JP2011197032A - Yellow toner for electrophotography - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a yellow toner, which is a toner obtained by aqueous granulation using a polyester resin as a binder resin, the toner having excellent color developing property and charging property without uneven distribution of a colorant.SOLUTION: The toner is granulated from an aqueous medium suspension prepared by suspending droplets of an oil phase containing at least a binder resin, a colorant and a release agent, and is characterized in that: the toner contains, as a colorant, C.I.Pigment yellow 155 which is a disazo pigment and C.I.Pigment yellow 185 which is an isoindoline pigment, in a mixing ratio of the C.I.Pigment yellow 155 as a disazo pigment to the C.I.Pigment yellow 185 as an isoindoline pigment, ranging from 95:5 to 50:50; and the toner contains the colorants by 5 to 15 pts.mass in total with respect to 100 pts.wt of the binder resin.

Description

  The present invention relates to an electrophotographic toner, and more particularly to a full-color toner used in an image forming apparatus using a so-called electrophotographic method such as an electrostatic copying machine or a laser beam printer.

Conventionally, in an electrophotographic apparatus, an electrostatic recording apparatus, or the like, an electric or magnetic latent image is visualized with toner.
For example, in electrophotography, an electrostatic charge image (latent image) is formed on a photoreceptor, and then the latent image is developed with toner to form a toner image. The toner image is usually transferred onto a transfer material such as paper and then fixed by a method such as heating.
Toners used for electrostatic image development are generally colored particles containing a colorant, a charge control agent, and other additives in a binder resin. There is a chemical method such as a turbid polymerization method (a method of forming toner droplets containing a toner material and eliminating liquid components from the droplets to obtain toner base particles).

In the pulverization method, a colorant, a charge control agent, an offset preventing agent and the like are melt-mixed in a thermoplastic resin and uniformly dispersed, and the resulting composition is pulverized and classified to produce a toner. According to the pulverization method, a toner having some excellent characteristics can be produced, but there is a limitation in the selection of the toner material.
For example, the composition obtained by melt mixing must be capable of being pulverized and classified by economically usable equipment. From this requirement, the melt-mixed composition must be made sufficiently brittle. For this reason, when the above composition is actually pulverized into particles, a wide range of particle size distribution is likely to be formed, and when attempting to obtain a copy image with good resolution and gradation, for example, a particle size of 5 μm Hereinafter, in particular, fine powder of 3 μm or less and coarse powder of 20 μm or more must be removed by classification, which has a disadvantage that the yield becomes very low.
Further, in the pulverization method, it is difficult to uniformly disperse the release agent, the pigment, and the like in the thermoplastic resin. In addition, since the colorant added to the toner is exposed on the surface of the obtained toner, there is a problem that the toner surface is not uniformly charged, the charge distribution of the toner is expanded, and the development characteristics are deteriorated.
Therefore, because of these problems, the kneading and pulverizing method cannot sufficiently meet the demand for high performance.

In recent years, in order to overcome these problems in the pulverization method, a toner production method by a suspension polymerization method has been proposed and implemented.
A technique for producing a toner for developing an electrostatic latent image by a polymerization method is known. For example, toner particles are obtained by a suspension polymerization method.
According to the polymerization method, the conventional pulverization process and kneading process can be omitted, energy saving, shortening of production time, improvement of process yield, etc. contribute greatly to cost reduction. At the same time, it is easy to make the particle size distribution sharper than that of the pulverization method, and the contribution to high image quality is great, so the polymerization method is a highly promising method.
In addition, in order to increase the image quality of a full-color image as in printing in electrophotography, it is necessary that each toner has a wide color reproducibility. In order to achieve the above object without any problems, a colorant having excellent transparency, light resistance and heat resistance is highly dispersed in the toner.

Conventionally known colorants for yellow toner have many problems.
For example, although dye-based colorants are generally excellent in transparency, they are inferior in light resistance and have a problem in image storage stability.
The yellow pigment system is superior in light resistance as compared with dyes, but still has a problem in light resistance as compared with copper phthalocyanine pigments used for magenta toners.
Furthermore, even a yellow pigment having excellent light resistance and heat resistance has a concealment property that is too strong, and the transparency is extremely lowered, which is not suitable for full color use.

A disazo compound excellent in light resistance and a production method thereof have already been proposed (see Patent Document 1).
This is a group of compounds represented by Pigment Yellow 180, and is one of the azo pigments that not only excels in light resistance and heat resistance, but also meets recent safety requirements.
In addition, a toner using a yellow toner using Pigment Yellow 180 (see Patent Documents 2 to 4) has poor coloring power and, in addition, transparency is never good. It is actively used.
However, Pigment Yellow 180 has a relatively high hydrophilicity and segregates on the particle surface in an emulsion dispersion method using an organic solvent (see Patent Document 5) or a method of dispersing an oil layer in water such as suspension polymerization. Or re-aggregate in the particles, making it difficult to use.

Patent Document 6 introduces a toner using Pigment Yellow 185, an isoindoline pigment.
Pigment Yellow 185 exhibits a bright yellow color and is not easily faded and has excellent light resistance. However, in the method of producing toner particles in an aqueous medium as in the present method, the reason is not clear, but the colorant is segregated on the surface of the toner because it is closer to the aqueous phase during granulation. When the colorant is segregated, the colorant tends to agglomerate, resulting in poor color development and affecting the chargeability.
On the other hand, as described in Patent Document 7, the yellow toner using Pigment Yellow 155 is not easily segregated on the toner surface layer even when the toner is produced by suspending and granulating in an aqueous system. Even when a color image formed on a sheet is projected, the transparency is excellent. However, the toner using the above pigment has poor coloring power, and a sufficient image density cannot be obtained.

The object of the present invention has been made in view of the above.
That is, it is a toner obtained by water-based granulation using at least a polyester resin as a binder resin, and provides a yellow toner having excellent color developability and chargeability without uneven distribution of colorants.

  As a result of intensive studies, the present inventors have found that the toner is obtained by water-based granulation using at least a polyester resin as a binder resin, and a C.I. I. Pigment Yellow 155 and an isoindoline pigment C.I. I. Pigment Yellow 185 and C.I. I. Pigment Yellow 155 and an isoindoline pigment C.I. I. Pigment Yellow 185 has a mixing ratio of 95: 5 to 50:50, and the total amount of the colorant is 5 to 15 parts by mass with respect to 100 parts by weight of the binder resin, thereby providing excellent colorability. The present inventors have found that a toner having hue and chargeability can be obtained.

That is, the said subject is solved by following (1)-(22).
(1) “In a toner granulated from an aqueous medium suspension obtained by suspending droplets of an oil phase containing at least a binder resin, a colorant, and a release agent, the disazo pigment C is used as a colorant. CI Pigment Yellow 155, an isoindoline pigment CI Pigment Yellow 185, and a disazo pigment CI Pigment Yellow 155 mixed with an isoindoline pigment CI Pigment Yellow 185 A yellow toner for electrophotography, wherein the ratio is 95: 5 to 50:50, and the total of the colorants is contained in an amount of 5 to 15 parts by mass with respect to 100 parts by weight of the binder resin. ”
(2) “Yellow toner for electrophotography according to item (1), wherein a masterbatch obtained by pre-dispersing in a binder resin is used as the colorant”;
(3) “Yellow toner for electrophotography according to item (1) and item (2), wherein the colorant is surface-treated with an acidic surface treatment agent”,
(4) The electrophotographic yellow as described in any one of (1) to (3) above, wherein the surface treatment agent has an acid value of 3 KOHmg / g or more and 20 KOHmg / g or less. toner",
(5) The electrophotography according to any one of (2) to (4), wherein the resin for the masterbatch has an acid value of 5 KOHmg / g or more and 40 KOHmg / g or less. For yellow toner ",
(6) The item (2), wherein the masterbatch is obtained in advance by dispersing a binder resin, a surface treatment agent, and a colorant, and the dispersion is melt kneading. Thru | or the yellow toner for electrophotography in any one of (5) term | claims,
(7) “Yellow toner for electrophotography according to item (6), wherein the melting point of the surface treatment agent is lower than the melting point of the binder resin”,
(8) “Yellow toner for electrophotography according to (6) or (7) above, wherein the melting point of the surface treatment agent is 70 ° C. or higher and 110 ° C. or lower”,
(9) “The mold release agent has a viscosity at 90 ° C. of not less than 5 centipoise and not more than 50 centipoise, for electrophotography according to any one of items (6) to (8)” Yellow toner ",
(10) The above items (6) to (9), wherein the dispersion in which the binder resin, the release agent, and the colorant are previously dispersed uses a presscake pigment after pigment washing as the colorant. ) Yellow toner for electrophotography according to any one of items
(11) “The electrophotographic yellow toner according to any one of (6) to (10) above, wherein the melt-mixing is performed using an open-type melt kneader”;
(12) “In a method for producing a toner having a step of suspending and granulating an oil phase containing at least a binder resin, a colorant and a release agent in an aqueous medium, C.I. Pigment Yellow 155 and CI Pigment Yellow 185, an isoindoline pigment, and a mixing ratio of CI Pigment Yellow 155, a disazo pigment, and CI Pigment Yellow 185, an isoindoline pigment Is 95: 5 to 50:50, and the total amount of the colorant is 5 to 15 parts by mass with respect to 100 parts by weight of the binder resin. ,
(13) “The method for producing a yellow toner for electrophotography according to item (12), wherein a master batch obtained by dispersing the colorant in a binder resin in advance” is used,
(14) “The method for producing a yellow toner for electrophotography according to the items (12) and (13), including a step of surface-treating the colorant with an acidic surface treatment agent” ,
(15) The yellow for electrophotography according to any one of (12) to (14), wherein the surface treatment agent has an acid value of 3 KOHmg / g or more and 20 KOHmg / g or less. Toner manufacturing method ",
(16) The electrophotography according to any one of (12) to (15), wherein the resin for the masterbatch has an acid value of 5 KOHmg / g or more and 40 KOHmg / g or less. Manufacturing method for yellow toner ",
(17) In any one of (14) to (16), wherein the dispersion step of dispersing the binder resin, the surface treatment agent, and the colorant in advance is a melt-kneading step. The manufacturing method of the electrophotographic yellow toner described in the above ",
(18) “The method for producing a yellow toner for electrophotography according to item (17), wherein the melting point of the surface treatment agent is lower than the melting point of the binder resin”,
(19) "The method for producing a yellow toner for electrophotography according to (17) or (18) above, wherein the melting point of the surface treatment agent is 70 ° C or higher and 110 ° C or lower",
(20) “The release agent has a viscosity at 90 ° C. of not less than 5 centipoise and not more than 50 centipoise, for electrophotography according to any one of items (17) to (19)” Yellow toner manufacturing method ",
(21) The item (17), wherein the dispersion step of dispersing the binder resin, the release agent, and the colorant in advance uses a presscake pigment after pigment washing as the colorant. Thru | or the manufacturing method of the yellow toner for electrophotography in any one of (20) ",
(22) Any of the above items (17) to (21), wherein an open-type melt kneader is used in the step of melt-mixing the binder resin, the release agent and the colorant in advance. The manufacturing method of the yellow toner for electrophotography as described in the above. "

