JP2003195568A - Yellow toner - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a yellow toner which has excellent blocking resistance, preservability under a high-temperature environment, low-temperature fixability, high-temperature offset resistance, glossiness, OHP transparency, and transferability and can form high-definition and high grade images. <P>SOLUTION: The yellow toner contain at least a binder resin, a wax and a coloring agent and is characterized in that the modulus of elasticity in storage (G'<SB>80</SB>) at 80°C of the toner exists in the range from 1×10<SP>6</SP>to 1×10<SP>8</SP>[dN/m<SP>2</SP>]; the loss section (tanδ) at 140°C exists in the range from 0.2 to 1.5 and the toner contains a compound expressed by the following general formula (1) as the coloring agent at 2 to 15 parts by mass per 100 parts by mass the binder resin and the wax at 0.5 to 10 parts by mass per 100 parts by mass the binder resin. <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a yellow toner of electrostatic charge development or toner jet system, and a heating / pressurizing fixing means which does not use oil for preventing high temperature offset or uses a small amount of oil. The present invention relates to a yellow toner that exhibits high definition even when used.

[0002]

2. Description of the Related Art As a toner to be mounted on a full-color copying machine, each toner is sufficiently mixed in a heat and pressure fixing process without improving color reproducibility and impairing transparency of an overhead projector (OHP) image. is necessary.
The full-color image toner is preferably a low-molecular-weight binder resin having a sharp melt property, as compared with a black toner for general black-and-white copying machines. However, in general, when a sharp melt binder resin is used, when the toner is melted in the heat and pressure fixing step, the self-cohesive force of the binder resin is low, so that a problem with the high temperature offset resistance tends to occur.

In general black toner for black-and-white copying machines, a relatively highly crystalline wax represented by polyethylene wax or polypropylene wax is used as a release agent in order to improve the high temperature offset resistance during fixing. For example, Japanese Patent Publication No. 52-3304 and Japanese Patent Publication No. 52-3305.
JP-A-57-52574. In the case of full-color image toner, the transparency is obstructed when projected on OHP due to the high crystallinity of the release agent itself and the difference in the refractive index from the material of the OHP sheet, and the projected image has saturation and brightness. Will be lower.

In order to solve such a problem, a toner having a specific storage elastic modulus has been proposed.

For example, in JP-A-11-84716 and JP-A-8-54750, 180 ° C. or 17
Toners having a specific storage modulus at 0 ° C have been proposed. However, it is necessary to have both low-temperature fixing and high-temperature offset resistance, use no oil to prevent high-temperature offset, or have good fixability and sufficient color-mixing characteristics with a heating / pressurizing fixing unit that uses a small amount of oil. As the color toner described above, the viscosity of the toner is too low, and the storability in a high temperature environment is not satisfactory.

Further, Japanese Patent Laid-Open No. 5-249735,
JP-A-7-92737, JP-A-7-234542
JP-A-7-295298, JP-A-8-2
No. 34480, JP-A-8-278662, and JP-A-10-171156 also propose a toner having a specific storage elastic modulus. However,
Ideal fixing property as color toner, storability, OH
There was room for improvement in order to obtain P transparency.

In order to solve this problem, a method of reducing the crystallinity of the wax by using a nucleating material together with the wax is disclosed in JP-A-4-149559 and JP-A-4-107.
It is proposed in Japanese Patent No. 467. Further, a method using a wax having a low crystallinity is proposed in JP-A-4-301853 and JP-A-5-61238. There is a montan wax as a wax having a relatively high transparency and a low melting point.
185660, JP-A-1-185661,
JP-A-1-185662 and JP-A-1-18566.
No. 3 and Japanese Patent Laid-Open No. 1-238672. However, these waxes do not fully satisfy all of the transparency with OHP, the low temperature fixability at the time of heat and pressure fixing, and the high temperature offset resistance.

Therefore, in the case of a normal color toner, an oil such as silicone oil or fluorine oil is applied to the heat fixing roller without adding a releasing agent as much as possible to improve the high temperature offset resistance and the transparency in OHP. There is. However, the fixed image thus obtained has extra oil attached to its surface. In some cases, the oil adheres to the photoreceptor and contaminates it, or the oil swells the fixing roller, which shortens the life of the fixing roller. Since oil streaks are not generated on the fixed image, it is necessary to uniformly and quantitatively supply the oil onto the surface of the fixing roller, which tends to increase the size of the fixing device.

Therefore, no oil is used, or
In the heating / pressurizing fixing unit that uses a small amount of oil, it is a toner in which the occurrence of offset is suppressed,
Further, a toner having excellent transparency of a fixed image is desired.

On the other hand, as the number of cases where a color copying machine is connected to a computer via a controller and used as a high-quality color printer has increased, a color management system for managing the color of the entire system has been proposed. . As a result, certain users strongly desire that the output image output by the electrophotographic color copier matches the output image of the process ink-based printing in terms of tint. A toner having a color tone similar to that has been demanded.

[0011] Today, many colorants for yellow toner are known in the art. For example, Japanese Patent Application Laid-Open No. 2-207273 describes solvent yellow 112, Japanese Patent Application Laid-Open No. 2-207274 describes solvent yellow 160, Japanese Patent Application Laid-Open No. 8-36275 describes solvent yellow 162, and the like. JP-A-50-62442 discloses a benzidine yellow pigment, JP-A-2-87160 discloses a monoazo yellow toner, and further JP-A-2-208.
No. 662, Pigment Yellow 120, 151,
Pigments such as 154 and 156 are described.

However, the conventionally known colorant for yellow toner has various problems. For example, although dye-based colorants are generally excellent in transparency,
It is inferior in light resistance and has a problem in image storage stability.

On the other hand, although the above-mentioned pigment group is superior in light resistance to dyes, it is used for magenta toner, for example, a quinacridone pigment, and a copper phthalocyanine pigment used for cyan toner. Compared with, there was still a problem in light resistance, and in a long-time light exposure test, there was a problem that fading occurred or a change in hue was noticeable.

Furthermore, although there are yellow pigments excellent in light resistance and heat resistance other than the above-mentioned pigments, on the contrary, the hiding property is too strong and the transparency is extremely lowered, which is not suitable for full-color use. there were.

Japanese Patent Publication No. 2-37949 discloses a disazo compound having excellent light resistance and a method for producing the same. This is a compound group typified by Pigment Yellow 180, and is one of the azo pigments that not only has excellent light resistance and heat resistance but also meets ecological requirements.

A yellow toner using Pigment Yellow 180 is disclosed in JP-A-6-230607 and JP-A-6-230607.
JP-A-266163 and JP-A-8-262799 disclose that toners using the above pigments have poor coloring power, and in addition, they cannot be said to have good transparency at all, and are further suitable for full-color use. There was an urgent need for improvement.

On the other hand, JP-A-8-209017 discloses an electrophotographic toner in which the pigment is made into fine particles to improve the specific surface area of the pigment to improve the transparency and coloring power, in order to solve the above-mentioned problems. Has been done. However, when the pigment classified as Pigment Yellow 180 is miniaturized, the self-aggregation property of the pigment itself is inevitably strong, so that the dispersibility in the binder resin constituting the toner is insufficient,
According to our study, it has been difficult to achieve the stabilization of charging in a toner having a poor dispersibility of the colorant, and there are problems such as fog and toner scattering.

Japanese Patent No. 2632423 describes a toner in which a group of condensed disazo yellow pigments is kneaded and dispersed in a resin.

The above-mentioned toner is prepared by kneading and dispersing a hardly dispersible compound into particles having an average particle diameter of 0.2 μm or less.
Although it has achieved clearness and sharpness of hue and improved transparency, when viewed as a high-definition full-color yellow toner, the level of pigment dispersibility has not reached the target level, and further, we In the study, it was difficult to stabilize charging, and there were problems such as durability, low density and fog.

On the other hand, in the case of using a two-component developer composed of a toner and a carrier as the developer, the toner is charged to a required charge amount and charge polarity by friction with the carrier, and electrostatic attraction is used. It develops an electrostatic image. Therefore, in order to obtain a good visible image, it is mainly necessary that the toner has good triboelectric chargeability.

[0021] Today, in order to solve the above problems or to prevent the charging property of the toner from being affected by the charging property of the colorant itself, the search for the carrier core material and the carrier coating material and the coating amount are performed. Many studies have been carried out to achieve excellent triboelectric chargeability in the materials constituting the developer, such as optimization of the charge control agent, examination of charge control agents and fluidity imparting agents to be added to the toner, and further improvement of the binder as the base. Has been done.

In recent years, the demand for high definition and high image quality of copying machines or printers has been increasing in the market, and in this technical field, an attempt has been made to achieve high image quality by reducing the particle size of color toner. ing. When the particle diameter of the toner is small, the surface area per unit weight is increased, and the charge amount of the toner tends to be large, and the image density is low and the durability is apt to deteriorate. In addition, since the charge amount of the toner is large, the adhesion between the toner particles is strong, the fluidity is lowered, and problems such as stability of toner replenishment and imparting tribo to the replenishment toner are likely to occur.

Further, since the color toner does not contain a black conductive material such as a magnetic material or carbon black, there is no portion for leaking charge, and the charge amount generally tends to increase. This tendency is more remarkable when a polyester binder having a high negative charging performance is used.

[0024] Today, polyester resins are often used as binder resins for color toners in the art, but color toners containing polyester resins are generally susceptible to temperature and humidity, and are charged under low humidity. Problems such as an excessive amount of charge and an insufficient amount of charge under high humidity are likely to occur, and development of a color toner having a stable amount of charge even in a wide range of environments is desired.

