts by mass of glass beads are put into a heat-resistant glass container, dispersed for 1 hour with a paint shaker, glass beads are removed with a nylon mesh, and colorant is dispersed. Liquid-C6 was obtained.

<Preparation of Colorant Dispersion-C7>
A first paste having a solid content of 40% by mass obtained by removing water from the pigment slurry to some extent from the filtration step of Cu phthalocyanine (CI Pigment Blue 15: 3) and without passing through the drying step. Pigment (the remaining 60% by weight is water)

100 parts by mass / 60 parts by mass of the above polyester-6 The above raw materials were charged into a kneader mixer, and the temperature was raised under no pressure while mixing. When reaching the maximum temperature (necessarily determined by the boiling point of the solvent in the paste. In this case, about 90 to 100 ° C.), the pigment in the aqueous phase was distributed or transferred to the molten resin phase.
After confirming the transfer, the mixture was further melted and kneaded for 30 minutes to sufficiently transfer the pigment in the paste to the molten resin phase. Thereafter, the mixer was stopped once, hot water was discharged, and the temperature was further raised to 130 ° C., followed by heating and melt-kneading for about 30 minutes to disperse the pigment and distill off the water. After finishing this process, it cooled and obtained the kneaded material. The kneaded product was crushed with a hammer and then roughly crushed with a speed mill (Okada Seiko Co., Ltd.) to obtain a 1 mm mesh pass crushed product. Next, 100 parts by mass of crushed material, 150 parts by mass of ethyl acetate and 200 parts by mass of glass beads are put into a heat-resistant glass container, dispersed for 1 hour with a paint shaker, glass beads are removed with a nylon mesh, and colorant is dispersed. Liquid-C7 was obtained.

<Preparation of Colorant Dispersion-C8>
A first paste having a solid content of 40% by mass obtained by removing water from the pigment slurry to some extent from the filtration step of Cu phthalocyanine (CI Pigment Blue 15: 3) and without passing through the drying step. Pigment (the remaining 60% by weight is water)

75 parts by mass / carnauba wax (melting point: 81 ° C.) 25 parts by mass / 45 parts by mass of the above polyester-4 The raw materials were charged into a kneader-type mixer and heated under non-pressurization while mixing. When reaching the maximum temperature (necessarily determined by the boiling point of the solvent in the paste. In this case, about 90 to 100 ° C.), the pigment in the aqueous phase was distributed or transferred to the molten resin phase.
After confirming the transfer, the mixture is further melted and kneaded for 30 minutes to sufficiently transfer the pigment in the paste to the molten resin phase. Thereafter, the mixer was stopped once, hot water was discharged, and the temperature was further raised to 130 ° C., followed by heating and melt-kneading for about 30 minutes to disperse the pigment and distill off the water. After finishing this process, it cooled and obtained the kneaded material. The kneaded product was crushed with a hammer and then roughly crushed with a speed mill (Okada Seiko Co., Ltd.) to obtain a 1 mm mesh pass crushed product. Next, 100 parts by mass of crushed material, 150 parts by mass of ethyl acetate and 200 parts by mass of glass beads are put into a heat-resistant glass container, dispersed for 1 hour with a paint shaker, glass beads are removed with a nylon mesh, and colorant is dispersed. Liquid-C8 was obtained.

<Preparation of Colorant Dispersion-M1>
・ C. I. A first pasty pigment having a solid content of 40% by mass (remaining 60% by mass of water) obtained by removing water to some extent from the pigment slurry from the pigment red 122 filtration step and without undergoing a drying step.
100 parts by mass / 60 parts by mass of the above polyester-4 The above raw materials were charged into a kneader-type mixer, and the temperature was raised under no pressure while mixing. When reaching the maximum temperature (necessarily determined by the boiling point of the solvent in the paste. In this case, about 90 to 100 ° C.), the pigment in the aqueous phase was distributed or transferred to the molten resin phase.
After confirming the transfer, the mixture is further melted and kneaded for 30 minutes to sufficiently transfer the pigment in the paste to the molten resin phase. Thereafter, the mixer was stopped once, hot water was discharged, and the temperature was further raised to 130 ° C., followed by heating and melt-kneading for about 30 minutes to disperse the pigment and distill off the water. After finishing this process, it cooled and obtained the kneaded material. The kneaded product was crushed with a hammer and then roughly crushed with a speed mill (Okada Seiko Co., Ltd.) to obtain a 1 mm mesh pass crushed product. Next, 100 parts by mass of crushed material, 150 parts by mass of ethyl acetate and 200 parts by mass of glass beads are put into a heat-resistant glass container, dispersed for 1 hour with a paint shaker, glass beads are removed with a nylon mesh, and colorant is dispersed. Liquid-M1 was obtained.