According to the present invention, a disazo pigment is used as a colorant in a toner granulated from an aqueous medium suspension obtained by suspending droplets of an oil phase containing at least a binder resin, a colorant, and a release agent. C. I. Pigment Yellow 155 and an isoindoline pigment C.I. I. Pigment Yellow 185, and C.I. I. Pigment Yellow 155 and an isoindoline pigment C.I. I. The mixing ratio with CI Pigment Yellow 185 is 95: 5 to 50:50, and the total amount of the colorant is 5 to 15 parts by mass with respect to 100 parts by weight of the binder resin, so that the saturation is also high. Thus, a yellow toner excellent in hue and free of background stains during running under high temperature and high humidity can be obtained.
In addition, according to the present invention, by using a master batch in which a colorant is previously dispersed in a binder resin, the color saturation is high, the hue is excellent, and there is no background stain in running under high temperature and high humidity. A yellow toner is obtained.
Furthermore, according to the present invention, since the colorant is surface-treated with an acidic surface treatment agent, the color is high, the hue is excellent, and there is no background stain in running under high temperature and high humidity. A yellow toner is obtained.
Furthermore, according to the present invention, the surface treatment agent has an acid value of 3 KOHmg / g or more and 20 KOHmg / g or less, so that it has high chroma, excellent hue, and stains during running under high temperature and high humidity. No yellow toner is obtained.
Furthermore, according to the present invention, since the resin for the master batch has an acid value of 5 KOHmg / g or more and 40 KOHmg / g or less, the saturation is high, the hue is excellent, and the ground for running under high temperature and high humidity. A yellow toner with no stain is obtained.
Furthermore, according to the present invention, the dispersion of the binder resin, the surface treatment agent, and the colorant in advance is melt kneading, so that the saturation is high, the hue is excellent, and the running under high temperature and high humidity is performed. A yellow toner having no background stain can be obtained.
Furthermore, according to the present invention, since the melting point of the surface treatment agent is lower than the melting point of the binder resin, a yellow toner having high saturation, excellent hue, and no background stains during running under high temperature and high humidity can be obtained. It is done.
Furthermore, according to the present invention, a yellow toner having a high saturation, excellent hue, and no stain on running under high temperature and high humidity, because the melting point of the surface treatment agent is 70 ° C. or higher and 110 ° C. or lower. can get.
Furthermore, according to the present invention, the release agent has a viscosity at 90 ° C. of not less than 5 centipoise and not more than 50 centipoise, so that it has high saturation, excellent hue, and is suitable for running under high temperature and high humidity. A yellow toner with no stain is obtained.
Furthermore, according to the present invention, the dispersion of the binder resin, the release agent, and the colorant in advance uses the presscake pigment after washing the pigment as the colorant, so that the chroma is high and the hue is increased. A yellow toner that is excellent and free of background stains during running under high temperature and high humidity can be obtained.
Furthermore, according to the present invention, by using an open-type melt kneader in the melt mixing of the binder resin, the release agent, and the colorant in advance, high saturation, excellent hue, high temperature and high humidity A yellow toner with no background stains during running is obtained.

Next, the form for implementing this invention is demonstrated. The toner of the present invention is not a pulverized toner but a kind of so-called chemical toner, and is granulated from an aqueous medium suspension obtained by suspending droplets of an oil phase containing a toner material.
That is, the toner of the present invention is a toner granulated from an aqueous medium suspension obtained by suspending at least a binder resin, a colorant, and a release agent. C. of a disazo pigment having the chemical structure (1A) I. Pigment Yellow 155 and C.I. of the indoline pigment having the chemical structure (1B) below. I. Pigment Yellow 185, and C.I. I. Pigment Yellow 155 and an isoindoline pigment C.I. I. The mixing ratio with Pigment Yellow 185 is 95: 5 to 50:50, and the total amount of the colorant is 5 to 15 parts by mass with respect to 100 parts by weight of the binder resin.

C. of a disazo pigment I. Pigment Yellow 155 has relatively good dispersion in the oil phase or resin among yellow toners. C. I. Although the cause of excellent dispersibility by using Pigment Yellow 155 is not clear, for example, in the case of using a modified polyester resin capable of urea bonding as a binder, the urea bonding portion of the polyester resin is particularly a pigment and The polyester resin part dissolves in the organic solvent, prevents aggregation of the pigments due to steric repulsion, and prevents segregation on the toner surface. It is done. Therefore, good OHP permeability / chargeability can be obtained. On the other hand, C.I. I. Since Pigment Yellow 155 has poor coloring power, a sufficient image density cannot be obtained.
C. of isoindoline pigment I. Pigment Yellow 185 shows a bright yellow color and has a strong coloring power. On the other hand, since the colorant is segregated on the surface layer of the toner particles, it easily aggregates.
Therefore, C.I. I. Pigment yellow 155 and C.I. I. Pigment Yellow 185 and C.I. I. Pigment yellow 155 and C.I. I. When the mixing ratio with Pigment Yellow 185 is 95: 5 to 50:50, a yellow toner having a good hue, coloring degree, and charging property can be obtained.

In the present invention, the total of the above colorants may be contained in an amount of 5 to 15 parts by weight, preferably 6 to 12 parts by weight, and more preferably 6 to 10 parts by weight with respect to 100 parts by weight of the binder resin. .
When the content of the colorant is more than 15 parts by mass, the transparency is lowered, and in addition, the reproducibility of intermediate colors as typified by human skin color is easily lowered. Further, the stability of the charging property of the toner is lowered, and it becomes difficult to obtain a target charge amount. On the other hand, when the amount is less than 5 parts by mass, it is difficult to obtain the desired coloring power and it is difficult to obtain a high-quality image having a high image density.

Further, the toner of the present invention is characterized by using a master batch in which a colorant is dispersed in advance in a binder resin.
By using a masterbatch, when the colorant is dispersed in the oil phase, the shock is alleviated, the colorant is prevented from agglomerating, the dispersibility of the colorant is improved, and a yellow toner having good hue, coloration degree and chargeability is obtained. be able to.

The toner of the present invention is characterized in that the colorant is surface-treated with an acidic surface treatment agent.
By subjecting the colorant to an acid treatment, the dispersibility of the colorant in the resin is improved, and a yellow toner having a good hue, coloration degree, and chargeability can be obtained.

The toner of the present invention is characterized in that the acid value of the surface treatment agent is 3 KOHmg / g or more and 20 KOHmg / g or less. When the acid value is 3 KOH mg / g or less, the colorant is not easily dispersed, and when it is 20 KOH mg / g or more, the external environment tends to be affected by the chargeability. For example, charging is reduced under high temperature and high humidity, resulting in background stains and scattering.
When the acid value is 3 KOHmg / g or more and 20 KOHmg / g or less, a toner having excellent pigment dispersibility and excellent running performance under high temperature and high humidity can be obtained.

The toner of the present invention is characterized in that the polyester resin has an acid value of 5 KOHmg / g or more and 40 KOHmg / g or less.
Since the acid value of the polyester resin contributes to the dispersibility of the pigment, it is difficult to disperse the pigment if it is 5 KOHmg / g or less.
On the other hand, it is preferably 40 KOHmg / g or less because it is easily affected by the external environment. When it is 40 KOHmg / g or more, for example, charging is reduced under high temperature and high humidity, and background staining or scattering occurs.

The toner of the present invention is characterized in that the step of previously dispersing the binder resin, the surface treatment agent, and the colorant is melt kneading.
Master batches by melt kneading can be effectively dispersed by using a surface treatment agent, and pigment dispersion agents such as steric hindrance do not re-aggregate pigments as in solvent-based dispersions. Therefore, a stable pigment dispersion can be obtained.

The toner of the present invention is characterized in that the melting point of the surface treatment agent is lower than the melting point of the binder resin.
When the melting point of the surface treatment agent is higher than the melting point of the binder resin, it cannot be effectively adsorbed on the pigment surface during melt kneading.
On the other hand, when the melting point is lower than the melting point of the binder resin, the surface treatment agent is melted at the time of melt-kneading, can be wetted with the pigment and adsorbed on the particle surface, and a great effect on the pigment dispersibility can be obtained.

In the toner of the present invention, the surface treatment agent has a melting point of 70 ° C. or higher and 110 ° C. or lower.
When the melting point of the surface treatment agent is lower than 70 ° C., the storage stability under high temperature and high humidity is adversely affected, and problems such as solidification of the toner occur.
On the other hand, if the melting point is higher than 110 ° C., it is necessary to increase the temperature in order to melt the surface treatment agent during melt kneading, the viscosity of the binder resin is lowered, and high shear cannot be imparted.

The toner of the present invention is characterized in that the release agent has a viscosity at 90 ° C. of 5 centipoise or more and 50 centipoise or less.
When the viscosity of the surface treatment agent is less than 5 centipoise at 90 ° C., the effect of the surface treatment agent exposed on the toner surface adversely affects the storage stability under high temperature and high humidity, causing the toner to solidify. Occurs.
On the other hand, when the viscosity of the surface treatment agent exceeds 50 centipoise at 90 ° C., the viscosity is too high, and it is difficult to get wet with the pigment at the time of melting and hardly adsorb on the pigment surface.

The toner of the present invention is characterized in that a presscake pigment after washing the pigment is used as a colorant in a step of melt-mixing a binder resin, a surface treatment agent, and a colorant in advance.
The press cake contains water between the pigment particles, and a toner having excellent pigment dispersibility can be obtained without agglomeration by substituting with a binder resin during melt kneading.

The toner of the present invention is characterized in that an open type melt kneader is used in the step of melt-mixing the binder resin, the surface treatment agent, and the colorant in advance.
An open-type melt kneader can release heat generated during shearing, so that it can be kneaded at a relatively low temperature. Since kneading at a low temperature can impart a high shearing force to the raw material, it is possible to obtain a toner with more excellent pigment dispersibility.

From the viewpoint of pigment dispersibility, the polyester resin used in the present invention preferably contains a propylene oxide adduct of bisphenols in an amount of 50 mol% or more based on the diol component used when polymerizing the polyester resin. More preferred is 70 mol% or more, and more preferred is 80 mol% or more.
When combined with a polyester resin containing a certain amount of propylene oxide adduct as a diol component and a polymer dispersant which is a polyester derivative having a predetermined acid value and amine value, the pigment dispersibility is excellent, and the color reproducibility of the toner is excellent. improves. The reason for this is not clear, but it is thought that the affinity between the polyester resin and the polymer dispersant is increased and the pigment is stabilized.

Alcohols and acids other than propylene oxide adducts of bisphenols can be arbitrarily selected in consideration of the glass transition point, molecular weight, softening point, etc. of the polyester resin.
The hydroxyl value and acid value can be arbitrarily adjusted by adding a trivalent or higher alcohol or acid.
Examples of diol components other than propylene oxide adducts of bisphenols include alkylene glycols such as ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butanediol, and 1,6-hexanediol; diethylene glycol Diols having an oxyalkylene group such as triethylene glycol, dipropylene glycol, polyethylene glycol, polypropylene glycol, polytetramethylene glycol; alicyclic diols such as 1,4-cyclohexanedimethanol and hydrogenated bisphenol A; alicyclic Diol added with alkylene oxide such as ethylene oxide, propylene oxide, butylene oxide; bisphenol such as bisphenol A, bisphenol F, bisphenol S Nord acids; the bisphenols include ethylene oxide, alkylene oxide adducts of bisphenols such as those obtained by adding alkylene oxides such as butylene oxide.
In addition, it is preferable that carbon number of alkylene glycol is 2-12. Among these, alkylene glycols having 2 to 12 carbon atoms or alkylene oxide adducts of bisphenols are preferred, alkylene oxide adducts of bisphenols or alkylene oxide adducts of bisphenols and alkylene glycols having 2 to 12 carbons. The mixture of is particularly preferred.

In addition, trihydric or higher alcohols can be used. As trihydric or higher alcohols, trihydric or higher aliphatic alcohols, trihydric or higher polyphenols, alkylene oxide adducts of trihydric or higher polyphenols, etc. should be used. Can do.
Specific examples of the trihydric or higher aliphatic alcohol include glycerin, trimethylolethane, trimethylolpropane, pentaerythritol, sorbitol and the like.
Specific examples of the trihydric or higher polyphenols include trisphenol PA, phenol novolak, cresol novolak and the like.
Specific examples of the alkylene oxide adducts of trihydric or higher polyphenols include those obtained by adding alkylene oxides such as ethylene oxide, propylene oxide and butylene oxide to trihydric or higher polyphenols.

Examples of the acid component include polycarboxylic acids.
The polycarboxylic acid can be appropriately selected according to the purpose, and dicarboxylic acid, trivalent or higher carboxylic acid, a mixture of dicarboxylic acid and trivalent or higher carboxylic acid, and the like can be used. And a small amount of a trivalent or higher polycarboxylic acid mixture is preferred.
These may be used alone or in combination of two or more.