Further, it is known that the toner charge varies greatly depending on the degree of dispersibility of the colorant in the binder resin and the charging characteristics of the colorant itself as described above. And toner scattering easily occur, and various problems such as toner spent on the carrier, toner filming on the drum, and contamination of the fixing roller are caused. Therefore, improving the dispersibility of the colorant is an important technical issue in addition to the color reproducibility.

[0026]

SUMMARY OF THE INVENTION An object of the present invention is to provide a yellow toner which solves the above problems.

That is, (1) excellent low temperature fixability / high speed fixability, (2) excellent storage stability, heat resistance and blocking resistance, and (3) covering a wide dynamic range from low density to high density. It has high coloring power, (4) high saturation and lightness, (5) excellent OHP transparency, (6) good dispersibility of colorant and excellent toner covering power (hiding power), 7) High light resistance, (8) Process ink yellow color tone, (9) Good fixability and color mixture, (10) Sufficient triboelectric chargeability,
(11) High gloss that enhances image quality, (12) High temperature offset is sufficiently prevented, fixing temperature is wide,
(13) There is no toner fusion to the developing device, that is, the parts such as the sleeve, the blade, and the application roller.
Further, it provides a yellow toner having excellent cleaning property, no filming on the photoconductor, (15) no fog, excellent highlight reproducibility, excellent solid uniformity, and excellent durability stability. Is.

[0028]

The present invention relates to a yellow toner containing at least a binder resin, a wax and a colorant, and has a storage elastic modulus (G ′) at 80 ° C. of the toner.
₈₀ ) is in the range of 1 × 10 ⁶ to 1 × 10 ⁸ [dN / m ² ] and the loss intercept (tan δ) at 140 ° C. is 0.2 to
Within the range of 1.5, the following general formula (1) is used as a colorant.
2 to 15 parts by mass per 100 parts by mass of the binder resin, and 0.5 to 10 parts by mass of wax per 100 parts by mass of the binder resin.

[0029]

[Chemical 3]

The present invention also provides at least a binder resin and a wax.
In a yellow toner containing a toner and a colorant,
The storage elastic modulus (G ′ of the toner at 80 ° C.)₈₀) Is 1 ×
10 ⁶~ 1 x 10⁸[DN / m²] Range, 140
Loss intercept (tan δ) in ° C range from 0.2 to 1.5
And is represented by the following general formula (1) as a colorant.
In total, the compound and the compound represented by the following general formula (2)
2 to 15 parts by mass per 100 parts by mass of the binder resin,
And a compound represented by the following general formula (1) and the following general formula
The mass ratio of the compound represented by (2) is 95: 5 to 70:
30 and wax per 100 parts by mass of binder resin
Yellow characterized by containing 0.5 to 10 parts by mass
-Regarding toner.

[0031]

[Chemical 4]

The yellow toner of the present invention has a temperature of 30 to 30 in the endothermic curve in differential thermal analysis (DSC) measurement.
It has one or more endothermic peaks in the range of 200 ° C., and the peak temperature of the maximum endothermic peak in the endothermic peak is 60 to 1
It is preferably in the range of 10 ° C.

Further, it preferably contains a metal compound of an aromatic carboxylic acid or its derivative, preferably an aluminum compound.

Further, the binder resin comprises (a) a polyester resin, (b) a hybrid resin having a polyester unit and a vinyl copolymer unit, and (c) a hybrid resin and a vinyl copolymer. A resin selected from any of a mixture and a mixture of (d) hybrid resin and polyester resin is preferable.

As a result of intensive studies, the inventors of the present invention have excellent resistance to high-temperature offset even in a heating and pressure fixing means which does not use oil or uses a small amount of oil, and is long-term storage in a high temperature environment. In order to achieve both stability and low temperature fixability, it was found that it is effective for the toner to satisfy the above requirements, and in addition, in order to obtain a yellow toner having excellent light resistance and good color tone. Has
It has been found that when the above compound (1) is mixed and dispersed, excellent pigment dispersibility and high OHT transparency can be obtained.

[0036]

DETAILED DESCRIPTION OF THE INVENTION The toner of the present invention will be described in detail.

First, the storage elastic modulus (G _'80 ) at a temperature of 80 ° C. is 1 × 10 in order to improve the storage stability, heat resistance and blocking resistance of the toner in a high temperature environment.
⁶ to 1 × 10 ⁸ [dN / m ² ] and preferably 1 × 1
It is 0 ^{6 to} 5 × 10 ⁷ [dN / m ² ]. When the storage elastic modulus (G ′ ₈₀ ) is smaller than 1 × 10 ⁶ [dN / m ² ], the storage stability in a high temperature environment, the heat resistance and the blocking resistance are poor, and the toner particles coalesce with each other. It is not preferable because a large toner aggregate is formed. In recent years, copiers,
Since the output speed of printers and miniaturization of the main body are advancing, the temperature inside the machine tends to rise, and in order to stably obtain high-definition and high-quality images, the toner is It is important to have sufficient storage stability, heat resistance, and blocking resistance in. When the storage elastic modulus (G ′ ₈₀ ) is larger than 1 × 10 ⁸ [dN / m ² ], the storage stability, heat resistance and blocking resistance are sufficient, but sufficient fixability at low temperature is obtained. Is not preferable because it cannot be obtained.

The loss intercept (t
an δ) is 0.2 to 1.5 [−], and preferably 0.3 in order to achieve both sufficient fixing property and high temperature offset resistance, and further to obtain an image having a uniform gloss. It is-1.0 [-]. When the loss intercept (tan δ) is larger than 1.5 [−], it is not preferable because sufficient high temperature offset resistance of the toner cannot be obtained. If the loss intercept (tan δ) is smaller than 0.2 [-], the toner cannot be sufficiently fixed, and the color developability of the toner is significantly lowered.

Further, the toner of the present invention has a temperature of 30 at the endothermic curve in differential thermal analysis (DSC) measurement from the viewpoint of achieving both low temperature fixing property and blocking resistance.
Have one or more endothermic peaks in the range of ~ 200 ° C,
The peak temperature of the maximum endothermic peak in the endothermic peak is 60 to
It is preferably in the range of 110 ° C. More preferably, the maximum peak of the endothermic curve is in the range of 65 to 100 ° C. When the peak temperature of the maximum endothermic peak is less than 60 ° C, the blocking resistance of the toner tends to deteriorate, and conversely, the peak temperature of the maximum endothermic peak is 110 ° C.
If it exceeds, the fixability tends to decrease.

The binder resin used in the toner of the present invention is (a) a polyester resin, (b) a hybrid resin having a polyester unit and a vinyl copolymer unit, (c) a hybrid resin and a vinyl resin. A resin selected from any of a mixture with a system copolymer and a mixture of (d) a hybrid resin and a polyester resin is preferable, but the molecular weight distribution of the resin component measured by gel permeation chromatography (GPC) is It has a main peak in the molecular weight range of 3,500 to 10,000, and preferably has a molecular weight of 4,000 to 9,0.
It is preferable that it has a Mw / Mn ratio of 5.0 or more. When the main peak is in the region where the molecular weight is less than 3,500, the hot offset resistance of the toner tends to be insufficient. On the other hand, when the main peak is in the region where the molecular weight exceeds 10,000, sufficient low-temperature fixability of the toner cannot be obtained, and OHP permeability tends to be insufficient, which is not preferable. Also, Mw / M
When n is less than 5.0, it tends to be difficult to obtain good offset resistance.

When a polyester resin is used as the binder resin, alcohol and carboxylic acid, carboxylic acid anhydride, carboxylic acid ester or the like can be used as a raw material monomer.

Specifically, for example, as the dihydric alcohol component, polyoxypropylene (2.2) -2,2-bis (4-hydroxyphenyl) propane, polyoxypropylene (3.3) -2,2 -Bis (4-hydroxyphenyl) propane, polyoxyethylene (2.0)-
2,2-bis (4-hydroxyphenyl) propane, polyoxypropylene (2.0) -polyoxyethylene (2.0) -2,2-bis (4-hydroxyphenyl)
Propylene, polyoxypropylene (6) -2,2-bis (4-hydroxyphenyl) propane and other bisphenol A alkylene oxide adducts, ethylene glycol, diethylene glycol, triethylene glycol,
1,2-propylene glycol, 1,3-propylene glycol, 1,4-butanediol, neopentyl glycol, 1,4-butenediol, 1,5-pentanediol, 1,6-hexanediol, 1,4- Examples thereof include cyclohexanedimethanol, dipropylene glycol, polyethylene glycol, polypropylene glycol, polytetramethylene glycol, bisphenol A, hydrogenated bisphenol A and the like.

Examples of trihydric or higher alcohol components include sorbitol, 1,2,3,6-hexanetetrol, 1,4-sorbitan, pentaerythritol, dipentaerythritol, tripentaerythritol, 1,
2,4-butanetriol, 1,2,5-pentanetriol, glycerol, 2-methylpropanetriol, 2-methyl-1,2,4-butanetriol, trimethylolethane, trimethylolpropane, 1,3.
5-trihydroxymethylbenzene etc. are mentioned.

As the acidic component, aromatic dicarboxylic acids such as phthalic acid, isophthalic acid and terephthalic acid or their anhydrides; alkyldicarboxylic acids such as succinic acid, adipic acid, sebacic acid and azelaic acid or their anhydrides;
Examples thereof include succinic acid substituted with an alkyl group having 6 to 12 carbon atoms or an anhydride thereof; unsaturated dicarboxylic acids such as fumaric acid, maleic acid and citraconic acid or an anhydride thereof.