<Preparation of Colorant Dispersion-Y1>
・ C. I. Pigment Yellow 155 40 parts by weight, polyester-4 60 parts by weight The above raw materials are charged into a kneader mixer, heated to 130 ° C. under non-pressurization while mixing, and heated and melt-kneaded for about 30 minutes to obtain a pigment. Dispersed. After finishing this process, it cooled and obtained the kneaded material. The kneaded product was crushed with a hammer and then roughly crushed with a speed mill (Okada Seiko Co., Ltd.) to obtain a 1 mm mesh pass crushed product. Next, 100 parts by mass of crushed material, 150 parts by mass of ethyl acetate and 200 parts by mass of glass beads are put into a heat-resistant glass container, dispersed for 1 hour with a paint shaker, glass beads are removed with a nylon mesh, and colorant is dispersed. Liquid-Y1 was obtained.

(Example of carrier production)
4.0% by mass of a silane coupling agent (3- (2-aminoethylaminopropyl) trimethyl) with respect to a magnetite powder having a number average particle diameter of 0.25 μm and a hematite powder having a number average particle diameter of 0.60 μm. Methoxysilane) was added, and the mixture was stirred and mixed at a high speed at 100 ° C. or higher to make each fine particle lipophilic.

・ Phenol 10 parts by mass ・ Formaldehyde solution (formaldehyde 40%, methanol 10%, water 50%)
6 parts by mass-lipophilic magnetite 63 parts by mass-lipophilic hematite 21 parts by mass The above materials, 5 parts by mass of 28% ammonia water, and 10 parts by mass of water are placed in a flask and stirred and mixed with 30 parts. The temperature was raised and maintained at 85 ° C. for 3 minutes, followed by polymerization reaction for 3 hours to cure. Then, after cooling to 30 degreeC and adding water, the supernatant liquid was removed, the precipitate was washed with water, and then air-dried. Subsequently, this was dried under reduced pressure (5 mmHg or less) at 60 ° C. to obtain spherical magnetic resin particles in which a magnetic material was dispersed.

As the coating resin, a copolymer of methyl methacrylate and methyl methacrylate having a perfluoroalkyl group (m = 7) (copolymerization ratio 8: 1 weight average molecular weight 45,000) was used. To 100 parts by weight of the coating resin, 10 parts by weight of melamine particles having a particle size of 290 nm, 6 parts by weight of carbon particles having a specific resistance of 1 × 10 ⁻² Ω · cm and a particle size of 30 nm are added, and dispersed for 30 minutes using an ultrasonic disperser. I let you. Further, a mixed solvent coating solution of methyl ethyl ketone and toluene was prepared so that the coating resin content was 2.5 parts by mass with respect to the carrier core (solution concentration: 10% by mass).

The coating solution was applied to the surface of the magnetic resin particles by volatilizing the solvent at 70 ° C. while continuously applying a shear stress. The resin-coated magnetic carrier particles were heat-treated with stirring at 100 ° C. for 2 hours, cooled and pulverized, and then classified by a 200-mesh sieve to obtain a number average particle diameter of 33 μm, a true specific gravity of 3.53 g / cm ³ , A carrier having an apparent specific gravity of 1.84 g / cm ³ and a magnetization strength of 42 Am ² / Kg was obtained.

<Example 1>
(Preparation of Liquid Toner Composition 1)
・ Wax dispersion-1 50 parts by mass (carnauba wax solid content: 20%)
Colorant dispersion-C1 25 parts by mass (pigment solid content: 16%, resin solid content: 24%)
-Polyester resin solution-1 160 parts by mass (resin solid content: 50%)
・ Triethylamine 0.5 parts by mass ・ Ethyl acetate 14.5 parts by mass

The above solution was charged into a container, and a liquid toner composition 1 was prepared by stirring and dispersing at 1500 rpm for 10 minutes using a homodisper (manufactured by Tokushu Kika Kogyo Co., Ltd.).

(Preparation of aqueous phase 1)
The following was put into a container, and stirred at 5000 rpm for 1 minute with a TK homomixer (manufactured by Tokushu Kika Co., Ltd.) to prepare an aqueous phase 1.
-245 parts by mass of ion-exchanged water-15 parts by mass of resin fine particle dispersion-1 (3 parts by mass of resin fine particles with respect to 100 parts by mass of toner base particles)
-50% aqueous solution of sodium dodecyl diphenyl ether disulfonate (Eleminol MON-7, manufactured by Sanyo Chemical Industries) 15 parts by mass-30 parts by mass of ethyl acetate

(Emulsification and solvent removal process)
The liquid toner composition 1 was put into the aqueous phase 1 and stirred for 3 minutes with a TK homomixer (rotation speed 8000 rpm) to suspend the liquid toner composition 1.
Next, a stirring blade was set in the container, and the system was heated to 50 ° C. while stirring at 200 rpm, and the solvent was removed over 5 hours in a state where the pressure was reduced to 500 mmHg to obtain an aqueous dispersion of toner particles. .