Specific examples of the dicarboxylic acid include divalent alkanoic acid, divalent alkenoic acid, and aromatic dicarboxylic acid.
Specific examples of the divalent alkanoic acid include succinic acid, adipic acid, sebacic acid and the like. The number of carbon atoms of the divalent alkenoic acid is preferably 4 to 20, and specific examples include maleic acid and fumaric acid.
The aromatic dicarboxylic acid preferably has 8 to 20 carbon atoms, and specific examples thereof include phthalic acid, isophthalic acid, terephthalic acid, and naphthalenedicarboxylic acid. Among these, a divalent alkenoic acid having 4 to 20 carbon atoms or an aromatic dicarboxylic acid having 8 to 20 carbon atoms is preferable.
As the trivalent or higher carboxylic acid, trivalent or higher aromatic carboxylic acid or the like can be used. The carbon number of the trivalent or higher aromatic carboxylic acid is preferably 9 to 20, and specific examples thereof include trimellitic acid and pyromellitic acid.

  As the polycarboxylic acid, an acid anhydride or lower alkyl ester of any of dicarboxylic acid, trivalent or higher carboxylic acid, and a mixture of dicarboxylic acid and trivalent or higher carboxylic acid can be used. Specific examples of the lower alkyl ester include methyl ester, ethyl ester, isopropyl ester and the like.

When dicarboxylic acid and trivalent or higher carboxylic acid are used in combination, the mass ratio of trivalent or higher carboxylic acid to dicarboxylic acid is 0.01 to 10%, although it depends on the type and composition of the polyol used. Is preferable, and 0.01 to 1% is more preferable.
As for the mixing ratio at the time of polycondensation of the polyol and the polycarboxylic acid, the equivalent ratio of the hydroxyl group of the polyol to the carboxyl group of the polycarboxylic acid is usually preferably 1 to 2, more preferably 1 to 1.5, 1.02-1.3 is particularly preferred.

As a colorant for toner, in the present invention, C.I. I. Pigment Yellow 155 and an isoindoline pigment C.I. I. Pigment Yellow 185 is used in combination.
In addition, the pigment and the surface treatment agent are preferably dispersed in the binder resin in advance before adjusting the oil phase. More preferably, it is melt kneaded and dispersed.
Examples of the melt kneader include a uniaxial extrusion kneader, a biaxial extrusion kneader, a twin roll, and a triple roll.
More preferably, a continuous open two-roll kneader is used for the purpose of improving the dispersibility of the surface treatment agent and the pigment. This kneading machine has the kneading force of the open roll kneading machine, in which a strong shearing force is applied over the entire kneading part, by making the roll gap on the kneaded product discharge side wider than the roll gap on the raw material charging side. By concentrating on the raw material charging part in the first half and mainly mixing by melting in the second half part, generation of heat of kneading itself can be suppressed, so that the kneading effect is increased. Two rolls arranged close to each other can be given a stronger shearing force by one being a heating roll through which a heating medium is passed and the other being a cooling roll through which a cooling medium is passed. Thus, the dispersibility of the release agent and the pigment is improved.

The wax used in the present invention is natural wax such as beeswax derived from animals, whale wax, shellac wax, carnauba wax derived from plants, wood wax, rice bran wax (rice wax), candelilla wax, paraffin wax derived from petroleum, microcrystalline. There are wax, mineral-derived montan wax, ozokerite and the like, and synthetic waxes include Fischer-Tropsch wax, polyethylene wax, oil-based synthetic wax (ester, ketones, amide), hydrogenated wax and the like.
The type is not limited, but preferably, a hydrocarbon wax obtained by separating and purifying a petroleum vacuum distillation distillate from a viewpoint of releasability is modified with a carboxylic acid or the like. This is because paraffin wax has a relatively low temperature and low viscosity, has a low penetration, and can be controlled easily by modifying the acid value.

The melting point of the wax is preferably lower than the melting point of the binder resin from the viewpoint of the releasing effect, and is preferably 70 ° C. or higher and 110 ° C. or lower. In addition, the amount of wax added is preferably 1 to 20 parts by weight, and the acid value is 3 to 20 KOHmg / g in consideration of the mold release effect, storage stability at high temperature and high humidity, and chargeability. It is preferable that
In consideration of the bleedability of the wax so as not to inhibit charging, the viscosity at 90 ° C. is preferably from 5 to 50. Further, if the addition amount is too small, the releasing effect is small, and if it is too large, it tends to be affected by the environment, so 3 to 10 parts are preferably added.

In the present invention, a charge control agent is preferably used.
The charge control agent can be appropriately selected from known ones according to the purpose. However, since a color tone may change when a colored material is used, it is preferable to use a colorless or nearly white material.
Specifically, triphenylmethane dyes, molybdate chelate pigments, rhodamine dyes, alkoxy amines, quaternary ammonium salts including fluorine-modified quaternary ammonium salts, alkylamides, phosphorus alone or compounds thereof, tungsten alone Or a compound thereof, a fluorosurfactant, a metal salt of salicylic acid, a metal salt of a salicylic acid derivative, and the like. These may be used alone or in combination of two or more.

  Commercially available products may be used as the charge control agent. Examples of commercially available products include quaternary ammonium salt Bontron P-51, oxynaphthoic acid metal complex E-82, salicylic acid metal complex E-84, and phenol. Condensate E-89 (above, Orient Chemical Industry Co., Ltd.), quaternary ammonium salt molybdenum complex TP-302, TP-415 (above, Hodogaya Chemical Industry 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, boron complex LR-147 (manufactured by Nippon Carlit), Quinacridone, azo pigments, other sulfonic acid groups, carboxyl groups, quaternary ammonium Polymers and the like having a functional group such as.

  The content of the charge control agent in the toner varies depending on the type of the binder resin, the presence or absence of the additive, the dispersion method, etc., and cannot be generally specified, but is 0.1 to 10 mass relative to the binder resin. % Is preferable, and 0.2 to 5% by mass is more preferable. When the content is less than 0.1% by mass, the charge controllability may not be obtained. When the content exceeds 10% by mass, the chargeability of the toner becomes too large and the electrostatic attraction with the developing roller increases. However, the fluidity of the developer and the image density may be reduced.

The weight average molecular weight of the binder resin contained in the oil phase is preferably 1000 to 30000, and more preferably 1500 to 15000. When the weight average molecular weight is less than 1000, the heat resistant storage stability may be lowered. For this reason, it is preferable that content of the component whose weight average molecular weight is less than 1000 is 8-28 mass%. On the other hand, if the weight average molecular weight exceeds 30000, the low-temperature fixability may be lowered.
The glass transition temperature of the binder resin is usually 30 to 70 ° C, more preferably 35 to 60 ° C, and still more preferably 35 to 55 ° C. When the glass transition temperature is less than 30 ° C., the heat-resistant storage stability of the toner may be lowered, and when it exceeds 70 ° C., the low-temperature fixability may be lowered.
The acid value of the binder resin is preferably 5 KOHmg / g or more and 40 KOHmg / g or less. Within this range, the dispersibility of the release agent and pigment is improved, and a toner excellent in color development, releasability, storage stability under high temperature and high humidity, and chargeability can be obtained.

The aqueous medium can be appropriately selected from known ones.
Specific examples include water, water-miscible solvents, and mixtures thereof. Among these, water is particularly preferable.
Examples of the water-miscible solvent include alcohol, dimethylformamide, tetrahydrofuran, cellosolves, and lower ketones.
Examples of the alcohol include methanol, isopropanol, and ethylene glycol. Examples of lower ketones include acetone and methyl ethyl ketone.
These may be used alone or in combination of two or more.

In the present invention, it is preferable that an oil phase containing a toner material containing at least a binder resin and a colorant is dissolved or dispersed in a solvent.
The solvent preferably contains an organic solvent. The organic solvent is preferably removed when forming the toner base particles or after forming the toner base particles.
The organic solvent can be appropriately selected according to the purpose, but since the removal is easy, the boiling point is preferably less than 150 ° C.
Specific examples include toluene, xylene, benzene, carbon tetrachloride, methylene chloride, 1,2-dichloroethane, 1,1,2-trichloroethane, trichloroethylene, chloroform, monochlorobenzene, dichloroethylidene, methyl acetate, and ethyl acetate. In addition to water-miscible solvents, water-miscible solvents such as ketones such as methyl ethyl ketone and methyl isobutyl ketone, alcohols such as tetrahydrofuran and ethanol, cyclic ethers such as dioxane, and nitrogen-containing organic solvents such as dimethylformamide It is done. Of these, toluene, xylene, benzene, methylene chloride, 1,2-dichloroethane, chloroform, carbon tetrachloride and the like are preferable, and ethyl acetate is particularly preferable. These may be used alone or in combination of two or more.
The amount of the organic solvent used can be appropriately selected according to the purpose, but is preferably 40 to 300 parts by mass, more preferably 60 to 140 parts by mass, and more preferably 80 to 140 parts by mass with respect to 100 parts by mass of the toner material. 120 parts by mass is more preferable.

The toner material can be appropriately selected according to the purpose, but usually contains at least a binder resin and a colorant, and a polymer having a reactive hydrogen group-containing compound and a reactive hydrogen group-containing compound. It is preferable to further contain other components such as a mold release agent and a charge control agent as necessary.
The mixing ratio of the colorant and the organic solvent in the oil phase containing the toner material can be appropriately selected according to the purpose, and is preferably 5:95 to 50:50. When the blending amount of the colorant is less than this range, the amount of the organic solvent is increased during the production of the toner, and the toner production efficiency may be lowered. When the blending amount is larger than this range, the dispersion of the pigment becomes insufficient. There is.

When emulsifying or dispersing the toner material in the aqueous medium using the oil phase containing the toner material, it is preferable to disperse the oil phase containing the toner material in the aqueous medium while stirring.
A known disperser or the like can be appropriately used for the dispersion.
Specific examples of the disperser include a low speed shear disperser, a high speed shear disperser, a friction disperser, a high pressure jet disperser, and an ultrasonic disperser. Especially, since the particle diameter of a dispersion (oil droplet) can be controlled to 2-20 micrometers, a high-speed shearing disperser is preferable.
When a high-speed shearing disperser is used, conditions such as the number of rotations, dispersion time, dispersion temperature and the like can be appropriately selected according to the purpose.
The rotation speed is preferably 1000 to 30000 rpm, more preferably 5000 to 20000 rpm. In the case of a batch system, the dispersion time is preferably 0.1 to 5 minutes, and the dispersion temperature is preferably 0 to 150 ° C. and more preferably 40 to 98 ° C. under pressure. In general, the dispersion is easier when the dispersion temperature is higher.

The method for forming the toner base particles can be appropriately selected from known methods.
Specific examples include a method of forming toner base particles using a dissolution suspension method and the like, and a method of forming toner base particles while producing a binder resin. A method of forming toner base particles while producing a resin is preferred. Here, the binder resin is a base material having adhesion to a recording medium such as paper.
A method of forming toner base particles while producing a binder resin is a method in which a toner material contains a compound having an active hydrogen group and a polymer having a site capable of reacting with the active hydrogen group-containing compound in an aqueous medium. In this method, toner particles are formed while a binder resin is formed by reacting a compound having an active hydrogen group with a polymer having a site capable of reacting with the active hydrogen group-containing compound.
The toner thus obtained may further contain other components such as a release agent and a charge control agent that are appropriately selected as necessary.

As the polymer having a site capable of reacting with an active hydrogen group-containing compound, a modified polyester resin capable of reacting with a compound having an active hydrogen group is preferably used.
The modified polyester resin capable of reacting with a compound having an active hydrogen group is preferably a polyester having an isocyanate group as a polymer having reactivity with the active hydrogen group.
In addition, you may form a urethane bond by adding alcohol when making the isocyanate group containing polyester resin and the compound which has an active hydrogen group react.
The molar ratio of the urethane bond to the urea bond thus formed (to distinguish it from the urethane bond of the polyester prepolymer having an isocyanate group) is preferably from 0 to 9, and preferably from 1/4 to 4. Is more preferable, and 2/3 to 7/3 is particularly preferable. If this ratio is greater than 9, the hot offset resistance may decrease.