Among them, particularly, the following general formula (3)
And a carboxylic acid component consisting of a carboxylic acid having a valence of 2 or more or a carboxylic acid thereof or an acid anhydride thereof or a lower alkyl ester thereof (for example, fumaric acid, maleic acid, maleic anhydride, phthalic acid, Polyester resin obtained by polycondensation of terephthalic acid, trimellitic acid, pyromellitic acid, etc.) as an acid component is preferable as a yellow toner because it has good charging characteristics.

[0046]

[Chemical 5]

[In the formula, R represents an ethylene or propylene group, x and y are each an integer of 1 or more, and x +
The average value of y is 2 to 10. ]

Further, when a hybrid resin having a polyester unit and a vinyl-based copolymer unit is used as the binder resin, the wax dispersibility is further improved,
It can be expected to improve low-temperature fixability and offset resistance. The "hybrid resin component" used in the present invention means a resin in which a vinyl-based copolymer unit and a polyester unit are chemically bonded. Specifically, a polyester unit and a vinyl-based copolymer unit obtained by polymerizing a monomer having a carboxylic acid ester group such as (meth) acrylic acid ester are formed by a transesterification reaction, preferably a vinyl-based copolymer. Polymer to trunk polymer,
It forms a graft copolymer (or block copolymer) using a polyester unit as a branch polymer.

As the vinyl-based monomer for producing the vinyl-based copolymer, styrene, o-methylstyrene,
m-methylstyrene, p-methylstyrene, α-methylstyrene, p-phenylstyrene, p-ethylstyrene, 2,4-dimethylstyrene, pn-butylstyrene, p-tert-butylstyrene, pn- Hexylstyrene, pn-octylstyrene, pn-nonylstyrene, pn-decylstyrene, pn-dodecylstyrene, p-methoxystyrene, p-chlorostyrene, 3,4-dichlorostyrene, m -Nitrostyrene,
Styrene and its derivatives such as o-nitrostyrene and p-nitrostyrene; ethylene, propylene, butylene,
Unsaturated monoolefins such as isobutylene; unsaturated polyenes such as butadiene and isoprene; vinyl chloride,
Vinyl halides such as vinylidene chloride, vinyl bromide, vinyl fluoride; vinyl esters such as vinyl acetate, vinyl propionate, vinyl benzoate; methyl methacrylate, ethyl methacrylate, propyl methacrylate,
Α, such as n-butyl methacrylate, isobutyl methacrylate, n-octyl methacrylate, dodecyl methacrylate, 2-ethylhexyl methacrylate, stearyl methacrylate, phenyl methacrylate, dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate.
-Methylene aliphatic monocarboxylic acid esters; methyl acrylate, ethyl acrylate, propyl acrylate, n-butyl acrylate, isobutyl acrylate, n-octyl acrylate, dodecyl acrylate, 2-acrylic acid acrylate
Ethylhexyl, stearyl acrylate, acrylic acid 2
-Acrylic esters such as chloroethyl and phenyl acrylate; Vinyl ethers such as vinyl methyl ether, vinyl ethyl ether and vinyl isobutyl ether; Vinyl ketones such as vinyl methyl ketone, vinyl hexyl ketone and methyl isopropenyl ketone; N-vinyl pyrrole , N-vinylcarbazole, N-vinylindole, N-vinyl compounds such as N-vinylpyrrolidone; vinylnaphthalene compounds; acrylic acid or methacrylic acid derivatives such as acrylonitrile, methacrylonitrile and acrylamide.

Further, unsaturated dibasic acids such as maleic acid, citraconic acid, itaconic acid, alkenylsuccinic acid, fumaric acid, mesaconic acid; maleic anhydride, citraconic anhydride, itaconic anhydride, alkenylsuccinic anhydride. Unsaturated dibasic acid anhydrides such as: maleic acid methyl half ester, maleic acid ethyl half ester, maleic acid butyl half ester, citraconic acid methyl half ester, citraconic acid ethyl half ester, citraconic acid butyl half ester, itaconic acid methyl ester Half ester of unsaturated dibasic acid such as half ester, methyl alkenyl succinic acid half ester, fumaric acid methyl half ester, mesaconic acid methyl half ester; unsaturated dibasic acid ester such as dimethyl maleic acid, dimethyl fumaric acid; Le acid, methacrylic acid, crotonic acid,
Α, β-unsaturated acids such as cinnamic acid; crotonic anhydride,
Α, β-unsaturated acid anhydrides such as cinnamic acid anhydride,
An anhydride of β-unsaturated acid and lower fatty acid; alkenylmalonic acid, alkenylglutaric acid, alkenyladipic acid,
Examples thereof include monomers having a carboxyl group such as acid anhydrides and monoesters thereof.

Further, acrylic acid or methacrylic acid esters such as 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate and 2-hydroxypropyl methacrylate; 4- (1-hydroxy-1-methylbutyl) styrene, 4- (1- Mention may be made of monomers having a hydroxy group such as hydroxy-1-methylhexyl) styrene.

In the toner of the present invention, the vinyl-based copolymer unit of the binder resin may have a crosslinked structure crosslinked with a crosslinking agent having two or more vinyl groups, which is used in this case. Examples of the cross-linking agent include aromatic divinyl compounds such as divinylbenzene and divinylnaphthalene; diacrylate compounds linked by an alkyl chain such as ethylene glycol diacrylate;
1,3-butylene glycol diacrylate, 1,4-
Examples include butanediol diacrylate, 1,5-pentanediol diacrylate, 1,6 hexanediol diacrylate, neopentyl glycol diacrylate and the above compounds in which acrylate is replaced with methacrylate; Examples of the bound diacrylate compounds include diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, polyethylene glycol # 400 diacrylate, polyethylene glycol # 600 diacrylate,
Examples include dipropylene glycol diacrylate and those obtained by replacing the acrylate of the above compounds with methacrylate; examples of diacrylate compounds linked by a chain containing an aromatic group and an ether bond include polyoxyethylene (2) -2. , 2-bis (4-hydroxyphenyl)
Propane diacrylate, polyoxyethylene (4)-
2,2-bis (4-hydroxyphenyl) propane diacrylate and those obtained by replacing the acrylates of the above compounds with methacrylates can be mentioned.

As the polyfunctional cross-linking agent, pentaerythritol triacrylate, trimethylol ethane triacrylate, trimethylol propane triacrylate, tetramethylol methane tetraacrylate, oligoester acrylate and those obtained by replacing the acrylate of the above compounds with methacrylate; Examples include triallyl cyanurate and triallyl trimellitate.

In the present invention, it is preferable that the vinyl copolymer component and / or the polyester resin component contain a monomer component capable of reacting with both resin components. Among the monomers constituting the polyester resin component, those capable of reacting with the vinyl-based copolymer include, for example, phthalic acid, maleic acid,
Examples thereof include unsaturated dicarboxylic acids such as citraconic acid and itaconic acid, or anhydrides thereof. Among the monomers constituting the vinyl-based copolymer component, those capable of reacting with the polyester resin component include those having a carboxyl group or a hydroxy group, and acrylic acid or methacrylic acid esters.

As a method for obtaining the reaction product of the vinyl copolymer and the polyester resin, a polymer containing a monomer component capable of reacting with each of the vinyl copolymer and the polyester resin mentioned above is present. The method obtained by polymerizing one or both of the resins is preferable.

The polymerization initiator used when producing the vinyl copolymer of the present invention is, for example, 2,2′-
Azobisisobutyronitrile, 2,2'-azobis (4
-Methoxy-2,4-dimethylvaleronitrile), 2,
2'-azobis (-2,4-dimethylvaleronitrile), 2,2'-azobis (-2 methylbutyronitrile), dimethyl-2,2'-azobisisobutyrate,
1,1'-azobis (1-cyclohexanecarbonitrile), 2- (carbamoylazo) -isobutyronitrile, 2,2'-azobis (2,4,4-trimethylpentane), 2-phenylazo-2,4- Dimethyl-4-methoxyvaleronitrile, 2,2'-azobis (2-methyl-propane), methyl ethyl ketone peroxide,
Ketone peroxides such as acetylacetone peroxide and cyclohexanone peroxide, 2,2-
Bis (t-butylperoxy) butane, t-butyl hydroperoxide, cumene hydroperoxide,
1,1,3,3-tetramethylbutyl hydroperoxide, di-t-butyl peroxide, t-butyl cumyl peroxide, di-cumyl peroxide, α,
α′-bis (t-butylperoxyisopropyl) benzene, isobutyl peroxide, octanoyl peroxide, decanoyl peroxide, lauroyl peroxide, 3,5,5-trimethylhexanoyl peroxide, benzoyl peroxide, m- Trioyl peroxide, di-isopropyl peroxydicarbonate, di-2-ethylhexyl peroxydicarbonate, di-n-propyl peroxydicarbonate,
Di-2-ethoxyethyl peroxycarbonate, di-
Methoxyisopropyl peroxydicarbonate, di (3-methyl-3-methoxybutyl) peroxycarbonate, acetylcyclohexylsulfonyl peroxide, t-butylperoxyacetate, t-butylperoxyisobutyrate, t-butylperoxyneo Decanoate, t-butylperoxy 2-ethylhexanoate, t-butylperoxylaurate, t-butylperoxybenzoate, t-butylperoxyisopropyl carbonate, di-t-butylperoxyisophthalate, t-butyl peroxyallyl carbonate,
t-amyl peroxy 2-ethylhexanoate, di-
t-butyl peroxyhexahydroterephthalate,
An example is di-t-butyl peroxyazelate.