(Washing and drying process)
Next, the aqueous dispersion of toner particles was filtered and reslurried to 500 parts by mass of ion-exchanged water. The system was stirred and hydrochloric acid was added until the system reached PH4 and stirred for 5 minutes. The slurry was filtered again, 200 parts by mass of ion-exchanged water was added, and the operation of stirring for 5 minutes was repeated three times to remove triethylamine remaining in the system and obtain a filter cake of toner particles.
Next, the filter cake was dried with a hot air dryer at 45 ° C. for 3 days, and sieved with a mesh having an opening of 75 μm to obtain toner particles 1.

(Toner preparation)
Next, 0.7 parts by mass of hydrophobic silica having an average particle diameter of 20 nm and 0.8 parts by mass of monodispersed silica having an average particle diameter of 120 nm are mixed with 100 parts by mass of the toner particles 1 using a Henschel mixer. Toner 1 was obtained. Table 4 shows the characteristics of Toner 1.

<Evaluation of heat-resistant storage stability of toner>
The heat-resistant storage stability of the toner was evaluated visually by putting about 10 g of toner in a 100 ml polycup and leaving it at 50 ° C. for 3 days.
(Evaluation criteria)
A: Aggregates are not seen.
B: Although aggregates are seen, they break apart easily.
C: Aggregates can be grasped and do not collapse easily.

<Preparation of two-component developer 1>
In the present invention, a two-component developer 1 prepared by mixing 8 parts by mass of [Toner 1] and 92 parts by mass of the carrier was prepared.

<Evaluation of low-temperature fixability>
For the evaluation, the above-mentioned two-component developer 1 and a color laser copying machine CLC5000 (manufactured by Canon Inc.) were used. Adjust the development contrast of the copier so that the amount of toner on the paper is 1.2 mg / cm ² , and in a single color mode, print a solid “unfixed” image with a 5 mm tip margin, 100 mm width, and 280 mm length. It was created in a room temperature and normal humidity environment (23 ° C./60% RH). As the paper, cardboard A4 paper (“Prober Bond paper”: 105 g / m ² , manufactured by Fox River) was used.
Next, the fixing device of CLC5000 (manufactured by Canon Inc.) was modified so that the fixing temperature can be manually set. Using the modified fixing device, each temperature of the above “solid” unfixed image was increased in a range of 80 ° C. to 200 ° C. by 10 ° C. in a normal temperature and humidity environment (23 ° C./60%). A fixed image was obtained.
Cover the image area of the obtained fixed image with a soft thin paper (for example, trade name “Dasper”, manufactured by Ozu Sangyo Co., Ltd.), and apply the load of 4.9 KPa on the thin paper for 5 reciprocations. Rubbed. The image density before and after rubbing was measured, respectively, and the reduction rate ΔD (%) of the image density was calculated by the following formula. The temperature when this ΔD (%) was less than 10% was taken as the fixing start temperature, and the low temperature fixability was evaluated according to the following evaluation criteria.
The image density was measured with a color reflection densitometer (Color reflection densitometer X-Rite 404A: manufacturer X-Rite).
(Expression): ΔD (%) = (Image density before rubbing−Image density after rubbing) / Image density before rubbing × 100
(Evaluation criteria)
A: Fixing start temperature is 120 ° C. or less B: Fixing start temperature is greater than 120 ° C. and 140 ° C. or less C: Fixing start temperature is greater than 140 ° C. and 160 ° C. or less D: Fixing start temperature is from 160 ° C. Large In the present invention, up to rank B was judged as good low-temperature fixability.

<Evaluation of charging property (tribo: triboelectric charge amount)>
The charging property (tribo: triboelectric charge amount) of the toner was measured by the following method and evaluated according to the following evaluation criteria.
First, the carrier and toner 1 are put in a plastic bottle with a lid, and shaken for 1 minute at a speed of 4 reciprocations per second with a shaker (YS-LD: manufactured by Yayoi Co., Ltd.). The developer consisting of is charged.
Next, the triboelectric charge amount is measured by the apparatus for measuring the triboelectric charge amount shown in FIG. In FIG. 4, about 0.5 to 1.5 g of the developer described above is placed in a metal measuring container 2 having a 500 mesh screen 3 at the bottom, and a metal lid 4 is formed. The total mass of the measurement container 2 at this time is weighed and is defined as W1 (g). Next, in the suction machine 1 (at least the part in contact with the measurement container 2) is sucked from the suction port 7 and the air volume control valve 6 is adjusted so that the pressure of the vacuum gauge 5 is 250 mmAq. In this state, suction is performed for 2 minutes to remove the toner particles 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 (mF). Moreover, the mass of the whole measurement container after suction is weighed and is defined as W2 (g). The triboelectric charge amount (mC / kg) of this sample is calculated as follows.