The compound having an active hydrogen group acts as an elongation agent, a crosslinking agent or the like when a polymer having a site capable of reacting with the active hydrogen group-containing compound undergoes an elongation reaction, a crosslinking reaction, or the like in an aqueous medium.
Specific examples of the active hydrogen group include a hydroxyl group (alcoholic hydroxyl group and phenolic hydroxyl group), amino group, carboxyl group, mercapto group and the like. In addition, an active hydrogen group may be individual, and 2 or more types of mixtures may be sufficient as it.

The compound having an active hydrogen group can be appropriately selected depending on the purpose, but when the polymer having a site capable of reacting with the active hydrogen group-containing compound is a polyester prepolymer having an isocyanate group, the polyester prepolymer is used. Amines are preferred because they can be made to have a high molecular weight by a polymer, elongation reaction, crosslinking reaction or the like.
The amines can be appropriately selected depending on the purpose, and specific examples include diamines, trivalent or higher amines, amino alcohols, amino mercaptans, amino acids, and those obtained by blocking these amino groups. Diamines and mixtures of diamines and small amounts of trivalent or higher amines are preferred. These may be used alone or in combination of two or more.
Examples of diamines include aromatic diamines, alicyclic diamines, and aliphatic diamines.
Specific examples of the aromatic diamine include phenylenediamine, diethyltoluenediamine, 4,4′-diaminodiphenylmethane, and the like.
Specific examples of the alicyclic diamine include 4,4′-diamino-3,3′-dimethyldicyclohexylmethane, diaminocyclohexane, isophorone diamine and the like.
Specific examples of the aliphatic diamine include ethylene diamine, tetramethylene diamine, hexamethylene diamine and the like.
Specific examples of the trivalent or higher amine include diethylenetriamine and triethylenetetramine.
Specific examples of amino alcohols include ethanolamine and hydroxyethylaniline.
Specific examples of amino mercaptans include aminoethyl mercaptan and aminopropyl mercaptan.
Specific examples of amino acids include aminopropionic acid and aminocaproic acid.
Specific examples of those in which the amino group is blocked include ketimine compounds and oxazolidone compounds obtained by blocking the amino group with ketones such as acetone, methyl ethyl ketone, and methyl isobutyl ketone.

In addition, a reaction terminator can be used to stop the elongation reaction, the cross-linking reaction, etc. of the compound having an active hydrogen group and the polymer having a site capable of reacting with the active hydrogen group-containing compound. When a reaction terminator is used, the molecular weight and the like of the adhesive substrate can be controlled within a desired range.
Specific examples of the reaction terminator include monoamines such as diethylamine, dibutylamine, butylamine and laurylamine, and ketimine compounds in which these amino groups are blocked.

  The ratio of the equivalent of the isocyanate group of the polyester prepolymer to the equivalent of the amino group of the amine is preferably 1/3 to 3, more preferably 1/2 to 2, and particularly preferably 2/3 to 1.5. . If this ratio is less than 1/3, the low-temperature fixability may be lowered. If it exceeds 3, the molecular weight of the urea-modified polyester resin may be lowered, and the hot offset resistance may be lowered.

The polymer having a site capable of reacting with the active hydrogen group-containing compound (hereinafter sometimes referred to as “prepolymer”) can be appropriately selected from known resins and the like, such as polyol resin, polyacrylic resin, polyester Examples thereof include resins, epoxy resins and derivatives thereof.
Among these, it is preferable to use a polyester resin in terms of high fluidity and transparency at the time of melting. These may be used alone or in combination of two or more.
Examples of the site capable of reacting with the active hydrogen group-containing compound of the prepolymer include an isocyanate group, an epoxy group, a carboxyl group, and a functional group represented by the chemical structural formula —COCl. Of these, an isocyanate group is preferable. The prepolymer may have one of such functional groups or two or more kinds.

As a prepolymer, it is easy to adjust the molecular weight of the polymer component, and oil-less low-temperature fixing characteristics in dry toners, in particular, good releasability and fixability even in the absence of a release oil application mechanism to a fixing heating medium. Since it can ensure, it is preferable to use the polyester resin which has an isocyanate group etc. which can produce | generate a urea bond.
The polyester prepolymer containing an isocyanate group can be appropriately selected depending on the purpose. Specific examples include a reaction product of a polyester resin having an active hydrogen group obtained by polycondensation of a polyol and a polycarboxylic acid, and a polyisocyanate.
The polyol can be appropriately selected according to the purpose, and a diol, a trihydric or higher alcohol, a mixture of a diol and a trihydric or higher alcohol, etc. can be used, but the diol or diol and a small amount of a trihydric or higher alcohol. Is preferred. These may be used alone or in combination of two or more.

  Specific examples of the diol include alkylene glycols such as ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butanediol, 1,6-hexanediol; diethylene glycol, triethylene glycol, dipropylene Diols having an oxyalkylene group such as glycol, polyethylene glycol, polypropylene glycol, polytetramethylene glycol; alicyclic diols such as 1,4-cyclohexanedimethanol and hydrogenated bisphenol A; alicyclic diols including ethylene oxide and propylene oxide , With addition of alkylene oxide such as butylene oxide; bisphenols such as bisphenol A, bisphenol F and bisphenol S; bisphenols with ethyleneoxy , Propylene oxide, alkylene oxide adducts of bisphenols such as those obtained by adding alkylene oxides such as butylene oxide. In addition, it is preferable that carbon number of alkylene glycol is 2-12. Among these, alkylene glycols having 2 to 12 carbon atoms or alkylene oxide adducts of bisphenols are preferred, alkylene oxide adducts of bisphenols or alkylene oxide adducts of bisphenols and alkylene glycols having 2 to 12 carbons. The mixture of is particularly preferred.

Examples of trihydric or higher alcohols include trihydric or higher aliphatic alcohols, trihydric or higher polyphenols, and alkylene oxide adducts of trihydric or higher polyphenols.
Specific examples of the trihydric or higher aliphatic alcohol include glycerin, trimethylolethane, trimethylolpropane, pentaerythritol, sorbitol and the like.
Specific examples of the trihydric or higher polyphenols include trisphenol PA, phenol novolak, cresol novolak and the like.
Specific examples of the alkylene oxide adducts of trihydric or higher polyphenols include those obtained by adding alkylene oxides such as ethylene oxide, propylene oxide and butylene oxide to trihydric or higher polyphenols.

  When a diol and a trihydric or higher alcohol are mixed and used, the mass ratio of the trihydric or higher alcohol to the diol is preferably 0.01 to 10%, and more preferably 0.01 to 1%.

The polycarboxylic acid can be appropriately selected according to the purpose, and dicarboxylic acid, trivalent or higher carboxylic acid, a mixture of dicarboxylic acid and trivalent or higher carboxylic acid, and the like can be used. And a small amount of a trivalent or higher polycarboxylic acid mixture is preferred.
These may be used alone or in combination of two or more.

Specific examples of the dicarboxylic acid include divalent alkanoic acid, divalent alkenoic acid, and aromatic dicarboxylic acid.
Specific examples of the divalent alkanoic acid include succinic acid, adipic acid, sebacic acid and the like.
The number of carbon atoms of the divalent alkenoic acid is preferably 4 to 20, and specific examples include maleic acid and fumaric acid.
The aromatic dicarboxylic acid preferably has 8 to 20 carbon atoms, and specific examples thereof include phthalic acid, isophthalic acid, terephthalic acid, and naphthalenedicarboxylic acid. Among these, a divalent alkenoic acid having 4 to 20 carbon atoms or an aromatic dicarboxylic acid having 8 to 20 carbon atoms is preferable.

As the trivalent or higher carboxylic acid, trivalent or higher aromatic carboxylic acid or the like can be used. The carbon number of the trivalent or higher aromatic carboxylic acid is preferably 9 to 20, and specific examples thereof include trimellitic acid and pyromellitic acid.
As the polycarboxylic acid, an acid anhydride or lower alkyl ester of any of dicarboxylic acid, trivalent or higher carboxylic acid, and a mixture of dicarboxylic acid and trivalent or higher carboxylic acid can be used.
Specific examples of the lower alkyl ester include methyl ester, ethyl ester, isopropyl ester and the like. In the case of using a mixture of dicarboxylic acid and trivalent or higher carboxylic acid, the mass ratio of trivalent or higher carboxylic acid to dicarboxylic acid is preferably 0.01 to 10%, more preferably 0.01 to 1%. preferable.

As for the mixing ratio at the time of polycondensation of the polyol and the polycarboxylic acid, the equivalent ratio of the hydroxyl group of the polyol to the carboxyl group of the polycarboxylic acid is usually preferably 1 to 2, more preferably 1 to 1.5, 1.02-1.3 is particularly preferred.
The content of the structural unit derived from the polyol in the polyester prepolymer having an isocyanate group is preferably 0.5 to 40% by mass, more preferably 1 to 30% by mass, and particularly preferably 2 to 20% by mass. When the content is less than 0.5% by mass, the hot offset resistance is lowered, and it may be difficult to achieve both the heat-resistant storage stability and the low-temperature fixability of the toner, and exceeds 40% by mass. In this case, the low-temperature fixability may be lowered.

The polyisocyanate can be appropriately selected depending on the purpose, but it is blocked with an aliphatic diisocyanate, an alicyclic diisocyanate, an aromatic diisocyanate, an araliphatic diisocyanate, an isocyanurate, or the like, blocked with a phenol derivative, oxime, caprolactam, or the like. And the like.
Specific examples of the aliphatic diisocyanate include tetramethylene diisocyanate, hexamethylene diisocyanate, methyl 2,6-diisocyanatocaproate, octamethylene diisocyanate, decamethylene diisocyanate, dodecamethylene diisocyanate, tetradecamethylene diisocyanate, trimethylhexane diisocyanate, tetra And methyl hexane diisocyanate.
Specific examples of the alicyclic diisocyanate include isophorone diisocyanate and cyclohexylmethane diisocyanate.
Specific examples of the aromatic diisocyanate include tolylene diisocyanate, diisocyanatodiphenylmethane, 1,5-naphthylene diisocyanate, 4,4′-diisocyanatodiphenyl, 4,4′-diisocyanato-3,3′-dimethyldiphenyl. 4,4′-diisocyanato-3-methyldiphenylmethane, 4,4′-diisocyanato-diphenyl ether, and the like.
Specific examples of the araliphatic diisocyanate include α, α, α ′, α′-tetramethylxylylene diisocyanate.
Specific examples of the isocyanurates include tris (isocyanatoalkyl) isocyanurate, tris (isocyanatocycloalkyl) isocyanurate, and the like. These may be used alone or in combination of two or more.

  When the polyisocyanate and the polyester resin having a hydroxyl group are reacted, the equivalent ratio of the isocyanate group of the polyisocyanate to the hydroxyl group of the polyester resin is usually preferably 1 to 5, more preferably 1.2 to 4, more preferably 1 .5-3 are particularly preferred. When the equivalent ratio exceeds 5, the low-temperature fixability may decrease, and when it is less than 1, the offset resistance may decrease.

  The content of the structural unit derived from polyisocyanate in the polyester prepolymer containing an isocyanate group is preferably 0.5 to 40% by mass, more preferably 1 to 30% by mass, and further 2 to 20% by mass. preferable. When this content is less than 0.5% by mass, the hot offset resistance may be lowered, and when it exceeds 40% by mass, the low-temperature fixability may be lowered.

  The average number of isocyanate groups that the polyester prepolymer has per molecule is preferably 1 or more, more preferably 1.2 to 5, and even more preferably 1.5 to 4. When the average number is less than 1, the molecular weight of the urea-modified polyester resin is lowered, and the hot offset resistance may be lowered.

  The diol component in the oil phase contains propylene oxide adducts of bisphenols in an amount of 50 mol% or more, and the mass ratio of the polyester prepolymer having an isocyanate group to the polyester resin having a specific hydroxyl value and an acid value is 5/95. -25/75 is preferable, and 10 / 90-25 / 75 is more preferable. When the mass ratio is less than 5/95, the hot offset resistance may be lowered, and when it exceeds 25/75, the low-temperature fixability and the glossiness of the image may be lowered.