Examples of the production method capable of preparing the hybrid resin used in the toner of the present invention include the production methods shown in the following (1) to (6).

(1) A method in which the vinyl copolymer, the polyester resin and the hybrid resin component are produced and then blended, and the blending is performed by dissolving and swelling in an organic solvent (for example, xylene) and then distilling the organic solvent off. Manufactured. The hybrid resin component is produced by separately producing a vinyl-based copolymer and a polyester resin, dissolving and swelling in a small amount of an organic solvent, adding an esterification catalyst and alcohol, and performing a transesterification reaction by heating. The synthesized ester compound can be used.

(2) A method for producing a polyester unit and a hybrid resin component in the presence of the vinyl copolymer unit after the production thereof. The hybrid resin component is produced by reacting a vinyl copolymer unit (a vinyl monomer can be added if necessary) with a polyester monomer (alcohol, carboxylic acid) and / or polyester. Also in this case, an organic solvent can be appropriately used.

(3) A method of producing a vinyl copolymer unit and a hybrid resin component in the presence of the polyester unit after the production. The hybrid resin component is produced by reacting a polyester unit (a polyester monomer can be added if necessary) with a vinyl monomer and / or vinyl copolymer unit.

(4) A hybrid resin component is produced by adding a vinyl monomer and / or a polyester monomer (alcohol, carboxylic acid) in the presence of these polymer units after producing the vinyl copolymer unit and the polyester unit. To be done. Also in this case,
Organic solvents can be used.

(5) After producing the hybrid resin component, a vinyl-based monomer unit and / or a polyester monomer (alcohol, carboxylic acid) is added to carry out addition polymerization and / or polycondensation reaction to obtain a vinyl-based copolymer unit and A polyester unit is manufactured. In this case, as the hybrid resin component, those manufactured by the above-mentioned manufacturing methods (2) to (4) can be used, and those manufactured by a known manufacturing method can be used as necessary. Furthermore, an organic solvent can be appropriately used.

(6) By mixing a vinyl-based monomer and a polyester monomer (alcohol, carboxylic acid, etc.) and continuously performing addition polymerization and polycondensation reaction, a vinyl-based copolymer unit, a polyester unit and a hybrid resin component are obtained. Manufactured. Furthermore, an organic solvent can be appropriately used.

In the above production methods (1) to (5), the vinyl-based copolymer unit and / or the polyester unit may be a plurality of polymer units having different molecular weights and crosslinking degrees.

The binder resin contained in the toner of the present invention is a mixture of the above polyester and vinyl copolymer, a mixture of the above hybrid resin and vinyl copolymer, the above polyester resin and the above hybrid resin. In addition to this, a mixture of vinyl-based copolymers may be used.

The glass transition temperature of the binder resin contained in the toner of the present invention is preferably 40 to 90 ° C, more preferably 45 to 85 ° C. The acid value of the resin is 1-40mgKO
It is preferably H / g.

Next, the wax used in the present invention will be described.

The toner of the present invention preferably contains one or more waxes. Further, the wax is 0.5 to 10 parts by mass per 100 parts by mass of the binder resin,
It is preferable to use 2 to 8 parts by mass.

Examples of the wax used in the present invention include low molecular weight polyethylene, low molecular weight polypropylene,
Aliphatic hydrocarbon waxes such as microcrystalline wax and paraffin wax, and oxides of aliphatic hydrocarbon waxes such as oxidized polyethylene wax, or block copolymers thereof; carnauba wax, sazol wax, montanic acid ester wax And waxes containing a fatty acid ester as a main component, and deoxidized fatty acid esters such as deoxidized carnauba wax.

Further, saturated straight-chain fatty acids such as palmitic acid, stearic acid and montanic acid; unsaturated fatty acids such as blancinic acid, eleostearic acid and varinaric acid;
Saturated alcohols such as stearyl alcohol, aralkyl alcohol, behenyl alcohol, carnaubayl alcohol, ceryl alcohol, and melissyl alcohol; polyhydric alcohols such as sorbitol; fatty acid amides such as linoleic acid amide, oleic acid amide, and lauric acid amide; Saturated fatty acid bisamides such as methylenebisstearic acid amide, ethylenebiscapric acid amide, ethylenebislauric acid amide, hexamethylenebisstearic acid amide; ethylenebisoleic acid amide,
Unsaturated fatty acid amides such as hexamethylene bisoleic acid amide, N, N'dioleyl adipamide, N, N'dioleyl sebacic acid amide; m-xylene bisstearic acid amide, N, N 'distearyl isophthalic acid Aromatic bisamides such as amides; calcium stearate, calcium laurate, zinc stearate,
Aliphatic metal salts such as magnesium stearate (generally referred to as metallic soap); Waxes obtained by grafting aliphatic hydrocarbon waxes with vinyl monomers such as styrene and acrylic acid; behenic acid monoglyceride, etc. Partial esterification products of fatty acids and polyhydric alcohols; and methyl ester compounds having a hydroxyl group obtained by hydrogenation of vegetable oils and the like.

As the wax particularly preferably used in the present invention, an aliphatic hydrocarbon wax can be mentioned. For example, a low molecular weight alkylene polymer obtained by radically polymerizing alkylene under a high pressure or a Ziegler catalyst under a low pressure; an alkylene polymer obtained by thermally decomposing a high molecular weight alkylene polymer; a synthesis gas containing carbon monoxide and hydrogen; A synthetic hydrocarbon wax obtained from the distillation residue of hydrocarbon obtained by the method or obtained by hydrogenating these is preferable. Further, the one in which the hydrocarbon wax is fractionated by the use of press sweating method, solvent method, vacuum distillation or fractional crystallization method is more preferably used. Hydrocarbons as a base are those synthesized by the reaction of carbon monoxide and hydrogen using a metal oxide catalyst (often two or more multi-component catalysts) [eg, gintol method, hydrocoal method (fluid catalyst bed Hydrocarbon compounds synthesized by the use)]; Hydrocarbons having up to several hundred carbons obtained by the Arge method (using an identification catalyst bed) in which a lot of waxy hydrocarbons are obtained; Alkylene such as ethylene by Ziegler catalyst The polymerized hydrocarbon is preferable because it is a straight chain hydrocarbon having little branching, small size, and long saturation. A wax synthesized by a method that does not rely on the polymerization of alkylene is particularly preferable because of its molecular weight distribution.

In the molecular weight distribution of the wax, the main peak is preferably in the region of molecular weight 400 to 2400, and more preferably in the region of 430 to 2000. By having such a molecular weight distribution, preferable thermal characteristics can be imparted to the toner.

Further, the melting point of the wax is preferably 60 to 110 ° C., and more preferably 65 to 100 ° C. so that the wax functions more effectively at the time of fixing the toner.

The wax is usually contained in the binder resin by a method of dissolving the resin in a solvent, raising the temperature of the resin solution, and adding and mixing while stirring, or a method of mixing at the time of kneading.

Next, the colorant (pigment) used in the present invention will be described.

Pigmen represented by the following general formula (1)
t Yellow-180 shows a vivid yellow color, and when this is used as a colorant for toner, a toner having high coloring power is obtained.

[0077]

[Chemical 6]

The inventors of the present invention have made earnest studies on a yellow toner having excellent light resistance, high lightness and saturation, and wide color reproducibility, which is in agreement with the yellow hue of the process ink. When the compound represented by the general formula (1) alone or the compound represented by the following general formula (2) is mixed in a specific mass ratio and uniformly dispersed, a toner having a good hue may be obtained. I found it.

[0079]

[Chemical 7]

With pigments other than the compound represented by the general formula (1), compatibility with light resistance is impossible even if the tint can be adjusted. The compounds represented by the general formulas (1) and (2) both have good dispersibility in a binder resin designed for the purpose of oilless fixing,
Excellent HT transparency.

Solvent represented by the general formula (2)
Yellow 162 is a dye used in various fields. This dye is excellent in transparency but inferior in light resistance, so that it is not suitable for full color by itself. However, when it is used in combination with the compound represented by the general formula (1), it can be matched with the yellow color tone of the target process ink.

In the present invention, the mass ratio of the compound represented by the general formula (1) to the compound represented by the general formula (2) is 9
5: 5 to 70:30, preferably 90:10 to 7
It is 5:25. When the ratio of the compound represented by the general formula (2) is more than 30, the light resistance of the toner is deteriorated,
In addition, the color tone largely shifts to green, and as described above, in the case of a color image, it is the three primary colors of the color material.
Since the colors are reproduced with three colors of yellow, magenta, and cyan or four colors with black added thereto, if the color tone of yellow is largely shifted to green, the reproducibility of the skin color system is greatly reduced, which is not preferable. .

In the toner of the present invention, the general formula (1) is used.
Or a total of the compound represented by the general formula (1) and the compound represented by the general formula (2) is 2 to 15 parts by mass, preferably 2.5 parts by mass with respect to 100 parts by mass of the binder resin. To 12 parts by mass, more preferably 3 to 10 parts by mass. When the total content of the compound represented by the general formula (1) or the compound represented by the general formula (1) and the compound represented by the general formula (2) is less than 2 parts by mass, the coloring power of the toner is It is difficult to obtain a high-quality image having a high image density, no matter how much the pigment dispersibility is improved. If the amount is more than 15 parts by mass, the transparency of the toner is deteriorated and the transparency is deteriorated. The transparency will decrease. In addition, the reproducibility of intermediate colors, which is typified by human skin tones, also deteriorates. Further, the chargeability of the toner becomes unstable, which causes problems such as fogging in a low temperature and low humidity environment and toner scattering in a high temperature and high humidity environment.