(Expression) Frictional charge of sample (mC / kg) = C × V / (W1−W2)

(Evaluation criteria)
A: -40.0 or more and -20.0 or less A good image is obtained.
B: -50.0 or more, -15.0 or less Image formation is possible by changing development conditions.
C: Less than −50.0 or more than −15.0. Difficult to develop due to poor toner scattering or separation from carrier.

<Evaluation of image density>
For the evaluation, the above-mentioned two-component developer 1 and a color laser copying machine CLC5000 (manufactured by Canon Inc.) were used. Adjust the development contrast of the above copier so that the toner load on paper is 1.2 mg / cm ² , and print a “solid” image with a margin of 5 mm, width of 100 mm, and length of 280 mm in single color mode at room temperature and normal humidity. It was created under the environment (23 ° C./60% RH). The density of the created image was measured with an X-Rite color reflection densitometer (X-rite 500 Series; X-Rite).

(Evaluation criteria)
A: Reflection density 1.50 or more, sufficient density can be obtained B: Reflection density 1.40 or more, less than 1.50 and slightly applied C: Reflection density 1.40 Less than density

<Measurement and evaluation of hue>
For the evaluation, the above-mentioned two-component developer 1 and a color laser copying machine CLC5000 (manufactured by Canon Inc.) were used. 7 levels (0.10 mg / cm ² , 0.2 mg / cm ² , 0.30 mg / cm ² , 0.40 mg / cm ² , 0.50 mg) on paper (color laser copier paper TKCLA4, manufactured by Canon) / Cm ² , 0.60 mg / cm ² , 0.70 mg / cm ² ) to form a fixed image, and for each fixed image, use Spectroscan manufactured by Gretag Macbeth (measurement condition: D65, viewing angle 2 °) ), CIE a ^* , b ^* were measured.
The chromaticity against the loading amount in 7 stages was plotted, and a curve connecting each point smoothly was drawn to obtain the relationship between c ^* and L ^* . From this relationship, the value of c ^* at L ^* = 70 and L ^* = 50 was determined. The value of ^{c * is} calculated by ^{c * = ((a *)} 2 + (b *) 2) 1/2.
About cyan images (evaluation criteria)
A: The value of c * when L ^* = 70 is 34.0 or more and L ^* = 55.0 or more Excellent image saturation B: The value of c * when L ^* = 70 is 32.0 Above, and L ^* = 50.0 or more Color reproducibility is narrow but good image C: c * value when L ^* = 70 is less than 32.0, or L ^* = less than 50.0 There is no problem in use, but the color reproducibility is poor.

<Example 2>
In Example 1, a toner 2 was obtained in the same manner as in Example 1 except that the following liquid toner composition 2 was used instead of the liquid toner composition 1. Table 3 shows the prescription of toner 2 and Table 4 shows the characteristics of toner 2. A two-component developer 2 prepared by mixing 8 parts by mass of the [Toner 2] and 92 parts by mass of the carrier was prepared.
Further, image evaluation was performed in the same manner as in Example 1 except that the toner 2 and the two-component developer 2 were used. The results are shown in Table 4.

(Preparation of Liquid Toner Composition 2)
・ Wax dispersion-1 50 parts by mass (carnauba wax solid content: 20%)
Colorant dispersion C-2 25 parts by mass (pigment solid content: 16%, resin solid content: 24%)
-Polyester resin solution-1 160 parts by mass (resin solid content: 50%)
・ Triethylamine 0.5 parts by mass ・ Ethyl acetate 14.5 parts by mass

The above solution was put into a container, and liquid toner composition 2 was prepared by stirring and dispersing at 1500 rpm for 10 minutes using a homodisper (manufactured by Tokushu Kika Kogyo Co., Ltd.).

<Comparative Example 1>
In Example 1, a toner 3 was obtained in the same manner as in Example 1 except that the following liquid toner composition 3 was used instead of the liquid toner composition 1. Table 3 shows the prescription of toner 3 and Table 4 shows the characteristics of toner 3. A two-component developer 3 prepared by mixing 8 parts by mass of the [Toner 3] and 92 parts by mass of the carrier was prepared.
Further, image evaluation was performed in the same manner as in Example 1 except that the toner 3 and the two-component developer 3 were used. The results are shown in Table 4.

(Preparation of Liquid Toner Composition 3)
・ Wax dispersion-1 50 parts by mass (carnauba wax solid content: 20%)
Colorant dispersion C-3 25 parts by mass (pigment solid content: 16%, resin solid content: 24%)
-Polyester resin solution-1 160 parts by mass (resin solid content: 50%)
・ Triethylamine 0.5 parts by mass ・ Ethyl acetate 14.5 parts by mass

The above solution was put into a container, and liquid toner composition 3 was prepared by stirring and dispersing at 1500 rpm for 10 minutes using a homodisper (manufactured by Tokushu Kika Kogyo Co., Ltd.).