  Therefore, as a specific example of the adhesive substrate contained in the toner, a polyester prepolymer obtained by reacting a polycondensate of bisphenol A propylene oxide 2 mol adduct and isophthalic acid with isophorone diisocyanate is uread with isophorone diamine. A polyester prepolymer prepared by reacting a polycondensate of bisphenol A propylene oxide 2 mol adduct and isophthalic acid with isophorone diisocyanate with isophorone diamine. Mixture of uread product with bisphenol A propylene oxide 2 mol adduct and terephthalic acid polycondensate; bisphenol A ethylene oxide 2 mol adduct / bisphenol A propylene oxide A polyester prepolymer obtained by reacting a polycondensate of idophthalic acid and a polycondensate of terephthalic acid with isophorone diisocyanate, and urethanized with isophorone diamine, bisphenol A ethylene oxide 2 mole adduct / bisphenol A propylene oxide 2 mole adduct ( Bisphenol A propylene oxide 2 mol adduct mixture ratio is 50 mol% or more) and polycondensate of terephthalic acid; polycondensation of bisphenol A ethylene oxide 2 mol adduct / bisphenol A propylene oxide 2 mol adduct and terephthalic acid A polyester prepolymer obtained by reacting a product with isophorone diisocyanate and uread with isophorone diamine, and a polycondensate of bisphenol A propylene oxide 2 mol adduct and terephthalic acid Compound: Polyester prepolymer obtained by reacting a polycondensate of bisphenol A ethylene oxide 2-mole adduct and terephthalic acid with isophorone diisocyanate, ureated with hexamethylenediamine, bisphenol A propylene oxide 2-mole adduct, and terephthalate Mixture with acid polycondensate; bisphenol A ethylene oxide 2 mol adduct and polyester prepolymer obtained by reacting terephthalic acid polycondensate with isophorone diisocyanate and urethanized with hexamethylenediamine, and bisphenol A ethylene oxide 2 Mole adduct / bisphenol A propylene oxide 2 mol adduct (mixing ratio of bisphenol A propylene oxide 2 mol adduct is 50 mol% or more) and polycondensate of terephthalic acid A polyester prepolymer obtained by reacting a polycondensate of bisphenol A ethylene oxide 2 mol adduct and terephthalic acid with isophorone diisocyanate with urea and ethylenediamine, a polycondensate of bisphenol A propylene oxide 2 mol adduct and terephthalic acid A mixture of bisphenol A ethylene oxide 2-mole adduct and a polycondensate of isophthalic acid with diphenylmethane diisocyanate, urealated with hexamethylenediamine, bisphenol A propylene oxide 2-mole adduct and isophthalic acid Mixtures with acid polycondensates; bisphenol A ethylene oxide 2-mole adduct / bisphenol A propylene oxide 2-mole adduct and terephthalic acid / dodecenyl A polyester prepolymer obtained by reacting a polycondensate of an acid anhydride with diphenylmethane diisocyanate and uread with hexamethylenediamine, and a bisphenol A ethylene oxide 2 mol adduct / bisphenol A propylene oxide 2 mol adduct (bisphenol A propylene oxide). 2 mol adduct mixture ratio is 50 mol% or more) and a mixture of terephthalic acid polycondensate; a polyester prepolymer obtained by reacting bisphenol A ethylene oxide 2 mol adduct and isophthalic acid polycondensate with toluene diisocyanate. Mixture of urealated with methylenediamine and bisphenol A propylene oxide 2 mol adduct and isophthalic acid polycondensate: bisphenol A ethylene oxide 2 mol adduct / bisph A polyester prepolymer obtained by reacting a 2-mole adduct of diol A propylene oxide, a polycondensate of terephthalic acid and trimellitic acid with isophorone diisocyanate, and urethanized with a ketimine compound whose amino group is blocked with ketones, and bisphenol A ethylene A mixture of oxide 2 mol adduct / bisphenol A propylene oxide 3 mol adduct (bisphenol A propylene oxide 3 mol adduct mixture ratio is 50 mol% or more) and polycondensate of terephthalic acid, adipic acid, trimellitic acid, etc. Can be mentioned.

The toner of the present invention is used by externally adding an external additive to the base particles.
As the external additive, organic fine particles such as PMMA and inorganic particles can be appropriately selected from known materials according to the purpose.
Specific examples of inorganic particles include silica, alumina, titanium oxide, barium titanate, magnesium titanate, calcium titanate, strontium titanate, zinc oxide, tin oxide, silica sand, clay, mica, wollastonite, and diatomaceous earth. , Chromium oxide, cerium oxide, bengara, antimony trioxide, magnesium oxide, zirconium oxide, barium sulfate, barium carbonate, calcium carbonate, silicon carbide, silicon nitride and the like. These may be used alone or in combination of two or more.

The primary particle diameter of the inorganic 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 particle is 20-500 m < ² > / g.
The content of inorganic particles in the toner is preferably 0.01 to 5.0% by mass, and more preferably 0.01 to 5.0% by mass.
These inorganic particles are used after surface treatment from the viewpoints of improvement in fluidity and blocking property, and preservation and water resistance.
Specific examples of the surface treatment 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. Can be mentioned.

Next, as an example of a toner production method, a method for forming toner base particles while producing an adhesive substrate will be described below. In such a method, preparation of an aqueous medium phase, preparation of an oil phase containing a toner material, emulsification or dispersion of the toner material, formation of an adhesive substrate, removal of the solvent, heavy weight having reactivity with active hydrogen groups. Synthesis of a compound, synthesis of a compound having an active hydrogen group, and the like are performed.
The aqueous medium can be prepared by dispersing the resin particles in the aqueous medium.
The addition amount of the resin particles in the aqueous medium is preferably 0.5 to 10% by mass.

The oil phase containing the toner material is prepared in a solvent by a compound having an active hydrogen group, a polymer having a site capable of reacting with the active hydrogen group-containing compound, a colorant, a release agent, a charge control agent, and the polyester. A toner material such as a resin can be dissolved or dispersed.
In the toner material, components other than the polymer having a site capable of reacting with the active hydrogen group-containing compound, the colorant, and the polyester resin are added and mixed in the aqueous medium when the resin particles are dispersed in the aqueous medium. Alternatively, the oil phase containing the toner material may be added to the aqueous medium when it is added to the aqueous medium.

  The emulsification or dispersion of the toner material can be performed by dispersing the oil phase containing the toner material in an aqueous medium. Then, when the toner material is emulsified or dispersed, an adhesive base material is obtained by subjecting a polymer having a site capable of reacting with the active hydrogen group-containing compound and the active hydrogen group-containing compound to an extension reaction and / or a crosslinking reaction. Generate.

Adhesive substrates such as urea-modified polyester-based resins contain, for example, an oil phase containing a polymer having reactivity with active hydrogen groups such as polyester prepolymers having isocyanate groups, and active hydrogen groups such as amines. The oil phase containing the toner material may have an active hydrogen group in advance. The oil phase may be emulsified or dispersed in an aqueous medium together with the compound to be produced, and then both may be subjected to an extension reaction and / or a crosslinking reaction in the aqueous medium. The oil phase containing the toner material may be emulsified or dispersed in an aqueous medium by emulsifying or dispersing it in an aqueous medium to which a compound is added, and subjecting both to an extension reaction and / or a crosslinking reaction in the aqueous medium. Then, a compound having an active hydrogen group is added, and an extension reaction and / or a cross-linking reaction are performed in the aqueous medium from the particle interface. It may be.
When both are subjected to an extension reaction and / or a crosslinking reaction from the particle interface, a urea-modified polyester resin is preferentially formed on the surface of the toner to be produced, and a concentration gradient of the urea-modified polyester resin can be provided in the toner.

  The reaction conditions for producing the adhesive substrate can be appropriately selected according to the combination of the polymer having a site capable of reacting with the active hydrogen group-containing compound and the compound having an active hydrogen group. The reaction time is preferably 10 minutes to 40 hours, more preferably 2 hours to 24 hours. The reaction temperature is preferably 0 to 150 ° C, more preferably 40 to 98 ° C.

  As a method for stably forming a dispersion containing a polymer having a site capable of reacting with an active hydrogen group-containing compound such as a polyester prepolymer having an isocyanate group in an aqueous medium, active hydrogen is added in the aqueous medium phase. An oil phase prepared by dissolving or dispersing a toner material such as a polymer having a site capable of reacting with a group-containing compound, a colorant, a release agent, a charge control agent and the polyester resin in a solvent is added, and shear force is applied. Examples of the method include dispersion.

Dispersion can be performed by using a known disperser, and examples of the disperser include a low speed shear disperser, a high speed shear disperser, a friction disperser, a high pressure jet disperser, an ultrasonic disperser, and the like. Although mentioned, since the particle diameter of a dispersion can be controlled to 2-20 micrometers, a high-speed shearing disperser is preferable.
When a high-speed shearing disperser is used, conditions such as the number of rotations, dispersion time, dispersion temperature and the like can be appropriately selected according to the purpose. The rotation speed is preferably 1000 to 30000 rpm, more preferably 5000 to 20000 rpm. In the case of a batch system, the dispersion time is preferably 0.1 to 5 minutes, and the dispersion temperature is preferably 0 to 150 ° C., more preferably 40 to 98 ° C. under pressure. The dispersion temperature is generally easier to disperse when the temperature is higher.

  The amount of the aqueous medium used when emulsifying or dispersing the toner material is preferably 50 to 2000 parts by mass, more preferably 100 to 1000 parts by mass with respect to 100 parts by mass of the toner material. If the amount used is less than 50 parts by mass, the dispersion state of the toner material may be deteriorated, and toner base particles having a predetermined particle diameter may not be obtained. May be.

In the step of emulsifying or dispersing the oil phase containing the toner material, it is preferable to use a dispersant from the viewpoints of stabilizing the dispersion such as oil droplets to obtain a desired shape and sharpening the particle size distribution.
The dispersant can be appropriately selected according to the purpose, and examples thereof include surfactants, sparingly water-soluble inorganic compound dispersants, and polymeric protective colloids, and surfactants are preferred. These may be used alone or in combination of two or more.

As the surfactant, an anionic surfactant, a cationic surfactant, a nonionic surfactant, an amphoteric surfactant, and the like can be used.
Examples of the anionic surfactant include alkylbenzene sulfonate, α-olefin sulfonate, phosphate ester, and the like, and those having a fluoroalkyl group are preferably used. As an anionic surfactant having a fluoroalkyl group, a fluoroalkylcarboxylic acid having 2 to 10 carbon atoms or a metal salt thereof, disodium perfluorooctanesulfonylglutamate, 3- [ω-fluoroalkyl (C6-C11) oxy ] Sodium 1-alkyl (C3-C4) sulfonate, sodium 3- [ω-fluoroalkanoyl (C6-C8) -N-ethylamino] -1-propanesulfonate, fluoroalkyl (C11-C20) carboxylic acid or Its metal salt, perfluoroalkylcarboxylic acid (C7 to C13) or its metal salt, perfluoroalkyl (C4 to C12) sulfonic acid or its metal salt, perfluorooctanesulfonic acid diethanolamide, N-propyl-N- (2 -Hydroxyethyl) perfluorooctance Lufonamide, perfluoroalkyl (C6-C10) sulfonamidopropyltrimethylammonium salt, perfluoroalkyl (C6-
C10) -N-ethylsulfonylglycine salt, monoperfluoroalkyl (C6-C16) ethyl phosphate, and the like. Commercially available surfactants having a fluoroalkyl group include Surflon S-111, S-112, S-113 (manufactured by Asahi Glass Co., Ltd.), Fluorard FC-93, FC-95, FC-98, FC-129. (Above, manufactured by Sumitomo 3M), Unidyne DS-101, DS-102 (above, manufactured by Daikin Industries, Ltd.), MegaFuck F-110, F-120, F-113, F-191, F-812, F- 833 (above, manufactured by Dainippon Ink Co., Ltd.), Xtop EF-102, 103, 104, 105, 112, 123A, 123B, 306A, 501, 201, 204 (above, manufactured by Tochem Products), Footage 100, 150 (above, manufactured by Neos).