The compound represented by the general formula (1) and the compound represented by the general formula (2) both show excellent dispersibility,
No detachment from the toner surface is observed, and various problems such as fog, drum contamination, and poor cleaning are not caused. Further, even when the toner is used as a two-component developer, it does not cause a problem such as carrier contamination and exhibits stable charging characteristics in long-term durability.

Further, the toner of the present invention has excellent light resistance,
The image sample is a JIS K
Almost according to 7102, even when a long-term exposure test was performed, almost no color change was observed.

The toner of the present invention preferably contains a metal compound of an aromatic carboxylic acid or its derivative. This not only functions as a charge control agent, but also contributes to improving the dispersibility of the compounds represented by the general formulas (1) and (2).

Although the reason why the metal compound of the aromatic carboxylic acid or its derivative improves the dispersibility of the pigment is not clear, it is partly due to the interaction between the binder resin and the metal compound of the aromatic carboxylic acid or its derivative. The crosslinking reaction proceeds,
It can be considered that the dispersibility of the hardly dispersible pigments of the general formula (1) and the general formula (2) is increased by increasing the share of the colorant at the time of kneading.

Examples of the aromatic carboxylic acid include the following three compounds (4) to (6).

[0089]

[Chemical 8]

[Wherein, R _{1 to} R ₇ represent the same or different groups, and are a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, —OH, —NH ₂ , —NH
_{(CH 3), - N (} CH 3) 2, -OCH 3, -O (C
₂ H _5), - shows a COOH or -CONH _2. ]

Preferred R ₁ is a hydroxyl group,
An amino group and a methoxy group are mentioned, and a hydroxyl group is preferable among them. As the aromatic carboxylic acid, a dialkyl salicylic acid such as di-tert-butyl salicylic acid is particularly preferable.

As the metal forming the metal compound, Mg
²⁺, Ca²⁺, Sr²⁺, Pb²⁺, Fe ²⁺, Co²⁺, N
i²⁺, Zn²⁺, Cu²⁺, Al³⁺, Cr³⁺, Fe³⁺, Zr
⁴⁺Can be given. In the present invention, as a metal compound
Aluminization of di-tert-butylsalicylic acid
Compounds are preferred.

The metal compound of an aromatic carboxylic acid or its derivative is, for example, an aromatic carboxylic acid or its derivative dissolved in an aqueous solution of sodium hydroxide, and an aqueous solution in which a divalent or higher valent metal atom is melted is an aqueous solution of sodium hydroxide. Then, the pH of the aqueous solution is adjusted, the solution is cooled to room temperature and then filtered and washed with water to synthesize a metal compound of an aromatic carboxylic acid or a derivative thereof. However, the synthesis method is not limited to the above.

The metal compound of the aromatic carboxylic acid or its derivative is preferably 0.5 per 100 parts by mass of the binder resin.
It is preferable to use 10 to 10 parts by mass, more preferably 1 to 9 parts by mass, and further preferably 1.5 to 8 parts by mass from the viewpoint of adjusting the viscoelastic property and triboelectric charging property of the toner. 0.5
When the amount is less than the amount by mass, not only the charge control agent does not function well, but also good pigment dispersibility tends to be unachievable. On the other hand, when the amount is more than 10 parts by mass, crosslinking tends to proceed too much, and the fixability as a toner tends to be impaired.

In the toner of the present invention, a compound other than the above-mentioned metal compound of the aromatic carboxylic acid or its derivative may be used as a charge control agent, if necessary, in order to further stabilize its chargeability.

To prepare the yellow toner particles used in the present invention, a binder resin, a pigment as a colorant, a wax, and if necessary, a charge control agent and other additives are mixed with a mixer such as a ball mill. After thoroughly mixing, use a heat kneader such as a heating roll, kneader, or extruder to melt / knead and knead the meat to make the resins compatible with each other, and disperse the pigment in it. It is possible to obtain yellow toner particles by performing various classifications.

In order to improve the dispersion state of the pigment particles in the yellow toner particles, the first binder resin and the paste pigment containing 5 to 50% by mass of the pigment particles insoluble in the dispersion medium are kneaded. In a mixing machine or a mixer, and heating while mixing under non-pressurization to melt the first binder resin, the paste pigment (that is, the pigment in the liquid phase) is mixed with the heated first binder resin. After transferring to the molten resin phase, the first binder resin and the pigment particles are melt-kneaded, the liquid content is removed and evaporated to dryness, and the first kneaded material having the first binder resin and the pigment particles is obtained. Then, the mixture obtained by adding the second binder resin to the first kneaded product and, if necessary, an additive such as a charge control agent, is melt-kneaded by heating to obtain a second kneaded product. It is preferable that the second kneaded product is cooled and then pulverized and classified to form a toner. Here, the first binder resin and the second binder resin may be the same or different resins.

In the paste pigment, it is desirable that the pigment particles exist in the pigment particle manufacturing step without any drying step. In other words, the pigment particles are in the state of almost primary particles in an amount of 5 to 50 mass% with respect to all the paste pigments. The remaining 50 to 95% by mass of the paste pigment is mostly volatile liquid together with some dispersants and auxiliaries. The volatile liquid is
There is no particular limitation as long as it is a liquid that evaporates by general heating, but the liquid that is preferably used in terms of ecology is water.

Examples of the kneading device include a heating kneader, a single-screw extruder, a twin-screw extruder, and a kneader.
A heating kneader is particularly preferable.

The yellow toner of the present invention preferably has a weight average particle diameter of 4 to 10 μm. The yellow toner of the present invention has a number average particle diameter of 3.5 to 9.5 μm.
And the particle size of the yellow toner is 4 μm in the number distribution.
The following particles are preferably 5 to 50% by number, and the particles having a particle size of 12.70 μm or more in the volume distribution of the yellow toner are preferably 5% by volume or less.

When the weight average particle diameter of the toner is larger than 10 μm or the number average particle diameter is larger than 9.5 μm, it means that there are few fine particles that can contribute to high image quality, and high image density is easily obtained. Although it has the advantage that the toner has excellent fluidity, it is difficult to faithfully adhere to the fine electrostatic image on the photosensitive drum, the reproducibility of the highlight part decreases, and the resolution also tends to decrease. is there. Further, there is a tendency that the toner excessively rides on the electrostatic charge image more than necessary, resulting in an increase in toner consumption.

On the contrary, when the weight average particle diameter of the toner is smaller than 4 μm or the number average particle diameter is smaller than 3.5 μm, the charge amount per unit mass of the toner becomes high and the image density is lowered, especially under low temperature and low humidity. The image density tends to decrease remarkably. This is not suitable for applications with a high image area ratio such as graphic images. Further, contact charging with a charge-imparting member such as a carrier is difficult to be performed smoothly, the amount of toner that cannot be sufficiently charged increases, and fogging due to scattering to non-image areas tends to be noticeable. In order to deal with this, it may be possible to reduce the diameter of the carrier in order to increase the specific surface area of the carrier, but the weight average diameter is 4
In the case of a toner having a particle size smaller than μm or a number average particle size smaller than 3.5 μm, toner self-aggregation easily occurs, uniform mixing with a carrier is difficult to be achieved in a short time, and fog occurs in continuous replenishment durability of toner. Tends to end.

In the toner of the present invention, it is preferable that the toner particles having a particle diameter of 4 μm or less account for 5 to 50% by number, preferably 5 to 25% by number of the total number of particles. If the number of toner particles having a particle size of 4 μm or less is less than 5% by number, it means that there are few fine toner particles that are essential components for high image quality. As it is continuously used, the effective toner particle component decreases, the balance of the toner particle size distribution shown in the present invention deteriorates, and the image quality tends to gradually deteriorate. In addition, toner particles having a particle diameter of 4 μm or less are 50% by number.
If it exceeds, the toner particles are likely to aggregate with each other, and the toner particles often behave as toner particles having a particle size larger than the original particle size, and as a result, a rough image is easily formed and the resolution is lowered, Alternatively, the density difference between the edge portion and the inside of the electrostatic charge image becomes large, and the image tends to be a hollow image.

Further, in order to improve image quality, it is preferable that particles having a particle diameter of 12.70 μm or more be 5% by volume or less.

Further, it is preferable that the fluidity improver is externally added to the toner particles of the present invention from the viewpoints of image quality improvement and storability in a high temperature environment. As the fluidity improver, inorganic fine powder such as silica, titanium oxide, aluminum oxide is preferable. The inorganic fine powder is preferably hydrophobized with a hydrophobizing agent such as a silane coupling agent, silicone oil, or a mixture thereof.

Examples of the hydrophobizing agent include coupling agents such as a silane coupling agent, a titanate coupling agent, an aluminum coupling agent and a zircoaluminate coupling agent.

Specifically, for example, as the silane coupling agent, those represented by the general formula (7) are preferable.

R _m SiY _n (7)

[In the formula, R represents an alkoxy group, and m is 1
To 3 are shown, Y shows an alkyl group, a vinyl group, a phenyl group, a methacryl group, an amino group, an epoxy group, a mercapto group, or these derivatives, and n shows an integer of 1-3. ]

For example, vinyltrimethoxysilane, vinyltriethoxysilane, γ-methacryloxypropyltrimethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, isobutyltrimethoxysilane,
Dimethyldimethoxysilane, dimethyldiethoxysilane, trimethylmethoxysilane, hydroxypropyltrimethoxysilane, phenyltrimethoxysilane, n-
Hexadecyltrimethoxysilane, n-octadecyltrimethoxysilane, etc. can be mentioned.