<Comparative example 2>
In Example 1, a toner 4 was obtained in the same manner as in Example 1 except that the aqueous phase 1 was changed to the aqueous phase 2 and the following (emulsification and solvent removal step) and (washing and drying step) were used. Table 3 shows the prescription of toner 4 and Table 4 shows the characteristics of toner 4. A two-component developer 4 prepared by mixing 8 parts by mass of the [Toner 4] and 92 parts by mass of the carrier was prepared.
Further, image evaluation was performed in the same manner as in Example 1 except that the toner 4 and the two-component developer 4 were used. The results are shown in Table 4.

(Aqueous phase 2: Preparation of inorganic aqueous dispersion)
After adding 451 parts by mass of a 0.1 mol / L Na ₃ PO ₄ aqueous solution to 709 parts by mass of ion-exchanged water and heating to 60 ° C., the mixture was stirred at 12,000 rpm with a TK homomixer (manufactured by Special Machine Industries). An inorganic aqueous dispersion medium containing Ca ₃ (PO ₄ ) ₂ was obtained by gradually adding 67.7 parts by mass of 1.0 mol / L CaCl ₂ aqueous solution.
next,
-293 parts by mass of the above inorganic aqueous dispersion-50% aqueous solution of sodium dodecyl diphenyl ether disulfonate (Eleminol MON-7, manufactured by Sanyo Chemical Industries) 6.0 parts by mass-23.5 parts by mass of ethyl acetate The mixture was stirred for 1 minute at 5000 rpm with a TK homomixer to prepare an aqueous phase 2.

(Emulsification and solvent removal process)
In the aqueous phase 2, the rotational speed of the TK homomixer was increased to 8000 rpm, the liquid toner composition 1 (250.0 parts by mass) was added, and stirring was continued for 3 minutes to suspend the liquid toner composition 1. Next, a stirring blade was set in a beaker, the system was heated to 50 ° C. while stirring at 200 rpm, and the solvent was removed in a draft chamber for 10 hours to obtain an aqueous dispersion of toner particles.

(Washing and drying process)
The aqueous dispersion of toner particles is filtered, charged into 500 parts by mass of ion-exchanged water and reslurried, and then the system is stirred and hydrochloric acid is added until the system reaches pH 1.5 to add Ca ₃ (PO ₄ ). ₂ was dissolved and stirred for 5 minutes.
The slurry was filtered again, 200 parts by mass of ion-exchanged water was added, and the operation of stirring for 5 minutes was repeated three times to remove triethylamine remaining in the system and obtain a filter cake of toner particles.
Next, the filter cake was dried with a hot air dryer at 45 ° C. for 3 days and sieved with a mesh of 75 μm to obtain toner particles.

<Example 3>
In Example 1, a toner 5 was obtained in the same manner as in Example 1 except that the following liquid toner composition 4 was used instead of the liquid toner composition 1. Table 3 shows the prescription of toner 5, and Table 4 shows the characteristics of toner 5. A two-component developer 5 prepared by mixing 8 parts by mass of the [Toner 5] and 92 parts by mass of the carrier was prepared.
Further, image evaluation was performed in the same manner as in Example 1 except that the toner 5 and the two-component developer 5 were used. The results are shown in Table 4.

(Preparation of Liquid Toner Composition 4)
・ Wax dispersion-1 50 parts by mass (carnauba wax solid content: 20%)
Colorant dispersion C-4 40 parts by mass (pigment solid content: 10%, resin solid content: 40%)
Polyester resin solution-1 136 parts by mass (resin solid content: 50%)
・ Triethylamine 0.5 parts by mass ・ Ethyl acetate 23.5 parts by mass

The above solution was put into a container, and a liquid toner composition 4 was prepared by stirring and dispersing at 1500 rpm for 10 minutes using a homodisper (manufactured by Tokushu Kika Kogyo Co., Ltd.).

<Example 4>
In Example 1, a toner 6 was obtained in the same manner as in Example 1 except that the liquid toner composition 5 shown below was used instead of the liquid toner composition 1. Table 3 shows the formulation of the toner 6 and Table 4 shows the characteristics of the toner 6. A two-component developer 6 prepared by mixing 8 parts by mass of the [Toner 6] and 92 parts by mass of the carrier was prepared.
Further, image evaluation was performed in the same manner as in Example 1 except that the toner 6 and the two-component developer 6 were used. The results are shown in Table 4.