As cationic surfactants, amine salt type surfactants such as alkylamine salts, amino alcohol fatty acid derivatives, polyamine fatty acid derivatives, imidazoline; alkyltrimethylammonium salts, dialkyldimethylammonium salts, alkyldimethylbenzylammonium salts, pyridinium salts And quaternary ammonium salt type surfactants such as alkylisoquinolinium salts and benzethonium chloride. Among them, aliphatic primary, secondary or tertiary amine acids having a fluoroalkyl group, aliphatic quaternary ammonium salts such as perfluoroalkyl (C6-C10) sulfonamidopropyltrimethylammonium salts, benzalkonium salts, benzethonium chloride, Examples include pyridinium salts and imidazolinium salts. Commercially available cationic surfactants include Surflon S-121 (Asahi Glass Co., Ltd.); Florard FC-13
5 (manufactured by Sumitomo 3M); Unidyne DS-202 (manufactured by Daikin Industries, Ltd.), MegaFac F-150, F-824 (manufactured by Dainippon Ink &Co.); Xtop EF-132 (manufactured by Tochem Products); It is preferable to use a footent F-300 (manufactured by Neos).

Examples of nonionic surfactants include fatty acid amide derivatives and polyhydric alcohol derivatives.
Specific examples of the amphoteric surfactant include alanine, dodecyldi (aminoethyl) glycine, di (octylaminoethyl) glycine, N-alkyl-N, N-dimethylammonium betaine.

Specific examples of the hardly water-soluble inorganic compound dispersant include tricalcium phosphate, calcium carbonate, titanium oxide, colloidal silica, and hydroxyapatite.
Polymeric protective colloids include monomers having carboxyl groups, alkyl (meth) acrylates having hydroxyl groups, vinyl ethers, vinyl carboxylates, amide monomers, acid chloride monomers, monomers having nitrogen atoms or heterocyclic rings thereof, and the like. Examples thereof include homopolymers or copolymers obtained by polymerization, polyoxyethylene resins, and celluloses. In addition, the homopolymer or copolymer obtained by polymerizing the above monomers includes those having a structural unit derived from vinyl alcohol.

Specific examples of the monomer having a carboxyl group include acrylic acid, methacrylic acid, α-cyanoacrylic acid, α-cyanomethacrylic acid, itaconic acid, crotonic acid, fumaric acid, maleic acid, maleic anhydride and the like.
Specific examples of the (meth) acrylic monomer containing a hydroxyl group include β-hydroxyethyl acrylate, β-hydroxyethyl methacrylate, β-hydroxypropyl acrylate, β-hydroxypropyl methacrylate, and γ-acrylate. -Hydroxypropyl, γ-hydroxypropyl methacrylate, 3-chloro-2-hydroxypropyl acrylate, 3-chloro-2-hydroxypropyl methacrylate, diethylene glycol monoacrylate, diethylene glycol monomethacrylate, glycerol monoacrylate, glycerol monomethacrylate, etc. Is mentioned.
Specific examples of vinyl ether include vinyl methyl ether, vinyl ethyl ether, vinyl propyl ether and the like.
Specific examples of vinyl carboxylate include vinyl acetate, vinyl propionate, vinyl butyrate and the like.
Specific examples of the amide monomer include acrylamide, methacrylamide, diacetone acrylamide, N-methylol acrylamide, N-methylol methacrylamide and the like.
Specific examples of the acid chloride monomer include acrylic acid chloride and methacrylic acid chloride.
Specific examples of the monomer having a nitrogen atom or a heterocyclic ring thereof include vinyl pyridine, vinyl pyrrolidone, vinyl imidazole, and ethyleneimine.
Specific examples of the polyoxyethylene-based resin include polyoxyethylene, polyoxypropylene, polyoxyethylene alkylamine, polyoxypropylene alkylamine, polyoxyethylene alkylamide, polyoxypropylene alkylamide, polyoxyethylene nonylphenyl ether, Examples include polyoxyethylene lauryl phenyl ether, polyoxyethylene phenyl stearate, and polyoxyethylene pelargonate phenyl.
Specific examples of celluloses include methyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose and the like.

  Specific examples of the dispersant include acids such as calcium phosphate salts and those that are soluble in alkali. When calcium phosphate is used as the dispersant, the calcium phosphate salt can be removed by dissolving the calcium salt with hydrochloric acid or the like and washing it with water or decomposing with an enzyme.

A catalyst can be used for the elongation reaction and / or the crosslinking reaction in producing the adhesive substrate.
Specific examples of the catalyst include dibutyltin laurate and dioctyltin laurate.

As a method for removing the organic solvent from the dispersion liquid such as an emulsified slurry, the temperature of the entire reaction system is gradually raised to evaporate the organic solvent in the oil droplets, and the dispersion liquid is sprayed in a dry atmosphere to obtain the oil. Examples include a method of removing the organic solvent in the droplets.
When the organic solvent is removed, toner base particles are formed. The toner base particles can be washed, dried, etc., and further classified. Classification may be performed by removing fine particle portions in a liquid by a cyclone, decanter, centrifugation, or the like, or classification may be performed after drying.

The obtained toner base particles may be mixed with particles such as a release agent and a charge control agent. At this time, by applying a mechanical impact force, it is possible to prevent particles such as a release agent from detaching from the surface of the toner base particles.
As a method of applying mechanical impact force, a method of applying impact force to a mixture using a blade rotating at a high speed, throwing the mixture into a high-speed air current, and accelerating the particles or particles to an appropriate collision plate The method of making it collide etc. is mentioned.
As an apparatus used in this method, an Ong mill (manufactured by Hosokawa Micron Corporation), an I-type mill (manufactured by Nippon Pneumatic Co., Ltd.) and a pulverization air pressure were lowered, and a hybridization system (manufactured by Nara Machinery Co., Ltd.) Kryptron system (manufactured by Kawasaki Heavy Industries, Ltd.), automatic mortar and the like.

Since the toner of the present invention has a smooth surface, it has excellent properties such as transferability and chargeability, and can form a high-quality image.
Further, when the toner of the present invention contains an adhesive substrate obtained by reacting a compound having an active hydrogen group with a polymer having reactivity to the active hydrogen group in an aqueous medium, the transferability and fixability are improved. Further excellent properties such as Therefore, the toner of the present invention can be used in various fields and can be suitably used for image formation by electrophotography.

The volume average particle diameter of the toner of the present invention is preferably 3 to 8 μm, and more preferably 4 to 7 μm. When the volume average particle diameter is less than 3 μm, in the two-component developer, the toner may be fused to the surface of the carrier during a long period of stirring in the developing device, and the charging ability of the carrier may be reduced.
In the case of a one-component developer, toner filming on the developing roller and toner fusion to a member such as a blade for thinning the toner may occur.
When the volume average particle diameter exceeds 8 μm, it becomes difficult to obtain a high-resolution and high-quality image, and when the balance of the toner in the developer is performed, the fluctuation of the toner particle diameter may increase. .

The ratio of the volume average particle diameter to the number average particle diameter of the toner of the present invention is preferably 1.00 to 1.25, and more preferably 1.05 to 1.25. As a result, with a two-component developer, even if the toner balance is maintained over a long period of time, there is little fluctuation in the toner particle diameter in the developer, and good and stable developability can be obtained even with long-term stirring in the developing device. .
In the case of a one-component developer, even if the balance of the toner is performed, the fluctuation of the toner particle diameter is reduced, and the toner is applied to a member such as a filming of the developing roller or a blade that thins the toner. Therefore, even when the developing device is used (stirred) for a long time, good and stable developability can be obtained, so that a high-quality image can be obtained. When this ratio exceeds 1.25, it becomes difficult to obtain a high-resolution and high-quality image, and when the balance of the toner in the developer is performed, the variation in the toner particle diameter may increase. is there.

The ratio of the volume average particle diameter to the volume average particle diameter and the number average particle diameter can be measured as follows using a particle size measuring device Multisizer III (manufactured by Beckman Coulter, Inc.).
First, 0.1 to 5 ml of a surfactant such as an alkylbenzene sulfonate is added as a dispersant to 100 to 150 ml of an electrolyte aqueous solution such as an approximately 1% by mass sodium chloride aqueous solution.
Next, about 2 to 20 mg of a measurement sample is added. The aqueous electrolyte solution in which the sample is suspended is subjected to a dispersion treatment for about 1 to 3 minutes using an ultrasonic disperser, and then the volume and number of toners are measured using a 100 μm aperture to obtain the volume distribution and number distribution. calculate.
From the obtained distribution, the volume average particle diameter and the number average particle diameter of the toner can be obtained.

The developer of the present invention contains the toner of the present invention, and may further contain other components appropriately selected such as a carrier. For this reason, it is excellent in transferability, chargeability, etc., and a high quality image can be formed stably. The developer may be a one-component developer or a two-component developer. However, when used in a high-speed printer or the like that supports an increase in information processing speed in recent years, the lifetime is shortened. A two-component developer is preferred because it improves.
When the developer of the present invention is used as a one-component developer, even if the balance of the toner is performed, there is little fluctuation in the toner particle diameter, the filming of the toner on the developing roller, the blade for thinning the toner, etc. Therefore, good and stable developability and images can be obtained even with long-term stirring in the developing device.
When the developer of the present invention is used as a two-component developer, there is little fluctuation in the particle diameter of the toner even if toner balance is performed over a long period of time, and good and stable developability even with long-term agitation in the developing device. An image is obtained.

The carrier can be appropriately selected according to the purpose, but a carrier having a core material and a resin layer covering the core material is preferable. The material of the core material can be appropriately selected from known materials, and examples thereof include 50 to 90 emu / g manganese-strontium-based material, manganese-magnesium-based material, and the like.
The volume average particle diameter of the core material is preferably 10 to 150 μm, and more preferably 40 to 100 μm. If the volume average particle size is less than 10 μm, fine particles are increased in the carrier, and magnetization per particle may be reduced to cause carrier scattering. If it exceeds 150 μm, the specific surface area is decreased, and In the case of a full color with many solid portions, the reproduction of the solid portions may be deteriorated.
The content of the carrier in the two-component developer is preferably 90 to 98% by mass, and more preferably 93 to 97% by mass.

  Examples of the present invention will be described below, but the present invention is not limited to the following examples. In the examples, “part” and “%” in each example are based on mass.

[Synthesis Example 1 of Binder Resin]
In a reaction vessel equipped with a condenser, a stirrer and a nitrogen inlet tube, 196 parts of bisphenol A propylene oxide 2 mol adduct, 553 parts of bisphenol A ethylene oxide 2 mol adduct, 210 parts terephthalic acid, 79 parts adipic acid and dibutyl Add 2 parts of tin oxide, react at 230 ° C. for 8 hours at normal pressure, and further react for 5 hours at a reduced pressure of 10 to 15 mmHg. By reacting for a period of time, a polyester binder resin 1 having an acid value (KOH mg / g) of 15.3 shown in Table 1 and a melting point of 94 ° C. was synthesized.

[Synthesis Example 2 of Binder Resin]
In a reaction vessel equipped with a condenser, a stirrer and a nitrogen inlet tube, 164 parts of bisphenol A propylene oxide 2-mole adduct, 500 parts of bisphenol A ethylene oxide 2-mole adduct, 143 parts of terephthalic acid, 126 parts of adipic acid and dibutyl 2 parts of tin oxide was added, reacted at 230 ° C. for 8 hours at normal pressure, and further reacted for 5 hours at a reduced pressure of 10 to 15 mmHg. By reacting for a time, a polyester binder resin 2 having an acid value (KOH mg / g) of 4.7 shown in Table 1 and a melting point of 118 ° C. was synthesized.

[Binder Resin Synthesis Example 3]
In a reaction vessel equipped with a condenser, a stirrer and a nitrogen inlet tube, 48 parts of bisphenol A propylene oxide 2-mole adduct, 500 parts of bisphenol A ethylene oxide 2-mole adduct, 143 parts of terephthalic acid, 126 parts of adipic acid and dibutyl Add 2 parts of tin oxide, react at 230 ° C. for 8 hours at normal pressure, and further react for 5 hours at a reduced pressure of 10-15 mmHg, then add 112 parts of trimellitic anhydride to the reaction vessel and add 2 parts at 180 ° C. at normal pressure. After reacting for a period of time, a polyester binder resin 3 having a melting point of 123 ° C. and an acid value (KOH mg / g) of 46 shown in Table 1 described later was synthesized.