The treatment amount is preferably 1 to 60 parts by mass, more preferably 3 parts by mass, relative to 100 parts by mass of the inorganic fine powder.
˜50 parts by mass.

Particularly preferred in the present invention is an alkylalkoxysilane coupling agent represented by the general formula (8). During _{C n H 2n + 1 -Si- (} OC m H 2m + 1) 3 (8) [wherein, n represents an integer of 4 to 12, m is an integer of 1-3. ]

In the alkylalkoxysilane coupling agent, when n is smaller than 4, the treatment is easy but the degree of hydrophobicity is low, which is not preferable. When n is greater than 12, the hydrophobicity is sufficient, but the titanium oxide fine particles are often coalesced with each other, so that the fluidity-imparting ability is likely to decrease. When m is larger than 3, the reactivity of the alkylalkoxysilane coupling agent is reduced, and it becomes difficult to favorably make hydrophobic.
More preferably, the alkylalkoxysilane coupling agent has n of 4 to 8 and m of 1 to 2.

The treatment amount of the alkylalkoxysilane coupling agent is also preferably 1 to 60 parts by mass, more preferably 3 to 50 parts by mass with respect to 100 parts by mass of the inorganic fine powder.

The hydrophobizing treatment may be carried out by using one kind of hydrophobizing agent alone, or by using two or more kinds of hydrophobizing agents.
For example, one type of coupling agent may be used alone for hydrophobic treatment, or two types of coupling agents may be used for hydrophobic treatment at the same time, or after another type of coupling agent is used for hydrophobic treatment, another coupling agent may be used for further hydrophobic treatment. You may perform a conversion process.

The fluidity improver is preferably added in an amount of 0.01 to 5 parts by mass with respect to 100 parts by mass of the toner particles.
It is more preferable to add 0.05 to 3 parts by mass.

The yellow toner of the present invention can be applied to a one-component type developer and a two-component type developer, and is not particularly limited thereto, but the yellow toner of the present invention can be used as a two-component type developer. When used for, the carrier used in combination can be, for example, surface-oxidized or non-oxidized iron, nickel, copper, zinc, cobalt, manganese, chromium, rare earth metals, and alloys thereof or oxides and ferrites. .

In particular, magnetic ferrite particles of three elements of Mn-Mg-Fe formed by using manganese, magnesium and iron as main components are preferable as carrier particles. The magnetic carrier particles are preferably coated with a resin, and the resin is preferably a silicone resin. In particular, a nitrogen-containing silicone resin or a modified silicone resin produced by reacting a nitrogen-containing silane coupling agent with a silicone resin is used to impart a negative triboelectric charge to the yellow toner of the present invention, environmental stability, and carrier. It is preferable in terms of suppressing the contamination of the surface of the.

The magnetic carrier has an average particle size of 15 to 60.
μm (more preferably 25 to 50 μm) is preferable in relation to the weight average particle diameter of the yellow toner. As a method for preparing the magnetic particles so as to have the above-mentioned average particle size and specific particle size distribution, for example, classification can be performed by using a sieve. In particular, in order to carry out classification with high accuracy, it is preferable to repeat the sieving a plurality of times by using a sieve having an appropriate opening. It is also an effective means to use a mesh whose opening shape is controlled by plating or the like.

When a two-component developer is prepared, good results are usually obtained when the mixing ratio is 2 to 15% by mass, preferably 4 to 13% by mass as the toner concentration in the developer. If the toner concentration is less than 2% by mass, the image density tends to be low, and if it exceeds 15% by mass, fog or in-machine scattering tends to increase.

Next, the measuring methods of each physical property will be described below.

<Measurement Method of Viscoelasticity of Toner> The toner is pressure molded into a disk-shaped sample having a diameter of 8 mm and a thickness of about 2 to 3 mm. Next, set on the parallel plate and
The temperature is gradually raised within the temperature range of ° C to measure the temperature dispersion. The temperature rising rate is 2 ° C./min, the angular frequency (ω) is fixed at 6.28 rad / sec, and the strain rate is automatic.
The temperature is plotted on the horizontal axis and the storage elastic modulus (G ') is plotted on the vertical axis, and the value at each temperature is read. For measurement, RDA-I
I (Rheometrics) is used. tan δ = storage viscosity (G ″) / storage elastic modulus (G ′)

<Method of measuring endothermic peak of toner> The toner endothermic peak is measured according to ASTM D3418-82 using a differential scanning calorimeter (DSC measuring device), DSC-7 (manufactured by Perkin Elmer Co., Ltd.). The measurement sample is 2 to 10 mg, preferably 5
Precisely weigh mg. This is placed in an aluminum pan, and an empty aluminum pan is used as a reference, and measurement is performed at a temperature rising rate of 10 ° C./min at a measurement temperature range of 30 to 200 ° C. under normal temperature and normal humidity. During this temperature raising process, the temperature of 30 to 20
The endothermic peak of the main peak of the DSC curve in the range of 0 ° C is obtained.

<GPC measurement> The molecular weight of the chromatogram by gel permeation chromatography (GPC) is measured under the following conditions.

The column was stabilized in a heat chamber at 40 ° C., and tetrahydrofuran (THF) as a solvent was passed through the column at this temperature at a flow rate of 1 ml / min to adjust the sample concentration to 0.05 to 0.6 mass%. About 50 to 200 μl of a THF sample solution of the resin is injected and measured.

When measuring the molecular weight of the sample,
The molecular weight distribution of various monodisperse polystyrene standard samples
Logarithmic value and count number (retention
Calculation time). Standard for creating a calibration curve
As the quasi-polystyrene sample, for example, manufactured by Tosoh Corporation or
Pressure Chemical Co. Made of molecules
The amount is 6 × 10², 2.1 x 10³4 x 10³1.75
× 10^Four5.1 × 10 ^Four, 1.1 x 10^Five3.9 x 1
0^Five, 8.6 × 10^Five2 x 10⁶4.48 × 10⁶Nomono
Of at least 10 standard polystyrene samples
It is appropriate to use a fee. RI (refractive index) for the detector
Use a detector.

As the column, a plurality of commercially available polystyrene gel columns are preferably combined in order to accurately measure the molecular weight region of 10 ³ to 2 × 10 ⁶ , and for example, Shodex GPC KF-801 manufactured by Showa Denko KK 80
2, 803, 804, 805, 806, 807 combinations and Waters μ-styragel 50
A combination of 0, 10 ³ , 10 ⁴ and 10 ⁵ can be mentioned.

<Measurement of Toner Particle Size Distribution> In the present invention, the average particle size and particle size distribution of the toner are measured by using Coulter Counter TA-II type (manufactured by Coulter Co.).
It is also possible to use Coulter Multisizer (manufactured by Coulter). As the electrolytic solution, a 1% NaCl aqueous solution is prepared using first grade sodium chloride. For example, ISOTO
NR-II (manufactured by Coulter Scientific Japan) can be used. As a measuring method, a surfactant, preferably an alkylbenzene sulfonate, as a dispersant is added in an amount of 0.1 to 5 in 100 to 150 ml of the electrolytic aqueous solution.
ml, and 2 to 20 mg of the measurement sample is further added. The electrolytic solution in which the sample is suspended is subjected to a dispersion treatment for about 1 to 3 minutes by an ultrasonic disperser, and 100 is used as an aperture by the measuring device.
The volume distribution and the number distribution were calculated by measuring the volume and number of toner particles having a size of 2.00 μm or more using a μm aperture. Then, the weight-based weight average particle diameter (D4) (the median value of each channel is used as a representative value for each channel) determined from the volume distribution according to the present invention was determined.

The channels are 2.00 to 2.52.
μm; 2.52 to 3.17 μm; 3.17 to 4.00 μm
m; 4.00 to 5.04 μm; 5.04 to 6.35 μ
m; 6.35 to 8.00 μm; 8.00 to 10.08 μm
m; 10.08-12.70 μm; 12.70-16.
00 μm; 16.0-20.20 μm; 20.20
25.40 μm; 25.40-32.00 μm; 32.
13 channels of 00-40.30 μm are used.

[0130]

EXAMPLES Hereinafter, specific examples of the present invention will be described, but the present invention is not limited to these examples.

(Hybrid Resin Production Example 1) Styrene 1.9 mol, 2-ethylhexyl acrylate 0.2
1 mol, fumaric acid 0.15 mol, α-methylstyrene dimer 0.03 mol, and dicumyl peroxide 0.05 mol are placed in a dropping funnel.

In addition, polyoxypropylene (2.2)-
2,2-bis (4-hydroxyphenyl) propane 7.
0 mol, polyoxyethylene (2.2) -2,2-bis (4-hydroxyphenyl) propane 3.0 mol,
Terephthalic acid 3.0 mol, trimellitic anhydride 2.0
mol, fumaric acid 5.0 mol and dibutyltin oxide 0.
2 g was placed in a glass 4-liter four-necked flask, a thermometer, a stirring rod, a condenser and a nitrogen introducing tube were attached and placed in a mantle heater.

Next, after replacing the inside of the flask with nitrogen gas,
The temperature was gradually raised while stirring, and the vinyl copolymer monomer, the crosslinking agent, and the polymerization initiator were added dropwise from the above dropping funnel over 4 hours while stirring at a temperature of 145 ° C. Then 2
The temperature was raised to 00 ° C. and the reaction was carried out for 4 hours to obtain a hybrid resin (1). The results of molecular weight measurement by GPC are shown in Table 1.