(Preparation of liquid toner composition 5)
・ Wax dispersion-1 50 parts by mass (carnauba wax solid content: 20%)
Colorant dispersion C-5 20 parts by mass (pigment solid content: 20%, resin solid content: 20%)
-Polyester resin solution-1 164 parts by mass (resin solid content: 50%)
・ Triethylamine 0.5 parts by mass ・ Ethyl acetate 15.5 parts by mass

The above solution was put into a container, and a liquid toner composition 5 was prepared by stirring and dispersing at 1500 rpm for 10 minutes using a homodisper (manufactured by Tokushu Kika Kogyo Co., Ltd.).

<Examples 5 and 6>
Toners 7 and 8 were obtained in the same manner as in Example 1 except that the aqueous phase 1 was changed to the aqueous phase 3 (Example 5) and the aqueous phase 4 (Example 6). The formulations for aqueous phases 3 and 4 are shown below. Table 4 shows the characteristics of the toners 7 and 8. As shown in Table 3, the amount of resin (b) was adjusted.
A two-component developer 7 prepared by mixing 8 parts by mass of the [Toner 7] and 92 parts by mass of the carrier was prepared (Example 5). A two-component developer 8 prepared by mixing 8 parts by mass of the [Toner 8] and 92 parts by mass of the carrier was prepared (Example 6).
Further, image evaluation was performed in the same manner as in Example 1 except that the toner 7 and the two-component developer 7 were used. The results are shown in Table 4 (Example 5). Image evaluation was performed in the same manner as in Example 1 except that the toner 8 and the two-component developer 8 were used. The results are shown in Table 4 (Example 6).

(Preparation of aqueous phase 3)
The following was put into a container, and stirred at 5000 rpm for 1 minute with a TK homomixer (manufactured by Tokushu Kika Co., Ltd.) to prepare an aqueous phase 3.
-Ion-exchanged water 242.5 parts by mass-Resin fine particle dispersion-1 7.5 parts by mass (1.5 parts by mass of resin fine particles with respect to 100 parts by mass of toner base particles)
-50% aqueous solution of sodium dodecyl diphenyl ether disulfonate (Eleminol MON-7, manufactured by Sanyo Chemical Industries) 25 parts by mass-30 parts by mass of ethyl acetate

(Preparation of aqueous phase 4)
The following was put into a container, and stirred at 5000 rpm for 1 minute with a TK homomixer (manufactured by Tokushu Kika Co., Ltd.) to prepare an aqueous phase 4.
-Ion-exchanged water 187.5 parts by mass-Resin fine particle dispersion-1 62.5 parts by mass (12.5 parts by mass of resin fine particles with respect to 100 parts by mass of toner base particles)
-50% aqueous solution of sodium dodecyl diphenyl ether disulfonate (Eleminol MON-7, manufactured by Sanyo Chemical Industries) 25 parts by mass-30 parts by mass of ethyl acetate

<Examples 7, 8 and 9>
In Example 1, resin fine particle dispersion-1 was changed to resin fine particle dispersion-2 (Example 7), 3 (Example 8), and 4 (Example 9). Toners 9, 10 and 11 and two-component developers 9, 10 and 11 were obtained in the same manner as in Example 1 except that the adjustment was made as described above. Table 4 shows the characteristics of the toners 9, 10, and 11.
Further, image evaluation was performed in the same manner as in Example 1 except that toners 9, 10, and 11 and two-component developers 9, 10, and 11 were used, respectively. The results are shown in Table 4.

<Example 10>
In Example 1, instead of the liquid toner composition 1, a toner 12 was obtained in the same manner as in Example 1 except that the liquid toner composition 6 shown below was used. Table 3 shows the prescription of toner 12 and Table 4 shows the characteristics of toner 12. A two-component developer 12 prepared by mixing 8 parts by mass of the [Toner 12] and 92 parts by mass of the carrier was prepared.
Further, image evaluation was performed in the same manner as in Example 1 except that the toner 12 and the two-component developer 12 were used. The results are shown in Table 4.

(Preparation of Liquid Toner Composition 6)
・ Wax dispersion-1 50 parts by mass (carnauba wax solid content: 20%)
Colorant dispersion-C6 25 parts by mass (pigment solid content: 16%, resin solid content: 24%)
Polyester resin solution-2 160 parts by mass (resin solid content: 50%)
・ Triethylamine 0.5 parts by mass ・ Ethyl acetate 14.5 parts by mass

The above solution was put into a container, and a liquid toner composition 6 was prepared by stirring and dispersing at 1500 rpm for 10 minutes using a homodisper (manufactured by Tokushu Kika Kogyo Co., Ltd.).

<Example 11>
In Example 1, a toner 13 was obtained in the same manner as in Example 1 except that the following liquid toner composition 7 was used instead of the liquid toner composition 1. Table 3 shows the prescription of toner 13 and Table 4 shows the characteristics of toner 13. A two-component developer 13 prepared by mixing 8 parts by mass of the [Toner 13] and 92 parts by mass of the carrier was prepared.
Further, image evaluation was performed in the same manner as in Example 1 except that the toner 13 and the two-component developer 13 were used. The results are shown in Table 4.