[Synthesis Example 4 of Binder Resin]
In a reaction vessel equipped with a condenser, a stirrer and a nitrogen introduction tube, 113 parts of bisphenol A propylene oxide 2-mole adduct, 500 parts of bisphenol A ethylene oxide 2-mole adduct, 143 parts of terephthalic acid, 126 parts of adipic acid and dibutyl 2 parts of tin oxide was added, reacted at 230 ° C. for 8 hours at normal pressure, and further reacted for 5 hours at a reduced pressure of 10 to 15 mmHg. Then 79 parts of trimellitic anhydride was added to the reaction vessel, and 2 parts at 180 ° C. and normal pressure. By reacting for a period of time, a polyester binder resin 4 having an acid value (KOH mg / g) of 15.3 and a melting point of 120 ° C. shown in Table 1 described later was synthesized.

[Synthesis Example 1 of Pigment Surface Treatment Agent]
In a reaction vessel equipped with a condenser, a stirrer and a nitrogen inlet tube, 41 parts of bisphenol A propylene oxide 2 mol adduct, 113 parts of bisphenol A ethylene oxide 2 mol adduct, 42 parts terephthalic acid, 16 parts adipic acid and dibutyl Add 2 parts of tin oxide, react at 230 ° C for 4 hours at normal pressure, and further react for 5 hours at a reduced pressure of 10 to 15 mmHg. By reacting for a time, a surface treatment agent 1 having a melting point of 76 ° C. and an acid value of 12.4 (KOH mg / g) shown in Table 1 described below and a viscosity of 12 (cp) was synthesized.

[Synthesis Example 2 of Pigment Surface Treatment Agent]
In a reaction vessel equipped with a condenser, a stirrer and a nitrogen introduction tube, 41 parts of bisphenol A propylene oxide 2 mol adduct, 113 parts of bisphenol A ethylene oxide 2 mol adduct, 32 parts of terephthalic acid, 6 parts adipic acid and dibutyl 2 parts of tin oxide was added, reacted at 230 ° C. for 8 hours at normal pressure, and further reacted for 5 hours at a reduced pressure of 10 to 15 mmHg. Then, 4 parts of trimellitic anhydride was added to the reaction vessel, and the reaction pressure was 2 By reacting for a time, a surface treating agent 2 having a melting point of 81 ° C. and an acid value of 12 (KOH mg / g) shown in Table 1 described below and a viscosity of 15 (cp) was synthesized.

[Synthesis Example 3 of Pigment Surface Treatment Agent]
In a reaction vessel equipped with a condenser, a stirrer and a nitrogen introduction tube, 41 parts of bisphenol A propylene oxide 2 mol adduct, 113 parts of bisphenol A ethylene oxide 2 mol adduct, 42 parts terephthalic acid, 16 parts adipic acid and dibutyl 2 parts of tin oxide was added, reacted at 230 ° C. for 8 hours at normal pressure, and further reacted for 5 hours at a reduced pressure of 10 to 15 mmHg. Then, 4 parts of trimellitic anhydride was added to the reaction vessel, and 2 parts at 180 ° C. and an upper pressure of 2 By reacting for a time, a surface treating agent 3 having a melting point of 93 ° C. and an acid value of 23 (KOH mg / g) shown in Table 1 described below and a viscosity of 23 (cp) was synthesized.

[Synthesis Example 4 of Pigment Surface Treatment Agent]
In a reaction vessel equipped with a condenser, a stirrer and a nitrogen inlet tube, 23 parts of bisphenol A propylene oxide 2 mol adduct, 100 parts of bisphenol A ethylene oxide 2 mol adduct, 27 parts terephthalic acid, 21 parts adipic acid and dibutyl 2 parts of tin oxide was added, reacted at 230 ° C. for 8 hours at normal pressure, and further reacted for 5 hours at a reduced pressure of 10-15 mmHg. Then, 6 parts of trimellitic anhydride was added to the reaction vessel, and 2 parts at 180 ° C. at normal pressure. By reacting for a time, a surface treating agent 4 having a melting point of 105 ° C. and an acid value of 18.9 (KOH mg / g) shown in Table 1 described below and a viscosity of 23 (cp) was synthesized.

[Synthesis Example 5 of Pigment Surface Treatment Agent]
In a reaction vessel equipped with a condenser, a stirrer and a nitrogen introduction tube, 41 parts of bisphenol A propylene oxide 2 mol adduct, 113 parts of bisphenol A ethylene oxide 2 mol adduct, 42 parts terephthalic acid, 16 parts adipic acid and dibutyl Add 2 parts of tin oxide, react at 230 ° C for 2 hours at normal pressure, and further react for 5 hours at reduced pressure of 10-15 mmHg, then add 4 parts of trimellitic anhydride to the reaction vessel, and add 2 parts at 180 ° C at the upper pressure. By reacting for a time, a surface treating agent 5 having a melting point of 63 ° C. and an acid value of 9.6 (KOH mg / g) shown in Table 1 and a viscosity of 6.3 (cp) was synthesized.

[Synthesis Example 6 of Pigment Surface Treatment Agent]
In a reaction vessel equipped with a condenser, a stirrer and a nitrogen inlet tube, 9 parts of bisphenol A propylene oxide 2 mol adduct, 100 parts of bisphenol A ethylene oxide 2 mol adduct, 28 parts terephthalic acid, 26 parts adipic acid and dibutyl 2 parts of tin oxide was added, reacted at 230 ° C. for 8 hours at normal pressure, and further reacted for 5 hours at a reduced pressure of 10 to 15 mmHg. By reacting for a time, a surface treatment agent 6 having a melting point of 120 ° C. and an acid value of 22.3 (KOH mg / g) shown in Table 1 described below and a viscosity of 31 (cp) was synthesized.

[Synthesis Example 7 of Pigment Surface Treatment Agent]
In a reaction vessel equipped with a condenser, a stirrer and a nitrogen inlet tube, 41 parts of bisphenol A propylene oxide 2 mol adduct, 113 parts of bisphenol A ethylene oxide 2 mol adduct, 34 parts terephthalic acid, 21 parts adipic acid and dibutyl 2 parts of tin oxide was added, reacted at 230 ° C. for 4 hours at normal pressure, and further reacted for 5 hours at a reduced pressure of 10 to 15 mmHg. Then, 21 parts of trimellitic anhydride was added to the reaction vessel, and 2 parts at 180 ° C. and an upper pressure of 2 After reacting for a time, a surface treating agent 7 having a melting point of 71 ° C. and an acid value of 10.5 (KOH mg / g) shown in Table 1 and a viscosity of 3.5 (cp) was synthesized.

[Synthesis Example 8 of Pigment Surface Treatment Agent]
In a reaction vessel equipped with a condenser, a stirrer and a nitrogen inlet tube, 9 parts of bisphenol A propylene oxide 2 mol adduct, 100 parts of bisphenol A ethylene oxide 2 mol adduct, 28 parts terephthalic acid, 26 parts adipic acid and dibutyl 2 parts of tin oxide was added, reacted at 230 ° C. for 8 hours at normal pressure, and further reacted for 5 hours at a reduced pressure of 10 to 15 mmHg. After reacting for a time, a surface treating agent 8 having a melting point of 108 ° C. and an acid value of 21.5 (KOH mg / g) shown in Table 1 and a viscosity of 55 (cp) was synthesized.

[Measurement method of acid value]
In accordance with the measurement method described in JIS K0070-1992, measurement is performed under the following conditions.
Sample preparation: 0.5 g of sample is added to 120 ml of toluene and dissolved by stirring at room temperature (23 ° C.) for about 10 hours. Further, 30 ml of ethanol is added to prepare a sample solution.
The measurement can be calculated by the apparatus described above, and specifically, the calculation is performed as follows.
Titrate with a pre-standardized N / 10 caustic potash to alcohol solution, and determine the acid value from the consumption of the alcohol potash solution by the following calculation.
Acid value = KOH (ml) × N × 56.1 / Sample weight
(N is a factor of N / 10KOH)

[Measurement of melting point of binder resin and pigment surface treatment resin]
The melting point in the present invention is determined by the peak top indicating the maximum endotherm of the DSC curve in differential scanning calorimetry (DSC).
The measurement was performed under the following measurement conditions using TA-60WS and DSC-60 manufactured by Shimadzu Corporation.
Measurement conditions Sample container: Aluminum sample pan (with lid)
Sample amount: 5mg
Reference: Aluminum sample pan (alumina 10mg)
Atmosphere: Nitrogen (flow rate 50 ml / min)
Temperature condition start temperature: 20 ° C
Temperature increase rate: 10 ° C / min
End temperature: 150 ° C
Holding time: None Temperature drop: 10 ° C / min
End temperature: 20 ° C
Holding time: None Temperature increase rate: 10 ° C / min
End temperature: 150 ° C

50% of the binder resin 1 obtained in the binder resin synthesis example 1 and the ratio shown in Table 1 (CI Pigment Yellow 155 / DIC Corporation: CI Pigment Yellow 185 / BASF Corporation = 75:25) and 10% of the surface treatment agent 1 obtained in the surface treatment agent synthesis example 1 were mixed at 1000 rpm for 5 minutes with a Henschel mixer (manufactured by Mitsui Mining Co., Ltd.). After that, the mixture was kneaded with an open roll kneader (manufactured by Mitsui Mining Co., Ltd.), and a pigment dispersion powder having a size of 2 mm was prepared with a rotoplex grinder to obtain a master batch.
In a beaker, 10 parts of a polyester prepolymer, 75 parts of a polyester resin and 130 parts of ethyl acetate were stirred and dissolved.
Next, 5 parts of paraffin wax and 20 parts of the above master batch were added, and the particle size was measured at a feeding speed of 1 kg / hour and a peripheral speed of the disk of 6 m / second using an ultra visco mill (manufactured by Imex). Three passes were performed under the condition of filling 80% by volume of 0.5 mm zirconia beads. Further, 2.7 parts of a ketimine compound was added and dissolved to prepare a toner material liquid.
Add 150 parts of an aqueous medium into a container, add 100 parts of toner material solution while stirring at 12,000 rpm using a TK homomixer (made by Tokushu Kika Kogyo Co., Ltd.), and mix for 10 minutes to prepare an emulsified slurry. did.
In a Kolben equipped with a stirrer and a thermometer, 100 parts of an emulsified slurry was charged, and the solvent was removed at 30 ° C. for 12 hours while stirring at a stirring peripheral speed of 20 m / min to obtain a dispersed slurry.
After filtering 100 parts of the dispersion slurry under reduced pressure, 100 parts of ion-exchanged water was added to the filter cake, followed by mixing at 12000 rpm for 10 minutes using a TK homomixer, followed by filtration.
To the obtained filter cake, 300 parts of ion-exchanged water was added, mixed for 10 minutes at 12000 rpm using a TK homomixer, and then filtered twice.
To the obtained filter cake, 20 parts of a 10% by weight aqueous sodium hydroxide solution was added, mixed at 12000 rpm for 30 minutes using a TK homomixer, and then filtered under reduced pressure. To the obtained filter cake, 300 parts of ion-exchanged water was added, mixed at 12000 rpm for 10 minutes using a TK homomixer, and then filtered.
To the obtained filter cake, 300 parts of ion-exchanged water was added, mixed for 10 minutes at 12000 rpm using a TK homomixer, and then filtered twice.
Further, 20 parts of 10 wt% hydrochloric acid was added to the obtained filter cake, and the mixture was mixed for 10 minutes at 12000 rpm using a TK homomixer, and then filtered.
To the obtained filter cake, 300 parts of ion-exchanged water was added, mixed for 10 minutes at 12000 rpm using a TK homomixer, and then filtered twice to obtain a filter cake.
The obtained final filter cake was dried at 45 ° C. for 48 hours using a circulating dryer, and sieved with a mesh having a mesh size of 75 μm to obtain toner mother particles.
To 100 parts of the obtained toner base particles, 1.0 part of hydrophobic silica as an external additive and 0.5 part of hydrophobized titanium oxide are added and mixed using a Henschel mixer (Mitsui Mining Co., Ltd.). Thus, a toner for evaluation was produced.