(Hybrid Resin Production Example 2) Styrene 3.8 mol, α-methylstyrene dimer 0.07 m
except that 0.1 mol of diol and dicumyl peroxide were used, a reaction was performed in the same manner as in Hybrid Resin Production Example 1 to obtain a hybrid resin (2). The results of molecular weight measurement by GPC are shown in Table 1.

(Hybrid Resin Production Example 3) 4.0 mol of maleic acid and 3.5 mol of itaconic acid were used in place of 5.0 mol of fumaric acid, and 0.1 mol of isobutyl peroxide was used instead of 0.05 mol of dicumyl peroxide. A hybrid resin (3) was obtained by carrying out the reaction in the same manner as in Hybrid Resin Production Example 1 except that was used. The results of molecular weight measurement by GPC are shown in Table 1.

(Hybrid Resin Production Example 4) Instead of 3.0 mol of terephthalic acid and 2.0 mol of trimellitic anhydride, trimellitic anhydride of 5.2 mol was used and reacted in the same manner as in Hybrid Resin Production Example 1 to prepare a hybrid resin (4 ) Got. The results of molecular weight measurement by GPC are shown in Table 1.

(Polyester Resin Production Example 1) Polyoxypropylene (2.2) -2,2-bis (4-hydroxyphenyl) propane 3.6 mol, polyoxyethylene (2.2) -2,2-bis ( 4-hydroxyphenyl)
Propane 1.6 mol, terephthalic acid 1.7 mol, trimellitic anhydride 1.1 mol, fumaric acid 2.4 mol
And 0.1 g of dibutyltin oxide in 4 liters of glass
The flask was placed in a one-necked flask, and a thermometer, a stirring rod, a condenser, and a nitrogen introducing tube were attached and placed in a mantle heater.
Under a nitrogen atmosphere, the reaction was carried out at 215 ° C. for 5 hours to obtain a polyester resin (5). The results of molecular weight measurement by GPC are shown in Table 1.

(Polyester Resin Production Example 2) 1.6 mol of polyoxypropylene (2.2) -2,2-bis (4-hydroxyphenyl) propane, polyoxyethylene (2.2) -2,2-bis ( 4-hydroxyphenyl)
Propane 3.3 mol, terephthalic acid 1.6 mol, trimellitic anhydride 0.3 mol, fumaric acid 3.2 mol
With the above monomer composition, the reaction was performed in the same manner as above to obtain a polyester resin (6). The results of molecular weight measurement by GPC are shown in Table 1.

(Production Example 1 of vinyl-based copolymer) 2.2 mol of styrene, 0.2 of 2-ethylhexyl acrylate
3 mol, 0.08 mol of dicumyl peroxide and 3.2 g of dibutyltin oxide were placed in a 3 liter four-necked flask equipped with a thermometer, a stainless steel stirring rod, a downflow condenser and a nitrogen introducing tube, and placed in a mantle heater. Then, the reaction was performed in a nitrogen atmosphere at a temperature of 225 ° C. with stirring to obtain a vinyl-based copolymer (7). The results of molecular weight measurement by GPC are shown in Table 1.

[0140]

[Table 1]

The waxes used in the present invention are listed in Table 2.

[0142]

[Table 2]

<Example 1> Yellow toner 1 was prepared by the following method.

[0144]   (First kneading step) ・ Hybrid resin (1) 70 parts by mass -Removing water to some extent from the pigment slurry containing compound (1), even once The first paste-like pigment having a solid content of 30 mass% obtained without undergoing a drying step (the remaining 70 pigments). 100% by weight

The above raw materials having the above formulation are first charged into a kneader type mixer, and the temperature is raised without pressure while mixing. When the maximum temperature (which is inevitably determined by the boiling point of the solvent in the paste, in this case about 90 to 100 ° C.), the pigment in the water phase is distributed or transferred to the molten resin phase, and this is confirmed. After that, the mixture is heated and melt-kneaded for another 30 minutes to sufficiently transfer the pigment in the paste. Then, once the mixer is stopped and hot water is discharged, another 1
The temperature was raised to 30 ° C., and the mixture was heated and melt-kneaded for about 30 minutes to disperse the pigment and distill off water, and after the step was finished, the mixture was cooled and the kneaded product was taken out to obtain a first kneaded product. The water content of the first kneaded product was about 0.5% by mass.

[0146]   (Second kneading step) -The above-mentioned first kneaded product (content of pigment particles: 30% by mass) 20.0 parts by mass ・ Hybrid resin (1) 86.0 parts by mass ・ Wax (A) 5.0 parts by mass .Aluminium compound of di-tert-butylsalicylic acid (charge control agent)                                                             5.0 parts by mass

The above formulation was sufficiently premixed with a Henschel mixer, and the temperature was raised to 100 ° C. with a twin-screw extrusion kneader.
Set to 1, melt and knead, cool, and then use a hammer mill to approximately 1
Coarsely pulverized to about 2 mm, and then finely pulverized to a particle size of 20 μm or less by an air jet type fine pulverizer. Further, the obtained finely pulverized product was classified, and selected so that the volume average diameter in the particle size distribution was 7.2 μm to obtain yellow toner particles (classified product).

Hydrophobic aluminum oxide (BET 170 m ² / g) treated with i-C ₄ H ₉ Si (OCH ₃ ) ₃ : 25 parts by mass for the purpose of improving fluidity and imparting charging characteristics.
Was combined with 100 parts by weight of the above yellow toner particles (classified product) to obtain yellow toner 1.

Further, yellow toner 1 and magnetic ferrite carrier particles surface-coated with a silicone resin (average particle diameter 45 μm) are mixed so as to have a toner concentration of 7% by mass, and two-component yellow developer 1 is obtained. did.

Table 3 shows the measurement results of the toner.

With this yellow developer 1, a color copying machine C
Using a modified machine in which the oil application mechanism of the fixing unit of LC-800 (manufactured by Canon) is removed, in a single-color mode, at room temperature and low humidity environment (23 ° C / 5%), high temperature and high humidity environment (30 ° C /
80%) and an original document with an image area ratio of 20%, a printing durability test of 10,000 sheets and a normal temperature and humidity environment (23 ° C / 6
The fixing test was conducted at 0%). Further, for the evaluation of the feasible area, the fusing unit was modified so that the fusing temperature could be set manually.

A yellow-color image faithfully reproducing the original without fog was obtained even after running 10,000 sheets, and the color reproducibility was excellent. Conveyance in the copying machine and detection of developer concentration were also good, and stable image density was obtained. Fixing temperature setting 170
No offset to the fixing roller occurred even after repeated copying of 10,000 sheets at ℃. The occurrence of offset on the fixing roller was determined by visually observing the surface of the fixing roller after repeated copying.

As a method of evaluating a color copy image, there is a method of determining the quality of a color image by measuring the gloss (glossiness) of the image surface. That is, it is determined that the higher the gloss value is, the smoother and glossy color quality the image surface has, and conversely, the lower the gloss value, the more the image surface with dull saturation is blurred. In Example 1, the image density at a contrast potential of 300 V was 1.70 (Macbeth reflection density), and the gloss at that time was 21%.

For the measurement of gloss (glossiness), a PG-3 type gloss meter manufactured by Nippon Denshoku Co., Ltd. was used. In the measurement, the light emitting angle and the light receiving angle are adjusted to 75 °, 0 point adjustment and standard plate are used, and after the standard setting, three blank sheets are stacked on the sample table, and the sample image is placed on it. Was carried out and the numerical value shown in the marking part was read in%.

The target chromaticity of the obtained image was obtained. That is, a * =-0.4, b * = 113, L *
= 89.0.

The color tone of the toner was quantitatively measured based on the definition of the color system standardized by the International Commission on Illumination (CIE) in 1976. At that time, the image density is fixed at 1.70,
a *, b * (a *, b * are chromaticities indicating hue and saturation), L
* (Brightness) was measured. An X-Rite spectrophotometer type 938 was used as a measuring instrument, a light source for observation was a C light source, and a viewing angle was 2 °.

Furthermore, the color image formed on the transparency film is transferred to an overhead projector (O
The transparency of the OHT image projected on HP) was also good.

The transparency of the OHT images in the above examples was evaluated by projecting a color image formed on a transparency film by using a commercially available overhead projector and based on the following evaluation criteria.

(Evaluation Criteria) A: Excellent transparency, no uneven brightness and excellent color reproducibility (good). Δ: Although there is slight unevenness in brightness and darkness, there is no problem in practical use (OK). X: There is uneven brightness, and color reproducibility is poor (impossible).

The light fastness of the obtained solid image (image density 1.70) was confirmed in accordance with JIS K7102, and the image after 400 hours of light irradiation had the same image density (1.66) as in the initial stage. As shown, almost no change in hue was observed (ΔE = 2.8). A carbon arc lamp was used as the light source. The light resistance was evaluated quantitatively by determining the ΔE value from the images before and after light irradiation.

(Light resistance rank) ◯: Almost no change in 400-hour test. Δ: Almost no change in 200-hour test. X: Discolored in the 100-hour test.

As a result of examining the storage stability of the yellow toner 1, good data were shown. That is, the blocking resistance of the sample toner was evaluated by leaving it in an oven at 50 ° C. for 2 weeks. The evaluation was based on the level of visual agglutination.

(Evaluation criteria for blocking resistance) ◯: Aggregates are not seen at all and fluidity is very good. Δ: Some agglomerates are seen, but they loosen immediately. X: Aggregates are not sufficiently loosened in the developer stirring device.