(Preparation of liquid toner composition 7)
・ Wax dispersion-1 50 parts by mass (carnauba wax solid content: 20%)
Colorant dispersion-C7 25 parts by mass (pigment solid content: 16%, resin solid content: 24%)
-Polyester resin solution-3 160 parts by mass (resin solid content: 50%)
・ Triethylamine 0.5 parts by mass ・ Ethyl acetate 14.5 parts by mass

The above solution was put into a container, and a liquid toner composition 7 was prepared by stirring and dispersing at 1500 rpm for 10 minutes using a homodisper (manufactured by Tokushu Kika Kogyo Co., Ltd.).

<Examples 12, 13, and 14>
In Example 11, instead of wax dispersion-1 constituting the liquid toner composition 7, wax dispersion-2 (Example 12), 3 (Example 13) and 4 (Example 14) were used. Toners 14, 15 and 16 and two-component developers 14, 15 and 16 were obtained in the same manner as in Example 11 except that the addition amounts of the materials were adjusted as shown in Table 3. Table 4 shows the characteristics of the toners 14, 15 and 16.
Further, image evaluation was performed in the same manner as in Example 1 except that toners 14, 15, and 16 and two-component developers 14, 15, and 16 were used, respectively. The results are shown in Table 4.

<Example 15>
In Example 1, a toner 17 was obtained in the same manner as in Example 1 except that the following liquid toner composition 8 was used instead of the liquid toner composition 1. The prescription of toner 17 is shown in Table 3, and the characteristics of toner 17 are shown in Table 4. A two-component developer 17 prepared by mixing 8 parts by mass of the [Toner 17] and 92 parts by mass of the carrier was prepared.
Further, image evaluation was performed in the same manner as in Example 1 except that the toner 17 and the two-component developer 17 were used. The results are shown in Table 4.

(Preparation of liquid toner composition 8)
Wax dispersion-1 33.3 parts by mass (Carnauba wax solid content: 20%)
Colorant dispersion-C8 33.3 parts by mass (pigment solid content: 12%, carnauba wax solid content 10%, resin solid content: 18%)
Polyester resin solution 1 160 parts by mass (resin solid content: 50%)
・ Triethylamine 0.5 parts by mass ・ Ethyl acetate 23.9 parts by mass

The above solution was put into a container, and a liquid toner composition 8 was prepared by stirring and dispersing at 1500 rpm for 10 minutes using a homodisper (manufactured by Tokushu Kika Kogyo Co., Ltd.).

<Examples 16 and 17>
In Example 1, the colorant dispersion liquid-C1 constituting the liquid toner composition 1 was changed to a colorant dispersion liquid-M1 (Example 16) and a colorant dispersion liquid-Y1 (Example 17), and various materials were used. Toners 18 and 19 and two-component developers 18 and 19 were obtained in the same manner as in Example 1 except that the addition amount of was adjusted as shown in Table 3. The characteristics of the toners 18 and 19 are shown in Table 4. Further, image evaluation was performed in the same manner as in Example 1 except that the toners 18 and 19 and the two-component developers 18 and 19 were used, respectively. The results are shown in Table 4.
The toner 19 does not drop to L ^* = 70. The value of c ^* when L ^* = 90 was 104.1.
In addition, a color image was produced using the toner 1 produced in Example 1 and the toners 18 and 19. In the secondary color region, the saturation and brightness were high, and a good image was obtained.

<Example 18>
In Example 1, a toner 20 was obtained in the same manner as in Example 1 except that the following liquid toner composition 9 was used instead of the liquid toner composition 1. The prescription of the toner 20 is shown in Table 3, and the characteristics of the toner 20 are shown in Table 4. A two-component developer 20 prepared by mixing 8 parts by mass of the [Toner 20] and 92 parts by mass of the carrier was prepared.
Further, image evaluation was performed in the same manner as in Example 1 except that the toner 20 and the two-component developer 20 were used. The results are shown in Table 4.

(Preparation of liquid toner composition 9)
・ Wax dispersion-1 50 parts by mass (carnauba wax solid content: 20%)
Colorant dispersion-C1 7.5 parts by mass (pigment solid content: 16%, resin solid content: 24%)
Polyester resin solution-1 174 parts by mass (resin solid content: 50%)
・ Triethylamine 0.5 parts by mass ・ Ethyl acetate 18.0 parts by mass

The above solution was put into a container, and liquid toner composition 9 was prepared by stirring and dispersing at 1500 rpm for 10 minutes using a homodisper (manufactured by Tokushu Kika Kogyo Co., Ltd.).