  Instead of the yellow pigment in Example 1, a yellow pigment mixed at a ratio shown in Table 1 (CI Pigment Yellow 155 / DIC Corporation: CI Pigment Yellow 185 / BASF Corporation = 85: 15) was used. A toner for evaluation was produced in the same manner as in Example 1 except that it was used.

  Without passing through the master batch of the yellow pigment in Example 2, mixing was performed at the ratio shown in Table 1 (CI Pigment Yellow 155 / DIC Corporation: CI Pigment Yellow 185 / BASF Corporation = 85: 15). An evaluation toner was prepared in the same manner as in Example 2 except that the yellow pigment was used.

  An evaluation toner was prepared in the same manner as in Example 2 except that the surface treatment of the yellow pigment in Example 2 was not performed.

  An evaluation toner was prepared in the same manner as in Example 2 except that the surface treatment agent 2 obtained in the surface treatment agent synthesis example 2 was used instead of the surface treatment agent 1 of the yellow pigment in Example 2. .

  A toner for evaluation was prepared in the same manner as in Example 2 except that the surface treatment agent 3 obtained in the surface treatment agent synthesis example 3 was used instead of the surface treatment agent 1 of the yellow pigment in Example 2. did.

  A toner for evaluation was produced in the same manner as in Example 2 except that the binder resin 2 obtained in the binder resin synthesis example 2 was used instead of the binder resin 1 in Example 2.

  An evaluation toner was prepared in the same manner as in Example 2 except that the binder resin 3 obtained in Binder Resin Synthesis Example 3 was used instead of the binder resin 1 in Example 2.

  An evaluation toner was prepared in the same manner as in Example 2 except that the surface treatment agent 4 obtained in the surface treatment agent synthesis example 4 was used instead of the surface treatment agent 1 of the yellow pigment in Example 2. did.

  A toner for evaluation was prepared in the same manner as in Example 2 except that the surface treatment agent 5 obtained in the surface treatment agent synthesis example 5 was used instead of the surface treatment agent 1 of the yellow pigment in Example 2. did.

  A toner for evaluation was produced in the same manner as in Example 2 except that the surface treatment agent 6 obtained in the surface treatment agent synthesis example 6 was used instead of the surface treatment agent 1 of the yellow pigment in Example 2. did.

  An evaluation toner was prepared in the same manner as in Example 2 except that the surface treatment agent 7 obtained in the surface treatment agent synthesis example 7 was used instead of the surface treatment agent 1 of the yellow pigment in Example 2. did.

  A toner for evaluation was produced in the same manner as in Example 2 except that the surface treatment agent 8 obtained in the surface treatment agent synthesis example 8 was used instead of the surface treatment agent 1 of the yellow pigment in Example 2. did. These are summarized in the following table.

[Comparative Example 1]
The binder resin 4 obtained in the binder resin synthesis example 4 was used in place of the binder resin 1 in Example 2, and the ratios shown in Table 1 (C.I.) were used instead of the yellow pigment in Example 2. Pigment Yellow 155 / manufactured by DIC: CI Pigment Yellow 185 / manufactured by BASF = 45: 55) Was made.

[Comparative Example 2]
The binder resin 4 obtained in the binder resin synthesis example 4 was used in place of the binder resin 1 in Example 2, and the ratios shown in Table 1 (C.I.) were used instead of the yellow pigment in Example 2. Pigment Yellow 155 / manufactured by DIC: CI Pigment Yellow 185 / manufactured by BASF = 98: 2) A toner for comparative evaluation was carried out in the same manner as in Example 2 except that the yellow pigment was used. Was made.

[Comparative Example 3]
The binder resin 4 obtained in the binder resin synthesis example 4 was used in place of the binder resin 1 in Example 2, and the ratios shown in Table 1 (C.I.) were used instead of the yellow pigment in Example 2. Pigment Yellow 155 / DIC Corporation: CI Pigment Yellow 185 / BASF Corporation = 75: 25, the same mixing ratio as in Example 1) except that a yellow pigment was used. A toner for comparative evaluation was produced in the same manner.

[Comparative Example 4]
A comparative evaluation toner was prepared in the same manner as in Example 2 except that the binder resin 4 obtained in Binder Resin Synthesis Example 4 was used instead of the binder resin 1 in Example 2. These are summarized in the following table.

(Color reproducibility evaluation and coloring degree evaluation)
As with the image density evaluation, only the paper is imaged on Tokishi Art N 110Kg (Mitsubishi Paper Co., Ltd.) so that the adhesion amount is 0.4 mg / cm ^2, and the fixing member temperature is always 160 ° C. After being controlled, the sample was fixed at a linear velocity of 280 mm / sec to obtain a sample for evaluation.
The chromaticness index a ^* and b ^* in the L ^* a ^* b ^* color system (CIE: 1976) was measured for the formed solid image using a chromaticity meter (X-Rite 938, manufactured by X-Rite). Then, the value of C ^{* represented by} the following formula (1) was determined, and the saturation of each color toner was evaluated.
C * = [(a ^* ) 2+ (b ^* ) 2] 1/2 Formula (1)
The evaluation criteria for saturation are as follows.
A: Very good. C ^* is 75 or more ○: Good. C ^* is 73 or more and less than 75 Δ: Somewhat poor. C ^* is 70 or more and less than 73 x: Defect. C ^* is less than 70 The results are shown in Table 2.
Further, from the calculated a ^* b ^* , the color difference from JapanColor was calculated from the following equation (2), and ΔE was evaluated.
ΔE = [(a ^* ) 2- (b ^* ) 2] 1/2 Formula (2)
The evaluation criteria for color difference are as follows.
A: Very good. ΔE is less than 1 ○: Good. ΔE is 1 or more and less than 3 Δ: Somewhat bad. ΔE is 3 or more and less than 5 x: Defect. ΔE is 5 or more The results are shown in Table 2.

Further, the image density of the sample was measured using a chromaticity meter (X-Rite 938, manufactured by X-Rite).
The image density evaluation criteria are as follows.
A: Very good. Image density of 1.5 or more ○: Good. C ^* is 1.4 or more and less than 1.5 Δ: Somewhat poor. C ^* is 1.3 or more and less than 1.4 x: Defect. C ^* is less than 1.3. The results are shown in Table 2.

(Long-term running test under high temperature and high humidity)
The toner obtained above and 60 μm ferrite carrier were mixed with stirring at a toner concentration of 4% for 20 minutes to obtain a two-component developer. The two-component developer was subjected to a printing durability test of 50000 sheets at a document density of 5% using a copying machine (Imagio Neo C355) manufactured by Ricoh Co., Ltd. in an environment of 40 ° C./80%.
The image densities of the formed first and 50,000th fixed images were measured by a reflection densitometer manufactured by Macbeth (modified so that three decimal places can be measured). Measure the density difference between the unused paper and the white area of the fixed image. If the density difference is less than 0.01, ◎, 0.01 to less than 0.02, ○, 0.02 to less than 0.03 Was judged as x for cases where Δ was 0.03 or more.
<Evaluation results>
Table 2 shows the results of the above evaluation.

According to the evaluation result, the toner of Comparative Example 1 was a toner having a low color saturation and a large color difference because of the high ratio of Pigment Yellow 185. Since the toner of Comparative Example 2 has a low ratio of Pigment Yellow 185, the toner has a large color difference and a low coloring degree. Since the toners of Comparative Examples 3 and 4 used Pigment Yellow 180 as the pigment, the pigment was segregated, resulting in a toner having low color saturation and a large color difference.
On the other hand, since the toners of Examples 1 to 13 satisfy the requirements of the scope of the present invention, toners having high saturation, excellent hue, and no stain on running under high temperature and high humidity were obtained.

JP-B-2-37949 JP-A-6-230607 JP-A-6-266163 JP-A-8-262799 JP-A-11-65172 JP 2005-106932 A Japanese Patent No. 4011476

Claims (22)

  In a toner granulated from an aqueous medium suspension obtained by suspending droplets of an oil phase containing at least a binder resin, a colorant, and a release agent, C.I. I. Pigment Yellow 155 and an isoindoline pigment C.I. I. Pigment Yellow 185, and C.I. I. Pigment Yellow 155 and an isoindoline pigment C.I. I. An electrophotography wherein the mixing ratio with CI Pigment Yellow 185 is 95: 5 to 50:50, and the total of the colorants is contained in an amount of 5 to 15 parts by mass with respect to 100 parts by weight of the binder resin. For yellow toner.   2. The electrophotographic yellow toner according to claim 1, wherein a master batch obtained by dispersing in advance in a binder resin is used as the colorant.   3. The yellow toner for electrophotography according to claim 1, wherein the colorant is surface-treated with an acidic surface treatment agent.   4. The electrophotographic yellow toner according to claim 1, wherein the surface treatment agent has an acid value of 3 KOHmg / g or more and 20 KOHmg / g or less.   5. The electrophotographic yellow toner according to claim 2, wherein the master batch resin has an acid value of 5 KOHmg / g or more and 40 KOHmg / g or less.   The master batch is obtained in advance by dispersing a binder resin, a surface treatment agent, and a colorant, and the dispersion is melt kneading. Yellow toner for electrophotography.   The electrophotographic yellow toner according to claim 6, wherein the melting point of the surface treatment agent is lower than the melting point of the binder resin.   The electrophotographic yellow toner according to claim 6, wherein the melting point of the surface treatment agent is 70 ° C. or higher and 110 ° C. or lower.   9. The yellow toner for electrophotography according to claim 6, wherein the release agent has a viscosity at 90 ° C. of 5 centipoise or more and 50 centipoise or less.   10. The electrophotographic apparatus according to claim 6, wherein the dispersion in which the binder resin, the release agent, and the colorant are dispersed in advance uses a press cake pigment that has been washed with a pigment as the colorant. Yellow toner.   11. The yellow toner for electrophotography according to claim 6, wherein the melt mixing is performed using an open type melt kneader.   In a toner manufacturing method including a step of suspending and granulating an oil phase containing at least a binder resin, a colorant and a release agent in an aqueous medium, C.I. I. Pigment Yellow 155 and an isoindoline pigment C.I. I. Pigment Yellow 185 and C.I. I. Pigment Yellow 155 and an isoindoline pigment C.I. I. An electrophotography wherein the mixing ratio with CI Pigment Yellow 185 is 95: 5 to 50:50, and the total of the colorants is contained in an amount of 5 to 15 parts by mass with respect to 100 parts by weight of the binder resin. Of manufacturing yellow toner.   13. The method for producing a yellow toner for electrophotography according to claim 12, wherein a master batch obtained by dispersing the colorant in a binder resin is used.   14. The method for producing a yellow toner for electrophotography according to claim 12, further comprising a step of surface-treating the colorant with an acidic surface treatment agent.   The method for producing a yellow toner for electrophotography according to any one of claims 12 to 14, wherein the surface treating agent has an acid value of 3 KOHmg / g or more and 20 KOHmg / g or less.   The method for producing a yellow toner for electrophotography according to any one of claims 12 to 15, wherein the resin for the masterbatch has an acid value of 5 KOHmg / g or more and 40 KOHmg / g or less.   17. The method for producing a yellow toner for electrophotography according to claim 14, wherein the dispersion step of dispersing the binder resin, the surface treatment agent and the colorant in advance is a melt kneading step.   The method for producing a yellow toner for electrophotography according to claim 17, wherein the melting point of the surface treatment agent is lower than the melting point of the binder resin.   The method for producing a yellow toner for electrophotography according to claim 17 or 18, wherein the melting point of the surface treatment agent is 70 ° C or higher and 110 ° C or lower.   The method for producing a yellow toner for electrophotography according to any one of claims 17 to 19, wherein the release agent has a viscosity at 90 ° C of 5 centipoise or more and 50 centipoise or less.   21. The method according to any one of claims 17 to 20, wherein the dispersion step of dispersing the binder resin, the release agent, and the colorant in advance uses a presscake pigment after pigment washing as the colorant. Of producing a yellow toner for electrophotography.   The production of a yellow toner for electrophotography according to any one of claims 17 to 21, wherein an open-type melt kneader is used in the step of previously melting and mixing the binder resin, the release agent, and the colorant. Method.