Instead of the pigment used in Yellow Toner 1,
Copper phthalocyanine cyan pigment (Pigment B
15: 3), a soluble azo magenta pigment (Pig)
ment Red 57: 1) and the same procedure as above for cyan toner 1 and magenta toner 1 respectively.
Was prepared, and a developer was prepared and an image was formed in substantially the same manner. When the reproduction of the secondary colors of red and blue was observed, an image with a good hue having both high saturation and lightness was obtained.

<Examples 2 to 5> Hybrid resin (1)
In the same manner as in Example 1 except that the hybrid resin (2), the hybrid resin (3), the polyester resin (5), and the vinyl copolymer (7) were used instead of the yellow toner 2 to 5 was produced, and yellow developers 2 to 5 were obtained in the same manner. The results are shown in Table 3.

Example 6 A yellow toner 6 was prepared in the same manner as in Example 1 except that the wax (A) was used in place of the wax (A), and the yellow developer was prepared in the same manner. Got 6. The results are shown in Table 3.

Example 7 A yellow toner 7 was prepared in the same manner as in Example 1 except that the wax (D) was used instead of the wax (A). Got 7. The results are shown in Table 3.

Example 8 In Example 1, except that the hybrid resin (1) was replaced by the hybrid resin (2) and the wax (A) was replaced by the wax (C). After that, a yellow toner 8 was produced in the same manner, and a yellow developer 8 was obtained in the same manner. The results are shown in Table 3.

Blocking resistance was poor and was at a practical level. In the fixing test, the offset generation temperature on the high temperature side was the same as that of the yellow toner 1 described in Example 1.
The temperature was about 40 ° C. lower than that, but was within the practical level.

Example 9 Except that in Example 1, the hybrid resin (1) was replaced by the hybrid resin (2) and the wax (A) was replaced by the wax (E). After that, a yellow toner 9 was produced in the same manner, and a yellow developer 9 was obtained in the same manner. The results are shown in Table 3.

The yellow toner 9 had a tendency that the transparency of the OHT slightly deteriorated due to the influence of the crystallinity of the wax, and the fixing property on the low temperature side deteriorated, but it was within the practical level.

<Embodiment 10> In Embodiment 1, the g-t
A yellow toner 10 was prepared in the same manner except that the amount of the aluminum ert-butylsalicylate compound was reduced to 2 parts by mass, and a yellow developer 10 was obtained in the same manner. The results are shown in Table 3.

Although the blocking resistance was slightly deteriorated, it was not at a level causing a problem in practical use.

<Embodiment 11> In the embodiment 1, the g-t
Yellow toner 11 was used in the same manner except that 4 parts by mass of a zinc compound of ert-butylsalicylic acid was used.
Was prepared, and in the same manner, a yellow developer 11 was obtained. The results are shown in Table 3.

Although the blocking resistance was slightly deteriorated, it was not at a level causing a problem in practical use. In the fixing test, the offset generation temperature on the high temperature side was about 30 ° C. lower than that of the yellow toner 1 described in Example 1, but it was within the practical level.

<Example 12> In Example 1, the mixing ratio of the compound (1) and the compound (2) was finally 95: 5.
A yellow toner 12 was prepared in the same manner as described above except that a toner was prepared as described above, and a yellow developer 12 was obtained in the same manner. The results are shown in Table 3.

The chromaticity when the image density is 1.70 is as shown in Example 1.
The hue was almost the same as that of That is, the chromaticity of the image was a * =-0.3, b * = 113, and L * = 88.

<Example 13> In Example 1, the mixing ratio of the compound (1) and the compound (2) was finally 85: 1.
Yellow toner 13 was prepared in the same manner as described above except that the toner was prepared in the same manner as in No. 5, and yellow developer 13 was obtained in the same manner. The results are shown in Table 3.

The chromaticity when the image density is 1.70 is as shown in Example 1.
Although it shifted to a slightly greener color, it was within the practical level. That is, the chromaticity of the image is a * =-2.0,
b * = 111 and L * = 87.0.

<Comparative Example 1> Yellow toner 14 was prepared in the same manner except that hybrid resin (4) was used instead of hybrid resin (1), and yellow developer 14 was obtained in the same manner. The results are shown in Table 3.

The yellow toner 14 was made of a resin having a large Mw / Mn, and as a result, G'at 80 ° C. was also large and the toner was a very hard toner. With this toner, the OHT transparency was poor and the low temperature fixability was also significantly degraded.

<Comparative Example 2> Yellow toner 15 was prepared in the same manner except that polyester resin (6) was used instead of hybrid resin (1), and yellow developer 15 was obtained in the same manner. The results are shown in Table 3.

The yellow toner 15 is made of a resin having a small Mw / Mn, and as a result, G'at 120 to 180 ° C. also shows a small value, and in the fixing test, the toner was wound around the upper roller at a low temperature (140 ° C.). .

<Comparative Example 3> In Example 1, the g-te
A yellow toner 16 was produced in the same manner except that the amount of the rt-butylsalicylic acid aluminum compound was reduced to 12 parts by mass, and a yellow developer 16 was obtained in the same manner. The results are shown in Table 3.

The tan δ at 140 ° C. was also small, and the toner was very hard. With this toner, the OHT transparency was poor and the low temperature fixability was also significantly degraded.

<Comparative Example 4> In Example 1, the mixing ratio of the compound (1) and the compound (2) was finally 65: 3.
Yellow toner 17 was prepared in the same manner as described above except that the toner was prepared in the same manner as in No. 5, and yellow developer 17 was obtained in the same manner. The results are shown in Table 3.

The color tone is slightly greener than that of Yellow Toner 1, but the light resistance is greatly deteriorated.

Comparative Example 5 A yellow toner 18 was prepared in the same manner as in Example 8 except that the wax (C) was not used, and a yellow developer 18 was obtained in the same manner. The results are shown in Table 3.

Since the yellow toner 18 does not contain a wax, the offset resistance on the high temperature side is greatly reduced,
The fixability on the low temperature side also deteriorated.

<Comparative Example 6> A yellow toner 19 was prepared in the same manner as in Example 8 except that the wax (C) was increased to 12 parts, and a yellow developer 19 was obtained in the same manner. The results are shown in Table 3.

Although the yellow toner 19 has improved offset resistance on low temperature fixing and high temperature side, it has poor OHT permeability and is not at a practical level.

<Comparative Example 7> A yellow toner 20 was prepared in the same manner as in Example 1 except that the toner was prepared by using 1 part of the compound (1). Got 20. The results are shown in Table 3.

With the present toner, coloring was extremely reduced and it was not at a practical level.

<Comparative Example 8> Yellow toner 21 was prepared in the same manner as in Example 1 except that 20 parts of compound (1) was prepared as a toner.
Similarly, a yellow developer 21 was obtained. The results are shown in Table 3.

The transparency of this toner was lowered and the OHT transparency was below the practical level.

[0196]

[Table 3]

[0197]

The yellow toner of the present invention is excellent in blocking resistance, storability under high temperature environment, low temperature fixing property, high speed fixing property, high temperature offset resistance, glossiness, OHP transparency and transferability. It is possible to stably obtain high-definition and high-quality images.

Continued front page    (72) Inventor Takaaki Kaji             3-30-2 Shimomaruko, Ota-ku, Tokyo             Non non corporation (72) Inventor Takayuki Itakura             3-30-2 Shimomaruko, Ota-ku, Tokyo             Non non corporation F-term (reference) 2H005 AA01 AA06 AA21 CA02 CA08                       CA14 CA21 CA25 DA06 DA10                       EA03 EA07 EA10

Claims (6)

[Claims] 1. At least a binder resin, wax and coloring
Of a yellow toner containing an agent
Storage modulus at C (G '₈₀) Is 1 × 10 ⁶~ 1 x 1
0⁸[DN / m²] Range and loss at 140 ℃
The intercept (tan δ) is in the range of 0.2 to 1.5 and is colored
As an agent, a compound represented by the following general formula (1)
Wack containing 2 to 15 parts by mass per 100 parts by mass of fat
0.5 to 10 parts by mass per 100 parts by mass of binder resin
A yellow toner containing the yellow toner. [Chemical 1] 2. At least a binder resin, wax and coloring
Of a yellow toner containing an agent
Storage modulus at C (G '₈₀) Is 1 × 10 ⁶~ 1 x 1
0⁸[DN / m²] Range and loss at 140 ℃
The intercept (tan δ) is in the range of 0.2 to 1.5 and is colored
As an agent, a compound represented by the following general formula (1) and one of the following
Binder resin 100 in total with the compound represented by general formula (2)
2 to 15 parts by mass per part by mass, and the following general formula
A compound represented by the formula (1) and a compound represented by the following general formula (2)
The mass ratio of the compounds is 95: 5 to 70:30,
0.5 to 10 parts by weight per 100 parts by weight of binder resin
Part of the yellow toner. [Chemical 2] 3. An endothermic curve in differential thermal analysis (DSC) measurement having one or a plurality of endothermic peaks in the temperature range of 30 to 200 ° C., and the peak temperature of the maximum endothermic peak among the endothermic peaks is 60 to 60 ° C. The yellow toner according to claim 1, which is in a range of 110 ° C. 4. The yellow toner according to claim 1, which contains a metal compound of an aromatic carboxylic acid or a derivative thereof. 5. The yellow toner according to claim 4, wherein the metal compound of the aromatic carboxylic acid or its derivative is an aluminum compound of the aromatic carboxylic acid or its derivative. 6. The binder resin comprises (a) a polyester resin, (b) a hybrid resin having a polyester unit and a vinyl copolymer unit, and (c) a hybrid resin and a vinyl copolymer. The yellow toner according to any one of claims 1 to 5, which is a resin selected from a mixture and a mixture of (d) a hybrid resin and a polyester resin.