<Comparative Example 3>
In Example 1, a toner 21 was obtained in the same manner as in Example 1 except that the following liquid toner composition 10 was used instead of the liquid toner composition 1. Table 3 shows the prescription of toner 21 and Table 4 shows the characteristics of toner 21. A two-component developer 21 prepared by mixing 8 parts by mass of the [Toner 21] and 92 parts by mass of the carrier was prepared.
Further, image evaluation was performed in the same manner as in Example 1 except that the toner 21 and the two-component developer 21 were used. The results are shown in Table 4.

(Preparation of Liquid Toner Composition 10)
・ Wax dispersion-1 50 parts by mass (carnauba wax solid content: 20%)
Colorant dispersion C-3 7.5 parts by mass (pigment solid content: 20%, resin solid content: 20%)
Polyester resin solution-1 174 parts by mass (resin solid content: 50%)
・ Triethylamine 0.5 parts by mass ・ Ethyl acetate 18.0 parts by mass

The above solution was put into a container, and a liquid toner composition 10 was prepared by stirring and dispersing at 1500 rpm for 10 minutes using a homodisper (manufactured by Tokushu Kika Kogyo Co., Ltd.).

The schematic diagram of the enlarged photograph of the cross section of the read toner particle is shown. It is a figure of the calculation method of Tg by the DSC curve which made "Reversing Heat Flow" the vertical axis | shaft. It is a figure of the flow curve based on the data from an elevated flow tester. It is the schematic of the apparatus which measures a triboelectric charge amount.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Suction machine 2 Metal measuring container 3 500 mesh screen 4 Metal lid 5 Vacuum gauge 6 Air flow control valve 7 Suction port 8 Condenser 9 Electrometer

Claims (12)

A toner containing capsule-type toner particles having a surface layer (B) on the surface of a toner base particle (A) containing at least a resin (a) containing a polyester as a main component, a colorant and a wax,
An enlarged photograph of the cross section of the toner particle is taken, and a straight line connecting the center of toner particle and the surface of the toner particle is drawn in the obtained image of the toner particle, and is divided 3: 1 from the center of gravity on the drawn straight line. The occupancy rate of the colorant in the region on the surface of the toner particle surface of the curve formed by connecting the set points is 1.5 of the occupancy rate of the colorant in the region inside the toner particle of the curve. A toner characterized by being at least double.   The toner according to claim 1, wherein the surface layer (B) is 1.0% by mass or more and 15.0% by mass or less with respect to the toner base particles.   The toner according to claim 1, wherein the resin (a) containing polyester as a main component contains at least a resin (a1) synthesized from an aliphatic diol.   The resin (a) containing the polyester as a main component contains at least a resin (a1) synthesized from an aliphatic diol and a resin (a2). The acid value of the resin (a2) It is larger than the acid value of a1), and the content of the resin (a2) is 5% by mass or more and 30% by mass or less with respect to the resin (a) containing the polyester as a main component. Item 4. The toner according to any one of Items 1 to 3.   The toner according to claim 4, wherein the colorant is mixed with the resin (a2) in advance.   In the obtained toner particle image, a straight line connecting the center of the toner particle and the surface of the toner particle is drawn, and a point divided 3: 1 from the center of gravity is set on the drawn straight line, and the set point is connected. 2. The occupancy ratio of the colorant in the region on the toner particle surface side of the curve formed by the step is 2.0 times or more of the occupancy ratio of the colorant in the region inside the toner particle of the curve. The toner according to any one of 5 to 5.   The toner according to claim 1, wherein the colorant has a number average particle diameter of 200 nm or less in an image of the obtained toner particles.   The toner according to claim 1, wherein a content of the colorant is 2.0% by mass or more and 15.0% by mass or less with respect to the toner.   9. The surface layer (B) contains a resin (b), and the resin (b) contains a compound formed by urethane bond between a diol component and a diisocyanate component. The toner described in 1.   The toner according to claim 1, wherein the surface layer (B) is formed of resin fine particles containing a resin (b) having a number average particle diameter of 10 nm to 120 nm. The toner particles were obtained by preparing a mixture containing at least the colorant and the resin (a2) in advance, and dissolving or dispersing the prepared mixture and a mixture containing at least the resin (a1) in an organic medium. The lysate or dispersion is dispersed in an aqueous medium in which resin fine particles containing the resin (b) are dispersed, and the solvent is removed from the obtained dispersion and dried. The toner according to any one of 4 to 9.   The toner particles are prepared by dissolving at least the resin (a) mainly composed of the polyester, the colorant, and the wax in an organic medium in an aqueous medium in which resin fine particles containing the resin (b) are dispersed. The toner according to claim 1, wherein the toner is obtained by dispersing a solution or dispersion obtained by dispersing, removing the solvent from the obtained dispersion, and drying.

Images